JP2009256569A - Coating film, coating material containing coloring material, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating film containing a coloring material which excels in contamination resistance, weatherability, and freeze damage resistance, and to provide a coating material containing a coloring material which can form a coating film which excels in contamination resistance, weatherability, and freeze damage resistance, and its manufacturing method. <P>SOLUTION: The coating material containing a coloring material comprises a polymer (A), a silica particle (B), an anionic surfactant, a nonionic surfactant and a coloring material (C), wherein the polymer (A) comprises 0.2-20 mass% of a radically polymerizable monomer unit containing a hydrolyzable silyl group and/or a polyfunctional monomer unit (a) having two or more radically polymerizable groups and 80-99.8 mass% of other monomer units (b), and the content of the coloring material (C) is 10-100 pts.mass based on 100 pts.mass of the polymer (A). The coating film comprises a polymer (A), silica particles (B) and a coloring material (C), wherein the area of the surface of silica particles (B) exposed on a coating film surface is 35% or more of the coating film surface. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a coating film, a coloring material-containing coating material, and a method for producing the same.

  In recent years, in the paint field, conversion from organic solvent-based paints to water-based paints (water-based coating materials) has been attempted from the viewpoints of environmental protection and health and safety. However, the coating film made of an aqueous coating material has low coating film performance such as weather resistance, water resistance, frost damage resistance, and contamination resistance, in particular, contamination resistance is lower than that of the solvent system, and there are many problems to be solved. is the current situation.

  Development of water-based coating materials and development of coating film laminating methods for the purpose of solving these problems have been carried out in various ways. For example, as a resin for an aqueous coating material, an emulsion of an acrylic resin by emulsion polymerization has been attracting attention because it has a characteristic that the weather resistance of the resulting coating film is relatively good. In addition, the water-based emulsion for undercoat, water-based emulsion for intermediate-coat, and water-based emulsion for top-coat are each given performance, and these water-based emulsions are sequentially layered to show the coating properties such as stain resistance as a whole. The idea to do is made.

  As a method for improving the stain resistance of the coating film, for example, the following method is known.

  (I) A method of increasing the hardness of the coating film (increasing the glass transition temperature (Tg) of the resin).

  (Ii) A method of imparting a self-cleaning action of hydrophilizing the coating surface and washing away contaminants with rainwater.

  (Iii) A method of controlling the chargeability of the coating film to suppress the adhesion of dirt due to static electricity.

  However, the method (i) has a problem that the film-forming property is lowered, the coating film is cracked in winter, and the frost damage resistance is problematic. In addition, it is difficult to greatly improve the stain resistance of the coating film.

  Examples of the method (ii) include a method using a resin containing a monomer unit having hydrophilicity, and adding a surfactant or the like. However, a resin containing a monomer unit having hydrophilicity has a problem of low weather resistance. Moreover, when surfactant etc. are added, the water resistance of a coating film falls and there exists a problem in sustaining the effect of stain resistance.

  In the method (iii), the addition of the antistatic agent has an adverse effect on the weather resistance and water resistance of the coating film, and there is a problem in the sustainability of the effect.

  As an aqueous coating material for solving these problems, an aqueous coating material containing an inorganic substance is known. As the aqueous coating material, for example, the following aqueous coating material has been proposed.

  (1) A coating composition in which colloidal silica is contained in an aqueous emulsion containing a copolymer of vinylsilane and an acrylic monomer (Patent Document 1).

  The coating film comprising the coating composition (1) is said to be excellent in heat resistance, water resistance and adhesion. However, the coating composition of (1) requires a large amount of colloidal silica having a solid content of 500 to 20000 parts by mass with respect to 100 parts by mass of the solid content of the aqueous emulsion. When a large amount of colloidal silica is used, there are problems that transparency of the coating film, weather resistance, storage stability of the coating composition, and coating workability are poor.

  On the other hand, as an aqueous coating material using a relatively small amount of colloidal silica, for example, the following aqueous coating material has been proposed.

  (2) A flame retardant containing 100 parts by mass of a polyorganosiloxane graft copolymer emulsion in which an unsaturated vinyl monomer is 10 to 90 parts by mass graft-copolymerized with respect to polyorganosiloxane, and 1 to 50 parts by mass of colloidal silica. Coating material (Patent Document 2).

  (3) An aqueous coating composition containing 100 parts by mass of a polyorganosiloxane-based graft copolymer emulsion and 1 to 300 parts by mass of colloidal silica (Patent Document 3).

  The coating film made of the flame retardant coating material (2) is said to be excellent in flame retardancy, extensibility, adhesiveness, temperature sensitive characteristics, moisture permeability, and stain resistance. However, the coating material (2) contains 52 parts by mass or more of the polyorganosiloxane component in 100 parts by mass of the solid content of the polyorganosiloxane-based graft block copolymer emulsion, and contains a large amount of water-repellent silicone component. Yes. For this reason, the hydrophilicity of the coating film becomes insufficient and the stain resistance is low. There are also problems in terms of storage stability of the coating material, transparency of the coating film, and hardness.

  The aqueous coating composition (3) is excellent in storage stability, and the coating film is said to be excellent in hardness, water resistance, and stain resistance. The coating film comprising the aqueous coating composition of (3) has significantly improved contamination resistance compared to the coating film comprising the coating material of (2), but further reduced contamination by making the coating film hydrophilic. Is required. Also, the storage stability of the aqueous coating composition is insufficient.

  For example, the following method has been proposed as a method for suppressing the adhesion of dirt due to static electricity.

  (4) In the surface coating of cementitious materials, it becomes a multi-layered structure of undercoat, intermediate coat, and topcoat, and silicate or silica sol is blended in all of them to prevent the accumulation of static electricity in the laminated coating, thereby preventing the adhesion of static electricity. A method of preventing and imparting stain resistance to the coating film (Patent Documents 4, 5, etc.).

  However, in the method (4), if any one of the undercoating, intermediate coating, and topcoating is a resin-only coating film, there is a problem that static electricity stays and stains adhere to the coating film.

  For example, the following coating films have been proposed as coating films having excellent stain resistance.

  (5) A coating film containing a coating component containing a polymer and colloidal silica (Patent Document 6, etc.).

However, there was no description about what (5) coating films were blended with coloring materials such as enamel particles.
JP-B-1-41180 JP-A-4-23857 JP-A-9-165554 Japanese Patent Publication No.53-34141 JP-A-5-96234 International Publication No. 05/075583 Pamphlet

  An object of the present invention is to provide a coating film containing a coloring material that is excellent in stain resistance, weather resistance, and frost damage resistance, and a coating material containing a coloring material that can form a coating film excellent in stain resistance, weather resistance, and frost damage resistance. It is in providing the manufacturing method.

  The first gist of the present invention is a coating film containing the polymer (A), the silica particles (B), and the coloring material (C), and the area occupied by the exposed silica particles (B) on the coating film surface. Is a coating film occupying 35% or more of the coating film surface.

  The second gist of the present invention is a coloring material-containing coating material containing a polymer (A), silica particles (B), a coloring material (C), an anionic surfactant, and a nonionic surfactant. The polymer (A) has a hydrolyzable silyl group-containing radically polymerizable monomer unit and / or a polyfunctional monomer unit (a) having two or more radically polymerizable groups (0.2) to 20% by mass. The other monomer unit (b) is 80 to 99.8% by mass (provided that the total of the monomer unit (a) and the monomer unit (b) is 100% by mass), It is a coloring material containing coating | covering material whose coloring material (C) is 10-100 mass parts with respect to 100 mass parts of polymers (A).

  The third gist of the present invention is a coloring containing a polymer (A), silica particles (B), a coloring material (C), an anionic surfactant, a nonionic surfactant, and an organic hydrazine compound (D). A polyfunctional monomer unit (a) 0, which is a material-containing coating material, wherein the polymer (A) has two or more hydrolyzable silyl group-containing radical polymerizable monomer units and / or radical polymerizable groups. 0.2 to 20% by mass, other monomer units (b) 80 to 99.8% by mass (provided that the total of the monomer units (a) and the monomer units (b) is 100% by mass). ), And the other monomer unit (b) contains 0.1 to 10% by mass of an ethylenically unsaturated monomer unit (b-1) containing a carbonyl group and / or an aldehyde group (however, The polymer (A) is 100% by mass), and the colorant (C) is a colored material-containing coating material is a polymer (A) 10 to 100 parts by weight per 100 parts by weight.

  The 4th summary of this invention is a coloring material containing coating | covering material whose said silica particle (B) is 0.5-25 mass parts with respect to 100 mass parts of polymers (A).

  The fifth gist of the present invention is a method for producing the coloring material-containing coating material, comprising mixing all or part of the silica particles (B) and all or part of the coloring material (C). It is a method including a step of preparing a mixture and then mixing the mixture and the polymer (A).

The coating film of the present invention is excellent in stain resistance, weather resistance, and frost damage resistance. Moreover, since the coating film of this invention contains a coloring material, it is excellent also in designability.
Moreover, the coloring material containing coating material of this invention can form the coating film which is excellent in stain resistance, a weather resistance, and frost damage resistance.

  In this specification, (meth) acrylate means an acrylate or a methacrylate.

<Coloring material-containing coating material>
The coloring material-containing coating material of the present invention contains a polymer (A), silica particles (B), a coloring material (C), a specific anionic surfactant, and a specific nonionic surfactant. It is a coloring material-containing coating material.

  The solid content concentration of the coloring material-containing coating material is usually 10 to 80% by mass.

(Polymer (A))
The polymer (A) is a film-forming component and is a component that imparts film formability, weather resistance, water resistance, and the like to the coating film.

  Examples of the polymer (A) include polyester resins, polyurethane resins, acrylic resins, acrylic silicone resins, and fluorine resins. Among these, acrylic resins and acrylic silicone resins are preferable, and acrylic silicone resins are more preferable from the viewpoint of stain resistance, weather resistance, water resistance, and frost damage resistance of the coating film.

