JP6859884B2 - Multicolored paint composition - Google Patents

Description

The present invention relates to a versatile coating composition.

Conventionally, a method of applying a hydrophobic paint to a building has been used for the purpose of protecting the building from external stimuli such as rain, light, heat, and humidity. Further, recently, a paint composed of a various paint compositions capable of forming a coating film having a plurality of colors has attracted attention, and as such a paint, for example, a paint having a plurality of colors in an aqueous dispersion medium has been attracting attention. A multicolored pattern paint containing gel-like colored particles obtained by dispersing the above has been proposed.

Here, while the coating film formed from the above-mentioned hydrophobic paint is excellent in water resistance, weather resistance, etc., hydrophobic stains are likely to adhere, and the adhered stains will be washed away with water. However, it tends not to run down easily. For this reason, in buildings coated with hydrophobic paint, oily stains and dust derived from car exhaust gas, etc. may adhere to the wall surface, or they may move with the rain and be emphasized as rain streaks. A phenomenon is seen, and depending on the shape of the building, rain streaks are more likely to appear. Such a phenomenon has a problem that the value of the building is significantly reduced.

In recent years, the importance of maintenance-free paints has increased from the viewpoint of resource saving, and the demand for paints having particularly excellent stain resistance is increasing. Generally, in low-contamination paints, the surface of the coating film to be formed is often hydrophilic, but this is because if the surface is hydrophilic, hydrophobic stains having different affinities are less likely to adhere to the surface. Also, when it rains, the surface is washed away by raindrops, and dirt is easily removed.

However, when the coating film formed from the above-mentioned low-contamination paint is exposed to the outdoors and is subjected to stimuli such as sunlight, rainfall, and temperature change, the hydrophilicity of the coating film surface is generally lowered. In such a case, for example, as a method of making the surface of the coating film hydrophilic to impart stain resistance, a method of incorporating colloidal silica or an aqueous dispersion of polysiloxane in the coating material is known. However, in this method, when exposed to the outdoors for a long period of time, the colloidal silica and the polysiloxane aqueous dispersion are washed away by rainwater and the like, and the hydrophilic effect is lost. As described above, when the hydrophilicity of the coating film surface is lowered, there is a problem that the stain resistance is also lowered.

Here, Patent Document 1 proposes a resin composition containing an emulsion obtained by emulsion polymerization of a monomer using colloidal silica as an emulsion stabilizer, and a coating film using this resin composition is resistant. It is said that the contamination is good for a long period of time. However, in the coating film using the resin composition described in Patent Document 1, the durability of stain resistance is not always sufficient.

Further, Patent Document 2 describes an aqueous coating material containing an aqueous dispersion of a cationic resin or an aqueous solution or an aqueous dispersion of a nonionic resin, a condensate of tetraalkoxysilane or the like and a silane compound having an amino group, and an acid. Compositions have been proposed. In Patent Document 2, the coating film of this water-based coating composition is said to have excellent physical properties such as stain resistance. However, even a coating film using the water-based coating composition described in Patent Document 2 does not always have sufficient durability of stain resistance.

Further, in Patent Document 3, a monomer mixture containing an ethylenically unsaturated monomer having an amino group, an ethylenically unsaturated monomer having an alkoxysilyl group, and an ethylenically unsaturated monomer having a carboxyl group at a specific ratio is copolymerized. A water-based coating material containing the obtained polymer and an aqueous polymer having a carbodiimide group in a specific ratio has been proposed. In Patent Document 3, it is said that the coating film of this water-based paint has excellent stain resistance and water resistance, and the stain resistance lasts for a long period of time. However, there is still room for improvement in the durability of stain resistance of the coating film using the water-based paint described in Patent Document 3.

Japanese Unexamined Patent Publication No. 2008-133361 Japanese Unexamined Patent Publication No. 2008-274242 Japanese Unexamined Patent Publication No. 2012-0262413

The present invention has been made in view of the above problems, and an object of the present invention is to provide a versatile coating composition capable of obtaining a coating film capable of maintaining excellent stain resistance even when exposed to the outdoors for a long period of time. And.

In order to solve the above problems, the present invention includes the following aspects.

[1] A versatile coating composition containing at least one color of colored gel-like particles (A) in which an emulsion coating is encapsulated with a gelled film, an aqueous resin (B), and a resin emulsion (C). The aqueous resin (B) contains a structural unit derived from a monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, and a structural unit derived from a monomer (b2) having a cross-linking group and an ethylenically unsaturated bond. The monomer (b1) and the structural unit derived from the monomer (b3) having an ethylenically unsaturated bond other than the monomer (b2), and the monomer (b1) with respect to the total mass of all the structural units in the aqueous resin (B). The proportion of the structural unit derived from b1) is 40 to 95% by mass, the proportion of the structural unit derived from the monomer (b2) is 0.01 to 20% by mass, and the weight average molecular weight of the aqueous resin (B) is from 50,000 to 50,000. 150,000, the resin emulsion (C) has a functional group capable of reacting with the cross-linking group contained in the aqueous resin (B), and the mass of the aqueous resin (B) is the mass of the resin emulsion (C). A versatile coating composition characterized in that the value divided by mass is 0.03 or more and less than 0.11.
[2] The hydrophilic group is at least one selected from the group consisting of an amino group, an amide group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, a quaternary ammonium group, a sulfate group, a morpholino group and a poly (oxyalkylene) group. The various coating composition according to the above [1], which is a seed.
[3] The above-mentioned [1] or [2], wherein the cross-linking group is at least one selected from the group consisting of a glycidyl group, a carboxyl group, an acid anhydride group, an alkoxysilyl group, a keto group and an aldehyde group. Multicolored paint composition.
[4] The functional group capable of reacting with the cross-linking group is at least one selected from the group consisting of a glycidyl group, a carboxyl group, an acid anhydride group, an alkoxysilyl group, a hydrazide group, a carbodiimide group, an oxazoline group and an aziridine group. The various coating compositions according to any one of the above [1] to [3].

