JP6552133B2 - Coatings, composite coatings, and painted products - Google Patents

Description

  The present invention relates to coatings, composite 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 pollutants discharged from the discharge port of the above, or organisms represented by algae and the like. Such contamination of the coating film is usually light black or green, which significantly impairs the aesthetics of buildings and outdoor structures.

As a coating film which suppresses the above-mentioned contamination, a multilayer coating film is proposed which is provided with an undercoating layer and an overcoating layer provided on the undercoating layer (see, for example, Patent Documents 1 and 2) .
Here, the undercoat layer contains a polymer emulsion particle (A) obtained by a method comprising the steps of respectively polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier. It is a film | membrane formed by drying the coating film of agent composition (I). In addition, the overcoat layer is a polymer obtained by a method including the steps of respectively polymerizing a metal oxide particle (B) having photocatalytic activity, and a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier. It is a film formed by drying a coating film of a coating agent composition (II) for topcoat containing emulsion particles (C) and colloidal silica (D).

  The primer layer and the overcoat layer provided on the undercoat layer, wherein the undercoat layer is a layer containing a silicone-modified resin and an organic antifungal agent, and the overcoat layer is a photocatalyst particle and an inorganic oxide particle The multiple coating film body which is a layer containing and hydrolysable silicone is proposed (for example, refer to patent documents 3). Furthermore, a composite coating film containing a copolymer having a specific structure in the undercoat layer and the overcoat layer has been proposed (see, for example, Patent Document 4).

JP 2010-005595 A Japanese Patent No. 5411574 Japanese Patent No. 4092434 Japanese Patent No. 5280120

The multilayer coating described in Patent Document 1 is a material having a high glass transition temperature as a subbing layer, so even if it is a top coating layer formed from a coating composition for top coating, sufficient stain resistance is obtained. And weather resistance.
However, for example, when a coating agent composition for top coating as described in Patent Document 1 is overcoated on a substrate using a material having a glass transition temperature of about -5 to 20 ° C., which is generally used for building exteriors and the like. The topcoat layer formed from the topcoat coating composition may not be able to sufficiently follow the substrate that 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, it may cause white turbidity and the like, thereby impairing the appearance.
Therefore, there is a need for a coating film which 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.

  The multilayer coating film described in Patent Document 2 is considered to be resistant to staining by setting the porosity and the constituent components in a specific range in the coating film. However, there is room for improvement with respect to dirt eluted from the sealing and biological contamination typified by algae and mold.

  The plurality of coating films described in Patent Document 3 are considered to have excellent biofouling resistance because the undercoat layer contains a fungicide. However, there is room for improvement with regard to spray suitability assuming coating at a construction site and appearance defects caused by the spread of the coating liquid onto the substrate.

  A plurality of coating films described in Patent Document 4 can provide a coating film having excellent weather resistance and contamination resistance by including a copolymer having a core-shell structure. However, there is room for improvement with regard to biological contamination such as soil and algae eluted from sealing.

  The present invention has been made in view of the above circumstances, maintains the appearance of the coating film at a high level, does not impair the appearance even if the base material is dark, and maintains the appearance, stain resistance and sealing for a long time It is an object of the present invention to provide a coating capable of maintaining a high level of stain resistance, biofouling resistance and gloss.

As a result of intensive studies, the present inventors have found that the coating film contains silicon dioxide, an inorganic oxide having photocatalytic activity, and a fluorocarbon surfactant, and has a crack with a specific width on the coating film surface. The coating film was found to be able to solve the above-mentioned problems, and the present invention was completed.
That is, the present invention is as follows.

[1]
Silicon dioxide (B),
An inorganic oxide (C) having photocatalytic activity;
A fluorocarbon surfactant (D);
A coating film containing
The coating film surface has cracks, more than 90% of the cracks, Ri following width der 5.0 .mu.m,
Containing 0 to 27.0% by mass of the polymer (A) in the coating film,
Paint film.
[2]
The coating film as described in [1] whose thickness of a coating film is 0.15 micrometer or more and less than 2.0 micrometers.
[3]
A substrate;
The coating film according to [1] or [2] formed on at least a part of the surface of the substrate,
A coated product.
[4]
An overcoat layer obtained from the coating film according to [1] or [2];
Having at least two subbing layers,
The subbing layer contains a polymer and an antialgal and / or antifungal agent,
Composite coating.
[5]
A substrate;
The composite coating film according to [4], formed on at least a part of the surface of the substrate
A coated product.
[6]
The coated product according to [3] or [5], wherein the substrate is an organic substrate.

  According to the present invention, the appearance of the coating is maintained at a high level, the appearance is not impaired even if the substrate is dark, and the appearance, the stain resistance, the biological stain resistance, the sealing stain resistance and the like over a long period of time A coating film capable of maintaining gloss at a high level can be provided.

It is a figure which shows the electron microscope image of the coating film of this embodiment. The arrows in the figure represent the measurement position of the width of the crack.

  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.

[Coating]
The coating film of the present embodiment is a coating film containing silicon dioxide (B), an inorganic oxide (C) having photocatalytic activity, and a fluorocarbon surfactant (D). Further, the coating film of the present embodiment has a crack on the surface of the coating film, and 90% or more of the crack has a width of 5.0 μm or less.

(Coat crack)
The coating film of the present embodiment has a crack on the surface of the coating film. The width of the crack on the coating surface is 5.0 μm or less, preferably 4.0 μm or less, more preferably 3.0 μm or less, still more preferably 2.5 μm from the viewpoint of further improving the biofouling resistance of the coating. Hereinafter, it is more preferably 2.0 μm or less.
The lower limit of the width of the crack on the coating surface is not particularly limited as long as it is greater than 0 μm.
The width of a crack in the present embodiment is, as shown in FIG. 1, a portion of a film (ie, a portion on which a coating film is formed) and a linear portion (ie, a crack portion) in which a crack occurs in the film. ) Is the shortest distance to the portion of the membrane that exists.
From the viewpoint of further improving the biofouling resistance of the coating film, the width of the crack is 5.0 μm or less, usually 90% or more of the cracks measured by the method described in the examples, 92% or more Is preferably 95% or more, more preferably 97% or more.

By setting the width of the crack within the above range, the biofouling resistance of the coating film can be further improved. Although it is not clear as these reasons, when the width of the crack of the coating film is 5.0 μm or less, organisms such as algae and molds are less likely to enter the crack, so that the biological contamination resistance can be improved. It is guessed. In addition, the coating film of the present embodiment has a crack on the surface of the coating film, thereby increasing the contact frequency of the photocatalytic inorganic oxide (C) contained in the coating film with dust, soot and the like in the air It is estimated that the stain resistance can be improved. Moreover, when the coating film of this embodiment is used as a top coating layer which comprises a composite coating film, the antialgal and / or antifungal agent contained in an undercoat layer by having a crack on the surface of a coating film is a top coating layer. In the coating film of the present embodiment, it is estimated that the resistance to biofouling by algae, mold, etc. can be improved earlier. The operation of the present embodiment is not limited to these.
The width of the crack can be measured by the method described in the examples below.
Although the coating film of this embodiment is not specifically limited, For example, a water-system paint and a solvent-type paint can be dried and obtained. The coating film of the present embodiment is preferably obtained by drying a water-based paint. The coating film of the present embodiment includes the above-mentioned cracks, and the method of setting the width is not particularly limited. For example, a method of reducing the film thickness of the water-based paint, a method of using a specific amount of polymer Can be mentioned.

(Polymer (A))
The coating film of the present embodiment may contain a polymer (A) (hereinafter, may be simply referred to as component (A)). The content of the component (A) in the coating film of the present embodiment is preferably 0 to 60.0% by mass, more preferably 0 to 50.0% by mass, still more preferably 0 to 40.0% by mass Still more preferably, it is 0-30.0 mass%, still more preferably 0-27.0 mass%. By making content of (A) component in a coating film into the said range, the coating film which was further excellent in the appearance in a dark-colored base material, a weather resistance, stain resistance, a sealing stain resistance, and a biological stain resistance is obtained. be able to.
The polymer (A) is not particularly limited, but, for example, a polymer obtained by a method such as emulsion polymerization can be used. Specific examples of the polymer (A) include, but are not particularly limited to, polymers obtained by performing any one of radical polymerization, anion polymerization and cation polymerization in an aqueous medium.

  The number average particle diameter of the polymer (A) is preferably 10 nm to 200 nm, more preferably 10 nm to 150 nm, still more preferably 10 nm to 100 nm, and still more preferably 10 nm to 40 nm. By using the polymer (A) having a number average particle diameter in the above range, there is no white turbidity even when applied to a dark colored substrate, and the resulting coated film 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 200 nm or less, The weather resistance of the film is further improved.

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), etc. By increasing the amount of activator, the number average particle size can be reduced.
In addition, the number average particle diameter here can be measured using a wet particle size analyzer.

The component (A) is not limited to the following, but for example, poly (meth) acrylate polymer, polyvinyl acetate polymer, vinyl acetate- (meth) acrylic polymer, ethylene vinyl acetate heavy polymer Combination, silicone polymer, fluorine polymer, polybutadiene polymer, styrene butadiene polymer, NBR polymer, polyvinyl chloride polymer, chlorinated polypropylene polymer, polyethylene polymer, polystyrene polymer Homopolymers or copolymers represented by polymers, vinylidene chloride polymers, polystyrene- (meth) acrylate polymers, styrene-maleic anhydride polymers; silicone-modified (meth) acrylic polymers, fluorine -(Meth) acrylic polymer, (meth) acrylic-silicone polymer, epoxy- (meth) acrylic Polymer; modified copolymer represented by like.
These may be used alone 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."

