JP5606715B2 - Coating material - Google Patents

Description

  The present invention relates to a novel coating material. The coating material of the present invention is particularly suitable as an aqueous coating material for outdoor use.

  In recent years, with respect to coating materials used for painting work such as buildings and civil engineering structures, a shift from solvent-type coating materials using an organic solvent as a solvent to water-based coating materials using a solvent as a solvent is being attempted. This is performed for the purpose of reducing the health hazards of painters and residents, and for the purpose of reducing air pollution. However, a coating film made of an aqueous coating material generally tends to adhere to contaminants as compared with a coating film made of a solvent-type coating material.

  As a technique for suppressing the adhesion of contaminants, a technique is disclosed in which an organosilicate and / or a condensate thereof (hereinafter referred to as “organosilicate etc.”) is blended in a coating material (Patent Document 1). The technology of Patent Document 1 is made by blending organosilicate or the like in a coating material, and making the coating surface hydrophilic by acid treatment after the coating is formed, making it difficult for oily contaminants to adhere, and further attaching the contaminants. It is characterized by having the performance of washing away with water droplets such as rain.

  However, generally organosilicates and the like have reactivity with water. Therefore, when the technique of Patent Document 1 is applied to an aqueous coating material, it is difficult to control hydrolysis condensation reaction such as organosilicate, the viscosity rapidly increases in a short time, and further gelation occurs. The problem of hindering the painting work and the problem that the compatibility between the aqueous resin and the organosilicate is poor and agglomerates are formed after mixing are likely to occur. In particular, the glossy type water-based coating material generally has a disadvantage that the surface gloss is extremely lowered due to the poor compatibility. Furthermore, even when coating is performed immediately after mixing and a coating film is formed, there is a drawback that sufficient stain resistance cannot be obtained. In particular, in the initial stage of coating film formation, there is a problem that contaminants are more likely to adhere due to adhesiveness caused by organosilicate or the like.

As a technique for solving the above problem, there is a technique using an alkoxysilane compound having a polyoxyalkylene group (Patent Document 2). According to this technique, the compatibility between the alkoxysilane compound and the aqueous resin is improved, and the formed coating film has relatively good gloss and also has stain resistance.
However, the alkoxysilane compound of Patent Document 2 also has an alkoxysilyl group having reactivity with water. Therefore, in order to distribute the coating material of Patent Document 2 in the market, it is necessary to use a two-component coating material in which an aqueous resin and an alkoxysilane compound are separate components and are mixed at the time of coating, and at the time of storage until coating During distribution, sufficient care must be taken not to mix moisture into the alkoxysilane compound.

  The present invention has been made in view of such problems, and can reduce labor during storage, distribution, etc., and can provide excellent stain resistance in the formed coating film. The purpose is to obtain a material.

  As a result of intensive studies in order to solve these problems, the present inventors have come up with a coating material in which a specific water-dispersible silica and a fluorine-containing compound are mixed at a specific mixing ratio with respect to a synthetic resin emulsion, The present invention has been completed.

That is, the present invention relates to the following coating materials.
1. Synthetic resin emulsion (A), water-dispersible silica (B) having a particle size of 1 to 200 nm, a coating material containing a polyfluoroalkyl group and a fluorine-containing compound (C) having a nonionic or amphoteric hydrophilic group as essential components Yes,
(A) The solid content of component (B) is 0.1 to 500 parts by weight, and (C) component is 0.01 to 10 parts by weight relative to 100 parts by weight of component (A),
A coating material, wherein the mixing ratio of the component (B) and the component (C) is 100: 0.01 to 100: 100 by weight.

  The coating material of the present invention exhibits excellent stain resistance in the formed coating film. The covering material of the present invention can reduce labor during storage, distribution, etc., and can also be made into a one-pack type.

WO94 / 06870 Publication WO99 / 05228

  Hereinafter, modes for carrying out the present invention will be described.

The coating material of the present invention comprises a synthetic resin emulsion (A) (hereinafter referred to as “component (A)”), water-dispersible silica (B) having a particle diameter of 1 to 200 nm (hereinafter referred to as “component (B)”), polyfluoroalkyl And a fluorine-containing compound (C) having a nonionic or amphoteric hydrophilic group (hereinafter referred to as “component (C)”) as an essential component.
In addition to the components (A) to (C), the coating material of the present invention can appropriately contain each component necessary as a target coating material in addition to the dispersion medium of the above components.

Of these, the component (A) acts as a binder and can be obtained by copolymerizing various polymerizable monomers. Examples of the polymerizable monomer component constituting the component (A) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n- Amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) (Meth) acrylic esters such as acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate;
Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its monoalkyl ester;
Contains amino groups such as N-methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl vinyl ether, N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide monomer;
Pyridine monomers such as vinylpyridine;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
Vinyl ester monomers such as vinyl acetate and vinyl propionate;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Aromatic monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene;
Amide group-containing monomers such as acrylamide, methacrylamide, maleic acid amide, N-methylol (meth) acrylamide and diacetone acrylamide;
Epoxy group-containing monomers such as glycidyl (meth) acrylate, diglycidyl (meth) acrylate, and allyl glycidyl ether;
Carbonyl group-containing monomers such as acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone;
Alkoxysilyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane Containing monomers;
Vinylidene halide monomers such as vinylidene chloride and vinylidene fluoride;
Other examples include ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride, vinyl ether, vinyl ketone, vinyl amide, and chloroprene. These can be used alone or in combination of two or more. Among these, when an alkoxysilyl group-containing monomer is included as the polymerizable monomer, the physical properties of the coating film can be improved by interaction with the component (B).

