JP6343066B2 - Coating film, aqueous composition, and painted product - Google Patents

Description

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

  The surface of outdoor structures such as building exteriors, bridges, tanks, etc. are painted with paints, 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 outlet. Such contamination of the paint film is usually dark and significantly impairs the aesthetics of buildings and outdoor structures.

  As an aqueous topcoat coating composition that suppresses contamination of the coating film as described above, the applicant comprises an undercoat layer and an overcoat layer provided on the undercoat layer, and the undercoat layer is composed of water and an emulsifier. Formed by drying the coating film of the coating composition (I) for the undercoat containing the polymer emulsion particles (A) obtained by a method comprising a step of polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of each other The metal oxide particles (B) having photocatalytic activity, and a method comprising polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier, respectively. A film formed by drying a coating film of a coating composition (II) for topcoat containing the obtained polymer emulsion particles (C) and colloidal silica (D) That, a multilayer coating film has been proposed (see Patent Document 1).

JP 2010-005595 A

  In the technique described in Patent Document 1, since a material having a high glass transition temperature is used as the undercoat layer, even if it is an overcoat layer formed from a coating composition for overcoating, sufficient stain resistance and weather resistance are obtained. can get. Thus, although the technique of patent document 1 is an outstanding technique, the present inventors tried further improvement and the development of the more outstanding technique. For example, when the overcoating composition as described in Patent Document 1 is overcoated on a base material using a material having a glass transition temperature of about 0 to 20 ° C. that is widely used for building exteriors and the like, The overcoat layer formed from the composition may not be able to sufficiently follow a base material that expands and contracts due to a change in the external temperature or the like. In such a case, cracks or the like may occur in the overcoat layer, and the gloss may decrease due to the cracks and the appearance may be impaired. Furthermore, dust, smoke, sand, etc. may adhere to the cracked part and become contaminated. If such a point can be improved with respect to the coating film, the realization of a coating film excellent in various physical properties such as appearance and stain resistance can be expected without being restricted by the base material.

  This invention is made | formed in view of the said situation, and it aims at providing the coating film which can maintain an external appearance and stain resistance at a high level.

  As a result of intensive studies, the present inventors have found that a polymer (B) containing a polymer (A) having a structural unit derived from dimethyldimethoxysilane (a) and an inorganic oxide (C) having no photocatalytic activity. It is a coating film containing, Comprising: The content of the polymer (A) which has a structural unit derived from dimethyldimethoxysilane (a) is 25 to 48 mass%, and it finds that the solution of the said subject is aimed at The present invention has been completed.

That is, the present invention is as follows.
[1]
A coating film containing a polymer (B) containing a polymer (A) having a structural unit derived from dimethyldimethoxysilane (a), and an inorganic oxide (C) having no photocatalytic activity, the coating film the content of the component (a) is 31.7 to 48 wt% in the coating film.
[2]
The coating film according to [1], wherein the inorganic oxide (C) is silicon dioxide.
[3]
The coating film according to [1] or [2], further containing an inorganic oxide (D) having photocatalytic activity.
[4]
The coating film according to any one of [1] to [3], further containing a fluorocarbon surfactant (E).
[5]
The coating film according to any one of [1] to [4], further containing a fading dye (F).
[6]
The coating film according to any one of [1] to [5], further containing a cellulose-based thickener (G).
[7]
The coating film according to any one of [1] to [6], further containing an algae and / or an antifungal agent (H).
[8]
The aqueous composition from which the coating film as described in any one of [1]-[7] is obtained.
[9]
The aqueous composition according to [8], containing the dispersion (BD) of the polymer (B) and the inorganic oxide (C).
[10]
[1] to [7] A coated product comprising the coating film according to any one of [7].

  ADVANTAGE OF THE INVENTION According to this invention, the coating film which can maintain an external appearance and stain resistance at a high level can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof. Unless otherwise specified, “(meth) acrylate” means “acrylate” and its corresponding “methacrylate”, and “(meth) acryl” means “acryl” and its corresponding “methacryl”. To do.

The coating film of this embodiment is a coating containing a polymer (B) containing a polymer (A) having a structural unit derived from dimethyldimethoxysilane (a) and an inorganic oxide (C) having no photocatalytic activity. It is a film and is a coating film whose content of the (A) component in a coating film is 25-48 mass%.
The coating film of this embodiment can be obtained from an aqueous composition. Although an aqueous composition will be described later, as a preferred embodiment, a dispersion (BD) of a polymer (B) containing a polymer (A) having a structural unit derived from dimethyldimethoxysilane (a), and photocatalytic activity And an aqueous composition containing an inorganic oxide (C) that does not contain a salt. Hereinafter, each component will be described.

<(A) component, (B) component, etc.>
The coating film of this embodiment contains at least (B) component containing (A) component, and content of the (A) component in a coating film is 25-48 mass%. The polymer (A) having a structural unit derived from dimethyldimethoxysilane (a) is a polymer (A) obtained by polymerizing at least dimethyldimethoxysilane (a) as a monomer. As will be described later, the polymer (A) of the present embodiment may use at least dimethyldimethoxysilane (a) as a monomer, and dimethyldimethoxysilane (a) and other monomers may be used. Needless to say, a polymer obtained by copolymerizing the above is also included. And a polymer (B) points out all the polymer components contained in the coating film of this embodiment. For example, it can be said that the polymer (B) is a polymer component including the polymer (A). For example, it can be said that the polymer (B) is a polymer component including not only the polymer (A) but also other polymers.

  When the content of the component (A) in the coating film is less than 25% by mass, the weather resistance of the coating film is not sufficient, and the appearance and stain resistance cannot be maintained at a high level. On the other hand, when the content of the component (A) in the coating exceeds 48% by mass, the contamination resistance of the coating becomes insufficient. From this viewpoint, the lower limit value of the ratio of the component (A) is 25% by mass or more, and preferably 35% by mass or more. (A) The upper limit of the ratio of a component is 48 mass% or less, Preferably it is 45 mass% or less, More preferably, it is 42 mass% or less.

The content (mass%) of the component (A) in the coating film is the total solid content of the aqueous composition, the solid content of the component (B), and the content of the component (A) contained in the component (B) described later ( Mass%) based on the following formula. In addition, content (mass%) of the (A) component in a coating film can be measured using Si solid state NMR.

Content (mass%) of component (A) of coating film = [solid content of component (B) × content of component (A) in component (B) (mass%)] ÷ total solid content

  The coating film of the present embodiment is, for example, various aqueous compositions containing a dispersion (BD) of the component (B) containing the component (A) and a dispersion of the inorganic oxide (C) having no photocatalytic activity. It can form suitably by apply | coating to the surface of a base material and making it dry.

  (BD) component includes (B) component including (A) component, octamethylcyclotetrasiloxane (m) and / or decamethylcyclopentasiloxane (n) (hereinafter referred to as (m) component and (n) component. It may be a dispersion of the component (B) further containing “(M) component”.

  The mode of the dispersion (BD) of the component (B) is not particularly limited, but is preferably an aqueous dispersion from the viewpoint of being aqueous. Examples of such an aqueous dispersion of the component (B) include an aqueous dispersion obtained by at least emulsion polymerization of dimethyldimethoxysilane (a). Further, it may be a water dispersion obtained by emulsion polymerization of dimethyldimethoxysilane (a) and a hydrolyzable silicon compound other than the component (a) and / or a vinyl monomer. Examples thereof include those in which the polymer (B) is dispersed in water as a dispersion medium. These can be appropriately selected in consideration of, for example, the structure of the (BD) component.

Although it does not specifically limit as a hydrolysable silicon compound other than (a) component, Preferably the compound represented by following formula (1), a silane coupling agent, and these condensates are mentioned.

SiWxRy (1)

Wherein W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group and an amide group. R represents at least one selected from the group consisting of: 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, It represents at least one group selected from the group consisting of aryl groups having 6 to 20 carbon atoms substituted with a halogen atom, x is an integer of 1 to 4 and y is an integer of 0 to 3 X + y = 4 When W is plural and when R is plural, each W and R may be the same or different.

  A silane coupling agent is, for example, a hydrolyzable silicon compound in which a functional group having reactivity with an organic substance such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a thiol group, or an isocyanate group exists in the molecule. Represents.

Specific examples of the silicon alkoxide and the silane coupling agent which are one embodiment of the hydrolyzable silicon compound represented by the formula (1) are not particularly limited as long as they are other than the component (a). For example, tetramethoxy Tetraalkoxysilanes such as silane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxy Run, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, 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-hydroxypro Lutriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysila , Trialkoxysilanes such as 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane , Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxy Silane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octy Dimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, etc. Dialkoxysilanes; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane;

  Among the above, the silicon alkoxide is not particularly limited, but tetrafunctional silicon alkoxide is preferably used, and tetramethoxysilane and tetraethoxysilane are more preferable from the viewpoint of hydrolysis rate.

  These silicon alkoxides and silane coupling agents may be used alone or in combination of two or more.

  The weight average molecular weight in terms of polystyrene of the condensate of silicon alkoxide or silane coupling agent is not particularly limited, but is preferably 200 to 5000, more preferably 300 to 1000. By using a condensate having a weight average molecular weight within the above range, the polymerization stability is further improved. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  The hydrolyzable silicon compound is not particularly limited, but is preferably a silane coupling agent having at least a vinyl polymerizable group and / or a thiol group, and preferably a silane coupling agent having at least a vinyl polymerizable group. More preferred. Since the vinyl polymerizable group and the thiol group have high reactivity with the vinyl monomer described above, chemical bonds can be efficiently formed by copolymerization reaction or chain transfer reaction with the vinyl monomer. Therefore, as the hydrolyzable silicon compound, other components constituting the component (A) by using a silane coupling agent having a vinyl polymerizable group or a thiol group having a thiol group (for example, a vinyl monomer) ). By using such a component (B) in which a hydrolyzable silicon compound (or a polymerization product thereof) and a vinyl monomer (or a polymerization product thereof) are combined by a chemical bond, weather resistance and strength are improved. Etc. can be formed (however, the action of the present embodiment is not limited to these).

  Specific examples of the silane coupling agent having a vinyl polymerizable group are not particularly limited. For example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- ( Meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane , 2-trimethoxysilylethyl vinyl ether and the like.

  Specific examples of the silane coupling agent having a thiol group are not particularly limited, and examples thereof include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

  The total amount of the silane coupling agent having at least a vinyl polymerizable group and / or a thiol group with respect to 100 parts by mass of component (B) is preferably 0.1 to 10 parts by mass from the viewpoint of polymerization stability.

  The vinyl monomer that can be used for producing the component (B) is not particularly limited as long as it is a vinyl monomer having a functional group. Specific examples of vinyl monomers include, for example, (meth) acrylic acid esters, aromatic vinyl compounds, vinyl cyanide compounds, carboxyl group-containing vinyl compounds, hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, and secondary amide groups. And / or vinyl compounds having a tertiary amide group, anionic vinyl compounds, and the like.

  It does not specifically limit as a specific example of (meth) acrylic acid ester, For example, it has a C1-C50 alkyl group (meth) acrylic-acid alkyl ester, C1-C100 ethylene oxide group (poly) Examples include oxyethylene di (meth) acrylate.

  Specific examples of the (meth) acrylic acid ester are not particularly limited. 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.

  Specific examples of (poly) oxyethylene di (meth) acrylate are not particularly limited, and examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, di ( And (meth) acrylic acid tetraethylene glycol.