  It is preferable that the homopolymer, copolymer, modified copolymer, etc. of the above-mentioned polymer (A) etc. (hereinafter, these may be generically referred to as "polymer") are in the state of aqueous dispersion. . Preferred embodiments 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. Although these are not limited to the following, for example, they can be obtained by emulsion polymerization of monomers such as (meth) acrylic acid ester, and a hydrolyzable silicon compound described later.

The coating film 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 Examples thereof include compounds, silyl compounds, alkoxy compounds, (meth) acrylate compounds and the like.
These may be used alone or in combination of two or more.

The said (A) component can use a vinyl monomer as a polymerization monomer.
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.

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

  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 include tetraethylene glycol di (meth) acrylate.

  Examples of the aromatic vinyl compound include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, 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. Thus, it is presumed that the stability as an emulsion can be further improved and a high resistance against an external dispersion breaking action can be imparted to the coating film (however, the action of the present embodiment is not limited thereto). 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 amount of the carboxyl group-containing vinyl monomer used in the total amount of the vinyl monomer is preferably 0 to 50% by mass from the viewpoint of water resistance, but is not limited thereto.

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

  Examples of (poly) oxyethylene mono (meth) acrylates include, but are not limited to, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and methoxy Examples include (meth) acrylic acid diethylene glycol, (meth) acrylic acid tetraethylene glycol, and methoxy (meth) acrylic acid tetraethylene glycol.

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

  The proportion of the hydroxyl group-containing vinyl monomer in the total amount of vinyl monomers used for the production of the polymer (A) is not limited to the following, but preferably from 0 to 80 from the viewpoint of the water resistance of the coating film. It is mass%, More preferably, it is 0.1-50 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.

  Among the vinyl monomers described above, when a glycidyl group-containing vinyl monomer is used, 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 vinyl monomer is preferably 0 to 50% by mass.

  The vinyl compound having a secondary and / or tertiary amide group is not limited to the following, and examples thereof include N-alkyl-substituted (meth) acrylamide and N-alkylene-substituted (meth) acrylamide.

  Examples of 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, Nn-propyl (meth) acrylamide, N-methyl-Nn-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-vinylacetamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide and the like.

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

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

The polymer (A) is preferably produced by a polymerization reaction between the vinyl monomer and the hydrolyzable silicon compound described above.
In such a case, the hydrolyzable silicon compound used to produce the polymer (A) is not limited to the following, but for example, a compound represented by the following formula (1), a silane coupling agent , And their condensates are preferred.

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 from 1 to 4, y is an integer from 0 to 3, and satisfies the relationship x + y = 4.
When there are a plurality of Ws, and when there are a plurality of Rs, each W and R may be the same as or different from each other.

  As a compound represented by said 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 silane coupling agents described above, a silane coupling agent having at least a vinyl polymerizable group and / or a thiol group is preferable, and a silane coupling agent having at least a vinyl polymerizable group is more preferable.

  Since the vinyl polymerizable group and the thiol group have high reactivity with the above-mentioned vinyl monomer, chemical bonds can be efficiently formed by a copolymerization reaction or a chain transfer reaction with the vinyl monomer. Therefore, by using a silane coupling agent having a vinyl polymerizable group or a thiol group, it can be efficiently combined with other components (for example, a vinyl monomer) constituting the component (A). By using such a component (A) in which a hydrolyzable silicon compound (or a polymerization product thereof) and / or a vinyl monomer (or a polymerization product thereof) is combined by a chemical bond, weather resistance is achieved. It is possible to obtain a coating film having further improved strength and the like. The operation 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 to the following as a silane coupling agent which has a thiol group, For example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc. are mentioned as a preferable thing.

The hydrolyzable silicon compound and the silane coupling agent represented by the formula (1) are not limited to the following, 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) acryloyloxypropyltrii 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 Monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane;

  Among these, tetraalkoxysilanes, trialkoxysilanes and dialkoxysilanes are preferable, and tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, dimethyldimethoxysilane From the viewpoint that the hydrolysis rate is high, tetramethoxysilane and tetraethoxysilane which are tetrafunctional silicon alkoxides are more preferable.

  When the compound represented by the formula (1) or the condensate of the silane coupling agent is applied as a hydrolyzable silicon compound used for producing the polymer (A), the compound represented by the formula (1) 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.

These silicon alkoxides and silane coupling agents represented by the formula (1) may be used alone or in combination of two or more.
Among these, from the viewpoint of improving the performance of the aqueous composition and the coating film obtained, it is preferable to use a silicon alkoxide represented by the formula (1) and a silane coupling agent in combination, tetraethoxysilane, methyltrimethoxysilane, More preferably, at least one selected from the group consisting of phenyltrimethoxysilane and dimethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane are used in combination.

  The total amount of the silane coupling agent having at least 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 0.1-10 mass parts.

  As the hydrolyzable silicon compound, in addition to those described above, cyclic siloxane oligomers 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 the cyclic siloxane oligomers, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferable from the viewpoint of reactivity and the like.
(A) When manufacturing a component, a titanium alkoxide, a zirconium alkoxide, those condensation products, or a chelate can also be used together with a 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, tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec- 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 zirconium alkoxide is used as the condensate, the weight average molecular weight in terms of polystyrene of the condensate is not particularly limited, but is preferably 200 to 5000, more preferably 300 to 1000.

  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 to 15/85.

The component (A) preferably contains 20 to 70% by mass of a structural unit derived from dimethyldimethoxysilane in terms of hydrolysis condensate. The lower limit 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 condensate. The upper limit of the content of structural units derived from dimethyldimethoxysilane in the component (A) is preferably 70% by mass or less, more preferably 65% by mass or less in terms of hydrolysis condensate. 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.
In addition, the hydrolysis condensate here is a condensate in which a reactive group (for example, an alkoxy group) of dimethyldimethoxysilane is converted into a silanol bond by hydrolysis or condensation reaction. The content (mass%) in terms of hydrolysis condensate of dimethyldimethoxysilane is the content (total solids) of the polymer (A) determined as the heating residue of the aqueous dispersion (AD) component containing the polymer (A). The amount of dimethyldimethoxysilane can be determined by the following 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 It is done.
The molecular weight of the chelating agent is not limited to the following, but is preferably 10,000 or less.
By using these chelating agents, the polymerization rate of the hydrolyzable silicon compound or the like can be controlled, and the polymerization stability in the presence of water and an emulsifier is further improved.
Although the compounding quantity of a chelating agent is not specifically limited, It is preferable that it is a ratio of 0.1 mol-2 mol with respect to 1 mol of free metal ions to coordinate.

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; , 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 ethers, polycarbonates 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, a reactive emulsifier having a radical polymerizable double bond (hereinafter sometimes simply referred to as a reactive emulsifier) is preferable. By using such a reactive emulsifier, the water dispersion stability of the polymer (A) becomes very good, and the water resistance of the resulting coating film is further improved.

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

As an anionic reactive emulsifier, for example, alkylallylsulfosuccinate (for example, Sanyo Kasei Co., Ltd., “Eleminol (trademark) JS-20”, for example, Kao Corporation, “Latemuru (trademark) S-120”, “Latemul S-180A”, “Latemul S-180”, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfate ester (for example, “Aqualon ™ HS-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, “ADEKA rear soap (trademark) SE manufactured by ADEKA) -10N ", etc.), ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypoly Xylene (for example, “AQUALON KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), styrene sulfonate (for example, “Spinomer (trademark) NaSS” manufactured by Tosoh Organic Chemical Co., Ltd.), α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, “ADEKA rear soap (trademark) SR-1025” manufactured by ADEKA) ), Sulfate ester of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, “Latemul (trademark) PD-104” manufactured by Kao Corporation) and the like.
Among these, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene Sulfate ester salts are preferred.

  Further, the nonionic reactive emulsifier is not limited to the following, and examples include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene. (For example, (made by ADEKA, "ADEKAREASOAP NE-20", "ADEKAREASOAP NE-30", "ADEKAREASOAP NE-40", etc. may be mentioned), polyoxyethylene alkyl propenyl phenyl ether (for example, , “Aqualon RN-10”, “Aqualon RN-20”, “Aqualon RN-30”, “Aqualon RN-50”, etc.), α- [2-[(allyloxy) )-(Alkyloxymethyl) ethyl] -ω-hydroxypolyoxyethylene (eg, Adeka, Inc., “Adekalyaso” (Trademark) ER-10 "), polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example," Latemul (trademark) PD-420 "manufactured by Kao Corporation) And the like.

  The use amount of the above-mentioned emulsifier is preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of raw materials (for example, hydrolyzable silicon compound and vinyl monomer) of the component (A) which is a polymer. More preferably, it is 0.001-5 mass parts. By making the usage-amount of an emulsifier into the said range, superposition | polymerization stability improves further and the water resistance of a coating film becomes much better.

The polymerization of the vinyl monomer and the hydrolyzable silicon compound is preferably carried out in the presence of a polymerization catalyst.
The polymerization catalyst for the vinyl monomer is not particularly limited, but a radical polymerization catalyst that causes addition polymerization of the vinyl monomer by radical decomposition itself by heat or a reducing substance is preferable.
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.

Examples of the radical polymerization catalyst include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2, 2 -Azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.
Although the compounding quantity of a radical polymerization catalyst is not specifically limited, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of total amounts of a vinyl monomer. In addition, when acceleration of the polymerization rate and efficient polymerization at a low temperature (for example, 70 ° C. or lower) are desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite is used as a radical polymerization catalyst. It is preferable to use 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 octylate, 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.

