TW201739854A - Aqueous coating composition and coating film - Google Patents

Abstract

The present invention provides an aqueous coating composition and a coating film which can strike stain resistance and weather resistance at a higher level as compared with the conventional one. The aqueous coating composition comprises the following polymer emulsion ([alpha]) and the following aqueous polymer ([beta]): ([alpha]) a polymer emulsion containing an organosiloxane polymer block (I) having a specific organosiloxane unit and a polymer block (II) of an ethylenically unsaturated monomer in particles; ([beta]) an aqueous polymer which is a copolymer composed of 40 mol% or more and less than 100 mol% of one or more ethylenically unsaturated monomers having an amide group and/or an amino group, and more than 0 mol% and 60 mol% or less of of other one or more ethylenically unsaturated monomers copolymerizable whith theses ethylenically unsaturated monomers; a homopolymer composed of one type of ethylenically unsaturated monomers having an amide group and/or an amino group; or a copolymer composed of two or more kinds of ethylenically unsaturated monomers having an amide group and / or an amino group. The coating film is a coating film containing inorganic particles having an average particle size of 100 nm or less and a binder component, wherein the area occupancy of the inorganic particles on the surface of the coating film is 49.9% or less, and the average domain size of the inorganic particles on the surface of the coating film is 500 square nm or more.

Description

Aqueous coating composition and coating film

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

The rain mark pollution seen on the walls of buildings and the like is caused by the difference between the rain and the place where the rain is not attached, which is detrimental to the aesthetics of the building. Generally, the rain stain contamination can be prevented by increasing the hydrophilicity of the surface of the coating film and increasing the surface hardness of the coating film.

In the water-based paint, as a method for preventing the contamination of the rain stain, Patent Document 1 discloses an aqueous coating composition containing a polyfluorene-modified acrylic emulsion, colloidal inorganic particles, and a sulfosuccinic acid-based interface. The active agent and the epoxy group-containing surfactant are excellent in reducing rain stain contamination and long-term persistence.

Patent Document 2 discloses a coating composition comprising an aqueous resin dispersion obtained by polymerizing an ethylenically unsaturated monomer, a hydrophilic portion derived from a mercaptoamine group or an amine group or a hydroxyl group, and a hydrophobic portion. An amphiphilic polymer and a water-dispersible colloidal cerium oxide, and can form a coating film having good long-term stain resistance.

Patent Document 3 discloses an aqueous resin composition for a coating comprising an acrylic emulsion and having an N-vinyl cyclic enthalpy A water-soluble resin of an amine unit, and these may form a crosslinked structure with each other, and the aqueous resin composition of the coating material can form a coating film excellent in stain resistance, weather resistance, and the like.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 4141388.

Patent Document 2: Japanese Patent No. 5,317,331.

Patent Document 3: Japanese Patent No. 5290951.

With the long life and high-rise of buildings, it is required to reduce the life cycle cost of recoating in the field of building exterior coatings, and it is required to have both higher levels of pollution resistance and weather resistance than in the past. Waterborne coatings.

However, the coating film formed by the composition described in Patent Document 1 is insufficient in rain stain pollution reduction and long-term sustainability, and is inferior in weather resistance. Further, the coating film formed of the composition described in Patent Document 2 is insufficient in the effect of stain resistance, and is inferior in weather resistance. Further, in the composition described in Patent Document 3, the stain resistance and weather resistance of the formed coating film are further improved.

As described above, in the conventional water-based paints, there are no two types of properties which are both high-grade and have both stain resistance and weather resistance. The present invention has been made in view of the above problems, and an object thereof is to provide a higher level of resistance than in the past. Aqueous coating composition and coating film for pollution and weather resistance.

The inventors of the present invention have repeatedly made efforts to solve the above problems, and as a result, have found an aqueous coating composition containing a polymer emulsion and an aqueous polymer having a specific functional group containing a specific organic hydrazine in the particles. An organic siloxane polymer block of an oxyalkyl unit and a polymer block of an ethylenically unsaturated monomer; the aqueous coating composition can form a coating film excellent in both stain resistance and weather resistance, and further discovers In the coating film surface, the area ratio of the inorganic particles in a specific range, and the average area size of the inorganic particles in the surface of the coating film are excellent in both the stain resistance and the weather resistance of the coating film in a specific range, thereby The present invention has been completed.

That is, the present invention is as follows.

[1] An aqueous coating composition comprising the following polymer emulsion (α) and an aqueous polymer (β): (α) polymer emulsion containing an organic siloxane polymer in a particle a polymer block (II) of the block (I) and the ethylenically unsaturated monomer, wherein the non-volatile content of the polymer emulsion contains 0.1% by mass or more and 30% by mass or less of the Si element, and the organic siloxane polymer block (I) containing 50 mol% or more and 99.9 mol% or less of the organooxane unit (A) represented by the formula (a); (β) an aqueous polymer, which is any one of the following: / or one or two or more of the amino group-containing ethylenically unsaturated monomers, 40 mol% or more and less than 100 mol %, and one or two other ethylenically unsaturated monomers copolymerizable with the same a copolymer composed of more than 0 mol% and less than 60 mol%; an ethylenically unsaturated monomer having a mercaptoamine group and/or an amine group A homopolymer composed of one type; and a copolymer of two or more kinds of ethylenically unsaturated monomers having a mercapto group and/or an amine group.

(In the formula (a), R ¹ and R ² are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different or the same. The basis.)

[2] The aqueous coating composition according to [1], wherein the organosiloxane polymer block (I) further contains 0.1 mole of the organic oxirane unit (B) represented by the formula (b). % or more and 50% or less.

(In the formula (b), R ³ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group; and R ⁴ is an alkenyl group having a vinyl group, a carbon number of 3 to 20, and an acrylonitrile group. Radical polymerization selected from the group consisting of an oxy group, an alkyl acrylate having 4 to 20 carbon atoms, a methacryloxy group, an alkyl methacrylate having 5 to 20 carbon atoms, and a phenyl group substituted with a vinyl group Any one of the group and the polymer block (II) polymerized by the radical polymerizable group; n is 0, 1 or 2.)

[3] The aqueous coating composition according to [1] or [2], further comprising colloidal inorganic particles (γ).

[4] The aqueous coating composition according to any one of [1] to [3] wherein the organic siloxane polymer block (I) contains: the aforementioned organic siloxane unit (A) 50 99% or more of the ear% or more, the organic oxirane unit (B) 0.1 mol% or more, 49.9 mol% or less, and the organic oxime represented by the formula (c) The oxyalkyl unit (C) is 0.1% by mole or more and 49.9 % by mole or less.

(wherein R ⁵ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group.)

[5] The aqueous coating composition according to any one of [1] to [4], which contains the aqueous polymer (β) with respect to 100 parts by mass of the nonvolatile portion of the polymer emulsion (α) The volatile matter is 0.1 part by mass or more and 30 parts by mass or less.

[6] The aqueous coating composition according to any one of [1] to [5], which contains colloidal inorganic particles (γ) with respect to 100 parts by mass of the nonvolatile portion of the polymer emulsion (α). The nonvolatile content is 0.1 part by mass or more and 30 parts by mass or less.

[7] A coating film comprising inorganic particles having an average particle diameter of 100 nm or less and a binder component; wherein an area occupation ratio of the inorganic particles in the surface of the coating film is 49.9% or less; and the inorganic substance in the surface of the coating film The average particle size of the particles is 500 square nm or more.

[8] The coating film according to [7], wherein the binder component contains a polymer containing the organosiloxane unit (A) represented by the formula (a).

(In the formula (a), R ¹ and R ² are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different or the same. The basis.)

[9] The coating film according to [7] or [8] wherein the binder component contains: A polymer containing the organomethoxyne unit (B) represented by the formula (b).

(In the formula (b), R ³ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group; and R ⁴ is an alkenyl group selected from a vinyl group, a carbon number of 3 to 20, and propylene. a radical group of a decyloxy group, an alkyl acrylate group having 4 to 20 carbon atoms, a methacryloxy group, an alkyl methacrylate group having 5 to 20 carbon atoms, and a phenyl group substituted by a vinyl group Any one of a polymerizable group and a copolymerization of the polymer block (II) by the radical polymerizable group; n is 0, 1, or 2.)

[10] The coating film according to any one of [7], wherein the binder component contains a polymer containing the organooxane unit (C) represented by the formula (c).

(wherein R ⁵ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group)

[11] The coating film according to any one of [7], wherein the binder component comprises the following aqueous polymer (β): (β) aqueous polymer, which is any one of the following One or more kinds of ethylenically unsaturated monomers having a mercapto group and/or an amine group, 40 mol% or more and less than 100 mol%, and other ethylenic groups copolymerizable with the same a copolymer composed of one or more saturated monomers exceeding 0 mol% and 60 mol% or less; an ethylenically unsaturated monomer having a mercaptoamine group and/or an amine group A homopolymer composed of one type; and a copolymer of two or more kinds of ethylenically unsaturated monomers having a mercapto group and/or an amine group.

Compared with the conventional water-based paint, the aqueous coating composition and the coating film of the present invention can be high-grade, have both stain resistance and weather resistance, and can impart long-term beauty and durability to the coated body.

Fig. 1 is an explanatory view of an anodized aluminum sulfate plate which is subjected to a tortuous process for evaluation of stain resistance in the examples.

Fig. 2 is a view showing image analysis (binarization) of a scanning electron microscope (SEM) secondary electron image on the surface of the coating film of Example 6.

Fig. 3 is a view showing the image analysis of the SEM secondary electron image on the surface of the coating film of Comparative Example 2.

Fig. 4 is a view showing the image analysis of the SEM secondary electron image on the surface of the coating film of Comparative Example 10.

Hereinafter, embodiments of the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The following embodiments are merely illustrative of the invention, and the invention is not limited to the following. The invention can be variously modified and implemented within the scope of the invention.

The aqueous coating composition of the present embodiment contains the following polymer emulsion (α) and the following aqueous polymer (β).

(α) polymer emulsion containing in the particle: polymerization of organic siloxane a polymer block (II) of the block (I) and the ethylenically unsaturated monomer, wherein the non-volatile content of the polymer emulsion contains 0.1% by mass or more and 30% by mass or less of the Si element, and the organic siloxane polymer is embedded The segment (I) contains the organooxane unit (A) represented by the formula (a): 50 mol% or more and 99.9 mol% or less; (β) an aqueous polymer, which is any one of the following: having a mercapto group And/or one or more of the amino group-containing ethylenically unsaturated monomers, 40 mol% or more and less than 100 mol%, and one of other ethylenically unsaturated monomers copolymerizable with the or a copolymer composed of two or more kinds of copolymers having more than 0 mol% and less than 60 mol%; a homopolymer composed of one of an ethylenically unsaturated monomer having a mercaptoamine group and/or an amine group; and having a decylamine A copolymer composed of two or more kinds of ethylenically unsaturated monomers having a group and/or an amine group.

(In the formula (a), R ¹ and R ² are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different or the same. The basis.)

<Polymer emulsion (α)>

In the present embodiment, the polymer emulsion (α) is obtained by dispersing polymer emulsion particles in an aqueous solvent, and embedding the polymer of the organosiloxane polymer block (I) and the ethylenically unsaturated monomer in the particles. The segment (II) coexists, and it is not particularly limited as long as the above requirements are satisfied, and the production method thereof is not limited. polymer The production method of the emulsion (α) may, for example, be the following production methods (i) to (iv).

The production method (i) is a method of simultaneously forming a polymer block (II) of an organic siloxane oxide polymer block (I) and an ethylenically unsaturated monomer, thereby obtaining a polymer emulsion (α). The method is not limited to the following, and specific examples thereof include a method in which a hydrolyzable decane and/or a low-to-medium polymer and an ethylenically unsaturated monomer are simultaneously subjected to emulsion polymerization in the presence of a surfactant in an aqueous solvent. In the present specification, the low polymer of hydrolyzable decane means a dimer and a trimer of hydrolyzable decane to a molecular weight of less than 1,000, and the polymer of hydrolyzable decane means a molecular weight of 1,000 or more and less than 10,000.