  Specific examples of the aromatic vinyl compound are not particularly limited, and examples thereof include styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, vinyltoluene and the like.

  Specific examples of the vinyl cyanide compound are not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like.

  Specific examples of the carboxyl group-containing vinyl compound are not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, maleic acid, and fumaric acid. Examples include half esters of dibasic acids.

  By using a vinyl monomer containing a carboxyl group, the carboxyl group can be introduced into the component (B). Accordingly, it is presumed that the stability as an emulsion can be further improved, and it is possible to have a high resistance to an external dispersion breaking action (however, the action of this embodiment is not limited thereto). At this time, a part or all of the introduced carboxyl group can be neutralized with an amine such as ammonia, triethylamine or dimethylethanolamine, or a base such as NaOH or KOH. The use amount of the carboxyl group-containing vinyl monomer in the total amount of the vinyl monomer is preferably 0 to 10% by mass from the viewpoint of water resistance, but is not limited thereto.

  Specific examples of the hydroxyl group-containing vinyl compound are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meta ) Hydroxyalkyl esters of (meth) acrylic acid such as acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fuma Rate, (poly) oxyethylene mono (meth) acrylate having 1 to 100 ethylene oxide groups; (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups; , ‘ Kuseru FM monomer "," PLACCEL FA Monomer "(both, trade names of Daicel Chemical Industries, Ltd. of caprolactone addition monomer) and other alpha, hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid.

  Specific examples of (poly) oxyethylene (meth) acrylate are not particularly limited. For example, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, methoxy (meth) Examples include diethylene glycol acrylate, tetraethylene glycol (meth) acrylate, and tetraethylene glycol methoxy (meth) acrylate.

  Specific examples of (poly) oxypropylene (meth) acrylate are not particularly limited. For example, propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, methoxy ( Examples thereof include dipropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, and tetrapropylene glycol methoxy (meth) acrylate.

  Specific examples of the glycidyl group-containing vinyl compound are not particularly limited, and examples thereof include glycidyl (meth) acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether.

  Specific examples of the vinyl monomer having a secondary amide group and / or a tertiary amide group are not particularly limited, and examples thereof include N-alkyl-substituted (meth) acrylamide and N-alkylene-substituted (meth) acrylamide. It is done.

  Specific examples of the N-alkyl-substituted (meth) acrylamide are not particularly limited. For example, 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-vinylcaprolactam , N, N′-methylenebis ( Examples include meth) acrylamide, N-vinylacetamide, diacetone (meth) acrylamide, and N-methylol (meth) acrylamide.

  Specific examples of vinyl monomers other than the above include, for example, olefins such as (meth) acrylamide, ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride, vinylidene chloride, tetrafluoroethylene, chlorotri Haloolefins such as fluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, lauric acid Carboxylic acid vinyl esters such as vinyl; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether; styrene Aromatic vinyl compounds such as vinyltoluene; 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, perfluoropropyromethyl (meth) Examples include acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate. Any of these may be used alone or in combination of two or more.

The content of the component (A) in the component (B) is not particularly limited, but is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less. preferable. By making content of (A) component below the said upper limit, the remaining unreacted (a) component and (M) component can be reduced and the stain resistance of the coating film can be further improved.
The content of the component (A) in the component (B) is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more. Is more preferable. By making content of (A) component more than the said lower limit, the weather resistance of a coating film can be improved further.

The content (mass%) of the component (A) in the component (B) is obtained as the heating residue of the component (BD). The content of the component (B) (total amount of the polymer), the preparation of the component (a) From the amount, the content of the unreacted component (a) obtained by measurement by gas chromatography, the content of octamethylcyclotetrasiloxane (m), and the content of decamethylcyclopentasiloxane (n), the following formula ( It can be obtained by calculation using I). Specifically, it can be determined according to the method described in Examples described later.
Formula (I):
A: Content (% by mass) of structural units derived from dimethyldimethoxysilane (a)
x: Charge amount of dimethyldimethoxysilane (a) (g)
a: Content (% by mass) of unreacted dimethyldimethoxysilane (a)
m: Content (mass%) of octamethylcyclotetrasiloxane (m)
n: Content (% by mass) of decamethylcyclopentasiloxane (n)

  In the case where the polymer dispersion (BD) contains the (M) component, the content of the (M) component in the (BD) component is not particularly limited, but is 0.1% with respect to 100 parts by mass of the (B) component. It is preferably 9 parts by mass or less, more preferably 0.8 parts by mass or less, and still more preferably 0.5 parts by mass or less. By reducing the content of the component (M) to the upper limit value or less, it is possible to obtain a coating film with further excellent contamination resistance.

  The component (M) may be generated simultaneously when the component (B) is obtained by emulsion polymerization. Therefore, the occurrence of the component (M) can be suppressed by adjusting the polymerization conditions such as the polymerization temperature, polymerization time, and catalyst amount of emulsion polymerization.

  As a preferable method for reducing the content of the component (M), for example, in the emulsion polymerization, after the dropping of the component (a) is completed, the catalyst is added to 0.5 to 3.0 with respect to the charged amount of the component (a). A method of adding mass% and stirring and mixing at a temperature of about 80 ° C. for 2 to 10 hours may be mentioned. As a catalyst, a C5-C30 alkylbenzenesulfonic acid (for example, dodecylbenzenesulfonic acid etc.) is preferable.

  The content of the (M) component can be measured by analyzing the (BD) component by gas chromatography.

  In the present embodiment, when the component (B) 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.

  Specific examples of the chain transfer agent are not particularly limited, and examples thereof include 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 and di (methylenetrimethylolpropane) xanthogen disulfide; allyl such as dimers of thioglycol and α-methylstyrene Compounds and the like. These may be used alone or in combination of two or more.

  The total amount of the chain transfer agent used relative to the total amount of the vinyl monomer is preferably 0.001 to 1% by mass.

  The emulsifier that can be used for the production of the component (B) is not particularly limited, and examples thereof include alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, and polyoxyethylene. Acidic emulsifiers such as distyrylphenyl ether sulfonic acid, alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, anionic surfactants such as fatty acid soaps, for example, alkyltrimethylammonium bromide, Quaternary ammonium salts such as alkylpyridinium bromides, imidazolinium laurates, pyridinium salts, imidazolinium salt type cationic surfactants, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan fats Acid ester, polyoxyethylene polyoxypropylene block copolymers, reactive emulsifier having a double bond of nonionic surface active agent and a radical polymerizable polyoxyethylene distyryl phenyl ether, and the like.

  Among these emulsifiers, a reactive emulsifier having a radical polymerizable double bond (reactive emulsifier) is preferable. By using such a reactive emulsifier, the water dispersion stability of the polymer particles becomes very good, and the water resistance of the resulting coating film is further improved.

Examples of the anionic emulsifier which is a reactive emulsifier include an ethylenically unsaturated monomer having a sulfonic acid group, a sulfonate group or a sulfate ester group and a salt thereof, and a sulfonic acid group or an ammonium salt thereof. A compound having a group (ammonium sulfonate group or alkali metal sulfonate group) which is an alkali metal salt is preferable. Specifically, for example, alkyl allylsulfosuccinate (for example, “Eleminol (trademark) JS-20” manufactured by Sanyo Chemical Co., Ltd., “Latemul (trademark) S-120”, “Latemuru S-180A” manufactured by Kao Corporation). , “Latemul S-180”, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfate ester salt (for example, “Aqualon ™ HS-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, “ADEKA rear soap (trademark) SE-10N” manufactured by ADEKA) Ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene (for example, the first construction) Pharmaceutical Co., Ltd., such as "Aqualon KH-1025" and the like.
), 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), sulfuric acid of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether Examples thereof include ester salts (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.

  Moreover, as a nonionic emulsifier which is a reactive emulsifier, for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (for example, (manufactured by ADEKA) "Adekalia Soap NE-20", "Adekalia Soap NE-30", "Adekalia Soap NE-40", etc.), polyoxyethylene alkylpropenyl phenyl ether (for example, manufactured by Daiichi 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, “ADEKA rear soap (trademark) ER-10, manufactured by ADEKA Corporation) Etc. The.), Polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (e.g., manufactured by Kao Corporation, "LATEMUL (trademark) PD-420", and the like.), And the like.

  The amount of the emulsifier used is the total amount of the (a) component which is the raw material of the component (B) which is a polymer, the hydrolyzable silicon compound other than the (a) component, and the vinyl monomer other than the (a) component. Preferably it is 10 mass parts or less with respect to a part, More preferably, it is 0.001-5 mass part. 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 reaction of the component (a), the hydrolyzable silicon compound other than the component (a), and the vinyl monomer is preferably carried out in the presence of a polymerization catalyst. As a polymerization catalyst for the hydrolyzable silicon compound other than the component (a) and the component (a), hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic 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 slightly 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, Diazabicik Basic compounds such as undecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; tin compounds such as dibutyltin octylate and dibutyltin dilaurate Is mentioned.

  Among these, as the polymerization catalyst for the hydrolyzable silicon compound, acidic emulsifiers are preferable from the viewpoint of not only a polymerization catalyst but also an action as an emulsifier. As the acidic emulsifier, an alkylbenzene sulfonic acid having 5 to 30 carbon atoms (for example, dodecylbenzene sulfonic acid) is more preferable.

  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. Such a radical polymerization catalyst is not particularly limited, and examples thereof include persulfates, peroxides, azobis compounds, and the like. These may be water-soluble or oil-soluble.

  Specific examples of the radical polymerization catalyst are not particularly limited, and examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, and 2,2-azo. Examples thereof include bisisobutyronitrile, 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 | stimulation of a polymerization rate and superposition | polymerization at low temperature, such as 70 degrees C or less are desired, it is preferable to use reducing agents, such as sodium bisulfite, ferrous chloride, ascorbate, a longgarite, together with a radical polymerization catalyst.

  The polymerization of the hydrolyzable silicon compound and the vinyl monomer can be carried out separately, but is preferably carried out at the same time from the viewpoint that complexation can be achieved.

  The number average particle diameter of the component (B) that is a polymer is not particularly limited, but is preferably 10 to 300 nm. By setting the number average particle diameter of the component (B) within the above range, the weather resistance and stain resistance of the resulting coating film tend to be further improved. Furthermore, the number average particle diameter of (B) component becomes like this. More preferably, it is 10-200 nm, More preferably, it is 100-200 nm. By using the component (B) having a number average particle size in the above range, the weather resistance of the resulting coating film is further improved. When the number average particle size is 10 nm or more, the stain resistance is particularly good, and when the number average particle size is 300 nm or less, the transparency of the coating film is particularly good. In addition, the number average particle diameter here can be measured using a wet particle size analyzer.

  As a suitable method for obtaining the component (B) having such a particle size, for example, the hydrolyzable silicon compound and the vinyl monomer are polymerized in the presence of a sufficient amount of water for the emulsifier to form micelles. So-called emulsion polymerization. The specific method of emulsion polymerization is not particularly limited. For example, the hydrolyzable silicon compound and the vinyl monomer are dropped into the reaction vessel as they are or in an emulsified state, in a batch, in a divided manner, or continuously. And a method of polymerizing in the presence of a polymerization catalyst, preferably at atmospheric pressure to 10 MPa, at a reaction temperature of about 30 to 150 ° C. The reaction temperature and reaction pressure may not be the above-mentioned conditions depending on the reaction conditions and the like. Although the solid content obtained by emulsion polymerization is not particularly limited, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.