According to the versatile coating composition of the present invention, as described above, the emulsion coating material is encapsulated in a gelled film at least one color of colored gel-like particles (A), an aqueous resin (B), and a resin emulsion ( By containing C) in a composition optimized in a unique range, a coating film having a plurality of colors can be obtained, which can maintain excellent stain resistance even when exposed to the outdoors for a long period of time.

Hereinafter, the various coating compositions according to the present invention will be described in detail.
The "water-based resin" described in this embodiment means a resin that can be dispersed or dissolved in water.

The versatile coating composition of the present invention comprises at least one colored gel-like particle (A) (hereinafter, may be referred to as "component (A)") in which an emulsion coating is encapsulated in a gelled film and water-based. It includes a resin (B) (hereinafter, may be referred to as “component (B)”) and a resin emulsion (C) (hereinafter, may be referred to as “component (C)”).

In the multicolored coating composition of the present invention, each of the component (A), the component (B) and the component (C) has the composition described below, and the mass of the component (B) is (C). The value divided by the mass of the component is within the predetermined range.
That is, in the versatile coating composition of the present invention, the component (B) described above has a structural unit derived from the monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, and a bridging group and an ethylenically unsaturated bond. It consists of a structural unit derived from the monomer (b2) and a structural unit derived from the monomer (b3) having an ethylenically unsaturated bond other than the monomer (b1) and the monomer (b2), and is the total of all the structural units in the component (B). The ratio of the structural unit derived from the monomer (b1) to the mass is 40 to 95% by mass, the ratio of the structural unit derived from the monomer (b2) is 0.01 to 20% by mass, and the weight average of the component (B). The molecular weight is 50,000 to 150,000.
In addition, the versatile coating composition of the present invention has a functional group in which the component (C) described above can react with the cross-linking group contained in the component (B).
In the multicolored coating composition of the present invention, the value obtained by dividing the mass of the component (B) by the mass of the component (C) is 0.03 or more and less than 0.11.

The multicolored coating composition of the present invention usually further contains water, and typically, the component (A), the component (B), and the component (C) are dispersed or dissolved in water.

<Colored gel-like particles (A)>
In the present invention, the component (A) (colored gel-like particles (A)) is an emulsion paint encapsulated in a gelled film and is colored with at least one color.
The emulsion coating material of the component (A) contains a coloring pigment, a resin emulsion, and a hydrophilic colloid-forming substance.

(Coloring pigment)
Color pigments include, for example, inorganic pigments such as carbon black, titanium oxide, iron oxide, lead chromate, cadmium yellow, and cadmium red; brilliance of pearl pigments, mica pigments, mica-coated pearl pigments, aluminum powders, stainless steel powders, and the like. Pigments: Organic pigments such as phthalocyanine blue, phthalocyanine green, and quinacridone red can be mentioned. In addition, one type of these coloring pigments may be used alone, or two or more types may be used in combination.

The content of the coloring pigment in the emulsion paint of the component (A) is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 50 parts by mass, based on 100 parts by mass of the solid content of all the resin emulsions contained in the emulsion paint. Is 0.1 to 30 parts by mass.

(Resin emulsion)
Examples of the resin emulsion include polyvinyl acetate, acrylic resin, polystyrene, acrylonitrile, beopa (branched fatty acid vinyl ester), natural rubber, synthetic rubber emulsion, and copolymer emulsions of these resins. In addition, one type of these resin emulsions may be used alone, or two or more types may be used in combination.

Among the above, the acrylic resin emulsion is particularly preferable as the resin emulsion contained in the emulsion paint of the component (A).
The content of the resin emulsion in the emulsion coating material of the component (A) is not particularly limited, but is usually 20 to 70% by mass, preferably 30 to 50% by mass.

(Hydrophilic colloid-forming substance)
Examples of the hydrophilic colloid-forming substance include an aqueous solution containing a natural polymer such as a cellulose derivative, polyethylene oxide, polyvinyl alcohol, casein, starch, galactomannone, guar rubber, and locust bean rubber. Further, these hydrophilic colloid-forming substances may be used alone or in combination of two or more.

As the hydrophilic colloid-forming substance contained in the emulsion coating material of the component (A), an aqueous solution of guar rubber is particularly preferable among the above aqueous solutions.
The concentration of these aqueous solutions is not particularly limited, and may be, for example, 0.5 to 5.0% by mass.
The content of the hydrophilic colloid-forming substance in the emulsion coating material of the component (A) is also not particularly limited, but is usually 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the resin emulsion. It is preferably 0.1 to 3.0 parts by mass.