A preferred method for obtaining the component (A) is, 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. Can be mentioned.
The specific method of emulsion polymerization is not particularly limited. For example, the vinyl monomer and the hydrolyzable silicon compound are dropped into the reaction vessel as they are or in an emulsified state, all at once or in a divided manner or continuously. And 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 are not limited to the above conditions 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. Here, the solid content is the ratio of the solid content in the emulsion.

  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 (borax, etc.), sodium hydrogen carbonate, ammonia and the like.

  (A) Although it does not specifically limit in the method of manufacturing a component, For example, after superposing | polymerizing a hydrolyzable silicon compound and a vinyl monomer in presence of a solvent in the presence of water and an emulsifier, it is superposition | polymerization production | generation. It is also possible to employ a method of further adding water until the product becomes an emulsion. In addition, it is preferable to obtain a polymer by emulsion polymerization from the viewpoint that control of the particle diameter of the obtained (A) component is easy.

  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 of polymerizing a hydrolyzable silicon compound and a vinyl monomer in the presence of the obtained seed particles (second stage).

The production of the component (A) by the two-stage emulsion polymerization is carried out by supplying the first series (vinyl monomer and / or hydrolyzable silicon compound) and emulsion polymerization to supply the first series, followed by the first stage. The second series (vinyl monomer and / or hydrolyzable silicon compound) is supplied, and this is carried out by a two-stage polymerization process consisting of a second stage polymerization in which emulsion polymerization is further carried out in an aqueous medium. 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 for adding the raw material in the multi-stage emulsion polymerization, a method of preparing seed particles (core) in the first stage polymerization and then adding another monomer or the like thereafter is preferable. This increases the particle diameter of the polymer particles obtained by the second stage polymerization without changing the ratio of the volume average particle diameter / number average particle diameter of the seed particles (core) obtained by the first stage polymerization. It is also possible to do.
When performing multistage emulsion polymerization of three or more stages, the number of stages of polymerization may be increased in the same manner as in the two-stage polymerization.

(Silicon dioxide (B))
The coating film of the present embodiment contains silicon dioxide (B) (hereinafter, may be simply referred to as component (B)).
Silicon dioxide (B) is preferably obtained from 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 manufacturing method of colloidal silica is not specifically limited, For example, it can also prepare with 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.
By setting the number average particle diameter of the component (B) to 1 nm or more, the storage stability of the aqueous composition for obtaining a coating film is further improved. 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 diameter 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 ™ AT-20Q” manufactured by ADEKA, “Crebosol ™ 20H12” manufactured by Clariant Japan, and "Clevozole 30 CAL 25" and the like can be mentioned.

  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 “Adelite AT-20”, “Adelite AT-30”, “Adelite AT-20N”, “Adelite AT-30N”, “Adela” "AT-20A", "Adelite AT-30A", "Adelite AT-40" and "Adelite AT-50"; "Clevosol 30R9", "Clebosol 30R50", "Crebosol 50R50" manufactured by Clariant Japan, 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 commercially available products include, but are not limited to, “MA-ST-M (methanol dispersion type with a particle size of 20 to 25 nm)”, “IPAST (particle size) manufactured by Nissan Chemical Industries, Ltd. “10-15 nm isopropyl alcohol dispersion type)”, “EG-ST (ethylene glycol dispersion type with particle diameter of 10-15 nm)”, “EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70-100 nm)”, “ NPC-ST (ethylene glycol monopropyl ether 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).

Content of (B) component in the coating film of this embodiment becomes like this. Preferably it is 50.0-95.0 mass%, More preferably, it is 50.0-84.0 mass%, More preferably, it is 56.0. -84.0 mass%.
By setting the content of the component (B) in the coating within the above range, a coating with further improved appearance, weather resistance, stain resistance, sealing stain resistance, and bio stain resistance on a dark base material is obtained. be able to.

(Inorganic oxide (C) having photocatalytic activity)
The coating film of the present embodiment contains an inorganic oxide (C) having a photocatalytic activity (hereinafter, may be described as a component (C)). Thereby, photocatalytic activity and hydrophilicity can be expressed by irradiating light to a coating film.
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 viewpoints of chemical stability, toxicity, environment, and the like. Titanium oxide may have any crystal structure of anatase type, rutile type or brookite type.

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

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

The method of modifying the surface of the component (C) will be described using titanium oxide as an example.
The method for modifying the surface of titanium oxide is not particularly limited, and examples thereof include a method of adding a silicon compound to a slurry of titanium oxide and precipitating silicon hydrated oxide through steps such as neutralization treatment. Be

  It does not specifically limit as a silicon compound, For example, water-soluble alkali metal silicate salts, such as sodium silicate, can be used. Among these, sodium silicate is preferable from the viewpoint of being colorless and not coloring the titanium oxide sol.

  The amount of modification treatment of silicon with a hydrous oxide is preferably 3 to 25% by mass, more preferably 4 to 23% by mass, and still more preferably 5 to 20% by mass, based on the oxide based on titanium oxide.

  Since the modification treatment amount is not less than the above lower limit value, an increase in the amount of active oxygen species can be suppressed, so that damage to the underlying coating film can be prevented. Moreover, since the aggregation of a titanium oxide can be suppressed and the viscosity raise of sol can also be suppressed because the said modification process amount is below the said upper limit, dispersibility and transparency improve further.

As the component (C), an inorganic oxide in which the surface of particles having photocatalytic activity is modified, and an inorganic oxide in which a metal element such as gold, silver, copper, or iron is supported on the inorganic oxide is used. You can also.
The method for supporting the metal on the component (C) is not particularly limited. For example, titanium chloride whose surface is modified is added with copper chloride dihydrate, silver nitrate, tetrachloroauric acid tetrahydrate, and the like. Examples thereof include methods obtained by reacting with trisodium citrate dihydrate, tannic acid and the like. The amount of supported metal is preferably 0.1 to 5% by mass, more preferably 0.1 to 4.8% by mass, and more preferably 0.1 to 4.6% by mass of the metal based on titanium oxide. % Is more preferable.
By setting the supported amount in the above-mentioned range, it is possible to suppress the sedimentation of the metal-supporting titanium oxide, and to obtain a coating film excellent in biofouling resistance.

Although content of (C) component in the coating film of this embodiment is not specifically limited, Preferably it is 2.0-34.0 mass%, More preferably, it is 3.0-34.0 mass%, Furthermore, Preferably it is 3.0-29.0 mass%.
By making content of (C) component into the said range, the coating film which was further excellent in the external appearance in a dark-colored base material, a weather resistance, stain resistance, sealing stain resistance, and bio-fouling resistance can be obtained.

(Fluorocarbon surfactant (D))
The coating film of this embodiment contains a fluorocarbon surfactant (D) (hereinafter may be referred to as component (D)).
By containing the component (D), the coating film of the present embodiment can further suppress troubles in appearance such as craters due to repelling or entrainment of bubbles. Furthermore, the uniformity of the coating is further improved.
Although it is not certain as these reasons, it is estimated that the surface tension of the water-based paint for obtaining a coating film can be reduced by containing (D) component. The operation of the present embodiment is not limited to these.

Although it does not specifically limit as (D) component, Amphoteric surfactant is preferable.
The amphoteric surfactant is not particularly limited, and examples thereof include nonionic amphoteric surfactants, anionic amphoteric surfactants, cationic amphoteric surfactants and the like. Preferable specific examples include amphoteric surfactants having a C 3-20 perfluoroalkyl group.

  Specific examples of the amphoteric surfactant having a C 3-20 perfluoroalkyl group include, but are not limited to, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl amine oxide, Perfluoroalkyl ethylene oxide adducts, perfluoroalkyl compounds having an anionic group and a cationic group, and the like can be mentioned. 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.

The perfluoroalkyl sulfonate is not limited to the following, and examples thereof include ammonium salts and potassium salts of perfluorooctane sulfonic acid.
As the perfluoroalkyl carboxylate, for example, a commercially available product can also be used. Examples of such commercially available products include, but are not limited to, “Surflon S-211” manufactured by AGC Seimi Chemical Co., Ltd.
As perfluoroalkylamine oxide, for example, commercially available products can also be used. Examples of such commercially available products include, but are not limited to, “Surflon S-241” manufactured by AGC Seimi Chemical Co., Ltd.
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, “Megafac F-444” manufactured by DIC, “Surflon S-242” manufactured by AGC Seimi Chemical, and the like.
As a perfluoroalkyl compound having an anionic group and a cationic group, for example, a commercially available product can be used. Examples of such commercially available products include, but are not limited to, “Surflon S-231”, “Surflon S-232”, “Surflon S-233” manufactured by AGC Seimi Chemical Co., Ltd., and the like.
One of these may be used alone, or two or more may be used in combination.

Although content of (D) component in the coating film of this embodiment is not specifically limited, Preferably it is 0.125 mass%-17.5 mass%, More preferably, it is 0.125 mass%-10.0. % By mass, more preferably 0.175% by mass to 10.0% by mass.
By making the content of component (D) within the above range, the appearance of craters and the like due to repellency and entrainment of bubbles is further improved, and the appearance, weather resistance, stain resistance, and biofouling resistance on dark base materials are improved. An even more excellent coating film can be obtained.