  If it is desired to control the particle size during emulsion polymerization, a seed polymerization method in which emulsion particles are preliminarily present in the aqueous phase for polymerization may be employed. The pH in 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.

  As a method for producing the (BD) component which is a dispersion, a hydrolyzable silicon compound and / or a vinyl monomer is polymerized in the presence of a solvent, if necessary, in the presence of water and an emulsifier, and then a polymerization product. A method of further adding water until the emulsion becomes an emulsion can be employed. However, emulsion polymerization is preferable as described above from the viewpoint of easy control of the particle size of the component (A) to be obtained.

  The component (B) in the coating film preferably has a core / shell structure having a core and one or more shell layers. By having a core / shell structure, the mechanical properties (balance of strength and flexibility, etc.) of the obtained coating film are further improved. The core / shell structure can be confirmed by, for example, morphological observation with a transmission electron microscope or the like, analysis by viscoelasticity measurement, or the like.

  As a method for producing the component (B) having a core / shell structure, for example, multistage emulsion polymerization is useful, but is not limited thereto. The multi-stage emulsion polymerization herein refers to preparing two or more kinds of reaction solutions having different compositions containing a vinyl monomer and a hydrolyzable silicon compound, and polymerizing them in separate stages. As an example of multistage emulsion polymerization, a method for synthesizing component (B) having a core / shell structure by two-stage emulsion polymerization will be mainly described. As an example of the two-stage emulsion polymerization, a step of obtaining seed particles by polymerizing a hydrolyzable silicon compound and / or vinyl monomer in the presence of water and an emulsifier, and the obtained seed particles In the presence of, there is a method having a step (second stage) of polymerizing each of the hydrolyzable silicon compound and the vinyl monomer.

  The synthesis of the component (B) by the two-stage emulsion polymerization is the first stage polymerization in which the first series (hydrolyzable silicon compound and / or vinyl monomer) is supplied and emulsion polymerization is performed. The second series (hydrolyzable silicon compound and / or vinyl monomer) is supplied, and this is carried out by a two-stage polymerization process consisting of a second stage polymerization in which emulsion polymerization is further carried out in an aqueous medium. In this case, the mass ratio ((M1) / (M2)) of the solid content mass (M1) in the first series to the solid content mass (M2) in the second series is not particularly limited, but preferably 9/1. Is 1/9, more preferably 8/2 to 2/8.

  By performing such multistage emulsion polymerization, polymer particles having a more uniform particle diameter can be obtained. As a method for adding the raw material in the multistage emulsion polymerization, a method in which seed particles (core) are prepared in the first stage polymerization and then a monomer or the like is added is preferable. This increases the particle diameter of the polymer particles obtained by the second stage polymerization without changing the ratio of the volume average particle diameter / number average particle diameter of the seed particles (core) obtained by the first stage polymerization. It is also possible to do. Furthermore, polymer particles having a sharp particle size distribution can be obtained.

  When performing multistage emulsion polymerization of three or more stages, the number of stages of polymerization may be increased in the same manner as in the two-stage polymerization.

  The content of the hydrolyzable silicon compound containing the component (a) in the component (B) is not particularly limited, but is preferably 80% by mass or more, more preferably 95% by mass in terms of the hydrolysis-condensation polymer. That's it. By making the content of the hydrolyzable silicon compound containing the component (a) within the above range, the weather resistance of the coating film is further improved.

  Although content of (B) component in an aqueous composition is not specifically limited, Preferably it is 0.5-10.0 mass%, More preferably, it is 1.0-5.0 mass%.

  Although content of (B) component in a coating film is not specifically limited, Preferably it is 10.0-80.0 mass%, More preferably, it is 50.0-80.0 mass%. By making content of (B) component more than the said lower limit, the weather resistance of a coating film improves further, and contamination resistance improves further by making it below the said upper limit.

  In addition to the component (B), the aqueous composition of the present embodiment may further include a compound having a functional group that reacts with the functional group contained in the polymer. Such a compound is not particularly limited, and examples thereof include (poly) isocyanate compounds, (poly) epoxy compounds, amino compounds, (poly) carboxy compounds, (poly) hydroxy compounds, glycol compounds, silanol compounds, silyl compounds, Examples include alkoxy compounds and (meth) acrylate compounds. These may be used alone or in combination of two or more.

<Inorganic oxide (C)>
The inorganic oxide (C) is an inorganic oxide having no photocatalytic activity. Here, having no photocatalytic activity means that neither an oxidation reaction nor a reduction reaction occurs due to light irradiation.

  The component (C) is not particularly limited. For example, any component selected from the group consisting of silicon dioxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide, and composite oxides thereof. 1 type etc. are mentioned. Among these, from the viewpoint that there are many surface hydroxyl groups, silicon dioxide, aluminum oxide, antimony oxide, and complex oxides thereof are preferable, and silicon dioxide is more preferable. (C) Since the hydrophilicity of a coating film improves by using what contains many such surface hydroxyl groups as a component, stain resistance improves further.

  The inorganic oxide used as the component (C) is preferably colloidal particles such as a hydrate. That is, the inorganic oxide colloidal particles can be further combined with other components such as the component (B) and the component (D), and the stability as an aqueous composition is further improved.

  The silicon dioxide 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), Rickey D. et al. Badley et al. Langmuir 6, 792-801 (1990), “Journal of Color Material Association”, 61 [9] 488-493 (1988), and the like can be referred to.

  Although the number average particle diameter of (C) component is not specifically limited, Preferably it is 1-400 nm, More preferably, it is 1-100 nm. By making the number average particle diameter of the component (C) 1 nm or more, the storage stability of the aqueous composition is further improved. By setting the number average particle diameter of the component (C) to 400 nm or less, the transparency of the obtained coating film is further improved. In addition, a number average particle diameter can be measured using a wet particle size analyzer based on the method as described in the Example mentioned later.

  Colloidal silica may be acidic, neutral 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 “Snowtex (trademark) -OXS”, “Snowtex-OS”, “Snowtex-O”, “Snowtex-O-40”, “Snowtex-O-40” manufactured by Nissan Chemical Industries, Ltd. "Snowtex-OL", "Snowtex-OYL", "Adelite (trademark) AT-20Q" manufactured by Asahi Denka Kogyo Co., Ltd., "Crebosol (trademark) 20H12", "Crebosol 30CAL25" manufactured by Clariant Japan .

  Examples of basic colloidal silica include 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 “Snowtex-XS”, “Snowtex-S”, “Snowtex-30”, “Snowtex-50”, and “Snowtex-20L” manufactured by Nissan Chemical Industries, Ltd. , "Snowtex-XL", "Snowtex-YL", "Snowtex-ZL", "Snowtex-NXS", "Snowtex-NS", "Snowtex-N", "Snowtex-N40", “Snowtex-CXS”, “Snowtex-C”, “Snowtex-CM”, “Snowtex-PS-S”, “Snowtex-PS-M”; “Adelite AT-20” manufactured by Asahi Denka Kogyo Co., Ltd. , "Adelite AT-30", "Adelite AT-20N", "Adelite AT-30N", "Adelite AT-20A", "Adelite “T-30A”, “Adelite AT-40”, “Adelite AT-50”; “Clevosol 30R9”, “Crebosol 30R50”, “Crebosol 50R50” manufactured by Clariant Japan, “Ludox ™ HS-” manufactured by DuPont 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 “MA-ST-M (methanol dispersion type with a particle size of 20 to 25 nm)” and “IPAST (isopropyl alcohol dispersion type with a particle size of 10 to 15 nm)” manufactured by Nissan Chemical Industries, Ltd. , “EG-ST (ethylene glycol dispersion type with a particle size of 10 to 15 nm)”, “EG-ST-ZL (ethylene glycol dispersion type with a particle size of 70 to 100 nm)”, “NPC-ST (with a particle size of 10 to 15 nm) Ethylene glycol monopropyl ether dispersion type) "and the like.

  The above colloidal silica 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 (C) component in an aqueous composition is not specifically limited, Preferably it is 0.10-5.0 mass%, More preferably, it is 0.20-3.0 mass%. By making content of (C) component in an aqueous composition into the said range, the coating film which was further excellent in the weather resistance and stain resistance can be obtained.

  Although content of (C) component in a coating film is not specifically limited, Preferably it is 5.0-70.0 mass%, More preferably, it is 10.0-50.0 mass%. By making content of (C) component in a coating film more than the said lower limit, the stain resistance of a coating film improves further, and the weather resistance of a coating film improves further by making it below the said upper limit. .

<Inorganic oxide (D) having photocatalytic activity>
The coating film of this embodiment preferably further contains inorganic oxide particles (D) having photocatalytic activity. Thereby, photocatalytic activity and hydrophilicity can be further expressed by irradiating light to a coating film.

The inorganic oxide (D) having photocatalytic activity is not particularly limited as long as it is an inorganic oxide having photocatalytic activity. Specific examples of the component (D) is not particularly limited, 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 ; from Ti, Nb, Ta, and V Layered oxides having at least one element selected from the group consisting of (for example, JP-A-62-274452, JP-A-02-172535, JP-A-07-024329, JP-A-08-089799) JP-A-08-089800, JP-A-08-089804, JP-A-09-248465, JP-A-10-099694, JP-A-10-244165, etc.) And the like.

The component (D) 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 (D) is an inorganic oxide having photocatalytic activity, and is preferably a metal compound whose particle surface is modified. By performing the modification treatment, the generation amount of active oxygen species such as H ₂ O ₂ and .OH can be suppressed, and damage to the base coating film can be further suppressed. The substance to be modified is not particularly limited, and examples thereof include silica, aluminum, copper oxide, and iron oxide. Among these, silica is preferable. The same effect can be obtained by modifying 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 (D) will be described with silica as an example. The method for modifying the surface of the silica 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 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 treatment amount of the hydrous oxide of silicon is preferably 3 to 25% by mass, more preferably 5 to 20% by mass with respect to titanium oxide. Since the increase in the amount of active oxygen species can be suppressed when the amount of treatment is at least the above lower limit, damage to the underlying coating film can be prevented. Further, when the treatment amount is not more than the above upper limit value, the aggregation of titanium oxide can be suppressed and the increase in the viscosity of the sol can be suppressed, so that dispersibility and transparency are further improved.

  Although content of (D) component in an aqueous composition is not specifically limited, Preferably it is 0.1-2.0 mass%, More preferably, it is 0.2-1.0 mass%. By making content of (D) component in an aqueous composition into the said range, the coating film which was further excellent in stain resistance and transparency can be obtained. Although content of (D) component in a coating film is not specifically limited, Preferably it is 3.0-25.0 mass%, More preferably, it is 5.0-20.0 mass%. By making content of (D) component in a coating film more than the said lower limit, the stain resistance of a coating film improves further, and the transparency of a coating film improves further by making it below the said upper limit. .

<Fluorocarbon surfactant (E)>
It is preferable that the coating film of this embodiment further contains a fluorocarbon surfactant (E). This further improves the wettability to the organic base material and the like when coating with the aqueous composition of the present embodiment and the aqueous paint containing the same, and further suppresses troubles in appearance such as repellency. it can. Furthermore, the uniformity of the coating film is further improved. Although it is not certain as these reasons, it is presumed that by containing the component (E), the surface vigor of the aqueous composition can be reduced, and the appearance of the coating film can be maintained at a higher level. (However, the operation of the present embodiment is not limited to these).