(Other ingredients)
The emulsion paint of the component (A) further contains, if necessary, an extender pigment such as hydrous magnesium silicate, a thickener, a dispersant, an antifoaming agent, a preservative and a leveling agent. May be.

(Encapsulation with gelled membrane)
In the present invention, the emulsion coating material of the component (A) is encapsulated with a gelled film. That is, the component (A) is obtained by encapsulating the emulsion paint with a gelled film.
In the gelled film, for example, a dark-colored emulsion coating material containing a hydrophilic colloid-forming substance and a dispersion medium containing a gelling agent are mixed, and the coating material is dispersed while stirring with a disperser such as a dissolver to disperse the above-mentioned dispersion medium. It is obtained by reacting the gelling agent inside with the above-mentioned hydrophilic colloid-forming substance.

As the above-mentioned dispersion medium, an aqueous dispersion medium containing a gelling agent is used. Examples of this gelling agent include an aqueous solution containing borate such as magnesium montmorillonite clay, sodium pentachlorophenol and ammonium diborate, tannic acid, titanium lactate and calcium chloride. Further, the dispersion medium may contain only one type of gelling agent or may contain two or more types of gelling agents. Among these, it is particularly preferable to use a borate such as ammonium bicarbonate as the dispersion medium. Further, if necessary, the dispersion medium may further contain an extender pigment such as hydrous magnesium silicate and a water-soluble polymer compound such as sodium carboxymethyl cellulose.

The dispersion medium as described above can be obtained, for example, by stirring and mixing an aqueous solution of a gelling agent and, if necessary, an aqueous solution of an extender pigment and an aqueous solution of a water-soluble polymer compound, and then adding water to dilute the dispersion medium. The content of the gelling agent in the dispersion medium is not particularly limited, and is, for example, 0.05 to 5.0% by mass in 100% by mass of the dispersion medium.

<Aqueous resin (B)>
In the present invention, the component (B) (aqueous resin (B)) is a structural unit derived from a monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, and a monomer having a cross-linking group and an ethylenically unsaturated bond (a monomer (B1)). It is a copolymer composed of a structural unit derived from b2) and a structural unit derived from the monomer (b1) and a monomer (b3) having an ethylenically unsaturated bond other than the monomer (b2).

The hydrophilic group in the monomer (b1) is selected from the group consisting of an amino group, an amide group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, a quaternary ammonium group, a sulfate group, a morpholino group and a poly (oxyalkylene) group. At least one is preferable.
Examples of the amino group include a primary amino group, a secondary amino group, a tertiary amino group and the like, and -NR ¹ R ^{2 (where R 1} and R ² each independently represent a hydrogen atom or an alkyl group. ) Is preferable.
As the poly (oxyalkylene) group, a poly (oxyethylene) group is preferable.

Specific examples of the monomer (b1) include dimethylaminoethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N. -Diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol mono (meth) Acrylate, N- (meth) acryloylmorpholine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-acrylamide-2-methylpropane Sulphonic acid, styrene sulfonic acid, sodium alkylallyl sulfosuccinate, allyl sulfonic acid, sulfoethoxy (meth) acrylate, sodium styrene sulfonate, 2- (meth) acryloyloxyethyl acid phosphate, N, N-dimethylaminoethyl (meth) Examples thereof include acrylate methyl chloride salt, N, N-dimethylaminopropyl (meth) acrylamide methyl chloride salt, N, N-dimethylaminoethyl (meth) acrylatebenzyl chloride salt and the like.
"(Meta) acrylate" is a general term for acrylate and methacrylate, "(meth) acrylic" is a general term for acrylic and methacrylic, and "(meth) acryloyl" is a general term for acryloyl and methacryloyl.

As the cross-linking group in the monomer (b2), at least one selected from the group consisting of a glycidyl group, a carboxyl group, an acid anhydride group, an alkoxysilyl group, a keto group and an aldehyde group is preferable.

Specific examples of the monomer (b2) include glycidyl (meth) acrylate, (meth) acrylic acid, maleic acid, maleic anhydride, crotonic acid, itaconic acid, 3- (meth) acryloxypropyltrimethoxysilane, 3-. (Meta) Acryloxypropyltriethoxysilane, 3- (Meta) Acryloxypropylmethyldimethoxysilane, 3- (Meta) Acryloxypropylmethyldiethoxysilane, 3- (Meta) Acryloxypropyltripropoxysilane, 3-( Meta) Examples thereof include acryloxypropylmethyldipropoxysilane, achlorine, crotonaldehyde, 2-acetoacetoxyethyl (meth) acrylate, diacetoneacrylamide, vinylmethylketone, vinylethylketone and vinylbutylketone.
The keto group of diacetone acrylamide functions as a cross-linking group, but the amide group does not function as a hydrophilic group. Therefore, diacetone acrylamide corresponds to the monomer (b2).

Examples of the monomer (b3) include the following monomers.
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, lauryl (Meta) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxypolyethylene glycol (meth) (Meta) acrylic acid esters such as acrylates;
Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, vinylnaphthalene, vinylpyridine, etc.;
Divinylbenzene, divinyl ether, allyl (meth) acrylate, diallyl phthalate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. Polyfunctional polymerizable monomer;
In addition, vinyl compounds such as (meth) acrylonitrile; etc.