  Although the minimum film-forming temperature of (A) component can be set suitably, it is 80 degrees C or less normally, Preferably it is 50 degrees C or less, More preferably, it is 30 degrees C or less. When the minimum film-forming temperature of the component (A) is within such a range, it is possible to exhibit the stain resistance while ensuring the coating film properties such as crack resistance.

  Although the manufacturing method of (A) component is not specifically limited, For example, emulsion polymerization, soap free emulsion polymerization, dispersion polymerization, feed emulsion polymerization, feed dispersion polymerization, seed emulsion polymerization, seed dispersion polymerization, etc. are employable. (A) The average particle diameter of a component is about 0.05-0.3 micrometer normally. The solid content ratio in the total amount of component (A) is not particularly limited, but is usually about 10 to 60% by weight.

  In the present invention, a crosslinking reaction type synthetic resin emulsion, a core-shell type synthetic resin emulsion, and the like can also be used as the component (A). Two or more synthetic resin emulsions can be used in combination. Among these, as the crosslinking reaction in the crosslinking reaction type synthetic resin emulsion, for example, carboxyl group and metal ion, carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group , A combination of carbonyl group and hydrazide group, epoxy group and hydrazide group, epoxy group and amino group, hydrolyzable silyl groups, and the like. Among these, preferred crosslinking reactions include a carboxyl group and an epoxy group, a carboxyl group and an oxazoline group, a carbonyl group and a hydrazide group, an epoxy group and a hydrazide group, and hydrolyzable silyl groups.

Moreover, it is preferable that (A) component can react with the (B) component mentioned later. The component (A) is, for example, an emulsion having a functional group such as a hydroxyl group or a hydrolyzable silyl group (preferably a hydrolyzable silyl group) that can react with the silanol group present in the component (B). Is preferred.
By chemically bonding the component (A) and the component (B), it becomes possible to exhibit the stain resistance while securing the coating film properties such as crack resistance.

Moreover, in this invention, (A) component containing 2 or more types of resin from which a glass transition temperature differs can also be used. A resin component with a low glass transition temperature works to improve adhesion to the base material and followability to an elastic base, and a resin component with a high glass transition temperature prevents coating strength and contamination. Therefore, by using resin components having different glass transition temperatures, it is possible to achieve both of the above performances.
In the present invention, a blend type using two or more types of synthetic resin emulsions having different glass transition temperatures may be used, or a core-shell type synthetic resin emulsion type comprising two or more types of synthetic resins having different glass transition temperatures may be used. These composite types may be used.
In the present invention, in particular, a synthetic resin emulsion (hereinafter referred to as “component (a-1)”) having a glass transition temperature of 0 ° C. or higher and 100 ° C. or lower (preferably 5 ° C. or higher and 90 ° C. or lower, more preferably 10 ° C. or higher and 80 ° C. or lower). And a synthetic resin emulsion (hereinafter referred to as “component (a-2)”) whose glass transition temperature is 5 ° C. or higher (preferably 10 ° C. or higher, more preferably 20 ° C. or higher). It is also preferable to use “. More specifically, the glass transition temperature of component (a-1) is 15 ° C. or higher and 100 ° C. or lower (preferably 20 ° C. or higher and 80 ° C. or lower), and the glass transition temperature of component (a-2) is −50 ° C. or higher and 15 ° C. or higher. It is preferably less than ℃ (preferably -40 ° C or more and 10 ° C or less).
Moreover, the mixing ratio of the (a-1) component and the (a-2) component is not particularly limited, but the (a-1) component: (a-2) component is 10:90 to 90: in terms of the solid content weight ratio. 10 (further, 20:80 to 80:20) is preferable. In addition to the component (a-1) and the component (a-2), other binders may be included as the component (A).
In addition, the glass transition temperature of this invention is a value calculated from the formula of Fox (FOX).

  The component (B) in the present invention is water-dispersible silica having a particle size of 1 to 200 nm. The particles constituting the component (B) are compounds having a high hardness because of silica as a main component, and having silanol groups on the particle surfaces. Such a component (B) greatly contributes to the effect of improving the stain resistance.

  The particle size of the component (B) is usually 1 to 200 nm, preferably 5 to 100 nm, more preferably 10 to 50 nm, and still more preferably 20 to 40 nm as the primary particle size. If the particle diameter is too large, the transparency of the coating film may be impaired in the clear type coating material, and the gloss of the glossy type coating material may be insufficient. is there. When the particle size is too small, there is a possibility that a sufficient effect cannot be obtained in the stain resistance. (B) The average primary particle diameter of a component is 5-100 nm, More preferably, it is 10-50 nm, More preferably, it is 20-40 nm. In the present invention, two or more kinds of water-dispersible silica having different average primary particle sizes can be used. The particle diameter of the component (B) is a value measured by a light scattering method.

  The pH of the component (B) is usually 5 or more and 12 or less, preferably 6 or more and 10 or less, more preferably 6 or more and 9 or less. The component (B) adjusted to such a pH can exhibit hydrophilicity due to abundant silanol groups on the particle surface, and greatly contributes to an improvement in stain resistance.

  Such a component (B) can be produced using, for example, sodium silicate, lithium silicate, potassium silicate, or a silicate compound as a raw material. Among these, as silicate compounds, for example, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetra-t-butoxy Examples thereof include silane, tetraphenoxysilane, and their condensates. In addition, alkoxysilane compounds other than the above silicate compounds, alcohols, glycols, glycol ethers, fluorine alcohols, silane coupling agents, polyoxyalkylene group-containing compounds, and the like can also be used. A catalyst etc. can also be used at the time of manufacture. Further, after the production process or after production, the metal contained in the catalyst or the like can be removed by ion exchange treatment or the like.