  Although it does not specifically limit as (E) component, Amphoteric surfactant is preferable. Examples of amphoteric surfactants include nonionic amphoteric surfactants, anionic amphoteric surfactants, and cationic amphoteric surfactants. Preferable specific examples include amphoteric surfactants having a C 3-20 perfluoroalkyl group.

  Specific examples of the amphoteric surfactant having a C 3-20 perfluoroalkyl group include, for example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkylamine oxide, and perfluoroalkylethylene oxide adducts. And 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. As a perfluoroalkyl carboxylate, a commercial item can also be used, for example. Examples of such commercially available products include “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 “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 “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 “Surflon S-231”, “Surflon S-232”, and “Surflon S-233” manufactured by AGC Seimi Chemical Co., Ltd. These may be used alone or in combination of two or more.

  Although content of (E) component in an aqueous composition is not specifically limited, Preferably it is 0.0001-0.50 mass%, More preferably, it is 0.01-0.10 mass%. (E) By making content of a component more than the said lower limit, the uniformity of the coating film obtained improves further. (E) By making content of a component below the said upper limit, the weather resistance of the coating film obtained improves further.

  Content of (E) component in the coating film formed from an aqueous composition becomes like this. Preferably it is 0.2-3.0 mass%, More preferably, it is 0.5-2.5 mass%. (E) By making content of a component more than the said lower limit, the external appearance of a coating film improves further, and the water resistance of a coating film improves further by setting it as the said upper limit or less.

<Discoloring dye (F)>
It is preferable that the coating film of this embodiment further contains a fading dye (F). As a result, troubles such as forgetting to paint, overlapping painting, and uneven painting can be prevented.

  (F) As a component, what loses color by light irradiation, such as sunlight, and does not impair the design property of a foundation | substrate is preferable. Although the time until decoloration varies depending on the light irradiation conditions such as the season and the irradiation direction, the period until the decoloration is confirmed visually is preferably 20 days or less, more preferably 10 days or less. More preferably, it is 3 days or less.

  The component (F) is not particularly limited as long as it has the property of being decolored by irradiation with light such as sunlight. Preferred specific examples include methylene blue, crystal violet, malachite green, brilliant blue FCF, Examples thereof include one selected from the group consisting of erythrosin, neucoccin, phloxine, rose bengal, acid red, and first green FCF. Among these, methylene blue is more 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 (F) component in an aqueous composition is not specifically limited, Preferably it is 0.0002-0.010 mass%, More preferably, it is 0.001-0.007 mass%. By making content of (F) 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 (F) component in a coating film is not specifically limited, Preferably it is 0.01-0.5 mass%, More preferably, it is 0.05-0.2 mass%, More preferably It is 0.1-0.2 mass%. By making content of (F) component more than the said lower limit, the coloring property of a coating film improves further, and the fading property of a coating film improves further by setting it as the said upper limit or less.

<Cellulose-based thickener (G)>
It is preferable that the coating film of this embodiment further contains a cellulosic thickener (G). As a result, even if the solid content in the state of the aqueous composition is low, it is possible to prevent dripping at the time of coating, and thus it is assumed that the appearance of the coating film can be maintained at a higher level (however, in this embodiment) The action is not limited to these.)

  The cellulose-based thickener (G) is not particularly limited, and examples thereof include one selected from the group consisting of methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, and modified products thereof. Among these, one selected from the group consisting of hydroxyethylcellulose, hydroxypropylmethylcellulose and modified products thereof is preferable, and hydroxyethylcellulose and modified products thereof are more preferable. Moreover, these cellulose type thickeners may be used individually by 1 type, and may use 2 or more types together.

  Furthermore, other thickeners may be used in combination as long as the effects of the present embodiment are obtained. Other thickeners are not particularly limited, for example, polyacrylate-based thickeners, polyacrylamide-based thickeners, acrylic acrylamide copolymer salt-based thickeners, polysaccharides other than cellulose-based A thickener, a vinyl ether type thickener, etc. are mentioned.

  A commercially available product can also be used as hydroxyethyl cellulose. Examples of such commercially available products include “HEC Daicel SP200”, “HEC Daicel SP400”, “HEC Daicel SP500”, “HEC Daicel SP550”, “HEC Daicel SP600”, and “HEC Daicel SP800” manufactured by Daicel Finechem. , “HEC Daicel SP850” and “HEC Daicel SP900”, “San Heck ™ HH”, “San Heck H”, “San Heck M” and “San Heck G & L” manufactured by Sansho, “HECSZ-” manufactured by Sumitomo Seika Co., Ltd. 25F "and the like.

  The weight average molecular weight of hydroxyethyl cellulose is not particularly limited, but is preferably 700,000 to 2,000,000, more preferably 1,000,000 to 1,600,000. When the weight average molecular weight is 700,000 or more, dripping of the aqueous composition can be further suppressed. When the weight average molecular weight is 2 million or less, the transparency of the coating film obtained from the aqueous composition is further improved. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  A commercial item can also be used as hydroxypropyl methylcellulose. Examples of commercially available products include “Metrozu 90SH-04”, “Metrozu 90SH-15”, “Metrozu 90SH-100”, “Metrozu 90SH-400”, “Metrozu 90SH-4000”, and “Metrozu 90SH” manufactured by Shin-Etsu Chemical Co., Ltd. -15000 "and" Metrouse 90SH-100000 "," NEOVISCO-MC HM4000S "," NEOVISCO-MC RM4000S "," NEOVISSCO-MC RM15000S "," NEOVISCO-MC RM30000S "and" NEOVISCO-MC RM50,000 "manufactured by Sansho. Etc.

  Although content of (G) component in an aqueous composition is not specifically limited, Preferably it is 0.04-0.30 mass%, More preferably, it is 0.08-0.20 mass%. By making content of (G) component in an aqueous composition into the said range, the coating film which was further excellent in transparency and a weather resistance can be obtained.

  Although content of (G) component in a coating film is not specifically limited, Preferably it is 2.0-15.0 mass%, More preferably, it is 4.0-9.0 mass%. By making content of (G) component in a coating film more than the said lower limit, transparency of a coating film improves further, and the weather resistance of a coating film improves further by making it into the said upper limit or less.

<Algae-proofing agent, mold-proofing agent (H)>
It is preferable that the coating film of this embodiment further contains an algae and / or antifungal agent (H). Thereby, even in a place where it is difficult to irradiate light such as sunlight, it is possible to form a coating film having excellent antifungal properties and / or antialgal properties (however, the action of the present embodiment is not limited to these). .

  The antialgae and / or antifungal agent (H) is not particularly limited, and examples thereof include organic iodine compounds, pyridine compounds, nitrile compounds, disulfide compounds, and nitrogen-containing ring compounds. Among these, a nitrogen-containing 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. Of course, those having both algae and fungicides may be used, and examples thereof include isothiazoline compounds containing chlorine atoms in the molecule. 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, and “KLARIX 4000” and “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” manufactured by Nippon Soda Co., Ltd., “Amorden NBP-8” manufactured by Daiwa Chemical Industry Co., Ltd., “Amorden NBPconc”, “San Aruga 1907” manufactured by Sankyo Kasei Co., Ltd. It is done.

  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.

  Although content of (H) component in an aqueous composition is not specifically limited, Preferably it is 0.01-0.80 mass%, More preferably, it is 0.05-0.50 mass%. By making content of (H) component in an aqueous composition into the said range, the coating film which was further excellent in transparency, a weather resistance, and microbial resistance can be obtained.

  Although content of (H) component in a coating film is not specifically limited, Preferably it is 0.1-30.0 mass%, More preferably, it is 1.0-15.0 mass%. By setting the content of the component (H) in the coating film to the above lower limit value or more, the microbial resistance of the coating film is further improved, and by setting the content to the above upper limit value or less, the transparency and weather resistance of the coating film are improved. Further improvement.

  Furthermore, other antibacterial agents may be used in combination as long as the effects of the present embodiment are obtained. Other antibacterial agents are not particularly limited, and examples thereof include silver compounds, copper compounds, and zinc compounds.

  Although content (solid content) of solid content in an aqueous composition is not specifically limited, From a viewpoint of the uniformity of a coating film, Preferably it is 0.5-10.0 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, the stain resistance is further improved. Transparency improves further by making content of solid content in an aqueous composition below into the said upper limit. 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 film thickness of the coating film is thin. Even in such a case, when the solid content in the aqueous composition is not more than the above upper limit value, it is possible to obtain a coating film having excellent physical properties such as weather resistance and stain resistance while having a thin film thickness. it can. When the amount of solid content in the aqueous composition is not less than the above lower limit value, the drying time required for forming the coating film can be shortened, and the working efficiency can be further improved.

  Next, the aqueous composition of this embodiment will be described in detail. The aqueous composition of this embodiment is an aqueous composition used for forming the above-described coating film. The aqueous composition contains a dispersion (BD) of a polymer (B) containing a polymer (A) having a structural unit derived from dimethyldimethoxysilane (a), and an inorganic oxide (C). It is preferable that it is a thing. In addition, the detail of each component which can be mix | blended with an aqueous composition is as above-mentioned, The description is abbreviate | omitted below about the overlapping content.

  When the aqueous composition of this embodiment contains (BD) component and (C) component, it is preferable that content of (A) component in solid content of an aqueous composition is 25-48 mass%. When the content of the component (A) in the solid content of the aqueous composition is 25% by mass or more, the weather resistance of the obtained coating film is further improved, and the appearance and stain resistance can be maintained at a higher level. . Further, when the content of the component (A) in the solid content of the aqueous composition is 48% by mass or less, the stain resistance of the coating film is further improved. From this viewpoint, the lower limit of the content of the component (A) in the solid content of the aqueous composition is preferably 25% by mass or more, and more preferably 35% by mass or more. The upper limit of the content of component (A) is preferably 48% by mass or less, more preferably 45% by mass or less, and still more preferably 42% by mass or less.

  The aqueous composition of the present embodiment may further contain other components other than those described above as necessary within the range in which the effect is obtained. Such other components are not particularly limited. For example, antifoaming agents, freezing stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, antiskinning agents, and dispersing agents. , Wetting agents, light stabilizers, antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, preservatives, deodorants, yellowing inhibitors, antistatic agents And a charge control agent. These may be used alone or in combination of two or more.

  The aqueous composition of this embodiment can be suitably used as an aqueous paint. When the aqueous composition of the present embodiment is used as an aqueous paint, other components include antifoaming agent, freezing stabilizer, matting agent, crosslinking reaction catalyst, pigment, curing catalyst, crosslinking agent, filler, and anti-skinning. Agents, dispersants, wetting agents, light stabilizers, antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, preservatives, deodorants, anti-yellowing agents, You may further contain an antistatic agent, a charge control agent, etc. The aqueous paint using the aqueous composition of the present embodiment can form a coating film excellent in appearance, stain resistance, transparency, weather resistance and the like.

  When using the aqueous composition of this embodiment as a water-based coating material, it can apply | coat with a suitable method suitably according to the use, the material of application object, etc. The coating method is not particularly limited. For example, spraying method, flow coating method, roll coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, gravure printing method, flexographic printing method. Is mentioned.

  After apply | coating the aqueous composition of this embodiment, a coating film is obtained by making it dry and removing a volatile matter. 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.