The production method (ii) is to form a polymer block (II) of an ethylenically unsaturated monomer after forming an emulsion composed of the organosiloxane polymer block (I), whereby a polymer emulsion (α) is obtained. ). The present invention is not limited to the following, and specific examples thereof include emulsifying and polymerizing a hydrolyzable decane and/or a low-to-medium polymer thereof in the presence of a surfactant in an aqueous solvent, thereby obtaining an organic siloxane polymer. After the emulsion, it is used as a seed particle and an ethylenically unsaturated monomer is subjected to emulsion polymerization in an aqueous solvent.

The production method (iii) is carried out by forming an emulsion composed of the polymer block (II) of an ethylenically unsaturated monomer to form an organosiloxane polymer block (I), whereby a polymer emulsion (α) is obtained. ). The present invention is not limited to the following, and specifically, for example, an ethylenically unsaturated monomer is subjected to emulsion polymerization in the presence of a surfactant in an aqueous solvent, whereby a polymer emulsion is obtained, and then used as a seed particle in an aqueous solvent. A method in which a hydrolyzable decane and/or a low-to-medium polymer thereof is subjected to emulsion polymerization.

Manufacturing method (iv) is to make ethylenically unsaturated monomer and polyoxyl A method in which a macromonomer is copolymerized, thereby obtaining a polymer emulsion (α). The method is not limited to the following, and specific examples thereof include a method in which an ethylenically unsaturated monomer and a polyfluorene macromonomer are subjected to emulsion polymerization in the presence of a surfactant in an aqueous solvent. From the viewpoint of the polymerization stability, the polyoxymethylene macromonomer preferably has a molecular weight of less than 10,000 and may be one of two or more radical polymerizable groups in the molecule.

In the present embodiment, the polymer emulsion (α) is preferably a polymer emulsion obtained by the production method (i) or (ii), and the aqueous coating composition of the embodiment using the polymer emulsion is stain-resistant. And the tendency to be more excellent in weather resistance.

In the present embodiment, the organosiloxane polymer block (I) must contain an organic siloxane unit having a specific structure in a specific ratio. Specifically, the organic siloxane oxide unit (A) represented by the formula (a) contains 50 mol% or more and 99.9 mol% or less, whereby the aqueous coating composition of the present embodiment can be provided with excellent stain resistance.

(In the formula (a), R ¹ and R ² are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different or the same. The basis.)

From the viewpoint of stain resistance, the ratio of the organooxane unit (A) is preferably in the range of 55 mol% or more and 95 mol% or less, more preferably The range is from 60 mol% to 90 mol%.

Further, the organic siloxane polymer block (I) contains the organic siloxane unit (B) represented by the formula (b) in an amount of 0.1 mol% or more and 50 mol% or less, thereby improving the aqueous coating composition of the present embodiment. The weather resistance of the material is preferred.

(In the formula (b), R ³ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group; and R ⁴ is an alkenyl group selected from a vinyl group, a carbon number of 3 to 20, and propylene. Radical polymerization of a group of a decyloxy group, an alkyl acrylate having 4 to 20 carbon atoms, a methacryloxy group, an alkyl methacrylate having 5 to 20 carbon atoms, and a phenyl group substituted with a vinyl group Any one of the group and the polymerizable block (II) which is polymerized by the radical polymerizable group; n is 0, 1, or 2.)

The ratio of the organic siloxane unit (B) is from 0.1 mol% to 50 mol%, whereby the weather resistance tends to be improved. The ratio of the organic siloxane unit (B) is more preferably 0.5 mol% or more and 45 mol% or less, and still more preferably 1 mol% or more and 40 mol% or less.

Further, the organosiloxane polymer block (I) contains: 50 mol% or more of 99.8 mol% or less of the organooxane unit (A), and 0.1 mol% or more of the organodecane unit (B). 49.9 mol% or less, and the organosiloxane unit (C) represented by the formula (c) is 0.1 mol% or more and 49.9 mol% or less, but the weather resistance of the aqueous coating composition of the present embodiment can be further improved. Therefore, it is better.

(wherein R ⁵ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group.)

The ratio of the organooxane unit (C) is 0.1 mol% or more and 49.9 mol% or less, whereby the weather resistance tends to be improved. The ratio of the organic siloxane unit (C) is more preferably 0.5 mol% or more and 45 mol% or less, and still more preferably 1 mol% or more and 40 mol% or less.

The structure of the oxirane unit contained in the organosiloxane polymer block (I) and its ratio can be obtained by ²⁹ Si nuclear magnetic resonance spectroscopy ( ²⁹ Si NMR), ¹³ C nuclear magnetic resonance spectroscopy ( ¹³ C NMR), and ¹ H nuclear magnetic resonance spectrum ( ¹ H NMR) and the like were analyzed. For example, when both R ¹ and R ² are methyl groups in the above organooxane unit (A), they can be displayed by a chemical shift δ (tetramethyl decane (TMS) basis) of -15 to -30 ppm at ²⁹ Si NMR. Identification by the peak. Similarly, when the organic silicon siloxane units (C), R ⁵ is methyl, can be identified from -50 to -80ppm by ^{29 SiNMR} displayed in the peak chemical shift δ (TMS reference). The molar ratio of each of the organomethoxyne units contained in the organosiloxane polymer block (I) can be calculated from the integrated values of the respective peaks in the ²⁹ Si NMR.

In the present embodiment, the weight average molecular weight of the organosiloxane polymer block (I) is preferably 2,000 or more from the viewpoint of further improving the weather resistance of the aqueous coating composition of the present embodiment. More preferably 5,000 or more, and still more preferably 10,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 1,000,000, more preferably 500,000, and still more preferably 200,000.

In the present embodiment, the organosiloxane polymer block (I) is preferably obtained by hydrolysis and condensation reaction of a hydrolyzable decane and/or its low to medium polymer, for example, by hydrolyzing decane and / or its low to medium polymer is obtained by mixing and stirring with 1 equivalent or more of water. When it is desired to accelerate the reaction rate, the reaction temperature is preferably maintained at 40 ° C or higher and 100 ° C or lower. Further, it is preferred to maintain the pH in the reaction system at 4 or less or 8 or more using an acid or a base as a catalyst. The present invention is not limited to the following, and specific examples of the acid and the base catalyst include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid; and acetic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, and dodecylbenzenesulfonic acid. Representative organic acids such as linear alkylbenzene sulfonic acids; inorganic bases such as sodium hydroxide, potassium hydroxide, ammonia; trimethylamine, triethylamine, tetramethylammonium hydroxide, tetrabutylphosphonium hydroxide And other organic bases.

The hydrolyzable decane is not particularly limited, and examples thereof include alkoxydecane, ethoxylated decane, and chlorodecane. From the viewpoint of polymerization stability, alkoxydecane is preferred. From the viewpoint of polymerization stability, the low-to-medium polymer of hydrolyzable decane preferably has a molecular weight of less than 2,000, and may be either a linear structure or a cyclic structure, and may remain as a part of the hydrolyzable group. Any of those in the polymer and the fully condensed.

Specific examples of the hydrolyzable decane which can be added to the organic siloxane unit (A) include dimethyl dimethoxy decane, dimethyl diethoxy decane, and diethyl dimethyl. Oxydecane, diethyldiethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, methylphenyldimethoxydecane, methylphenyldiethoxydecane Cyclohexyl An alkoxy decane such as dimethoxy decane or cyclohexylmethyl diethoxy decane; ethoxylated decane such as dimethyldiethoxy decane or diphenyl ethane decyl oxane; Chlorotropins such as dimethyldichlorodecane and diphenyldichlorodecane.

Specific examples of the structure having a linear structure in the low-to-medium polymer of the hydrolyzable decane of the organic siloxane unit (A) are not limited to the following, but the following formulas (1) and (2) are mentioned. The compound shown has a ring-shaped structure, and is not limited to the following, but a compound represented by the following formula (3) is mentioned.

(In the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different or the same. a group; X is an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an ethyloxy group, or a chlorine; and m is an integer of 1 or more and 100 or less.)

(In the formula (2), R ¹ and R ² are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different or the same. R ⁶ and R ⁷ are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a phenyl group, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, an acryloxy group, and a carbon group. a 4 to 20 alkyl acrylate, a methacryloxy group, an alkyl methacrylate having a carbon number of 5 to 20, or a phenyl group substituted with a vinyl group, and R ⁶ and R ⁷ may be mutually different or The same base; m is an integer of 1 or more and 100 or less.)

(In the formula (3), R ¹ and R ² are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different or the same. The base; m is an integer of 3 or more and 50 or less.)

The compound represented by the formula (1) is not limited to the following, but examples thereof include 1,3-dimethoxy-1,1,3,3-tetramethyldioxane and 1,5-dichloro-1. 1,3,3,5,5-hexamethyltrioxane, 1,7-diethyloxy-1,1,3,3,5,5,7,7-octamethyltetraindole Oxytomane, manufactured by Toray Dow Corning Co., Ltd., PRX413, etc. Examples of the compound represented by the formula (2) include decamethyltetraoxane, dodecamethylpentaoxane, tetradecyl hexaoxane, and KF-96-10 manufactured by Shin-Etsu Chemical Co., Ltd. KF-56, X-24-8201, X-22-174DX, etc. The compound represented by the formula (3) may, for example, be hexamethylcyclotrioxane, octamethylcyclotetraoxane, decamethylcyclopentaoxane, dodecamethylcyclohexaoxane or fourteen. Methylcyclopentaoxane, hexadecylcyclooctaneoxane, trimethyltriphenylcyclotrioxane, hexaphenylcyclotrioxane, and the like.

a hydrolyzable decane capable of imparting an organic siloxane unit (B) The constitution is not limited to the following, but examples thereof include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltriethoxydecane, allyltrimethoxydecane, and p-styryltrimethoxy. Decane, γ-(meth)acryloxypropyltrimethoxydecane, γ-(meth)acryloxypropyltriethoxydecane, γ-(methyl)propenyloxyoctyltrimethyl Oxaloxane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(meth)acryloxypropylmethyldiethoxydecane, and the like.

Specific examples of the hydrolyzable decane to which the organic siloxane unit (C) can be added are not limited to the following, and examples thereof include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, and n-propyl. Trimethoxy decane, isobutyl trimethoxy decane, n-hexyl trimethoxy decane, cyclohexyl trimethoxy decane, phenyl trimethoxy decane, n-decyl trimethoxy decane, and the like.

Specific examples of the low-to-medium polymer which can be used for the hydrolyzable decane of the organic siloxane unit (C) are not limited to the following, and examples thereof include compounds represented by the following formulas (4) and (5).

(In the formula (4), R ⁵ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group; X is an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group or an ethoxy group. Or chlorine; m is an integer of 1 or more and 100 or less.)

(In the formula (5), R ⁵ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group; X is an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group or an ethoxy group. Or chlorine; m is an integer of 3 or more and 50 or less.)

The compound represented by the formula (4) is not limited to the following, and may be, for example, KC-89S, KR-515, KR-500, X-40-9227, KR-213, KR-9218, etc. manufactured by Shin-Etsu Chemical Co., Ltd. . The compound represented by the formula (5) may, for example, be tetraethoxytetramethylcyclotetraoxane or pentaethoxypentamethylcyclopentaoxane.

In the present embodiment, the organosiloxane polymer block (I) may contain the organosiloxane unit (D) represented by the formula (d) or the organosiloxane unit (E) represented by the formula (e). .

(In the formula (e), R ⁸ , R ⁹ and R ¹⁰ are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ⁸ , R ⁹ and R ¹⁰ may be each other. Different base or the same base.)

a hydrolyzable decane capable of imparting an organic oxoxane unit (D) Specific examples of the low-to-medium polymer are not limited to the following, and examples thereof include tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, and X-40-2308 manufactured by Shin-Etsu Chemical Co., Ltd., and X- 40-9238 and so on. Specific examples of the hydrolyzable decane and the low-to-medium polymer which can be imparted to the organic siloxane unit (E) include trimethyl methoxy decane, tripropoxy methoxy decane, and triphenyl methoxy group. Decane, hexamethyldioxane, hexaphenyldioxane, and the like.