The structural unit derived from the monomer (b1), the structural unit derived from the monomer (b2), and the structural unit derived from the monomer (a3) in the component (B) may be one kind or two or more kinds, respectively.

The ratio of the structural unit derived from the monomer (b1) to the total mass (100% by mass) of all the structural units in the component (B) is 40 to 95% by mass, preferably 50 to 90% by mass. When the ratio of the constituent units derived from the monomer (b1) is not more than the lower limit of the above range, the hydrophilic effect is sufficiently exhibited, the stain resistance of the coating film is excellent, and the storage stability of the various coating compositions is improved. Is also excellent. When the proportion of the structural unit derived from the monomer (b1) is not more than the upper limit of the above range, the water resistance and weather resistance of the coating film are excellent.

The ratio of the structural unit derived from the monomer (b2) to the total mass of all the structural units in the component (B) is 0.01 to 20% by mass, preferably 0.1 to 10% by mass. When the ratio of the constituent units derived from the monomer (b2) is equal to or higher than the lower limit of the above range, the hydrophilicity of the coating film surface does not easily decrease with time under outdoor exposure, and the stain resistance is maintained for a long period of time. When the ratio of the constituent units derived from the monomer (b2) is not more than the upper limit of the above range, the film-forming property of the coating film is excellent and a smooth coating film can be easily obtained.

The ratio of the structural unit derived from the monomer (b3) to the total mass of all the structural units in the component (B) is preferably 5.0 to 59.99% by mass, more preferably 5.0 to 49.9% by mass.
The ratio of the total mass of the structural unit derived from the monomer (b1), the structural unit derived from the monomer (b3), and the structural unit derived from the monomer (b3) to the total mass of all the structural units in the component (B) is 100. It is mass%.

The weight average molecular weight of the component (B) is 50,000 to 150,000, preferably 80,000 to 120,000. When the weight average molecular weight of the component (B) is at least the lower limit of the above range, the hydrophilicity of the coating film surface does not easily decrease with time under outdoor exposure, and the stain resistance is maintained for a long period of time. If the weight average molecular weight of the component (B) exceeds the upper limit of the above range, the viscosity of the component (B) increases too much when it is produced by solvent polymerization, which makes synthesis difficult.
The weight average molecular weight of the component (B) described in this embodiment is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC).

The component (B) is typically blended into a versatile coating composition in the form of an aqueous dispersion or aqueous solution.
The solid content of the aqueous dispersion or aqueous solution of the component (B) (content in terms of solid content of the component (B) relative to the total mass of the aqueous dispersion or aqueous solution) is 5 to 5 with respect to the total mass of the aqueous dispersion or aqueous solution. 15% by mass is preferable. If the solid content is less than the lower limit of the above range, the viscosity of the paint when it is made into a paint may be too low and the painting workability may be lowered. On the other hand, if the solid content exceeds the upper limit of the above range, the aqueous dispersion may become unstable and gel.

In the aqueous dispersion of the component (B), the particle size of the component (B) is preferably 0.01 to 0.10 μm. When the particle size of the component (B) is in the above range, the water resistance of the coating film is good.
The particle size of the component (B) described in this embodiment is an average particle size measured by a scanning electron microscope.

(Method for manufacturing component (B))
The component (B) is obtained by polymerizing a monomer mixture composed of a monomer (b1), a monomer (b2), and a monomer (b3).
The ratio (mass%) of each monomer to the total mass of the monomer mixture is the same as the ratio of the constituent units derived from each monomer to the total mass of all the constituent units constituting the component (B).
The polymerization method is not particularly limited, and known polymerization methods such as solution polymerization, emulsion polymerization, and suspension polymerization can be used.

As an example of the method for producing the component (B), a monomer mixture composed of a monomer (b1), a monomer (b2), and a monomer (b3) is dissolved in an organic solvent, heated, and reacted using a polymerization initiator (a polymerization initiator). (Polymerization reaction), cooling, neutralizing if necessary, adding water, and removing the organic solvent can be mentioned. As a result, a translucent liquid aqueous dispersion in which fine particles of the component (B) are uniformly dispersed in water can be obtained. This aqueous dispersion can be used as it is for the preparation of various coating compositions.
The temperature at which the monomer mixture is reacted can be, for example, 60 to 90 ° C. The reaction time can be, for example, 3 to 10 hours.

As the organic solvent, a water-soluble organic solvent is desirable. Specific examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, ethylene glycol, diethylene glycol, propylene glycol, and di. Examples thereof include propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and the like. In the production of the component (B), the above-mentioned organic solvent may be used alone or in combination of two or more. As the organic solvent, 1-propanol or 2-propanol is preferable from the viewpoint of polymerization stability, water displacement of the solvent, and solvent removability.

As the polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethyl) Azo compounds such as valeronitrile), benzoyl peroxide, lauroyl peroxide, organic peroxides such as tert-butyl hydroperoxide, tert-butyl-α-cumyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, Examples thereof include inorganic peroxides such as sodium persulfate. In the production of the component (B), the above-mentioned polymerization initiator may be used alone or in combination of two or more. In addition, the reaction can be accelerated by combining the above-mentioned polymerization initiator and reducing agent.

Examples of the neutralizing agent include ammonia, sodium hydroxide, potassium hydroxide, triethylamine, triethanolamine, aminomethyl propanol and the like. As the neutralizing agent, ammonia is preferable from the viewpoint of water resistance and stain resistance of the coating film.