(Fading dye (E))
The coating film of the present embodiment may contain a fading dye (E) (hereinafter sometimes simply referred to as the component (E)).
When the coating film of the present embodiment contains the color-fading pigment (E), it is possible to prevent problems such as forgetting to paint the water-based paint for obtaining the coating film, double coating, coating unevenness and the like.
(E) As a component, the thing which loses color by irradiation of sunlight and does not impair the design of the base is preferable. Although the time until 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 Less than a day.
The component (E) is not particularly limited as long as it has the property of being decolored by irradiation with sunlight. For example, methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosin, new coxin, 1 type selected from the group consisting of Phloxin, Rose Bengal, Acid Red, and First Green FCF. Among these, methylene blue is more preferable from the viewpoint of good color developability and fast decoloration rate.
These may be used alone or in combination of two or more.

The content of the component (E) in the coating film of the present embodiment is not particularly limited, but is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.9% by mass. More preferably, it is 0.1-0.8 mass%.
By making content of (E) component into the said range, the coating film which the appearance in a dark-colored base material, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance are further excellent can be obtained.

(Defoamer (F))
The coating film of the present embodiment may contain an antifoaming agent (F) (hereinafter sometimes referred to as "(F) component").
By containing the antifoaming agent (F), it is possible to further suppress the appearance troubles such as craters and the like of the coating film of the present embodiment due to the inclusion of repelling and bubbles.

The antifoaming agent (F) is not particularly limited, and for example, mineral oil-based, polyether-based, and silicone-based antifoaming agents are used, and mineral oil-based antifoaming agents are preferable.
Although it does not specifically limit as a mineral oil type antifoamer, A commercial item can also be used.
Examples of hydrophobic silica type mineral oil based defoamers include, but are not limited to, for example, NOPCO 8034, NOPCO 8034-L, SN deformer AP, SN deformer H-2, SN deformer TP-33, SN deformer VL, SN deformer 113, SN deformer 154, SN deformer 154S, SN deformer 313, SN deformer 314, SN deformer 316, SN deformer 317, SN deformer 318, SN deformer 319, SN deformer 321, SN deformer 323, SN deformer 364, SN deformer 414, SN deformer 456, SN deformer 474, SN deformer 476-L, SN deformer 480, SN deformer 777, SN deformer -1341, SN deformer 1361 (manufactured by San Nopco) BYK-1740 (manufactured by BYK) may be mentioned, and the metal soap type mineral oil-based antifoaming agent is not limited to the following, for example, Nopco DF -122, Nopco DF-122-NS, Nopco NDW, Nopco NXZ, SN deformer 122-SV, SN deformer 269, SN deformer 1010 (manufactured by San Nopco), and as an amide wax type mineral oil antifoaming agent, For example, but not limited to, NOPCO 267-A, NOPCO DF-124-L, SN deformer TP-39, SN deformer 477T, SN deformer 477-NS, SN deformer 479, SN deformer 1044, SN deformer 1320, SN deformer 1340, N Defoamer 1360, SN Defoamer 5100 (manufactured by San Nopco Limited) and the like.
These may be used alone or in combination of two or more.
Among these defoamers, preferred are mineral oil-based defoamers of hydrophobic silica type.

  Although content of (F) component in the coating film of this embodiment is not specifically limited, Preferably 0.024 mass%-1.250 mass%, More preferably, 0.00 400 mass%-1.2000 mass %, More preferably 0.0625 to 1.1000% by mass. By setting the content of the component (F) in the above range, the appearance such as crater due to the inclusion of repelling and bubbles is further improved, and the appearance on a dark base material, weather resistance, stain resistance, and biological stain resistance A more excellent coating film can be obtained.

In the coating film of this embodiment, the mass ratio of the fluorocarbon surfactant (D) to the antifoaming agent (F) (fluorocarbon surfactant (D) / antifoaming agent (F)) is preferably 2/1 to The ratio is preferably 10/1, more preferably 2/1 to 90/1, still more preferably 2.3 / 1 to 90/1. By setting the mass ratio (fluorocarbon surfactant (D) / defoaming agent (F)) in the above-described range, the coating film of the present embodiment further improves the appearance such as crater due to the inclusion of repelling and bubbles, and is concentrated It is possible to obtain a coating film with further excellent appearance, weather resistance, stain resistance, and biofouling resistance on the color base material.
The above-described coating film may be obtained, for example, by mixing other components in the above-described coating film as necessary.

The coating film of the present embodiment can also be obtained, for example, by mixing other components with the water-based composition for obtaining the coating film, if necessary.
Examples of the other components include, but are not limited to, for example, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skin agents, dispersing agents, wetting agents, light Stabilizers, antioxidants, UV absorbers, film forming aids, rust inhibitors, plasticizers, thickeners, lubricants, reducing agents, preservatives, fungicides, algaecides, deodorants, yellowing Examples thereof include an inhibitor, an antistatic agent, and a charge adjusting agent.
These may be used alone or in combination of two or more.

  Examples of the pigment include inorganic oxides having no photocatalytic activity. Although it is not limited to the following, for example, copper (II) oxide (manufactured by CIK Nanotech Co., Ltd., "CUAP15WT% -G180"), zinc oxide, aluminum oxide and the like can be mentioned.

  Although content of the pigment in the coating film of this embodiment is not specifically limited, Preferably it is 0.01-5.0 mass%, More preferably, it is 0.02-4.5 mass%. By setting the pigment content in the above range, it is possible to obtain a coating film having excellent appearance on a dark base material and excellent biofouling resistance.

[Thickness of coating film]
It is preferable that the coating film of this embodiment is 0.15 micrometer or more and less than 2.0 micrometers. The coating film of this embodiment is more preferably 0.15 μm or more and 1.5 μm or less, further preferably 0.15 μm or more and 1.0 μm or less, and still more preferably 0.15 μm or more and 0.9 μm or less. When the thickness of the coating film is within the above range, it becomes easy to control the crack width of the coating film, and the appearance, weather resistance, stain resistance, sealing stain resistance, and bio stain resistance on the dark base material are further improved. An excellent coating film can be obtained.
The coating film of the present embodiment can be obtained, for example, by drying a water-based paint, and the solid content (solid content) in the water-based paint is not particularly limited. Therefore, it is preferably 0.5 to 15.0% by mass, more preferably 0.5 to 10.0% by mass, and further preferably 1.0 to 8.0% by mass. By setting the solid content of the water-based paint to the above lower limit value or more, the stain resistance is further improved. Transparency improves further by making content of solid content in an aqueous composition below the said upper limit. Solid content here can be calculated | required by the method as described in the Example mentioned later. Furthermore, depending on the application of the coating film, it may be required that the film thickness of the coating film is thin. Even in such a case, the solid content in the aqueous composition is not more than the above upper limit value, so that the physical properties such as weather resistance, stain resistance, sealing stain resistance, and biofouling resistance can be achieved while having a thin film thickness. It can be set as the coating film excellent in. 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.

  The coating film can be obtained, for example, by applying a water-based paint and drying, and can be applied by a suitable method as appropriate. 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 Method and flexographic printing method. For example, in the case of the spray spraying method, a coating overlap portion occurs, but the thickness of the coating film of the present embodiment is a film thickness at a set coating amount without coating overlap.

  The coating film of this embodiment is obtained by, for example, applying a water-based paint to a predetermined application target and then drying 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.

[Composite coating film]
The composite coating film of the present embodiment includes an overcoat layer obtained from the coating film of the present embodiment, and at least two layers of an undercoat layer. In addition, the undercoat layer in the composite coating film of the present embodiment contains a polymer and an anti-algal and / or anti-fungal agent.
The composite coating film of this embodiment can be obtained, for example, by applying a water-based paint capable of obtaining the coating film to the surface of the undercoat layer and drying it.

(Polymer contained in undercoat layer)
The undercoat layer constituting the composite coating film of the present embodiment further contains a polymer. Thereby, a composite coating film excellent in weather resistance can be formed. The operation of the present embodiment is not limited to these.

  Although it does not specifically limit as a polymer, For example, the polymer obtained by methods, such as emulsion polymerization, can be used. Specific examples of the polymer include, but are not particularly limited to, a polymer obtained by performing any one of radical polymerization, anionic polymerization, and cationic polymerization in an aqueous medium.

The polymer contained in the undercoat layer of the composite coating film of the present embodiment is not limited to the following, for example, poly (meth) acrylate polymers, polyvinyl acetate polymers, vinyl acetate- (meth) ) Acrylic polymer, ethylene vinyl acetate polymer, silicone polymer, fluorine polymer, polybutadiene polymer, styrene butadiene polymer, NBR polymer, polyvinyl chloride polymer, chlorinated polypropylene polymer Homopolymers or copolymers represented by polymers, polyethylene polymers, polystyrene polymers, vinylidene chloride polymers, polystyrene- (meth) acrylate polymers, styrene-maleic anhydride polymers, etc .; Silicone-modified (meth) acrylic polymer, fluorine- (meth) acrylic polymer, (meth) acrylic-silico System polymer, an epoxy - (meth) acrylic polymer; modified copolymer represented by like.
These may be used alone 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 above-mentioned polymer homopolymers, copolymers, modified copolymers, etc. (hereinafter sometimes referred to as “polymers”) are preferably in the form of an aqueous dispersion. Preferred embodiments 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. Although these are not limited to the following, for example, they can be obtained by emulsion polymerization of a monomer such as (meth) acrylic acid ester or a hydrolyzable silicon compound described later.

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

The polymer can use a vinyl monomer as a polymerization monomer.
Examples of the vinyl monomer that can be used for producing the polymer include, but are not limited to, (meth) acrylic esters, aromatic vinyl compounds, vinyl cyanide compounds, and carboxyl group-containing vinyl compounds. And vinyl monomers containing functional groups such as hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, vinyl compounds having secondary and / or tertiary amide groups, and anionic vinyl compounds.