As the component (B), those having an electric conductivity of 3 mS / cm or less (preferably 2 mS / cm or less, more preferably 1 mS / cm or less) are suitable. In addition, the electrical conductivity said here is a value measured using "Model SC82 personal SC meter SC8221-J" (made by Yokogawa Electric Corporation) (measurement temperature 25 degreeC).
By using such a component (B), the water resistance and stain resistance of the formed coating film can be further enhanced.

  As the medium for the component (B), water and / or a water-soluble solvent can be used. Examples of the water-soluble solvent include alcohols, glycols, glycol ethers and the like. In the present invention, it is particularly desirable that the medium is composed only of water. By using such a component (B), it is possible to reduce the volatile organic solvent (low VOC) of the coating material. Moreover, the aggregate generation | occurrence | production at the time of mixing with (A) component can also be suppressed.

  The solid content of the component (B) is usually 5 to 60% by weight, preferably 10 to 55% by weight, and more preferably 15 to 50% by weight. If the solid content of the component (B) is within such a range, the stability of the component (B) itself, and the stability when the component (A) and the component (B) are mixed can be ensured. . If the solid content is too large, the component (B) itself may become unstable, or the coating material may become unstable when mixed with the component (A). If the solid content is too small, a large amount of component (B) must be mixed in order to obtain a sufficient anti-staining effect, which is not practical.

The mixing ratio of the component (B) is such that the solid content of the component (B) is 0.1 parts by weight or more and 500 parts by weight or less (preferably 0.3 parts by weight or more and 300 parts by weight or less) with respect to 100 parts by weight of the solid content of the component (A). Parts by weight or less, more preferably 0.5 parts by weight or more and 100 parts by weight or less, and still more preferably 1.0 parts by weight or more and 30 parts by weight or less. With such a mixing ratio, the effects of the present invention can be sufficiently exerted.
When the amount of the component (B) is too small, sufficient contamination resistance cannot be obtained. Moreover, when there are too many (B) components, it will become easy to produce a crack in a coating film. In addition, in a glossy type coating material, it is difficult to obtain a highly glossy coating film.

The component (C) in the present invention is a fluorine-containing compound having a polyfluoroalkyl group and a nonionic or amphoteric hydrophilic group. In the present invention, excellent contamination resistance can be exhibited by using the component (C) and the component (B) together. Furthermore, it is possible to suppress the adhesion of contaminants in the initial stage of film formation, and to improve the drying property and flexibility of the coating film.
Although the specific mechanism of action in which such an effect is exhibited is not clear, the component (B) and the component (C) are orientated on the surface of the coating film during the formation of the coating film, and the hardness of the coating film surface is due to the synergistic action of both. The hydrophilicity and the like are effectively increased, and at the same time, it is presumed that the flexibility and the film-forming property are improved by the action of the component (A) in the coating film.

  Such a polyfluoroalkyl group of component (C) is a group in which all or part of the hydrogen atoms bonded to carbon atoms in the alkyl group having a linear, branched or cyclic skeleton are substituted with fluorine atoms. is there. This polyfluoroalkyl group may have an etheric oxygen atom, a thioetheric sulfur atom or the like between carbon atoms in the polyfluoroalkyl group. The polyfluoroalkyl group may contain a halogen atom other than the fluorine atom. The number of carbon atoms in the polyfluoroalkyl group is usually 1 or more, preferably 3 or more, more preferably 6 or more. The upper limit of the number of carbon atoms in the polyfluoroalkyl group is usually 40 or less, preferably 20 or less. As the polyfluoroalkyl group of component (C), a perfluoroalkyl group is particularly suitable.

Examples of nonionic hydrophilic groups include polyalkylene oxide groups and amine oxide groups. Among these, as a polyalkylene oxide group, a polyethylene oxide group, a polypropylene oxide group, etc. are mentioned, for example, What mixed ethylene oxide group and a propylene oxide group can also be used. The repeating number of alkylene oxide is usually 2-100.
Examples of amphoteric hydrophilic groups include nitrogen-containing amphoteric hydrophilic groups such as quaternary ammonium halogen salts and betaines. Among these, examples of the halogen in the quaternary ammonium halogen salt include a chlorine atom, a bromine atom, and an iodine atom. Betaine has a quaternary ammonium and an anion of an acid, and examples of the acid include carboxylic acid. The hydrophilic group in component (C) is particularly preferably a nitrogen-containing amphoteric hydrophilic group having a betaine structure or a polyalkylene oxide group.

As (C) component in this invention, what has the said functional group together can be used. Such a component (C) is prepared by synthesizing a polyfluoroalkyl group-containing compound as an intermediate by, for example, an electrolytic fluorination method, a telomerization method, an oligomerization method, etc., and then adding a hydrophilic group to the intermediate. It can manufacture by introducing.
As the component (C), a 0.01% aqueous solution having a surface tension at 25 ° C. of 20 mN / m or less (more preferably 18 mN / m or less) is suitable.

The mixing ratio of the component (C) is 0.01 parts by weight or more and 10 parts by weight or less (preferably 0.05 parts by weight or more and 5 parts by weight or less) with respect to 100 parts by weight of the solid content of the component (A). More preferably, it is 0.1 to 3 parts by weight.
When the amount of the component (C) is less than the above mixing ratio, it is difficult to obtain sufficient physical properties in terms of contamination resistance. Moreover, when there are too many (C) components, there exists a possibility of affecting the external appearance of a coating film, water resistance, etc.
The mixing ratio of the component (B) and the component (C) is 100: 0.01 to 100: 100 (preferably 100: 0.05 to 100: 30, more preferably 100: 0.1 to 100) by weight ratio. : 10). When there are too few (C) components with respect to (B) component, it will become difficult to obtain sufficient physical property in terms of stain resistance. Moreover, when there are too many (C) components with respect to (B) component, there exists a possibility of affecting the external appearance of a coating film, water resistance, stain | pollution resistance, etc.