In the present embodiment, the polymer block (II) of the ethylenically unsaturated monomer can be obtained, for example, by radical polymerization of one or two or more kinds of ethylenically unsaturated monomers. The radical polymerization catalyst is not particularly limited as long as it can decompose a radical by heat or a reducing substance and cause addition polymerization of an ethylenically unsaturated monomer, and for example, a water-soluble or oil-soluble persulfuric acid can be used. Salt, peroxide, azobis compound, and the like. Specifically, it is not limited to the following, and examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, and tert-butyl peroxybenzoate, 2. 2'-azobis(isobutyronitrile), 2,2'-azobis(2-diaminopropane) hydrochloride, 2,2'-azobis(2,4-dimethylvaleronitrile )Wait.

In general, the radical polymerization reaction is preferably carried out at a polymerization temperature of 65 to 90 ° C under normal pressure, but it may be carried out under high pressure in accordance with characteristics such as vapor pressure in the polymerization temperature of the ethylenically unsaturated monomer. Further, in order to promote the polymerization rate and the low-temperature polymerization at 70 ° C or lower, it is advantageous to use, for example, a reducing agent such as sodium hydrogen sulfite, ferrous chloride, ascorbate or a white block, in combination with a radical polymerization catalyst. Further, in order to adjust the molecular weight, a chain transfer agent such as dodecyl mercaptan may be optionally added.

Specific examples of the ethylenically unsaturated monomer are not limited to the following. However, alkyl (meth)acrylates, cycloalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, (poly)oxyalkylene mono(meth)acrylates, ( Poly)oxyalkylene di(meth)acrylates, aminoalkyl (meth)acrylates, (meth)acrylamides, aromatic vinyl monomers, halogenated vinyl monomers, cyanidation Ethylene monomer, N-vinyl guanamine monomer, ethylenically unsaturated carboxylic acid, and the like.

More specifically, it is not limited to the following, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and second butyl (meth)acrylate. Alkyl methacrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. (meth)acrylic acid alkyl esters having a base number of 1 to 18; cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isodecyl (meth)acrylate, etc. (meth)acrylic acid Cycloalkyl esters; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates; methoxypolyethylene glycol (meth) acrylate , phenoxy polyethylene glycol (meth) acrylate and the like, an alkylene oxide addition molar number of 1 to 100 (poly)oxyalkylene mono (meth) acrylate; polyethylene glycol II ( (Methyl) acrylate, polypropylene glycol di(meth) acrylate, etc., alkylene oxide addition molar number of 1 to 100 (poly)oxyalkylene di(meth) acrylates; (meth)acrylic acid 2-aminoethyl ester, 2-dimethylamino (meth)acrylate Aminoalkyl (meth) acrylate such as ester; (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N-isopropyl (A) Base acrylamide, N-tert-butyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methoxy Methyl (meth) acrylonitrile Amine, N-n-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, etc. Amines; aromatic vinyl monomers such as vinyl toluene, styrene, and α-methylstyrene; halogenated ethylene monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride; (methyl) Cyanide ethylene monomer such as acrylonitrile; N-vinyl such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinyl-ε-caprolactam Indoleamine monomers; (meth)acrylic acid, itaconic acid and its half esters, fumaric acid and its half esters, maleic acid and its half esters, ethylenically unsaturated carboxylic acids; (meth)acrylic acid butyl acrylate Other ethylenically unsaturated monomers such as vinyl acetate.

Further, an ethylenically unsaturated monomer such as a radical polymerizable ultraviolet absorber or a radical polymerizable hindered amine light stabilizer may be used in combination with the above ethylenically unsaturated monomer. The radically polymerizable ultraviolet absorber is not limited to the following, and examples thereof include 2-hydroxy-4-(methyl)propenyloxydiphenyl ketone and 2-hydroxy-5-(meth)acryloxyloxy group. Diphenyl ketone ultraviolet absorber such as phenyl ketone or 2-hydroxy-4-[2-(methyl) propylene oxyethoxy] diphenyl ketone; 2-(2'-hydroxy-5'- Methacryloxyethylphenyl)-2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.), 3-methylpropenyloxy-2-hydroxypropyl-3-[3' -(2"-benzotriazolyl)-4-hydroxy-5-t-butyl]phenylpropionate (CGL-104, manufactured by Ciba-Geigy Co., Ltd., Japan) and other benzotriazole-based ultraviolet absorption Agents, etc. The radically polymerizable hindered amine light stabilizer is not limited to the following, and may, for example, be 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (LA-made by ADEKA Co., Ltd.) 82), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (ADEKA shares) Co., Ltd. LA-87) and so on.

In the present embodiment, the polymer block (II) of the ethylenically unsaturated monomer has a glass transition temperature (T _g ) of 50 ° C or less, and it is preferable to impart flexibility to the aqueous coating composition of the present embodiment. . More preferably, it is 45 ° C or less, and more preferably 40 ° C or less.

Further, in the present embodiment, T _g means a calculated value obtained by the Fox equation. Fox type refers to the following relationship.

1/(T _g +273)=Σ[W _i /(T _gi +273)].

(wherein, W _i represents the mass fraction of the monomer i constituting the polymer; and T _gi represents the T _g (unit: ° C) of the homopolymer of the monomer i.)

Further, the _Tg of the homopolymer of each monomer is described in the Polymer Handbook (Wiley-Interscience), the introduction of synthetic resin for coatings, and the like. Specifically, the values described in the examples and the like can be used.

In the present embodiment, the polymer emulsion (α) can be obtained, for example, by emulsion polymerization in an aqueous solvent. The aqueous solvent mainly uses water, but a water-soluble solvent such as ethanol, isopropyl alcohol or butyl quercetin may be added to the water.

In the present embodiment, the surfactant which can be used in the emulsion polymerization of the polymer emulsion (α) is not particularly limited, but an anionic surfactant and a nonionic surfactant are preferred from the viewpoint of polymerization stability. In particular, a reactive anionic surfactant having a polymerizable unsaturated double bond and a reactive nonionic surfactant are preferred because a polymer emulsion having excellent water resistance of a coating film can be obtained. Specific examples of the reactive anionic surfactant and the reactive nonionic surfactant are not limited to the following, but may be mentioned A compound represented by the formula (6) to (10).

(In the formula (6), R ¹¹ is hydrogen or methyl; R ¹² is an alkyl group having 5 to 30 carbon atoms; A is a C 2 to 4 alkyl group or a substituted alkyl group; X is hydrogen Or SO ₃ M (M is an alkali metal or ammonium.); m is an integer of 1 or more and 200 or less.)

(In the formula (7), R ¹³ is hydrogen or methyl; R ¹⁴ is an alkyl group having 5 to 30 carbon atoms; A is a C 2 to 4 alkyl group or a substituted alkyl group; X is hydrogen Or SO ₃ M (M is an alkali metal or ammonium.); m is an integer of 1 or more and 200 or less.)

(In the formula (8), R ¹⁵ is hydrogen or methyl; R ¹⁶ is an alkyl group having 1 to 30 carbon atoms; A is a C 2 to 4 alkyl group or a substituted alkyl group; X is hydrogen Or SO ₃ M (M is an alkali metal or ammonium.); m is an integer of 1 or more and 200 or less.)

(In the formula (9), R ¹⁷ is hydrogen or an alkyl group having 1 to 20 carbon atoms; A is a C 2 to 4 alkyl group or a substituted alkyl group; X is hydrogen or SO ₃ M (M) It is an alkali metal or ammonium.); m is an integer of 1 or more and 200 or less.)

(In the formula (10), any one of R ¹⁸ and R ¹⁹ is an alkyl group having 1 to 20 carbon atoms, and the other one is an alkenyl group having 1 to 20 carbon atoms or a part thereof is substituted with a hydroxyl group, a carboxyl group or the like; Alkali metal or ammonium.)

The formula (6) is not limited to the following, and examples thereof include ADEKARIASOAP (trademark) ER-10, ER-30, SR-1025, and SR-3025 manufactured by ADEKA CORPORATION. The formula (7) is not limited to the following, and examples thereof include AQUALON (trademark) KH-05, KH-1025, and the like manufactured by First Industrial Pharmaceutical Co., Ltd. The formula (8) is not limited to the following, and examples thereof include ADEKARIASOAP NE-10, NE-30, and SE-1025A manufactured by ADEKA Co., Ltd. The formula (9) is not limited to the following, and examples thereof include AQUALON HS-1025, BC-1025, and RN-2025 manufactured by First Industrial Pharmaceutical Co., Ltd., and the like. The formula (10) is not limited to the following, and examples thereof include ANTOX (trademark) SAD manufactured by Japan Emulsifier Co., Ltd., ELEMINOL (trademark) JS-20 manufactured by Sanyo Chemical Co., Ltd., and Kao shares. LATEMUL (trademark) S-180A, etc.

The reactive surfactant other than the above is not limited to the following, but examples thereof include sodium p-styrenesulfonate, potassium p-styrenesulfonate, sodium (2-sulfoethyl)methacrylate, and (a) Base) potassium (2-sulfoethyl)acrylate, sodium (3-sulfopropyl) (meth)acrylate, potassium (3-sulfopropyl) (meth)acrylate, and the like.

The nonvolatile content of the polymer emulsion (α) in the present embodiment is preferably 60% or less from the viewpoint of polymerization stability. More preferably, it is 55% or less, and more preferably 45% or less. The lower limit of the nonvolatile content is not particularly limited, but is preferably 1%, more preferably 5%, still more preferably 10%. The above nonvolatile content can be measured by the method described in the examples below. Further, in the present embodiment, for example, in the production of a polymer emulsion, a low-to-medium polymer, a polyfluorene macromonomer, and an interfacial activity which contribute to an ethylenically unsaturated monomer, a hydrolyzable decane, and a hydrolyzable decane are appropriately adjusted. The non-volatile content of the polymer emulsion (α) can be obtained by using a raw material of a non-volatile component such as a solvent and a radical polymerization catalyst, and a ratio of a raw material which contributes to a volatile component such as an aqueous solvent. The rate is adjusted to the above range.

In the present embodiment, the volume average particle diameter of the polymer emulsion (α) is preferably 250 nm or less, and it is preferable to impart water resistance to the aqueous coating composition of the present embodiment. More preferably, it is 200 nm or less, and still more preferably 150 nm or less. The lower limit of the volume average particle diameter is not particularly limited, but is preferably 10 nm, more preferably 20 nm, still more preferably 50 nm. The volume average particle diameter can be measured by the method described in the examples below, and can be adjusted to the above range by, for example, appropriately selecting the amount and type of the surfactant.

In the present embodiment, in order to maintain dispersion stability for a long period of time, the polymer emulsion (α) is preferably adjusted to pH after polymerization using an alkali such as ammonia, sodium hydroxide, potassium hydroxide or dimethylaminoethanol. It is in the range of 6 or more and 10 or less. Further, when the organooxane polymer block (I) is produced, when an alkoxy decane is used as a raw material, the alcohol which hydrolyzes by-products lowers the dispersion stability of the polymer emulsion, so it is preferably as needed. After the polymerization step of the polymer emulsion (α), distillation under reduced pressure, blowing of steam or the like is carried out to distill off the alcohol.

In the present embodiment, the non-volatile content of the polymer emulsion (α) is 0.1% by mass or more and 30% by mass or less based on the Si element, and it is necessary to impart stain resistance and weather resistance to the aqueous coating composition of the present embodiment. When the Si element contained in the nonvolatile matter of the polymer emulsion (α) exceeds 30% by mass, the stain resistance is insufficient. On the other hand, when it is less than 0.1% by mass, both the stain resistance and the weather resistance may be insufficient. The preferred amount of the Si element contained in the nonvolatile matter of the polymer emulsion (α) is 0.2% by mass or more and 25% by mass or less, and more preferably 0.5% by mass or more and 20% by mass or less. The amount of the Si element contained in the nonvolatile matter of the polymer emulsion (α) can be analyzed by ICP emission spectrometry (ICP-AES) or the like. Further, in the present embodiment, for example, by adjusting the content of the organosiloxane polymer block (I) in the polymer emulsion (α), the Si element in the nonvolatile portion of the polymer emulsion (α) can be contained. The amount is adjusted to the above range.

