JP6509757B2 - 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.

  The surface of outdoor structures such as building exteriors, bridges, and tanks are painted with paint etc. However, the surface of the coating film is dust, smoke, sand, etc. in the air, dirt components eluted from sealing materials, buildings, etc. It is polluted by the pollutant etc. which are discharged from the discharge port of Such coating contamination is usually dull and significantly impairs the aesthetics of buildings and outdoor structures.

  As an aqueous top coat composition composition for suppressing the contamination of the coating film as described above, the applicant of the present invention comprises a subbing layer and a top coat layer provided on the subbing layer, the subbing layer comprising water and an emulsifier. Drying the coated film of primer coating composition (I) containing polymer emulsion particles (A) obtained by the method comprising the steps of respectively polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of And the step of polymerizing the vinyl monomer and the hydrolyzable silicon compound in the presence of water and an emulsifying agent, respectively. Formed by drying the coating film of the coating composition (II) for top coating containing the polymer emulsion particles (C) obtained by the method and the colloidal silica (D) A film, a multilayer coating film has been proposed (e.g., see Patent Document 1).

JP, 2010-005595, A

  In the technology described in Patent Document 1, since a material having a high glass transition temperature is used as a subbing layer, sufficient stain resistance and weather resistance can be obtained even with a top coating layer formed from a coating composition for top coating. Is obtained. Thus, although the technology of Patent Document 1 is an excellent technology, the present inventors made further improvements and tried to develop a better technology. For example, when a coating agent composition for top coating as described in Patent Document 1 is top-coated on a substrate using a material having a glass transition temperature of about -5 to 20 ° C, which is generally used for building exteriors, etc. The top coat layer formed from the coating agent composition may not be able to sufficiently follow the substrate which expands and contracts due to the temperature change of the external environment and the like. In such a case, the top coat layer may be cracked or the like, and the crack may reduce the gloss to impair the appearance. Furthermore, the undercoat layer is often colored with a pigment or the like, and when it is overcoated on a dark base material having an L * value of about 10 to 40, the appearance such as white turbidity may be impaired. If such points can be improved with respect to the coating film, the coating film is excellent in various physical properties including appearance and stain resistance over a long period of time without being limited by the base material and color of the undercoat layer. Realization can be expected.

  The present invention has been made in view of the above circumstances, and provides a composition capable of forming a coating film capable of maintaining the appearance and the stain resistance at a high level for a long time without losing the appearance even with a dark color substrate The purpose is to

  As a result of intensive investigations, the present inventors contain an aqueous dispersion (AD) of a polymer (A) having a number average particle diameter of 10 to 40 nm and silicon dioxide (B), and a polymer (A) And, by using the aqueous composition in which the mass ratio of silicon dioxide (B) is 1/1 to 1/4, it is found that the above-mentioned problems can be solved, and the present invention has been completed.

  That is, the present invention is as follows.

[1]
Containing an aqueous dispersion (AD) of polymer (A) having a number average particle diameter of 10 to 40 nm, and silicon dioxide (B), and a mass ratio of polymer (A) to silicon dioxide (B) (The aqueous composition whose polymer (A) / silicon dioxide (B)) is 1/1 to 1/4.
[2]
The aqueous composition according to [1], wherein the polymer (A) contains 20 to 70% by mass of a structural unit derived from dimethyldimethoxysilane (a) in terms of hydrolysis and condensation product.
[3]
The aqueous composition as described in [1] or [2] which further contains the inorganic oxide (C) which has photocatalytic activity.
[4]
The water-based composition as described in any one of [1] to [3], which further contains a fluorocarbon surfactant (D).
[5]
The water-based composition as described in any one of [1] to [4], which further contains a bleaching dye (E).
[6]
The water-based paint containing the water-based composition as described in any one of [1] to [5].
[7]
The coating film obtained from the water-based paint as described in [6].
[8]
A substrate,
A coated product comprising: the coating film according to [7] formed on at least a part of the surface of the substrate.
[9]
The coated product according to [8], wherein the substrate is an organic substrate.

  According to the present invention, it is possible to provide a composition capable of forming a coating film capable of maintaining the appearance and the stain resistance at a high level for a long time without losing the appearance even with a dark substrate.

  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.

[Water-based composition]
The aqueous composition of the present embodiment is
An aqueous dispersion (AD) of a polymer (A) having a number average particle diameter of 10 to 40 nm,
Containing silicon dioxide (B),
The mass ratio of the polymer (A) to the silicon dioxide (B) (polymer (A) / silicon dioxide (B)) is 1/1 to 1/4.

  The coating film obtained from the water-based composition of the present embodiment can maintain the appearance and the stain resistance at a high level for a long time without losing the appearance even with a dark color substrate.

[Number-average particle size of polymer (A)]
The aqueous composition of the present embodiment contains an aqueous dispersion (AD) of a polymer (A) having a number average particle diameter of 10 to 40 nm.

  The polymer (A) is not particularly limited, but, for example, a polymer obtained by a method such as emulsion polymerization can be used. Although it does not specifically limit in particular, For example, the polymer etc. which are obtained by performing the polymerization reaction in any one of radical polymerization, anion polymerization, and cation polymerization in an aqueous medium etc. are mentioned.

  The number average particle diameter of the polymer (A) is 10 nm to 40 nm.

  By using the polymer (A) having a number average particle diameter in the above range, the water-based composition of the present embodiment has no white turbidity even when applied to a dark color substrate, and the obtained coating does not impair the appearance . Furthermore, when the number average particle diameter of the polymer (A) is 10 nm or more, the stain resistance of the coating film is further improved, and when the number average particle diameter of the polymer (A) is 40 nm or less, The weatherability of the film is further improved.

  The lower limit value of the number average particle diameter of the polymer (A) is 10 nm, preferably 15 nm. The upper limit value of the number average particle diameter of the polymer (A) is 40 nm, preferably 35 nm.

  The method of controlling the number average particle diameter of the polymer (A) in the above range is not particularly limited, and examples thereof include a method of adjusting the amount of surfactant used for producing the polymer (A). The number average particle size can be reduced by increasing the amount of the agent.

  In addition, the number average particle diameter here can be measured using a wet particle size analyzer.

[Mass ratio of polymer (A) to silicon dioxide (B)]
In the water-based composition according to the present embodiment, the mass ratio of the polymer (A) to the silicon dioxide (B) (polymer (A) / silicon dioxide (B)) is 1/1 to 1/4.

  The water-based composition of the present embodiment has a mass ratio of the polymer (A) to the silicon dioxide (B) within the above range, so that there is no white turbidity even when coated on a dark color substrate, and the obtained coating is obtained Does not impair the appearance. Furthermore, when the mass ratio of the polymer (A) to the silicon dioxide (B) is 1/1 or less, the stain resistance of the coating film is further improved, and the polymer (A) and the silicon dioxide (B) The weather resistance of the coating film is further improved by setting the mass ratio to (1) to not less than 1/4.

  The mass ratio of the polymer (A) to the silicon dioxide (B) (polymer (A) / silicon dioxide (B)) is 1/1 to 1/4, preferably 1/2 to 1/4. More preferably, it is 1 / 2.7 to 1 / 3.3.

[Component of water-based composition]
<Water Dispersion of Polymer (A) (AD)>
The aqueous composition of the present embodiment contains an aqueous dispersion (AD) of the polymer (A). In the present specification, the polymer (A) may be described as the component (A).

  Examples of component (A) include, but are not limited to, poly (meth) acrylate polymers, polyvinyl acetate polymers, vinyl acetate- (meth) acrylic polymers, ethylene vinyl acetate polymers Combination, silicone polymer, fluorine polymer, polybutadiene polymer, styrene butadiene polymer, NBR polymer, polyvinyl chloride polymer, chlorinated polypropylene polymer, polyethylene polymer, polystyrene polymer Homopolymer or copolymer represented by combination, vinylidene chloride polymer, polystyrene- (meth) acrylate polymer, styrene-maleic anhydride polymer etc., silicone modified (meth) acrylic polymer, fluorine -(Meth) acrylic polymer, (meth) acrylic-silicon polymer, epoxy-(meth) acrylic Modified copolymer represented by the polymer, and the like.

  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 homopolymer, copolymer, modified copolymer, etc. of the polymer (A) described above (hereinafter sometimes referred to collectively as "polymer") can be obtained in the state of aqueous dispersion preferable. Preferred examples of these polymers include emulsions, and specific examples thereof include, but are not limited to, acrylic emulsions, acrylic silicone emulsions, silicone emulsions and the like. These are not particularly limited, but can be obtained, for example, by emulsion polymerization of monomers such as (meth) acrylic acid ester or a hydrolyzable silicon compound described later.

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

  Examples of vinyl monomers that can be used for the production of component (A) include, but are not limited to, (meth) acrylic esters, aromatic vinyl compounds, vinyl cyanide compounds, and carboxyl group-containing compounds. Examples thereof include vinyl compounds, hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, vinyl compounds having secondary and / or tertiary amide groups, and vinyl monomers having functional groups such as anionic vinyl compounds.

  Examples of (meth) acrylic acid esters include, but are not limited to, (meth) acrylic acid alkyl esters having an alkyl group having 1 to 50 carbon atoms and ethylene oxide groups having 1 to 100 carbon atoms (for example) Examples include poly) oxyethylene di (meth) acrylate 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.

  The (poly) oxyethylene di (meth) acrylate is not limited to, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, Examples thereof include tetraethylene glycol di (meth) acrylate and the like.

  Examples of the aromatic vinyl compound include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, vinyl toluene and the like.

  Examples of the cyanided vinyl compound include, but are not limited to, (meth) acrylonitrile, α-chloroacrylonitrile and the like.