In the present invention, it is preferable to include a film-forming aid (hereinafter also referred to as “component (D)”). Examples of the component (D) include cellosolve, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl ether, triplicate Propylene glycol methyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, ethers such as tripropylene glycol isobutyl ether compound,
Ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol mono Ethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monoisobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3- Esters such as pentanediol diisobutyrate
Etc.

  The mixing ratio of the component (D) is such that the component (D) is 0.01 part by weight or more and 30 parts by weight or less (preferably 0.05 part by weight or more and 25 parts by weight or less) with respect to 100 parts by weight of the solid content of the component (A). More preferably, it is 0.1 to 20 parts by weight.

Furthermore, in the present invention, an alkylene oxide chain-containing compound (hereinafter also referred to as “component (E)”) is preferably included. By including the alkylene oxide chain-containing compound, it is possible to obtain a coating film having excellent storage stability and excellent gloss.
Examples of the component (E) include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene-polypropylene glycol, polyethylene-polybutylene glycol, polyethylene-polypropylene-polybutylene glycol, and other polyalkylene glycols, and methoxypolyethylene. Glycol, methoxy polypropylene glycol, ethoxy polyethylene glycol, ethoxy polypropylene glycol, propoxy polyethylene glycol, propoxy polypropylene glycol, butoxy polyethylene glycol, butoxy polypropylene glycol, hexyl alkoxy polyethylene glycol, cyclohexyl alkoxy polyethylene glycol, 2-ethylhexyl alkoxy polyethylene glycol , Cetyl alkoxy polyethylene glycol, stearyl alkoxy polyethylene glycol, methyl phenoxy polyethylene glycol, nonyl phenoxy polyethylene glycol, alkoxy polyalkylene glycols such as decyl phenoxy polyethylene glycol, naphthoxy polyethylene glycol, etc., and amino groups and epoxies of these compounds And functional group-modified products such as alkoxysilyl groups.
Although the weight average molecular weight of (E) component is not specifically limited, It is preferable that they are 200 or more and 5000 or less, Furthermore, 300 or more and 3000 or less, Furthermore, 500 or more and 2000 or less. If it is smaller than 200, it is difficult to obtain an improvement effect by addition.

  The mixing ratio of the component (E) is 0.01 parts by weight or more and 50 parts by weight or less (preferably 0.05 parts by weight or more and 40 parts by weight or less) with respect to 100 parts by weight of the solid content of the component (A). More preferably, it is 0.1 to 30 parts by weight.

Furthermore, in the present invention, a silane coupling agent (hereinafter also referred to as “component (F)”) is preferably included. By including a silane coupling agent, it is possible to obtain a coating film having excellent storage stability and excellent contamination and adhesion.
As the component (F), for example, as the component (F), for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane Γ-aminopropylethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylsilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyltrimethoxysilane, isocyanate functional silane, γ-methacryloxypropyltri Methoxysilane, γ-methacryloxy Examples include propyltriethoxysilane, γ-methacryloxyproopylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, and the like. These can be used alone or in combination of two or more.
Particularly in the present invention, epoxy group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxy Vinyl group-containing silane coupling agents such as silane are preferred.
The mixing ratio of the component (F) is such that the component (F) is 0.5 parts by weight or more and 50 parts by weight or less (preferably 1.5 parts by weight or more and 25 parts by weight or less) with respect to 100 parts by weight of the solid content of the component (A). More preferably, it is 2.5 to 15 parts by weight.

In addition to the above components, the coating material of the present invention includes, as other components, water, a dispersion medium such as a solvent, colored pigments, extender pigments, aggregates, plasticizers, antifreezing agents, antiseptics, antifungal agents, antibacterial agents Agent, antifoaming agent, pigment dispersant, thickener, leveling agent, wetting agent, pH adjusting agent, fibers, matting agent, UV absorber, antioxidant, light stabilizer, adsorbent, catalyst, crosslinking agent, etc. Can be mixed. By using such components in appropriate combinations, various forms of coating materials can be designed.
In addition to the above components (A) to (C) (if necessary, the (D) component, the (E) component, etc.), the coating material of the present invention can be mixed by mixing these other components uniformly as required. Can be manufactured. Processing such as pre-combination of the component (B) and the component (C) is not necessary.

In addition, the present invention provides a clear type coating material, a glossy type coating material including a color pigment, an extender pigment, etc., a matte type coating material, a natural stone coating material, a thin finish coating material, and a thick finish coating material. It can be applied to a covering material such as a material.
Further, the type and mixing amount of the dispersion medium such as water and solvent can be appropriately designed according to the intended use, but in the present invention, it is particularly preferable to use water, and the mixing ratio of water is based on the total amount of the coating material. It may be about 5 wt% or more and 95 wt% or less (preferably 10 wt% or more and 90 wt% or less).