<Aqueous polymer (β)>

In the present embodiment, the aqueous polymer (β) is any one of the following: One or more of the ethylenically unsaturated monomers having a mercapto group and/or an amine group, 40 mol% or more and less than 100 mol%, and other ethylenically unsaturated monomers copolymerizable with the same a copolymer composed of one or more kinds of copolymers having more than 0 mol% and 60 mol% or less; and a homopolymer composed of one of an ethylenically unsaturated monomer having a mercaptoamine group and/or an amine group; And a copolymer of two or more kinds of ethylenically unsaturated monomers having a mercapto group and/or an amine group. When the ethylenically unsaturated monomer having a guanamine group and/or an amine group is less than 40 mol%, the water-repellent composition of the present embodiment is insufficient in stain resistance. It is preferably 50 mol% or more, more preferably 60 mol% or more.

The aqueous coating composition of the present embodiment preferably contains 0.1 parts by mass or more and 30 parts by mass or less of the nonvolatile matter of the aqueous polymer (β), based on 100 parts by mass of the nonvolatile matter of the polymer emulsion (α). The ratio of the range makes the aqueous coating composition particularly excellent in stain resistance and weather resistance. More preferably, it is 1 part by mass or more and 25 parts by mass or less, and more preferably 3 parts by mass or more and 20 parts by mass or less.

In the present embodiment, the aqueous polymer (β) may be either a water-soluble polymer or a water-dispersible polymer, and may be in any form of a random polymer, a block polymer or a graft polymer. The production method is not particularly limited, but, for example, by using an ethylenically unsaturated monomer having a mercapto group and/or an amine group alone or in combination with other copolymerizable ethylenically unsaturated monomers in the absence of a solvent or in a solvent Obtained by radical polymerization. The radical polymerization catalyst is not particularly limited as long as it is radically decomposed by heat or a reducing substance and causes addition polymerization of an ethylenically unsaturated monomer. For example, water-soluble or oil-soluble persulfuric acid can be used. Salt, peroxide, azobis compound, and the like. Specifically, it is not limited to the following, and examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, and tert-butyl peroxybenzoate, 2. 2'-azobis(isobutyronitrile), 2,2'-azobis(2-diaminopropane) hydrochloride, 2,2'-azobis(2,4-dimethylvaleronitrile )Wait.

In general, the radical polymerization reaction is preferably carried out at a polymerization temperature of 65 to 90 ° C under normal pressure, but may be carried out under high pressure in combination with characteristics such as vapor pressure in the polymerization temperature of the ethylenically unsaturated monomer. Further, when it is desired to accelerate the polymerization rate and the low-temperature polymerization of 70 ° C or lower, it is advantageous to use, for example, a reducing agent such as sodium hydrogen sulfite, ferrous chloride, ascorbate or a white block, in combination with a radical polymerization catalyst. Further, in order to adjust the molecular weight, a chain transfer agent such as dodecyl mercaptan may be optionally added.

The solvent is not limited to the following, and an aqueous solvent such as water, ethanol, isopropyl alcohol or butyl siatone, and an organic solvent such as diethyl ether, tetrahydrofuran, ethyl acetate or toluene can be used. These solvents are preferably removed by vacuum distillation, steam blowing, or the like after the polymerization step of the aqueous polymer (β), as needed. In the present embodiment, the nonvolatile content of the aqueous polymer (β) is not particularly limited, and may be more than 0% and not more than 100%.

In the present embodiment, the weight average molecular weight of the aqueous polymer (β) is preferably 2,000,000 or less. When the aqueous coating composition of the present embodiment is further prevented from agglomerating by 2,000,000 or less, the storage stability tends to be better. More preferably, it is 1,500,000 or less, and still more preferably 1,000,000 or less. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 1,000, more preferably 2,000, still more preferably 5,000.

Specific examples of the ethylenically unsaturated monomer having a guanamine group The present invention is limited to the following, and examples thereof include (meth)acrylamides represented by formula (11), N-vinylcarboxylates represented by formula (12), and N- represented by formula (13). Vinyl linoleamides.

In the formula (11), R ²⁰ is hydrogen or methyl. R ²¹ and R ²² may be mutually different or the same group, and are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 5 to 10 carbon atoms, and a carbon number. A hydrocarbon group such as an aralkyl group of 6 to 19 or a part thereof is substituted with a hydroxyl group, a carbonyl group, a carboxyl group or the like.

In the formula (12), R ²³ is a hydrocarbon group such as hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 5 to 10 carbon atoms, or an aryl group having 6 to 19 carbon atoms; Or a part thereof is substituted with a hydroxyl group, a carbonyl group, a carboxyl group or the like.

(In the formula (13), m is an integer of 2 or more and 16 or less)

The compound represented by the formula (11) is not limited to the following, but may be mentioned For example, (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N - n-Butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N, N'-methylene double (Methyl) acrylamide and the like. The compound represented by the formula (12) is not limited to the following, and examples thereof include N-vinylformamide and N-vinylacetamide. The compound represented by the formula (13) is not limited to the following, and examples thereof include N-vinyl-2-pyrrolidone and N-vinyl-ε-caprolactam.

Specific examples of the ethylenically unsaturated monomer having an amine group are not limited to the following, and examples thereof include an aminoalkyl (meth)acrylate represented by the formula (14) and an aminobenzene represented by the formula (15). Vinyl.

In the formula (14), R ²⁴ is hydrogen or methyl. R ²⁵ and R ²⁶ may be mutually different or the same group, and are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 5 to 10 carbon atoms, and a carbon number. A hydrocarbon group such as a 6 to 19 aralkyl group or a part thereof is substituted with a hydroxyl group, a carbonyl group, a carboxyl group or the like. m is an integer of 1 or more and 8 or less.

In the formula (15), R ²⁷ and R ²⁸ may be mutually different or the same group, and are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a carbon number of 5 to 10. The hydrocarbon group such as an aryl group or a carbon number of 6 to 19 aralkyl group or a part thereof is substituted with a hydroxyl group, a carbonyl group, a carboxyl group or the like.

The compound represented by the formula (14) is not limited to the following, and examples thereof include 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate. The compound represented by the formula (15) is not limited to the following, and examples thereof include 4-aminostyrene and 3-dimethylaminostyrene.

The ethylenically unsaturated monomer having a functional group of both a mercapto group and an amine group is not limited to the following, and examples thereof include (meth)acrylamide amines represented by the formula (16).

In the formula (16), R ²⁹ is hydrogen or methyl. R ³⁰ and R ³¹ may be mutually different or the same group, and are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 5 to 10 carbon atoms, and a carbon number. A hydrocarbon group such as a 6 to 19 aralkyl group or a part thereof is substituted with a hydroxyl group, a carbonyl group, a carboxyl group or the like. m is an integer of 1 or more and 8 or less.

The compound represented by the formula (16) is not limited to the following, but may be mentioned For example, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, and the like.

Specific examples of the other ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having a mercapto group and/or an amine group are not limited to the following, but an alkyl (meth)acrylate may be mentioned. a naphthyl acrylate, a hydroxyalkyl (meth) acrylate, a (poly)oxyalkylene mono(meth) acrylate, a (poly)oxyalkylene di(meth) acrylate, An aromatic vinyl monomer or an ethylenically unsaturated carboxylic acid.

More specifically, it is not limited to the following, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and second butyl (meth)acrylate. Tert-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. An alkyl (meth)acrylate having 1 to 18 carbon atoms; cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isodecyl (meth)acrylate, etc. (methyl) Cycloalkyl acrylates; 2-hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 2-hydroxypropyl (meth) acrylate; methoxy polyethylene glycol (meth) acrylate Ethylene oxides such as esters, phenoxy polyethylene glycol (meth) acrylate, etc. (poly)oxyalkylene mono(meth)acrylates having a molar number of 1 to 100; polyethylene glycol II (Methyl) acrylate, polypropylene glycol di(meth) acrylate, etc., alkylene oxide addition molar number of 1 to 100 (poly)oxyalkylene di(meth) acrylates; vinyl toluene, Aromatic such as styrene or α-methylstyrene Ethylene monomer; (meth)acrylic acid, itaconic acid and its half ester, fumaric acid and its half ester, maleic acid and its half esters, etc.; ethyl (meth) acrylate Other ethylenically unsaturated monomers such as acid glycidyl ester and vinyl acetate.

Further, an ethylenically unsaturated monomer such as a radical polymerizable ultraviolet absorber or a radical polymerizable hindered amine light stabilizer may be used in combination with the above ethylenically unsaturated monomer. The radically polymerizable ultraviolet absorber is not limited to the following, and examples thereof include 2-hydroxy-4-(methyl)propenyloxydiphenyl ketone and 2-hydroxy-5-(meth)acryloxyloxy group. Diphenyl ketone ultraviolet absorber such as phenyl ketone or 2-hydroxy-4-[2-(methyl) propylene oxyethoxy] diphenyl ketone; 2-(2'-hydroxy-5'- Methacryloxyethylphenyl)-2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.), 3-methylpropenyloxy-2-hydroxypropyl-3-[3' -(2"-benzotriazolyl)-4-hydroxy-5-t-butyl]phenylpropionate (CGL-104, manufactured by Ciba-Geigy Co., Ltd., Japan) and other benzotriazole-based ultraviolet absorption Agents, etc. The radically polymerizable hindered amine light stabilizer is not limited to the following, and may, for example, be 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (LA-made by ADEKA Co., Ltd.) 82), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (LA-87, manufactured by ADEKA Co., Ltd.), and the like.

A commercially available product can be used for the water-soluble polymer (β), and specific examples thereof are not limited to the following, but PITTSCALL (trademark) K-30, K-30L, K-30A, K- manufactured by Daiichi Kogyo Co., Ltd. 30AL, K-50, K-60L, K-80, K-85, K-90, V-7154; PNVA (trademark) GE191-104, GE191-107, GE191-408, manufactured by Showa Denko Co., Ltd.; BASF JAPAN KOLLIDON (trademark) 12PF, 17PF, 25, 30, 90F manufactured by Otsuka Co., Ltd.; APA P-280 manufactured by Otsuka Chemical Co., Ltd., etc.

<colloidal inorganic particles (γ)>

The aqueous coating composition of the present embodiment preferably contains colloidal inorganic particles (γ) to further improve the stain resistance. More preferably, the non-volatile content of the colloidal inorganic particles (γ) is 0.1 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the nonvolatile matter of the polymer emulsion (α), and the aqueous coating composition is stain-resistant and The tendency to be particularly excellent in weather resistance. More preferably, it is 1 part by mass or more and 20 parts by mass or less. The aqueous coating composition of the present embodiment allows a polymer emulsion containing the specific organic siloxane polymer block, an aqueous polymer having a guanamine group and/or an amine group, and inorganic particles to coexist. The polymer emulsion containing the specific organic siloxane polymer block is effectively phase-separated from the inorganic particles, and a form in which the inorganic particles are partially localized can be formed on the surface of the coating film. This makes it possible to combine both low pollution and weather resistance.

In the present embodiment, the colloidal inorganic particles (?) are preferably colloidal cerium oxide, which is easy to obtain and inexpensive. The colloidal ceria can also be prepared by a sol-gel method, or a commercially available product can also be used. For the preparation of colloidal cerium oxide by sol-gel method, for example, see Werner Stober et al; J. Colloid and Interface Sci., 26, 62-69 (1968), Rickey D. Badley et al; Langmuir 6, 792-801 ( 1990), Color Materials Association, 61 [9] 488-493 (1988) and so on. The colloidal cerium oxide is a dispersion of water or an aqueous solvent of cerium oxide having cerium oxide as a basic unit, and the average particle diameter thereof is preferably 5 nm or more and 120 nm or less, more preferably 10 nm or more and 80 nm or less. When the particle diameter is 5 nm or more, the storage stability of the coating liquid tends to be increased, and when it is 120 nm or less, the water whitening resistance tends to be improved. The colloidal ceria having a particle diameter in the above range may be acidic or alkali in the state of an aqueous dispersion. Sexuality can be selected according to the stability field of the mixed polymer emulsion (α).