  Examples of the monomer unit constituting the acrylic resin and the acrylic silicone resin include those derived from the following monomers (monomer units (a) and (b)). Note that these may be any radically polymerizable ones, and are not limited to the following.

  The polymer (A) is a polyfunctional compound having two or more hydrolyzable silyl group-containing radical polymerizable monomer units and / or radical polymerizable groups from the viewpoint of stain resistance, weather resistance and water resistance of the coating film. The monomer unit (a) is 0.2 to 20% by mass and the other monomer unit (b) is 80 to 99.8% by mass (provided that the monomer unit (a) and the monomer unit (b) )) Is preferably 100 mass%.

Monomer unit (a);
The monomer unit (a) is composed of a hydrolyzable silyl group-containing radical polymerizable monomer unit and / or a polyfunctional monomer unit having two or more radical polymerizable groups. By using the monomer unit (a), the polymer (A) and the silica particles (B) are easily bound to each other, and the exposure amount of the silica particles (B) to the formed coating film surface is reduced. The silica particle layer can be increased in thickness, and stain resistance, weather resistance, and water resistance can be obtained.

  Specific examples of the hydrolyzable silyl group-containing radical polymerizable monomer include, for example, vinyl silanes and (meth) acryloyloxyalkylsilanes. Of these, (meth) acryloyloxyalkylsilanes are particularly preferable.

  As vinyl silanes, (meth) acryloyloxyalkyl silanes, etc., one or more selected from the following vinyl silanes, (meth) acryloyloxyalkyl silanes and the like can be selected and used.

  Vinylsilanes: vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinyltrichlorosilane and the like.

  (Meth) acryloyloxyalkylsilanes: γ- (meth) acryloyloxyethylmethyldimethoxysilane, γ- (meth) acryloyloxyethyltrimethoxysilane, γ- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) Acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxyethylmethyldichlorosilane, γ- (meth) acryloyloxy Ethyltrichlorosilane, γ- (meth) acryloyloxypropylmethyldichlorosilane, γ- (meth) acryloyloxypropyltrichlorosilane, and the like.

  As a specific example of the polyfunctional monomer having two or more radical polymerizable groups, one or more of the following compounds can be selected and used.

  Polyfunctional monomer having two or more radical polymerizable groups: ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) ) Acryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy · Polyethoxy) phenyl] propane 2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) ) Acrylate, ethylene oxide modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide modified hydrogenated bisphenol A di (meth) acrylate, diglycidyl ether of bisphenol A with hydroxyalkyl (meth) acrylate such as hydroxy (meth) acrylate Diester compound of diol such as added epoxy (meth) acrylate, polyoxyalkylenated bisphenol A di (meth) acrylate and (meth) acrylic acid; Roll propane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , A compound having three or more hydroxyl groups per molecule such as dipentaerythritol hexa (meth) acrylate and a polyester compound of (meth) acrylic acid; allyl (meth) acrylate, divinylbenzene, triallyl cyanurate, tris (2- (Acryloyloxyethylene) isocyanurate, ε-caprolactone-modified tris (acryloxyethyl) isocyanurate, and the like.

Hydrolyzable silyl group-containing radical polymerizable monomer units and polyfunctional monomer units having two or more radical polymerizable groups are used for the purpose of improving the stain resistance, weather resistance and water resistance of the coating film. However, when these are contained, frost damage resistance may be reduced. Therefore, it is preferable to improve the stain resistance, weather resistance and water resistance of the coating film with a small content.
Content of a monomer unit (a) is 0.2-20 mass% in a polymer (A), and it is preferable that it is 0.5-18 mass%. If content of a monomer unit (a) is 0.2 mass% or more, the coating film excellent in stain resistance, a weather resistance, and water resistance can be formed. Moreover, if a monomer unit (a) is 20 mass% or less, the coating film excellent in stain resistance, a weather resistance, and water resistance can be formed, without reducing frost damage resistance.

Monomer unit (b);
The monomer unit (b) is a monomer unit (other monomer unit) other than the monomer unit (a).
Content of another monomer unit (b) is 80-99.8 mass% in a polymer (A), and it is preferable that it is 82-99.5 mass%. If content of a monomer unit (b) is 80 mass% or more, the coating film excellent in stain resistance, a weather resistance, and water resistance can be formed, without reducing frost damage resistance. Moreover, if a monomer unit (b) is 99.8 mass% or less, the coating film excellent in stain resistance, a weather resistance, and water resistance can be formed.

  Other monomer units (b) are not particularly limited, but ethylenically unsaturated monomer units (b-1) containing carbonyl groups and / or aldehyde groups, carboxyl group-containing monomer units, hydroxyl groups Group-containing radical polymerizable monomer unit and / or polyoxyalkylene group-containing radical polymerizable monomer unit, alkyl (meth) acrylate unit having an alkyl group having 1 to 18 carbon atoms, self-crosslinkable functional group-containing radical polymerization It is preferable to use a polymerizable monomer unit and a UV-resistant radical polymerizable monomer unit.

By using an ethylenically unsaturated monomer unit (b-1) containing a carbonyl group and / or an aldehyde group (hereinafter abbreviated as “monomer unit (b-1)”), an organic hydrazine described later is used. A crosslinking reaction proceeds with the compound (D) to form a coating film excellent in low contamination maintenance, weather resistance, water resistance, frost damage resistance, blocking resistance, solvent resistance, and adhesion to various substrates. can do.
Examples of the monomer that gives the monomer unit (b-1) include acrolein, diacetone acrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, pivalin aldehyde, diacetone (meth) acrylate, and acetonitrile. Examples thereof include acrylate and acetoacetoxyethyl (meth) acrylate. Of these, diacetone acrylamide is preferable.
These may be used alone or in combination of two or more.

  The content of the monomer unit (b-1) in the polymer (A) is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass. If the content of the monomer unit (b-1) is 0.1% by mass or more, low contamination maintenance, weather resistance, water resistance, frost damage resistance, blocking resistance, solvent resistance, adhesion to various substrates A coating film excellent in properties can be formed. Further, if the content of the monomer unit (b-1) is 10% by mass or less, the low contamination maintenance property, weather resistance, water resistance, frost damage resistance, A coating film excellent in blocking property, solvent resistance, and adhesion to various bases can be formed.

  In addition, the polymer (A) contains additives such as coloring materials, viscosity modifiers and solvents, and blending stability when producing the coloring material-containing coating material and storage stability of the coloring material-containing coating material. As other monomer units (b), it is preferable to contain units derived from carboxyl group-containing monomers.

  0.1-10 mass% is preferable in a polymer (A), and, as for content of a carboxyl group-containing monomer unit, 0.5-8 mass% is more preferable. If the content of the carboxyl group-containing monomer unit is 0.1% by mass or more, the storage stability of the coloring material-containing coating material is improved, and aggregates are generated when the coloring material-containing coating material is produced. Can avoid problems. If the content of the carboxyl group-containing monomer unit is 10% by mass or less, the blending stability during the production of the coloring material-containing coating material without reducing the weather resistance and water resistance of the coating film, the coloring material-containing coating material The storage stability of can be further improved.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate, vinylbenzoic acid, monohydroxy oxalate Ethyl (meth) acrylate, tetrahydrophthalic acid monohydroxyethyl (meth) acrylate, tetrahydrophthalic acid monohydroxypropyl (meth) acrylate, 5-methyl-1,2-cyclohexanedicarboxylic acid monohydroxyethyl (meth) acrylate, phthalic acid mono Hydroxyethyl (meth) acrylate, monohydroxypropyl (meth) acrylate phthalate, monohydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate DOO, tetrahydrophthalic acid mono-hydroxybutyl (meth) acrylate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The polymer (A) contains other monomer units (b) from the viewpoint of blending stability at the time of producing the coloring material-containing coating material, stain resistance of the coating film, weather resistance, water resistance and adhesion to various substrates. ) Preferably contains a unit derived from a hydroxyl group-containing radical polymerizable monomer and / or a polyoxyalkylene group-containing radical polymerizable monomer.

  The content of the hydroxyl group-containing radically polymerizable monomer unit and the polyoxyalkylene group-containing radically polymerizable monomer unit is preferably 0.5 to 20% by mass and 1 to 12% by mass in the polymer (A). % Is more preferable. If the content of these monomer units is 0.5% by mass or more, the blending stability during the production of the coloring material-containing coating material, the stain resistance of the coating film, the weather resistance, the water resistance, and the adhesion to various substrates Will improve. If the content of these monomer units is 20% by mass or less, the blending stability during the production of the coloring material-containing coating material, the stain resistance of the coating film, and the like, without reducing the weather resistance and water resistance of the coating film, The adhesion to various base materials can be further improved.

  Examples of the hydroxyl group-containing radical polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycerol mono (meth) acrylate, p-hydroxycyclohexyl (meth) acrylate, hydroxymethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and the like.

  Examples of the polyoxyalkylene group-containing radical polymerizable monomer include terminal hydroxy-type polyoxyalkylene group-containing radical polymerizable monomers, alkyl group-terminated polyoxyalkylene group-containing radical polymerizable monomers, Specifically, hydroxy polyethylene oxide mono (meth) acrylate, hydroxy polypropylene oxide mono (meth) acrylate, hydroxy (polyethylene oxide-polypropylene oxide) mono (meth) acrylate, hydroxy (polyethylene oxide-propylene oxide) mono (meth) acrylate Hydroxy (polyethylene oxide-polytetramethylene oxide) mono (meth) acrylate, hydroxy (polyethylene oxide-tetramethylene oxide) mono (meth) acrylate, Roxy (polypropylene oxide-polytetramethylene oxide) mono (meth) acrylate, hydroxy (polypropylene oxide-tetramethylene oxide) mono (meth) acrylate, methoxypolyethylene oxide mono (meth) acrylate, lauroxypolyethylene oxide mono (meth) acrylate, Stearoxy polyethylene oxide mono (meth) acrylate, allyloxy polyethylene oxide mono (meth) acrylate, nonylphenoxy polyethylene oxide mono (meth) acrylate, nonylphenoxypolypropylene oxide mono (meth) acrylate, octoxy (polyethylene oxide-polypropylene oxide) mono ( (Meth) acrylate, nonylphenoxy (polyethylene oxide-propylene oxide) Mono (meth) acrylate.