  Thus, in this embodiment, it can also be set as the coating film containing an above-mentioned aqueous coating material. In this case, for example, the above-described aqueous paint can be applied to the surface of various substrates and dried to form a coating film formed on the substrate. That is, in this embodiment, it can also be set as the coating product containing a base material and the above-mentioned coating film formed in at least one part of the surface of a base material.

  The material of the substrate that can be used in 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 substrate or an inorganic substrate, but an organic substrate is preferable. The material for the substrate is not particularly limited, and examples thereof include synthetic resins, natural resins, metals, ceramics, glass, stones, cement, and concrete. These may be used alone or in combination of two or more. In particular, in the present embodiment, even an organic substrate composed of a material having a low glass transition temperature such as 0 to 20 ° C. can form a coating film that can maintain the appearance and stain resistance at a high level. It is also suitable in terms of points.

  The synthetic resin is not particularly limited, and examples thereof include a thermoplastic resin and a curable resin (such as a thermosetting resin, a photocurable resin, and a moisture curable resin). Specific examples of the synthetic resin are not particularly limited. For example, silicone resin, acrylic resin, methacrylic resin, fluorine resin, alkyd resin, aminoalkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, 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, phenol resin , Melamine resin, epoxy resin, urethane resin, silicone-acrylic resin and the like.

  The natural resin is not particularly limited, and examples thereof include 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. Since the coating film obtained by this embodiment can maintain an external appearance and antifouling property at a high level over a long period of time, it can be suitably used in an environment that has been difficult to use. From this viewpoint, specific examples of the coated product of the present embodiment include, for example, building materials, building exteriors, building interiors, window frames, window glass, various lenses, structural members, building equipment such as houses, covers for vehicle lighting, and Window glass, 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, bridges, exteriors of guardrails and Examples include exterior parts of electronic and electrical equipment used outside, such as painting, tunnel interior and painting, insulators, solar battery covers, solar water heater heat collection covers, especially exteriors such as transparent members, greenhouses and greenhouses.

  As a manufacturing method of the coated product of this embodiment, for example, the above-described aqueous composition (in this case, sometimes referred to as a water-based paint) is applied to at least a part of the surface of the substrate, and if necessary, A method for forming a coating film by drying and the like is not limited thereto. 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 adhere | attach to another base material in the state closely_contact | adhered with the base material.

  As described above, the coating film of the present embodiment is excellent in appearance, stain resistance, transparency, weather resistance, and the like, and can be used in a wide range of applications including exterior paints for buildings.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example. Various physical properties were measured by the following methods.

<Preparation of base material pre-coated with enamel paint>
-Preparation of pigment dispersion Dispersant (BASF Japan, "Pig. Disperser MD20") 5.35g, ammonia water 0.50g, propylene glycol 23.50g, water 147.50g, titanium oxide (chlorine method rutile type oxidation) Titanium; manufactured by Ishihara Sangyo Co., Ltd., “Taipeku CR-97”) 333.50 g, antifoaming agent (modified silicone type; manufactured by San Nopco, “SN Deformer 1310”) 2.85 g , A batch type tabletop sand mill) for 20 minutes to obtain a pigment dispersion.

-Production of enamel paint 10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso Corporation, "CS-12") to 109.0 g of the polymer emulsion of each production example, ethylene glycol 10.0 g of a mixed solution of 50 parts by mass of monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained above, and 0.5 g of a 10% aqueous solution of a thickener (manufactured by ADEKA, “Adecanol UH-438”) Was added and mixed for 1 hour to obtain an enamel paint.

-Preparation of base material pre-coated with enamel paint The enamel paint obtained above was applied to a 7 cm x 15 cm and 5 cm x 5 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 7 cm × 15 cm and 5 cm × 5 cm substrates pre-coated with enamel paint.

1. Content and solid content of each component 2 g of a sample 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 composition were measured.
The content of the component (A) in the coating film is calculated from the total solid content of the aqueous composition, the solid content of the component (B), and the content of the component (A) contained in the component (B). Based on.

Content (mass%) of component (A) of coating film = [solid content of component (B) × content of component (A) in component (B) (mass%)] ÷ total solid content

2. Number average particle size Ion-exchanged water was added to dilute the number-average particle size to 1.5 to 3.0, and measurement was performed using a wet particle size analyzer (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. Measurement of the amount of dimethyldimethoxysilane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane Dilute the sample with ion-exchanged water so that the solid content is 2% by mass, add 1-hexanol as an internal standard substance, and measure A sample was used. 1 μL of the measurement sample was injected into a gas chromatography (“GC353B” manufactured by GL Sciences Inc.) with a syringe, and the content ratio of dimethyldimethoxysilane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane was determined from the measurement results. The measurement conditions for gas chromatography are shown below.
Column: “TC-5” manufactured by GL Sciences Inc. (inner diameter 0.25 mm, length 30 m)
-Injection temperature: 150 ° C, detector temperature: 220 ° C
-Detector: FID, carrier gas: Nitrogen (100 kPa pressure)
Split ratio: 1:20
・ Temperature rising condition: 50 ° C. × 8 minutes maintained + temperature rising rate up to 170 ° C. at 8 ° C./minute+170° C. × 7 minutes maintained

4). Viscosity Viscosity was measured using a BM viscometer (manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are shown below.
・ Temperature: 23 ℃
・ Rotor: No. 1
・ Rotation speed: 60rpm

5. Glass Transition Temperature Using a Seiko Instruments Inc., “DCS 6220”, the glass transition temperature was measured under the measurement condition of 10 ° C./min. 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.

6). Weathering test: in advance painted 7 cm × 15cm substrate 1000 hours and 3000 hours after the gloss retention enamels, coating with the amount of the aqueous composition at a ratio of 17 g / m ² or 50 g / m ² Painted using a spray. The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate. An exposure test (black panel temperature 63 ° C., rainfall 18 minutes / 2 hours) was conducted using “Sunshine Weather Meter” manufactured by Suga Test Instruments Co., Ltd. The 60 ° gloss after 1000 hours and 2000 hours after exposure was measured using a gloss meter (manufactured by BYK Gardner, “Micro Trigloss μ”). And gloss retention was computed based on the following formula. In addition, the result evaluated only with the base material which applied the enamel paint beforehand is the gloss retention 95% after 1000 hours of exposure, and the gloss retention 85% after 3000 hours of exposure. A large value indicates that the weather resistance is good.

Gloss retention (%) = 60 ° gloss after exposure test / 60 ° gloss before exposure test × 100

7). Contamination resistance A 7 cm × 15 cm base material previously coated with an enamel paint was applied using a spray so that the coating amount of the aqueous composition was 17 g / m ² or 50 g / m ² . The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate. The test plate was stuck to a fence facing a general road (traffic volume of about 500 to 1000 vehicles / day) and left 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.

○: Dirt was hardly confirmed.
Δ: Some contamination was confirmed.
X: A large amount of dirt was confirmed.

8). Anti-mold performance A 5 cm × 5 cm base material previously coated with an enamel paint was applied by spraying so that the coating amount of the aqueous composition was 17 g / m ² or 50 g / m ² . The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate.
For conditions other than the above, in accordance with JIS Z-2911 (mold resistance test method) “8 Coating Test”, Aspergillus niger, Penicillium pinopiumum, Cladospodium cladosporoids, Aureobasidium pullulans, Triblandum, and Aureobasidium pullulans, It was tested with the one. After the test, evaluation based on the following criteria was performed.

0: No growth of mycelium was observed on the coating film.
1: The area of the growth part of the mycelium recognized on a coating film exceeded 0 of the total area, and was 1/3 or less.
2: The area of the growth part of the mycelium recognized on the coating film exceeded 1/3 of the total area.

9. The algae performance enamel paint previously painted 5 cm × 5 cm substrates were coated using a spray as coat-weight of the aqueous composition at a ratio of 17 g / m ² or 50 g / m ^2. The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate.
“7 c) Textile product wet test of JIS Z-2911 (fungal resistance test method) except that a mixture of Chlorella vulgaris and Osillatoria laetevirens was used instead of mold, and the above test piece was used. Tested in accordance with the Law. After the test, evaluation based on the following criteria was performed.

0: No growth of algae was observed on the coating film.
1: The area of the growth part of the algae recognized on a coating film exceeded 1 of the total area, and was 1/3 or less.
2: The area of the growth part of the algae recognized on a coating film exceeded 1/3 of the total area.

10. Wet Decomposition Performance A 7 cm × 15 cm base material previously coated with an enamel paint was applied using a spray so that the coating amount of the aqueous composition was 17 g / m ² or 50 g / m ² . The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate. The test plate was tested in accordance with JIS R1703-2 (Fine ceramics-Test method for self-cleaning performance of photocatalytic material-Part 2: wet decomposition performance) to obtain a decomposition activity index. The higher the decomposition activity index, the better the self-cleaning property.

[Production Example 1]
Synthesis of polymer emulsion In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 292 g of ion-exchanged water, a reactive emulsifier (manufactured by ADEKA, “Adekaria soap SR-1025”; solid content: 25% by mass Aqueous solution (8 g) was added, and the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 10 g of a 2 mass% ammonium persulfate aqueous solution was added, and after 5 minutes, 15 g of methyl methacrylate, 10 g of cyclohexyl methacrylate, 65 g of butyl acrylate, 5 g of methacrylic acid, 10 g of 2-hydroxyethyl methacrylate, Reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25 mass% aqueous solution) 4 g, 2 mass% ammonium persulfate aqueous solution 15 g, ion exchange water 49 g, The solution was added dropwise over 60 minutes while maintaining the temperature at 80 ° C. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 60 minutes. Next, 115 g of methyl methacrylate, 90 g of cyclohexyl methacrylate, 187 g of butyl acrylate, 8 g of methacrylic acid, reactive emulsifier (manufactured by ADEKA, “Adekalya soap SR-1025”; aqueous solution with a solid content of 25% by mass), 2 g % Of an aqueous solution of ammonium persulfate 60 g and 196 g of ion-exchanged water, and 1 g of 3-methacryloxypropyltrimethoxysilane, 20 g of dimethyldimethoxysilane, and 20 g of methyltrimethoxysilane from separate dropping tanks. The solution was added dropwise 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% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, and then the reaction solution was filtered through a 100-mesh wire mesh to obtain a 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 above-mentioned method was 11 degreeC.

[Production Example 2]
Synthesis of Polymer (B-1) Water Dispersion (BD-1) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 850 g of ion-exchanged water, 10% by mass of dodecylbenzenesulfonic acid aqueous solution 5 After charging .6 g, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, a mixed solution consisting of 93.9 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane, and 29.4 g of methyltrimethoxysilane was added for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It was dripped over. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes. Next, 5.6 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. Thereto, 6.6 g of a 2% by mass aqueous ammonium persulfate solution was added, then 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 12.3 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, -A mixed solution composed of 1.1 g of methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, 1.2 g of reactive emulsifier (manufactured by ADEKA, "ADEKA rear soap SR-1025"; 25 mass% solid content aqueous solution), Reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., “Aqualon KH-1025”; solid content 25% by weight aqueous solution) 1.2 g, mixed solution of ammonium persulfate 2.0% by weight aqueous solution 30 g, ion-exchanged water 286.4 g Were simultaneously added dropwise over about 2 hours while maintaining the temperature in the reactor at 80 ° C. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, followed by cooling to room temperature, adjusting the pH to 8 by adding 25% aqueous ammonia solution to the reaction solution, and then adding 100 mesh. Filtered through a wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water, and a polymer aqueous dispersion (BD-1) having a number average particle diameter of 155 nm was obtained as a polymer.
The content of dimethyldimethoxysilane (a), the content of octamethylcyclotetrasiloxane (m), and the content of decamethylcyclopentasiloxane (n) in this aqueous dispersion are 100 masses of polymer (B-1). The amount was 0.001 part by mass or less, 0.006 part by mass, and 0.004 part by mass, respectively. That is, the total amount (M) of the content of the compound (m) and the content of the compound (n) with respect to 100 parts by mass of the polymer (B-1) was 0.01 part by mass.
Based on the above formula (I), the amount of dimethyldimethoxysilane used in the production, the content of the compound (a), the content of the compound (m) and the content of the compound (n) were calculated. The proportion of structural units derived from dimethyldimethoxysilane in the polymer (B-1) was 33.3% by mass.