The commercially available acidic colloidal cerium oxide is not limited to the following. For example, SNOWTEX (trademark)-OS, SNOWTEX-O, SNOWTEX-OL, and ADEKA Co., Ltd., manufactured by Nissan Chemical Industries, Ltd., can be used. ADELITE (trademark) AT-20Q, KUREBOZORU (trademark) 20H12, KUREBOZORU 30CAL25, manufactured by CLARIANT JAPAN Co., Ltd., and the like.

The basic colloidal cerium oxide is cerium oxide which is stabilized by the addition of an alkali metal ion, an ammonium ion or an amine, and is not limited to the following, and may be, for example, SNOWTEX-20, SNOWTEX- manufactured by Nissan Chemical Industries Co., Ltd. 30, SNOWTEX-C, SNOWTEX-C30, SNOWTEX-CM40, SNOWTEX-N, SNOWTEX-N30, SNOWTEX-K, SNOWTEX-XL, SNOWTEX-YL, SNOWTEX-ZL, SNOWTEXPS-M, SNOWTEXPS-L, etc.; Company made ADELITE AT-20, ADELITE AT-30, ADELITE AT-20N, ADELITE AT-30N, ADELITE AT-20A, ADELITE AT-30A, ADELITE AT-40, ADELITE AT-50, etc.; KUREBOZORU made by CLARIANT JAPAN Co., Ltd. 30R9, KUREBOZORU 30R50, KUREBOZORU 50R50, etc.; LUDOX (trademark) HS-40, LUDOX HS-30, LUDOX LS, LUDOX SM-30, etc. manufactured by DuPont.

The colloidal cerium oxide which is an aqueous medium as a dispersion medium is not limited to the following, and may be, for example, MA-ST-M (methanol dispersion type), IPAST (isopropyl alcohol dispersion type), EG- manufactured by Nissan Chemical Industries, Ltd. ST (B Glycol dispersion type), EG-ST-ZL (ethylene glycol dispersion type), NPC-ST (ethylene glycol monopropyl ether dispersion type), and the like. These colloidal cerium oxides may be used alone or in combination of two or more kinds, and may contain alumina, sodium aluminate or the like as a small amount of components. Further, the colloidal cerium oxide may contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia or an organic base such as tetramethylammonium as a stabilizer.

An inorganic compound which can obtain colloidal particles other than cerium oxide can be used as the colloidal inorganic particles (γ), and specific examples thereof are not limited thereto, and examples thereof include TiO ₂ , TiO ₃ , SrTiO ₃ , FeTiO ₃ , and WO ₃ . SnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , ZnO, Fe ₂ O ₃ , RuO ₂ , CdO, CdS, CdSe, GaP, GaAs, CdFeO ₃ , MoS ₂ , LaRhO ₃ , GaN, CdP, ZnS, ZnSe, _{ZnTe, Nb 2 O 5, ZrO} 2, InP, GaAsP, InGaAlP, AlGaAs, PbS, InAs, PbSe, InSb , etc. capable of having a photocatalytic semiconductor, in addition include _{Al 2 O 3, AlGa, As} , Al (OH) 3 , Sb ₂ O ₅ , Si ₃ N ₄ , Sn-In ₂ O ₃ , Sb-In ₂ O ₃ , MgF, CeF ₃ , CeO ₂ , 3Al ₂ O ₃ . 2SiO ₂ , BeO, SiC, AlN, Fe, Co, Co-FeOX, CrO ₂ , Fe ₄ N, BaTiO ₃ , BaO-Al ₂ O ₃ -SiO ₂ , Ba ferrite, SmCO ₅ , YCO ₅ , CeCO ₅ PrCO ₅ , Sm ₂ CO ₁₇ , Nd ₂ Fe ₁₄ B, Al ₄ O ₃ , α-Si, SiN ₄ , CoO, Sb-SnO ₂ , Sb ₂ O ₅ , MnO ₂ , MnB, Co ₃ O ₄ , Co ₃ B, LiTaO ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂ O ₄ , ZrSiO ₄ , ZnSb, PbTe, GeSi, FeSi ₂ , CrSi ₂ , COSi ₂ , MnSi _1.73 , Mg ₂ Si, β-B, BaC, BP, BaC, BP, TiB ₂ , ZrB ₂ , HfB ₂ , Ru ₂ Si ₃ , TiO ₂ (rutile), TiO ₃ , PbTiO ₃ , Al ₂ TiO ₅ , Zn ₂ SiO ₄ , Zr ₂ SiO ₄ , 2MgO ₂ - Al ₂ O ₂ -5SiO ₂ , Nb ₂ O ₅ , Li ₂ O-Al ₂ O ₃ -4SiO ₂ , Mg ferrite iron, Ni ferrite iron, Ni-Zn ferrite iron, Li ferrite iron, Sr fertilizer Iron and so on. These colloidal inorganic particles can be used alone or in combination of two or more.

The aqueous coating composition of the present embodiment can be produced by mixing a polymer emulsion (α), an aqueous polymer (β), optionally colloidal inorganic particles (γ), and optionally water, and the production method is not Specially limited. The order of mixing is not particularly limited. For example, (α), (β), optionally (γ), and optionally water may be mixed together, or may be sequentially mixed in any order. The temperature at the time of mixing is not particularly limited, but is preferably 90 ° C or lower. By setting it as 90 ° C or less, the aggregation of the aqueous coating composition of this embodiment can be further prevented, and the manufacturing stability tends to be good. More preferably, it is 70 ° C or less, and more preferably 50 ° C or less. The lower limit is not particularly limited, but is preferably 0 ° C, more preferably 5 ° C.

<Other added ingredients>

The aqueous coating composition of the present embodiment can be optionally blended with components which can be added to an aqueous coating material, such as a film forming aid, a plasticizer, a freeze preventing agent, an antifoaming agent, a tackifier, an ultraviolet absorber, and a hindered amine system. Light stabilizer, preservative, antioxidant, algicide, mold inhibitor, pigment, pigment dispersion, dye, matting agent, etc.

In the aqueous coating composition of the present embodiment, for example, after the centrifugal separator is applied, the polymer emulsion (α) component of the shoal can be supplied to various analyses such as ICP-AES or NMR, whereby the polymer emulsion contained can be qualitatively analyzed ( α). Further, for example, after the above-described centrifugation operation, the obtained supernatant liquid is concentrated and supplied to various analyses such as NMR or mass spectrometry to qualitatively analyze the aqueous polymer (β) contained therein. Further, for example, the colloidal inorganic particle (γ) component of the Shen Dian can be supplied to the elemental analysis after the centrifugal separation operation described above. By various analyses, the colloidal inorganic particles (γ) contained in the qualitative analysis can be confirmed by using a dynamic light scattering type nanometer particle size analyzer or an electron microscope as a measuring means.

<Use of aqueous coating composition>

The aqueous coating composition of the present embodiment can be used for directly coating various bodies and members such as buildings, architectural finishing materials, building materials, steel structures, steel materials, mortars, concrete, automobiles, woven fabrics, non-woven fabrics, and plastics, or It is used as a coating for surface coating, a transparent paint, a top coater, and the like.

<coating film>

Next, the coating film of this embodiment will be described.

The coating film of the present embodiment contains inorganic particles and a binder component having an average particle diameter of 100 nm or less, and the area ratio of the inorganic particles on the surface of the coating film is 49.9% or less, and the inorganic particles are on the surface of the coating film. The average area size is 500 square nm or more. According to the above configuration, the coating film of the present embodiment can have excellent stain resistance and weather resistance.

In the case of the stain resistance, for example, the color difference ⊿E (the rain stained portion - the non-rain mark dirty portion) in the outdoor exposure test described later is 2.5 or less, and it can be evaluated as excellent in the stain resistance. In addition, the weather resistance is, for example, 1,500 hours or more in which the gloss retention rate is maintained at 80% or more in the accelerated weather resistance test using the weather resistance tester described later, and it is evaluated as excellent in weather resistance.

Generally, the more inorganic particles are present on the surface of the coating film, the higher the stain resistance. On the other hand, the more inorganic particles are present on the surface of the coating film, the lower the weather resistance. In the coating film of the present embodiment, the area ratio of the inorganic particles in the surface of the coating film is 49.9% or less, and the weather resistance can be exhibited, and the average particle size of the inorganic particles on the surface of the coating film is 500 square nm or more. Range, but can show the pollution resistance.

In the coating film of the present embodiment, the area ratio of the inorganic particles in the surface of the coating film is preferably 44.9% or less, more preferably 39.9% or less, and particularly preferably 34.9% or less from the viewpoint of further improving the weather resistance.

In the coating film of the present embodiment, the average particle size of the inorganic particles on the surface of the coating film is more preferably 600 square nm or more, more preferably 800 square nm or more, and still more preferably 1000, from the viewpoint of further improving the stain resistance. Above square nm.

The area ratio of the inorganic particles in the surface of the coating film and the average area size of the inorganic particles on the surface of the coating film are not limited to the following, but for example, by adjusting the mass ratio of the inorganic particles to the binder component, etc., Adjust to the above preferred range. In the above-mentioned embodiment, it is preferable that the inorganic particles are contained in an amount of 0.1 part by mass or more and 25 parts by mass or less, more preferably 0.5 part by mass, based on 100 parts by mass of the total of the inorganic particles and the binder component. More than 20 parts by mass or less, and more preferably 1 part by mass or more and 15 parts by mass or less.

<Weather resistance>

In the present embodiment, the so-called pollution resistance evaluation of the outdoor exposure test 1 The darkness of the rain marks attached after months, 6 months, and 1 year later, specifically, the color difference meter is used to calculate the value of the excellent difference E (the part of the rain mark and the part of the non-rain mark). Evaluator.

<Weather resistance>

In the present embodiment, the weather resistance is evaluated by using a weathering resistance test for promoting the weather resistance tester. Specifically, an ultraviolet illuminometer UVP365-01 (manufactured by Iwasaki Electric Co., Ltd.) was used and adjusted to an accelerated weather resistance tester having an irradiance of 81 mW/cm ² ; Step 1) maintaining a blackboard temperature of 63 ° C and irradiating light for 4 hours; Step 2) Spray water for 30 seconds in the dark; Step 3) Keep the blackboard temperature 30 ° C and the humidity in the tank 98%, wet for 4 hours under darkness; Step 4) Spray water for 30 seconds in the dark; Step 5) Keep the temperature of the blackboard The temperature was 40% at 40 ° C and dried in the dark for 20 minutes.

The cycle test was carried out by the above steps 1) to 5), and the gloss retention of the coating film was maintained at 80% or more, and the obtained value was evaluated.

<The area occupancy of inorganic particles in the surface of the coating film>

As a method for obtaining the area occupation ratio of the inorganic particles on the surface of the coating film, a method of performing image processing by scanning a secondary electron image of a scanning electron microscope (SEM) on the surface of the coating film; element The SEM (SEM-EDX) of the analyzer determines the concentration of the inorganic element derived from the inorganic particles on the surface of the coating film, and converts it into the area occupancy ratio of the inorganic particles; and by X-ray photoelectron spectroscopy (XPS) The method of determining the concentration of the inorganic element derived from the inorganic particles in the surface of the coating film and converting it into the area occupancy ratio of the inorganic particles is obtained. In the present embodiment, the area occupation ratio of the inorganic particles on the surface of the coating film is a value obtained by subjecting a secondary electron image of the SEM of the surface of the coating film to image processing. More specifically, it can be measured by the method described in the examples below.

<Average area size of inorganic particles in the surface of the coating film>

In the present embodiment, the average size of the inorganic particles in the surface of the coating film is determined by subjecting the secondary electron image of the SEM of the surface of the coating film to image processing. More specifically, it can be measured by the method described in the examples below.

