JP6509977B2 - Water-based composition, water-based paint, coating film, and painted product - Google Patents

Description

  The present invention relates to water-based compositions, water-based paints, coatings, and painted products.

  In recent years, attempts have been made to maintain houses and protect construction materials for a long period of 20 to 30 years while using water-based paints to suppress the impact on the environment and human body. By using such a water-based paint, if maintenance of a house and protection of building materials can be achieved for a long time as compared with the prior art, it will lead to a drastic reduction of labor and cost, and the economic merit is large. . However, since the coating film itself is exposed outdoors for a long period of time, problems such as contamination in which dust, soot, sand, etc. adhere to the coating film become more significant.

As a technique relating to such a coating film, for example, in Patent Document 1, an organic resin and silica are contained at a solid content weight ratio of 100: 50 to 100: 500, and the silica contained in the coating layer has an average primary order. There is disclosed a coated film laminate which is an aggregate derived from a silica sol having a particle diameter of 1 to 200 nm, and the coating amount of the coating layer is 0.1 to 50 g / m ² in solid content.

JP 2007-118567 A

  However, the paint described in Patent Document 1 causes dripping when forming a coating film on the exterior of a building to be coated on a vertical surface, etc., and further, the film thickness of the coating film becomes thick in the reservoir part of the paint due to the dripping This causes cracking. Contamination is caused by the adhesion of dust, smoke, sand and the like to the broken part.

  Then, this invention is made in view of the said situation, and it aims at providing the water-based composition which can form the coating film which can maintain an external appearance and stain resistance at a high level over a long period of time.

  The inventors of the present invention conducted intensive studies and found that the above-mentioned problem is caused by using an aqueous composition containing polymer particles (A), inorganic oxide particles (B), and a cellulose-based thickener (C). The present invention has been achieved by finding that the solution of

That is, the present invention is as follows.
[1]
An aqueous composition comprising polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C),
The cellulose-based thickener (C) is hydroxyethyl cellulose having a weight average molecular weight of 700,000 to 2,000,000,
The aqueous composition whose content of solid content in an aqueous composition is 0.5-10 mass%.
[ 2 ]
The aqueous composition according to [1], wherein the component (B) is silicon dioxide.
[ 3 ]
The aqueous composition as described in [1] or [2] which further contains the inorganic oxide particle (D) which has photocatalytic activity.
[ 4 ]
The water-based composition as described in any one of [1]-[ 3 ] which further contains a color-fading pigment (E).
[ 5 ]
The aqueous composition as described in any one of [1] to [ 4 ], which further contains a fluorocarbon surfactant (F).
[ 6 ]
The aqueous composition as described in any one of [1]-[ 5 ] which contains a saturated hydrocarbon alcohol (G) further.
[ 7 ]
The water-based paint containing the water-based composition as described in any one of [1] to [ 6 ].
[ 8 ]
The coating film obtained from the water-based paint as described in [ 7 ].
[9]
A substrate,
The coating film according to [ 8 ], formed on at least a part of the surface of the substrate
Painted products containing.
[10]
The coated product according to [ 9 ], wherein the substrate is an organic substrate.
[11]
Production of an aqueous composition according to [1], which comprises, as the component (A), polymer particles obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier. Method.
[12]
The manufacturing method of the water-based composition as described in [11] whose said (B) component is silicon dioxide.
[13]
The aqueous composition according to [11] or [12], which contains, as the component (B), particles having a number average particle diameter of 25 to 100 nm and particles having a number average particle diameter of 4 to 8 nm. Production method.
[14]
The manufacturing method of the water-system composition as described in any one of [11]-[13] which further contains the inorganic oxide particle (D) which has photocatalytic activity.
[15]
The manufacturing method of the water-based composition as described in any one of [11]-[14] which further contains a discolorable pigment | dye (E).
[16]
The manufacturing method of the water-based composition as described in any one of [11]-[15] which further contains a fluorocarbon surfactant (F).
[17]
The manufacturing method of the water-based composition as described in any one of [11]-[16] which further contains saturated hydrocarbon alcohol (G).
[18]
It contains polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C), and the cellulose-based thickener (C) has a weight average molecular weight Of hydroxyethyl cellulose of 700,000 to 2,000,000, and the solid content in the aqueous composition is 0.5 to 10% by mass, and as the component (A), vinyl alone in the presence of water and an emulsifying agent. Aqueous composition containing polymer particles obtained by polymerizing a monomer and a hydrolyzable silicon compound
A method of producing a water-based paint containing
[19]
It contains polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C), and the cellulose-based thickener (C) has a weight average molecular weight Of hydroxyethyl cellulose of 700,000 to 2,000,000, and the solid content in the aqueous composition is 0.5 to 10% by mass, and as the component (A), vinyl alone in the presence of water and an emulsifying agent. Aqueous composition containing polymer particles obtained by polymerizing a monomer and a hydrolyzable silicon compound
The manufacturing method of the coating film obtained from the water-based paint containing.
[20]
A substrate,
Formed on at least part of the surface of the substrate,
It contains polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C), and the cellulose-based thickener (C) has a weight average molecular weight Of hydroxyethyl cellulose of 700,000 to 2,000,000, and the solid content in the aqueous composition is 0.5 to 10% by mass, and as the component (A), vinyl alone in the presence of water and an emulsifying agent. A coating film obtained from a water-based paint containing a water-based composition, comprising a polymer particle obtained by polymerizing a monomer and a hydrolyzable silicon compound,
A method of producing a painted product containing

  ADVANTAGE OF THE INVENTION According to this invention, the water-based composition which can form the coating film which can maintain an external appearance and stain resistance at a high level over a long period of time can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described. The following present embodiment is an example for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist of the present invention.

  The aqueous composition of the present embodiment is an aqueous composition containing polymer particles (A), inorganic oxide particles (B), and a cellulose-based thickener (C). The coating film obtained from this aqueous composition can maintain the appearance and the stain resistance at a high level for a long time.

<Polymer particles (A)>
As polymer particles (A), polymer particles obtained by a method such as emulsion polymerization can be used. Specific examples thereof include polymer particles obtained by performing any one of radical polymerization, anionic polymerization and cationic polymerization in an aqueous medium.

  The component (A) is not particularly limited. For example, poly (meth) acrylate polymers, polyvinyl acetate polymers, vinyl acetate- (meth) acrylic polymers, ethylene vinyl acetate polymers, silicone polymers Combination, fluorine-based polymer, polybutadiene-based polymer, styrene butadiene-based polymer, NBR-based polymer, polyvinyl chloride-based polymer, chlorinated polypropylene-based polymer, polyethylene-based polymer, polystyrene-based polymer, vinylidene chloride-based polymer Homopolymers or copolymers represented by polymers, polystyrene- (meth) acrylate polymers, styrene-maleic anhydride polymers, etc .; silicone-modified (meth) acrylic polymers, fluorine- (meth) acrylics Representative for base polymers, (meth) acrylic-silicon polymers, epoxy- (meth) acrylic polymers, etc. Modified copolymer thereof. These may be used singly or in combination of two or more. In addition, "(meth) acrylate" means "acrylate" and the corresponding "methacrylate", "(meth) acrylic" means "acrylic" and the corresponding "methacryl."

  The homopolymers, copolymers, modified copolymers and the like described above (hereinafter, these may be generically referred to as "polymer") are preferably in the state of aqueous dispersion. Preferred examples of these polymers include emulsions, and specific examples thereof include acrylic emulsions and acrylic silicone emulsions. These can be obtained, for example, by emulsion polymerization of a monomer such as (meth) acrylic acid ester or a hydrolyzable silicon compound described later.

  The component (A) preferably contains a functional group capable of interacting with the inorganic oxide particles (B) described later. The interaction referred to here may be a chemical interaction, and examples thereof include hydrogen bond, covalent bond, ionic bond, van der Waals force. As a hydrogen bond, the hydrogen bond between the hydroxyl group which metal oxide particle etc. have, and the functional group (for example, a hydroxyl group, an amino group, an amide group etc.) which polymer particle has is mentioned, for example. As a covalent bond, the covalent bond which arises by the condensation reaction (dehydration condensation reaction) between the hydroxyl group which metal oxide particle etc. have, and the hydroxyl group which polymer particle has is mentioned, for example. As an ionic bond, the ionic bond between the hydroxyl group which metal oxide particle etc. have, and the cationic group (for example, amino group, imino group etc.) in polymer particle is mentioned, for example.

  The functional group capable of interacting with the inorganic oxide particles (B) is not particularly limited, and examples thereof include an amide group, a hydroxyl group, a carboxyl group, a carbonyl group, a silanol group, a thiol group, an amino group and an imino group Ureido group etc. are mentioned. These functional groups may contain only one kind or two or more kinds.

  The aqueous composition of the present embodiment may further include, in addition to the component (A), a compound having a functional group that reacts with the functional group contained in the polymer. Such compounds are not particularly limited. For example, (poly) isocyanate compounds, (poly) epoxy compounds, amino compounds, (poly) carboxy compounds, (poly) hydroxy compounds, glycol compounds, silanol compounds, silyl compounds, An alkoxy compound, a (meth) acrylate compound, etc. are mentioned. These may be used singly or in combination of two or more.

  Component (A) is preferably a polymer particle obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifying agent.

  The number average particle diameter of the component (A) is not particularly limited, but is preferably 10 to 300 nm, more preferably 10 to 200 nm, still more preferably 50 to 200 nm, and still more preferably 50 to 180 nm. is there. By using the component (A) having a number average particle diameter in the above range, the weather resistance of the resulting coated film is further improved. Furthermore, when the number average particle diameter is 10 nm or more, the stain resistance of the coating film is further improved, and when the number average particle diameter is 300 nm or less, the transparency of the coating film is further improved.

  It does not specifically limit as a specific example of the vinyl monomer which can be used for manufacture of (A) component, For example, (meth) acrylic acid ester, an aromatic vinyl compound, a vinyl cyanide compound, a carboxyl group-containing vinyl compound And vinyl monomers containing functional groups such as hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, vinyl compounds having secondary and / or tertiary amide groups, and anionic vinyl compounds.

  The (meth) acrylic acid ester is not particularly limited, and, for example, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 50 carbon atoms, (poly) oxyethylene resin having an ethylene oxide group having 1 to 100 carbon atoms Examples include (meth) acrylates and the like. Specific examples thereof are not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Methyl cyclohexyl acid, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate and the like can be mentioned.

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

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

  It does not specifically limit as a specific example of a vinyl cyanide compound, For example, (meth) acrylonitrile, alpha-chloro acrylonitrile, etc. are mentioned.

  It does not specifically limit as a specific example of a carboxyl group-containing vinyl compound, For example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, maleic acid, fumaric acid etc. And half esters of dibasic acids. A carboxyl group can be introduce | transduced into (A) component by using the vinyl monomer containing a carboxyl group. Thereby, it is presumed that the stability as an emulsion is further improved, and a high resistance to the external dispersion and destruction action can be imparted to the coating film (however, the action of the present embodiment is not limited to these). A part or all of the carboxyl groups to be introduced can be neutralized with ammonia, amines such as triethylamine or dimethylethanolamine, or bases such as NaOH or KOH. The use amount of the carboxyl group-containing vinyl monomer in the total amount of the above-mentioned vinyl monomers is preferably 0 to 50% by mass from the viewpoint of water resistance, but is not limited thereto.

  It does not specifically limit as a specific example of a hydroxyl-containing vinyl compound, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Hydroxyalkyl esters of (meth) acrylic acid such as acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc .; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate Rate, allyl alcohol or (poly) oxyethylene mono (meth) acrylate having 1 to 100 ethylene oxide groups; (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups, and , " Kuseru FM, and (trade name manufactured by Daicel Chemical Industries caprolactone addition monomer) FA Monomer ", 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) Diethylene glycol acrylate, tetraethylene glycol (meth) acrylate, tetraethylene glycol methoxy (meth) acrylate and the like can be mentioned.

  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 (eg, Examples include meta) acrylic acid dipropylene glycol, (meth) acrylic acid tetrapropylene glycol, and methoxy (meth) acrylic acid tetrapropylene glycol.

  The proportion of the hydroxyl group-containing vinyl monomer in the total amount of the above-mentioned vinyl monomers is not particularly limited, but is preferably 0 to 80% by mass, more preferably 0.1 to 20% by mass from the viewpoint of water resistance of the coating film. It is 50% by mass.