[Production Example 3]
Synthesis of aqueous dispersion (BD-2) of polymer (B-2) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 850 g of ion-exchanged water and a 10% by mass aqueous solution of dodecylbenzenesulfonic acid After charging 8.0 g, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, a mixed solution consisting of 105.0 g of dimethyldimethoxysilane, 10.0 g of phenyltrimethoxysilane, and 65.7 g of methyltrimethoxysilane was added for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It was dripped over. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes. Next, 16.8 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. Then, after adding 6.6 g of a 2% by mass aqueous ammonium persulfate solution, 26.8 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by weight aqueous solution) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “AQUALON KH-1025” In a state where the temperature in the reactor was kept at 80 ° C., a mixed solution consisting of 2.3 g of a solid content of 25% by mass aqueous solution), 30 g of 2.0% by mass aqueous solution of ammonium persulfate and 170.0 g of ion-exchanged water. It was dripped simultaneously over about 2 hours. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, followed by cooling to room temperature, adjusting the pH to 8 by adding 25% aqueous ammonia solution to the reaction solution, Filtered through a wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water, and an aqueous dispersion (BD-2) of a polymer (B-2) having a number average particle size of 133 nm was obtained as a polymer.
The content of dimethyldimethoxysilane (a), the content of octamethylcyclotetrasiloxane (m), and the content of decamethylcyclopentasiloxane (n) in this aqueous dispersion are 100 masses of polymer (B-2). The amount was 0.001 part by mass or less, 0.06 part by mass, and 0.04 part by mass, respectively. That is, the total amount (M) of the content of the compound (m) and the content of the compound (n) with respect to 100 parts by mass of the polymer (B-2) was 0.1 part by mass.
Based on the above formula (I), the amount of dimethyldimethoxysilane used in the production, the content of the compound (a), the content of the compound (m) and the content of the compound (n) were calculated. The ratio of the structural unit derived from dimethyldimethoxysilane in the polymer (B-2) was 47.8% by mass.

[Production Example 4]
Synthesis of aqueous dispersion (BD-3) of polymer (B-3) In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 850 g of ion-exchanged water and a 10% by mass aqueous solution of dodecylbenzenesulfonic acid After charging 8.0 g, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, a mixed solution consisting of 131.0 g of dimethyldimethoxysilane, 10.0 g of phenyltrimethoxysilane, and 33.1 g of methyltrimethoxysilane was added for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It was dripped over. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes. Next, 16.8 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. Then, after adding 6.6 g of a 2% by mass aqueous ammonium persulfate solution, 26.8 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by weight aqueous solution) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “AQUALON KH-1025” In a state where the temperature in the reactor was kept at 80 ° C., a mixed solution consisting of 2.3 g of a solid content of 25% by mass aqueous solution), 30 g of 2.0% by mass aqueous solution of ammonium persulfate and 170.0 g of ion-exchanged water. It was dripped simultaneously over about 2 hours. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, followed by cooling to room temperature, adjusting the pH to 8 by adding 25% aqueous ammonia solution to the reaction solution, and then adding 100 mesh. Filtered through a wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water, and an aqueous dispersion (BD-3) of a polymer (B-3) having a number average particle diameter of 170 nm was obtained as a polymer.
The content of dimethyldimethoxysilane (a), the content of octamethylcyclotetrasiloxane (m), and the content of decamethylcyclopentasiloxane (n) in this aqueous dispersion are 100 masses of polymer (B-3). The amount was 0.001 part by mass, 0.35 part by mass, and 0.3 part by mass, respectively. That is, the total amount (M) of the content of the compound (m) and the content of the compound (n) with respect to 100 parts by mass of the polymer (B-3) was 0.65 parts by mass.
Based on the above formula (I), the amount of dimethyldimethoxysilane used in the production, the content of the compound (a), the content of the compound (m) and the content of the compound (n) were calculated. The ratio of the structural unit derived from dimethyldimethoxysilane in the polymer (B-3) was 59.2% by mass.

[Production Example 5]
Synthesis of aqueous dispersion (BD-4) of polymer (B-4) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 850 g of ion-exchanged water and a 10% by mass aqueous solution of dodecylbenzenesulfonic acid After adding 10.0 g, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 154 g of dimethyldimethoxysilane, 10.0 g of phenyltrimethoxysilane, and 5.0 g of methyltrimethoxysilane were added for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It was dripped. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes. Next, 16.8 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. Then, after adding 6.6 g of a 2% by mass aqueous ammonium persulfate solution, 26.8 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by weight aqueous solution) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “AQUALON KH-1025” In a state where the temperature in the reactor was kept at 80 ° C., a mixed solution consisting of 2.3 g of a solid content of 25% by mass aqueous solution), 30 g of 2.0% by mass aqueous solution of ammonium persulfate and 170.0 g of ion-exchanged water. It was dripped simultaneously over about 2 hours. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, followed by cooling to room temperature, adjusting the pH to 8 by adding 25% aqueous ammonia solution to the reaction solution, and then adding 100 mesh. Filtered through a wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water, and an aqueous dispersion (BD-4) of a polymer (B-4) having a number average particle diameter of 119 nm was obtained as a polymer.
The content of dimethyldimethoxysilane (a), the content of octamethylcyclotetrasiloxane (m), and the content of decamethylcyclopentasiloxane (n) in this aqueous dispersion are 100 masses of polymer (B-4). The amount was 0.001 parts by mass or less, 0.38 parts by mass, and 0.38 parts by mass, respectively. That is, the total amount (M) of the content of the compound (m) and the content of the compound (n) with respect to 100 parts by mass of the polymer (B-4) was 0.76 parts by mass.
Based on the above formula (I), the amount of dimethyldimethoxysilane used in the production, the content of the compound (a), the content of the compound (m) and the content of the compound (n) were calculated. The ratio of the structural unit derived from dimethyldimethoxysilane in the polymer (B-4) was 69.2% by mass.

[Production Example 6]
Synthesis of inorganic oxide (D-1) having photocatalytic activity Silica-modified rutile-type titanium oxide 700 mL of titanium tetrachloride aqueous solution having a concentration of 200 g / L as TiO ₂ and sodium hydroxide aqueous solution having a concentration of 100 g / L as Na ₂ O Was added while maintaining the pH of the reaction solution at 5-9. 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%, and then dispersed for 3 hours with an ultrasonic cleaner to obtain an alkaline solution having a pH of 10.5 and a solid content of 10% by mass. A titanium oxide sol was obtained. 2 L of this alkaline titanium oxide sol was charged into a 3 L flask, heated to a temperature of 70 ° C., 69.4 mL of a sodium silicate aqueous solution having a concentration of 432 g / L was added as SiO ₂ , and then heated to 90 ° C. to 1 After maintaining the time, the pH was adjusted to 6 by adding 10% sulfuric acid 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 7]
Synthesis of inorganic oxide (D-2) having photocatalytic activity Silica-modified anatase-type titanium oxide Titanium dioxide solution formed by heating and hydrolyzing a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid was converted into TiO ₂ It was set as 30 mass% aqueous slurry in conversion. 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 an aqueous solution was added simultaneously with 20% sulfuric acid. Thereafter, it was aged for 30 minutes. Subsequently, 10% sodium hydroxide aqueous solution was added to adjust pH to 8, and then pH was adjusted to 6 with 2% sulfuric acid aqueous solution, followed by filtration and washing to obtain a wet cake. 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 .

[ Reference Example 1]
240 g of water dispersion (BD-1) of polymer (B-1) (solid content 10.0 mass%), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) 30 g, ethanol 50 g, and ion-exchanged water 18
By mixing and stirring 0 g, an aqueous composition (I-1) having a solid content of 6.0% by mass was obtained. The viscosity of this aqueous composition (I-1) was 2 mPa · s.
Next, one side of a 7 cm × 15 cm and 5 cm × 5 cm base material pre-coated with enamel paint (
The aqueous composition (I-1) was applied to the surface on which the enamel paint was previously applied using a spray so that the application amount was 17 g / m ² . Keep the coated substrate horizontal, temperature 23 ° C, relative humidity 50
% For 48 hours to obtain a test plate (J-1) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-1), the coating film, and the test plate (J-1).

[Example 2]
Other than using 240 g of aqueous dispersion (BD-2) of polymer (B-2) instead of 240 g of aqueous dispersion (BD-1) of polymer (B-1) (solid content 10.0 mass%) In the same manner as in Reference Example 1, an aqueous composition (I-2) having a solid content of 6.0% by mass was obtained. The viscosity of this aqueous composition (I-2) was 2 mPa · s.
Next, the aqueous composition (I-2) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating to a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-2) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-2), the coating film, and the test plate (J-2).

[Example 3]
Other than using 240 g of aqueous dispersion (BD-3) of polymer (B-3) instead of 240 g of aqueous dispersion (BD-1) of polymer (B-1) (solid content 10.0 mass%) In the same manner as in Reference Example 1, an aqueous composition (I-3) having a solid content of 6.0% by mass was obtained. The viscosity of this aqueous composition (I-3) was 2 mPa · s.
Next, the aqueous composition (I-3) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-3) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-3), the coating film, and the test plate (J-3).

[Example 4]
120 g of aqueous dispersion (BD-1) of polymer (B-1) (solid content 10.0 mass%) and 120 g of aqueous dispersion (BD-4) of polymer (B-4) (solid content 10. 0 mass%), 30 g of water-dispersed colloidal silica (C-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%), 50 g of ethanol, and ion-exchanged water. By mixing and stirring 180 g, an aqueous composition (I-4) having a solid content of 6.0% by mass was obtained. The viscosity of this aqueous composition (I-4) was 2 mPa · s.
Next, the aqueous composition (I-4) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-4) having a coating film formed on the substrate. Table 1 shows the various physical properties and evaluation results of this aqueous composition (I-4), coating film and test plate (J-4).

[Example 5]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS” (solid content 20% by mass) 45 g, ethanol 50 g, and ion-exchanged water 195 g were mixed and stirred to obtain an aqueous composition (I-5) having a solid content of 6.0% by mass. . This aqueous composition (I-5) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-5) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-5) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-5), the coating film, and the test plate (J-5).

[Example 6]
180 g of polymer (B-3) aqueous dispersion (BD-3) (solid content 10.0 mass%), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS” (solid content 20% by mass) 60 g, ethanol 50 g, and ion-exchanged water 210 g were mixed and stirred to obtain an aqueous composition (I-6) having a solid content of 6.0% by mass. . The viscosity of this aqueous composition (I-6) was 2 mPa · s.
Next, the aqueous composition (I-6) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-6) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-6), the coating film, and the test plate (J-6).