  These may be used individually by 1 type and may be used in combination of 2 or more type.

  The polymer (A) is a unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms as the other monomer unit (b) from the viewpoint of the weather resistance and water resistance of the coating film. It is preferable to contain.

  The content of units derived from alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms is preferably 50 to 95% by mass, more preferably 70 to 95% by mass in the polymer (A), and 80 -95% by weight is particularly preferred. When the content of these monomer units is 50% by mass or more, the water resistance and weather resistance of the coating film are improved. When the content of these monomer units is 95% by mass or less, the weather resistance and water resistance can be further improved without reducing the frost damage resistance of the coating film.

Examples of the alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms include the following alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms. These may be used individually by 1 type and may be used in combination of 2 or more type.
Alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) ) Acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, n-hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) A) Relate, p-t-butylcyclohexyl (meth) acrylate.

  The polymer (A) is a self-crosslinkable functional group-containing radical polymerisable as another monomer unit (b) from the viewpoint of stain resistance, weather resistance, water resistance and adhesion to various substrates. It is preferable to contain a unit derived from a monomer. Self-crosslinkable functional group-containing radical polymerizable monomer is chemically stable while the polymer is dispersed in an aqueous dispersion and stored at room temperature. It means a radically polymerizable monomer having a functional group that causes a reaction between side chain functional groups due to external factors of the above and causes a chemical bond between the side chain groups.

  0.1-15 mass% is preferable in a polymer (A), and, as for content of a self-crosslinkable functional group containing radically polymerizable monomer unit, 0.5-12 mass% is more preferable. When the content of the self-crosslinkable functional group-containing radical polymerizable monomer unit is 0.1% by mass or more, the stain resistance, weather resistance, water resistance and adhesion to various substrates of the coating film are improved. If the content of the self-crosslinkable functional group-containing radical polymerizable monomer unit is 15% by mass or less, the coating film is resistant to contamination and various substrates without deteriorating the water resistance and weather resistance of the coating film. Adhesion can be further improved.

Self-crosslinkable functional group-containing radical polymerizable monomers include the following self-crosslinkable functional group-containing radical polymerizable monomers (oxirane group-containing radical polymerizable monomers, alkylols of ethylenically unsaturated amides or Alkoxyalkyl compounds). These may be used individually by 1 type and may be used in combination of 2 or more type.
Oxirane group-containing radical polymerizable monomer: glycidyl (meth) acrylate and the like.
Alkyol or alkoxyalkyl compound of ethylenically unsaturated amide: alkylol or alkoxy of ethylenically unsaturated amide such as N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide Alkyl compounds and the like.

  It is preferable that a polymer (A) contains the unit derived from an ultraviolet-ray radically polymerizable monomer as another monomer unit (b) from the point of the weather resistance of a coating film.

  0.1-10 mass% is preferable in a polymer (A), and, as for content of an ultraviolet-ray radical polymerizable monomer unit, 0.5-8 mass% is more preferable. When the content of the UV-resistant radical polymerizable monomer unit is 0.1% by mass or more, the weather resistance of the coating film is improved. When the content of the ultraviolet-resistant radical polymerizable monomer unit is 10% by mass or less, the weather resistance of the coating film can be further improved without lowering the polymerization stability.

  Examples of the UV-resistant radical polymerizable monomer include (meth) acrylate having a light stabilizing action and (meth) acrylate having an UV-absorbing component.

  Examples of the (meth) acrylate having a light stabilizing action include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6. -Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4 -Cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and the like.

  Examples of the (meth) acrylate having an ultraviolet absorbing component include 2- [2-hydroxy-5- (meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-3-t-butyl. -5- (meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-3-t-amyl-5- (meth) acryloyloxyethylphenyl] -2H-benzotriazole, and the like.

  These may be used individually by 1 type and may be used in combination of 2 or more type.

  Other monomer unit (b) (ethylenically unsaturated monomer unit (b-1) containing carbonyl group and / or aldehyde group, carboxyl group-containing monomer unit, hydroxyl group-containing radical polymerizability) Monomer unit and / or polyoxyalkylene group-containing radical polymerizable monomer unit, alkyl (meth) acrylate unit having an alkyl group having 1 to 18 carbon atoms, self-crosslinkable functional group-containing radical polymerizable monomer unit UV-resistant radical polymerizable monomer units) may be used in combination of two or more.

A polymer (A) may contain the unit derived from the monomer shown below other than the above as another monomer unit (b).
Amide group-containing polymerizable monomer: (meth) acrylamide and the like.

  Lactone-modified hydroxyl group-containing radical polymerizable monomers.

  Aminoalkyl (meth) acrylates: 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, and the like.

  Metal-containing radical polymerizable monomers: zinc diacrylate, zinc dimethacrylate, and the like.

  Other (meth) acrylic monomers: dimethylaminoethyl (meth) acrylate methyl chloride salt, allyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, phenyl (meth) acrylate, benzyl (meth) acrylate , Isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and the like.

  Aromatic vinyl monomers: styrene, methylstyrene, chlorostyrene, methoxystyrene, etc.

  Conjugated diene monomers: 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and the like.

  Radical polymerizable monomer: vinyl acetate, vinyl chloride, ethylene, vinyl propionate, etc.

  In addition, the polymer (A) is composed of a polymer block (E) containing dimethylsiloxane as a repeating unit, and a radical from the viewpoint of exhibiting higher stain resistance, weather resistance, water resistance, and frost damage resistance of the coating film. A graft comprising a polymer block (F) having a polymerizable monomer as a repeating unit, and a silicon-containing graft crossing agent unit (G) copolymerized with the polymer block (E) and the polymer block (F) A block polymer is preferred.

  The polymer block (E) is a so-called polyorganosiloxane obtained by polymerizing the following raw materials.

  Dimethyl dialkoxysilanes: dimethyldimethoxysilane, dimethyldiethoxysilane and the like.

  Dimethylsiloxane cyclic oligomers: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane, dimethyl cyclic (dimethylsiloxane cyclic oligomer 3-7mer Mixture) and the like.

  Other: Dimethyldichlorosilane and the like.

  As a raw material for the polymer block (E), a dimethylsiloxane cyclic oligomer is most preferable from the viewpoint of performance such as thermal stability of the obtained graft block polymer and cost.

  The mass average molecular weight of the polymer block (E) is preferably 10,000 or more, and more preferably 50,000 or more. When the mass average molecular weight is 10,000 or more, a coating film having sufficient durability can be obtained.

  The content of the polymer block (F) is preferably 50 to 99.7 parts by mass and more preferably 60 to 99.5 parts by mass with respect to 100 parts by mass of the graft block polymer (polymer (A)). If content of a polymer block (F) is 50 mass parts or more, the hardness of a coating film, intensity | strength, and stain resistance will improve. If content of a polymer block (F) is 99.7 mass parts or less, it exists in the tendency which can suppress the fall of the weather resistance of a coating film, water resistance, and frost damage resistance.

  The silicon-containing graft crossing agent unit (G) is a component that ensures the transparency of the resulting coating film. Examples of the silicon-containing graft crossing agent include the hydrolyzable silyl group-containing radical polymerizable monomer described above. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The content (in terms of silicon atoms) of the silicon-containing graft crossover agent unit (G) is preferably 0.5 to 50 mol%, and preferably 1 to 15 mol%, out of a total of 100 mol% of silicon atoms in the graft block polymer. Is more preferable. When the content of the silicon-containing graft crossing agent is 0.5 mol% or more, the transparency of the coating film is improved. When the content of the silicon-containing graft crossing agent is 50 mol% or less, the coating film performance is improved. Further, when the content of the silicon-containing graft crossing agent is 1 mol% or more, the transparency of the obtained coating film is extremely good. Further, when the content of the silicon-containing graft crossing agent is 15 mol% or less, the latex stability during emulsion polymerization is good.

In the present invention, a polymer block (E) and a silicon-containing graft-crossing agent unit are first polymerized by polymerizing dimethyl dialkoxysilanes or dimethylsiloxane cyclic oligomers and a hydrolyzable silyl group-containing radical polymerizable monomer. It is preferable to produce a polyorganosiloxane composed of (G) and then produce a polymer block (F).
The polyorganosiloxane is preferably 0.3 to 50% by mass, more preferably 0.5 to 40% by mass in the polymer (A).

  The content of each monomer unit in the polymer (A) can be measured using various devices. For example, gas chromatograph, pyrolysis gas chromatograph, gas chromatograph mass spectrometer, pyrolysis gas chromatograph mass spectrometer, high performance liquid chromatograph, liquid chromatograph, liquid chromatograph mass spectrometer, Fourier transform infrared spectrophotometer, nuclear magnetic Examples include a resonance apparatus, a fluorescent X-ray apparatus, and an ICP emission analysis apparatus. These may be used individually by 1 type and may be used in combination of 2 or more type. Furthermore, an appropriate pretreatment may be performed when using each device.

(Silica particles (B))
The silica particles (B) are components that impart hydrophilicity, antistatic properties, hardness, and weather resistance to the coating film. Moreover, it is a component which exhibits sufficient stain resistance by imparting hydrophilicity and antistatic properties to the coating film. Furthermore, it is preferable to use two or more types of silica particles having different average particle diameters as the silica particles (B) because the stain resistance persistence of the coating film is further improved.

  In addition, the value measured by BET method can be employ | adopted for the average particle diameter of a silica particle.

  Examples of the silica particles having different average particle diameters include a silica particle A group having an average particle diameter of 1 nm or more and less than 20 nm and a silica particle B group having an average particle diameter of 20 nm or more and 100 nm or less, and at least selected from each of these groups. One type is preferably used.