  Examples of the carboxyl group-containing vinyl compound include, but are not limited to, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, maleic acid, fumaric acid, for example. There may be mentioned half esters of dibasic acids such as 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.

  The hydroxyl group-containing vinyl compound is not limited to, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl Hydroxyalkyl esters of (meth) acrylic acid such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono Butyl fumarate, (poly) oxyethylene mono (meth) acrylate having 1 to 100 allyl alcohol and ethylene oxide groups; (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups, further , And (trade name manufactured by Daicel Chemical Industries caprolactone addition monomer) "PLACCEL FM, FA monomer", and other alpha, hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid.

  Examples of (poly) oxyethylene mono (meth) acrylates include, but are not limited to, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and methoxy Diethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, tetraethylene glycol methoxy (meth) acrylate and the like can be mentioned.

  Examples of the (poly) oxypropylene mono (meth) acrylate include, but are not limited to, propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, and dipropylene glycol (meth) acrylate. And methoxy (meth) acrylic acid dipropylene glycol, (meth) acrylic acid tetrapropylene glycol, methoxy (meth) acrylic acid tetrapropylene glycol and the like.

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

  Examples of the glycidyl group-containing vinyl compound include, but are not limited to, glycidyl (meth) acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether and the like.

  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.

  Examples of the vinyl compound having a secondary and / or tertiary amide group include, but are not limited to, N-alkyl-substituted (meth) acrylamide, N-alkylene-substituted (meth) acrylamide and the like.

  Examples of the N-alkyl-substituted (meth) acrylamide include, but are not limited to, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethylacrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, 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- Vinylcaprolactam, N, N'-methyle Bis (meth) acrylamide, N-vinyl acetamide, diacetone (meth) acrylamide, N- methylol (meth) acrylamide etc. are mentioned.

  Examples of vinyl monomers other than the above include, but are not limited to, olefins such as (meth) acrylamide, ethylene, propylene and isobutylene; dienes such as butadiene; vinyl chloride and vinylidene chloride fluoride Haloolefins such as vinyl, tetrafluoroethylene and chlorotrifluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl p-tert-butyl benzoate, vinyl pivalate, 2-ethylhexanoic acid Vinyl, carboxylic acid vinyl esters such as vinyl versatate, vinyl laurate; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and the like Nyl ethers; 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.

  When the component (A) is produced by a polymerization reaction, a chain transfer agent may be used to control the molecular weight of the polymerization product of the vinyl monomer used.

  The chain transfer agent is not limited to the following, for example, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan Thiocarboxylic acids such as thiomalic acid or salts thereof or alkyl esters thereof Polythiols; Diisopropylxanthogen disulfide, Disulfides such as di (methylenetrimethylolpropane) xanthogen disulfide; Dimers of thioglycol, α-methylstyrene, etc. An allyl compound etc. are mentioned. 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%.

  When the polymer (A) is produced by the polymerization reaction of a vinyl monomer and a hydrolyzable silicon compound, the hydrolyzable silicon compound used to produce the polymer (A) is limited to the following: Although it is not a thing, the compound represented by following formula (1), a silane coupling agent, and these condensates are mentioned as a preferable thing, for example.

SiW _x R _y (1)

  In the above formula (1), W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group And at least one member selected from the group consisting of and amide groups.

  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.

  As a compound represented by Formula (1), although it is not limited to the following, 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, although it is not limited to the following, for example, hydrolysable group (For example, a C1-C20 alkoxy group, a hydroxyl group, a C1-C20 acetoxy group, a halogen atom, hydrogen) Functional group having reactivity with another compound (eg, vinyl polymerizable group), and at least one selected from the group consisting of an atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group And hydrolyzable silicon compounds (silane coupling agents) having an epoxy group, an amino group, a methacryl group, a thiol group, an isocyanate group and the like. By using such a silane coupling agent as a hydrolysable silicon compound, 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).

  The silane coupling agent having a vinyl polymerizable group is not limited to, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3 -(Meth) acryloyloxypropylmethyldimethoxysilane, 3- (Meth) acryloyloxypropyltri n-propoxysilane, 3- (Meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane Preferred are methoxysilane, 2-trimethoxysilylethyl vinyl ether and the like.

  Although it does not limit as a silane coupling agent which has a thiol group, For example, 3-mercaptopropyl trimethoxysilane, 3-mercapto propyl triethoxysilane etc. are mentioned as a preferable thing.

  The hydrolyzable silicon compound and the silane coupling agent represented by the formula (1) are not limited to the following, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetraiso. Tetraalkoxysilanes such as propoxysilane and tetra-n-buxilesilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyl Trimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octy Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloro Propyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxy Ethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltriethoxysilane Toxisilane, 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) acryloyloxypropyltriyl Trialkoxysilanes such as sopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane Silane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldisilane Diethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldimethoxysilane Dialkoxysilanes such as n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane And monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane.

  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 a condensate of a compound represented by the formula (1) or a silane coupling agent is applied as a hydrolyzable silicon compound used to produce the polymer (A), the compound represented by the formula (1) or Although the weight average molecular weight of polystyrene conversion of the condensate of a silane coupling agent is not specifically limited, Preferably it is 200-5000, More preferably, it is 300-1000. 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.

  As a cyclic siloxane oligomer, although it is not limited to the following, For example, the compound represented by following formula (2) is mentioned.

(R ' ₂ SiO) _m (2)

  In the above formula (2), each R ′ 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, or 1 to 20 carbon atoms. And at least one selected from the group consisting of an alkoxy group of and an aryl group of 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.

  Examples of the titanium alkoxide include, but are not limited to, tetramethoxytitanium, tetraethoxytitanium, tetra-i-propoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra-sec-, for example. Examples include butoxytitanium, tetra-tert-butoxytitanium and the like.

  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.

  Examples of the zirconium alkoxide include, but are not limited to, tetramethoxyzirconium, tetraethoxyzirconium, tetra-i-propoxyzirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-sec-, for example. Examples include butoxy zirconium and tetra-tert-butoxy zirconium.

  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 mass ratio of the hydrolyzable silicon compound to the vinyl monomer used when polymerizing the polymer (A) is preferably 0.5 / 99.5 to 99.5 / 0.5, more preferably 0. 5 / 99.5-15 / 85.

  The component (A) preferably contains 20 to 70% by mass of a structural unit derived from dimethyldimethoxysilane in terms of hydrolysis condensation product. The lower limit value of the content of the structural unit derived from dimethyldimethoxysilane in the component (A) is preferably 20% by mass or more, more preferably 35% by mass or more, in terms of hydrolysis condensation product. The upper limit of the content of the structural unit derived from dimethyldimethoxysilane in the component (A) is preferably 70% by mass or less, and more preferably 65% by mass or less, in terms of hydrolysis condensation product. When the content of the structural unit derived from dimethyldimethoxysilane in the component (A) is in the above range, the effect of improving the weather resistance of the coating film is obtained.

  The hydrolytic condensate as referred to herein is a condensate in which a reactive group (for example, an alkoxy group etc.) of dimethyldimethoxysilane is converted into a silanol bond by hydrolysis or condensation reaction. The content (mass%) of the hydrolyzate condensate equivalent of dimethyldimethoxysilane is determined from the content of polymer (A) (total solid content) determined as the heating residue of the (AD) component, and the charged amount of dimethyldimethoxysilane , Can be determined by calculation.

  Content in terms of hydrolysis and condensation product of dimethyldimethoxysilane (mass%) = feed amount of dimethyldimethoxysilane (g) × 0.617 / total solid content (g) × 100

  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, but are not limited to, for example, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; ethyl acetoacetate and the like Be

  The molecular weight of the chelating agent is not limited to the following, but is preferably 10,000 or less.

  By using these chelating agents, the polymerization rate of the hydrolyzable silicon compound 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 limited to the following, but, for example, alkyl benzene sulfonic acid, alkyl sulfonic acid, alkyl sulfo succinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl Acidic emulsifiers such as sulfuric acid and polyoxyethylene distyryl phenyl ether sulfonic acid; alkali metal (Li, Na, K etc.) salts of the acidic emulsifiers, ammonium salts of the acidic emulsifiers; anionic surfactants such as fatty acid soaps, For example, quaternary ammonium salts such as alkyltrimethyl ammonium bromide, alkyl pyridinium bromide, imidazolinium laurate, pyridinium salts, cationic surfactants of the imidazolinium salt type; polyoxyethylene alkyl aryl ether, polio Shi sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block copolymer, nonionic surface active agent polyoxyethylene distyryl phenyl ether; reactive emulsifier or the like having a radical polymerizable double bond.

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

  Examples of the anionic reactive emulsifier include, but are not limited to, sulfonic acid groups, sulfonate groups or sulfate ester groups, and ethylenically unsaturated monomers having these salts, and the like. The compound is preferably a compound having an acid group or a group (an ammonium sulfonate group or an alkali metal sulfonate group) which is an ammonium salt or an alkali metal salt thereof.

  For example, alkyl allyl sulfosuccinate (for example, “Eleminol (registered trademark) JS-20” manufactured by Sanyo Chemical Industries, Ltd., for example, “Lateml (trademark) S-120” manufactured by Kao Corporation, “Latemul S-180A”, “Latemul S-180 ′ ′ etc.), for example, polyoxyethylene alkylpropenyl phenyl ether sulfate (eg, “Aqualon.TM. HS-10”, etc., manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), for example, Α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (eg, “ADECARIA SOAPTM SE-10N” manufactured by ADEKA ), For example, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylen (For example, “Aqualon KH-1025” or the like manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), for example, styrene sulfonate (for example, “Tosona Organic Chemical Co.,” “SpinomerTM NaSS” or the like) ), For example, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene sulfuric acid ester salt (eg, “ADECARIA SOAPTM SR-1025” manufactured by ADEKA Co., Ltd.) Etc.), for example, sulfuric acid ester salts of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (eg, “Latem.RTM. PD-104” manufactured by Kao Corporation). Etc.).