<Inorganic Particles>

Specific examples of the inorganic particles in the present embodiment are not limited to the following, and examples thereof include SiO ₂ , TiO ₂ , TiO ₃ , SrTiO ₃ , FeTiO ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , and ZnO. , Fe ₂ O ₃ , RuO ₂ , CdO, CdS, CdSe, GaP, GaAs, CdFeO ₃ , MoS ₂ , LaRhO ₃ , GaN, CdP, ZnS, ZnSe, ZnTe, Nb ₂ O ₅ , ZrO ₂ , InP, GaAsP, Semiconductors having photocatalytic properties such as InGaAlP, AlGaAs, PbS, InAs, PbSe, and InSb, and examples thereof include Al ₂ O ₃ , AlGa, As, Al(OH) ₃ , Sb ₂ O ₅ , Si ₃ N ₄ , and Sn-In. ₂ O ₃ , Sb-In ₂ O ₃ , MgF, CeF ₃ , CeO ₂ , 3Al ₂ O ₃ . 2SiO ₂ , BeO, SiC, AlN, Fe, Co, Co-FeOX, CrO ₂ , Fe ₄ N, BaTiO ₃ , BaO-Al ₂ O ₃ -SiO ₂ , Ba ferrite, SmCO ₅ , YCO ₅ , CeCO ₅ PrCO ₅ , Sm ₂ CO ₁₇ , Nd ₂ Fe ₁₄ B, Al ₄ O ₃ , α-Si, SiN ₄ , CoO, Sb-SnO ₂ , Sb ₂ O ₅ , MnO ₂ , MnB, Co ₃ O ₄ , Co ₃ B, LiTaO ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂ O ₄ , ZrSiO ₄ , ZnSb, PbTe, GeSi, FeSi ₂ , CrSi ₂ , CoSi ₂ , MnSi _1.73 , Mg ₂ Si, β-B, BaC, BP, BaC, BP, TiB ₂ , ZrB ₂ , HfB ₂ , Ru ₂ Si ₃ , TiO ₂ (rutile), TiO ₃ , PbTiO ₃ , Al ₂ TiO ₅ , Zn ₂ SiO ₄ , Zr ₂ SiO ₄ , 2MgO ₂ - Al ₂ O ₂ -5SiO ₂ , Nb ₂ O ₅ , Li ₂ O-Al ₂ O ₃ -4SiO ₂ , Mg ferrite iron, Ni ferrite iron, Ni-Zn ferrite iron, Li ferrite iron, Sr fertilizer Iron or the like may be used alone or in combination of two or more. Preferred is TiO ₂ or SiO ₂ .

From the viewpoint of transparency of the coating film, in the present embodiment, the average particle diameter of the inorganic particles must be 100 nm or less. The average particle diameter of the inorganic particles is more preferably 60 nm or less, still more preferably 50 nm or less, and particularly preferably 40 nm or less. The average particle diameter of the inorganic particles can be determined from the secondary electron image of the SEM of the surface of the coating film.

<Binder composition>

The coating film of this embodiment contains a binder component, and the binder component contains a polymer.

The binder component contains a polymer containing the organosiloxane unit (A) represented by the above formula (a) and an aqueous polymer (β), whereby the area of the inorganic particles in the surface of the coating film can be obtained. The rate is 49.9% or less and the average area size of the inorganic particles in the surface of the coating film is 500 square nm or more. Coating film.

Moreover, from the viewpoint of imparting weather resistance to the coating film, it is preferred that the binder component contains a polymer containing the organosiloxane unit (B) represented by the above formula (b).

Moreover, from the viewpoint of imparting weather resistance to the coating film, it is preferred that the binder component contains a polymer containing the organosiloxane unit (C) represented by the above formula (c).

The coating film of the present embodiment having the above-described characteristics is not limited to the following, and it is preferably obtained by, for example, forming the aqueous coating composition of the present embodiment. As described above, for example, the aqueous coating composition of the present embodiment can be applied to the surface of the coated body and dried, whereby the area occupation ratio of the inorganic particles in the surface of the coating film and the average area size of the inorganic particles in the surface of the coating film can be respectively Adjust to the above preferred range.

In the present embodiment, the coating method of the aqueous coating composition can be appropriately selected depending on the use of the object to be coated, the material of the object to be coated, and the like, and is not particularly limited, and examples thereof include a spray blowing method and a roll coating method. , curtain coating method, spin coating method, dip coating method, bar coating method, brush coating method, and the like. After coating, it was dried and volatiles were removed, whereby a coating film was obtained. At this time, heat treatment at a temperature of about 40 to 200 ° C or ultraviolet irradiation treatment may be further performed as needed.

<Other ingredients>

The coating film of the present embodiment may contain a component which is usually added to an aqueous coating material, such as a film forming aid, a plasticizer, a freeze preventing agent, an antifoaming agent, Adhesives, ultraviolet absorbers, hindered amine light stabilizers, preservatives, antioxidants, algaecides, fungicides, pigments, pigment dispersions, dyes, matting agents, etc.

The coating film of the present embodiment can be qualitatively and quantitatively analyzed for inorganic particles present on the surface of the coating film by, for example, supplying the surface to various analyses such as SEM, SEM-EDX, and XPS. Further, for example, the organic oxirane unit contained in the binder can be qualitatively analyzed by supplying the pulverized material of the coating film to various analyses such as solid state NMR. Further, the aqueous polymer (β) contained in the adhesive can be qualitatively analyzed by supplying the surface of the coating film to various analyses such as time-of-flight secondary ion mass spectrometry (TOF-SIMS).

<Use of coating film>

The coating film of the present embodiment is not limited to the following, but can be used, for example, for various bodies and members such as buildings, architecturally modified coating materials, building materials, steel structures, steel materials, mortars, concrete, automobiles, woven fabrics, non-woven fabrics, and plastics. Use for direct coating, or as a coating for surface coating, transparent paint, top coat, etc.

[Examples]

This embodiment will be described in detail by way of examples and comparative examples, but the embodiment is not limited to the examples. In addition, "parts" and "%" in the examples and comparative examples indicate "mass parts" and "mass%", respectively.

Non-volatile content of polymer emulsion (α) and aqueous polymer (β), volume average particle diameter of polymer emulsion (α), Si element analysis of polymer emulsion (α), and organic siloxane polymer embedding The identification of paragraph (I) is as follows Find the analytical method.

<nonvolatile content>

About 1 g of the polymer emulsion (α) or the aqueous polymer (β) was weighed in an aluminum pan, and dried by heating at 105 ° C for 3 hours in a hot air dryer, and the residue was weighed, and the nonvolatile content was calculated by the following formula.

Nonvolatile content (%) = mass of residual portion after heating and drying / mass before heating and drying × 100.

<Volume average particle size>

The volume average particle diameter of the polymer emulsion (α) was measured by a particle size analyzer (manufactured by Nikkiso Co., Ltd., model: Microtrac UPA-150) using a dynamic light scattering method.

<Si element analysis>

After the non-volatile matter of the polymer emulsion (α) was pretreated by a wet chemical decomposition and an alkali fusion method, Si element analysis was carried out by ICP-AES (manufactured by Thermo Fisher Scientific Co., Ltd., type: iCAP6300Duo).

< ²⁹ Si NMR analysis>

For the non-volatile portion of the polymer emulsion (α), ²⁹ Si solid state NMR measurement was carried out under the following conditions.

Device: manufactured by Bruker, model: Biospin DSX400.

Frequency: 79.48 MHz.

Determination method: DD/MAS method.

Chemical shift reference: TMS (CHCl ₃ solution).

The organooxane units corresponding to the respective peaks were determined on the ²⁹ Si solid NMR spectrum, and the molar ratio of each organooxane unit was calculated from the integrated values of the peaks.

<Production Example of Polymer Emulsion (α)>

[Manufacturing Example 1] (α1)

In a reaction vessel equipped with a stirrer, a reflux condenser, two dropping tanks, and a thermometer, 680 parts of deionized water was added as a surfactant, AQUALON KH-1025 (trade name, manufactured by Daiichi Kogyo Co., Ltd., 25% aqueous solution). 30 parts, and 1 part of dodecylbenzenesulfonic acid. 465 parts of methyl methacrylate, 250 parts of cyclohexyl methacrylate, 265 parts of 2-ethylhexyl acrylate, 20 parts of methacrylic acid, 660 parts of deionized water, and ammonium persulfate as a polymerization initiator A mixture of 60 parts of % aqueous solution, 30 parts of AQUALON KH-1025 as a surfactant, and 1 part of dodecylbenzenesulfonic acid was stirred by a homogenizer, and the obtained pre-emulsion was added to a dropping tank. Further, a mixed liquid composed of 130 parts of dimethyldimethoxydecane and 35 parts of γ-methylpropoxypropyltrimethoxydecane was placed in another dropping tank. When the temperature of the reaction vessel was raised to 80 ° C, 15 parts of a 2% aqueous solution of ammonium persulfate was added, and after 5 minutes, the pre-emulsion and the decane mixture were dropped into the reaction vessel at a fixed flow rate for 200 minutes. After the completion of the dropwise addition, the mixture was kept at 80 ° C for 200 minutes, and then cooled to room temperature. The hydrogen ion concentration was measured and the pH was in the range of 2.0 to 3.0. After adding ammonia water and adjusting the pH to a range of 8.0 to 9.0, it was filtered with a mesh filter to obtain a polymer emulsion (α1) having a volume average particle diameter of 95 nm. At this time, the nonvolatile content of the polymer emulsion was 42.4%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 2.9%.

²⁹ Si NMR analysis: δ -23 ppm (88Si, organic oxirane unit derived from dimethyl dimethoxy decane condensate), δ -85ppm (12Si, derived from γ-methyl propylene methoxy propylene An organic oxoxane unit of a condensate of a trimethoxy decane.

[Manufacturing Example 2] (α2)

The volume average particle diameter was obtained by the same operation as in Production Example (α1) except that the decane mixture was changed to a mixed liquid of 140 parts of dimethyldimethoxydecane and 30 parts of phenyltrimethoxydecane. 95 nm polymer emulsion (α2). At this time, the nonvolatile content of the polymer emulsion was 42.3%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 3.1%.

²⁹ Si NMR analysis: δ -23 ppm (88Si, an organic oxoxane unit derived from a condensate of dimethyldimethoxydecane), δ -74 to -81 ppm (12Si, derived from phenyltrimethoxydecane) The organic oxirane unit of the condensate).

[Manufacturing Example 3] (α3)

In addition to changing the decane mixture to a mixture of 125 parts of dimethyldimethoxydecane, 35 parts of γ-methylpropoxypropyltrimethoxydecane, and 5 parts of phenyltrimethoxydecane A polymer emulsion (α3) having a volume average particle diameter of 93 nm was obtained in the same manner as in Production Example (α1). At this time, the nonvolatile content of the polymer emulsion was 42.4%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 2.9%.

²⁹ Si NMR analysis: δ -23 ppm (86Si, organic oxirane unit derived from condensate of dimethyl dimethoxy decane), δ -74 to -81 ppm (2Si, derived from phenyltrimethoxydecane) The organic oxirane unit of the condensate, δ -85 ppm (12Si, an organic oxirane unit derived from a condensate of γ-methacryloxypropyltrimethoxydecane).

[Manufacturing Example 4] (α4)

A polymer emulsion (α4) having a volume average particle diameter of 91 nm was obtained by the same operation as in Production Example (α1) using the polymerization raw materials shown in Table 1 below. At this time, the nonvolatile content of the polymer emulsion was 42.5%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 2.7%

²⁹ Si NMR analysis: δ -23 ppm (66Si, an organic oxoxane unit derived from a condensate of dimethyldimethoxydecane), δ -74 to -81 ppm (28Si, derived from phenyltrimethoxydecane) The organic oxirane unit of the condensate, δ -85 ppm (6Si, an organic oxirane unit derived from a condensate of γ-methacryloxypropyltrimethoxydecane).

[Manufacturing Example 5] (α5)

A polymer emulsion (α5) having a volume average particle diameter of 95 nm was obtained by using the polymerization raw material shown in Table 1 below and operating in the same manner as in Production Example (α1). At this time, the nonvolatile content of the polymer emulsion was 42.5%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 2.4%.