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

  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 include tetraethylene glycol di (meth) acrylate.

  Examples of the aromatic vinyl compound include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, 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. Examples thereof include half esters of dibasic acids such as acids. The carboxyl group can be introduced into the polymer by using a carboxyl group-containing vinyl monomer. Thereby, it is estimated that the stability as an emulsion can be further improved and a high resistance to an external dispersion breaking action can be imparted to the coating film. The operation 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 amount of use of the carboxyl group-containing vinyl monomer in the total amount of vinyl monomers used for producing the polymer is preferably 0 to 50% by mass from the viewpoint of water resistance.

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

  Examples of (poly) oxyethylene mono (meth) acrylates include, but are not limited to, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and methoxy Examples include (meth) acrylic acid diethylene glycol, (meth) acrylic acid tetraethylene glycol, and methoxy (meth) acrylic acid tetraethylene glycol.

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

  The proportion of the hydroxyl group-containing vinyl monomer in the total amount of vinyl monomers used for the production of the polymer is not limited to the following, but preferably from 0 to 95% by mass from the viewpoint of water resistance of the coating Although there is, it is not limited to this.

  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.

  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 N-alkyl-substituted (meth) acrylamides include, but are not limited to, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethylacrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-methyl-Nn-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N- (meth) 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-vinylacetamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide and the like.

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

When the polymer is produced by a polymerization reaction, a chain transfer agent may be used 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. Examples include allyl compounds.
These may be used alone or in combination of two or more.

The polymer is preferably produced by the polymerization reaction of the above-mentioned vinyl monomer and hydrolyzable silicon compound.
In such a case, the hydrolyzable silicon compound used for producing the polymer is not limited to the following, but for example, a compound represented by the following formula (1), a silane coupling agent, and these The condensate of is mentioned as a preferable thing.

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 from 1 to 4, y is an integer from 0 to 3, and satisfies the relationship x + y = 4.
When there are a plurality of Ws, and when there are a plurality of Rs, each W and R may be the same as or different from each other.

  The compound represented by the formula (1) is not limited to the following, and examples thereof include silicon alkoxide represented by the formula (1).

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 silane coupling agents described above, a silane coupling agent having at least a vinyl polymerizable group and / or a thiol group is preferable, and a silane coupling agent having at least a vinyl polymerizable group is more preferable.

  Since the vinyl polymerizable group and the thiol group have high reactivity with the above-mentioned vinyl monomer, chemical bonds can be efficiently formed by a copolymerization reaction or a 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 polymer. By using such a polymer in which a hydrolyzable silicon compound (or a polymerization product thereof) and / or a vinyl monomer (or a polymerization product thereof) is combined by a chemical bond, weather resistance and strength are improved. The composite coating film which etc. improved further can be obtained. The operation 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 to the following as a silane coupling agent which has a thiol group, For example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc. are mentioned as a preferable thing.

The hydrolyzable silicon compound and the silane coupling agent represented by the above formula (1) are not limited to the following, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra Tetraalkoxysilanes such as isopropoxysilane and tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-o Tiltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- Chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- Hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyl Limethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) ) Acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropylto Trialkoxysilanes such as lysopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n- Pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane Dialkoxy such as di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane Examples of the silanes include 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.

  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 above formula (1) in combination with a silane coupling agent from the viewpoint of the performance improvement of the aqueous composition and the obtained coating film, and tetraethoxysilane, methyltrimethoxy More preferably, at least one selected from the group consisting of silane, phenyltrimethoxysilane and dimethyldimethoxysilane is used in combination with 3- (meth) acryloxypropyltrimethoxysilane.

  When producing a polymer, 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, tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec- Examples include butoxytitanium, tetra-tert-butoxytitanium and the like.

  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.

  In producing the polymer, a chelating agent that forms a chelated product by coordinating with the free metal ion of the metal compound may be used in combination.

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

Emulsifying agents that can be used for producing the polymer include, but are not limited to, for example, alkyl benzene sulfonic acid, alkyl sulfonic acid, alkyl sulfo succinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, Acidic emulsifiers such as polyoxyethylene distyryl phenyl ether sulfonic acid; alkali metal (Li, Na, K etc.) salts of the acidic emulsifiers, ammonium salts of the acidic emulsifiers; anionic surfactants such as fatty acid soaps; Quaternary ammonium salts such as trimethyl ammonium bromide, alkyl pyridinium bromide, imidazolinium laurate, pyridinium salts, cationic surfactants of the imidazolinium salt type; polyoxyethylene alkyl aryl ethers, polyoxyethylene Rensorubitan fatty acid esters, polyoxyethylene polyoxypropylene block copolymer, nonionic surface active agent polyoxyethylene distyryl phenyl ether; reactive emulsifier or the like having a radical polymerizable double bond.
Among these emulsifiers, a reactive emulsifier having a radical polymerizable double bond (hereinafter sometimes simply referred to as a reactive emulsifier) is preferable. By using such a reactive emulsifying agent, the water dispersion stability of the polymer becomes very good, and the water resistance of the resulting coating film is further improved.

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

As an anionic reactive emulsifier, for example, alkyl allyl sulfosuccinate (for example, “Eleminol (registered trademark) JS-20”, manufactured by Sanyo Chemical Industries, Ltd., manufactured by Kao Corporation, “Latemul (registered trademark) S-120”, “Latemul, S-180A "," Latemul S-180 ", etc.), polyoxyethylene alkylpropenyl phenyl ether sulfuric acid ester salt (eg," Aqualon (trademark) HS-10 ", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc.) Α- [1-[(Allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (eg, “ADECARIASOAPTM SE-10N” manufactured by ADEKA Co., Ltd.) Etc.), ammonium-.alpha.-sulfonato-.omega.-1- (allyloxymethyl) alkyloxypolyoxye. Ren (for example, “Aqualon KH-1025” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., etc.), styrene sulfonate (eg, manufactured by Tosoh Organic Chemicals, “SpinomerTM NaSS”, etc.), α- [2-[(Allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene sulfuric acid ester salt (eg, “ADEKAREASOAPTM SR-1025” manufactured by ADEKA Corporation) And sulfuric acid ester salts of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, Kao Corporation “Latem.RTM. PD-104” may be mentioned) and the like.
Among these, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene Sulfate ester salts are preferred.

  Further, the nonionic reactive emulsifier is not limited to the following, and examples include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene. (For example, (made by ADEKA, "ADEKAREASOAP NE-20", "ADEKAREASOAP NE-30", "ADEKAREASOAP NE-40", etc. may be mentioned), polyoxyethylene alkyl propenyl phenyl ether (for example, , “Aqualon RN-10”, “Aqualon RN-20”, “Aqualon RN-30”, “Aqualon RN-50”, etc.), α- [2-[(allyloxy) )-(Alkyloxymethyl) ethyl] -ω-hydroxypolyoxyethylene (eg, Adeka, Inc., “Adekalyaso” (Registered trademark) ER-10 "and the like), polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (eg, Kao Corp.," Latem.RTM. PD-420 "and the like). And the like.

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

The polymerization of the vinyl monomer and the hydrolyzable silicon compound is preferably carried out in the presence of a polymerization catalyst.
The polymerization catalyst for the vinyl monomer is not particularly limited, but a radical polymerization catalyst that causes addition polymerization of the vinyl monomer by radical decomposition itself by heat or a reducing substance is preferable.
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.

Examples of the radical polymerization catalyst include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2, 2 -Azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.
Although the compounding quantity of a radical polymerization catalyst is not specifically limited, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of total amounts of a vinyl monomer. In addition, when acceleration of the polymerization rate and efficient polymerization at a low temperature (for example, 70 ° C. or lower) are desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite is used as a radical polymerization catalyst. It is preferable to use 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 octylate, 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.

Suitable methods of obtaining the polymer include, 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. .
The specific method of emulsion polymerization is not particularly limited. For example, the vinyl monomer and the hydrolyzable silicon compound are dropped into the reaction vessel as they are or in an emulsified state, all at once or in a divided manner or continuously. And 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 are not limited to the above conditions depending on the reaction conditions and the like.

The amount of solid content in the emulsion obtained by the emulsion polymerization is not particularly limited, but is preferably 0.1 to 70% by mass, and more preferably 1 to 55% by mass.
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 polymer is not particularly limited. For example, after polymerizing the hydrolyzable silicon compound and the vinyl monomer in the presence of a solvent, if necessary, in the presence of water and an emulsifier, a polymerization product is obtained. It is also possible to employ a method in which water is further added to form an emulsion. From the viewpoint of easy control of the particle diameter of the obtained polymer, it is preferable to obtain the polymer by emulsion polymerization.

The content of the polymer in the undercoat layer of the composite coating film of the present embodiment is not particularly limited, but preferably 0.1 to 80% by mass, more preferably 1.0 to 75% by mass in the undercoat layer. More preferably, it is 5.0-70 mass%.
By setting the content of the polymer in the undercoat layer of the composite coating film of the present embodiment in the above-mentioned range, the appearance on a dark substrate, the weather resistance, the stain resistance, the sealing stain resistance and the biological stain resistance are further enhanced. An excellent composite coating film can be obtained.

(An algal and antifungal agent contained in the undercoat layer)
It is preferable that the subbing layer which comprises the composite coating film of this embodiment further contains an antialgal and / or antifungal agent.
Thereby, even in a place where it is difficult to be irradiated with light such as sunlight, it is possible to form a composite coating film excellent in biofouling resistance. The operation of the present embodiment is not limited to these.