  Among these, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene Sulfate ester salts are preferred.

  The nonionic reactive emulsifier is not limited to the following. For example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (For example, (made by ADEKA, "ADEKAREASOAP NE-20", "ADEKAREASOAP NE-30", "ADEKAREASOAP NE-40", etc. may be mentioned), for example, polyoxyethylene alkyl propenyl phenyl ether (For example, “Aqualon RN-10”, “Aqualon RN-20”, “Aqualon RN-30”, “Aqualon RN-50” and the like manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), for example, α- [2 -[(Allyloxy) -1- (alkyloxymethyl) ethyl] -ω-hydroxypolyoxyethylene (eg, manufactured by ADEKA Such as, for example, polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (eg, manufactured by Kao Corporation, “Latem.RTM. PD-”). And the like) and the like.

  The amount of the emulsifier used is preferably 10 parts by mass or less based on 100 parts by mass of the total amount of the raw material (for example, hydrolyzable silicon compound and vinyl monomer) of the component (A) which is a polymer. Preferably, it is 0.001 to 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.

  As such a radical polymerization catalyst, although it is not limited to the following, a persulfate, a peroxide, an azobis compound etc. are mentioned, for example. These may be water soluble or oil soluble.

  The radical polymerization catalyst includes, but is not limited to, for example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2, 2 -Azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.

  Although the compounding quantity of a radical polymerization catalyst is not specifically limited, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of total amounts of a vinyl monomer. 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 hydrolyzable silicon compounds is not limited to the following, for example, hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; sulfuric acid Sulfonic acids such as p-toluenesulfonic acid; acidic emulsifiers such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid Acidic compounds or weakly acidic inorganic salts; acidic compounds such as phthalic acid, phosphoric acid and nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine , The Basic compounds such as zabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, etc .; dibutyltin octyrate, dibutyltin dilaurate etc. And tin compounds of

  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.

  As a suitable method for obtaining the component (A), for example, so-called emulsion polymerization in which 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 It can be mentioned. 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 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.

  When it is desired to further control the particle size in the emulsion polymerization, it is preferable to adopt a seed polymerization method in which emulsion particles are made to exist in the aqueous phase in advance 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.

  The method for producing the component (A) is not particularly limited. For example, after polymerizing the hydrolyzable silicon compound and the vinyl monomer in the presence of a solvent, if necessary, in the presence of water and an emulsifier, a polymerization product is obtained. It is also possible to employ a method of further adding water until it becomes an emulsion. 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 multistage emulsion polymerization is mentioned as a preferred method.

  The multistage emulsion polymerization as referred to herein is a method of preparing two or more kinds of reaction solutions having different compositions containing a vinyl monomer and a hydrolyzable silicon compound, and dividing them into separate stages for polymerization.

  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.

  An example of the two-stage emulsion polymerization is not particularly limited. For example, a step of polymerizing a vinyl monomer and / or a hydrolyzable silicon compound in the presence of water and an emulsifier to obtain seed particles (first stage) And a method (second stage) of polymerizing the hydrolyzable silicon compound and the vinyl monomer in the presence of the obtained seed particles.

  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.

  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 the water-based composition of this embodiment is not specifically limited, Preferably it is 0.1-5.0 mass%, More preferably, it is 0.3-3.0 mass% is there. By making content of (A) component in a water-system composition into the said range, the coating film in which the external appearance in a dark-colored base material, weather resistance, and stain resistance are further excellent can be obtained.

  Content of (A) component in the coating film obtained from the water-based composition of this embodiment is 10.0-50.0 mass%, Preferably it is 15.0-35.0 mass%. By making content of (A) component in a coating film into the said range, the coating film which was further excellent in the external appearance in a dark-colored base material, a weather resistance, and stain resistance can be obtained.

<Silicon dioxide (B)>
The aqueous composition of the present embodiment contains silicon dioxide (B).

  In the present specification, silicon dioxide (B) may be simply referred to as component (B).

  The silicon dioxide (B) 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 (1988), and the like.

  The number average particle diameter of the component (B) is not particularly limited, but is preferably 1 to 100 nm, more preferably 4 to 30 nm, and still more preferably 8 to 25 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 100 nm or less, the appearance of the obtained dark color substrate is further improved. The number average particle size can be measured using a wet particle size analyzer.

  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. Such commercial products include, but are not limited to, for example, “SnowtexTM-OXS”, “Snowtex-OS”, “Snowtex-O” manufactured by Nissan Chemical Industries, Ltd., "Snowtex-O-40", "Snowtex-OL" and "Snowtex-OYL", "Adelite (trademark) AT-20Q" manufactured by ADEKA, "Klevozole (trademark) 20H12" manufactured by Clariant Japan, and "Clevozole 30 CAL 25" and the like.

  Examples of basic colloidal silica include, but are not limited to, colloidal silica stabilized by the addition of alkali metal ions, ammonium ions, amines and the like. A commercial item can also be used for these. Such commercial products include, but are not limited to, for example, "Snowtex-XS", "Snowtex-S", "Snowtex-30", "Snowtex" manufactured by Nissan Chemical Industries, Ltd. -50 "," Snowtex-20L "," Snowtex-XL "," Snowtex-YL "," Snowtex-ZL "," Snowtex-NXS "," Snowtex-NS "," Snowtex- " N "," Snowtex-N40 "," Snowtex-CXS "," Snowtex-C "," Snowtex-CM "," Snowtex-PS-S "and" Snowtex PS-M "; made by ADEKA "Adelight AT-20", "Adelight AT-30", "Adelight AT-20N", "Adelight AT-30N", "Adela "AT-20A", "Adelite AT-30A", "Adelite AT-40" and "Adelite AT-50"; "Clevozole 30R9", "Clevozole 30R50", "Clevozole 50R50" manufactured by Clariant Japan Co., Ltd., manufactured by DuPont “RUDOX (trademark) HS-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. Examples of such commercial products include, but are not limited to, for example, “MA-ST-M (methanol dispersion type with particle diameter 20 to 25 nm)” manufactured by Nissan Chemical Industries, Ltd., “IPAST (particle diameter 10-15 nm isopropyl alcohol dispersion type), "EG-ST (ethylene glycol dispersion type with particle diameter 10-15 nm)", "EG-ST-ZL (ethylene glycol dispersion type with particle diameter 70-100 nm)", NPC-ST (ethylene glycol monopropyl ether tail dispersion type having a particle diameter of 10 to 15 nm) and the like can be mentioned.

  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 of the present embodiment is not particularly limited, but is preferably 0.3 to 8.0% by mass, and more preferably 1.2 to 4.8% by mass. is there.

  By making content of (B) component in a water-system composition into the said range, the coating film in which the external appearance in a dark-colored base material, weather resistance, and contamination resistance were further excellent can be obtained.

  The content of the component (B) in the coating film obtained from the aqueous composition of the present embodiment is preferably 50.0 to 81.0% by mass, and more preferably 52.0 to 75.0% by mass. is there. By making content of (B) component in a coating film into the said range, the coating film which was further excellent in the external appearance in a dark-colored base material, a weather resistance, and stain resistance can be obtained.

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

  In the present specification, the inorganic oxide (C) having photocatalytic activity may be described simply as the component (C).

  The inorganic oxide (C) having photocatalytic activity may be an inorganic oxide having photocatalytic activity, and the type thereof is not particularly limited.

Examples of the component (C) include, but are not limited to, TiO ₂ , ZnO, SrTiO ₃ , BaTiO ₃ , BaTiO ₄ , BaTi ₄ O ₉ , K ₂ NbO ₃ , Nb ₂ O ₅ , Fe _{2, for example.} O ₃ , Ta ₂ O ₅ , K ₃ Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO ₂ ; Ti, Nb, Ta, and Layered oxides having at least one element selected from the group consisting of V (eg, JP-A-62-074452, JP-A-2-172535, JP-A-07-024329, JP-A-08-089799 Patent Publication Nos. 08-089800, 08-089804, 09-248465, 10-099694, and 10-244165. Etc.) and the like.

The component (C) 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 (C) is preferably an inorganic oxide having photocatalytic activity, and is an inorganic oxide having photocatalytic activity obtained by modifying the surface of the particles. By modifying the particle surface, the generation amount of active oxygen species such as H ₂ O ₂ and .OH can be suppressed, and damage to the undercoat can be further suppressed.

  Examples of the substance that modifies the particle surface include, but are not limited to, silica, aluminum, copper oxide, iron oxide and the like. Among these, silica is preferred. The same effect can be obtained even if the particle surface is modified with a metal such as Fe, Cu, Al or Pt, or a complex such as chloroplatinic acid.

  The method of modifying the surface of the component (C) will be described using titanium oxide as an example.

  The method of modifying the surface of titanium oxide 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. Be

  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 processing amount being the above lower limit value or the like, damage to the undercoat film can be prevented. Moreover, since the aggregation of a titanium oxide can be suppressed and the viscosity raise of sol can be suppressed because the said processing amount is below the said upper limit, a dispersibility and transparency improve further.

  The content of the component (C) in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.05 to 2.5% by mass, and more preferably 0.15 to 1.3% by mass. is there. By making content of (C) component into the said range, the coating film which the appearance in a dark-colored base material, weather resistance, and contamination resistance were further excellent can be obtained.

  Although content of (C) component in the coating film obtained from the water-based composition of this embodiment is not specifically limited, Preferably it is 5.0-30.0 mass%, More preferably, it is 11.0-24 It is .0 mass%. By making content of (C) component into the said range, the coating film which the appearance in a dark-colored base material, weather resistance, and contamination resistance were further excellent can be obtained.