Examples of the color pigment include titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, ferric oxide (valve), yellow iron oxide, titanium yellow, Inorganic pigments such as ocher, ultramarine, chrome green, cobalt green, azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, quinophthalone These organic pigments and the like can be used, and one or more of these can be used.
The mixing ratio of the color pigment is preferably 1 part by weight or more and 300 parts by weight or less (preferably 3 parts by weight or more and 200 parts by weight or less) with respect to 100 parts by weight of the solid content of the component (A).
Examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, porcelain clay, china clay, diatomaceous earth, hydrous finely divided silicic acid, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate. , Silica powder, aluminum hydroxide, and the like, and one or more of these can be used. The particle size of the extender pigment is usually less than 50 μm (preferably 0.5 μm or more and 30 μm or less).
The mixing ratio of the extender pigment is preferably 1 to 300 parts by weight (preferably 3 to 200 parts by weight) of the extender pigment with respect to 100 parts by weight of the solid content of the component (A).
As the aggregate, for example, at least one selected from natural aggregates such as natural stones and pulverized natural stones and artificial aggregates such as colored aggregates can be suitably used. Specifically, for example, marble, granite, serpentine, granite, fluorite, cryolite, feldspar, limestone, quartzite, quartz sand, crushed stone, mica, siliceous shale, and pulverized products thereof, ceramic pulverized products, ceramic pulverized products Products, crushed glass, glass beads, crushed resin, resin beads, rubber particles, metal particles, and the like. In addition, pulverized products such as shells, shells, wood, charcoal, activated carbon and the like can be used. Furthermore, those whose surfaces are colored and coated by performing surface treatment with pigments, dyes, glazes, and the like can also be used. The particle diameter of the aggregate is usually 0.05 mm or more and 5 mm or less.
The mixing ratio of the aggregate is preferably 1 part by weight or more and 1000 parts by weight or less (preferably 10 parts by weight or more and 800 parts by weight or less) with respect to 100 parts by weight of the solid content of the component (A).
In particular, when an aggregate or extender pigment is included, it is possible to improve the swelling resistance and the like.

The coating material of the present invention can be applied to various base materials such as concrete, mortar, metal, plastic, slate plate, extruded plate, siding board, ALC plate, plywood, glass, and porcelain tile. In particular, it is suitable for the protection and beauty of buildings such as buildings and civil engineering structures.
At this time, the coating material of the present invention is applied to the final finished surface, and can be directly applied to the base material, or surface treatment (sealer treatment, filler treatment, surfacer using any surface treatment material). It is also possible to paint after applying treatment, putty treatment, etc.).
The coating method is not particularly limited, and it may be applied to the substrate by a method such as spray coating, roller coating, trowel coating, brush coating, etc., and may be applied only once or multiple times. When coating a plurality of times, the same or different types of coating materials may be applied a plurality of times.
For example, when the substrate or the surface treatment material layer applied to the substrate surface has elasticity including an organic material, etc., after coating a coating material having a high elongation rate, the coating material having a low elongation rate is applied in order. In addition to imparting followability to the substrate, it is possible to exhibit contamination resistance.
Specifically, a first coating material is applied to a base material having an elongation rate of 50% or more (more than 80% or more) by applying a first coating material having an elongation rate of 30% or more and 90% or less of the base material. Forming a second coating material layer by coating a second coating material that is 30% or more and 90% or less of the elongation of the first coating material layer on the first coating material layer; Thus, it is possible to impart followability to the substrate and to exhibit stain resistance.
Moreover, when the surface treatment material layer applied to the substrate or the substrate surface has elasticity including an organic material or the like, by sequentially coating the coating materials having different mixing ratios of the component (A) and the component (B), Adhesiveness and followability can be imparted to the organic substrate, and contamination resistance can be exhibited.
Specifically, a first covering material layer is formed by coating a first covering material having a content of the component (B) (solid content) of 0% by weight or more and 1% by weight or less on the base material, On the first coating material layer, the content of the component (B) is larger than that of the first coating material, and the content of the component (B) (solid content) is 0.5 wt% or more and 20 wt% or less. By coating 2 coating materials and forming a 2nd coating material layer, while providing adhesiveness and followable | trackability with respect to a base material, stain resistance can be exhibited.

The coating amount when coating the coating material of the present invention may be appropriately selected depending on the form and application of the coating material. For example, in the case of a clear type, a glossy type, a matte type, etc., 0.1 to 0.5 kg / In the case of about m ² , natural stone-like coating material, thin finish coating material, thick finish coating material, etc., it is about 0.5 to 10 kg / m ² . The viscosity of the coating material can be appropriately adjusted by diluting with water or the like during coating. The dilution ratio is usually about 0 to 20% by weight. Drying after coating is usually performed at room temperature, but can be appropriately heated as necessary.

Experimental examples are shown below to clarify the features of the present invention. In the experimental examples, each coating material was manufactured using the raw materials shown below.
Moreover, among the experimental examples in Test Examples 1 to 3 shown below, Experimental Examples 13 to 19, 23 to 25, 32, 47 to 49, 65, 66, and 68 using a silane coupling agent as an essential component. Are used as examples, and other experimental examples and test examples 4 and 5 are used as reference examples.