  The average particle size of the silica particles A group is more preferably 1 nm or more and 18 nm or less, and further preferably 1 nm or more and 16 nm or less. On the other hand, the average particle size of the silica particle group B is more preferably 20 nm or more and 80 nm or less, and further preferably 20 nm or more and 60 nm or less.

  When the average particle diameter of the silica particles (B) used in the present invention is 100 nm or less, the silica particles (B) are likely to float on the surface layer of the coating film during formation of the coating film, and the silica particles (B ) Closely fills the polymer particle gap and forms a silica particle layer having a thickness, and the polymer (A), the silica particle (B), and the silica particle (B) are chemically bonded or physically adsorbed to each other. Therefore, it is present in the outermost layer of the coating film, and the stain resistance is sufficiently exhibited.

  Further, when at least one silica particle selected from the group of silica particles A having an average particle diameter of 1 nm to less than 20 nm and the group of silica particles B of 20 nm to 100 nm is used as the silica particles (B), A rough structure with nano-order irregularities formed on the surface layer can be formed, and the coarse structure also changes with the movement of the resin with time, but the new coarse structure is different due to the difference in the average particle diameter of the silica particles (B). Formed and more resistant to contamination.

  The compounding amount of silica particles (B) (when using two or more types of silica particles having different average particle sizes, the total amount) is 0.5 to 25 parts by mass with respect to 100 parts by mass of the polymer (A). Preferably, 1-23 mass parts is more preferable, and 1-20 mass parts is further more preferable. When the blending amount of the silica particles (B) is 0.5 parts by mass or more, the stain resistance (hydrophilicity and antistatic property) of the coating film is improved. If the blending amount of the silica particles (B) is 25 parts by mass or less, the coating film has stain resistance (hydrophilicity, antistatic property) without lowering the weather resistance, water resistance, and frost damage resistance of the coating film. improves. Moreover, if the compounding quantity of a silica particle (B) is less than 25 mass parts, whitening of a coating film will be suppressed.

  When two or more types of silica particles having different average particle diameters are used as the silica particles (B), the proportion of silica particles selected from the silica particle group A is 90% by mass to 10% of the total amount of all silica particles (B). It is preferable to use it so that it may become mass%, More preferably, it is 85 mass%-20 mass%, More preferably, it is 80 mass%-30 mass%. On the other hand, it is preferable to use it so that the ratio of the silica particles selected from the silica particle B group is 10% by mass to 90% by mass, more preferably 15% by mass to 80% by mass in the total amount of all silica particles (B). %, And more preferably 20% by mass to 70% by mass.

  Further, the silica particles (B) may be subjected to a surface treatment with a silane compound represented by the following general formula (1).

SiR ¹ _{n + 1} (OR ² ) _3-n (1)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms that may contain an ether bond, n represents an integer of 0 to 2.)
Examples of the silane compound represented by the general formula (1) include trimethoxysilane, dimethoxysilane, dimethoxydimethylsilane, methoxytrimethylsilane, triethoxysilane, diethoxymethylsilane, dimethylethoxysilane, phenyltrimethoxysilane, and dimethoxyphenylsilane. , Phenyltriethoxysilane, diethoxyphenylsilane and the like. These may be used alone or in combination of two or more. Of these, trimethoxymethylsilane is particularly preferred.

  Examples of the method for surface-treating the silica particles (B) with a silane compound include the following methods.

  (I) A method in which colloidal silica and a silane compound are added to an aqueous dispersion of a polymer, and the mixture is stirred for an arbitrary time in a temperature range from room temperature to 100 ° C.

  (Ii) Silica particles surface-treated with a silane compound obtained by stirring colloidal silica and a silane compound in a temperature range of room temperature to 100 ° C. for an arbitrary time are added to an aqueous dispersion of the polymer. Method.

  (Iii) A method in which a silane compound is applied to silica particles unevenly distributed on the outermost layer of the coating film after the coating film has been prepared, and heat-treated at a temperature range of room temperature to 100 ° C. for an arbitrary time.

  1-60 mass parts is preferable with respect to 100 mass parts of silica particles, and, as for content of a silane compound, 5-40 mass parts is more preferable. If content of a silane compound is 1 mass part or more, the weather resistance of a coating film will improve. If the content of the silane compound is 60 parts by mass or less, the weather resistance of the coating film can be further improved without reducing the storage stability of the coloring material-containing coating material, the stain resistance of the coating film, and the water resistance. it can.

Colloidal silica;
Colloidal silica is a colloidal liquid in which the above-described silica particles are dispersed in a dispersion medium. By using colloidal silica for the silica particles (B), the silica particles (B), the polymer (A), and the particles of the coloring material (C) continue to maintain dispersion stability in the coating material containing the coloring material. When forming the film, the silica particles (B) float on the surface of the coating film so that the silica particles (B) pass through the particles of the polymer (A) and coloring material (C), and the silica particle film is formed with a thickness to cover the coating film surface. I think that.

  The dispersion medium may be water or an organic solvent.

  As the colloidal silica, one type of silica particles or one obtained by dispersing at least one selected from the above-described silica particle group A and silica particle group B in a dispersion medium may be used. It may be used. When using a commercially available product, it is preferable to use one or more colloidal silicas or two or more colloidal silicas having different average particle diameters in combination. As the colloidal silica having different average particle diameters, it is preferable to use at least one selected from a colloidal silica group A having an average particle diameter of 1 nm to less than 20 nm and a colloidal silica group B having a particle diameter of 20 nm to 100 nm. . The colloidal silica may be one using water as a dispersion medium or one using an organic solvent as a dispersion medium.

  Examples of the aqueous colloidal silica having an average particle diameter of 1 nm or more and less than 20 nm include the following commercially available products.

Product name: Snowtex OXS (SiO ₂ solid content 10% by mass), Snowtex OS (SiO ₂ solid content 20% by mass), Snowtex O (SiO ₂ solid content 20% by mass), manufactured by Nissan Chemical Industries, Ltd. Snowtex XS (SiO ₂ solid content 20% by mass), Snowtex S (SiO ₂ solid content 30% by mass), Snowtex 20 (SiO ₂ solid content 20% by mass), Snowtex 30 (SiO ₂ solid content 30% by mass) ), Snowtex 40 (SiO ₂ solid content 40% by mass), Snowtex NXS (SiO ₂ solid content 10% by mass), Snowtex NS (SiO ₂ solid content 20% by mass), Snowtex N (SiO ₂ solid content 20) Mass%), Snowtex N-30G (SiO ₂ solid content 30 mass%), Snowtex C (SiO ₂ solid content 20 mass%), Notex AK (SiO ₂ solid content 19% by mass) and the like.

  Examples of the aqueous colloidal silica having a particle diameter of 20 nm to 100 nm include the following commercially available products.

Product name: Snowtex O-40 (SiO ₂ solid content 40% by mass), Snowtex OL (SiO ₂ solid content 20% by mass), Snowtex N-40 (SiO ₂ solid content 40) manufactured by Nissan Chemical Industries, Ltd. %), SNOWTEX 50 (SiO ₂ solid content 50% by mass), SNOWTEX CM (SiO ₂ solid content 30% by mass), SNOWTEX 20L (SiO ₂ solid content 20% by mass), SNOWTEX XL (SiO ₂ solids) 40% by mass), Snowtex ZL (SiO ₂ solid content 40% by mass), Snowtex OUP (SiO ₂ solid content 15% by mass), Snowtex UP (SiO ₂ solid content 20% by mass), Snowtex PS-S (SiO ₂ solid content 19% by mass) and the like.

  The colloidal silica used in the present invention is not limited to these.

(Coloring material (C))
The coloring material (C) is a component that gives the coating film a multi-colored design feeling, and in general, those blended in the paint can be used. The coloring material (C) is preliminarily coated in a water-based dispersion medium with a gelled film of a hydrophilic colloid-forming substance and dispersed in a water-based dispersion medium containing the polymer (A) and silica particles (B). A method of coating and dispersing a hydrophilic colloid-forming substance with a gelled film, a method of coating and dispersing a hydrophilic colloid-forming substance with a gelled film in an aqueous dispersion medium contained in the polymer (A), silica particles (B) A method of coating and dispersing with a gelled film of a hydrophilic colloid-forming substance in an aqueous dispersion medium contained in is preferable, but it is not limited to these methods. Moreover, you may add a specific anionic surfactant and nonionic surfactant in the arbitrary steps in the said method.

  In the gelled film, a hydrophilic colloid-forming substance such as a cellulose derivative and polyvinyl alcohol and an insolubilizing agent (gelling agent) such as boron and magnesium montmorillonite capable of insolubilizing the colloid-forming substance interact with each other. That is, a kind of three-dimensional network is formed.

  Examples of the coloring material (C) include titanium oxide, zinc oxide, calcium carbonate, alumina, silica, kaolin, carbon black, lamp black, bone black, graphite, iron black, copper chrome black, cobalt black, and copper manganese iron black. , Bengara, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine blue, bitumen, Examples thereof include cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, and the like, and one or more of these can be used. The particle size of these coloring materials (C) is usually less than 50 μm.

  As for the compounding quantity of a coloring material (C), 10-100 mass parts is preferable with respect to 100 mass parts of polymers (A). When the amount of the coloring material (C) is 10 parts by mass or more, the design properties of the coating film are improved. If the amount of the coloring material (C) is 100 parts by mass or less, the design properties of the coating film can be further improved without reducing the weather resistance of the coating film.

(Organic hydrazine compound (D))
The coloring material-containing coating material of the present invention may contain an organic hydrazine compound (D). The organic hydrazine compound (D) is a compound having at least two hydrazino groups in the molecule. When the coating film is dried, a crosslinking reaction proceeds between the carbonyl group and / or aldehyde group of the monomer unit (b-1) and the hydrazino group of the blended organic hydrazine compound (D). The coating material that contains the coloring material contains the organic hydrazine compound (D), which makes it possible to maintain low contamination, weather resistance, water resistance, frost resistance, blocking resistance, solvent resistance, and adhesion to various substrates. A coating film excellent in properties can be obtained.