  It does not specifically limit as a specific example of a glycidyl group containing vinyl compound, For example, glycidyl (meth) acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether etc. are mentioned.

  When the glycidyl group-containing vinyl monomer is used among the above-mentioned vinyl monomers, the reactivity of the component (A) is further improved. Therefore, by crosslinking using a hydrazine derivative, a carboxylic acid derivative, an isocyanate derivative or the like, a coating film having further excellent solvent resistance and the like can be obtained. From this viewpoint, the total amount of the glycidyl group-containing vinyl monomer used in the total amount of the above-mentioned vinyl monomers is preferably 0 to 50% by mass.

  It does not specifically limit as a specific example of the vinyl monomer which has a secondary and / or tertiary amide group, For example, N-alkyl substituted (meth) acrylamide, N-alkylene substituted (meth) acrylamide etc. are mentioned.

  It does not specifically limit as a specific example of N-alkyl substituted (meth) acrylamide, 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, N-n-propyl (meth) acrylamide, N-methyl-N-n-propyl (meth) acrylamide, N- Methyl-N-isopropyl (meth) acrylamide, N- (meth) acryloyl pyrrolidine, N- (meth) acryloyl piperidine, N-acryloyl hexahydroazepine, N- (meth) acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl caprolactam , N, N'- methylene bis ( Meta) acrylamide, N-vinyl acetamide, diacetone (meth) acrylamide, N- methylol (meth) acrylamide etc. are mentioned.

  It does not specifically limit as a specific example of vinyl monomers other than the above, For example, Olefins, such as (meth) acrylamide, ethylene, propylene, isobutylene; Dienes, such as butadiene; Vinyl chloride, vinylidene chloride vinyl fluoride, Haloolefins such as tetrafluoroethylene and chlorotrifluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, Carboxylic acid vinyl esters such as vinyl versatate and vinyl laurate; 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 Teryls; aromatic vinyl compounds such as styrene and vinyl toluene; allyl esters such as allyl acetate and allyl benzoate; allyl ethers such as allyl ethyl ether and allyl phenyl ether; 4- (meth) acryloyloxy-2,2 6,6,6-Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropyl Examples thereof include methyl (meth) acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate and the like. These may be used singly or in combination of two or more.

  In the case where the component (A) is produced by a polymerization reaction in the present embodiment, a chain transfer agent may be used in order to control the molecular weight of the polymerization product of the vinyl monomer used. Specific examples of the chain transfer agent are not particularly limited. For example, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; thioapple Thiocarboxylic acids such as acids or their salts or their alkyl esters; Polythiols; Diisopropylxanthogen disulfide, Disulfides such as di (methylene trimethylolpropane) xanthogen disulfide; Allyl compounds such as thioglycol, dimer of α-methylstyrene Etc. These may be used singly or in combination of two or more.

  Although the usage-amount of the chain transfer agent with respect to the total amount of the above-mentioned vinyl monomers is not specifically limited, Preferably it is 0.001-30 mass%, More preferably, it is 0.05-10 mass%.

The hydrolyzable silicon compound used to produce the polymer particles (A) of the present embodiment is not particularly limited, but preferably a compound represented by the following formula (1), a silane coupling agent and condensation of these The thing is mentioned.

SiW _x R _y (1)

  In the formula, W represents 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 And at least one selected from the group consisting of R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms substituted with a halogen atom And at least one group selected from the group consisting of aryl groups of x is an integer of 1 or more and 4 or less, y is an integer of 0 or more and 3 or less, and the relationship of x + y = 4 is satisfied. When W is plural, when R is plural, each W and R may be the same as or different from each other.

  It does not specifically limit as a compound represented by Formula (1), For example, the silicon alkoxide etc. which are represented by Formula (1) are mentioned. As the silicon alkoxide, a tetrafunctional silicon alkoxide is preferable from the viewpoint of the hydrolysis rate.

  As a silane coupling agent, a hydrolysable group (for example, 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 Functional group having reactivity with another compound (eg, vinyl polymerizable group, epoxy group, amino group, methacryl group, thiol group) And hydrolyzable silicon compounds (silane coupling agents) having an isocyanate group etc.). By using such a silane coupling agent, the polycondensate etc. of a hydrolysable silicon compound and a vinyl monomer can be chemically couple | bonded. Thereby, the compatibility is further improved, and the transparency of the coating film is further improved.

  Among the above, silane coupling agents having at least a vinyl polymerizable group and / or a thiol group are preferable, and silane coupling agents having at least a vinyl polymerizable group are more preferable. Since the vinyl polymerizable group and the thiol group have high reactivity with the above-mentioned vinyl monomer, chemical bonds can be efficiently formed by the copolymerization reaction and the chain transfer reaction with the vinyl monomer. Therefore, by using a silane coupling agent having a vinyl polymerizable group or a thiol group, it can be efficiently complexed with other components (for example, vinyl monomer etc.) constituting the component (A). By using the component (A) in which such a hydrolyzable silicon compound (or a polymerization product thereof) and / or a vinyl monomer (or a polymerization product thereof) or the like is complexed by a chemical bond, weatherability can be obtained. It is possible to obtain a coating film with further improved strength and the like (however, the action of the present embodiment is not limited to these).

  Preferred specific examples of the silane coupling agent having a vinyl polymerizable group include, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyl Oxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2- Trimethoxy silyl ethyl vinyl ether etc. are mentioned.

  Preferred specific examples of the silane coupling agent having a thiol group include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like.

  It does not specifically limit as a specific example of the hydrolysable silicon compound represented by Formula (1), and a silane coupling agent, For example, tetramethoxysilane, tetraethoxysilane, tetra- n-propoxysilane, tetraisopropoxysilane And tetraalkoxysilanes such as tetra-n-buxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxy Silane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrime Xysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane Ethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyl trioxide Methoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxy Orchid, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acrylic Oxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropanol Trialkoxysilanes such as xysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, Di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxy Silane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-o Dialkoxysilanes such as chilldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; trimethyl Monoalkoxysilanes, such as methoxysilane and trimethylethoxysilane, etc. are mentioned. Among these, tetraalkoxysilanes, trialkoxysilanes and dialkoxysilanes are preferable, and tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, dimethyldimethoxysilane Is more preferable, and tetramethoxysilane and tetraethoxysilane, which are tetrafunctional silicon alkoxides, are more preferable from the viewpoint of high hydrolysis rate.

  When used as a condensate of a compound represented by the formula (1) or a silane coupling agent, the weight average molecular weight in terms of polystyrene is not particularly limited, but is preferably 200 to 5,000, and more preferably 300 to 500. It is 1000. The polymerization stability is further improved by using a condensate having a weight average molecular weight in the above range.

  The silicon alkoxide and silane coupling agent represented by these Formula (1) may be used individually by 1 type, and may use 2 or more types together. Among them, it is preferable to use the silicon alkoxide represented by the formula (1) in combination with a silane coupling agent from the viewpoint of improving the performance of the aqueous composition and the obtained coating film, tetraethoxysilane, methyltrimethoxysilane, It is more preferable to use 3- (meth) acryloxypropyltrimethoxysilane in combination with at least one selected from the group consisting of phenyltrimethoxysilane and dimethyldimethoxysilane.

  The total amount of the silane coupling agent used at least having a vinyl polymerizable group and / or a thiol group in 100 parts by mass of component (A) is preferably 0.01 to 20 parts by mass from the viewpoint of polymerization stability, More preferably, it is 0.1 to 10 parts by mass.

  In the present embodiment, as the hydrolyzable silicon compound, in addition to those described above, a cyclic siloxane oligomer can be used in combination. By using the cyclic siloxane oligomer in combination, it is possible to obtain a coating film having more excellent flexibility and the like.

It does not specifically limit as cyclic siloxane oligomer, For example, the compound represented by following formula (2) is mentioned.

(R ' ₂ SiO) _m (2)

In the formula, R ′ each independently represents a hydrogen atom, 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, And at least one selected from the group consisting of aryl groups having 6 to 20 carbon atoms substituted with a halogen atom. m is an integer of 2 or more and 20 or less.

  Among cyclic siloxane oligomers, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferable from the viewpoint of reactivity and the like.

  When producing the component (A), a titanium alkoxide, a zirconium alkoxide, a condensation product or a chelate thereof may be used in combination with the hydrolyzable silicon compound. By using these compounds in combination, it is possible to obtain a coating film having further excellent water resistance and the like.

  It does not specifically limit as a specific example of a titanium alkoxide, For example, tetramethoxy titanium, tetra-ethoxy titanium, tetra-i-propoxy titanium, tetra- n- propoxy titanium, tetra- n- butoxy titanium, tetra- sec- butoxy titanium And tetra-tert-butoxytitanium.

  When a condensate of titanium alkoxide is used, the weight average molecular weight in terms of polystyrene is not particularly limited, but is preferably 200 to 5,000, and more preferably 300 to 1,000.

  Specific examples of the zirconium alkoxide are not particularly limited. For example, tetramethoxyzirconium, tetraethoxyzirconium, tetra-i-propoxyzirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-sec-butoxyzirconium And tetra-tert-butoxyzirconium.

  When a zirconium alkoxide is used as a condensate, the polystyrene equivalent weight average molecular weight of the condensate is not particularly limited, but is preferably 200 to 5,000, and more preferably 300 to 1,000.

  The weight ratio of hydrolyzable silicon compound to vinyl monomer is preferably 0.5 / 99.5 to 99.5 / 0.5, more preferably 0.5 / 99.5 to 15/85. is there.

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

  The emulsifier which can be used for the production of the component (A) is not particularly limited. For example, alkyl benzene sulfonic acid, alkyl sulfonic acid, alkyl sulfo succinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene Acidic emulsifiers such as distyryl phenyl 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; alkyl trimethyl ammonium bromide, alkyl pyridinium bromide , Quaternary ammonium salts such as imidazolinium laurate, pyridinium salts, cationic surfactants of the imidazolinium salt type; polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester Polyoxyethylene polyoxypropylene block copolymers, nonionic surface active agent polyoxyethylene distyryl phenyl ether; reactive emulsifier or the like having a radical polymerizable double bond.

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

  The reactive emulsifier having a radically polymerizable double bond is not particularly limited. For example, a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate ester group, and alkali metal salts thereof And ammonium salts, vinyl monomers having a nonionic group represented by polyoxyethylene and the like, and vinyl monomers having a quaternary ammonium salt and the like.

  It does not specifically limit as a salt of the vinyl monomer which has a sulfonic acid group or a sulfonate group, For example, it has a double bond of (i) radically polymerizable, and the ammonium salt of a sulfonic acid group, sodium salt, or potassium From an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group, an aryl group having 6 to 10 carbon atoms, and a succinic acid group, which is partially substituted by a salt group A compound having at least one type of substituent selected from the group consisting of: (ii) a vinyl sulfonate compound having a vinyl group to which a group which is an ammonium salt, a sodium salt or a potassium salt of a sulfonic acid group is bonded, (iii) Examples thereof include compounds having an aryl group which has a radically polymerizable double bond and which is partially substituted from a sulfonate group.

  The vinyl monomer having a sulfuric acid ester group is not particularly limited. For example, some of the vinyl monomers having a radical polymerizable double bond and an ammonium salt, a sodium salt or a potassium salt of a sulfuric acid ester group are used. At least one substituent selected from the group consisting of a substituted alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group, and an aryl group having 6 to 10 carbon atoms The compound etc. which it has are mentioned.

  Among the compounds (i) of vinyl monomers having a sulfonic acid group, specific examples of the compound having a succinic acid group partially substituted by a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group are It is not particularly limited, and examples thereof include allyl sulfosuccinate and the like. A commercial item can also be used for these. As these commercial items, for example, "Eleminol JS-2" (manufactured by Sanyo Chemical Industries, Ltd.), "Latemul S-120", "Ramtel S-180A", "Ramtel S-180" (manufactured by Kao Corporation) and the like are listed. Be

  Among the compounds (i) of vinyl monomers having a sulfonic acid group, an alkyl ether group having 2 to 4 carbon atoms, which is partially substituted by a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group, or A commercial item can also be used as a compound which has a polyalkyl ether group. As these commercial products, for example, “Aqualon HS-10”, “Aqualon KH-1025” (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), “Adecaria soap SE-1025 N”, “Adecaria soap SR-1025” (Asahi And the like.