<Fluorocarbon Surfactant (D)>
The aqueous composition of the present embodiment preferably further contains a fluorocarbon surfactant (D). In the present specification, the fluorocarbon surfactant (D) may be simply referred to as the component (D). 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 tension of the water-based composition can be reduced by containing the component (D) (however, the function of the present embodiment is not limited to these. ).

  The component (D) is not particularly limited, but an amphoteric surfactant is preferable. The amphoteric surfactant is not particularly limited, and examples thereof include nonionic amphoteric surfactants, anionic amphoteric surfactants, cationic amphoteric surfactants and the like. As a preferable specific example, the amphoteric surfactant which has a C3-C20 perfluoroalkyl group is mentioned, for example.

  Although it does not specifically limit as a specific example of the amphoteric surfactant which has a C3-C20 perfluoroalkyl group, For example, perfluoro alkyl sulfonate, perfluoro alkyl carboxylate, perfluoro alkyl amine oxide, per And fluoroalkyl ethylene oxide adducts, perfluoroalkyl compounds having an anionic group and a cationic group, and the like. Among these, perfluoroalkyl ethylene oxide adducts and perfluoroalkyl compounds having an anionic group and a cationic group are preferable from the viewpoint of lowering the surface tension of the paint.

  As the perfluoroalkyl carboxylate, for example, a commercially available product can also be used. Such commercial products are not particularly limited, and examples thereof include “Surflon S-211” manufactured by AGC Seimi Chemical Co., Ltd., and the like. As perfluoroalkylamine oxide, for example, commercially available products can also be used. Such commercial products are not particularly limited, and examples thereof include "Surflon S-241" manufactured by AGC Seimi Chemical Co., Ltd., and the like. For example, commercially available products can be used as the perfluoroalkyl ethylene oxide adduct. Examples of such commercially available products include, but are not limited to, for example, "Megafuck F-444" manufactured by DIC, "Surflon S-242" manufactured by AGC Seimi Chemical, and the like. As a perfluoroalkyl compound which has an anionic group and a cationic group, a commercial item can also be used, for example. Examples of such commercially available products include, but are not limited to, “Surflon S-231”, “Surflon S-232”, “Surflon S-233” and the like manufactured by AGC Seimi Chemical Co., Ltd. These may be used singly or in combination of two or more.

  Although content of (D) component in a water-based composition is not specifically limited, Preferably it is 0.0001-0.50 mass%, More preferably, it is 0.01-0.25 mass%. By making content of (D) component into the said range, the coating film which the appearance in a dark-colored base material, weather resistance, and contamination resistance were further excellent can be obtained.

<Flighting dye (E)>
It is preferable that the water-based composition of the present embodiment further contains a bleaching dye (E). In the present specification, the bleaching dye (E) may be simply referred to as component (E).

  When the water-based composition of the present embodiment contains the color-fading pigment (E), it is possible to prevent problems such as coating forgetting, double coating, coating unevenness 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 color loss varies depending on the season, irradiation direction, etc., usually, the period until color loss is visually confirmed is preferably 20 days or less, more preferably 10 days or less, and still more preferably 3 It is less than a day.

  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.

  The content of the component (E) in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.0005 to 0.04 mass%, more preferably 0.005 to 0.03 mass%. is there. 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. The color development referred to herein means the property that the coated surface and the unpainted surface are colored to the extent that they are visually distinguished from differences in color, and the color fading is color fading to the extent of the color that does not impair the design of the substrate. Say the nature of

  Although content of (E) component in the coating film obtained from the water-based composition of this embodiment is not specifically limited, Preferably it is 0.01-1.0 mass%, More preferably, it is 0.1-0 .8 mass%. By making content of (E) component into the said range, the coating film in which the external appearance in a dark-colored base material, weather resistance, and stain resistance are further excellent can be obtained.

  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 1.5 from the viewpoint of uniformity of the coating film. It is -6.0 mass%. By making content of solid content in a water-based composition more than the said lower limit, pollution resistance will improve further. By setting the content of the solid content in the water-based composition to the upper limit value or less, the transparency is further improved. The solid content referred to here can be determined by the method described in the examples described later. Furthermore, depending on the application of the coating, it may be required that the thickness of the coating is small. Even in such a case, when the solid content in the aqueous composition is not more than the above upper limit, a coating film excellent in physical properties such as weather resistance and stain resistance can be obtained while having a thin film thickness. it can. When the solid content in the water-based composition is at least the above lower limit value, the drying time required for forming a coating film can be shortened, and the working efficiency can be further improved.

Water-based paint
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.

  The water-based paint of the present embodiment can be obtained, for example, by mixing the above-described water-based composition with other components as necessary.

  Examples of the other components include, but are not limited to, for example, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skinning agents , Dispersant, wetting agent, light stabilizer, antioxidant, UV absorber, film forming aid, rust inhibitor, plasticizer, thickener, lubricant, reducing agent, preservative, fungicide, algaecide Agents, deodorants, anti-yellowing agents, antistatic agents, charge control agents and the like. These may be used singly or in combination of two or more.

  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 limited to the following, for example, spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing And flexographic printing.

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

[Painted products]
The coated product of the present embodiment contains a substrate and the coating film formed on at least a part of the surface of the substrate.

  The coated product of the present embodiment can be obtained, for example, by applying the above-mentioned aqueous paint to the surface of various substrates and drying it.

  The substrate used for the coated product of the present embodiment is not particularly limited as long as a coating film can be formed on the surface, and any of an organic substrate and an inorganic substrate may be used. From the viewpoint of improving the properties, organic substrates are preferred.

  Examples of the material of the substrate include, but are not limited to, organic substrates such as synthetic resins and natural resins; and inorganic substrates such as metals, ceramics, glass, stones, cement, and concrete. These may be used singly or in combination of two or more.

  Examples of the synthetic resin include, but are not limited to, thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, etc.).

  Specific examples of the synthetic resin include, but are not limited to, silicone resin, acrylic resin, methacrylic resin, fluorine resin, alkyd resin, amino alkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, and the like. Polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, Urea resin, phenol resin, melamine resin, epoxy resin, urethane resin, silicone-acrylic resin, etc. may be mentioned.

  Examples of the natural resin include, but are not limited to, cellulose resins, isoprene resins such as natural rubber, and protein resins such as casein.

  When the base material is a resin base material using 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 water-based paint of the present embodiment can maintain the appearance and the contamination resistance at a high level for a long time without losing the appearance even with a dark colored base material, so that it is also difficult to use in the conventional environment It can be used suitably.

  From this point of view, the coated products of the present embodiment are not limited to the following, but, for example, building materials, building exteriors, building interiors, window frames, window glasses, various lenses, structural members, building equipment such as houses, Covers and window glass for vehicle lamps, exteriors of machinery and articles, dustproof covers and coatings, display devices, their covers, traffic signs, various display devices, displays such as advertising towers, noise barriers for roads and railways, etc. Exteriors and coatings of bridges, guardrails, tunnel interiors and coatings, insulators, solar cell covers, solar water collectors, etc. Electronic parts used outside, such as exterior parts of electrical equipment, especially exterior parts such as transparent members, plastic houses, greenhouses etc. Can be mentioned.

  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 make it 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 embodiment will be described in more detail by way of examples and comparative examples, but the present embodiment is not limited to the following examples. Various physical properties were measured by the following methods in Examples and Comparative Examples.

<Production of 7 cm × 15 cm substrate coated with enamel paint in advance>
Preparation of pigment dispersion 5.35 g of dispersant ("Pig. Disperser MD20" manufactured by BASF Japan Ltd.), 0.5 g of ammonia water, 23.5 g of propylene glycol, 147.5 g of water, titanium oxide (chlorination rutile type oxidation) Titanium; 333.5 g of “Taipek CR-97” manufactured by Ishihara Sangyo Kaisha Ltd. and 2.85 g of a defoaming agent (modified silicone type; manufactured by San Nopco, “SN deformer 1310”) in a table sand mill (manufactured by Campe Papio Co., Ltd.) 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 obtained in Production Example 1 described later, 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso Corporation, “CS-12”) 10.0 g, 10.0 g of a mixed solution of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained above, a thickener (manufactured by Asahi Denka Kogyo Co., Ltd., “Adecanol UH-438” The enamel paint X was obtained by adding 0.5g of 10 mass% aqueous solution of ") and mixing for 1 hour.

Preparation of 7 cm × 15 cm substrate coated with enamel paint X in advance The enamel paint X obtained above was applied to a 7 cm × 15 cm sulfuric acid alumite plate according to wire coater No. 1; The coating was performed using a 50, dried at a temperature of 23.degree. C. and a relative humidity of 50% for 48 hours to obtain a substrate of 7 cm.times.15 cm previously coated with enamel paint X.

1. Content of Each Component and Solid Content 2.0 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. Based on this method, the content of each component and the solid content in the aqueous composition were each measured.

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. Glass transition temperature It measured on the measurement conditions of the temperature increase rate of 10 degree-C / min using Seiko Instruments Inc. "DCS6220", and the glass transition temperature was calculated | required from the inflection point of the obtained DSC curve. The measurement conditions are shown below.
Measurement Cell: Aluminum Container Preparation of Measurement Sample: 40 mg of the emulsion as a measurement sample was put in an aluminum container and dried at 130 ° C. for 1 hour.

4. Color difference before and after painting JISK 5600 paint General test method Cover ratio of the aqueous composition is 17.0 g / m ^{2 on} the black part (value 7 of L *) of concealed sheet (made by Nippon Test Panel Co., Ltd.) Painted using a sprayer. The coated test paper was kept horizontal and allowed to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux for 48 hours, and used as a test plate. The color difference before and after painting was measured using a "Color Guide" manufactured by BYK Gardner. If the color difference is 3.0 or less, it indicates that the color difference change in the dark background is small and good.