The anti-algal agent and / or the anti-fungal agent are not particularly limited, and, for example, organic iodine compounds, alcohol compounds, nitrile compounds, disulfide compounds, thiocarbamate compounds, nitrogen-containing ring compounds, etc. It can be mentioned. Among these, a nitrogen-containing ring compound is preferable. Examples of the nitrogen-containing cyclic compound include thiazoline compounds, isothiazoline compounds, triazine compounds, and imidazole compounds.
Among these, one or more selected from the group consisting of isothiazoline compounds, triazine compounds, and imidazole compounds is preferable, and one or more selected from the group consisting of isothiazoline compounds and triazine compounds is more preferable.
Examples of particularly excellent algae-proofing properties include triazine compounds.
Especially as a thing excellent in mold resistance, a thiazoline type compound, an isothiazoline type compound, an imidazole type compound etc. are mentioned, for example.
In the subbing layer of the composite coating film of the present embodiment, one having both algal resistance and mildew resistance may be used, and as such, for example, an isothiazoline compound containing a chlorine atom in the molecule, etc. Can be mentioned.
These may be used alone or in combination of two or more.

  A commercial item can also be used as a thiazoline type-compound. Examples of such commercially available products include “Milcut-180” and “Biocut-LC3” manufactured by Nippon Soda Co., Ltd., “Amorden ALK” manufactured by Yamato Chemical Co., Ltd. and the like.

A commercial item can also be used as an isothiazoline type compound. As such commercial products, for example, "Bio-cut-TR120" manufactured by Nippon Soda Co., Ltd., "PROXEL GXL" manufactured by Arch Chemicals, "PROXEL BDN", "KLARIX 4000" manufactured by Dow Chemical, "ROZONE 2000" “ROCIMA 252”, “ROCIMA 200”, “ROCIMA 345”, “ROCIMA 350”, “ROCIMA 553”, “BIOBAN 551S”, “Skein M-8” and the like.
A commercial item can also be used as a triazine type compound. Examples of commercially available products include “Biocut-N35”, “DP-2159”, and “DP-2615” manufactured by Nippon Soda Co., Ltd. “DP-2619”, “DP-2623”, “Amorden NBP-8” manufactured by Daiwa Chemical Industry Co., Ltd., “Amorden NBPconc”, “Sun Alga 1907” manufactured by Sankyo Kasei Co., Ltd., and the like.
A commercial item can also be used as an imidazole compound. Examples of commercially available products include “Bio-cut-N35”, “Bio-cut-AF40” and “DX-2” manufactured by Nippon Soda Co., Ltd., “ROCIMA 363” manufactured by Dow Chemical Co., and the like.

  Although the content of the antialgal and / or antifungal agent in the undercoat layer is not particularly limited, it is preferably 0.01% by mass to 30.0% by mass, more preferably 0.01% by mass to 15.0%. It is mass%, More preferably, it is 0.1 mass%-15.0 mass%. By setting the content of the anti-algae and / or fungicide component in the undercoat layer to the lower limit value or more, the biofouling resistance of the composite coating film is further improved, and by setting the content to the upper limit value or less, the composite coating The weather resistance of the film is further improved.

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

  The subbing layer of the composite coating film of the present embodiment can also be mixed with other components as necessary, for example, in addition to the above-described polymer and the anti-algal and / or anti-fungal agent.

Examples of the other components include, but are not limited to, for example, a freezing stabilizer, a matting agent, a crosslinking reaction catalyst, a pigment, a curing catalyst, a crosslinking agent, a filler, an antiskinning agent, a dispersant, Wetting agent, light stabilizer, antioxidant, UV absorber, film forming aid, rust inhibitor, plasticizer, thickener, lubricant, reducing agent, preservative, deodorant, anti-yellowing agent, static Examples thereof include an antistatic agent and a charge control agent.
These may be used alone or in combination of two or more.

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

  The undercoat layer contained in the composite coating film of the present embodiment is obtained, for example, by applying an undercoating water-based paint to a predetermined application target, and then drying it to remove volatile components. At this time, if necessary, heat treatment at a temperature of about 40 to 120 ° C., ultraviolet irradiation treatment, and the like may be further performed.

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

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

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

  The synthetic resin is not limited to, for example, silicone resin, acrylic resin, methacrylic resin, fluorocarbon resin, alkyd resin, amino alkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, Polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, A phenol resin, a melamine resin, an epoxy resin, a urethane resin, a silicone-acrylic resin etc. are 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, plasma treatment, etc. may be performed as necessary.

  The coated product of this embodiment comprises a base material and the coating film or composite coating film formed on the base material, and the coating film or composite coating film is also useful as a coating or the like. is there.

  The coating film or composite coating film of the present embodiment can maintain the appearance, the contamination resistance, the sealing contamination property, and the biofouling resistance at a high level for a long time without losing the appearance even with a dark base material, It can be used suitably also in the environment which was difficult to use.

  From this point of view, the coated product of the present embodiment is not limited to the following, for example, building materials, building exterior, building interior, window frame, window glass, various lenses, structural members, building equipment such as houses, Covers and window glass for vehicular lamps, exteriors of machinery and equipment, dust covers and coatings, display devices, covers, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads and railways, etc. Exteriors and 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. Is mentioned.

As a manufacturing method of the coated product of the present embodiment, for example, a method of forming a coating film by applying the above-described water-based paint to at least a part of the surface of the base material and performing drying or the like as necessary. Although it is not limited to this.
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.

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

The base material used in the measurement of the characteristics described later was manufactured as follows.
[Preparation of 7cm x 15cm base material pre-coated with enamel paint]
(Preparation of pigment dispersion)
Dispersing agent (BASF Japan Ltd., "Pig.Disperser MD20") 5.35g, ammonia water 0.5g, propylene glycol 23.5g, water 147.5g, titanium oxide (chlorinated rutile type titanium oxide; manufactured by Ishihara Sangyo Co., Ltd. 33. 5 g of "Taipek CR-97" and 2.85 g of an antifoaming agent (modified silicone type; Sannopco's "SN deformer 1310"), a table-top sand mill (Camppe-Papio, batch-type table-top sand mill) For 20 minutes to obtain a pigment dispersion.

(Preparation of enamel paint that does not contain algae and fungicides)
To 109.0 g of the polymer emulsion obtained in [Production Example 1] described later, 10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso Corporation, “CS-12”) 10.0 g of a mixed solution of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained as described above, a thickener (manufactured by Asahi Denka Kogyo Co., Ltd., “Adecanol UH-438” The enamel paint X was obtained by adding 0.5 g of a 10% by weight aqueous solution of “)” and mixing for 1 hour.

(Preparation of a 7 cm × 15 cm base material pre-coated with an enamel paint X not containing an anti-algal and anti-fungal agent)
The enamel paint X obtained as described above was applied to a 7 cm × 15 cm sulfate alumite plate using a wire coater No. 50 and dried at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a 7 cm × 15 cm base material pre-coated with the enamel paint X.

(Preparation of enamel paint containing algae and fungicides)
To 109.0 g of the polymer emulsion obtained in [Production Example 1] described later, 10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso Corporation, “CS-12”) 10.0 g of a mixed solution of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained as described above, a thickener (manufactured by Asahi Denka Kogyo Co., Ltd., “Adecanol UH-438” ) Of a 10% aqueous solution by weight of an aqueous solution of an algae-antifungal agent N-35 (Nippon Soda Co., Ltd., solid content 35% by mass) 0.9 g, an algae-antifungal agent AF-40 (Nippon Soda, solid content 40 mass%) 0.4 g was added and mixed for 1 hour to obtain an enamel paint Y.

(Preparation of 7 cm × 15 cm base material pre-coated with enamel paint Y containing anti-algal and anti-fungal agents)
The enamel paint Y obtained as described above was applied to a 7 cm × 15 cm alumite sulfate plate with a wire coater No. 50 and dried at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a 7 cm × 15 cm base material pre-coated with the enamel paint Y.

Various physical properties and characteristics were measured by the following 1 to 12.
(1. Content and solid content of each component)
A sample (2.0 g) was placed in an aluminum dish and heated at 150 ° C. for 1 hour. The mass of the sample before and after heating was measured, and the solid content (mass%) was calculated from the difference. Based on this method, the content of each component and the solid content in the aqueous composition were each measured.

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

(3. Glass transition temperature)
The glass transition temperature was determined from the inflection point of the obtained DSC curve, using Seiko Instruments Inc. “DCS 6220” under measurement conditions of a temperature rising rate of 10 ° C./min. 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)
JISK5600 paint general test method Coverage rate test paper (manufactured by Nippon Test Panel Co., Ltd.) is sprayed so that the coating amount of the aqueous composition is 17.0 g / m ^{2 on} the black background part (L * value 7). It used and painted. 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 coating was measured using a “color guide” manufactured by BYK Gardner. If the color difference is 3.0 or less, it indicates that the change in color difference on the dark color background is small and good.

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

(6. Biofouling resistance (enamel paint that does not contain anti-algal and anti-fungal agents))
A 7 cm × 15 cm substrate previously coated with an enamel paint containing no antialgal / antifungal agent prepared as described above was sprayed so that the application amount of the aqueous composition was 17.0 g / m ^2. It painted using. The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. Attach a test plate to the fence facing the north face of the building with thick trees in Kasama, Ibaraki Prefecture, by tilting it 45 ° from the horizontal plane so that the painted face is facing upward, from 2 to 6 It stood still for a month.
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 paint which does not contain an anti-algal antifungal agent previously was evaluation of "x".
[Evaluation criteria]
○: Almost no stain of algae or mold was found.
Δ: Some algae and mold stains were confirmed, but there was no problem in practical use.
X: A large amount of algae and mold stains were confirmed.