  It does not specifically limit as a specific example of compound (i) of the vinyl monomer which has a sulfonic acid group, For example, the ammonium salt of p-styrenesulfonic acid, a sodium salt, potassium salt etc. are mentioned.

  It does not specifically limit as a specific example of compound (ii) of the vinyl monomer which has a sulfonate group, For example, the alkyl sulfonic acid (meth) acrylate represented by 2-sulfoethyl acrylate, methylpropane sulfonic acid (meth) Acrylamide, ammonium salts, sodium salts and potassium salts of allylsulfonic acid and the like can be mentioned.

  A vinyl monomer having a sulfuric acid ester group, having a radically polymerizable double bond, and having a carbon number of 2 to 4 partially substituted by an ammonium salt, sodium salt or potassium salt of a sulfuric acid ester group It does not specifically limit as a specific example of the compound which has an alkyl ether group or a polyalkyl ether group, For example, the compound which has the alkyl ether group which was partially substituted by the sulfonate group is mentioned.

  The vinyl monomer having a nonionic group is not particularly limited. For example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (eg, commercially available product) As “Adekaria soap NE-20”, “Adekaria soap NE-30”, “Adekaria soap NE-40”, etc., all manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene alkyl propenyl phenyl ether (eg, commercially available) As a product, "Aqualon RN-10", "Aqualon RN-20", "Aqualon RN-30", "Aqualon RN-50", etc., all manufactured by Daiichi Pharmaceutical Industry Co., Ltd., etc. may be mentioned.

  The amount of the emulsifier used is preferably 10 parts by mass or less, more preferably 0.001 parts by mass, based on 100 parts by mass of the total of the hydrolyzable silicon compound and the vinyl monomer which are the raw materials of the polymer particles (A). 5 parts by mass. By setting the amount of the emulsifier used in the above range, the polymerization stability is further improved, and the water resistance of the coating film is further improved.

  The polymerization of the vinyl monomer and the hydrolyzable silicon compound is preferably carried out in the presence of a polymerization catalyst.

  The polymerization catalyst for the vinyl monomer is not particularly limited, but is preferably a radical polymerization catalyst that causes addition polymerization of the vinyl monomer by radical decomposition of itself by heat or a reducing substance. Such a radical polymerization catalyst is not particularly limited, and examples thereof include persulfates, peroxides, and azobis compounds. These may be water soluble or oil soluble.

  Specific examples of the radical polymerization catalyst are not particularly limited. For example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2,2-azo Examples 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. When it is desired to accelerate the polymerization rate or to perform efficient polymerization at a low temperature (eg, 70 ° C. or less), for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite or the like is used as a radical polymerization catalyst. It is preferable to use in combination with

  The polymerization catalyst for the hydrolyzable silicon compound is not particularly limited, and, for example, hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; sulfuric acid, p-toluene sulfone Sulfonic acids such as acids; alkyl benzene sulfonic acids, alkyl sulfonic acids, alkyl sulfosuccinic acids, polyoxyethylene alkyl sulfuric acids, polyoxyethylene alkyl aryl sulfuric acids, and polyoxyethylene emulsifiers such as polyoxyethylene distyryl phenyl ether sulfonic acids; acidic or weakly acidic Inorganic salts; acid compounds such as phthalic acid, phosphoric acid and nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethyl ammonium chloride, tetramethyl ammonium hydroxide, tributylamine, diazabicycloune Basic compounds such as sen, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane and the like; tin compounds such as dibutyltin octilate and dibutyltin dilaurate Can be mentioned.

  Among these, as a polymerization catalyst for hydrolyzable silicon compounds, acidic emulsifiers are preferable from the viewpoint of having not only a polymerization catalyst but also a function as an emulsifier. As an acidic emulsifier, a C5-C30 alkyl benzene sulfonic acid (for example, dodecylbenzene sulfonic acid etc.) is more preferable.

  The polymerization of the vinyl monomer and the hydrolyzable silicon compound can be carried out separately, but is preferably carried out at the same time because the compounding can be efficiently achieved.

  Although the number average particle diameter of (A) component is not specifically limited, Preferably it is 10-300 nm. By making the number average particle diameter of (A) component into the said range, the weather resistance and stain resistance of the coating film obtained further improve. Further, the number average particle diameter of the component (A) is more preferably 10 to 200 nm, and still more preferably 50 to 200 nm. By making the number average particle diameter of (A) component into the said range, the transparency of the coating film obtained is also improved further. 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 (A) having such a particle size, for example, a vinyl monomer and a hydrolyzable silicon compound are polymerized in the presence of a sufficient amount of water for the emulsifier to form micelles. And so-called emulsion polymerization. It does not specifically limit as a specific method of emulsion polymerization, For example, a vinyl monomer and a hydrolysable silicon compound are dripped in the reaction container at once, in a division, or continuously in the state which was or was emulsified. And polymerization at a reaction temperature of about 30 to 150 ° C. in the presence of a polymerization catalyst, preferably under a pressure of atmospheric pressure to 10 MPa. The reaction temperature and reaction pressure may not be as described above depending on the reaction conditions and the like. The amount of solid content in the emulsion obtained by emulsion polymerization is not particularly limited, but is preferably 0.1 to 70% by mass, more preferably 1 to 55% by mass, and still more preferably 5 to 30% by mass. is there.

  If it is desired to further control the particle size in the emulsion polymerization, a seed polymerization method may be employed in which emulsion particles are previously present in the aqueous phase for polymerization. The pH of the polymerization system in this case is not particularly limited, but is preferably 1.0 to 10.0, and more preferably 1.0 to 6.0. This pH can be adjusted using a pH buffer such as disodium phosphate, sodium tetraborate (such as borax), sodium hydrogen carbonate, ammonia and the like.

  As a method of producing the component (A), after the hydrolyzable silicon compound and the vinyl monomer are polymerized in the presence of a solvent, if necessary, in the presence of water and an emulsifier, the water is added until the polymerization product becomes an emulsion. Furthermore, the method of adding can also be adopted. However, emulsion polymerization is preferred from the viewpoint of easy control of particle diameter of the component (A) obtained.

  Component (A) preferably has a core / shell structure having a core and one or more shell layers. Having a core / shell structure is preferable because mechanical properties (such as balance between strength and flexibility) of the resulting coating film are further improved. The core / shell structure of the component (A) can be confirmed by, for example, form observation with a transmission electron microscope or analysis by viscoelasticity measurement.

  The method for producing the component (A) having a core / shell structure is not particularly limited, but preferred examples include multistage emulsion polymerization. The multistage emulsion polymerization as referred to herein is to prepare two or more kinds of reaction solutions having different compositions containing a vinyl monomer and a hydrolysable silicon compound, and divide these into separate stages to polymerize them. As an example of multistage emulsion polymerization, a method of synthesizing the component (A) having a core / shell structure by two-stage emulsion polymerization will be mainly described. As an example of the two-stage emulsion polymerization, for example, a step (first stage) of polymerizing a vinyl monomer and / or a hydrolyzable silicon compound in the presence of water and an emulsifying agent to obtain seed particles, and The method etc. which have the process (2nd step | stage) of respectively polymerizing a hydrolysable silicon compound and a vinyl monomer in presence of seed particle | grains are mentioned.

  Production of the component (A) by two-stage emulsion polymerization is carried out by supplying a first series (vinyl monomer and / or hydrolyzable silicon compound) and performing emulsion polymerization; The second series (vinyl monomer and / or hydrolyzable silicon compound) is supplied, and it is carried out by a two-stage polymerization process consisting of a second stage polymerization which is further emulsion-polymerized in an aqueous medium. At this time, the mass ratio ((M1) / (M2)) of the solid content (M1) in the first series to the solid content (M2) in the second series is not particularly limited, but preferably 9/1 to 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 of adding raw materials in multistage emulsion polymerization, a method of producing seed particles (core) in the first stage polymerization and then additionally adding another monomer or the like is preferable. As a result, the particle diameter of the polymer particles obtained in the second-stage polymerization is increased without changing the ratio of the volume average particle diameter / number-average particle diameter of the seed particles (core) obtained in the first-stage polymerization. It will also be possible.

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

  Although content of (A) component in a water-based composition is not specifically limited, Preferably it is 0.20-3.00 mass%, More preferably, it is 0.60-2.50 mass%. By making content of (A) component in a water-based 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 (A) component in the coating film obtained from a water-based composition is not specifically limited, Preferably it is 10.0-80.0 mass%, More preferably, 30.0-70.0 mass% It is. By making content of (A) component in a coating film more than the said lower limit, the weather resistance of a coating film improves further, and the contamination resistance of a coating film improves further by making it below the said upper limit. .

<Inorganic oxide particles (B)>
The inorganic oxide particles (B) are particles of inorganic oxide having no photocatalytic activity. The absence of photocatalytic activity as used herein means that neither oxidation reaction nor reduction reaction occurs by light irradiation.

  The component (B) is not particularly limited, and examples thereof include silicon dioxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide and composite oxides thereof. Among these, silicon dioxide, aluminum oxide, antimony oxide, and composite oxides of these are preferable, and silicon dioxide is more preferable, from the viewpoint of having a large number of surface hydroxyl groups.

  The inorganic oxide particles used as the component (B) are preferably present as colloidal particles such as hydrates. That is, by being inorganic oxide colloidal particles, further complexation with other components such as the (A) component and the (C) component becomes possible, and the stability as a water-based composition is further improved.

  The silicon dioxide is preferably colloidal silica. Examples of colloidal silica include colloidal silica, which is a dispersion of water or a water-soluble solvent of silica having silicon dioxide as a basic unit.

The method for producing colloidal silica is not particularly limited, and can also be prepared, for example, by a sol-gel method. When prepared by the sol-gel method, Werner Stober et al .; Journal of Colloid And Interface Science, vol. 26, pp. 62-69 (1968), Rickey D. Badley et al .; Lang muir 6, 792-801 (1990), “Colorant Society Journal”, 61 [9] 488-493 (19
88) and so on.

  Although the number average particle diameter of (B) component is not specifically limited, Preferably it is 1-400 nm, More preferably, it is 1-100 nm. The storage stability of the aqueous composition is further improved by setting the number average particle diameter of the component (B) to 1 nm or more. By setting the number average particle diameter of the component (B) to 400 nm or less, the transparency of the resulting coated film is further improved. The number average particle size can be measured using a wet particle size analyzer.

  It is preferable to contain, as the component (B), particles having a number average particle diameter of 25 to 100 nm and particles having a number average particle diameter of 4 to 8 nm. A film having more excellent weatherability by using in combination particles (first particles) having a number average particle diameter of 25 to 100 nm and particles (second particles) having a number average particle diameter of 4 to 8 nm You can get The mass ratio of the first particle to the second particle (first particle / second particle) is not particularly limited, but is preferably 1/9 to 9/1, more preferably 2/8 to 8 It is / 2. By setting the mass ratio of the first particles to the second particles in the above range, the balance between the weather resistance and the stain resistance is further improved. The mass ratio of the first particle to the second particle (first particle / second particle) is obtained by observing the cross section of the coating film with a transmission electron microscope (TEM) and measuring the particle diameter of each. You can ask for it by doing.

  Colloidal silica may be either acidic or basic in the form of an aqueous dispersion.

  A commercial item can also be used as acidic colloidal silica which makes water a dispersion medium. As such commercial products, for example, “SnowtexTM-OXS”, “Snowtex-OS”, “Snowtex-O”, “Snowtex-O-40”, manufactured by Nissan Chemical Industries, Ltd. "Snowtex-OL" and "Snowtex-OYL", "Adelight (trademark) AT-20Q" manufactured by Asahi Denka Kogyo Co., Ltd., "Clevosol (trademark) 20H12" and "Clevosol 30CAL25" manufactured by Clariant Japan, etc. may be mentioned. .

  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. As such commercial products, for example, “Snowtex-XS”, “Snowtex-S”, “Snowtex-30”, “Snowtex-50”, “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" and "Snowtex PS-M"; "ADELITE AT-20" manufactured by Asahi Denka Kogyo Co., Ltd. "Adelight AT-30", "Adelight AT-20N", "Adelight AT-30N", "Adelight AT-20A", "Aderai "AT-30A", "adelite AT-40" and "adelite AT-50"; "Klevozole 30R9" made by Clariant Japan, "Kerevozole 30R50", "Kerevozole 50R50", "Ludox (trademark) HS-made by DuPont 40 "," RUDOX HS-30 "," RODOX LS ", and" RUDOX SM-30 "and the like.