5. Weatherability test: Gloss retention after 3000 hours On a 7 cm x 15 cm substrate previously coated with an enamel paint, the paint is applied using a spray so that the application amount of the water-based composition is 17.0 g / m ² did. The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illumination intensity of 20000 lux for 48 hours, and used as a test plate. An exposure test (black panel temperature 63 ° C., rainfall 18 minutes / 2 hours) was performed using Suga Test Instruments'"Sunshine Weather Meter". The 60 ° glossiness after 3000 hours of exposure was measured using a gloss meter (manufactured by BYK Gardner, “Micro Trigloss μ”).

  Then, the gloss retention was calculated based on the following equation. In addition, the result evaluated only with the base material to which the enamel paint was previously coated is 80% of gloss retention after exposure for 3000 hours, and when the value of gloss retention is larger than this value, the weather resistance is good. Indicates

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

6. Contamination resistance A 7 cm × 15 cm substrate coated beforehand with an enamel paint was applied using a spray so that the amount of the aqueous composition applied was 17.0 g / m ² . The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illumination intensity of 20000 lux for 48 hours, and used as 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 based on 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.

[Evaluation criteria]
○: Almost no contamination was observed.
Δ: Although some stains were confirmed, it was a level that causes no problem in practical use.
X: A large amount of dirt was confirmed.

Production Example 1
Synthesis of Polymer Emulsion In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 292.0 g of ion-exchanged water, a reactive emulsifier ("ADEKAREASOAP SR-1025" manufactured by ADEKA Co., Ltd .; solid content 25) 8.0 g of a mass% aqueous solution) was charged, and the temperature in the reactor was heated to 80 ° C. with stirring. Into this reactor, 10.0 g of a 2% by mass aqueous ammonium persulfate solution was added, and after 5 minutes, 10.0 g of methyl methacrylate, 5.0 g of cyclohexyl methacrylate, 75.0 g of n-butyl acrylate, methacrylic acid 5.0 g, 10.0 g of 2-hydroxyethyl methacrylate, 4.0 g of a reactive emulsifier (manufactured by Adeka Co., Ltd., "ADEKAREASOAP SR-1025"; 25 mass% solid content aqueous solution), 2 mass% ammonium persulfate aqueous solution 15 An emulsified mixed solution consisting of 0. 0 g and 49.0 g of ion-exchanged water was dropped over 60 minutes 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 60 minutes.

  Next, 70.0 g of methyl methacrylate, 90.0 g of cyclohexyl methacrylate, 232.0 g of n-butyl acrylate, 8.0 g of methacrylic acid, a reactive emulsifying agent (ADEKA manufactured by "ADEKAREASOAP SR-1025"; solid) An emulsified mixture comprising 16.0 g of a 25 mass% aqueous solution, 60.0 g of a 2 mass% aqueous ammonium persulfate solution, and 196.0 g of ion-exchanged water, 1.0 g of 3-methacryloxypropyltrimethoxysilane, and 20 parts of dimethyldimethoxysilane A mixed solution consisting of 0. 0g and 20.0g of methyltrimethoxysilane was dropped from separate dropping baths over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured and found to be pH 2.2. A 25% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0, and then the reaction solution was filtered with a 100 mesh wire mesh to obtain a polymer emulsion for enamel paint. The solid content of the obtained polymer emulsion was 44.5% by mass. The glass transition temperature of the polymer contained in this polymer emulsion, which was determined from the inflection point of the DSC curve according to the method described above, was -5 ° C.

Production Example 2
Synthesis of aqueous dispersion (AD-1) of polymer (A-1) A reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 1364.2 g of ion exchanged water, a reactive emulsifier (manufactured by ADEKA Co., Ltd.) Then, 28.8 g of “ADEKAREASOAP SR-1025” (solid content: 25 mass% aqueous solution) was added, and the temperature in the reactor was heated to 80 ° C. with stirring. Into this reactor, 10.0 g of a 2% by mass aqueous ammonium persulfate solution was added, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (Adeka company make, "ADEKAREASOAP SR-1025"; solid content 25 mass% aqueous solution) Reaction of the emulsion mixed liquid which consists of 12.0 g of 2 mass% ammonium persulfate aqueous solution and 34.8 g of ion exchange water With the temperature in the vessel kept at 80.degree. C., it was added dropwise over 60 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 60 minutes.

  Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (manufactured by ADEKA Corporation, "ADECARIA SOAP SR-1025"; solid content 25 mass% aqueous solution) 12 An emulsified mixture comprising 8 g, 48.0 g of a 2% by mass aqueous ammonium persulfate solution, and 149.2 g of ion-exchanged water was dropped from the dropping tank over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. After cooling to room temperature, 25% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0, and then the reaction solution was filtered through a 100 mesh wire mesh. The reaction product was adjusted to a solid content of 10.0% by mass with ion exchanged water, and an aqueous dispersion (AD-1) of a polymer (A-1) having a number average particle diameter of 30 nm was obtained as a polymer.

[Production Example 3]
Synthesis of aqueous dispersion (AD-2) of polymer (A-2) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 1364.2 g of ion exchanged water, a reactive emulsifier (manufactured by ADEKA Co., Ltd.) Then, 28.8 g of “ADEKAREASOAP SR-1025” (solid content: 25 mass% aqueous solution) was added, and the temperature in the reactor was heated to 80 ° C. with stirring. Into this reactor, 10.0 g of a 2% by mass aqueous ammonium persulfate solution was added, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (Adeka company make, "ADEKAREASOAP SR-1025"; solid content 25 mass% aqueous solution) Reaction of the emulsion mixed liquid which consists of 12.0 g of 2 mass% ammonium persulfate aqueous solution and 34.8 g of ion exchange water With the temperature in the vessel kept at 80.degree. C., it was added dropwise over 60 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 60 minutes.

  Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (manufactured by ADEKA Corporation, "ADECARIA SOAP SR-1025"; solid content 25 mass% aqueous solution) 12 .8 g, an emulsified mixed solution comprising 48.0 g of a 2% by mass aqueous solution of ammonium persulfate and 149.2 g of ion-exchanged water, 2.0 g of 3-methacryloxypropyltrimethoxysilane, 20.0 g of dimethyldimethoxysilane, methyltrimethoxysilane The mixed solution consisting of 20.0 g was dropped from separate dropping tanks over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. After cooling to room temperature, a 25 mass% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0, and the reaction solution was then filtered through a 100 mesh wire mesh. The reaction product was adjusted to a solid content of 10.0% by mass with ion exchanged water, and an aqueous dispersion (AD-2) of a polymer (A-2) with a number average particle diameter of 30 nm was obtained as a polymer.

  It was 2.8 mass% in a polymer (A-2), when the quantity of the dimethyl dimethoxysilane used when synthesize | combining this aqueous dispersion was converted into hydrolysis condensation product.

Production Example 4
Synthesis of aqueous dispersion (AD-3) of polymer (A-3) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 850.0 g of ion exchanged water, 10% by mass of dodecylbenzene sulfone After charging 40.0 g of an aqueous acid solution, the temperature in the reactor was heated to 80 ° C. with stirring. Into this reactor, a mixed solution consisting of 85.5 g of dimethyldimethoxysilane and 193.0 g of methyltrimethoxysilane was added dropwise over 120 minutes 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, 14.8 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid was charged, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. Thereto, 6.6 g of a 2% by mass aqueous solution of ammonium persulfate was introduced, and then 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 20.0 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, 3 -A mixed liquid consisting of 1.1 g of methacryloxypropyl trimethoxysilane, 0.9 g of acrylic acid, 1.2 g of a reactive emulsifier ("ADECARIA SOAP SR-1025"; solid content 25% by mass aqueous solution manufactured by ADEKA), A mixed liquid consisting of 1.2 g of a reactive emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., “Aqualon KH-1025”; solid content of 25 mass% aqueous solution), 30.0 g of 2 mass% aqueous ammonium persulfate solution, and 286.4 g of ion exchanged water Were simultaneously added dropwise over 120 minutes while maintaining the temperature in the reactor at 80.degree. Further, the temperature in the reactor is maintained at 80 ° C. and stirring is continued for 60 minutes, and then cooled to room temperature, and 25 mass% ammonia aqueous solution is added to the reaction liquid to adjust pH to 8.0, and then the reaction The solution was filtered through a 100 mesh wire mesh. The reaction product was adjusted to a solid content of 10.0% by mass with ion exchanged water, and an aqueous dispersion (AD-3) of a polymer (A-3) with a number average particle diameter of 15 nm was obtained as a polymer.

  It was 25.0 mass% in a polymer (A-3), when the quantity of the dimethyl dimethoxysilane used when synthesize | combining this aqueous dispersion was converted into hydrolysis condensation product.