(7. Biofouling resistance (enamel paint containing anti-algal and anti-fungal agents))
Apply a spray to the 7 cm x 15 cm substrate previously coated with the enamel coating containing the antialgal fungicide prepared as described above so that the application amount of the aqueous composition is 17.0 g / m ² Used to paint. The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. A test board is attached to a fence facing the north face of a building with trees around it in Kasama, Ibaraki Prefecture, inclined 45 ° from the horizontal plane so that the painted side is facing upward, for 1 year from June Let stand.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
In addition, the result evaluated only with the base material which coated the enamel coating containing an anti-algal antifungal agent previously was evaluation of "(circle)."
[Evaluation criteria]
○: Almost no stain of algae or mold was found.
Δ: Some algae and mold stains were confirmed, but there was no problem in practical use.
X: A large amount of algae and mold stains were confirmed.

(8. Weather resistance test: gloss retention after 3000 hours)
A 7 cm × 15 cm base material previously coated with an enamel paint containing an anti-algal and fungicidal agent was applied using a spray so that the applied amount of the aqueous composition was 17.0 g / m ² . The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. An exposure test (black panel temperature: 63 ° C., rainfall: 18 minutes / 2 hours) was performed using a “Sunshine Weather Meter” manufactured by Suga Test Instruments. 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 previously coated with the enamel paint is a gloss retention of 80% after 3000 hours of exposure, and if the 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

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

(10. Sealing contamination)
A 7 cm × 15 cm base material previously coated with an enamel paint containing an anti-algal and fungicidal agent was applied using a spray so that the applied amount of the aqueous composition was 17.0 g / m ² . The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. On the test plate, apply one-component silicone sealing material silicone sealing material 8060 pro (made by Cemedine) so that the size of the sealing material after drying is 1 cm × 2 cm in area and 1 cm in height, The sealing material was dried for 10 days.
The test plate was attached to a fence facing a general road (about 500 to 1000 trucks per day) and allowed to stand for a predetermined period. The degree of contamination of the test plate after standing was measured for color difference (L value) before and after standing using a “color guide” manufactured by BYK Gardner. Evaluation was based on the following criteria.
[Evaluation criteria]
◎: The difference in L value was 2 or less in the stationary state for 8 weeks, and the difference in L value was 3 or less in the stationary state for 12 weeks.
○: The difference in L value was 2 or less in the case of standing for 8 weeks, and the difference in L value was 3 or more and 4 or less in the case of standing for 12 weeks.
Δ: The difference in L value was 2 or less in the stationary state for 8 weeks, and the difference in L value was 4 in the stationary state for 12 weeks.
X: The difference in L value was more than 2 after standing for 8 weeks.

(11. Film thickness)
A 7 cm × 15 cm acrylic plate (trade name “Delagrass K”, manufactured by Asahi Kasei Co., Ltd., thickness 2 mm) was applied using a spray so that the coating amount of the aqueous composition was 17.0 g / m ² . The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. The film thickness was determined using a reflection spectroscopy film thickness meter FE-3000 manufactured by Otsuka Electronics.

(12. Crack)
Spray on the 3 cm × 3 cm base material previously coated with the enamel paint containing the anti-algal and anti-fungal agent prepared as described above so that the coating amount of the aqueous composition is 17.0 g / m ^2. The aqueous composition was painted using The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. On the test plate, gold was coated for 3 to 9 nm using a sample coater MP-19010NCTR manufactured by JEOL Ltd. The surface of the coating film was observed using a desktop scanning electron microscope JCM-5000 manufactured by JEOL Ltd. The observation magnification was 500 times for a test plate with a crack width exceeding 5 μm, 1000 times for a test plate with a crack width of more than 3 μm and 5 μm or less, and 3000 times for a crack width of 3 μm or less. The evaluation was performed by observing four visual fields on each test plate and measuring the widths at five locations for one visual field. The range of the minimum value and the maximum value of the crack width for 18 places from the one with the smallest crack width among the total 20 places was determined.

In the following Production Example 1, a polymer emulsion for the enamel paint was produced.
[Production Example 1] (Synthesis of polymer emulsion)
In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 292.0 g of ion-exchanged water, a reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 8 0.0 g was added, and the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 10.0 g of a 2% by mass ammonium persulfate aqueous solution was added, and 5 minutes later, 10.0 g of methyl methacrylate, 5.0 g of cyclohexyl methacrylate, 75.0 g of n-butyl acrylate, methacrylic acid 5.0 g, 10.0 g of 2-hydroxyethyl methacrylate, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 4.0 g, 2% by mass ammonium persulfate aqueous solution 15 An 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 emulsifier (manufactured by ADEKA, “Adekari Soap SR-1025”; solid 25 wt% aqueous solution) 16.0 g, 2 wt% aqueous ammonium persulfate solution 60.0 g, ion-exchanged water 196.0 g emulsified mixed solution, 3-methacryloxypropyltrimethoxysilane 1.0 g, dimethyldimethoxysilane 20 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 obtained polymer emulsion had a solid content of 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.

In the following Production Examples 2 to 7, a polymer (A) was produced.
[Production Example 2] (Synthesis of aqueous dispersion (AD-1) of polymer (A-1))
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device, 1364.2 g of ion-exchanged water, a reactive emulsifier (ADEKAYA manufactured by ADEKA, “ADECARIA SOAP SR-1025”; solid content 25 mass% aqueous solution) 28 8 g was charged and the temperature in the reactor was heated to 80 ° C. 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 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, a 25% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. At this time, the total solid content in the reaction solution was 412.6 g. 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 equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device, 1364.2 g of ion-exchanged water, a reactive emulsifier (ADEKAYA manufactured by ADEKA, “ADECARIA SOAP SR-1025”; solid content 25 mass% aqueous solution) 28 8 g was charged and the temperature in the reactor was heated to 80 ° C. 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% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. At this time, the total solid content in the reaction solution was 436.2 g. 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-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))
After charging 850.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature in the reactor under stirring Was heated to 80 ° C. 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 with the temperature in the reactor kept at 80 ° C. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 60 minutes, and then cooled to room temperature, and 25 mass% ammonia aqueous solution was added to the reaction liquid to adjust pH to 8.0. At this time, the total solid content in the reaction solution was 210.0 g. 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-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)
After charging 850.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the temperature in the reactor under stirring Was heated to 80 ° C. In this reactor, a mixed liquid consisting of 109.0 g of dimethyldimethoxysilane, 29.5 g of phenyltrimethoxysilane, and 136.5 g of methyltrimethoxysilane was added over 120 minutes while maintaining the temperature in the reactor at 80 ° C. And 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 dodecylbenzenesulfonic acid solution was added, 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 weight aqueous ammonium persulfate solution was added, 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 methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, 4.5 g of reactive emulsifier (made by ADEKA, "ADEKA rear soap SR-1025"; solid content 25% by mass aqueous solution), Reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., “AQUALON KH-1025”; solid content 25% by mass aqueous solution) 2.3 g, mixed solution comprising 2% by 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 was maintained at 80 ° C. and stirring was continued for 60 minutes, and then cooled to room temperature, and 25 mass% ammonia aqueous solution was added to the reaction liquid to adjust pH to 8.0. At this time, the total solid content in the reaction solution was 192.4 g. 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-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 Water Dispersion (AD-5) of Polymer (A-5))
A reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer is charged with 1000.0 g of ion-exchanged water and 40.0 g of a 10 mass% dodecylbenzenesulfonic acid aqueous solution, and then the temperature in the reactor under stirring. Was heated to 80 ° C. In this reactor, a mixture of 220.0 g of dimethyldimethoxysilane, 5.0 g of phenyltrimethoxysilane, and 106.0 g of methyltrimethoxysilane was added over 120 minutes while maintaining the temperature in the reactor at 80 ° C. And 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 dodecylbenzenesulfonic acid solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 120 minutes. Then, 6.6 g of a 2 mass% ammonium persulfate aqueous solution was added, 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 was maintained at 80 ° C. and stirring was continued for 60 minutes, and then cooled to room temperature, and 25 mass% ammonia aqueous solution was added to the reaction liquid to adjust pH to 8.0. At this time, the total solid content in the reaction solution was 208.9 g. The reaction solution was filtered through a 100 mesh wire mesh. The reaction product was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-5) of a polymer (A-5) having a number average particle size of 35 nm as a polymer.
When the amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was converted into a hydrolysis condensate, it was 65.0% by mass in the polymer (A-5).

Production Example 7 Synthesis of Aqueous Dispersion (AD-6) of Polymer (A-6)
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirrer, 241.8 g of ion-exchanged water, a reactive emulsifier (ADEKAYA manufactured by ADEKA, “ADEKAREASOAP SR-1025”; solid content 25 mass% aqueous solution) 3 2 g was charged and the temperature in the reactor was heated to 80 ° C. 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% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. At this time, the total solid content in the reaction solution was 431.6 g. 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-6) of a polymer (A-6) with a number average particle diameter of 120 nm was obtained as a polymer.
It was 2.8 mass% in a polymer (A-6), when the quantity of the dimethyl dimethoxysilane used when synthesize | combining this aqueous dispersion was converted into a hydrolysis condensation product.