²⁹ Si NMR analysis: δ -23 ppm (48Si, organic oxirane unit derived from condensate of dimethyl dimethoxy decane), δ -74 to -81 ppm (45Si, derived from phenyltrimethoxydecane) The organic oxirane unit of the condensate, δ -85 ppm (6Si, an organic oxirane unit derived from a condensate of γ-methacryloxypropyltrimethoxydecane).

[Manufacturing Example 6] (α6)

A polymer emulsion (α6) having a volume average particle diameter of 96 nm was obtained by using the polymerization raw material shown in Table 1 below and operating in the same manner as in Production Example (α1). At this time, the nonvolatile content of the polymer emulsion was 42.2%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si elemental analysis: 3.3%.

²⁹ Si NMR analysis: δ -23 ppm (99Si, organic oxirane unit derived from condensate of dimethyl dimethoxy decane), δ -85 ppm (1Si, derived from γ-methyl propylene methoxy propylene An organic oxoxane unit of a condensate of a trimethoxy decane.

[Manufacturing Example 7] (α7)

A polymer emulsion (α7) having a volume average particle diameter of 96 nm was obtained by the same operation as in Production Example (α1) using the polymerization raw materials shown in Table 1 below. At this time, the nonvolatile content of the polymer emulsion was 42.1%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 3.4%

²⁹ Si NMR analysis: δ -23 ppm (organomethoxy oxane unit derived from a condensate of dimethyl dimethoxy decane).

[Manufacturing Example 8] (α8)

In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 680 parts of deionized water and 30 parts of AQUALON KH-1025 as a surfactant were added. 465 parts of methyl methacrylate, 250 parts of cyclohexyl methacrylate, 265 parts of 2-ethylhexyl acrylate, 20 parts of methacrylic acid, 660 parts of deionized water, and ammonium persulfate as a polymerization initiator A mixture of 60 parts of a 2% aqueous solution and 30 parts of AQUALON KH-1025 as a surfactant was stirred by a homogenizer, and the obtained pre-emulsion was added to a dropping tank. When the temperature of the liquid in the reaction vessel reached 80 ° C, 15 parts of a 2% aqueous solution of ammonium persulfate was added, and after 5 minutes, the pre-emulsion was dropped into the reaction vessel at a fixed flow rate for 200 minutes. After the completion of the dropwise addition, the mixture was kept at 80 ° C for 200 minutes, and then cooled to room temperature. The hydrogen ion concentration was measured and the pH was in the range of 2.0 to 3.0. After adding ammonia water and adjusting the pH to a range of 8.0 to 9.0, it was filtered with a mesh filter to obtain a polymer emulsion (α8) having a volume average particle diameter of 92 nm. At this time, the nonvolatile content of the polymer emulsion was 41.1%.

No Si element was detected from the nonvolatile portion of the polymer emulsion (α8), and no peak was detected in the ²⁹ Si NMR measurement.

[Manufacturing Example 9] (α9)

In a reaction vessel equipped with a stirrer, a reflux condenser, two dropping tanks and a thermometer, 2,040 parts of deionized water, 30 parts of AQUALON KH-1025 as a surfactant, and 2 parts of dodecylbenzenesulfonic acid were added. 465 parts of methyl methacrylate, 250 parts of cyclohexyl methacrylate, 265 parts of 2-ethylhexyl acrylate, 20 parts of methacrylic acid, 660 parts of deionized water, and ammonium persulfate as a polymerization initiator 60 parts of a 2% aqueous solution, and a mixture of 30 parts of AQUALON KH-1025 as a surfactant and 8 parts of dodecylbenzenesulfonic acid were stirred by a homogenizer, and the obtained pre-emulsion was added to a dropping tank. Further, a mixed liquid composed of 1,050 parts of dimethyldimethoxydecane and 20 parts of γ-methylpropoxypropyltrimethoxydecane was placed in another dropping tank. The reaction vessel was heated, and when the liquid temperature in the reaction vessel reached 80 ° C, 15 parts of a 2% aqueous solution of ammonium persulfate was added. After 5 minutes, the pre-emulsion and the decane mixture were dropped into the reaction vessel at a fixed flow rate for 200 minutes. Inside. After the completion of the dropwise addition, the mixture was kept at 80 ° C for 200 minutes, and then cooled to room temperature. At this time, the nonvolatile content of the polymer emulsion was 33.2%. Next, methanol was distilled off under reduced pressure using a rotary evaporator, and the hydrogen ion concentration was measured, and the pH was in the range of 2.0 to 3.0. After adding ammonia water and adjusting the pH to a range of 8.0 to 9.0, it was filtered with a mesh filter to obtain a polymer emulsion (α9) having a volume average particle diameter of 112 nm. At this time, the nonvolatile content of the polymer emulsion was 42.0%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 13.8%.

²⁹ Si NMR analysis: δ -23 ppm (99Si, organic oxirane unit derived from condensate of dimethyl dimethoxy decane), δ -85 ppm (1Si, derived from γ-methyl propylene methoxy propylene An organic oxoxane unit of a condensate of a trimethoxy decane.

[Manufacturing Example 10] (α10)

20,400 parts of deionized water, 30 parts of AQUALON KH-1025 as a surfactant, and 18 parts of dodecylbenzenesulfonic acid were added to a reaction vessel equipped with a stirrer, a reflux condenser, two dropping tanks, and a thermometer. 465 parts of methyl methacrylate, 250 parts of cyclohexyl methacrylate, 265 parts of 2-ethylhexyl acrylate, 20 parts of methacrylic acid, 660 parts of deionized water, and ammonium persulfate as a polymerization initiator 60 parts of a 2% aqueous solution, and a mixture of 30 parts of AQUALON KH-1025 as a surfactant and 72 parts of dodecylbenzenesulfonic acid were stirred by a homogenizer, and the obtained pre-emulsion was added to a dropping tank. Further, a mixed liquid composed of 9,450 parts of dimethyldimethoxydecane and 180 parts of γ-methylpropenyloxypropyltrimethoxydecane was placed in another dropping tank. The reaction vessel was heated, and when the liquid temperature in the reaction vessel reached 80 ° C, 15 parts of a 2% aqueous solution of ammonium persulfate was added. After 5 minutes, the pre-emulsion and the decane mixture were dropped into the reaction vessel at a fixed flow rate for 200 minutes. Inside. After the completion of the dropwise addition, the mixture was kept at 80 ° C for 200 minutes, and then cooled to room temperature. At this time, the nonvolatile content of the polymer emulsion was 20.3%. Next, methanol was distilled off under reduced pressure using a rotary evaporator, and the hydrogen ion concentration was measured, and the pH was in the range of 2.0 to 3.0. After adding ammonia water and adjusting the pH to a range of 8.0 to 9.0, it was filtered with a mesh filter to obtain a polymer emulsion (α10) having a volume average particle diameter of 130 nm. At this time, the nonvolatile content of the polymer emulsion was 42.0%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 30.9%.

²⁹ Si NMR analysis: δ -23 ppm (99Si, organic oxirane unit derived from condensate of dimethyl dimethoxy decane), δ -85 ppm (1Si, derived from γ-methyl propylene methoxy propylene Organic oxoxane unit of condensate of trimethoxy decane)

[Manufacturing Example 11] (α11)

The same operation as in Production Example (α1) except that the decane mixture was changed to a mixed liquid of 130 parts of dimethyldimethoxynonane and 35 parts of γ-propyleneoxypropyltrimethoxydecane. A polymer emulsion (α11) having a volume average particle diameter of 95 nm was obtained. At this time, the nonvolatile content of the polymer emulsion was 42.3%. The Si element analysis results and the ²⁹ Si NMR analysis results are shown below.

Si element analysis: 2.9%.

²⁹ Si NMR analysis: δ -23 ppm (87Si, organic oxirane unit derived from condensate of dimethyl dimethoxy decane), δ -85 ppm (13Si, derived from γ-acryloxypropyltrimethyl) The analysis results of the polymerization raw materials of the polymer emulsions (α1) to (α11) and the polymer emulsions are shown in Table 1 for the organic oxirane unit of the condensed product of oxydecane. Further, in the table, the Tg of the polymer (II) of the ethylenically unsaturated monomer is a calculated value obtained from the Fox formula, and the T _g of the homopolymer of each monomer is the following value.

<T _{g of} homopolymer of ethylenically unsaturated monomer>

Methyl methacrylate: 105 ° C.

Cyclohexyl methacrylate: 83 ° C.

2-ethylhexyl acrylate: -55 ° C.

Methacrylic acid: 144 ° C.

<Production Example of Aqueous Polymer (β)>

[Manufacturing Example 12] (β1)

100 parts of N-vinylpyrrolidone, 1 part of 2,2'-azobis(isobutyronitrile), and 300 parts of isopropyl alcohol were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer. The reaction vessel was heated while stirring the liquid temperature in the reaction vessel at 80 ° C for 240 minutes, and then cooled to room temperature. After adding 500 parts of deionized water, isopropanol was distilled off under reduced pressure on a rotary evaporator to obtain an aqueous polymer (β1). At this time, the non-volatile content of the aqueous polymer was 30.0%.

[Manufacturing Example 13] (β2)

Adding 85 parts of 2-dimethylaminoethyl methacrylate, 15 parts of methyl methacrylate, 2,2'-azo double (different) to a reaction vessel equipped with a stirrer, a reflux cooler, a dropping tank and a thermometer 1 part of butyronitrile) and 300 parts of isopropanol. Hereinafter, the aqueous polymer (β2) was obtained in the same operation as in Production Example (β1). At this time, the non-volatile content of the aqueous polymer was 30.0%.

[Manufacturing Example 14] (β3)

In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 30 parts of N-vinylpyrrolidone, 60 parts of methyl methacrylate, 10 parts of methacrylic acid, and 2,2'-azobis ( Isobutyronitrile) 1 part, and isopropanol 300 parts. The reaction vessel was heated while stirring the liquid temperature in the reaction vessel at 80 ° C for 240 minutes, and then cooled to room temperature. Adding ammonia After 500 parts of deionized water and stirring, the isopropanol was distilled off under reduced pressure to obtain an aqueous polymer (β3). At this time, the non-volatile content of the aqueous polymer was 30.0%.

[Manufacturing Example 15] (β4)

100 parts of N-vinylacetamide, 1 part of 2,2'-azobis(isobutyronitrile), and 300 parts of isopropyl alcohol were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer. The reaction vessel was heated while stirring the liquid temperature in the reaction vessel at 80 ° C for 240 minutes, and then cooled to room temperature. After adding 500 parts of deionized water, isopropanol was distilled off under reduced pressure on a rotary evaporator to obtain an aqueous polymer (β4). At this time, the non-volatile content of the aqueous polymer was 30.0%.

The polymerization raw materials and nonvolatile content of the aqueous polymers (β1) to (β4) are shown in Table 2.

<Production Example of Aqueous Coating Composition>

[Example 1]

The polymer emulsion (α1) and the aqueous polymer (β1) were mixed and stirred at 23 ° C in a mass ratio (α1):(β1)=100:10 of a nonvolatile matter to obtain an aqueous coating composition. The obtained aqueous coating composition was subjected to evaluation as described later. The evaluation results are shown in Table 3.

[Embodiment 2]

The polymer emulsion (α2) and the aqueous polymer (β1) were mixed and stirred at 23 ° C in a mass ratio (α2):(β1)=100:10 of a nonvolatile matter to obtain an aqueous coating composition. The obtained aqueous coating composition was subjected to evaluation as described later. The evaluation results are shown in Table 3.

[Example 3]

The polymer emulsion (α1) and the aqueous polymer (β2) were mixed and stirred at 23 ° C in a mass ratio (α1):(β2)=100:10 of a nonvolatile matter to obtain an aqueous coating composition. The obtained aqueous coating composition was subjected to evaluation as described later. The evaluation results are shown in Table 3.