Production Example 5
Synthesis of aqueous dispersion (AD-4) of polymer (A-4) In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 850.0 g of ion exchanged water, 10% by mass of dodecylbenzene sulfone After charging 40.0 g of an aqueous acid solution, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, a mixture consisting of 109.0 g of dimethyldimethoxysilane, 29.5 g of phenyltrimethoxysilane, and 136.5 g of methyltrimethoxysilane is taken over 120 minutes while maintaining the temperature in the reactor at 80 ° C. Dripped. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 30 minutes. Next, 14.8 g of a 10.0% by mass aqueous solution of dodecylbenzenesulfonic acid was charged, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. Thereto, 6.6 g of a 2% by mass aqueous solution of ammonium persulfate was introduced, and then 1.0 g of methyl methacrylate, 1.0 g of n-butyl acrylate, 29.5 g of phenyltrimethoxysilane, 27.8 g of tetraethoxysilane, 3 -A mixed solution consisting of 1.1 g of methacryloxypropyl trimethoxysilane, 0.9 g of acrylic acid, 4.5 g of a reactive emulsifier (ADEKAYA, "ADECARIA SOAP SR-1025"; solid content 25 mass% aqueous solution), A mixed liquid consisting of a reactive emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., “Aqualon KH-1025”; solid content 25 mass% aqueous solution) 2.3 g, 2 mass% ammonium persulfate aqueous solution 30.0 g, ion exchanged water 256.4 g Were simultaneously added dropwise over 120 minutes while maintaining the temperature in the reactor at 80.degree. Further, the temperature in the reactor is maintained at 80 ° C. and stirring is continued for 60 minutes, and then cooled to room temperature, and 25 mass% ammonia aqueous solution is added to the reaction liquid to adjust pH to 8.0, and then the reaction The solution was filtered through a 100 mesh wire mesh. The reaction product was adjusted to a solid content of 10.0% by mass with ion exchanged water, and an aqueous dispersion (AD-4) of a polymer (A-4) with a number average particle diameter of 20 nm was obtained as a polymer.

  It was 35.0 mass% in a polymer (A-4), when the quantity of the dimethyl dimethoxysilane used when synthesize | combining this aqueous dispersion was converted into hydrolysis condensation product.

Production Example 6
Synthesis of aqueous dispersion (AD-5) of polymer (A-5) A reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 1000.0 g of ion exchanged water, 10% by mass of dodecylbenzene sulfone After charging 40.0 g of an aqueous acid solution, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, a mixture consisting of 220.0 g of dimethyldimethoxysilane, 5.0 g of phenyltrimethoxysilane, and 106.0 g of methyltrimethoxysilane is taken over 120 minutes while the temperature in the reactor is kept at 80 ° C. Dripped. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 30 minutes. Next, 14.8 g of a 10.0% by mass aqueous solution of dodecylbenzenesulfonic acid was charged, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. Thereto, 6.6 g of a 2% by mass aqueous solution of ammonium persulfate is introduced, and then 1.0 g of methyl methacrylate, 1.0 g of n-butyl acrylate, 5.0 g of phenyltrimethoxysilane, 10.0 g of tetraethoxysilane, 3 -A mixed solution consisting of 1.1 g of methacryloxypropyl trimethoxysilane, 0.9 g of acrylic acid, 4.5 g of a reactive emulsifier (ADEKAYA, "ADECARIA SOAP SR-1025"; solid content 25 mass% aqueous solution), A mixed liquid consisting of a reactive emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., “Aqualon KH-1025”; solid content 25 mass% aqueous solution) 2.3 g, 2 mass% ammonium persulfate aqueous solution 30.0 g, ion exchanged water 256.4 g Were simultaneously added dropwise over 120 minutes while maintaining the temperature in the reactor at 80.degree. Further, the temperature in the reactor is maintained at 80 ° C. and stirring is continued for 60 minutes, and then cooled to room temperature, and 25 mass% ammonia aqueous solution is added to the reaction liquid to adjust pH to 8.0, and then the reaction The solution was filtered through a 100 mesh wire mesh. The reaction product was adjusted to a solid content of 10.0% by mass with ion exchanged water, and an aqueous dispersion (AD-5) of a polymer (A-5) with a number average particle diameter of 35 nm was obtained as a polymer.

  It was 65.0 mass% in a polymer (A-5), when the quantity of the dimethyl dimethoxysilane used when synthesize | combining this aqueous dispersion was converted into hydrolysis condensation product.

Production Example 7
Synthesis of aqueous dispersion (A′D-6) of polymer (A′-6) A reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 335.8 g of ion exchanged water, a reactive emulsifier ( 19.2 g of "ADEKAREASOAP SR-1025" (solid content 25% by mass aqueous solution) manufactured by ADEKA Corporation was added, and the temperature in the reactor was heated to 80 ° C. with stirring. Into this reactor, 10.0 g of a 2% by mass aqueous ammonium persulfate solution was added, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (Adeka company make, "ADEKAREASOAP SR-1025"; solid content 25 mass% aqueous solution) Reaction of the emulsion mixed liquid which consists of 12.0 g of 2 mass% ammonium persulfate aqueous solution and 34.8 g of ion exchange water With the temperature in the vessel kept at 80.degree. C., it was added dropwise over 60 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 60 minutes.

  Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (manufactured by ADEKA Corporation, "ADECARIA SOAP SR-1025"; solid content 25 mass% aqueous solution) 12 An emulsified mixture comprising 8 g, 48.0 g of a 2% by mass aqueous ammonium persulfate solution, and 149.2 g of ion-exchanged water was dropped from the dropping tank over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. After cooling to room temperature, 25% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0, and then the reaction solution was filtered through a 100 mesh wire mesh. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (A'D-6) of a polymer (A'-6) having a number average particle diameter of 60 nm as a polymer. .

Production Example 8
Synthesis of aqueous dispersion (A'D-7) of polymer (A'-7) A reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 241.8 g of ion exchanged water, a reactive emulsifier ( Adeka Co., Ltd. make, "Adekaria soap SR-1025; solid content 25 mass% aqueous solution" 3.2 g was added, and the temperature in a reactor was heated to 80 degreeC under stirring. Into this reactor, 10.0 g of a 2% by mass aqueous ammonium persulfate solution was added, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (Adeka company make, "ADEKAREASOAP SR-1025"; solid content 25 mass% aqueous solution) Reaction of the emulsion mixed liquid which consists of 12.0 g of 2 mass% ammonium persulfate aqueous solution and 34.8 g of ion exchange water With the temperature in the vessel kept at 80.degree. C., it was added dropwise over 60 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 60 minutes.

  Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, reactive emulsifier (manufactured by ADEKA Corporation, "ADECARIA SOAP SR-1025"; solid content 25 mass% aqueous solution) 12 .8 g, an emulsified mixed solution comprising 48.0 g of a 2% by mass aqueous solution of ammonium persulfate and 149.2 g of ion-exchanged water, 2.0 g of 3-methacryloxypropyltrimethoxysilane, 20.0 g of dimethyldimethoxysilane, methyltrimethoxysilane The mixed solution consisting of 20.0 g was dropped from separate dropping tanks over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. After cooling to room temperature, a 25 mass% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0, and the reaction solution was then filtered through a 100 mesh wire mesh. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water, and an aqueous dispersion (A'D-7) of a polymer (A'-7) with a number average particle diameter of 120 nm was obtained as a polymer .

  The amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 2.8% by mass in the polymer (A'-7) when converted to hydrolysis condensate.

Production Example 9
Synthesis of inorganic oxide (C-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 to the reactor 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 obtained 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 a temperature of 95 ° C., and maintained at this temperature for 2 hours The acid heat treatment was performed. 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 became 100 μS / cm, to obtain a wet titanium oxide cake 2 having a solid content of 25% by mass.

An aqueous solution of sodium hydroxide having a concentration of 10% by mass is added to the obtained titanium oxide wet cake 2 and repulped, and then dispersed for 3 hours with an ultrasonic cleaner to obtain a pH of 10.5 and a solid content of 10% by mass An alkaline titanium oxide sol was obtained. 2 L of this alkaline titanium oxide sol is charged in a 3 L flask, the flask is heated to a temperature of 70 ° C., 69.4 mL of a sodium silicate aqueous solution having a concentration of 432 g / L as SiO ₂ is added, and then raised to 90 ° C. After warming and maintaining for 1 hour, pH was adjusted to 6 by addition of 10% sulfuric acid to obtain a titanium oxide sol surface-treated with titanium hydrous oxide on the surface of titanium oxide.

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, pH 7.3, solid content 29% by mass, conductivity A neutral rutile titanium oxide sol of 1.18 mS / cm was obtained. The neutral rutile titanium oxide sol contained 15 mass% of silicon hydrous oxide of SiO ₂ basis relative to TiO _2. The number average particle diameter of primary particles of titanium oxide in this sol was 9 nm.

Production Example 10
Synthesis of inorganic oxide (C-2) having photocatalytic activity Silica-modified anatase-type titanium oxide TiO ₂ Aggregated metatitanic acid formed by thermal hydrolysis of a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid, TiO ₂ It was set as a 30 mass% aqueous slurry in conversion. Ammonia water was added to this slurry to neutralize to pH 7, then the sulfate ion was removed by filtration and washing 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 comprising titanium oxide fine 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 sodium silicate having a SiO ₂ conversion concentration of 432 g / L 20.8 mL of an aqueous solution was added to the reactor simultaneously with 20% sulfuric acid. After that, it was aged for 30 minutes. Next, 10% aqueous sodium hydroxide solution is added to adjust the pH of the reaction solution to 8, and then the pH of the reaction solution is adjusted to 6 with a 2% aqueous sulfuric acid solution, and the reaction solution is filtered and washed to obtain a wet cake. Obtained. The wet cake was repulped in pure water and then ultrasonically dispersed to obtain anatase-type titanium oxide sol (solid content 20 mass%, pH 7.5) stable in the neutral region. In this, 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 .

[ Reference Example 1 ]
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 20.0 g (solid content 10.0 mass%) of a water dispersion (AD-1) of the polymer (A-1) (Nissan Chemical Industries Co., Ltd.) Product, “Snowtex OS”; solid content: 20% by mass, 10.0 g of ethanol, 10.0 g of ethanol, and 60.0 g of ion-exchanged water, and stirring the mixture, the aqueous composition having a solid content of 4.0% by mass Obtained (F-1).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-1) was applied using a spray to a coating weight of 17 g / m ² . The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 48 hours at an illuminance of 20000 lux, and a test paper on which a coating was formed on the black area of the cover ratio test paper (G-1) And the test board (H-1) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-1), the coating film and the test paper (G-1), and the coating film and the test plate (H-1).