Emulsion A: acrylic resin emulsion (methyl methacrylate-cyclohexyl methacrylate- (2-ethylhexyl acrylate) -methacrylic acid copolymer, pH 8.7, solid content 50% by weight, glass transition temperature 15 ° C., minimum film-forming temperature 19 ° C.)
Emulsion B: Acrylic resin emulsion (methyl methacrylate- (n-butyl acrylate)-(2-ethylhexyl acrylate)-(γ-methacryloyloxypropyltrimethoxysilane) -methacrylic acid copolymer, pH 8.9, solid content 50 weight %, Glass transition temperature 23 ° C, minimum film-forming temperature 25 ° C)
Emulsion C: acrylic resin emulsion (methyl methacrylate-cyclohexyl methacrylate- (2-ethylhexyl acrylate)-(n-butyl methacrylate)-(n-butyl acrylate) -methacrylic acid copolymer, pH 8.9, solid content 50% by weight Glass transition temperature -20 ° C, minimum film-forming temperature 1 ° C)
Emulsion D: Acrylic resin emulsion (methyl methacrylate-styrene-cyclohexyl methacrylate- (2-ethylhexyl acrylate) -methacrylic acid copolymer, pH 8.7, solid content 50% by weight, glass transition temperature-2 ° C., minimum film-forming temperature 0 ℃)
Emulsion E: Acrylic resin emulsion (methyl methacrylate-cyclohexyl methacrylate- (2-ethylhexyl acrylate)-(n-butyl methacrylate)-(n-butyl acrylate) -methacrylic acid copolymer, pH 8.8, solid content 50% by weight) Glass transition temperature 11 ° C, minimum film-forming temperature 12 ° C)
Coloring pigment: Titanium oxide dispersion (solid content 70% by weight)
-Film-forming aid: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate-Thickener: Polyurethane thickener-Defoamer: Silicone defoamer-Water dispersible silica A : Silica sol (pH 7.6, solid content 20% by weight, average primary particle size 27 nm, electric conductivity 0.6 mS / cm
Water-dispersible silica B: silica sol (pH 9.3, solid content 20% by weight, average primary particle size 20 nm, electrical conductivity 1.8 mS / cm)
Water-dispersible silica C: silica sol (pH 9.5, solid content 40% by weight, average primary particle diameter 20 nm, electric conductivity 1.7 mS / cm)
Fluorine-containing compound A: perfluoroalkylamine oxide (surface tension of 16.0% aqueous solution 16.0 mN / m (25 ° C.))
Fluorine-containing compound B: perfluoroalkyl ethylene oxide adduct (0.01% aqueous solution surface tension 17.5 mN / m (25 ° C.))
Fluorine-containing compound C: perfluoroalkylbetaine (0.01% aqueous solution surface tension of 16.0 mN / m (25 ° C.))
Fluorine-containing compound D: perfluoroalkyltrimethylammonium salt (surface tension of 17.0% aqueous solution 17.0 mN / m (25 ° C.))
Fluorine-containing compound E: trifluoroethanol / alkylene oxide chain-containing compound A: methoxypolyethylene glycol (weight average molecular weight: 225)
Alkylene oxide chain-containing compound B: methoxypolyethylene glycol (weight average molecular weight: 400)
Alkylene oxide chain-containing compound C: methoxypolyethylene glycol (weight average molecular weight: 700)
Alkylene oxide chain-containing compound D: methoxypolyethylene glycol (weight average molecular weight: 1000)
-Aggregate: Colored aggregate mixture with a particle size of 120-300 µm-Body pigment: Body pigment mixture with a particle size of 3-15 µm-Silane coupling agent: γ-glycidoxypropyltrimethoxysilane

[1] Test example 1
<Manufacture of coating material>
According to the formulations shown in Tables 1, 2, 3, and 4, the raw materials were uniformly mixed by a conventional method to produce a coating material. The blending amounts in Tables 1, 2, 3, and 4 are expressed in parts by weight.

<Test method>
(1) Storage stability test After manufacturing the coating material, the viscosity was measured immediately. Next, the covering material was put in a container, sealed, stored for 15 days in an atmosphere at 50 ° C., and then the viscosity was measured again.

The viscosity change by the above operation was investigated. The evaluation criteria are as follows. The viscosity was measured using a BH viscometer in a standard state (temperature 23 ° C., relative humidity 50%). The results are shown in Tables 1, 2, 3, and 4.
5: Change in viscosity less than 10% 4: Change in viscosity from 10% to less than 20% 3: Change in viscosity from 20% to less than 30% 2: Change in viscosity from 30% to less than 50% 1: Change in viscosity from 50% or more

(2) Specular Gloss Measurement A coating material was applied to a transparent glass plate of 150 × 120 × 3 mm using a film applicator with a gap of 150 μm, and the glass plate was placed horizontally and dried and cured in a standard state for 48 hours. Thereafter, the specular gloss was measured according to JIS K 5600-4-7. The measurement angle was 60 degrees. In addition, the coating | covering material measured about what was stored in the atmosphere of temperature 50 degreeC and relative humidity 30% for 24 hours and 1 month after manufacture, respectively. The results are shown in Tables 1, 2, 3, and 4.

(3) Contact angle measurement A slate plate of 150 mm x 75 mm x 3 mm was spray-coated with an epoxy-based primer so that the dry film thickness was 30 µm, dried in standard conditions for 8 hours, and then the coating material was dried. A test specimen was prepared by spray-coating to a thickness of 40 μm and drying in a standard state for 7 days.
The contact angle of the coating surface of the test specimen obtained by the above method was measured. The contact angle was measured with a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Tables 1, 2, 3, and 4.

(4) Rainproof stain resistance test A 300 × 150 × 3 mm aluminum plate bent at a position one third from the upper end so that the inner angle was 135 degrees was used as a test substrate. On the convex surface of this test substrate, an epoxy-based primer was spray-coated so that the dry film thickness was 30 μm, and dried in a standard state for 8 hours. Next, the coating material was spray-coated so that the dry film thickness was 40 μm, and was dried and cured in a standard state for 7 days.
The specimen obtained by the above method was placed facing south on Ibaraki City, Osaka, with the wide area vertical, and exposed outdoors for 3 months. At this time, the rain streak stain state on the vertical surface was visually observed and evaluated in 10 stages (excellent: 10> 1: poor) depending on the degree of the stain. The results are shown in Tables 1, 2, 3, and 4.