[Example 7]
150 g of polymer (B-4) aqueous dispersion (BD-4) (solid content 10.0 mass%), water-dispersed colloidal silica (C-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS” (solid content 20% by mass) 75 g, ethanol 50 g, and ion-exchanged water 225 g were mixed and stirred to obtain an aqueous composition (I-7) having a solid content of 6.0% by mass. . This aqueous composition (I-7) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-7) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-7) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-7), the coating film, and the test plate (J-7).

[Example 8]
150 g of polymer (B-4) aqueous dispersion (BD-4) (solid content 10.0 mass%), water-dispersed colloidal silica (C-2) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex O” (solid content 30% by mass) 50 g, ethanol 50 g, and ion-exchanged water 250 g were mixed and stirred to obtain an aqueous composition (I-8) having a solid content of 6.0% by mass. .
This aqueous composition (I-8) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-8) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-8) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-8), the coating film, and the test plate (J-8).

[Example 9]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) 37.5 g, photocatalytic activity inorganic oxide (D-1) 5.2 g (solid content 29 mass%), ethanol 50 g, ion-exchanged water 197. 3 g of the mixture was mixed and stirred to obtain an aqueous composition (I-9) having a solid content of 6.0% by mass.
This aqueous composition (I-9) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-9) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating to a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-9) having a coating film formed on the substrate. Various physical properties and evaluation results of this aqueous composition (I-9), coating film and test plate (J-9) are shown in Table 1.

[Example 10]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) 30 g, photocatalytic activity inorganic oxide (D-1) 10.3 g (solid content 29% by mass), ethanol 50 g, and ion-exchanged water 199.7 g By mixing and stirring, an aqueous composition (I-10) having a solid content of 6.0% by mass was obtained.
This aqueous composition (I-10) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-10) is applied at 17 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm substrate (the surface on which the enamel coating has been previously applied) which has been previously coated with the enamel coating. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-10) having a coating film formed on the substrate. Table 1 shows various physical properties and evaluation results of the aqueous composition (I-10), the coating film, and the test plate (J-10).

[Example 11]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass% 22.5 g, photocatalytic activity inorganic oxide (D-1) 15.5 g (solid content 29 mass%), ethanol 50 g, and ion-exchanged water 202 g By mixing and stirring, an aqueous composition (I-11) having a solid content of 6.0% by mass was obtained. The viscosity of this aqueous composition (I-11) was 2 mPa · s.
Next, the aqueous composition (I-11) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating to a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-11) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-11), the coating film, and the test plate (J-11).

[Example 12]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) 37.5 g, photocatalytic activity inorganic oxide (D-2) 7.5 g (solid content 20 mass%), ethanol 50 g, and ion-exchanged water 195 g By mixing and stirring, an aqueous composition (I-12) having a solid content of 6.0% by mass was obtained. The viscosity of this aqueous composition (I-12) was 2 mPa · s.
Next, the aqueous composition (I-12) is applied at 17 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-12) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-12), the coating film, and the test plate (J-12).

[Example 13]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) 30 g, photocatalytic activity inorganic oxide (D-1) 10.3 g (solid content 29% by mass), fluorocarbon surfactant (E-1) (DIC) The aqueous composition (I-13) having a solid content of 6.0% by mass was mixed with 0.2 g of “Megafac F-444”), 50 g of ethanol, and 199.5 g of ion-exchanged water and stirred. Obtained. This aqueous composition (I-13) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-13) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-13) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-13), the coating film, and the test plate (J-13).

[Example 14]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) 30 g, photocatalytic activity inorganic oxide (D-1) 10.3 g (solid content 29 mass%), fluorocarbon surfactant (E-2) (AGC) Semy Chemical Co., “Surflon S-232”) 0.7 g, ethanol 50 g, and ion-exchanged water 199.0 g were mixed and stirred to obtain an aqueous composition (I-14) having a solid content of 6.0% by mass. Got. This aqueous composition (I-14) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-14) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating to a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-14) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-14), the coating film, and the test plate (J-14).

[Example 15]
To 210 g (solid content 10.0 mass%) of an aqueous dispersion (BD-3) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) 30 g, photocatalytic activity inorganic oxide (D-1) 10.3 g (solid content 29% by mass), fluorocarbon surfactant (E-1) (DIC) "Megafac F-444") 0.2g, and fading dye (F-1) (Methylene Blue, manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water Then, 50 g of ethanol and 196.5 g of ion-exchanged water were mixed and stirred to obtain an aqueous composition (I-15) having a solid content of 6.0% by mass. This aqueous composition (I-15) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-15) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating to a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-15) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-15), the coating film, and the test plate (J-15).

[Example 16]
Change to 3 g of the fading dye (F-1) (manufactured by Kishida Chemical Co., “Methylene Blue”) whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and the solid content to 1.0% by mass with ion-exchanged water. Except for using 3 g of the adjusted fading dye (F-2) (“Acid Red” manufactured by Hodogaya Chemical Co., Ltd.), an aqueous composition (I -16) was obtained. This aqueous composition (I-16) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-16) is applied at a coating amount of 17 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-16) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-16), the coating film, and the test plate (J-16).

[ Reference Example 17]
230 g of polymer (B-1) aqueous dispersion (BD-1) (solid content 10.0% by mass), water-dispersed colloidal silica (C-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; 20 g of solid content 20% by mass, and inorganic oxide (D-1) having photocatalytic activity
) 10.3 g (solid content 29% by mass) and fluorocarbon surfactant (E-1) (DI
C company, "Megafuck F-444") 0.2g and solid content with ion-exchanged water 1.0
Fading dye (F-2) adjusted to mass% (Hodogaya Chemical Industries, “Acid Red”)
3 g, 50 g of ethanol, and 186.5 g of ion-exchanged water were mixed and stirred to obtain an aqueous composition (I-17) having a solid content of 6.0% by mass. This aqueous composition (I-17) had a viscosity of 2 mPa · s.
Next, one side of a 7 cm × 15 cm and 5 cm × 5 cm base material pre-coated with enamel paint (
The above-mentioned aqueous composition (I-17) was applied to the surface on which the enamel paint was previously applied using a spray so that the application amount was 17 g / m ² . The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-17) having a coating film formed on the substrate. Various physical properties and evaluation results of this aqueous composition (I-17), coating film and test board (J-17) are shown in Table 2.
Shown in

[Example 18]
To an aqueous dispersion (BD-3) 60 g (solid content 10.0% by mass) of the polymer (B-3), an aqueous dispersion colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., "Snowtex OS"; solid content 20 mass%) 7.5g, photocatalytic activity inorganic oxide (D-1) 5.2g (solid content 29 mass%), fluorocarbon surfactant (E-1) (DIC, “MegaFuck F-444”) 0.2 g and a fading dye (F-1) whose solid content was adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “Methylene Blue”) ) 40 g of cellulose thickener (G-1) (manufactured by Daicel Finechem, “HEC Daicel SP900”) whose solid content is adjusted to 1.0 mass% with ion-exchanged water, 50 g of ethanol, and ion exchange Water 336.1 To give a solid content 1.9% by weight of the aqueous composition (I-18) by stirring a mixture of. This aqueous composition (I-18) had a viscosity of 15 mPa · s.
Next, the aqueous composition (I-18) is applied to 50 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm substrate (the surface on which the enamel coating has been previously applied) which has been previously applied with the enamel coating. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-18) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-18), the coating film, and the test plate (J-18).

[Example 19]
To an aqueous dispersion (BD-3) 60 g (solid content 10.0 mass%) of a polymer (B-3), a water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., "Snowtex OS"; solid content 20 mass%) 7.5g, photocatalytic activity inorganic oxide (D-1) 5.2g (solid content 29 mass%), fluorocarbon surfactant (E-1) (DIC, “MegaFuck F-444”) 0.2 g and a fading dye (F-1) whose solid content was adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “Methylene Blue”) ) 1 g, 80 g of cellulose thickener (G-1) (manufactured by Daicel Finechem, "HEC Daicel SP900") whose solid content was adjusted to 1.0 mass% with ion-exchanged water, 50 g of ethanol, and ion exchange Water 296. To give a solid content 2.0% by weight of the aqueous composition (I-19) by stirring a mixture of g. This aqueous composition (I-19) had a viscosity of 28 mPa · s.
Next, the aqueous composition (I-19) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 50 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-19) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-19), the coating film, and the test plate (J-19).

[Example 20]
To an aqueous dispersion (BD-3) 60 g (solid content 10.0 mass%) of a polymer (B-3), a water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., "Snowtex OS"; solid content 20 mass%) 7.5g, photocatalytic activity inorganic oxide (D-1) 5.2g (solid content 29 mass%), fluorocarbon surfactant (E-1) (DIC, “MegaFuck F-444”) 0.2 g and a fading dye (F-1) whose solid content was adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “Methylene Blue”) ) 1 g, 80 g of cellulose thickener (G-2) (manufactured by Shin-Etsu Chemical Co., Ltd., “Metrozu 90SH-30000”) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, 50 g of ethanol, Ion exchange water 296.1 To give a solid content 2.0% by weight of the aqueous composition (I-20) by stirring a mixture of. This aqueous composition (I-20) had a viscosity of 25 mPa · s.
Next, the aqueous composition (I-20) is applied to 50 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel paint has been applied in advance) previously applied with the enamel paint. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-20) having a coating film formed on the substrate. Table 2 shows various physical properties and evaluation results of the aqueous composition (I-20), the coating film, and the test plate (J-20).

[Example 21]
An aqueous dispersion colloidal silica (C-1) having a number average particle diameter of 8 nm (C-1) (Nissan Chemical Industry Co., Ltd.) was added to 205.8 g (solid content 10.0 mass%) of the aqueous dispersion (BD-3) of the polymer (B-3) “Snowtex OS”; solid content 20% by mass) 29.4 g, photocatalytic activity inorganic oxide (D-1) 10.1 g (solid content 29% by mass), fluorocarbon surfactant (E- 1) 0.2 g (manufactured by DIC, “Megafac F-444”) and a fading dye (F-1) whose solid content is adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “ Methylene blue ”) 3 g, 15 g of anti-algae and fungicide (H-1) (manufactured by Dow Chemical,“ KLARIX 4000 ”, isothiazoline-based compound; active ingredient 4% by mass), 50 g of ethanol, and 186.5 g of ion-exchanged water Mix and stir To give a solid content 6.0% by weight of the aqueous composition (I-21) by. The viscosity of this aqueous composition (I-21) was 2 mPa · s.
Next, the aqueous composition (I-21) is applied at a rate of 17 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel paint has been applied in advance) previously applied with the enamel paint. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-21) having a coating film formed on the substrate. Table 3 shows various physical properties and evaluation results of the aqueous composition (I-21), the coating film, and the test plate (J-21).

[Example 22]
An aqueous dispersion colloidal silica (C-1) having a number average particle diameter of 8 nm (C-1) (Nissan Chemical Industry Co., Ltd.) was added to 207.2 g (solid content: 10.0% by mass) of an aqueous dispersion (BD-3) of the polymer (B-3). “Snowtex OS”; solid content 20 mass%) 29.6 g, photocatalytic activity inorganic oxide (D-1) 10.2 g (solid content 29 mass%), fluorocarbon surfactant (E- 1) 0.2 g (manufactured by DIC, “Megafac F-444”) and a fading dye (F-1) whose solid content is adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “ 3 g of methylene blue ”, 3 g of anti-algae / antifungal agent (H-2) (manufactured by Dow Chemical Co.,“ ROCIMA 345 ”, a mixture of isothiazoline-based compound and triazine-based compound; active ingredient 12 mass%), 50 g of ethanol, Ion exchange By stirring a mixture of water 196.8g give a solid content 6.0% by weight of the aqueous composition (I-22). This aqueous composition (I-22) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-22) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel paint has been applied in advance) to which the enamel paint has been applied in advance to a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-22) having a coating film formed on the substrate. Table 3 shows various physical properties and evaluation results of the aqueous composition (I-22), the coating film, and the test plate (J-22).