[ Reference Example 2 ]
13.2 g (solid content 10.0 mass%) of a water dispersion (AD-1) of the polymer (A-1), a water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex OS”; 13.4 g of solid content: 20% by mass, 10.0 g of ethanol, and 63.4 g of ion-exchanged water, and the mixture is stirred to obtain an aqueous composition having a solid content of 4.0% by mass. Obtained (F-2).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-2) was coated using a spray to a coating weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C, a relative humidity of 50%, and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-2) And the test board (H-2) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-2), the coating film and the test paper (G-2), and the coating film and the test plate (H-2).

[ Reference Example 3 ]
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 10.0 g (solid content 10.0 mass%) of an aqueous dispersion (AD-2) of the polymer (A-2) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex OS”; 15.0 g of solid content 20 mass%), 10.0 g of ethanol, and 65.0 g of ion-exchanged water are mixed and stirred to obtain an aqueous composition having a solid content of 4.0 mass% Obtained (F-3).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-3) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-3) And the test board (H-3) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-3), the coating film and the test paper (G-3), and the coating film and the test plate (H-3).

[ Reference Example 4 ]
13.2 g (solid content 10.0 mass%) of a water dispersion (AD-3) of the polymer (A-3), a water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex OS”; 13.4 g of solid content: 20% by mass, 10.0 g of ethanol, and 63.4 g of ion-exchanged water, and the mixture is stirred to obtain an aqueous composition having a solid content of 4.0% by mass. Obtained (F-4).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-4) was applied using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-4) And the test board (H-4) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-4), the coating film and the test paper (G-4), and the coating film and the test plate (H-4).

[Example 5]
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 10.0 g (solid content 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries Co., Ltd.) Product, “Snowtex OS”; 15.0 g of solid content 20 mass%), 10.0 g of ethanol, and 65.0 g of ion-exchanged water are mixed and stirred to obtain an aqueous composition having a solid content of 4.0 mass% (F-5) was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-5) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-5) And the test board (H-5) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-5), the coating film and the test paper (G-5), and the coating film and the test plate (H-5).

[Example 6]
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 10.0 g (solid content 10.0 mass%) of an aqueous dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industries Co., Ltd.) Product, “Snowtex OS”; 15.0 g of solid content 20 mass%), 10.0 g of ethanol, and 65.0 g of ion-exchanged water are mixed and stirred to obtain an aqueous composition having a solid content of 4.0 mass% Obtained (F-6).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-6) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-6) And the test board (H-6) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-6), the coating film and the test paper (G-6), and the coating film and the test plate (H-6).

[Example 7]
Water-dispersed colloidal silica (B-3) having a number average particle diameter of 25 nm in 8.0 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex O-40”; solid content 40% by mass, 8.0 g of ethanol, 10.0 g of ethanol, and 74.0 g of ion-exchanged water, and stirring is performed to obtain an aqueous system with a solid content of 4.0% by mass. A composition (F-7) was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-7) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 48 hours at an illuminance of 20000 lux, and a test paper with a coating formed on the black area of the cover ratio test paper (G-7) And the test board (H-7) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-7), the coating film and the test paper (G-7), and the coating film and the test plate (H-7).

[ Reference Example 5 ]
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 10.9 g (solid content 10.0 mass%) of a water dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industries Co., Ltd.) Manufactured by "Snowtex OS" (solid content: 20% by mass), 2.3 g (solid content: 29% by mass) of inorganic oxide (C-1) having photocatalytic activity, and ethanol; A mixture of 1.0 g of a fluorocarbon surfactant (D-1) ("Megafuck F-444" manufactured by DIC) adjusted to 0% by mass, 10.0 g of ethanol, and 65.1 g of ion-exchanged water is stirred. Thus, a water-based composition (F-8) having a solid content of 4.0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-8) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50%, and an intensity of 20000 lux, and a test paper (G-8) in which a coating is formed on the black area of the cover ratio test paper And the test board (H-8) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-8), the coating film and the test paper (G-8), and the coating film and the test plate (H-8).

[Example 9]
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 8.1 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industry Co., Ltd. Manufactured by "Snowtex OS" (solid content: 20% by mass), 2.3 g (solid content: 29% by mass) of inorganic oxide (C-1) having photocatalytic activity, and ethanol; A mixture of 1.0 g of a fluorocarbon surfactant (D-1) ("Megafuck F-444" manufactured by DIC Corporation) adjusted to 0% by mass, 10.0 g of ethanol, and 66.5 g of ion-exchanged water is stirred. Thus, an aqueous composition (F-9) having a solid content of 4.0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-9) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-9) And the test board (H-9) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-9), the coating film and the test paper (G-9), and the coating film and the test plate (H-9).

[Example 10]
A water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in an aqueous dispersion (AD-5) of the polymer (A-5) (6.5 g (solid content: 10.0 mass%)) (Nissan Chemical Industry Co., Ltd. Manufactured by "Snowtex OS" (solid content: 20% by mass), 2.3 g (solid content: 29% by mass) of inorganic oxide (C-1) having photocatalytic activity, and ethanol; A mixture of 1.0 g of a fluorocarbon surfactant (D-1) ("Megafuck F-444" manufactured by DIC Corporation) adjusted to 0% by mass, 10.0 g of ethanol, and 67.3 g of ion-exchanged water is stirred. Thus, an aqueous composition (F-10) having a solid content of 4.0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-10) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-10) And the test board (H-10) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-10), the coating film and the test paper (G-10), and the coating film and the test plate (H-10).

[Example 11]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm in 8.1 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Manufactured by "Snowtex OS" (solid content: 20% by mass), 2.3 g (solid content: 29% by mass) of inorganic oxide (C-1) having photocatalytic activity, and ethanol; A mixture of 1.0 g of a fluorocarbon surfactant (D-1) ("Megafuck F-444" manufactured by DIC Corporation) adjusted to 0% by mass, 10.0 g of ethanol, and 66.5 g of ion-exchanged water is stirred. Thus, an aqueous composition (F-11) having a solid content of 4.0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-11) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux, and a test paper with a coating formed on the black area of the cover ratio test paper (G-11) And the test board (H-11) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-11), the coating film and the test paper (G-11), and the coating film and the test plate (H-11).

[Example 12]
Water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm in 8.1 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex NS” (solid content: 20% by mass), 12.1 g of inorganic oxide (C-1) having photocatalytic activity (solid content: 29% by mass), and ethanol; A mixture of 1.0 g of a fluorocarbon surfactant (D-1) ("Megafuck F-444" manufactured by DIC Corporation) adjusted to 0% by mass, 10.0 g of ethanol, and 66.5 g of ion-exchanged water is stirred. Thus, an aqueous composition (F-12) having a solid content of 4.0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-12) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-12) And the test board (H-12) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-12), the coating film and the test paper (G-12), and the coating film and the test plate (H-12).

[Example 13]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm in 8.1 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Manufactured by "Snowtex OS" (solid content: 20% by mass), 1.7 g (solid content: 29% by mass) of inorganic oxide (C-1) having photocatalytic activity, and ethanol; A mixture of 1.0 g of a fluorocarbon surfactant (D-1) ("Megafuck F-444" manufactured by DIC Corporation) adjusted to 0% by mass, 10.0 g of ethanol, and 66.2 g of ion-exchanged water is stirred. Thus, a water-based composition (F-13) having a solid content of 4.0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-13) was coated using a spray to a coating weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-13) And the test board (H-13) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-13), the coating film and the test paper (G-13), and the coating film and the test plate (H-13).

[ Reference Example 6 ]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm in 8.1 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Manufactured by "Snowtex OS" (solid content: 20% by mass), 3.2 g (solid content: 29% by mass) of inorganic oxide (C-1) having photocatalytic activity, and ethanol; A mixture of 1.0 g of a fluorocarbon surfactant (D-1) ("Megafuck F-444" manufactured by DIC) adjusted to 0% by mass, 10.0 g of ethanol, and 66.9 g of ion-exchanged water is stirred. Thus, a water-based composition (F-14) having a solid content of 4.0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-14) was applied using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-14) And the test board (H-14) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-14), the coating film and the test paper (G-14), and the coating film and the test plate (H-14).

[Example 15]
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 8.0 g (solid content 10.0 mass%) of a water dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex OS”; solid content 20 mass%, 13.0 g, inorganic oxide (C-2) having photocatalytic activity 2.4 g (solid content 20 mass%), fluorocarbon surfactant (D- 2) (AGC Seimi Chemical Co., Ltd., “Surflon S-232”; solid content 30 mass%) 0.4 g, ethanol 10.0 g and ion-exchanged water 66.2 g mixed and stirred, solid content 4 The aqueous composition (F-15) was obtained in an amount of 0% by mass.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-15) was applied using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-15) And the test board (H-15) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-15), the coating film and the test paper (G-15), and the coating film and the test plate (H-15).

[Example 16]
Water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm in 8.1 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex NS”; solid content 20 mass%, 12.0 g, inorganic oxide (C-1) having photocatalytic activity 2.3 g (solid content 29 mass%), fluorocarbon surfactant (D- 2) (AGC Seimi Chemical Co., Ltd., “Surflon S-232”; solid content 30 mass%) 0.4 g, ethanol 10.0 g, and ion exchange water 67.2 g mixed and stirred, solid content 4 The aqueous composition (F-16) was obtained in an amount of 0% by mass.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-16) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-16) And the test board (H-16) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-16), the coating film and the test paper (G-16), and the coating film and the test plate (H-16).