<Resin emulsion (C)>
In the present invention, the component (C) (resin emulsion (C)) has a functional group capable of reacting with the cross-linking group of the structural unit (b2) contained in the component (B).
As such a functional group, at least one selected from the group consisting of a glycidyl group, a carboxyl group, an acid anhydride group, an alkoxysilyl group, a hydrazide group, a carbodiimide group, an oxazoline group and an aziridine group is preferable.

The functional group contained in the component (C) is appropriately selected according to the cross-linking group contained in the component (B).
When the cross-linking group contained in the component (B) is a glycidyl group, the functional group contained in the component (C) is preferably either one or both of a carboxyl group and an acid anhydride group.
When the cross-linking group of the component (B) is one or both of a carboxyl group and an acid anhydride group, the functional group of the component (C) is a group consisting of a glycidyl group, a carbodiimide group, an oxazoline group and an aziridine group. At least one selected from the above is preferable.
When the cross-linking group contained in the component (B) is an alkoxysilyl group, the functional group contained in the component (C) is preferably an alkoxysilyl group.
When the cross-linking group contained in the component (B) is either one or both of a keto group and an aldehyde group, the functional group contained in the component (C) is preferably a hydrazide group.

As the component (C), it suffices to have the functional group, and an aqueous resin having various resin skeleton compositions can be used.
Specific examples of the component (C) include, for example, an aqueous acrylic copolymer resin, an aqueous urethane copolymer resin, an aqueous acrylic silicon copolymer resin, an aqueous acrylic urethane copolymer resin, an aqueous fluoroacrylic copolymer resin, and an aqueous fluorovinyl copolymer. Examples include resin. As the component (C), any one of the above may be used alone, or two or more thereof may be used in combination.
The content of the functional group in the component (C) is appropriately defined by the structure of the functional group.

The glass transition temperature (Tg) of the component (C) is preferably 0 to 50 ° C, more preferably 20 to 30 ° C. When the Tg of the component (C) is in the above temperature range, the rain muscle contamination resistance is good.
The glass transition temperature (Tg) described in this embodiment is measured by a differential scanning calorimeter.

When the component (C) is granular, the particle size of the component (C) is preferably 0.1 to 0.25 μm from the viewpoint of stability of the various coating compositions, water resistance of the coating film and accelerated weather resistance.
The particle size of the component (C) described in the present embodiment is, for example, an average particle size measured by a concentrated particle size analyzer manufactured by Otsuka Electronics Co., Ltd.

(Method for manufacturing component (C))
Examples of the method for producing the component (C) include a method of polymerizing a monomer component containing the monomer having the functional group. Introducing a hydrazide group usually involves first polymerizing a monomer having a keto group capable of reacting with the hydrazide group, and then reacting the monomer having a keto group with the hydrazide group. Examples of the monomer having a keto group include diacetone acrylamide, and examples of the compound having a hydrazide group include adipic acid dihydrazide.

Examples of the monomer having a functional group include, among the monomers (b2), a monomer having the functional group and an ethylenically unsaturated bond such as the monomer having the functional group.
At this time, the monomer component may further contain a monomer other than the monomer having the functional group. The other monomer may be a monomer copolymerizable with the monomer having a functional group, and may be a monomer known as a monomer used for a coating resin, depending on the desired resin skeleton composition of the component (C). It can be selected as appropriate.
The polymerization method of the monomer component is not particularly limited, and known polymerization methods such as solution polymerization, emulsion polymerization and suspension polymerization can be used.

<Solid content ratio of component (B) and component (C)>
In the versatile coating composition of the present invention, the value obtained by dividing the mass of the component (B) by the mass of the component (C), that is, the solid content ratio (B) / (C) is 0.03 or more and less than 0.11. is there.
When the solid content ratio (B) / (C) in the various coating compositions is equal to or higher than the lower limit of the above range, the hydrophilic effect of the component (B) is sufficiently exhibited, and the stain resistance of the obtained coating film is improved. Excellent. Further, when the solid content ratio (B) / (C) is not more than the upper limit of the above range, the obtained coating film is excellent in stain resistance, water resistance and weather resistance.
Further, from the viewpoint of obtaining the above effect, the solid content ratio (B) / (C) is more preferably 0.04 or more and 0.1 or less, and most preferably 0.06 or more and 0.1 or less.

<Arbitrary component in various paint compositions>
In addition to the above-mentioned components, the various coating compositions of the present invention further include resin emulsions other than the above, and extender pigments such as hydrous magnesium silicate, if necessary, as long as the effects of the present invention are not impaired. Additives such as thickeners, dispersants, defoamers, preservatives and leveling agents may be included. As these components, known ones can be used.

<Manufacturing method of various paint compositions>
The various coating compositions of the present invention include the component (A) (colored gel-like particles (A)), the component (B) (aqueous resin (B)), and the component (C) (resin emulsion (C)) as described above. )) Can be adjusted by stirring with a disperser such as a dissolver, for example. At this time, in addition to the above-mentioned components (A), (B) and (C), other optional components described above can be further mixed, if necessary. At this time, the total content of the component (A), the component (B) and the component (C) in the multicolored coating composition is appropriately defined depending on the use of the multicolored coating composition.