  A commercial item can also be used as colloidal silica which makes a water-soluble solvent a dispersion medium. As such commercial products, for example, "MA-ST-M (methanol dispersion type with particle diameter 20 to 25 nm)", "IPAST (isopropyl alcohol dispersion type with particle diameter 10 to 15 nm)" manufactured by Nissan Chemical Industries, Ltd. “EG-ST (ethylene glycol dispersion type with particle diameter 10 to 15 nm)”, “EG-ST-ZL (ethylene glycol dispersion type with particle diameter 70 to 100 nm)”, “NPC-ST (particle diameter 10 to 15 nm) Ethylene glycol monopropyl ether dispersion type) and the like.

  The above-mentioned colloidal silica may be used alone or in combination of two or more. Furthermore, alumina, sodium aluminate, etc. may be contained as a minor component. The colloidal silica may contain, as a stabilizer, an inorganic base (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia or the like) or an organic base (tetramethylammonium or the like).

  The content of the component (B) in the aqueous composition is not particularly limited, but is preferably 0.10 to 1.40% by mass, and more preferably 0.20 to 1.30% by mass. By making content of (B) component in a water-system 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 (B) component in the coating film obtained from a water-based composition is not specifically limited, Preferably it is 5.0-70.0 mass%, More preferably, it is 10.0-50.0 mass% It is. By making content of (B) component in a coating film more than the said lower limit, the contamination resistance of a coating film improves further, and the weather resistance of a coating film improves further by setting it below the said upper limit. .

<Cellulose-based thickener (C)>
The cellulose-based thickener (C) is not particularly limited, and examples thereof include one selected from the group consisting of methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropyl methylcellulose, and modified products thereof. Among these, one selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl methyl cellulose and their modified products is preferable, and hydroxyethyl cellulose and its modified product are more preferable. Moreover, these cellulose 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 can be obtained. The other thickeners are not particularly limited, and, for example, polyacrylate thickeners, polyacrylamide thickeners, acrylic acid acrylamide copolymer salt thickeners, polysaccharides other than celluloses Thickeners, vinyl ether thickeners and the like can be mentioned.

  A commercial item can also be used as hydroxyethyl cellulose. As such commercial products, for example, “HEC Daicel SP200”, “HEC Daicel SP 400”, “HEC Daicel SP 500”, “HEC Daicel SP 550”, “HEC Daicel SP 600”, “HEC Daicel SP 800” manufactured by Daicel Finechem Co., Ltd. “HEC Daicel SP 850” and “HEC Daicel SP 900”, “San Heck (trademark) HH”, “San Heck H”, “San Heck M” and “San Hek G & L” manufactured by Sanchang, “HECS Z − 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, and more preferably 1,000,000 to 1,600,000. When the weight average molecular weight is at least 700,000, dripping of the water-based composition can be further suppressed. When the weight average molecular weight is 2,000,000 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. As a commercial item, for example, Shin-Etsu Chemical "Metroz 90SH-04", "Metroz 90SH-15", "Metroz 90SH-100", "Metroz 90SH-400", "Metroz 90SH-4000", "Metroz 90SH" -15000 "and" Metroze 90SH- 100000 "," NEOVISCO-MC HM4000S "made by Sanchang," NEOVISCO-MC RM4000S "," NEOVISCO-MC RM15000S "," NEOVISCO-MC RM30000S "and" NEOVISCO-MC RM50000S " Etc.

  Although content of (C) component in a water-based composition is not specifically limited, Preferably it is 0.04-0.50 mass%, More preferably, it is 0.08-0.40 mass%. By making content of (C) component in a water-based composition into the said range, the coating film which transparency and weather resistance were further excellent can be obtained.

  Although content of (C) component in the coating film obtained from a water-based composition is not specifically limited, Preferably it is 2.0-15.0 mass%, More preferably, it is 4.0-9.0 mass% It is. By making content of (C) component in a coating film more than the said lower limit, the transparency of a coating film improves further, and the weather resistance of a coating film improves further by setting it below the said upper limit.

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

The inorganic oxide particles (D) may be inorganic oxide particles having photocatalytic activity, and the type thereof is not particularly limited. 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 ; Ti, Nb, Ta, and V (For example, JP-A-62-074452, JP-A-02-172535, JP-A-07-024329, JP-A-08-089799) JP-A 08-089800, JP-A 08-089804, JP-A 08-198061, JP-A 09-248465, JP-A 10-099694, JP-A 10-244165 discloses the like).

The component (D) is preferably TiO ₂ (titanium oxide) from the viewpoint of chemical stability, toxicity, environment and the like. The titanium oxide may have any crystal structure of anatase type, rutile type and brookite type.

The component (D) is preferably an inorganic oxide having photocatalytic activity, and is a metal compound having a particle surface 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 undercoat film can be further suppressed. The substance to be modified is not particularly limited, and examples thereof include silica, aluminum, copper oxide, iron oxide and the like. Among these, silica is preferred. The same effect can be obtained by modifying with a metal such as Fe, Cu, Al, Pt, or a complex such as chloroplatinic acid.

  The method of modifying the surface of the component (D) will be described using silica as an example. The method of modifying the surface of silica is not particularly limited. For example, a method of adding a silicon compound to a slurry of titanium oxide and depositing a hydrous oxide of silicon through steps such as neutralization treatment may be mentioned. .

  The silicon compound is not particularly limited, and for example, a water-soluble alkali metal silicate such as sodium silicate can be used. Among these, sodium silicate is preferable from the viewpoint of being colorless and not coloring the titanium oxide sol.

  The processing amount of the hydrous oxide of silicon is preferably 3 to 25% by mass, and more preferably 5 to 20% by mass, based on the oxide based on titanium oxide. Since the increase in the amount of active oxygen species can be suppressed by the throughput being at least the above lower limit value, damage to the undercoat film can be prevented. In addition, when the processing amount is equal to or less than the above upper limit, the aggregation of titanium oxide can be suppressed, and the increase in viscosity of the sol can be suppressed, whereby the dispersibility and the transparency are further improved.

  Although content of (D) component in a water-based composition is not specifically limited, Preferably it is 0.06-0.40 mass%, More preferably, it is 0.20-0.30 mass%. By making content of (D) component in a water-based 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 the coating film obtained from a water-based composition is not specifically limited, Preferably it is 3.0-20.0 mass%, More preferably, it is 10.0-15.0 mass% It is. By making content of (D) component in a coating film more than the said lower limit, the contamination resistance of a coating film improves further, and by setting it below the said upper limit, the transparency of a coating film improves further. .

<Flighting dye (E)>
It is preferable that the water-based composition of the present embodiment further contains a bleaching dye (E). In this way, it is possible to prevent troubles such as paint failure, repeated paint, uneven paint and the like.

  As the component (E), those which do not lose color by irradiation of sunlight and do not impair the design of the base are preferable. Although the time until the color loss varies depending on the season, the irradiation direction, etc., it is usually preferable that the period until the color loss is confirmed visually is not visually distinguishable within 20 days, preferably 10 days or less, More preferably, it is 3 days or less.

  The component (E) is not particularly limited as long as it has the property of being decolorized by irradiation with sunlight, but preferred examples include methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosine, new Examples thereof include one selected from the group consisting of coxcin, phloxine, rose bengal, acid red, and fast green FCF. Among these, methylene blue is more preferable from the viewpoint of good color developability and fast color loss speed. These may be used singly or in combination of two or more.

  Although content of (E) component in a water-based composition is not specifically limited, Preferably it is 0.0002-0.010 mass%, More preferably, it is 0.001-0.004 mass%. By making content of (E) component in a water-based composition into the said range, the coloring property and the color-fading property of a coating film improve further. Coloring property as used herein means the property that the coated surface and the unpainted surface are colored by visual difference due to the difference in color, and the color fading property is the property of fading to the extent of the color that does not impair the design of the substrate. Say

  Although content of (E) component in the coating film obtained from a water-based composition 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 (E) component more than the said lower limit, the color development property of a coating film improves further, and when below the said upper limit, the fading property of a coating film improves further.

<Fluorocarbon Surfactant (F)>
The aqueous composition of the present embodiment preferably further contains a fluorocarbon surfactant (F). Thereby, when coating is performed using the water-based composition of the present embodiment or the water-based paint containing the same, wettability to an organic base material and the like is further improved and appearance problems such as repelling are further suppressed. it can. Furthermore, the uniformity of the coating is further improved. Although it is not clear as these reasons, it is presumed that the surface surface power of the water-based composition can be reduced by containing the component (F) (however, the function of the present embodiment is not limited to these. ).

  The component (F) is not particularly limited, and examples thereof include nonionic amphoteric surfactants, anionic amphoteric surfactants, cationic amphoteric surfactants, and amphoteric surfactants. Among these, it is preferably an amphoteric surfactant, more preferably an amphoteric surfactant having a perfluoroalkyl group having 3 to 20 carbon atoms.

  Specific examples of the amphoteric surfactant having 3 to 20 perfluoroalkyl groups include perfluoroalkylsulfonic acid salts, perfluoroalkylcarboxylic acid salts, perfluoroalkylethylene oxide adducts and the like. Among these, perfluoroalkyl ethylene oxide adducts are preferable from the viewpoint of the effect of reducing the surface tension of the paint. For example, commercially available products can be used as the perfluoroalkyl ethylene oxide adduct. As such commercial products, for example, "Megafuck F-444" manufactured by DIC, "Surflon S-242" manufactured by AGC Seimi Chemical, etc. may be mentioned. These may be used singly or in combination of two or more.

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

<Saturated hydrocarbon alcohol (G)>
The aqueous composition of the present embodiment preferably further contains a saturated hydrocarbon alcohol (G). By containing the component (G), the wettability to organic base materials and the like tends to be further improved. Furthermore, freezing of the aqueous composition at low temperature can also be prevented.

  The component (G) is not particularly limited as long as it is a saturated hydrocarbon alcohol, but from the viewpoint of volatility, odor, wettability to a substrate etc., methyl alcohol, ethyl alcohol, propyl alcohol and isopropyl At least one selected from the group consisting of alcohols is preferred. Among these, from the viewpoint of safety, ethyl alcohol is more preferable. These may be used singly or in combination of two or more.

  Although content of (G) component in a water-based composition is not specifically limited, Preferably it is 5.0-40.0 mass%, More preferably, it is 10.0-20.0 mass%. By making content of (G) component more than the said lower limit, the wettability to an organic base material etc. improves further. By setting the content of the component (G) in the aqueous composition to the upper limit value or less, the safety and the cost are further improved.

  The content (solid content) of the solid content in the water-based composition is not particularly limited, but is preferably 0.5 to 10.0% by mass, more preferably 1.0 from the viewpoint of uniformity of the coating film. It is -5.0 mass%, More preferably, it is 1.5-5.0 mass%. When the solid content in the water-based composition is at least the lower limit value, dripping of the water-based composition can be further suppressed. When the solid content in the aqueous composition is less than or equal to the above upper limit, the transparency is further improved. The solid content referred to here can be determined by the method described in the examples described later. There are cases where it is required that the film thickness is small as the coating film, and there are applications. In order to produce a coating film having such a thin film thickness, conventionally, attempts have been made to lower the solid content in a water-based composition, and the like. However, if this is done, it is not possible to sufficiently prevent the dripping of the water-based composition (or water-based paint), which may cause a problem such as the appearance of the coating film being inferior. On the other hand, when the solid content in the water-based composition is increased to prevent the water-based composition (or water-based paint) from dripping, the film thickness of the coating film becomes too thick and uneven. Problems such as inferior physical properties may occur. However, in the water-based composition of the present embodiment, by containing the above-described specific component composition, it is possible to surprisingly prevent a liquid drip and to form a coating film having excellent physical properties. Furthermore, the formation of thin coatings is also sufficiently possible. Furthermore, these effects can be further improved by setting the amount of solid content in the aqueous composition of the present embodiment in the above range.

  The water-based composition of the present embodiment may further contain other components other than the above, as needed, as long as the effect is obtained. Such other components are not particularly limited. For example, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skinning agents, dispersants , Wetting agents, light stabilizers, antioxidants, UV absorbers, film forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, preservatives, fungicides, deodorants, anti-yellowing agents, Antistatic agents or charge control agents may, for example, be mentioned. These may be used singly or in combination of two or more.