[Example 23]
197.4 g of polymer (B-3) in water dispersion (BD-3) (solid content: 10.0% by mass) and water-dispersed colloidal silica (C-1) having a number average particle size of 8 nm (Nissan Chemical Industry Co., Ltd.) “Snowtex OS”; solid content 20% by mass (28.2 g), photocatalytic activity of inorganic oxide (D-1) 9.7 g (solid content 29% by mass), fluorocarbon surfactant (E- 1) 0.2 g (manufactured by DIC, “Megafac F-444”) and a fading dye (F-1) whose solid content is adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “ Methylene blue ”) 3 g, Algae / antifungal agent (H-3) (manufactured by Nippon Soda Co., Ltd.,“ Biocut-N35 ”, mixture of imidazole compound and triazine compound; active ingredient 35 mass%) 5 g, ethanol 50g and ion-exchanged water 1 To give a solid content 6.0% by weight of the aqueous composition (I-23) by stirring a mixture of 6.8 g. This aqueous composition (I-23) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-23) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-23) having a coating film formed on the substrate. Table 3 shows various physical properties and evaluation results of the aqueous composition (I-23), the coating film, and the test plate (J-23).

[Example 24]
A water-dispersed colloidal silica (C-1) (manufactured by Nissan Chemical Industries, Ltd.) having a number average particle size of 8 nm was added to 58 g (solid content: 10.0% by mass) of an aqueous dispersion (BD-3) of the polymer (B-3). "Snowtex OS"; solid content 20 mass%) 7.3 g, photocatalytic activity inorganic oxide (D-1) 5.0 g (solid content 29 mass%), fluorocarbon surfactant (E-1) (DIC, “MegaFuck F-444”) 0.2 g and a fading dye (F-1) whose solid content was adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “Methylene Blue”) ) 1 g, 80 g of cellulose thickener (G-1) (“HEC Daicel SP900” manufactured by Daicel Finechem Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and an algal / antifungal agent (H-1) (Dow Chemical Company) , “KLARIX 4000”, isothiazoline compound; active ingredient 4% by mass), 50 g of ethanol, and 288.5 g of ion-exchanged water were mixed and stirred to obtain an aqueous composition (I-24) having a solid content of 2.0% by mass. ) This aqueous composition (I-24) had a viscosity of 28 mPa · s.
Next, the aqueous composition (I-24) is applied to 50 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been applied in advance) previously coated with the enamel coating. It was painted using a spray. The coated base material was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-24) having a coating film formed on the base material. Table 3 shows various physical properties and evaluation results of the aqueous composition (I-24), the coating film, and the test plate (J-24).

[Example 25]
To an aqueous dispersion (BD-3) 60 g (solid content 10.0 mass%) of a polymer (B-3), a water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., "Snowtex OS"; solid content 20 mass%) 7.5g, photocatalytic activity inorganic oxide (D-1) 5.2g (solid content 29 mass%), fluorocarbon surfactant (E-1) (DIC, “MegaFuck F-444”) 0.2 g and a fading dye (F-1) whose solid content was adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “Methylene Blue”) ) 1 g, 80 g of cellulose thickener (G-1) (“HEC Daicel SP900” manufactured by Daicel Finechem Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and an algal / antifungal agent (H-2) (Dow Chemical Company) , “ROCIMA345”, a mixture of isothiazoline-based compound and triazine-based compound; active ingredient 12% by mass) 1.3 g, ethanol 50 g, and ion-exchanged water 294.8 g are mixed and stirred to obtain a solid content of 2.0% by mass An aqueous composition (I-25) was obtained. This aqueous composition (I-25) had a viscosity of 28 mPa · s.
Next, the aqueous composition (I-25) is applied to 50 g / m ^{2 on} one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-25) having a coating film formed on the substrate. Table 3 shows various physical properties and evaluation results of the aqueous composition (I-25), the coating film, and the test plate (J-25).

[Example 26]
54.4 g of polymer (B-3) in water dispersion (BD-3) (solid content 10.0 mass%) and water-dispersed colloidal silica (C-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) “Snowtex OS”; solid content 20% by mass) 6.8 g, photocatalytic activity inorganic oxide (D-1) 4.7 g (solid content 29% by mass), fluorocarbon surfactant (E- 1) 0.2 g (manufactured by DIC, “Megafac F-444”) and a fading dye (F-1) whose solid content is adjusted to 1.0 mass% with ion-exchanged water (manufactured by Kishida Chemical Co., “ 1 g of methylene blue ”), 80 g of a cellulose-based thickener (G-1) (“ HEC Daicel SP900 ”manufactured by Daicel Finechem Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and algae / anti-proof Mold agent (H-3) (Nippon Soda Co., Ltd.) , “Biocut-N35”, 2.8 g of a mixture of an imidazole compound and a triazine compound; active ingredient 35 mass%), 50 g of ethanol, and 294.8 g of ion-exchanged water were mixed and stirred to obtain a solid content of 2. 0 mass% aqueous composition (I-26) was obtained. The viscosity of this aqueous composition (I-26) was 28 mPa · s.
Next, the aqueous composition (I-26) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 50 g / m ^2. It was painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-26) having a coating film formed on the substrate. Table 3 shows various physical properties and evaluation results of the aqueous composition (I-26), the coating film, and the test plate (J-26).

[Comparative Example 1]
120 g of polymer (B-1) aqueous dispersion (BD-1) (solid content 10.0% by mass), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) 90 g, ethanol 50 g, and ion-exchanged water 240 g were mixed and stirred to obtain an aqueous composition (I-27) having a solid content of 6.0 mass%. . This aqueous composition (I-27) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-27) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-27) having a coating film formed on the substrate. Table 4 shows various physical properties and evaluation results of the aqueous composition (I-27), the coating film, and the test plate (J-27).

[Comparative Example 2]
180 g of polymer (B-1) aqueous dispersion (BD-1) (solid content 10.0 mass%), water-dispersed colloidal silica (C-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS” (solid content 20% by mass) 60 g, ethanol 50 g, and ion-exchanged water 210 g were mixed and stirred to obtain an aqueous composition (I-28) having a solid content of 6.0% by mass. . The viscosity of this aqueous composition (I-28) was 2 mPa · s.
Next, the aqueous composition (I-28) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-28) having a coating film formed on the substrate. Table 4 shows various physical properties and evaluation results of the aqueous composition (I-28), the coating film, and the test plate (J-28).

[Comparative Example 3]
To 120 g of water dispersion (BD-2) of polymer (B-2) (solid content: 10.0% by mass), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) 90 g, ethanol 50 g, and ion-exchanged water 240 g were mixed and stirred to obtain an aqueous composition (I-29) having a solid content of 6.0% by mass. . The viscosity of this aqueous composition (I-29) was 2 mPa · s.
Next, the aqueous composition (I-29) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-29) having a coating film formed on the substrate. Table 4 shows various physical properties and evaluation results of the aqueous composition (I-29), the coating film, and the test plate (J-29).

[Comparative Example 4]
To 90 g of water dispersion (BD-3) of polymer (B-3) (solid content: 10.0% by mass), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS” (solid content 20% by mass) 105 g, ethanol 50 g, and ion-exchanged water 255 g were mixed and stirred to obtain an aqueous composition (I-30) having a solid content of 6.0% by mass. . This aqueous composition (I-30) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-30) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-30) having a coating film formed on the substrate. Table 4 shows various physical properties and evaluation results of the aqueous composition (I-30), the coating film, and the test plate (J-30).

[Comparative Example 5]
To the aqueous dispersion (BD-3) 255g (solid content 10.0% by mass) of the polymer (B-3), water-dispersed colloidal silica (C-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) 22.5 g, ethanol 50 g, and ion-exchanged water 172.5 g were mixed and stirred to obtain an aqueous composition (I-31) having a solid content of 6.0 mass%. ) The viscosity of this aqueous composition (I-31) was 2 mPa · s.
Next, the aqueous composition (I-31) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-31) having a coating film formed on the substrate. Table 4 shows various physical properties and evaluation results of the aqueous composition (I-31), the coating film, and the test plate (J-31).

[Comparative Example 6]
240 g of water dispersion (BD-4) of polymer (B-4) (solid content 10.0% by mass), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS” (solid content 20% by mass) 30 g, ethanol 50 g, and ion-exchanged water 180 g were mixed and stirred to obtain an aqueous composition (I-32) having a solid content of 6.0% by mass. . This aqueous composition (I-32) had a viscosity of 2 mPa · s.
Next, the aqueous composition (I-32) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-32) having a coating film formed on the substrate. Table 4 shows various physical properties and evaluation results of the aqueous composition (I-32), the coating film, and the test plate (J-32).

[Comparative Example 7]
270 g of polymer (B-4) in water dispersion (BD-4) (solid content 10.0 mass%), water-dispersed colloidal silica (C-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS” (solid content 20% by mass) 15 g, ethanol 50 g, and ion-exchanged water 165 g were mixed and stirred to obtain an aqueous composition (I-33) having a solid content of 6.0% by mass. . The viscosity of this aqueous composition (I-33) was 2 mPa · s.
Next, the aqueous composition (I-33) is applied to one side of the 7 cm × 15 cm and 5 cm × 5 cm base material (the surface on which the enamel coating has been previously applied) previously coated with the enamel coating so as to have a coating amount of 17 g / m ^2. Painted using a spray. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (J-33) having a coating film formed on the substrate. Table 4 shows various physical properties and evaluation results of the aqueous composition (I-33), the coating film, and the test plate (J-33).

  From the above, it was confirmed at least that a coating film capable of maintaining the appearance and the stain resistance at a high level can be formed in each example.

  The coating film, aqueous composition and coated product of the present invention can be used as various members such as architectural exterior applications, exterior display applications, automotive parts, and optical parts such as displays and lenses.

Claims (10)

A coating film containing a polymer (B) containing a polymer (A) having a structural unit derived from dimethyldimethoxysilane (a), and an inorganic oxide (C) having no photocatalytic activity, the coating film the content of the component (a) is 31.7 to 48 wt% in the coating film.   The coating film according to claim 1, wherein the inorganic oxide (C) is silicon dioxide.   The coating film of Claim 1 or 2 which further contains the inorganic oxide (D) which has photocatalytic activity.   The coating film as described in any one of Claims 1-3 which further contains a fluorocarbon surfactant (E).   The coating film as described in any one of Claims 1-4 which further contains a fading dye (F).   The coating film as described in any one of Claims 1-5 which further contains a cellulose thickener (G).   The coating film as described in any one of Claims 1-6 which further contains an anti-algae agent and / or a fungicide (H).   The aqueous composition from which the coating film as described in any one of Claims 1-7 is obtained.   The aqueous composition according to claim 8, comprising a dispersion (BD) of the polymer (B) and the inorganic oxide (C).   Painted product containing the coating film as described in any one of Claims 1-7.