The mixing method of each of the above components is not particularly limited as long as each material can be mixed uniformly. Further, the mixing order when mixing each of the above components is not particularly limited.

<Coating film of various paint compositions>
The coating film obtained from the multicolored coating composition of the present invention can be formed by applying the multicolored coating composition to an object to be coated and drying it.
The object to be coated of the various coating composition of the present invention is not particularly limited, and examples thereof include a siding board and a flexible plate. Further, an undercoat coating film may be formed on these objects to be coated in advance before the various coating compositions are applied. This undercoat film can be formed by using a known undercoat paint.

The method for applying the various coating compositions is not particularly limited, and examples thereof include a method using a brush, a roller, a gun, and the like.
Further, as a drying condition of the various coating compositions after application, for example, a condition of leaving at 23 ° C. for 14 days can be mentioned.
The thickness of the coating film of the various coating compositions is not particularly limited, but for example, the thickness after drying can be 50 to 500 μm.

<Effect>
As described above, according to the versatile coating composition of the present invention, the emulsion coating material is encapsulated in a gelled film at least one color of colored gel-like particles (A) (component (A)) and an aqueous resin (components (A)). B) (component (B)) and resin emulsion (C) (component (C)) are contained in a composition optimized in a unique range. In the present invention, in particular, the solid content ratio (B) / (C) obtained by dividing the mass of the component (B) by the mass of the component (C) in the various coating compositions is 0.03 or more and less than 0.11. This makes it possible to form a coating film that is less likely to be contaminated even when exposed to the outdoors for a long period of time.

Further, since the component (B) has a structural unit derived from the monomer (b1) and a structural unit derived from the monomer (b2), it has a hydrophilic group and a cross-linking group. Since the component (B) has a hydrophilic group, the surface of the coating film has hydrophilicity, and the resulting coating film has excellent stain resistance. Further, since the component (B) has a cross-linking group and the component (C) has a functional group capable of reacting with the cross-linking group, the component (B) and the component (C) react in the coating film. Since the chemical bond is strong, the hydrophilicity of the coating film surface is not easily lost, and the stain resistance of the coating film is maintained for a long period of time.

Therefore, according to the versatile coating composition of the present invention, it is possible to obtain a coating film having a plurality of colors that can maintain excellent stain resistance even when exposed to the outdoors for a long period of time.
Further, the coating film formed from the various coating compositions of the present invention is also excellent in water resistance and weather resistance.

Hereinafter, the various coating compositions of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass".

<Manufacturing of water-based resin (B)>
The synthesis example of the aqueous resin (B) in Production Examples B1 to B13 is shown below.

[Manufacturing Example B1]
In a round bottom flask having a content of 3 L equipped with a stirrer, 500 g of 2-propanol, 30 g of methyl methacrylate, 150 g of dimethylaminoethyl methacrylate, 4 g of methacrylic acid and 16 g of diacetone acrylamide were charged, and the temperature was raised while stirring at 75 ° C. 2 g of 2,2'-azobisisobutyronitrile was charged and the reaction was started. The mixture was reacted at an internal temperature of 75 ° C. for 5 hours and cooled. At 40 ° C. or lower, 15 g of 25% -ammonia water and 1800 g of water were charged and stirred until uniform to obtain a liquid having a solid content of 8%. Then, 2-propanol was distilled off from this liquid using a rotary evaporator to obtain an aqueous resin (B1) having a solid content of 10% and a weight average molecular weight of 110,000.

[Manufacturing Examples B2 to B13]
Aqueous resins (B2) to (B13) in the same manner as in Production Example B1 except that the amount (g) of the raw material to be used was changed as shown in Tables 1 to 3 below by the same method as in Production Example B1. ) Was obtained. The solid content, particle size, and weight average molecular weight in each of Production Examples B1 to B13 are shown in Tables 1 to 3 below.

Regarding the aqueous resin (B11) obtained in Production Example B11 (*), the solid content and particle size could not be measured because the copolymer was not homogenized when aqueous ammonia was added and was in a highly viscous state. It was. However, the weight average molecular weight could be measured when unneutralized before the addition of aqueous ammonia.

<Manufacturing of resin emulsion (C)>
The synthesis example of the resin emulsion (C) of Production Examples C1 to C5 is shown below.

[Manufacturing Example C1]
520 parts of water and 10 parts of ADEKA CORPORATION SR10 (manufactured by ADEKA) were placed in a separable round bottom flask having a content of 3 L equipped with a stirrer, and the temperature was raised to 60 ° C. while stirring.
Next, 210 parts of water was charged into a beaker having a content of 2 L, and 10 parts of ADEKA REASORP SR10 (manufactured by ADEKA) was added thereto to dissolve the mixture, and while stirring, 520 parts of methyl methacrylate and 400 parts of 2-ethylhexyl acrylate were added. 30 parts of diacetone acrylamide and 50 parts of methacrylic acid were charged and emulsified to obtain a monomer emulsion. Next, 50 parts of water was placed in a beaker having an internal volume of 100 mL, and 3 parts of potassium persulfate was dissolved therein to obtain an initiator aqueous solution.
Next, 10% of each of the total amounts of the monomer emulsion and the initiator aqueous solution was added to the separable round bottom flask at 60 ° C., and further, 1 part of sodium bisulfite dissolved in 30 parts of water. Was added. Then, after confirming heat generation and color tone change (blueish white), the rest of the monomer emulsion and the initiator aqueous solution were added dropwise to the separable round-bottom flask over 4 hours. The reaction temperature at this time was maintained at 65 ° C. Then, after completion of the dropping, the mixture was reacted for 2 hours to cool, and at 40 ° C. or lower, an aqueous dispersion prepared by adding 60 parts of ammonia and 20 parts of adipic acid dihydrazide to 150 parts of water and 5 parts of a preservative were added and evaporated. An acrylic polymer emulsion with a residue of 50% was obtained. Then, 100 parts of texanol and 100 parts of water were added to this emulsion to obtain a resin emulsion (C1) having an evaporation residue of 50%, Tg of 20 ° C., a minimum film forming temperature of 0 ° C., a particle size of 0.10 μm, and a pH of 8.
Adecaria soap SR10 (manufactured by ADEKA) is a compound represented by the following chemical formula, and in the following formula, R represents an alkyl group.