  The water-based composition described above can be suitably used as a water-based paint. That is, the water-based paint of the present embodiment contains the above-described water-based composition. As water-based paints, as other components, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skin agents, dispersants, wetting agents, light stability Agents, antioxidants, UV absorbers, film forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, preservatives, fungicides, deodorants, anti-yellowing agents, antistatic agents, charging You may further contain a modifier etc.

  The water-based paint of the present embodiment can be applied by a suitable method as appropriate depending on the application, the material to be applied, and the like. The coating method is not particularly limited. For example, spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing Can be mentioned.

  After the water-based paint of this embodiment is applied and dried to remove volatile components, a coating film is obtained. Under the present circumstances, you may further heat-process at the temperature of about 40-120 degreeC, an ultraviolet irradiation process, etc. as needed.

  Thus, in this embodiment, it can be set as the coating film containing the above-mentioned water-based paint. This coating film is obtained from a water-based paint, and for example, the above-described water-based paint may 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 considered as a coated product containing a substrate and the above-mentioned coating film formed on at least a part of the surface of the substrate.

  The material of the base material that can be used in the present embodiment may be either an organic base material or an inorganic base material, as long as a film can be formed on the surface, and the type is not particularly limited. It does not specifically limit as a material of a base material, For example, a synthetic resin, a natural resin, a metal, ceramics, glass, a stone, cement, concrete etc. are mentioned. These may be used singly or in combination of two or more.

  The synthetic resin is not particularly limited, and examples thereof include thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, etc.). It does not specifically limit as a specific example of a synthetic resin, For example, a silicone resin, an acrylic resin, a methacrylic resin, a fluorine resin, an alkyd resin, an amino alkyd resin, a vinyl resin, a polyester resin, a styrene-butadiene resin, a polyolefin resin, a 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, etc. may be mentioned.

  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 a synthetic resin, a natural resin, or the like as described above, surface treatment such as corona discharge treatment, flame treatment, or plasma treatment may be performed as necessary.

  The coated product of the present embodiment comprises a substrate and the coating film formed on the substrate, and the coating film is also useful as a coating or the like. The coating film obtained by the present embodiment can maintain the appearance and the contamination resistance at a high level for a long time, and therefore can be suitably used in an environment which has been difficult to use conventionally. From this point of view, specific examples of the painted product of the present embodiment include, for example, building materials, building exteriors, building interiors, window frames, window glasses, various lenses, structural members, building equipment such as houses, covers for vehicle lighting Window glass, exterior of machinery and articles, dustproof cover and painting, display equipment, its cover, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads and railways, bridges, guardrail exteriors Examples of the exterior parts of electronic devices and electric devices used outside, such as painting, tunnel interior and painting, insulators, solar cell cover, solar water heater heat collecting cover, etc., particularly, transparent members, vinyl houses, greenhouses, etc. are listed.

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

  The water-based composition of the present embodiment may be blended in various water-based paints. Such a water-based paint can form a coating film excellent in appearance, stain resistance, transparency, weather resistance and the like. 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 coatings of buildings.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples. In Examples and Comparative Examples, various physical properties were measured by the following methods.

<Production of 7 cm × 15 cm substrate prepainted with enamel paint>
Preparation of pigment dispersion 5.35 g of a dispersant ("Pig. Disperser MD20" manufactured by BASF Japan Ltd.), 0.50 g of ammonia water, 23.50 g of propylene glycol, 147.50 g of water, titanium oxide (chlorinated rutile type oxidation) Titanium; Ishihara Sangyo Co., Ltd. “Tipek CR-97”, Ishihara Sangyo Co., Ltd. 333.50 g, antifoaming agent (San Nopco Co., “SN deformer 1310”) 2.85 g The mixture was dispersed for 20 minutes in a batch type table-top sand mill to obtain a pigment dispersion.

Preparation of Enamel Coating To 109.0 g of the polymer emulsion of Production Example 1, 10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso, “CS-12”), 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 a 10% aqueous solution of a thickener ("Adecanol UH-438" manufactured by Asahi Denka Kogyo Co., Ltd.) .5g was added and mixed for 1 hour to obtain an enamel paint.

Preparation of a 7 cm × 15 cm substrate coated beforehand with an enamel paint The enamel paint obtained above is coated on a 7 cm × 15 cm sulfuric acid alumite plate using a wire coater No. 50, temperature 23 ° C., relative humidity 50% for 48 hours Drying gave a 7 cm × 15 cm substrate prepainted with an enamel paint. The glossiness of the obtained substrate was 75.

1. Solid content 2 g of a sample was placed in an aluminum pan 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.

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

3. Viscosity Measured using a BM viscometer (manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are shown below.
・ Temperature: 23 ° C
-Rotor: No 1
・ Number of revolutions: 60 rpm

4. Coating film appearance (liquid dripping)
A substrate pre painted 7 cm × 15cm enamel paint coat-weight of the aqueous composition was coated using a spray so that a rate of 0.05 kg / m ² or 0.025 kg / m ^2. The coated substrate was kept vertical, and the degree of dripping after standing for 10 minutes under conditions of a temperature of 23 ° C. and a relative humidity of 50% was visually evaluated. The paint appearance (liquid drip) was evaluated according to the following criteria.

○: Almost no dripping was observed.
Δ: Some dripping was confirmed.
X: Many drips were confirmed.

5. Coating film appearance (Hajiki)
A substrate pre painted 7 cm × 15cm enamel paint coat-weight of the aqueous composition was coated using a spray so that a rate of 0.05 kg / m ² or 0.025 kg / m ^2. The coated substrate was kept vertical, and the degree of repelling after standing for 24 hours under the conditions of temperature 23 ° C. and relative humidity 50% was visually evaluated. The paint appearance (heep) was evaluated according to the following criteria.

○: Almost no repelling was confirmed.
Δ: Some repelling was confirmed.
X: A lot of fasting was confirmed.

6. Using a gloss meter (manufactured by BYK Gardner, "Micro Trigloss μ"), the 60 ° gloss of the measurement sample was measured.

7. A substrate pre painted 7 cm × 15cm gloss retention enamel paint after aqueous composition coating, as a coating with the amount of the aqueous composition at a ratio of 0.05 kg / m ² or 0.025 kg / m ² It painted using a spray. The coated substrate is held vertically and kept at a temperature of 23 ° C and a relative humidity of 50% for 24 hours, after which the 60 ° glossiness is measured with a gloss meter (BYK Gardner, "Microtrigloss μ"). It measured using. In addition, the 60 ° glossiness of the substrate surface prior to the application of the water-based composition was also measured in advance using a gloss meter. Then, the gloss retention was calculated based on the following equation. The higher the value of the gloss retention, the better the transparency, and the better the design of the substrate without impairing it.

Gloss retention (%) = 60 ° gloss after application of aqueous composition / 60 ° gloss before application of aqueous composition × 100

8. A substrate of 7 cm × 15cm in advance painted gloss retention enamel paint after weathering test 3000 hours, so that the coat-weight of the aqueous composition at a ratio of 0.05 kg / m ² or 0.025 kg / m ² Was painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to prepare a test plate. An exposure test (black panel temperature 63 ° C., rainfall 18 minutes / 2 hours) of this test plate was performed using “Sunshine Weather Meter” manufactured by Suga Test Instruments Co., Ltd. The 60 ° glossiness before and after the exposure test was measured using a gloss meter (manufactured by BYK Gardner, “Micro Trigloss μ”). Then, the gloss retention was calculated based on the following equation. The higher the gloss retention value, the better the weather resistance. In addition, the 60 ° glossiness of only the base material on which the enamel paint was previously coated was 95%.

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

9. A substrate pre painted 7 cm × 15cm stain resistance enamels, coating with the amount of the aqueous composition was coated using a spray so that a rate of 0.05 kg / m ² or 0.025 kg / m ² . The coated substrate was held vertically, and was left at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to prepare a test plate. The test plate was attached to a fence facing an open road (about 500 to 1000 trucks per day) and left for 6 months or for 1 year. The degree of contamination of the test plate after standing was visually evaluated according to the following criteria. In addition, the result evaluated only with the base material which coated the enamel coating beforehand was evaluation of "x" for 6 months and 1 year.

○: Almost no contamination was observed.
Fair: some stains were confirmed.
X: A large amount of dirt was confirmed.

10. Wet decomposition performance enamel paint previously painted 7 cm × 15cm substrate, the coating with the amount of the aqueous composition was coated using a spray so that a rate of 0.05 kg / m ² or 0.025 kg / m ² . The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to prepare a test plate. The test plate was tested according to JIS R 1703-2 (Fine ceramics-Test method for self-cleaning performance of photocatalytic material-Part 2: Wet decomposition performance) to determine the dye decomposition activity index. The higher the dye decomposition activity index, the better the self-cleaning property.

Production Example 1
Synthesis of Polymer Emulsion In a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, 290 g of ion exchanged water, a reactive emulsifier (manufactured by Asahi Denka Kogyo Co., Ltd., "ADEKAREASOAP SR-1025"; solid content 25 After charging 8.0 g of a mass% aqueous solution), the temperature in the reactor was heated to 80 ° C. while stirring. In the reactor, 10 g of a 2% by mass aqueous solution of ammonium persulfate was charged. Five minutes after that, 25 g of methyl methacrylate, 50 g of cyclohexyl methacrylate, 15 g of butyl acrylate, 5 g of methacrylic acid, 10 g of 2-hydroxyethyl methacrylate, a reactive emulsifier (manufactured by Asahi Denka Kogyo Co., Ltd., "ADECARIA SOAP SR-1025" An emulsified mixed solution consisting of 4.0 g of a solid content (25 mass% aqueous solution), 15 g of a 2 mass% aqueous solution of ammonium persulfate, and 48 g of ion-exchanged water was dropped from a dropping tank over 40 minutes. The temperature of the reaction vessel was maintained at 80 ° C. during the addition. After completion of the addition, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 30 minutes. Next, a mixed solution of 109 g of methyl methacrylate, 160 g of cyclohexyl methacrylate, 123 g of butyl acrylate and 8 g of methacrylic acid and a reactive emulsifier ("Adecaria soap SR-1025" manufactured by Asahi Denka Kogyo Co., Ltd .; solid content 25% by mass) Aqueous solution) Emulsified mixed liquid consisting of 16.0 g of a 2 mass% aqueous solution of ammonium persulfate and 60 g of ion-exchanged water, and a mixed liquid consisting of 1 g of 3-methacryloxypropyltrimethoxysilane, 20 g of dimethyldimethoxysilane and 20 g of methyltrimethoxysilane Were separately added from separate dropping tanks over 160 minutes while maintaining the temperature in the reactor at 80.degree. Furthermore, after completion of dropping, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. After cooling to room temperature, 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. The solid content of the obtained polymer emulsion was 44.5% by mass.

Production Example 2
Synthesis of aqueous dispersion of polymer particles (A-1) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 500 g of ion exchanged water, a reactive emulsifier (manufactured by Asahi Denka Kogyo Co., Ltd. Soap SR-1025 ′ ′ (solid content: 25% by mass aqueous solution) 8.0 g and 15% 2% by mass aqueous solution of ammonium persulfate were charged, and then the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 400 g of methyl methacrylate, 250 g of cyclohexyl methacrylate, 300 g of n-butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 30 g of methacrylic acid, a reactive emulsifier (manufactured by Asahi Denka Kogyo Co., Ltd., "Adekaria soap SR-" 1025 ′ ′; an emulsion mixture comprising 40 g of solid content 25% by weight aqueous solution, 50 g of a 2% by weight aqueous solution of ammonium persulfate, and 700 g of ion-exchanged water over about 4 hours while maintaining the temperature in the reactor at 80 ° C. It dripped. After completion of the addition, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured to be pH 2.1. The pH was adjusted to 8 by adding a 25% aqueous ammonia solution to the reaction solution, and the reaction solution was then filtered through a 100 mesh wire mesh. Furthermore, it adjusted so that solid content might be 10.0 mass% with ion-exchange water, and the water dispersion of the polymer particle (A-1) whose number average particle diameter is 130 nm was obtained.