[Example 17]
Water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm in 7.5 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex NS”; solid content 20 mass%, 12.0 g, inorganic oxide (C-1) having photocatalytic activity 2.3 g (solid content 29 mass%), fluorocarbon surfactant (D- 2) (AGC Seimi Chemical Co., Ltd., “Surflon S-232”; solid content 30 mass%) 0.6 g, ethanol 10.0 g, and ion-exchange water 67.6 g mixed and stirred, solid content 4 An aqueous composition (F-17) having a content of 0% by mass was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-17) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-17) And the test board (H-17) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-17), the coating film and the test paper (G-17), and the coating film and the test plate (H-17).

[Example 18]
Water dispersion colloidal silica (B-2) of a number average particle diameter of 8 nm to 8.7 g (solid content 10.0 mass%) of a water dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries Co., Ltd.) Product, “Snowtex NS”; solid content 20 mass%, 12.0 g, inorganic oxide (C-1) having photocatalytic activity 2.3 g (solid content 29 mass%), fluorocarbon surfactant (D- 2) (AGC Seimi Chemical Co., Ltd., “Surflon S-232”; solid content 30 mass%) 0.2 g, ethanol 10.0 g, and ion exchange water 66.8 g mixed and stirred, solid content 4 The aqueous composition (F-18) was obtained in an amount of 0% by mass.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-18) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux, and a test paper (G-18) in which a coating is formed on the black area of the cover ratio test paper And the test board (H-18) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-18), the coating film and the test paper (G-18), and the coating film and the test plate (H-18).

[Example 19]
Water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm in 8.0 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex NS”; solid content 20 mass%, 12.0 g, inorganic oxide (C-1) having photocatalytic activity 2.3 g (solid content 29 mass%), fluorocarbon surfactant (D- 2) A bleachable pigment (E-1) whose solid content was adjusted to 1.0% by mass with 0.4 g of (Surflon S-232; solid content 30% by mass, manufactured by AGC Seimi Chemical Co., Ltd.) and ion-exchanged water An aqueous composition (F-19 having a solid content of 4.0% by mass) by mixing and stirring 1.2 g of “methylene blue” (manufactured by Kishida Chemical Co., Ltd.), 10.0 g of ethanol, and 66.1 g of ion-exchanged water Got).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-19) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-19) And the test board (H-19) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-19), the coating film and the test paper (G-19), and the coating film and the test plate (H-19).

[Example 20]
The solid content is changed to 1.2 g of decolorizable dye (E-1) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") whose solid content is adjusted to 1.0% by mass with ion exchanged water, and the solid content is 1.0 mass by ion exchanged water An aqueous system having a solid content of 4.0% by mass in the same manner as in Example 19 except that 1.2 g of a color-fading pigment (E-2) ("Hidogaya Chemical Industry Co., Ltd.," Acid Red ") adjusted to 10% was used. A composition (F-20) was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-20) was applied using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C, a relative humidity of 50%, and an illuminance of 20000 lux, and a test paper (G-20) in which a coating is formed on the black area of the cover ratio test paper And the test board (H-20) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-20), the coating film and the test paper (G-20), and the coating film and the test plate (H-20).

[Example 21]
Water dispersion colloidal silica (B-2) of a number average particle diameter of 8 nm to 4.0 g (solid content 10.0 mass%) of a water dispersion (AD-4) of a polymer (A-4) (Nissan Chemical Industries Co., Ltd.) Product, “Snowtex NS” (solid content: 20% by mass), 5.9 g of inorganic oxide (C-1) having photocatalytic activity (29% by mass of solid content), fluorocarbon surfactant (D- 2) (AGC Seimi Chemical Co., Ltd., "Surflon S-232"; solid content of 30% by mass) 0.2 g and a color-fading dye (E-2) whose solid content was adjusted to 1.0% by mass with ion-exchanged water An aqueous composition having a solid content of 2.0 mass% by mixing and stirring 1.2 g of “Acid Red,” manufactured by Hodogaya Chemical Industry Co., Ltd., 10.0 g of ethanol, and 77.5 g of ion-exchanged water -21) was obtained.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-21) was coated using a spray to a coating weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C, a relative humidity of 50%, and an illuminance of 20000 lux for a test paper on which a coating is formed on the black area of the cover ratio test paper (G-21) And the test board (H-21) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-21), the coating film and the test paper (G-21), and the coating film and the test plate (H-21).

Example 22
Water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm in 4.1 g (solid content: 10.0% by mass) of a water dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industry Co., Ltd.) Product, “Snowtex NS” (solid content: 20% by mass), 5.9 g of inorganic oxide (C-1) having photocatalytic activity (29% by mass of solid content), fluorocarbon surfactant (D- 2) (AGC Seimi Chemical Co., Ltd., "Surflon S-232"; solid content of 30% by mass) 0.2 g of the color-fading dye (E-1) whose solid content is adjusted to 1.0% by mass with ion-exchanged water An aqueous composition having a solid content of 2.0 mass% (F-22) by mixing and stirring 0.6 g of “methylene blue” (manufactured by Kishida Chemical Co., Ltd.), 10.0 g of ethanol, and 78.0 g of ion-exchanged water Got).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-22) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux, and a test paper with a coating formed on the black area of the cover ratio test paper (G-22) And the test board (H-22) by which the coating film was formed on the base material was obtained. Table 1 shows various physical properties and evaluation results of the water-based composition (F-22), the coating film and the test paper (G-22), and the coating film and the test plate (H-22).

Comparative Example 1
The aqueous dispersion (AD ') of the polymer (A-1) is changed to 20.0 g and the aqueous dispersion (A'D-6) of the polymer (A'-6) is 20.0 g (solid content 10.0 An aqueous composition (F-23) having a solid content of 4.0% by mass was obtained in the same manner as in Reference Example 1 except that mass%) was used.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-23) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C, a relative humidity of 50%, and an illuminance of 20000 lux, and a test paper with a coating formed on the black area of the cover ratio test paper (G-23) And the test board (H-23) by which the coating film was formed on the base material was obtained. Table 2 shows various physical properties and evaluation results of the water-based composition (F-23), the coating film and the test paper (G-23), and the coating film and the test plate (H-23).

Comparative Example 2
Instead of 20.0 g of the aqueous dispersion (AD-1) of the polymer (A-1), 20.0 g (solid content: 10.0) of the aqueous dispersion (A 'D-7) of the polymer (A'-7) An aqueous composition (F-24) having a solid content of 4.0% by mass was obtained in the same manner as in Reference Example 1 except that mass%) was used.

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-24) was applied using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50%, and an intensity of 20000 lux, and a test paper (G-24) in which a coating is formed on the black area of the cover ratio test paper And the test board (H-24) by which the coating film was formed on the base material was obtained. Table 2 shows various physical properties and evaluation results of the water-based composition (F-24), the coating film and the test paper (G-24), and the coating film and the test plate (H-24).

Comparative Example 3
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 22.0 g (solid content 10.0 mass%) of a water dispersion (AD-1) of the polymer (A-1) (Nissan Chemical Industry Co., Ltd. Product, “Snowtex OS”; solid content: 20% by mass, 9.0 g of ethanol, 10.0 g of ethanol, and 59.0 g of ion-exchanged water, and stirring; an aqueous composition having a solid content of 4.0% by mass Obtained (F-25).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-25) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50%, and an intensity of 20000 lux, and a test paper (G-25) in which a coating is formed on the black area of the cover ratio test paper And the test board (H-25) by which the coating film was formed on the base material was obtained. Table 2 shows various physical properties and evaluation results of the water-based composition (F-25), the coating film and the test paper (G-25), and the coating film and the test plate (H-25).

Comparative Example 4
Water dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm in 6.6 g (solid content 10.0 mass%) of a water dispersion (AD-1) of the polymer (A-1) (Nissan Chemical Industry Co., Ltd. Product, “Snowtex OS”; 16.7 g of solid content 20 mass%, 10.0 g of ethanol, and 66.7 g of ion-exchanged water are mixed and stirred to obtain an aqueous composition having a solid content of 4.0 mass% Obtained (F-26).

Next, the black area (L * value 7) of concealment percentage test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side (pre-painted surface of enamel paint) of 7 cm × 15 cm substrate coated with enamel paint in advance are water-based The composition (F-26) was coated using a spray to a coat weight of 17 g / m ² . The coated substrate is kept horizontal and left for 48 hours at a temperature of 23 ° C and a relative humidity of 50% and an illuminance of 20000 lux for a test paper with a coating formed on the black area of the cover ratio test paper (G-26) And the test board (H-26) by which the coating film was formed on the base material was obtained. Table 2 shows various physical properties and evaluation results of the water-based composition (F-26), the coating film and the test paper (G-26), and the coating film and the test plate (H-26).

  From the above, it is possible that the aqueous 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 without impairing the appearance even with a dark colored base material. confirmed.

  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, optical components such as displays and lenses.

Claims (8)

Containing an aqueous dispersion (AD) of a polymer (A) having a number average particle diameter of 10 to 35 nm, and silicon dioxide (B), the mass of the polymer (A) and silicon dioxide (B) Ratio (polymer (A) / silicon dioxide (B)) is 1 / 2.8 to 1/4,
The aqueous composition in which the said polymer (A) contains 35-70 mass% of structural units derived from dimethyl dimethoxysilane (a) in conversion of a hydrolysis condensation product.   The aqueous composition according to claim 1, further comprising an inorganic oxide (C) having photocatalytic activity.   The aqueous composition according to claim 1, further comprising a fluorocarbon surfactant (D).   The water-based composition as described in any one of Claims 1-3 which further contains a color-fading pigment (E).   The water-based paint containing the water-based composition as described in any one of Claims 1-4.   The coating film obtained from the water-based paint of Claim 5. A substrate,
A coated product according to claim 6, which is formed on at least a part of the surface of the substrate.   The coated product according to claim 7, wherein the substrate is an organic substrate.