[Manufacturing Example C2]
670 g of water and 10 g of Adecaria Soap SR10 (manufactured by ADEKA) were placed in a separable round bottom flask having a content of 3 L equipped with a stirrer, and the temperature was raised to 60 ° C. while stirring.
Next, 105 g of water was placed in a beaker having a content of 1 L, and 5 g of ADEKA REASORP SR10 (manufactured by ADEKA) was added thereto to dissolve the beaker, and while stirring, 270 g of methyl methacrylate, 205 g of 2-ethylhexyl acrylate, and 25 g of glycidyl methacrylate were added. It was charged and emulsified to obtain a monomer emulsion I. Next, 50 g of water was placed in a beaker having an internal volume of 100 mL, and 3 g of potassium persulfate was dissolved therein to obtain an initiator aqueous solution.
Next, 20% of the total amount of the monomer emulsion I and 10% of the total amount of the initiator aqueous solution were added to the separable round bottom flask at 60 ° C., and further dissolved in 30 g of water. 1 g of the allowed sodium bisulfite was added. Next, after confirming heat generation and color change (blueish white), the remaining total amount of the monomer emulsion I and 45% of the remaining amount of the initiator aqueous solution were added dropwise to the separable round-bottom flask over 2 hours. did. The reaction temperature at this time was maintained at 65 ° C. Then, after the completion of the dropping, the reaction was carried out for 1 hour.
Next, 105 g of water was placed in a beaker having a content of 1 L, and 5 g of ADEKA REASORP SR10 (manufactured by ADEKA) was added thereto to dissolve the beaker, and while stirring, 270 g of methyl methacrylate, 205 g of 2-ethylhexyl acrylate, and 25 g of methacrylic acid were added. Was charged and emulsified to obtain a monomer emulsion II. Then, the total amount of the monomer emulsion II and 45% of the remaining amount of the initiator aqueous solution were added dropwise to the separable round-bottom flask after the reaction for 1 hour over 2 hours. The reaction temperature at this time was maintained at 65 ° C. After completion of the dropping, the mixture was reacted for 2 hours and cooled, and 30 g of ammonia and 5 g of a preservative were added at 40 ° C. or lower to obtain an acrylic polymer emulsion having an evaporation residue of 50%. 100 g of texanol and 100 g of water were added to this emulsion to obtain a resin emulsion (C2) having an evaporation residue of 50%, Tg of 20 ° C., a minimum film forming temperature of 0 ° C., a particle size of 0.20 μm, and a pH of 8.

[Manufacturing Example C3]
670 g of water and 5 g of ADEKA rear soap SR10 (manufactured by ADEKA) were placed in a separable round bottom flask having a content of 3 L equipped with a stirrer, and the temperature was raised to 60 ° C. while stirring.
Next, 210 g of water was placed in a beaker having a content of 2 L, and 15 g of ADEKA REASORP SR10 (manufactured by ADEKA) was added thereto to dissolve the beaker, and while stirring, 580 g of methyl methacrylate, 360 g of 2-ethylhexyl acrylate, and Z6030 (Toray) were added. 10 g (manufactured by Dow Corning) and 50 g of methacrylic acid were charged and emulsified to obtain a monomer emulsified solution. Next, 100 g of water was placed in a beaker having a content of 200 mL, and 3 g of potassium persulfate was dissolved therein to obtain an initiator aqueous solution.
Next, 10% of the total amount of each of the monomer emulsion and the initiator aqueous solution was added to the separable round bottom flask at 60 ° C., and 1 g of sodium bisulfite dissolved in 60 g of water was further added. .. After confirming heat generation and color change (blueish white), the remainder of the monomer emulsion and the initiator aqueous solution was added dropwise to the separable round-bottom flask over 3 hours. The reaction temperature at this time was maintained at 65 ° C. After completion of the dropping, the mixture was reacted for 2 hours and cooled, and 60 g of ammonia and 5 g of a preservative were added at 40 ° C. or lower to obtain an acrylic silicon polymer emulsion having an evaporation residue of 50%. 120 g of texanol and 180 g of water were added thereto to obtain a resin emulsion (C3) having an evaporation residue of 50%, Tg of 30 ° C., a minimum film forming temperature of 0 ° C., a particle size of 0.15 μm, and a pH of 8.
Z6030 (manufactured by Toray Dow Corning Co., Ltd.) is a compound represented by the following chemical formula.