[Production Example 3]
Synthesis of aqueous dispersion of polymer particles (A-2) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 609 g of ion exchanged water, reactive emulsifier (manufactured by Kao Corporation, "Latem S-180A A) 25% aqueous solution, 26 g of cyclohexyl methacrylate, 8 g of n-butyl methacrylate, 14 g of methyl methacrylate, 2.5 g of n-butyl acrylate, 0.8 g of methacrylic acid, 0.8 g of acrylic acid, 0.4 g of acrylamide The temperature in the reactor was heated to 80.degree. C. with stirring. Into this reactor, 5 g of a 2% by mass aqueous solution of ammonium persulfate, 1 g of 3-methacryloxypropyltrimethoxysilane, 68 g of methyltrimethoxysilane, and 27 g of dimethyldimethoxysilane were charged. Thereafter, after an exotherm due to the initiation of polymerization was confirmed, the temperature in the reactor was heated to 85 ° C. and held for 30 minutes. Next, 45 g of ion exchanged water, 10 g of a 25% aqueous solution of a reactive emulsifier ("Latemul S-180A" manufactured by Kao Corporation), 26 g of cyclohexyl methacrylate in a state where the temperature in the reactor is lowered and maintained at 80 ° C. Emulsion mixing consisting of 8 g of n-butyl methacrylate, 14 g of methyl methacrylate, 2.5 g of n-butyl acrylate, 0.8 g of methacrylic acid, 0.8 g of acrylic acid, 0.4 g of acrylamide, 5 g of a 2% by mass aqueous solution of ammonium persulfate The solution and a mixed solution consisting of 46 g of methyltrimethoxysilane and 18 g of dimethyldimethoxysilane were poured into the reactor from separate dropping tanks over 30 minutes and maintained at 80 ° C. for 2 hours. Next, while maintaining the temperature in the reactor at 80 ° C., 130 g of ion-exchanged water, 50 g of a 25% aqueous solution of a reactive emulsifier ("Latem S-180A" manufactured by Kao Corporation), 123 g of cyclohexyl methacrylate, methacrylic acid An emulsion mixture comprising 37 g of n-butyl, 4 g of methyl methacrylate, 79 g of n-butyl acrylate, 4 g of methacrylic acid and 12 g of a 2% by mass aqueous solution of ammonium persulfate, 2 g of 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane A mixed solution consisting of 170 g and 68 g of dimethyldimethoxysilane was injected into the reactor from separate dropping tanks over 2 hours and maintained at 80 ° C. for 1.5 hours. After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured to be pH 2.8. Next, a 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, and the mixture was filtered through a 100-mesh wire mesh. Furthermore, it adjusted so that solid content might be 10.0 mass% with ion-exchange water, and the water dispersion of the polymer particle (A-2) whose number average particle diameter is 127 nm was obtained.

Production Example 4
Synthesis of aqueous dispersion of polymer particles (A-3) 880 g of ion exchanged water, 10.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid in a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer After charging, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, a mixture consisting of 83.4 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane, and 42.6 g of methyltrimethoxysilane, for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It dripped over simultaneously. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 30 minutes. Next, after 5.6 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid was charged, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. Next, a mixed liquid consisting of 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 12.3 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane Acrylic acid 0.9 g, Reactive emulsifier (Asahi Denka Kogyo Co., Ltd., "Adecaria soap SR-1025"; solid content 25 mass% aqueous solution) 1.5 g, Reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., Aqualon KH-1025 ′ ′; a mixed solution consisting of 0.8 g of solid content 25% by weight aqueous solution, 146.4 g of 0.5% by weight aqueous solution of ammonium persulfate and 256.4 g of ion exchanged water, and the temperature in the reactor is 80 ° C. The solution was dropped simultaneously over about 2 hours while maintaining Furthermore, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, and after cooling to room temperature, the hydrogen ion concentration of the liquid in the reactor was measured, and it was pH 2.0. Next, a 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, and the mixture was filtered through a 100-mesh wire mesh. Furthermore, it adjusted so that solid content might be 10.0 mass% with ion-exchange water, and the water dispersion of the polymer particle (A-3) of number average particle diameter 80 nm was obtained.

Production Example 5
Synthesis of aqueous dispersion of polymer particles (A-4) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 560 g of ion exchanged water and 10.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid After charging, the temperature in the reactor was heated to 80 ° C. with stirring. Into this reactor, a mixture consisting of 125.9 g of dimethyldimethoxysilane and 39.4 g of methyltrimethoxysilane was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reactor at 80 ° C. 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 aqueous solution of dodecylbenzenesulfonic acid was charged, and the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 2 hours. A mixed solution consisting of 36.8 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, a reactive emulsifier (manufactured by Asahi Denka Kogyo Co., Ltd., “ADECA” Rear soap SR-1025 "; solid content 25% by mass aqueous solution) 1.5 g, reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd." Aqualon KH-1025 "solid content 25% by mass aqueous solution) 3.0 g ammonium persulfate A mixed solution consisting of 146.4 g of a 0.5% by mass aqueous solution and 256.4 g of ion-exchanged water was simultaneously dropped over about 2 hours while maintaining the temperature in the reactor at 80 ° C. After completion of the addition, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for about 1 hour. After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured to be pH 1.9. The pH of the solution was adjusted to 8 by adding a 25% aqueous ammonia solution to the reaction solution, and then the reaction solution was filtered through a 100 mesh wire mesh. Furthermore, it adjusted so that solid content might be 10.0 mass% with ion-exchange water, and the water dispersion of the polymer particle (A-4) whose number average particle diameter is 150 nm was obtained.

Production Example 6
Synthesis of inorganic oxide (D-1) having photocatalytic activity Silica modified rutile titanium dioxide TiO ₂ 700 mL of titanium tetrachloride aqueous solution having a concentration of 200 g / L 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. Thereafter, the pH of the reaction solution was adjusted to 7 and the solution was filtered and washed until the conductivity of the filtrate was 100 μS / cm, to obtain a wet titanium oxide 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 was 8 nm.
The titanium oxide wet cake 1 was diluted with pure water to prepare a 1 mol / L slurry. 1 L of this slurry is charged in a 3 L flask, and 1 N nitric acid is added so that the molar ratio of titanium oxide / nitric acid is 1/1, heated to 95 ° C., and maintained for 2 hours, acid heat treatment Did. The acid heat-treated slurry was cooled to room temperature, neutralized to pH 6.7 with 28% aqueous ammonia and filtered. Thereafter, the filtrate was washed until the conductivity of the filtrate reached 100 μS / cm, to obtain a wet titanium oxide cake 2 having a solid content of 25% by mass.
A 10% strength aqueous sodium hydroxide solution is added to the obtained titanium oxide wet cake 2 and repulped, and then dispersed for 3 hours with an ultrasonic cleaner, pH 10.5, solid content 10% by mass Alkaline titanium oxide sol was obtained. Charge ₂ L of this alkaline titanium oxide sol into a 3 L flask, raise the temperature to 70 ° C, add 69.4 mL of an aqueous sodium silicate solution with a concentration of 432 g / L as SiO ₂ and then increase the temperature to 90 ° C After maintaining for a time, 10% sulfuric acid was added to adjust the pH to 6 to obtain a titanium oxide sol whose surface was surface-treated with a hydrous oxide of silicon.
The obtained titanium oxide sol is cooled to room temperature, 5.4 L of pure water is added, impurities are removed and concentrated using a desalting and concentration apparatus, and the conductivity is pH 7.3, and the solid content is 30% by mass. A neutral rutile titanium oxide sol having a rate of 1.18 mS / cm was obtained. The neutral rutile titanium oxide sol contained a hydrous oxide of 15 wt% of silicon in SiO ₂ basis relative to TiO _2. The number average particle diameter of primary particles of titanium oxide in this sol was 9 nm.

Production Example 7
Synthesis of Inorganic Oxide (D-2) Having Photocatalytic Activity Silica-Modified Anatase-Type Titanium Oxide By heating and hydrolyzing a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid, it is 30% by mass in terms of TiO ₂ The resulting slurry was an aqueous slurry containing aggregated metatitanic acid. Aqueous ammonia was added to the aqueous slurry to neutralize the pH to 7, and then filtered and washed to remove sulfate ions to obtain a dewatered cake. The obtained dehydrated cake was peptized by adding nitric acid to obtain an acidic titanium oxide sol having a pH of 1.5 composed of titanium oxide particles (number average particle diameter of primary particles: 7 nm) having anatase-type crystal structure.
The obtained acidic titanium oxide sol is diluted with pure water to make 600 mL of titanium oxide sol having a TiO ₂ conversion concentration of 200 g / L, and then the temperature is raised to 70 ° C., and a sodium silicate aqueous solution having a SiO ₂ conversion concentration of 432 g / L 20.8 mL was added simultaneously with 20% sulfuric acid. Then, it was left to stand for 30 minutes. Then, 10% aqueous sodium hydroxide solution was added to adjust the pH to 8, and then the pH was adjusted to 6 with a 2% aqueous sulfuric acid solution, followed by filtration and washing to obtain a wet cake. The wet cake was repulped in pure water and then ultrasonically dispersed to obtain a titanium oxide sol (solid content 20.0 mass%, pH 7.5) stable in a neutral region. In this sample, aggregated silica was adhered in a porous state on the surface of 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 .

Example 1
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 61.2 g of a water dispersion of polymer particles (A-1) (solid content: 10.0% by mass) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-1) whose solid content was adjusted to 1.0% by mass with 15.3 g of solid content 20.0% by mass) and ion-exchanged water (Shin-Etsu Chemical Co., Ltd .; A water-based composition (H-1) having a solid content of 2.0% by mass was obtained by mixing and stirring 82.0 g of METROZ 90SH-30000 ") and 341.5 g of ion-exchanged water. The viscosity of this aqueous composition (H-1) was 35 mPa · s.
Next, the coating amount of the water-based composition (H-1) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). , Painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-1) having a coating formed on the substrate. The various evaluation results of this test plate (I-1) are shown in Table 1.

Example 2
Example except using 61.2 g (solid content 10.0 mass%) of the aqueous dispersion of polymer particles (A-2) in place of 61.2 g of the aqueous dispersion of polymer particles (A-1) In the same manner as in 1, an aqueous composition (H-2) with a solid content of 2.0% by mass was obtained. The viscosity of this water-based composition (H-2) was 30 mPa · s.
Next, the coating amount of the water-based composition (H-2) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-2) having a coating formed on the substrate. The various evaluation results of this test plate (I-2) are shown in Table 1.

[Example 3]
Example except using 61.2 g (solid content 10.0 mass%) of the water dispersion of polymer particles (A-3) in place of 61.2 g of water dispersion of polymer particles (A-1) In the same manner as in 1, an aqueous composition (H-3) having a solid content of 2.0% by mass was obtained. The viscosity of this aqueous composition (H-3) was 38 mPa · s.
Next, the ratio of the amount of the water-based composition (H-3) applied is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm substrate coated with the enamel paint beforehand (the surface coated beforehand with the enamel paint) It painted using a spray so that it might become. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-3) having a coating formed on the substrate. The various evaluation results of this test plate (I-3) are shown in Table 1.

Example 4
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-1) whose solid content was adjusted to 1.0 mass% with ion exchange water and 15.0 g of “Tex OS”, solid content 20.0 mass%), manufactured by Shin-Etsu Chemical Co., “ By mixing and stirring 80.0 g of METROZ 90SH-30000 "), 0.20 g of a fluorocarbon surfactant (F-1) (" Megafuck F-444 "manufactured by DIC Corporation), and 344.8 g of ion-exchanged water The aqueous composition (H-4) having a solid content of 2.0% by mass was obtained. The viscosity of this aqueous composition (H-4) was 39 mPa · s.
Next, the application amount of the water-based composition (H-4) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-4) having a coating formed on the substrate. The various evaluation results of this test plate (I-4) are shown in Table 1.

[Example 5]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-2) whose solid content was adjusted to 1.0 mass% with ion exchange water and 15.0 g of “Tex OS”, solid content 20.0 mass%), manufactured by Daicel Fine Chem, “HEC By mixing and stirring 80.0 g of Daicel SP 900 ′ ′), 0.20 g of a fluorocarbon surfactant (F-1) (“Megafuck F-444” manufactured by DIC Corporation), and 344.8 g of ion-exchanged water, An aqueous composition (H-5) having a solid content of 2.0% by mass was obtained. The viscosity of this aqueous composition (H-5) was 30 mPa · s.
Next, the application amount of the water-based composition (H-5) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-5) having a coating formed on the substrate. The various evaluation results of this test plate (I-5) are shown in Table 1.