Examples of the organic hydrazine compound (D) having at least two hydrazino groups in the molecule include ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, and sulphur. C2-C15 dicarboxylic acids such as acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, isophthalic acid dihydrazide, itaconic acid dihydrazide Dihydrazide and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 1,3-bis (hydrazinocarboethyl) -5- (2-methylmercaptoethyl) hydantoin, 1-hydrazinocarboethyl-3 -Hide Organic hydrazine compound having Gino carbo-isopropyl-5- (2-methyl-mercaptoethyl) hydantoin skeleton such hydantoin and the like.
These may be used alone or in combination of two or more.

  The content of the organic hydrazine compound (D) in the coloring material-containing coating material that forms the coating film is usually 0.1 to 10 parts by mass when the total mass of the polymer (A) is 100 parts by mass. . In addition, the content of the organic hydrazine compound (D) in the coloring material-containing coating material is P, the total number of moles of the carbonyl group and aldehyde group of the monomer unit (b-1), and the organic hydrazine compound ( When the number of moles of the hydrazino group in D) is Q, the ratio (P / Q) is preferably 0.1 to 10, and more preferably 0.8 to 2. If the ratio (P / Q) is 0.1 or more, the organic hydrazine compound (D) that does not cause a crosslinking reaction with a carbonyl group or an aldehyde group tends to be excessive, and it is easy to suppress a decrease in water resistance. Moreover, if ratio (P / Q) is 10 or less, it will become a sufficient crosslinking degree and the effect by bridge | crosslinking will be easy to be acquired.

(Surfactant)
The specific anionic surfactant and nonionic surfactant are components that impart stain resistance to the coating film. The coloring material-containing coating material contains a specific anionic surfactant and nonionic surfactant, so that the outermost silica particle layer of the coating film can be made thick, and the hydrophilic layer can be effectively and effectively markedly hydrophilic. And a coating film having antistatic properties can be obtained.

Anionic surfactants;
The specific anionic surfactant is at least one anionic surfactant selected from the group shown in (I) below.

  (I): sulfate ester salt of polyoxyalkylene aryl ether, sulfate ester salt of polyoxyalkylene alkyl aryl ether, formalin condensate of sulfate ester salt of polyoxyalkylene aryl ether, sulfate ester salt of polyoxyalkylene alkyl aryl ether Formalin condensate.

  0.1-10 mass parts is preferable with respect to 100 mass parts of polymers (A), and, as for content of an anionic surfactant, 0.5-8 mass parts is more preferable. If the content of the anionic surfactant is 0.1 parts by mass or more, the stain resistance of the coating film, the stability during the preparation of the coloring material-containing coating material, and the storage stability of the coloring material-containing coating material are improved. When emulsion polymerization is performed in the presence of a surfactant, the stability during polymerization is also improved. If the content of the anionic surfactant is 10 parts by mass or less, the coating film is resistant to contamination, the stability during preparation of the coating material containing the coloring material, and the coating material containing the coloring material, without impairing the water resistance of the coating film. The storage stability of the material is improved, and when emulsion polymerization is performed in the presence of a surfactant, the stability during polymerization is also improved.

  The polyoxyalkylene part of the anionic surfactant is used to increase the thickness of the outermost silica particle layer of the coating film, and to efficiently and effectively obtain a coating film having remarkable hydrophilicity and antistatic properties. Ethylene is preferable, and the number of repeating units is preferably 30 or less, and more preferably 20 or less.

  Examples of the aryl part of the anionic surfactant include phenyl, naphthyl, biphenyl, cumylphenyl, styrylphenyl, (mono-penta) benzylphenyl, (mono-penta) styrylphenyl, (mono-penta) styrylcyclohexylphenyl, ( Mono-penta) benzylbiphenyl, styrylcumylphenyl and the like.

  Examples of the sulfate salt of the anionic surfactant include sulfate ester sodium salt, sulfate ester potassium salt, sulfate ester calcium salt, sulfate ester ammonium salt and the like.

Nonionic surfactants;
Specific nonionic surfactants include polyoxyalkylene alkyl ethers.

  The content of the nonionic surfactant is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 9 parts by mass, and 0.1 to 8 parts by mass with respect to 100 parts by mass of the polymer (A). Is more preferable. If the content of the nonionic surfactant is 0.1 part by mass or more, the stain resistance of the coating film, the stability during preparation of the coloring material-containing coating material, and the storage stability of the coloring material-containing coating material are improved. When emulsion polymerization is performed in the presence of a surfactant, the stability during polymerization is also improved. If the content of the nonionic surfactant is 10 parts by mass or less, the water resistance of the coating film is not impaired, the stain resistance of the coating film, the stability during the preparation of the coating material containing the coloring material, the coating containing the coloring material The storage stability of the material is improved, and when emulsion polymerization is performed in the presence of a surfactant, the stability during polymerization is also improved.

  The polyoxyalkylene part of the nonionic surfactant is used to increase the thickness of the outermost silica particle layer of the coating film, and to efficiently and effectively obtain a coating film having remarkable hydrophilicity and antistatic properties. Ethylene is preferred, and the repeating unit is preferably 10 or more, more preferably 20 or more. This effect becomes higher as the number of repeating units of polyoxyethylene is larger.

  Examples of the alkyl part of the nonionic surfactant include, for example, a linear or branched alkyl group having 4 to 18 carbon atoms, naphthyl, biphenyl, cumylphenyl, styrylphenyl, (mono-penta) benzylphenyl, (mono- Penta) styrylphenyl, (mono-penta) styrylcyclohexylphenyl, (mono-penta) benzylbiphenyl, styrylcumylphenyl and the like.

Other surfactants;
In order to improve the stability at the time of preparation of the coloring material-containing coating material, the storage stability of the coloring material-containing coating material, and the polymerization stability when emulsion polymerization is performed in the presence of a surfactant, the anionic surfactant described above is used. Surfactants such as known anionic, cationic, nonionic surfactants, polymeric emulsifiers, reactive emulsifiers having a radical polymerizable unsaturated bond in the surfactant component, and nonionic surfactants. You may use together. However, in order to thicken the outermost silica particle layer of the coating film and to obtain a coating film having remarkable hydrophilicity and antistatic properties efficiently and effectively, the above-mentioned anionic surfactant and nonionic surfactant are used. It is preferable to use an agent.

(Other ingredients)
The coating material containing the coloring material of the present invention has a defoaming agent, a pigment dispersant, a leveling agent, a matting agent, an ultraviolet absorber, an antioxidant, and an improvement in heat resistance in order to develop a high performance as a coating material. Various additives such as additives, slip agents, preservatives, plasticizers, film-forming aids; other emulsion resins, water-soluble resins, viscosity control agents, and curing agents such as melamines may be added.

  In addition, it is preferable to adjust the viscosity of the coloring material-containing coating material to a specific viscosity by adding a viscosity modifier. Viscosity modifiers include bentonite, sericite, ultrafine silica, surface treated calcium carbonate and other inorganic materials, amide wax, hydrogenated castor oil wax, benrididene sorbitol, metal soap, polyethylene oxide, sulfate anion activator, etc. These are organic types.

  The preferred viscosity is a viscosity at 20 rpm measured by a BH type viscometer at 20 ° C. (guide value for the fourth rotation) in the range of 0.2 to 15 Pa · s and a TI value of 1.0 to 8.0. . When satisfying such a value, the colored particles are not destroyed by the shear stress during coating, and a large circular pattern can be formed on the surface to be coated. In particular, a viscosity of 0.3 to 10 Pa · s and a TI value of 2.0 to 6.0 are preferable because the above-described effects are stably exhibited.

  Here, when the viscosity at 20 rpm (the guide value for the fourth rotation) is lower than 0.2 Pa · s, the particles are greatly deformed by shear stress, making it impossible to form a circular pattern, There is a tendency that the pattern formed on the surface to be coated flows and the design properties are impaired. Conversely, when the viscosity (guide value at the fourth rotation) is higher than 15 Pa · s, the fluidity is poor, and spherical colored particles are formed when the coloring material-containing coating material is dispersed in an aqueous solution containing polyvinyl alcohol. It is difficult to form a circular pattern on the surface to be coated. On the other hand, if the TI value is smaller than 1.0, the pattern formed on the coated surface tends to flow even if the viscosity is 0.2 to 15 Pa · s. Due to the stress, the colored particles may be crushed and coated.

  When adding a viscosity modifier, it is suitable to add a viscosity modifier so that it may become a ratio of about 1-10 mass parts with respect to 100 mass parts of polymers (A).

  Furthermore, you may mix | blend a fiber substance, an extender pigment, and an aggregate with a coloring material containing coating material. Examples of such fiber materials include pulp fiber, cellulose fiber, sepiolite, wollastonite, and extender pigments include heavy calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, porcelain clay, china clay, barium sulfate, Examples thereof include barium carbonate, calcium silicate, calcium phosphate, magnesium carbonate, silica stone powder, diatomaceous earth, aluminum oxide, and resin beads, and one or more of these can be used. The particle size of these extender pigments is usually less than 50 μm.

  As the aggregate, at least one kind selected from natural aggregates such as natural stones, pulverized natural stones, and artificial aggregates such as colored aggregates can be used. For example, marble, granite, serpentinite, granite, fluorite, cryolite, feldspar, limestone, quartzite, quartz sand, crushed stone, mica, siliceous tribute, and pulverized materials thereof, ceramic pulverized material, ceramic pulverized material, glass pulverized Products, glass beads, glass flakes, resin pulverized products, resin beads, rubber particles, shell pieces, wooden pieces, plastic pieces, and the like. Those obtained by coloring them can also be used. By using two or more kinds of such aggregates in appropriate combination, various multicolor patterns can be expressed. The particle diameter of the aggregate is usually about 0.05 to 5 mm.

  Examples of the film-forming aid include those used in ordinary water-based paints, and examples thereof include the following.

  C5-C10 linear, branched or cyclic aliphatic alcohols.