(5) Thermal Cooling Repeat Test An elastic coating material (JIS A 6909 waterproof multi-layer coating material E) is spray-coated on a 300 × 150 × 6 mm slate plate so that the thickness of the dry coating film is 1 mm. After drying for a period of time, the coating material was spray-coated on the coating film so that the coating amount was 0.2 kg / m ² and dried for one week in a standard state to obtain a test specimen.
The prepared specimen was subjected to a total of 30 cycles of water-cooling (23 ° C.) 18 hours → −20 ° C. 3 hours → 80 ° C. 3 hours for one cycle, and then the surface condition was visually evaluated. . The evaluation was performed in a five-step evaluation with “5” indicating that no crack was generated and “1” indicating that a crack was clearly generated. The results are shown in Tables 1, 2, 3, and 4.

(6) Water resistance test Spray coating of an acrylic primer to a 150 × 75 × 3 mm slate plate so that the dry film thickness is 30 μm, and after drying for 8 hours in a standard state, the coating material is then subjected to dry film thickness Was spray-coated so as to be 40 μm and dried in a standard state for 7 days to prepare a test specimen.
The prepared specimen was immersed in water at 23 ° C. for 96 hours, and the state of the specimen surface was evaluated. Evaluation was performed in a five-step evaluation, with “5” indicating no abnormality and “1” indicating abnormality such as swelling. The results are shown in Tables 1, 2, 3, and 4.

[2] Test example 2
<Manufacture of coating material>
According to the formulations shown in Tables 5 and 6, the raw materials were uniformly mixed by a conventional method to produce a coating material. The blending amounts in Tables 5 and 6 are expressed in parts by weight.

<Test method>
(1) Storage stability test After manufacturing the coating material, the viscosity was measured immediately. Next, the covering material was put in a container, sealed, stored for 15 days in an atmosphere at 50 ° C., and then the viscosity was measured again. .

The viscosity change by the above operation was investigated. The evaluation criteria are as follows. The viscosity was measured using a BH viscometer in a standard state (temperature 23 ° C., relative humidity 50%). The results are shown in Tables 5 and 6. 5: Change in viscosity less than 10% 4: Change in viscosity from 10% to less than 20% 3: Change in viscosity from 20% to less than 30% 2: Change in viscosity from 30% to less than 50% 1: Change in viscosity from 50 %that's all

(2) Contact angle measurement An epoxy base coat material was applied to a 150 mm × 75 mm × 3 mm slate plate so that the dry film thickness was 30 μm, dried in a standard state for 8 hours, and then the coating material was dried. Was made to be 40 μm and dried in a standard state for 7 days to prepare a test specimen.
The contact angle of the coating surface of the test specimen obtained by the above method was measured. The contact angle was measured with a CA-A type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Tables 5 and 6.

(3) Rain-resistant stain resistance test A 300 × 150 × 3 mm aluminum plate bent at a position one third from the upper end so that the inner angle was 135 degrees was used as a test base material. On the convex surface of this test substrate, an epoxy-based primer was spray-coated so that the dry film thickness was 30 μm, and dried in a standard state for 8 hours. Next, the coating material was spray-coated so that the dry film thickness was 40 μm, and was dried and cured in a standard state for 7 days.
The specimen obtained by the above method was placed facing south on Ibaraki City, Osaka, with the wide area vertical, and exposed outdoors for 3 months. At this time, the rain streak stain state on the vertical surface was visually observed and evaluated in 10 stages (excellent: 10> 1: poor) depending on the degree of the stain. The results are shown in Tables 5 and 6.

(4) Warm / cool repeated test An elastic coating material (JIS A 6909 waterproof multi-layer coating material E) is spray-coated on a 300 × 150 × 6 mm slate plate so that the dry coating thickness becomes 1 mm. After drying for a period of time, the coating material was spray-coated on the coating film so that the coating amount was 0.05 kg / m ² and dried for one week in a standard state to obtain a test specimen.
The prepared specimen was subjected to a total of 30 cycles of water-cooling (23 ° C.) 18 hours → −20 ° C. 3 hours → 80 ° C. 3 hours for one cycle, and then the surface condition was visually evaluated. . The evaluation was performed in a five-step evaluation with “5” indicating that no crack was generated and “1” indicating that a crack was clearly generated. The results are shown in Tables 5 and 6.

(5) Water resistance test Spray coating of an acrylic primer to a 150 × 75 × 3 mm slate plate so that the dry film thickness is 30 μm, and after drying for 8 hours in a standard state, the coating material is then subjected to dry film thickness Was spray-coated so as to be 40 μm and dried in a standard state for 7 days to prepare a test specimen.
The prepared specimen was immersed in water at 23 ° C. for 96 hours, and the state of the specimen surface was evaluated. Evaluation was performed in a five-step evaluation, with “5” indicating no abnormality and “1” indicating abnormality such as swelling. The results are shown in Tables 5 and 6.

[3] Test example 3
<Manufacture of coating material>
According to the formulation shown in Tables 7 and 8, each raw material was uniformly mixed by a conventional method to produce a coating material. The blending amounts in Tables 7 and 8 are expressed in parts by weight.

<Test method>
(1) Rain-strip stain resistance A 300 × 150 × 3 mm aluminum plate bent at a position one third from the upper end so that the inner angle is 135 degrees was used as a test substrate. On the convex surface of this test substrate, an epoxy-based primer was spray-coated so that the dry film thickness was 30 μm, and dried in a standard state for 8 hours. Next, the coating material was spray-coated so that the dry film thickness was about 2 mm, and was dried and cured in a standard state for 7 days.
The specimen obtained by the above method was placed facing south on Ibaraki City, Osaka, with the wide area vertical, and exposed outdoors for 3 months. At this time, the rain streak stain state on the vertical surface was visually observed and evaluated in 10 stages (excellent: 10> 1: poor) depending on the degree of the stain. The results are shown in Tables 7 and 8.