[Example 6]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-2) whose solid content was adjusted to 1.0 mass% with ion exchange water and 15.0 g of “Tex OS”, solid content 20.0 mass%), manufactured by Daicel Fine Chem, “HEC Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, ion exchange water 269.8 g, saturated hydrocarbon alcohol (G -1) 75.0 g of ethanol was mixed and stirred to obtain an aqueous composition (H-6) having a solid content of 2.0% by mass. The viscosity of this aqueous composition (H-6) was 25 mPa · s.
Next, the application amount of the water-based composition (H-6) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-6) having a coating formed on the substrate. The various evaluation results of this test plate (I-6) are shown in Table 1.

[Example 7]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-2) whose solid content was adjusted to 1.0 mass% with ion exchange water and 15.0 g of “Tex OS”, solid content 20.0 mass%), manufactured by Daicel Fine Chem, “HEC Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, ion exchange water 57.3 g, saturated hydrocarbon alcohol (G -1) An aqueous composition (H-7) having a solid content of 4.0% by mass was obtained by mixing and stirring 37.5 g of ethanol. The viscosity of this aqueous composition (H-7) was 35 mPa · s.
Next, the coating amount of the water-based composition (H-7) is 0.025 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint has been previously coated (the surface on which the enamel paint has been previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand in a standard state (temperature 23 ° C., relative humidity 50%) for 24 hours to obtain a test plate (I-7) in which a coating film was formed on the substrate. The various evaluation results of this test plate (I-7) are shown in Table 1.

[Example 8]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 30.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-2) (made by Daicel Fine Chem Co., Ltd.), whose solid content was adjusted to 1.0 mass% with ion exchange water, 30.0 g) and 30.0 g of solid content 20.0 mass%). HEC Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (made by DIC, “Megafuck F-444”) 0.20 g, ion exchange water 284.8 g, saturated hydrocarbon alcohol ( G-1) An aqueous composition (H-8) having a solid content of 2.0% by mass was obtained by mixing and stirring 75.0 g of ethanol. The viscosity of this aqueous composition (H-8) was 40 mPa · s.
Next, the coating amount of the water-based composition (H-8) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-8) having a coating formed on the substrate. The various evaluation results of this test plate (I-8) are shown in Table 1.

[Example 9]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 70.0 g of a water dispersion of polymer particles (A-3) (solid content: 10.0% by mass) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose thickener (C-2) (solid content 20.0 mass%) 10.0 g and solid content adjusted to 1.0 mass% with ion exchange water (manufactured by Daicel Finechem Co., Ltd., "HEC" Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, ion exchange water 264.8 g, saturated hydrocarbon alcohol (G -1) 75.0 g of ethanol was mixed and stirred to obtain an aqueous composition (H-9) having a solid content of 2.0% by mass. The viscosity of this aqueous composition (H-9) was 20 mPa · s.
Next, the coating amount of the water-based composition (H-9) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-9) having a coating formed on the substrate. The various evaluation results of this test plate (I-9) are shown in Table 1.

[Example 10]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 62.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-2) whose solid content was adjusted to 1.0 mass% with ion exchange water and 15.5 g of “Tex OS”, solid content 20.0 mass%), manufactured by Daicel Fine Chem, “HEC Daicel SP 900 ′ ′) 50.0 g, fluorocarbon surfactant (F-1) (made by DIC, “Megafuck F-444”) 0.20 g, ion-exchanged water 297.3 g, saturated hydrocarbon alcohol (G -1) 75.0 g of ethanol was mixed and stirred to obtain an aqueous composition (H-10) having a solid content of 2.0% by mass. The viscosity of this aqueous composition (H-10) was 18 mPa · s.
Next, the coating amount of the water-based composition (H-10) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-10) having a coating formed on the substrate. The various evaluation results of this test plate (I-10) are shown in Table 1.

[Example 11]
A water dispersion colloidal silica (B-3) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose thickener (C-2) (solid content 30 mass%) 10.0 g and solid content adjusted to 1.0 mass% with ion exchange water (manufactured by Daicel Finechem Co., Ltd., “HEC Daicel SP 900” 8), fluorocarbon surfactant (F-1) (made by DIC, “Megafuck F-444”) 0.20 g, ion exchange water 274.8 g, saturated hydrocarbon alcohol (G-1) 7) A water-based composition (H-11) having a solid content of 2.0% by mass was obtained by mixing and stirring 75.0 g of ethanol. The viscosity of this aqueous composition (H-11) was 26 mPa · s.
Next, the coating amount of the water-based composition (H-11) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-11) having a coating formed on the substrate. The various evaluation results of this test plate (I-11) are shown in Table 1.

[Example 12]
The solid content is 2.0 mass in the same manner as in Example 6, except that 75.0 g of saturated hydrocarbon alcohol (G-1) ethanol is replaced with 75.0 g of saturated hydrocarbon alcohol (G-2) isopropyl alcohol. % Aqueous composition (H-12) was obtained. The viscosity of this aqueous composition (H-12) was 33 mPa · s.
Next, the coating amount of the water-based composition (H-12) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-12) having a coating formed on the substrate. The various evaluation results of this test plate (I-12) are shown in Table 1.

[Example 13]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-2) whose solid content was adjusted to 1.0 mass% with ion exchange water and 15.0 g of “Tex OS”, solid content 20.0 mass%), manufactured by Daicel Fine Chem, “HEC Daicel SP 900 ”) 80.0 g, fluorocarbon surfactant (F-1) (made by DIC,“ Megafuck F-444 ”) 0.20 g, and solid content adjusted to 1.0 mass% with ion-exchanged water Mixed with 1.0 g of the discolorable dye (E-1) ("Acid Red" manufactured by Hodogaya Chemical Industry Co., Ltd.), 268.8 g of ion exchanged water, and 75.0 g of saturated hydrocarbon alcohol (G-1) ethanol Stir By obtain solid content 2.0% by weight of the aqueous composition (H-13). The viscosity of this aqueous composition (H-13) was 31 mPa · s.
Next, the coating amount of the water-based composition (H-13) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-13) having a coating formed on the substrate. The various evaluation results of this test plate (I-13) are shown in Table 2.

Example 14
The solid content was changed to 1.0 g of decolorable dye (E-1) (Hodogaya Chemical Industry Co., Ltd., "Acid Red") whose solid content was adjusted to 1.0% by mass with ion exchange water, and the solid content was adjusted with ion exchange water 1. An aqueous system having a solid content of 2.0% by mass in the same manner as in Example 13 except that 1.0 g of a bleaching dye (E-2) ("Methylene blue" manufactured by Kishida Chemical Co., Ltd.) adjusted to 0% by mass was used. A composition (H-14) was obtained. The viscosity of this aqueous composition (H-14) was 30 mPa · s.
Next, the application amount of the water-based composition (H-14) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-14) having a coating formed on the substrate. The various evaluation results of this test plate (I-14) are shown in Table 2.

[Example 15]
Example 14 except using 60.0 g (solid content 10.0 mass%) of the aqueous dispersion of polymer particles (A-4) in place of 60.0 g of the aqueous dispersion of polymer particles (A-3) A water-based composition (H-15) having a solid content of 2.0% by mass was obtained in the same manner as in the above. The viscosity of this aqueous composition (H-15) was 28 mPa · s.
Next, the coating amount of the water-based composition (H-15) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-15) having a coating formed on the substrate. The various evaluation results of this test plate (I-15) are shown in Table 2.

[Example 16]
It changes to 1.0 g of pigment (E-2) (Kishida Chemical Co., Ltd. make, "methylene blue") which adjusted solid content to 1.0 mass% with ion exchange water, 1.0 mass% of solid content with ion exchange water A water-based composition (H-16 having a solid content of 2.0% by mass) in the same manner as in Example 15 except that 2.0 g of the pigment (E-2) ("Methylene blue" manufactured by Kishida Chemical Co., Ltd.) was used. Got). The viscosity of this aqueous composition (H-16) was 25 mPa · s.
Next, the coating amount of the water-based composition (H-16) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-16) having a coating formed on the substrate. The various evaluation results of this test plate (I-16) are shown in Table 2.

[Example 17]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.6 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-4) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-3) whose solid content was adjusted to 1.0 mass% with ion exchange water and 15.2 g of “Tex OS”, solid content 20.0 mass%), manufactured by Sanchang, “NEOVISCO -MCRM 50000 S ") 70.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC," Megafuck F-444 ") 0.20 g, ion exchange water 279.0 g, saturated hydrocarbon alcohol (G -1) 75.0 g of ethanol was mixed and stirred to obtain an aqueous composition (H-17) having a solid content of 2.0% by mass. The viscosity of this aqueous composition (H-17) was 30 mPa · s.
Next, the coating amount of the water-based composition (H-17) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-17) having a coating formed on the substrate. The various evaluation results of this test plate (I-17) are shown in Table 2.

[Example 18]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-4) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose thickener (C-2) (solid content 20.0 mass%) 10.0 g and solid content adjusted to 1.0 mass% with ion exchange water (manufactured by Daicel Finechem Co., Ltd., "HEC" Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, and inorganic oxide (D-1) having photocatalytic activity. An aqueous composition (H-18) having a solid content of 2.0 mass% is obtained by mixing and stirring 3 g, 271.5 g of ion-exchanged water, and 75.0 g of saturated hydrocarbon alcohol (G-1) ethanol. The The viscosity of this aqueous composition (H-18) was 26 mPa · s.
Next, the coating amount of the water-based composition (H-18) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-18) having a coating formed on the substrate. The various evaluation results of this test plate (I-18) are shown in Table 2.

[Example 19]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-4) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose-based thickener (C-2) whose solid content was adjusted to 1.0 mass% with ion exchange water and 7.5 g of “Tex OS”, solid content 20.0 mass%), manufactured by Daicel Fine Chem, “HEC Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, and inorganic oxide (D-1) having photocatalytic activity. An aqueous composition (H-19) having a solid content of 2.0% by mass is obtained by mixing and stirring 0 g, 272.3 g of ion exchanged water, and 75.0 g of saturated hydrocarbon alcohol (G-1) ethanol. The The viscosity of this aqueous composition (H-19) was 20 mPa · s.
Next, the coating amount of the water-based composition (H-19) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-19) having a coating formed on the substrate. The various evaluation results of this test plate (I-19) are shown in Table 2.

[Example 20]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 60.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-4) (manufactured by Nissan Chemical Industries, Ltd., "Snow Cellulose thickener (C-2) (solid content 20.0 mass%) 10.0 g and solid content adjusted to 1.0 mass% with ion exchange water (manufactured by Daicel Finechem Co., Ltd., "HEC" Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, inorganic oxide (D-2) having photocatalytic activity. An aqueous composition (H-20) having a solid content of 2.0 mass% is obtained by mixing and stirring 0 g, 269.8 g of ion exchanged water, and 75.0 g of saturated hydrocarbon alcohol (G-1) ethanol. The The viscosity of this aqueous composition (H-20) was 25 mPa · s.
Next, the coating amount of the water-based composition (H-20) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-20) having a coating formed on the substrate. The various evaluation results of this test plate (I-20) are shown in Table 2.

[Example 21]
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 30.0 g of an aqueous dispersion of polymer particles (A-4) (solid content: 10.0% by mass) (manufactured by Nissan Chemical Industries, Ltd., Snow Cellulose-based thickener (C-2) whose solid content was adjusted to 1.0 mass% with ion exchange water and 22.5 g of “Tex OS”, solid content 20.0 mass%), manufactured by Daicel Fine Chem, “HEC Daicel SP 900 ′ ′) 80.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, and inorganic oxide (D-1) having photocatalytic activity. An aqueous composition (H-21) having a solid content of 2.0% by mass is obtained by mixing and stirring 0 g, 287.3 g of ion exchanged water, and 75.0 g of saturated hydrocarbon alcohol (G-1) ethanol. The The viscosity of this aqueous composition (H-21) was 25 mPa · s.
Next, the coating amount of the water-based composition (H-21) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-21) having a coating formed on the substrate. The various evaluation results of this test plate (I-21) are shown in Table 2.