In the following Preparation Examples 8 and 9, inorganic oxides having photocatalytic activity were prepared.
Production Example 8
(Synthesis of Inorganic Oxide (C-1) Having Photocatalytic Activity)
<Silica modified rutile type titanium oxide>
700 mL of a titanium tetrachloride aqueous solution having a concentration of 200 g / L as TiO ₂ and an aqueous sodium hydroxide solution having a concentration of 100 g / L as Na ₂ O were added to the reactor while maintaining the pH of the reaction solution at 5 to 9. . Then, after adjusting the pH of the reaction liquid to 7, it was filtered and washed until the electric conductivity of the filtrate became 100 μS / cm to obtain a titanium oxide wet cake 1 having a solid content of 28.3 mass%. This titanium oxide wet cake 1 contained fine particles having a rutile structure, and the number average particle diameter of the primary particles thereof was 8 nm.
The obtained titanium oxide wet cake 1 was diluted with pure water to prepare a 1 mol / L slurry. 1 L of this slurry was charged into a 3 L flask, and 1N nitric acid was added so that the molar ratio of titanium oxide / nitric acid was 1/1, and the mixture was heated to a temperature of 95 ° C. and maintained at this temperature for 2 hours. 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. Then, it wash | cleaned until the electrical conductivity of a filtrate was set to 100 microsiemens / cm, and obtained the titanium oxide wet cake 2 whose solid content is 25 mass%.
The obtained titanium oxide wet cake 2 is repulped by adding an aqueous solution of sodium hydroxide having a concentration of 10% by mass, and then dispersed for 3 hours by an ultrasonic cleaner to have a pH of 10.5 and a solid content of 10% by mass. An alkaline titanium oxide sol was obtained.
2 L of this alkaline titanium oxide sol was charged into a 3 L flask, the flask was heated to a temperature of 70 ° C., 69.4 mL of a sodium silicate aqueous solution having a concentration of 432 g / L as SiO ₂ was added, and then the temperature was raised to 90 ° C. After warming and maintaining for 1 hour, 10% sulfuric acid was added to adjust the pH to 6 to obtain a titanium oxide sol whose surface was treated with a hydrous oxide of silicon.
The obtained titanium oxide sol was cooled to room temperature, 5.4 L of pure water was added, impurities were removed and concentrated using a desalting and concentrating device, pH 7.3, solid content 29 mass%, conductivity A neutral rutile 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 9]
(Synthesis of Inorganic Oxide (C-2) Having Photocatalytic Activity)
<Silica modified anatase type titanium oxide>
Aggregated metatitanic acid produced by heating and hydrolyzing a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid was made into an aqueous slurry of 30% by mass in terms of TiO ₂ . Ammonia water was added to the slurry to neutralize to pH 7, and then sulfate ions were removed by filtration and washing to obtain a dehydrated cake.
The resulting dehydrated cake was peptized by adding nitric acid to obtain an acidic titanium oxide sol having a pH of 1.5 comprising titanium oxide fine particles having an anatase type crystal structure (number average particle diameter of primary particles: 7 nm).
The obtained acidic titanium oxide sol is diluted with pure water to make 600 mL of titanium oxide sol having a TiO ₂ 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. Thereafter, it was aged for 30 minutes.
Next, 10% aqueous sodium hydroxide solution was added to adjust the pH of the reaction solution to 8, and then the pH of the reaction solution was adjusted to 6 with 2% aqueous sulfuric acid solution. Obtained.
This wet cake was repulped into pure water and then ultrasonically dispersed to obtain anatase-type titanium oxide sol (solid content 20% by mass, pH 7.5) stable in the neutral range.
In this, the aggregated silica was deposited in a porous state on the surface of the titanium oxide fine particles, and the content thereof was 7 parts by mass in terms of SiO _{2 with} respect to 100 parts by mass of TiO ₂ .

Example 1
An aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 4.000 g of the aqueous dispersion (AD-1) of the polymer (A-1) (solid content: 10.0% by mass). “Snowtex OS”; solid content 20% by mass) 6.000 g, photocatalytic activity inorganic oxide (C-1) 1.379 g (solid content 29% by mass), and ethanol. Fluorocarbon surfactant (D-1) adjusted to 0% by mass (DIC Corporation, “Megafac F-444”) 1.000 g, and fading property adjusted to 1.0% by mass with ion exchange water Dye (E-2) (Hodogaya Chemical Industry Co., Ltd., "Acid Red") 1.200 g, Mineral oil-based antifoam (F-1) (Sannopco, "SN deformer AP") 0.020 g, Ethanol 10.00 And g, was mixed with deionized water 76.401G, by stirring, to obtain a solid content 2.0% by weight of the aqueous composition (G-1).
Next, one side of a 7 cm × 15 cm base material pre-coated with a black background portion (L * value 7) of a concealment rate test paper (manufactured by Nippon Test Panel Co., Ltd.) and an enamel paint that does not contain an anti-algae and anti-fungal agent ( A water-based composition for each of a surface coated with an enamel coating beforehand), a single side (a surface coated beforehand with an enamel coating) of a 7 cm x 15 cm substrate previously coated with an enamel coating containing an anti-algal and antifungal agent (G-1) was applied using a spray so that the application amount was 17 g / m ² . A test paper (H-1) in which the coated substrate is kept horizontal and left at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux for 48 hours, and a coating film is formed on the black background portion of the concealment rate test paper A test plate (I-1) on which a coating film containing no antifungal agent was formed on the substrate, and a test plate (J) on which a coating film containing the antifungal agent was formed on the substrate -1) A test plate (K-1) having a coating film formed on an acrylic plate was obtained.
Evaluation results of various physical properties and characteristics of water-based composition (G-1), coating film and test paper (H-1), coating film and test plate (I-1, J-1, K-1) Shown in 1.

[Examples 2 to 8 and 10 to 15 , Reference Example 1, Comparative Examples 1 to 6]
Aqueous composition (G-2 to G-21), coating film and test paper (H-2 to H-21), and coating film in the weight ratio described in Table 1 and Table 2 by the same procedure as in Example 1 And various physical properties and evaluation results of test plates (I-2 to I-21, J-2 to J-21, K-2 to K-21) are shown in Table 1 and Table 2. The coating film and test paper (H-18) obtained in Comparative Example 3, and the coating film and test plate (I-18, J-18, K-18) had too thin a film thickness and were used as a substrate. There were unpainted spots and uneven coating occurred.

The following were used for silicon dioxide (B), fluorocarbon surfactant (D), fading dye (E), and mineral oil-based antifoaming agent (F) in Tables 1 and 2, respectively.
(B-1): Water-dispersed colloidal silica having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”; solid content 20% by mass)
(B-2): Water-dispersed colloidal silica having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex NS”; solid content 20% by mass)
(B-3): Water-dispersed colloidal silica having a number average particle size of 25 nm (manufactured by Nissan Chemical Industries, “Snowtex O-40”; solid content 40% by mass)
(B-4): Water-dispersed colloidal silica having a number average particle size of 25 nm (manufactured by Nissan Chemical Industries, “Snowtex 50”; solid content 48 mass%)
(D-1): Fluorocarbon surfactant whose solid content is adjusted to 10.0% by mass with ethanol (manufactured by DIC, “Megafac F-444”)
(D-2): Fluorocarbon surfactant (manufactured by AGC Seimi Chemical Co., “Surflon S-232”; solid content 30% by mass)
(D-3): A polyether-modified silicone surfactant whose solid content was adjusted to 10.0% by mass with ethanol (“KF-643” manufactured by Shin-Etsu Chemical Co., Ltd.)
(E-1): A fading dye whose solid content is adjusted to 1.0 mass% with ion-exchanged water (“Methylene Blue” manufactured by Kishida Chemical Co., Ltd.)
(E-2): Fading dye whose solid content was adjusted to 1.0 mass% with ion-exchanged water (“Acid Red” manufactured by Hodogaya Chemical Co., Ltd.)
(F-1): Mineral oil-based antifoaming agent (San Nopco, “SN deformer AP”)
(F-2): Mineral oil-based antifoaming agent (San Nopco, “SN deformer VL”)
(F-3): Mineral oil-based antifoaming agent (manufactured by San Nopco, “Nopco 8034L”)

  From the above, all of the coating films of the present example maintain the coating film appearance at a high level, and even when used for a dark-colored base material, the appearance and stain resistance are maintained over a long period of time without impairing the appearance. It has been confirmed that a coating film capable of maintaining biofouling resistance, sealing contamination and gloss at a high level can be formed.

  The coating film, the composite coating film and the coated product of the present invention have industrial applicability as various members such as building exterior applications, exterior display applications, automotive parts, optical components such as displays and lenses, etc. Yes.

Claims (6)

Silicon dioxide (B),
An inorganic oxide (C) having photocatalytic activity;
A fluorocarbon surfactant (D);
A coating film containing
The coating film surface has cracks, more than 90% of the cracks, Ri following width der 5.0 .mu.m,
Containing 0 to 27.0% by mass of the polymer (A) in the coating film,
Paint film.   The coating film of Claim 1 whose thickness of a coating film is 0.15 micrometer or more and less than 2.0 micrometers. A substrate;
The coating film according to claim 1 or 2 formed on at least a part of the surface of the substrate;
A coated product. A topcoat layer obtained from the coating film according to claim 1 or 2,
Having at least two subbing layers,
The subbing layer contains a polymer and an antialgal and / or antifungal agent,
Composite coating. A substrate;
The composite coating film according to claim 4 formed on at least a part of the surface of the substrate;
A coated product.   The coated product according to claim 3 or 5, wherein the substrate is an organic substrate.