  Alcohols containing aromatic groups.

  Monoethers: (poly) ethylene glycol monoether or (poly) propylene glycol monoether represented by the following general formula (2).

^{_{HO- (CH 2 CHXO) n -R}} 3 ··· (2).

(Wherein R ³ represents a linear or branched alkyl group having 1 to 10 carbon atoms, X represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 5)
Ether ester: (poly) ethylene glycol ether ester or (poly) propylene glycol ether ester represented by the following general formula (3).

_{^{R 4 COO- (CH 2 CHXO)}} n -R 5 ··· (3).

(In the formula, R ⁴ and R ⁵ represent a linear or branched alkyl group having 1 to 10 carbon atoms, X represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 5. .)
Aromatic organic solvents: toluene, xylene, etc.

  Other: 2,2,4-trimethyl-1,3-pentanediol mono- or diisobutyrate, 3-methoxybutanol, 3-methoxybutanol acetate, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxy Butanol acetate etc.

<Method for producing coloring material-containing coating material>
The coloring material-containing coating material is produced by mixing the polymer (A), the silica particles (B), and the coloring material (C).

  The polymer (A) is preferably prepared and used as an aqueous dispersion.

  The specific anionic surfactant and nonionic surfactant may be added during the production process of the aqueous dispersion of the polymer (A), and after the production of the aqueous dispersion of the polymer (A), the coloring material You may add when preparing a content coating material. When adding when adjusting a coloring material containing coating material, it can add in the arbitrary steps in the said mixing method.

(Aqueous dispersion of polymer (A))
As the aqueous dispersion of the polymer (A), an emulsion obtained by an emulsion polymerization method, a solution obtained by diluting the emulsion with water, and a solution of the polymer (A) obtained by a solution polymerization method are diluted with water and removed. Examples include solvents. Of these, emulsions obtained by emulsion polymerization or those diluted with water are preferred.

  The emulsion is, for example, a hydrolyzable silyl group-containing radical polymerizable monomer unit and / or a polyfunctional monomer unit (a) 0.2 to 2 having two or more radical polymerizable groups in the presence of a surfactant. 20% by mass, other monomer units (b) 80 to 99.8% by mass (provided that the total of the monomer units (a) and the monomer units (b) is 100% by mass). It is preferable to prepare the radical polymerizable monomer mixture to be polymerized by a radical polymerization initiator.

  Surfactants used for the preparation of the emulsion include known anionic surfactants (including the specific anionic surfactants), cationic surfactants, nonionic surfactants (the specific nonionic surfactants). A polymer emulsifier). Further, a so-called reactive emulsifier having a radical polymerizable unsaturated bond in the surfactant component may be used.

  Examples of the radical polymerization initiator include the following compounds.

  Persulfates: potassium persulfate, sodium persulfate, ammonium persulfate, etc.

  Oil-soluble azo compounds: azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like.

  Water-soluble azo compounds: 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl- N- [2- (1-hydroxyethyl)] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}, 2,2′-azobis [ 2- (5-Methyl-2-imidazolin-2-yl) propane] and its salts, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and its salts, 2,2′- Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] and its salts, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazoline-2 -Ile Propane} and its salts, 2,2′-azobis (2-methylpropionamidine) and its salts, 2,2′-azobis (2-methylpropyneamidine) and its salts, 2,2′-azobis [N— (2-carboxyethyl) -2-methylpropionamidine] and salts thereof.

  Organic peroxides: benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate and the like.

  These may be used individually by 1 type and may be used in combination of 2 or more type.

  When acceleration of the polymerization rate or low temperature polymerization at 70 ° C. or lower is desired, it is advantageous to use a reducing agent such as sodium bisulfite, ferrous sulfate, ascorbate, Rongalite in combination with a radical polymerization initiator. It is.

  The compounding amount of the radical polymerization initiator is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the radical polymerizable monomer, and 0 in consideration of the progress of polymerization and control of the reaction. 0.05 to 5 parts by mass is preferable.

  When adjusting the molecular weight of a polymer (A), you may use a well-known chain transfer agent as a molecular weight modifier. Examples of the chain transfer agent include the following compounds.

  Mercaptans: n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan and the like.

  Halogen compounds: carbon tetrachloride, ethylene bromide and the like.

  Other: α-methylstyrene dimer and the like.

  The blending amount of the chain transfer agent is usually 1 part by mass or less with respect to 100 parts by mass of the total amount of the radical polymerizable monomer.

  The emulsion obtained by the emulsion polymerization method can be improved in stability by adding a basic compound to adjust its pH from neutral to weakly alkaline, that is, in the range of about pH 6.5 to 10.0. Examples of the basic compound include ammonia, triethylamine, propylamine, dibutylamine, amylamine, 1-aminooctane, 2-dimethylaminoethanol, ethylaminoethanol, 2-diethylaminoethanol, 1-amino-2-propanol, 2- Amino-1-propanol, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-propylaminoethanol, Examples include ethoxypropylamine, aminobenzyl alcohol, morpholine, sodium hydroxide, potassium hydroxide and the like.

  Examples of the particle structure of the polymer (A) in the emulsion include a single layer structure and a multilayer structure.

Hydrolyzable silyl group-containing radical polymerizable monomer units and polyfunctional monomer units having two or more radical polymerizable groups are used for the purpose of improving the stain resistance, weather resistance and water resistance of the coating film. However, if the amount is large, the frost damage resistance of the coating film is reduced. Therefore, it is preferable to improve the stain resistance, weather resistance, and water resistance of the coating film with a small content.
In order to improve the stain resistance, weather resistance and water resistance of the coating film with a smaller content, for example, when the polymer (A) is a high Tg core / low Tg shell type emulsion particle, the outermost layer is hydrolyzed. A monomer (a) obtained by copolymerizing a monomer unit comprising a functional silyl group-containing radical polymerizable monomer unit and / or a polyfunctional monomer having two or more radical polymerizable groups preferable.

  As the silica particles (B), it is preferable to use one kind or two or more kinds of silica particles having different average particle diameters. Further, a colloidal liquid (colloidal silica) in which silica particles (B) are dispersed in a dispersion medium may be used.

  The mixing order of the three components of the polymer (A), the silica particles (B), and the coloring material (C) is not particularly limited, but the total amount of the two components among the three components is first mixed and mixed. And the remaining component (hereinafter referred to as the third component) is mixed, or the two components are mixed in an arbitrary ratio (hereinafter referred to as the mixture I), and the mixture I and the third component are mixed together (hereinafter referred to as the following). A method of mixing the mixture II) and separately mixing the remaining two components at an arbitrary ratio (hereinafter referred to as mixture III) and mixing the mixture III and mixture II (hereinafter referred to as mixture IV) can be mentioned. Since the mixture III can be mixed at an arbitrary ratio, the mixture of the remaining two components at an arbitrary ratio, or a single component can be further mixed in a plurality of times.

  In the above mixing method, a mixture composed of two components in an arbitrary ratio may be mixed with the third component or the mixture containing the third component, and the mixture containing the third component or the third component is arbitrarily selected. You may mix in the mixture which consists of 2 components of the ratio.

In the manufacturing method of the coloring material-containing coating material, from the viewpoint of the stain resistance of the coating film and the storage stability of the coloring material-containing coating material,
(1) A method of mixing all the silica particles (B) and the coloring material (C) in advance and then mixing the polymer (A) is preferable.
(2) A method of previously mixing the silica particles (B) and the coloring material (C) in an arbitrary ratio, then mixing the polymer (A), and further adding the remaining silica particles (B) is more preferable,
(3) Silica particles (B) and coloring material (C) are mixed in an arbitrary ratio in advance (mixture V), and separately polymer (A) and silica particles (B) are mixed in an arbitrary ratio (mixture VI). Then, a method of mixing the mixture V and the mixture VI (mixture VII) or a method of further mixing the remaining silica particles (B) into the mixture VII is particularly preferable.
In the mixing methods (1) to (3), silica particles having a small particle diameter may be used for the silica particles (B). In the methods (2) and (3), silica particles having a smaller particle diameter than the silica particles (B) mixed with the polymer (A) are added to the silica particles (B) mixed with the coloring material (C). It may be used.
Since the coloring material-containing coating material produced by the mixing method of (1) to (3) described above is likely to cause the silica particles (B) to be unevenly distributed on the coating film surface when the coating material is applied, the exposed silica on the coating film surface A coating film in which the area occupied by the particles (B) is 35% or more of the coating film surface can be easily formed.

<Coating film>
The coating film of the present invention contains at least the polymer (A), the silica particles (B), and the coloring material (C), and the area occupied by the exposed silica particles (B) on the coating film surface is the coating film surface. More than 35% of the total.

  When the occupied area of the exposed silica particles (B) on the coating film surface is less than 35%, sufficient contamination resistance and water contact angle cannot be obtained. The occupied area is preferably 40% or more, more preferably 60% or more, and most preferably 70% or more.

The occupied area of the silica particles (B) in the present invention is the area occupied by the silica particles (B) exposed on the coating film surface when the coating film surface is viewed from the vertical direction. Specifically, as shown in FIG. 1, the total of the planar occupation area S of silica particles (B) exposed on the coating film surface (F) (ie, S ₁ + S ₂ +...) That is.
The area occupied by the silica particles (B) can be determined by subjecting the secondary electron image of the scanning electron micrograph on the surface of the coating film to image processing. Moreover, the distribution state and magnitude | size of the coating component which are not covered with the silica particle (B) can be judged visually using the secondary electron image of a scanning electron micrograph. Specific examples of software used for electron micrograph photographing conditions and image processing are given below.

(Electron micrograph)
“JSM-6340F type” field emission scanning electron microscope manufactured by JEOL Ltd.,
Acceleration voltage: 2.5 kV, magnification: 50,000 times, image processing analysis,
Planetron Inc. Image-Pro Plus,
Analysis target minimum area 1e-5 μm 2.