Example 22
A water dispersion colloidal silica (B-1) having a number average particle diameter of 4 nm was added to 30.0 g of an aqueous dispersion of polymer particles (A-4) (solid content 10.0 mass%) (manufactured by Nissan Chemical Industries, Ltd., "Snow "Tex OXS", solid content 10 mass%) 20.0 g, and water-dispersed colloidal silica (B-4) with a number average particle diameter of 22 nm (Nissan Chemical Industries, Ltd., "Snowtex OL", solid content 20.0 mass% And 80.0 g of a cellulose-based thickener (C-2) (“HEC Daicel SP 900” manufactured by Daicel Finechem Corp.) whose solid content is adjusted to 1.0 mass% with ion-exchanged water, and a fluorocarbon interface. Activator (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, inorganic oxide (D-1) having photocatalytic activity 5.0 g, ion-exchanged water 277.3 g, Saturated carbonization By stirring a mixture of iodine alcohol (G-1) ethanol 75.0 g, was obtained solid content 2.0% by weight of the aqueous composition (H-22). The viscosity of this aqueous composition (H-22) was 25 mPa · s.
Next, the coating amount of the water-based composition (H-22) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-22) having a coating formed on the substrate. The various evaluation results of this test plate (I-22) are shown in Table 2.

[Example 23]
Water dispersed colloidal silica (B-4) with a number average particle diameter of 22 nm (Nissan Chemical Industries Co., Ltd., “Snowtex OL”, solid content 20.0 mass%) instead of 12.5 g of water with a number average particle diameter of 90 nm In the same manner as in Example 22, except that dispersed colloidal silica (B-5) (manufactured by Nissan Chemical Industries, "Snowtex OYL", solid content 20.0 mass%) was used, solid content 2.0 mass% The aqueous composition (H-23) of The viscosity of this aqueous composition (H-23) was 20 mPa · s.
Next, the coating amount of the water-based composition (H-23) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was kept vertical and dried at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-23) having a coating formed on the substrate. The various evaluation results of this test plate (I-23) are shown in Table 2.

[Example 24]
A water dispersion colloidal silica (B-1) having a number average particle diameter of 4 nm was added to 30.0 g of an aqueous dispersion of polymer particles (A-4) (solid content 10.0 mass%) (manufactured by Nissan Chemical Industries, Ltd., "Snow "Tex OXS", solid content 10 mass%) 36.0 g, water-dispersed colloidal silica (B-5) with a number average particle diameter of 90 nm (Nissan Chemical Industries, Ltd., "Snowtex OYL", solid content 20.0 mass% And 4) 8 g of a cellulose-based thickener (C-2) (“DiCel Fine Chem Co., Ltd.,“ HEC Daicel SP 900 ”) whose solid content has been adjusted to 1.0 mass% with ion-exchanged water, and a fluorocarbon interface Activator (F-1) (manufactured by DIC, “Megafuck F-444”) 0.20 g, inorganic oxide (D-1) having photocatalytic activity 5.0 g, ion-exchanged water 269.3 g, Saturated carbonization By stirring a mixture of iodine alcohol (G-1) ethanol 75.0 g, was obtained solid content 2.0% by weight of the aqueous composition (H-24). The viscosity of this aqueous composition (H-24) was 30 mPa · s.
Next, the coating amount of the water-based composition (H-24) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-24) having a coating formed on the substrate. The various evaluation results of this test plate (I-24) are shown in Table 2.

[Example 25]
A water dispersion colloidal silica (B-1) having a number average particle diameter of 4 nm was added to 30.0 g of an aqueous dispersion of polymer particles (A-4) (solid content 10.0 mass%) (manufactured by Nissan Chemical Industries, Ltd., "Snow "Tex OXS", solid content 10% by mass, 9.0 g of water-dispersed colloidal silica (B-5) having a number average particle diameter of 90 nm (Nissan Chemical Industries, Ltd., "Snowtex OYL", solid content 20.0% by mass And 18.0 g of a cellulose-based thickener (C-2) (“HEC Daicel SP 900”, manufactured by Daicel Finechem Co., Ltd.) having a solid content adjusted to 1.0 mass% with ion-exchanged water, and a fluorocarbon interface. Activator (F-1) (DIC Corporation, “Megafuck F-444”) 0.20 g, inorganic oxide (D-1) having photocatalytic activity 5.0 g, ion exchanged water 282.8 g, Saturated carbonization By stirring a mixture of iodine alcohol (G-1) ethanol 75.0 g, was obtained solid content 2.0% by weight of the aqueous composition (H-25). The viscosity of this aqueous composition (H-25) was 18 mPa · s.
Next, the coating amount of the water-based composition (H-25) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-25) having a coating formed on the substrate. The various evaluation results of this test plate (I-25) are shown in Table 2.

Comparative Example 1
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 66.0 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow "Tex OS", solid content 20.0% by mass), 16.0 g, fluorocarbon surfactant (F-1) (manufactured by DIC, "Megafuck F-444") 0.20 g, and ion exchanged water 342.8 g By mixing and stirring 75.0 g of saturated hydrocarbon alcohol (G-1) and ethanol, an aqueous composition (H-26) having a solid content of 2.0% by mass was obtained. The viscosity of this aqueous composition (H-26) was 3 mPa · s.
Next, the coating amount of the water-based composition (H-26) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-26) having a coating formed on the substrate. The various evaluation results of this test plate (I-26) are shown in Table 3.

Comparative Example 2
It changes to 80.0 g of cellulose system thickener (C-2) (The Daicel Fine Chem Co., Ltd. make, "HEC Daicel SP 900") which adjusted solid content to 1.0 mass% with ion exchange water, and the solid content is changed with ion exchange water. A solid was prepared in the same manner as in Example 6, except that 80.0 g of xanthan gum-based thickener (C'-1) ("KELZAN ST" manufactured by CP Kelco A Huber Company) adjusted to 1.0% by mass was used. An aqueous composition (H-27) with a mass of 2.0% by mass was obtained. The viscosity of this aqueous composition (H-27) was 150 mPa · s.
Next, the coating amount of the water-based composition (H-27) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and dried at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-27) having a coating formed on the substrate. The various evaluation results of this test plate (I-27) are shown in Table 3.

Comparative Example 3
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 63.3 g (solid content 10.0 mass%) of the water dispersion of the polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow Xanthan gum-based thickener (C′-1) (CP Kelco A Huber Company, Inc.) having a solid content of 15.9 g and a solid content of 1.0 mass% adjusted with ion-exchanged water. Product, "KELZAN ST") 30.0 g, fluorocarbon surfactant (F-1) (DIC Corporation, "Megafuck F-444") 0.20 g, ion-exchanged water 315.6 g, saturated hydrocarbon 75.0 g of alcohol (G-1) ethanol was mixed and stirred to obtain an aqueous composition (H-28) having a solid content of 2.0% by mass. The viscosity of this aqueous composition (H-28) was 25 mPa · s.
Next, the coating amount of the water-based composition (H-28) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-28) having a coating formed on the substrate. The various evaluation results of this test plate (I-28) are shown in Table 3.

Comparative Example 4
Change to 30.0 g of xanthan gum based thickener (C'-1) (CP Kelco A Huber Company, "KELZAN ST") whose solid content has been adjusted to 1.0% by mass with ion exchange water, using ion exchange water Comparative Example except using 30.0 g of a leutan gum-based thickener (C'-2) (CP Kelco A Huber Company, "KELCO-CRETE DG") whose solid content was adjusted to 1.0% by mass In the same manner as in 3, an aqueous composition (H-29) having a solid content of 2.0% by mass was obtained. The viscosity of this aqueous composition (H-29) was 30 mPa · s.
Next, the coating amount of the water-based composition (H-29) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint has been previously coated (the surface on which the enamel paint has been previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-29) having a coating formed on the substrate. The various evaluation results of this test plate (I-29) are shown in Table 3.

Comparative Example 5
A water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 61.4 g (solid content 10.0 mass%) of a water dispersion of polymer particles (A-3) (manufactured by Nissan Chemical Industries, Ltd., "Snow "Tex OS", 15.3 g of solid content 20.0 mass%, and vinyl ether thickener (C'-3) (solid content is adjusted to 1.0 mass% with ion-exchanged water) (manufactured by ISP Japan Ltd.) 60.0 g of “STABILEZE QM”, 0.20 g of a fluorocarbon surfactant (F-1) (made by DIC, “Megafuck F-444”), 288.1 g of ion exchanged water, and a saturated hydrocarbon alcohol (G-1) An aqueous composition (H-30) having a solid content of 2.0% by mass was obtained by mixing and stirring 75.0 g of ethanol. The viscosity of this aqueous composition (H-30) was 25 mPa · s.
Next, the coating amount of the water-based composition (H-30) is 0.05 kg / m ^{2 on} one side of the 7 cm × 15 cm base material on which the enamel paint is previously coated (the surface on which the enamel paint is previously coated). And painted using a spray. The coated substrate was held vertically and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test plate (I-30) having a coating formed on the substrate. The various evaluation results of this test plate (I-30) are shown in Table 3.

  From the above, it has been confirmed that the water-based composition of this example can form a coating film capable of maintaining the appearance and the stain resistance at a high level for a long time.

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

Claims (20)

An aqueous composition comprising polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C),
The cellulose-based thickener (C) is hydroxyethyl cellulose having a weight average molecular weight of 700,000 to 2,000,000,
The aqueous composition whose content of solid content in an aqueous composition is 0.5-10 mass%. The water-based composition according to claim 1, wherein the component (B) is silicon dioxide. The aqueous composition according to claim 1, further comprising inorganic oxide particles (D) having photocatalytic activity. The water-based composition according to any one of claims 1 to 3 , further comprising a bleaching dye (E). The aqueous composition according to any one of claims 1 to 4 , further comprising a fluorocarbon surfactant (F). The aqueous composition according to any one of claims 1 to 5 , further comprising a saturated hydrocarbon alcohol (G). A water-based paint comprising the water-based composition according to any one of claims 1 to 6 . The coating film obtained from the water-based paint of Claim 7 . A substrate,
The coating film according to claim 8 , formed on at least a part of the surface of the substrate.
Painted products containing. 10. The coated product of claim 9 , wherein the substrate is an organic substrate. The water-based composition according to claim 1, containing polymer particles obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier as the component (A). Method. The manufacturing method of the water-based composition of Claim 11 whose said (B) component is silicon dioxide. The method for producing an aqueous composition according to claim 11, wherein the component (B) contains particles having a number average particle diameter of 25 to 100 nm and particles having a number average particle diameter of 4 to 8 nm. . The manufacturing method of the water-based composition as described in any one of Claims 11-13 which further contains the inorganic oxide particle (D) which has photocatalytic activity. The manufacturing method of the water-based composition as described in any one of Claims 11-14 which further contains a color-fading pigment (E). The manufacturing method of the water-based composition as described in any one of Claims 11-15 which further contains a fluorocarbon surfactant (F). The manufacturing method of the water-based composition as described in any one of Claims 11-16 which further contains saturated hydrocarbon alcohol (G). It contains polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C), and the cellulose-based thickener (C) has a weight average molecular weight Of hydroxyethyl cellulose of 700,000 to 2,000,000, and the solid content in the aqueous composition is 0.5 to 10% by mass, and as the component (A), vinyl alone in the presence of water and an emulsifier Aqueous composition containing polymer particles obtained by polymerizing a monomer and a hydrolyzable silicon compound
A method of producing a water-based paint containing It contains polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C), and the cellulose-based thickener (C) has a weight average molecular weight Of hydroxyethyl cellulose of 700,000 to 2,000,000, and the solid content in the aqueous composition is 0.5 to 10% by mass, and as the component (A), vinyl alone in the presence of water and an emulsifying agent. Aqueous composition containing polymer particles obtained by polymerizing a monomer and a hydrolyzable silicon compound
A method of producing a coating film obtained from a water-based paint containing A substrate,
Formed on at least part of the surface of the substrate,
It contains polymer particles (A), inorganic oxide particles (B) not having photocatalytic activity, and a cellulose-based thickener (C), and the cellulose-based thickener (C) has a weight average molecular weight Of hydroxyethyl cellulose of 700,000 to 2,000,000, and the solid content in the aqueous composition is 0.5 to 10% by mass, and as the component (A), vinyl alone in the presence of water and an emulsifying agent. A coating film obtained from a water-based paint containing a water-based composition, comprising a polymer particle obtained by polymerizing a monomer and a hydrolyzable silicon compound,
A method of producing a painted product containing