  For Experimental Example 69, the coating material obtained in Experimental Example 69 was spray-coated on the specimen of Experimental Example 59 obtained by the above method so that the dry film thickness was about 0.1 mm. The test piece was dried and cured for 7 days in the standard state, and the above-mentioned rain-strip stain resistance test was conducted. The test results are shown in Table 4. In Experimental Example 69, good results could be obtained.

[4] Test example 4
<Manufacture of coating material>
Emulsion A 200 parts by weight, film-forming aid 18 parts by weight, thickener 3 parts by weight, antifoaming agent 0.3 part by weight, water-dispersible silica A 13 parts by weight, and fluorine-containing compound C 2 parts by weight are uniformly mixed by a conventional method. Thus, a covering material 4-1 was produced.
Moreover, what mixed emulsion A200 weight part, film-forming aid 18 weight part, thickener 3 weight part, antifoamer 0.3 weight part, and water dispersible silica A13 weight part was used as coating | covering material 4-2. .
A mixture of 200 parts by weight of emulsion A, 18 parts by weight of a film-forming aid, 3 parts by weight of a thickener, 0.3 parts by weight of an antifoaming agent and 2 parts by weight of a fluorine-containing compound C was used as a coating material 4-3.

<Test methods and test results>
The coating materials 4-1 to 4-3 were each applied to an aluminum plate with a thickness of 1 mm, and then left in an environment of 5 ° C. About this test body, the weight reduction rate of the coating film after 72 hours and 168 hours was measured.
As a result, the coating material 4-1 had a weight loss rate of 20% by weight and 42% by weight after 72 hours and 168 hours, respectively. In contrast, the coating material 4-2 was 11% by weight (after 72 hours), 27% by weight (after 168 hours), and the coating material 4-3 was 11% by weight (after 72 hours), 25% by weight (after 168 hours). )Met. The covering material 4-1 resulted in better drying than the covering materials 4-2 and 4-3.

[5] Test example 5
<Manufacture of coating material>
Emulsion A 200 parts by weight, film-forming aid 18 parts by weight, thickener 5 parts by weight, antifoaming agent 1 part by weight, and aggregate 450 parts by weight were uniformly mixed by a conventional method to produce a coating material 5-1. .
In addition, 200 parts by weight of emulsion A, 18 parts by weight of film-forming aid, 5 parts by weight of thickener, 1 part by weight of defoaming agent, 10 parts by weight of water-dispersible silica A, 2 parts by weight of fluorine-containing compound C, 450 parts by weight of aggregate By uniformly mixing by a conventional method, a coating material 5-2 was produced.
Emulsion A 200 parts by weight, film-forming aid 18 parts by weight, thickener 5 parts by weight, antifoaming agent 1 part by weight, fluorine-containing compound C 2 parts by weight, and aggregate 450 parts by weight are uniformly mixed and coated. Material 5-3 was produced.
150 parts by weight of emulsion A, 50 parts by weight of emulsion B, 18 parts by weight of film-forming aid, 5 parts by weight of thickener, 1 part by weight of defoaming agent, 10 parts by weight of water-dispersible silica A, 2 parts by weight of fluorine-containing compound C, 450 of aggregate Part by weight was uniformly mixed by a conventional method to produce a coating material 5-4.

<Test method>
(Followability test A)
Using a modified silicone sealant, two siding boards (300 mm × 170 mm × 12 mm) were joined together with a gap of 10 mm to prepare a substrate.
On the base material, the coating material 5-1 was spray-coated so that the coating amount was 1.0 kg / m ² and dried at a temperature of 23 ° C. and a humidity of 50%.
Next, 2 hours after the coating, the coating material 5-2 was spray-coated so that the coating amount was 2.0 kg / m ² and dried at a temperature of 23 ° C. and a humidity of 50% for 24 hours. Obtained.
Evaluation was performed according to the surface condition when the produced specimen was displaced by 30% in the horizontal direction with a tensile tester. As a result, no abnormality was observed in the specimen.
(Followability test B)
The test was performed in the same manner as the follow-up test A, except that the coating material 5-1 was replaced with the coating material 5-3 and the coating material 5-2 was replaced with the coating material 5-4. As a result, no abnormality was observed in the specimen.
(Followability test C)
Using a modified silicone sealant, two siding boards (300 mm × 170 mm × 12 mm) were joined together with a gap of 10 mm to prepare a substrate.
On the base material, the coating material 5-2 was spray-coated so that the coating amount was 2.0 kg / m ² and dried at a temperature of 23 ° C. and a humidity of 50% to obtain a test specimen.
Evaluation was performed according to the surface condition when the produced specimen was displaced by 30% in the horizontal direction with a tensile tester. As a result, almost no abnormality was observed in the test specimen.

Claims (1)

Synthetic resin emulsion (A),
Water-dispersible silica (B) having a particle size of 1 to 200 nm,
A fluorine-containing compound (C) having a polyfluoroalkyl group and a nonionic or amphoteric hydrophilic group , and
Silane coupling agent (F)
Is a covering material containing as an essential component,
(A) The solid content of component (B) is 0.1 to 500 parts by weight, and (C) component is 0.01 to 10 parts by weight relative to 100 parts by weight of component (A),
A coating material, wherein the mixing ratio of the component (B) and the component (C) is 100: 0.01 to 100: 100 by weight.