  In the electron micrograph, if the contrast between the part derived from the polymer particles and the silica particles is insufficient, it is difficult to obtain an image processing result in line with the actual situation. Therefore, it is also effective to perform image processing after processing with software such as Photo Shop in order to add contrast to a digital image of an electron micrograph.

  If the polymer part exposed without being covered with the silica particles (B) is excessively large or the exposed polymer part is biased to a part of the coating film, the stain resistance of the entire coating film Tend to decrease.

  In order to form the said coating film, it can obtain easily by apply | coating the coloring material containing coating material of this invention to a base material etc. and drying, for example.

  Examples of the base material include cement mortar, slate board, gypsum board, extruded board, foamable concrete, metal, glass, porcelain tile, asphalt, wood, waterproof rubber material, plastic, and calcium silicate base material. The coloring material-containing coating material of the present invention can be positioned as a surface finishing material for these various substrates.

  Examples of the method of applying the coloring material-containing coating material on the surface of various substrates include various coating methods such as spray coating, roller coating, bar coating, air knife coating, brush coating, and dipping. .

  A coating film is obtained by heating and drying the coloring material-containing coating material applied to the substrate surface at normal temperature (5-35 ° C.) or 40-200 ° C. In addition, after drying at a low temperature of about room temperature to about 50 ° C. to form a coating film, the coating film is heated to a temperature higher than the glass transition temperature of the polymer (A) to bind the particles of the polymer (A). It is also possible to obtain a coating film with higher weather resistance. Furthermore, it is possible to form a coating film only at room temperature.

In the coating film of the present invention described above, the polymer (A), the silica particles (B), and the coloring material (C) are contained, and the occupied area of the exposed silica particles (B) on the coating film surface is Since it occupies 35% or more of the coating film surface, it is excellent in stain resistance. Furthermore, if content of a silica particle (B) is 0.5-25 mass parts with respect to 100 mass parts of polymers (A), it will become a coating film which is more excellent in stain resistance.
Moreover, since the coating film of this invention contains a coloring material (C), it is excellent also in designability, such as having glossiness.

  Such a coating includes a polymer (A) composed of the monomer unit (a) and the monomer unit (b), a silica particle (B), a coloring material (C), and a specific material. The coloring material of the present invention containing at least an anionic surfactant and a specific nonionic surfactant, and the coloring material (C) is 10 to 100 parts by mass with respect to 100 parts by mass of the polymer (A). Easily formed from the coating material containing the coloring material of the present invention in which the content of the coating material, preferably the silica particles (B) is 0.5 to 25 parts by mass with respect to 100 parts by mass of the polymer (A) can do.

  In the coated article having the coating film of the present invention, the coating film is excellent in weather resistance and contamination resistance (carbon contamination removal resistance). That is, by using the coating film of the present invention, a silica particle layer is formed on the outermost layer of the coating film with a certain thickness or more and spreading on the surface of the coating film. The self-cleaning effect of rainwater will be demonstrated. Furthermore, since the silica particles come into contact with each other on the surface of the coating film, the coating film surface has conductivity, and adhesion of dirt due to static electricity is suppressed. As a result, the coating film of the present invention exhibits excellent stain resistance. Furthermore, when silica particles having different average particle diameters are used in combination, a coarse structure having nano-order irregularities is formed on the outermost layer of the coating film, and the coarse structure also changes in response to the movement of the resin due to changes in diameter. However, when the average particle diameter of the silica particles is different, a new coarse structure is formed, and the stain resistance is exhibited over a long period of time.

  In addition, in order to exhibit sufficient stain resistance only by the coating film of this invention, a coated material does not necessarily need to be made into the multilayer structure which consists of conventional topcoat, intermediate coating, and undercoat.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this Example.

  The evaluation of the coating film was performed according to the following method.

<Content of monomer unit>
The content of the monomer unit in the polymer (A) is determined using pyrolysis gas chromatograph (gas chromatograph: manufactured by Agilent Technologies, thermal decomposition apparatus: manufactured by Nippon Analytical Industries, Ltd.), pyrolysis gas chromatograph mass spectrometer ( Measurement was performed using a gas chromatograph mass spectrometer: manufactured by Agilent Technologies, a thermal decomposition apparatus: manufactured by Nihon Analytical Industry Co., Ltd., a Fourier transform infrared spectrophotometer (manufactured by Nicolet Japan Co., Ltd.), and the like.

<Preparation of test plate for measuring area occupied by silica particles (B)>
A coloring material-containing coating material was applied to the PET film at 40 ° C. in an atmosphere of 40 ° C., and dried at 40 ° C. for 12 hours. Then, what was dried at room temperature for 1 day was used as a test plate for occupying area measurement.

<Preparation of test plate for evaluation of water contact angle, carbon decontamination, frost damage resistance, weather resistance>
A coating material containing a coloring material was applied to a zinc phosphate-treated steel plate (bonderite # 100-treated steel plate, plate thickness 0.8 mm, length 150 mm × width 70 mm) at 40 ° C. with a bar coater # 48. Dry at 12 ° C. for 12 hours. Then, what was dried at room temperature for 1 day was used as a test plate for evaluating water contact angle carbon contamination removal resistance, frost damage resistance, and weather resistance.

<Measurement of area occupied by silica particles (B)>
The area occupied by the exposed silica particles (B) on the surface of the coating film was measured using a field emission scanning electron microscope ("JSM-6340F type" manufactured by JEOL Ltd.) The obtained secondary electron image was obtained by image processing. The observation conditions are as follows.
・ Acceleration voltage: 2.5 kV, magnification: 50,000 times ・ Image processing analysis
-Planetron Inc. Image-Pro Plus,
・ Analysis target minimum area 1e-5 μm2.

<Measurement of water contact angle>
Using a CA-X150 type FACE contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), 0.4 μL (three scales on the screen) of water droplets was dropped on the coating film of the evaluation test plate, and 30 seconds later. The water contact angle was measured.

<Evaluation of carbon decontamination property: antifouling property at the initial stage of coating film preparation>
Immediately after spraying water on the coating film of the test plate for evaluation with a spray, a carbon solution containing 10% by mass of carbon MA100 (manufactured by Mitsubishi Chemical Corporation) in petroleum benzine was dropped using a dropper, and after 5 seconds. Rinse with tap water. About the part which dipped the carbon solution, the adhesion degree to the coating film of carbon was observed visually, and the following reference | standard determined.

  “◎”: No adhesion.

  “◯”: Slightly adhered partially.

  "X": It adheres to the whole surface deeply.

<Evaluation of frost resistance>
The measurement was performed by the ASTM-C666A method (200 cycles), and the determination was made according to the following criteria.

  “◎”: No crack or gloss change.

  “◯”: No crack, but slightly glossy.

<Evaluation of weather resistance>
A test plate having a size of 70 mm × 50 mm is cut from the test plate for evaluation, and the test plate is put into a die plastic metal weatherer KU-R4-W type (manufactured by Daipura Wintes Co., Ltd.). Test cycle: irradiation 4 hours ( Spray 5 seconds / 15 minutes) / condensation 4 hours, UV intensity: 85 mW / cm ² , black panel temperature: 63 ° C. during irradiation / 30 ° C. during condensation, humidity: 50% RH during irradiation / 96% RH during condensation A weather resistance test was conducted. Using the 60 ° gloss retention of the coating after 600 hours as an indicator of weather resistance, the following criteria were used.

  “◎”: 80% or more.

  “◯”: 70% or more and less than 80%.

[Production Example 1]
Preparation of aqueous dispersion of polyorganosiloxane:
95 parts by mass of cyclic dimethylsiloxane oligomer 3-7-mer mixture, 5 parts by mass of γ-methacryloyloxypropyltrimethoxysilane, 250 parts by mass of deionized water, 0.4 parts by mass of sodium dodecylbenzenesulfonate, and dodecylbenzenesulfonic acid A composition consisting of 0.4 parts by mass was premixed with a homomixer and forcibly emulsified with a pressure homogenizer at a pressure of 200 kg / cm ² to obtain a raw material pre-emulsion.

  Next, 55 parts by mass of water and 5 parts by mass of dodecylbenzenesulfonic acid were charged into a flask equipped with a stirrer, a reflux condenser, a temperature controller and a dropping pump, and the internal temperature of the flask was maintained at 85 ° C. with stirring. The raw material pre-emulsion was added dropwise over 4 hours. After completion of the dropwise addition, the polymerization was further allowed to proceed for 1 hour, cooled, and dodecylbenzenesulfonic acid and an equimolar amount of ammonia were added to prepare a polyorganosiloxane aqueous dispersion (SiEm). The solid content was 22.7 parts by mass.

[Example 1]
In a flask equipped with a stirrer, reflux condenser, temperature controller, and dropping pump, 87 parts by mass of deionized water, New Coal 707SF (trade name, manufactured by Nippon Emulsifier Co., Ltd., anionic surfactant, polyoxyalkylene alkylaryl) Sulfuric ester of ether (Chemical Examination Law Official Journal publication name: polyoxyalkylene (C = 2 to 3) alkyl (C = 1,8,9) (mono-penta) styryl-phenyl ether sulfate) 2.5 Radical polymerizability, which is a constituent of the polymer shown in parts by mass (solid content: 0.75 parts by mass), SiEm (4 parts by mass (solid content: 0.9 parts by mass)) and “first stage (inner layer)” in Table 1 A mixture of monomers was charged. After raising the internal temperature of the flask to 50 ° C., an initiator aqueous solution of 0.15 part by weight of ammonium persulfate / 1 part by weight of deionized water was added, and 0.05 part by weight of sodium bisulfite / 1 part by weight of deionized water. Part of the reducing agent aqueous solution was added. After confirming the peak top temperature due to polymerization exotherm, the internal temperature of the flask was maintained at 65 ° C., and 1 hour after the addition of the reducing agent aqueous solution, Emulgen 1150S-60 (trade name, manufactured by Kao Corp., nonionic surfactant) (Solid content: 60% by mass): polyoxyalkylene alkyl ether represented by the following formula: R— (C ₂ H ₄ O) _n —H (R: alkyl group mainly having 11 carbon atoms, n = 50)) 1 .17 parts by mass (solid content 0.7 parts by mass) / deionized water 1.17 parts by mass was added to a surfactant aqueous solution.