[Example 4]

Polymer emulsion (α1), aqueous polymer (β1), and SNOWTEX-OS (product name, manufactured by Nissan Chemical Industries, Ltd., SiO ₂ fraction 20%, particle size 8 to 5%) 11 nm) (hereinafter, referred to as ST-OS) was mixed and stirred at 23 ° C in a mass ratio (α1):(β1):ST-OS=100:10:5 of a nonvolatile matter to obtain an aqueous coating composition. . The obtained aqueous coating composition was subjected to evaluation as described later. The evaluation results are shown in Table 3.

[Examples 5 to 14] and [Comparative Examples 1 to 10]

The polymer emulsion (α), the aqueous polymer (β), and the ST-OS as colloidal inorganic particles (γ) were mixed and stirred at 23 ° C according to the non-volatile mass ratio shown in Table 3 to obtain an aqueous coating. Composition. The obtained aqueous coating composition was subjected to evaluation as described later. The evaluation results are shown in Table 3.

<Evaluation of aqueous coating composition>

[Modulation of paint]

(1) Modulation of pigment dispersion

Titanium oxide: 700 parts of Ti-Pure R-706 (trade name, manufactured by DuPont, intermediate particle size 360 nm); deionized water: 310 parts; propylene glycol: 49 parts; dispersant: SN DISPERSANT 5027 (trade name, sannopco limited stock) 11 parts of the company; defoamer: SN DEFORMER 1310 (trade name sannopco Co., Ltd.) 6 parts; ammonia water: 1 part.

The above blend was dispersed in a table sander for 20 minutes to prepare a pigment dispersion.

(2) Modulation of waterborne enamel paint

The aqueous coating composition: 100 parts by weight of non-volatile matter; film-forming auxiliary agent: 10 parts of ethylene glycol monobutyl ether; and a film-forming auxiliary agent: TEXANOL CS-12 (trade name, manufactured by Chisso Co., Ltd.); The above (1) pigment dispersion liquid: 102.6 parts; tackifier: ADEKANOL UH-438 (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.).

The aqueous enamel paint was prepared by mixing and stirring in this order.

[Evaluation of pollution resistance]

The above-obtained aqueous enamel paint was applied by a 0.1 mm applicator to a tortuously processed sulfuric acid anodized aluminum plate (see Fig. 1 and thickness: 1 mm), dried at 23 ° C for 6 hours, and further dried at 100 ° C for 10 minutes. The test plate is set to the south of the house in the Kawasaki Manufacturing Plant of Asahi Kasei Chemicals Co., Ltd. (1-3-1, Kawasaki-ku, Kawasaki-ku, Kanagawa Prefecture, Japan). At this time, the gantry having a length of 50 cm with a length of 30 degrees with respect to the horizontal plane (valley depth of 10 mm, pitch of 12 mm) is vertically installed so that the rainwater falling on the roof flows linearly on the surface of the test plate. Test board. The appearance of the test panels after 3 months, 6 months, and 1 year after exposure was measured with a gloss color difference meter (Spectro-guide 45/0 gloss manufactured by BYK-Gardner Co., Ltd.), and evaluated in a 4-stage according to the following evaluation criteria. Its pollution status.

- Evaluation criteria -

◎: Color difference ⊿E (stained parts of rain marks - non-rain marks and dirty parts) ≦ 0.5.

○: 0.5 <color difference ⊿ E (stained parts of rain marks - non-rain marks and dirty parts) ≦ 1.0.

△: 1.0 <color difference ⊿ E (stained parts of rain marks - non-rain marks and dirty parts) ≦ 2.5.

×: 2.5 <color difference ⊿ E (stained parts of rain marks - non-rain marks and dirty parts).

[Evaluation of weather resistance]

The aqueous enamel paint obtained above was applied to a sulfate anodized aluminum plate (size 36 mm × 36 mm × thickness 1 mm) with a 0.1 mm applicator, dried at 23 ° C for 6 hours, and further dried at 100 ° C for 10 minutes. The 60°-60° specular reflectance of the test plate was measured by a gloss color difference meter (Spectro-guide 45/0 gloss manufactured by BYK-Gardner Co., Ltd.) to obtain an initial gloss value. The weather resistance test was carried out under the following test conditions, and the specular reflectance of 60° to 60° after the test was measured to obtain the gloss value after the test. The gloss value after the test was divided by the value of the initial gloss value as the gloss retention ratio, and the test time required for the gloss retention rate to be less than 80% was measured, and evaluated in four stages according to the following evaluation criteria.

-Test conditions-

Test machine: promotes weather resistance (manufactured by DAYPLA WINTES Co., Ltd., type: KW-R6TP-A).

Test cycle:

Irradiation for 4 hours (illuminance 81 mW/cm ² (illuminance meter using Iwasaki Electric Co., Ltd. UVP365-01); irradiation wavelength range 295 to 780 nm; blackboard temperature 63 ° C; tank humidity 50%]; wetting 4 hours (blackboard temperature 30 °C; humidity in the tank 98%); stop for 20 minutes (blackboard temperature 40 ° C; humidity in the tank 20%); 30 seconds shower spray before and after wetting.

- Evaluation criteria -

◎: 2,500 hours or more.

○: 2,000 hours or more and less than 2,500 hours.

△: 1,500 hours or more and less than 2,000 hours.

×: Less than 1,500 hours.

[Evaluation of area occupancy of inorganic particles in the surface of the coating film] and [Evaluation of the average area size of inorganic particles in the surface of the coating film]

The above-obtained aqueous enamel paint was applied on a PET substrate with a 0.1 mm applicator, dried at 23 ° C for 6 hours, and further dried at 100 ° C for 10 minutes. For the surface of the test piece, a secondary electron image of a scanning electron microscope (SEM) was obtained according to the test conditions described below. The secondary electron image (analytical field: 1.7 μm in length × 2.5 μm in width) was used to remove the region containing the inorganic pigment particles, and the area occupancy of the inorganic particles on the surface of the coating film and the inorganic particles in the surface of the coating film were calculated by image analysis. The average area size.

-SEM measurement conditions -

Device: Field emission scanning electron microscope (manufactured by Hitachi High-Technologies Co., Ltd., type: SU-8220).

Acceleration voltage: 1.0kV.

Magnification: 50,000 times.

- Image processing conditions -

Image analysis software: A-like (trade name, manufactured by Asahi Kasei Engineering Co., Ltd.).

Analytic application: particle parsing.

Analysis parameters: (particle brightness) bright, (binarization method) manual, (range specification) none, (edge correction) 4 sides, (fill in blank) none, (small graphic removal area) 10 pixels, (correction method) manual (Broken noise removal filter) Yes, (shade processing), (shading processing size) 180, (measurement item selection) area.

The binarized images obtained by performing image analysis on the secondary electron image of the SEM on the surface of the coating film of Example 6, Comparative Example 2, and Comparative Example 10 are shown in Figs. 2 to 4, respectively. In the figures, bright parts indicate inorganic components.

(industrial availability)

The aqueous coating composition of the present invention can form a coating film excellent in both stain resistance and weather resistance, and can impart long-term beauty and durability to the coated body, and can be used for building, architectural finishing materials, building materials, steel. Various bodies and members such as structures, steel materials, mortars, concrete, automobiles, woven fabrics, non-woven fabrics, and plastics are directly coated, or may be suitably used as a coating for surface coating, a transparent paint, a top coating agent, and the like.

Claims (11)

An aqueous coating composition comprising the following polymer emulsion (α) and an aqueous polymer (β), wherein the (α) polymer emulsion contains an organic siloxane polymer block in the particle (I) And a polymer block (II) of an ethylenically unsaturated monomer, wherein the non-volatile content of the polymer emulsion contains 0.1% by mass or more and 30% by mass or less of the Si element, and the organosiloxane polymer block (I) is The organooxane unit (A) represented by the formula (a) contains 50 mol% or more and 99.9 mol% or less; (β) an aqueous polymer, which is any one of the following: having a mercapto group and/or an amine One or more of the ethylenically unsaturated monomers, one or more than 40% by mole or less and less than 100% by mole, and one or more of the other ethylenically unsaturated monomers copolymerizable with the above-mentioned ethylenically unsaturated monomers a copolymer composed of 0 mol% and 60 mol% or less; a homopolymer composed of one of an ethylenically unsaturated monomer having a mercaptoamine group and/or an amine group; and having a mercaptoamine group and/or a copolymer composed of two or more kinds of amino group-containing ethylenically unsaturated monomers; In the formula (a), R ¹ and R ² are each independently a C 1 to 16 alkyl group, a C 5 to 6 cycloalkyl group or a phenyl group, and R ¹ and R ² may be mutually different or the same. base. The aqueous coating composition according to claim 1, wherein the organic siloxane polymer block (I) further contains 0.1% by mole of the organic oxirane unit (B) represented by the formula (b). Above 50% by mole; In the formula (b), R ³ is selected from an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group; and R ⁴ is an alkenyl group having a vinyl group, a carbon number of 3 to 20, and propylene. a radical group of a decyloxy group, an alkyl acrylate group having 4 to 20 carbon atoms, a methacryloxy group, an alkyl methacrylate group having 5 to 20 carbon atoms, and a phenyl group substituted by a vinyl group Any one of a polymerizable group and a copolymerizable with the polymer block (II) by the radical polymerizable group; n is 0, 1, or 2. The aqueous coating composition according to claim 1 or 2, further comprising colloidal inorganic particles (γ). The aqueous coating composition according to claim 1 or 2, wherein the organic siloxane polymer block (I) contains the organic oxirane unit (A) in an amount of 50 mol% or more and 99.8 mol%. Hereinafter, the organooxane unit (B) is 0.1 mol% or more and 49.9 mol% or less, and the organodecane unit (C) represented by the formula (c) is 0.1 mol% or more and 49.9 mol% or less; In the formula, R ⁵ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group. The aqueous coating composition according to claim 1 or 2, which contains 0.1 parts by mass or more of the non-volatile content of the aqueous polymer (β) per 100 parts by mass of the nonvolatile portion of the polymer emulsion (α). Mass by under. The aqueous coating composition according to the first or second aspect of the invention, which contains 0.1 parts by mass or less of the nonvolatile content of the colloidal inorganic particles (γ) per 100 parts by mass of the nonvolatile matter of the polymer emulsion (α). 30 parts by mass or less. a coating film containing inorganic particles having an average particle diameter of 100 nm or less and a binder component; the area ratio of the inorganic particles in the surface of the coating film is 49.9% or less; and the inorganic particles in the surface of the coating film The average area size is 500 square nm or more. The coating film according to claim 7, wherein the binder component comprises: a polymer containing the organooxane unit (A) represented by the formula (a); In the formula (a), R ¹ and R ² are each an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, and R ¹ and R ² may be mutually different groups. For the same base. The coating film according to claim 7 or 8, wherein the binder component comprises: a polymer containing the organooxane unit (B) represented by the formula (b); In the formula (b), R ³ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group; and R ⁴ is an alkenyl group selected from a vinyl group, a carbon number of 3 to 20, and an acrylonitrile group. Radical polymerization of an oxygen group, an alkyl acrylate group having 4 to 20 carbon atoms, a methacryloxy group, an alkyl methacrylate group having 5 to 20 carbon atoms, and a phenyl group substituted with a vinyl group And a group which is copolymerized with the polymer block (II) by the radical polymerizable group; n is 0, 1, or 2. The coating film according to claim 7 or 8, wherein the binder component comprises: a polymer containing the organooxane unit (C) represented by the formula (c); In the formula, R ⁵ is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group. The coating film according to claim 7 or 8, wherein the binder component contains the following aqueous polymer (β): (β) aqueous polymer, which is any one of the following: And/or one or more of the amino group-containing ethylenically unsaturated monomers, 40 mol% or more and less than 100 mol%, and one of other ethylenically unsaturated monomers copolymerizable with the above or a copolymer composed of two or more kinds of copolymers having more than 0 mol% and less than 60 mol%; a homopolymer composed of one of an ethylenically unsaturated monomer having a mercaptoamine group and/or an amine group; and having a decylamine A copolymer composed of two or more kinds of ethylenically unsaturated monomers having a group and/or an amine group.