  0.5 hours after addition of the surfactant aqueous solution, a mixture of radical polymerizable monomers shown in “Second stage (outer layer)” in Table 1, 19 parts by mass of deionized water, 10 parts by mass of New Coal 707SF ( A pre-emulsion liquid in which 0.115 part of a solid content of 3 parts by mass, an anionic surfactant) and AMP-90 (trade name, manufactured by Dow Chemical Japan Co., Ltd., basic compound) are emulsified and dispersed in advance, and VA -061 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., radical polymerization initiator) 0.1 parts by weight / methanol 2 parts by weight / deionized water 3 parts by weight of initiator solution over 1.5 hours Two series were dripped. During the dropping, the internal temperature of the flask was maintained at 65 ° C., and after the dropping was completed, the temperature was maintained at 65 ° C. for 1 hour. Further, 1.33 parts by mass of 28% ammonia water was added as a final neutralizing agent, and the mixture was further maintained at 65 ° C. for 0.5 hour. Then, it cooled to room temperature and obtained the aqueous dispersion liquid of the polymer (A). The content of the unit derived from the hydrolyzable silyl group-containing radical polymerizable monomer was 2.05 parts by mass with respect to 100 parts by mass of the polymer (solid content).

  In the aqueous dispersion of the polymer (A), 50 parts by mass (solid content) of Snowtex NS (trade name, manufactured by Nissan Chemical Industries, Ltd., colloidal silica, average particle diameter of silica particles) as silica particles (B). 10 parts by mass) and 5 parts by mass of butyl cellosolve as a film forming aid were added to obtain a coating material mixture. The amount of silica particles (solid content) was 10 parts by mass with respect to 100 parts by mass of the polymer (solid content).

  Next, Taipei R-930 (sulfuric acid method titanium oxide coloring material manufactured by Ishihara Sangyo Co., Ltd.) 196.3 parts by mass, OROTAN SG (pigment dispersant manufactured by Rohm & Haas) 2.1 parts by mass, Surfynol DF-58 ( Air Products, Defoamer) 0.08 parts by mass, 29.4 parts by mass of propylene glycol, 34.3 parts by mass of deionized water, 1.8 parts by mass of 28% aqueous ammonia solution, and then mixed with glass beads Then, pigment dispersion was performed for 30 minutes with a high-speed disperser, and then glass beads and the like were separated by filtration with a 300-mesh nylon basket to make a mill base for evaluation.

  To 120 parts by mass of the coating material mixture (solid content: 40.4 parts by mass), 55 parts by mass of the above-mentioned mill base and 1.5 parts by mass of RHEOLATE 350 (thickener manufactured by RHEOX) are sequentially added and sufficiently stirred. After that, deionized water was added to the Ford Cup # 4 to adjust the viscosity so as to be about 100 seconds to 140 seconds.

  Thereafter, filtration was again performed using a 300 mesh nylon bag, and a white coloring material-containing coating material for test was produced.

  A coating film was formed using the obtained white coloring material-containing coating material, and the area occupied by the exposed colloidal silica (silica particles (B)) on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

[Example 2]
Except that the type and amount of colloidal silica were changed as shown in Table 1, a mixture for coating material and a white coloring material-containing coating material for testing were prepared in the same manner as in Example 1.

  A coating film was formed using the obtained white coloring material-containing coating material, and the occupation area of the exposed colloidal silica on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

Example 3
A mixture for a coating material and a test in the same manner as in Example 1 except that the mixture of radically polymerizable monomers that are constituents of the polymer (A) and the amount of colloidal silica were changed as shown in Table 1. A white coloring material-containing coating material was prepared.

  A coating film was formed using the obtained white coloring material-containing coating material, and the occupation area of the exposed colloidal silica on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

Example 4
Except for changing the mixture of the radically polymerizable monomers that are constituents of the polymer (A) as shown in Table 1, the mixture for the coating material and the white color for testing were the same as in Example 2. A material-containing coating was prepared.

  A coating film was formed using the obtained white coloring material-containing coating material, and the occupation area of the exposed colloidal silica on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

Example 5
15 minutes before charging the final neutralizer (28% aqueous ammonia 1.33 parts by mass), an aqueous dispersion of an organic hydrazine compound (D) containing 0.93 parts by mass of adipic acid dihydrazide (ADH) / 2 parts by mass of deionized water was added. A mixture for a coating material and a white coloring material-containing coating material for testing were prepared in the same manner as in Example 2 except for the addition.

  A coating film was formed using the obtained white coloring material-containing coating material, and the occupation area of the exposed colloidal silica on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

Example 6
15 minutes before the final neutralizer (28% aqueous ammonia 1.33 parts) was added 0.93 parts by weight of adipic acid dihydrazide (ADH) / 2 parts by weight of deionized water, and an organic hydrazine compound (D) aqueous dispersion was added. A mixture for coating material and a white coloring material-containing coating material for test were prepared in the same manner as in Example 4 except that.

  A coating film was formed using the obtained white coloring material-containing coating material, and the occupation area of the exposed colloidal silica on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

Example 7
A coating material mixture was prepared in the same manner as in Example 1 except that the amount of colloidal silica was changed as shown in Table 1. The mill base was also produced in the same manner as in Example 1.
Next, 8 parts by mass of colloidal silica (Snowtex NXS) is added to and mixed with 100 parts by mass of the mill base, and 55 parts by mass thereof is mixed with 120 parts by mass of the coating material mixture (solid content: 42.5 parts by mass). In addition, after adding 1.5 parts by mass of RHEOLATE 350 (RHEOX thickener) and stirring well, adjust the viscosity by adding deionized water with Ford Cup # 4 so that it is about 100 to 140 seconds. did. The amount of silica particles (solid content) was 9 parts by mass with respect to 100 parts by mass of the polymer (solid content).
Thereafter, filtration was again performed using a 300 mesh nylon bag, and a white coloring material-containing coating material for test was produced.

  A coating film was formed using the obtained white coloring material-containing coating material, and the occupation area of the exposed colloidal silica on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

[Comparative Example 1]
Except for changing the mixture of the radically polymerizable monomers, which are constituents of the polymer (A), as shown in Table 1, the mixture for the coating material and the white color for testing were the same as in Example 1. A material-containing coating was prepared.

  A coating film was formed using the obtained white coloring material-containing coating material, and the occupation area of the exposed colloidal silica on the coating film surface and the water contact angle of the coating film were measured. The results are shown in Table 2.

  Further, the formed coating film was evaluated for carbon stain removability, frost damage resistance, and weather resistance. The results are shown in Table 2.

  (* 1) and (* 2) in Table 1 are as follows, and abbreviations in Table 1 indicate the following compounds.

(* 1): Numerical values are parts by mass, and numerical values in parentheses are mass%.
(* 2): Numerical values are parts by mass when the polymer (A) is 100 parts by mass.

“MMA”: methyl methacrylate,
“2-HEMA”: 2-hydroxyethyl methacrylate,
“EDMA”: ethylene glycol dimethacrylate,
“SZ-6030”: Hydrolyzable silyl group-containing radical polymerizable monomer (a), γ-methacryloyloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone),
“TAC”: triallyl cyanurate “MAA”: methacrylic acid,
“N-BA”: n-butyl acrylate,
“DAAm”: diacetone acrylamide,
“ADH”: adipic acid dihydrazide.

  As is apparent from Table 2, the coating film made of the white-colored coloring material-containing coating material of the example is excellent in the stain resistance (carbon decontamination property) of the coating film because the water contact angle of the coating film is low. It had frost damage resistance and weather resistance.

  On the other hand, it was difficult for the coating film made of the white coloring material-containing coating material of the comparative example to exhibit the stain resistance, frost resistance, and weather resistance of the coating film in a well-balanced manner.

  The coating film comprising the coating film of the present invention and the coating material containing the coloring material is excellent in stain resistance and has good frost damage resistance and weather resistance. Such a coating material containing a coloring material and its coating film can be used for various coating applications for the purpose of protecting a structural body or the like, and is extremely useful industrially.

It is a cross-sectional schematic diagram explaining the occupation area of the exposed silica particle (B) in the coating-film surface.

Explanation of symbols

F: coating film surface,
B: Silica particles,
S: Occupied area.

Claims (5)

  A coating film containing a polymer (A), silica particles (B), and a coloring material (C), and the occupied area of the exposed silica particles (B) on the coating film surface is 35% or more of the coating film surface Coating film. A coloring material-containing coating material containing a polymer (A), silica particles (B), a coloring material (C), an anionic surfactant, and a nonionic surfactant,
The polymer (A) is a hydrolyzable silyl group-containing radical polymerizable monomer unit and / or a polyfunctional monomer unit (a) having two or more radical polymerizable groups (a) 0.2 to 20% by mass, Composed of 80 to 99.8% by mass of other monomer units (b) (provided that the total of the monomer units (a) and the monomer units (b) is 100% by mass);
The coloring material containing coating | covering material whose said coloring material (C) is 10-100 mass parts with respect to 100 mass parts of polymers (A).   The organic hydrazine compound (D) is further contained, and the ethylenically unsaturated monomer unit (b-1) containing a carbonyl group and / or an aldehyde group is added as the other monomer unit (b). The coloring material containing coating | covering material of Claim 2 containing 0.1-10 mass% (however, the mass of the said polymer (A) shall be 100 mass%).   The coloring material-containing coating material according to claim 2 or 3, wherein the silica particles (B) are 0.5 to 25 parts by mass with respect to 100 parts by mass of the polymer (A). A method for producing a coloring material-containing coating material according to any one of claims 2 to 4,
Including a step of preparing a mixture by mixing all or part of the silica particles (B) and all or part of the coloring material (C), and then mixing the mixture and the polymer (A). Method.

Images