[Manufacturing Example C4]
670 g of water and 5 g of ADEKA rear soap SR10 (manufactured by ADEKA) were placed in a separable round bottom flask having a content of 3 L equipped with a stirrer, and the temperature was raised to 60 ° C. while stirring.
Next, 210 g of water was charged into a beaker having a content of 2 L, and 15 g of ADEKA Riasoap SR10 (manufactured by ADEKA) was added thereto to dissolve the beaker, and 540 g of methyl methacrylate, 410 g of 2-ethylhexyl acrylate and 50 g of methacrylic acid were charged while stirring. It was emulsified to obtain a monomer emulsion. Then, 50 g of water was placed in a beaker having an internal volume of 100 mL, and 3 g of potassium persulfate was dissolved therein to obtain an initiator aqueous solution.
Next, 10% of the total amount of each of the monomer emulsion and the initiator aqueous solution was added to the separable round bottom flask at 60 ° C., and 1 g of sodium bisulfite dissolved in 30 g of water was further added. .. Then, after confirming heat generation and color tone change (bluish white), the remainder of the monomer emulsion and the initiator aqueous solution was added dropwise to the separable round-bottom flask over 4 hours. The reaction temperature at this time was maintained at 65 ° C. After completion of the dropping, the mixture was reacted for 2 hours and cooled, and 60 g of ammonia and 5 g of a preservative were added at 40 ° C. or lower to obtain an acrylic polymer emulsion having an evaporation residue of 50%. To this, 100 g of texanol and 100 g of water were added to obtain a resin emulsion (C4) having an evaporation residue of 50%, Tg of 20 ° C., a minimum film forming temperature of 0 ° C., a particle size of 0.20 μm, and a pH of 8.

[Manufacturing Example C5]
670 g of water was placed in a separable round-bottom flask having an internal volume of 3 L equipped with a stirrer, and the temperature was raised to 60 ° C. while stirring.
In addition, 210 g of water was charged into a beaker having an internal capacity of 2 L, and 20 g of ADEKA Risorp SR10 (manufactured by ADEKA) was charged therein, dissolved, and stirred while stirring to obtain 520 g of methyl methacrylate, 380 g of 2-ethylhexyl acrylate, and Blemmer (registered trademark) PE350. (Manufactured by Nichiyu Co., Ltd.) 100 g was charged and emulsified to obtain a monomer emulsified solution.
Next, 100 g of water was placed in a beaker having an internal volume of 200 mL, and 3 g of potassium persulfate was dissolved therein to obtain an initiator aqueous solution.
Next, 10% of the total amount of each of the monomer emulsion and the initiator aqueous solution was added to the separable round bottom flask at 60 ° C., and 1 g of sodium bisulfite dissolved in 60 g of water was further added. Then, after confirming heat generation and color tone change (bluish white), the remainder of the monomer emulsion and the initiator aqueous solution was added dropwise to the separable round-bottom flask for 3 hours. The reaction temperature at this time was maintained at 65 ° C. After completion of the dropping, the mixture was reacted for 2 hours and cooled, and 20 g of ammonia and 5 g of a preservative were added at 40 ° C. or lower to obtain an acrylic polymer emulsion having an evaporation residue of 50%. 120 g of texanol and 180 g of water were added thereto to obtain a resin emulsion (C5) having an evaporation residue of 50%, Tg of 20 ° C., a minimum film forming temperature of 0 ° C., a particle size of 0.25 μm, and a pH of 8.
Blemmer PE350 (manufactured by NOF CORPORATION) is a compound represented by the following chemical formula.

Table 4 below shows the resin skeleton composition, evaporation residue, glass transition temperature (Tg), minimum image film temperature, particle size, pH, and types of functional groups of the resin emulsions (C1) to (C5).

<Adjustment of emulsion paint (E)>
The acrylic resin emulsion shown below and the hydrophilic colloid-forming substance were blended in the blending ratios shown in Table 5 below, and the mixture was stirred and mixed to obtain a mixed solution (a). On the other hand, the following coloring pigments (D-1) to (D-5), the dispersant shown below, and water are blended in the blending ratios shown in Table 5 below, and the mixture is stirred and mixed to obtain a mixed solution (b). Obtained. Then, the mixed solution (b) was added to the mixed solution (a) and stirred and mixed to obtain monochromatic emulsion paints (E-1) to (E-5) as shown in Table 5 below. In Table 5 below, the unit of the blending ratio of each component is parts by mass.

[Acrylic resin emulsion]
Anionic high molecular weight acrylic resin emulsion ("Primal AC-38 (registered trademark)" manufactured by Nippon Acrylic Chemical Co., Ltd.)
[Hydrophilic colloid-forming substance]
1.5% aqueous solution of nonionic guar rubber derivative [coloring pigment]
(D-1) Black ("Mitsubishi Carbon Black MA-100", manufactured by Mitsubishi Chemical Corporation, carbon black)
(D-2) Brown ("T-10", manufactured by Titan Kogyo, Ltd., iron-zinc composite oxide)
(D-3) Yellow ("LLXLO", manufactured by Titan Kogyo, Ltd., iron oxide)
(D-4) White ("R-930", manufactured by Ishihara Sangyo Co., Ltd., titanium oxide)
[Dispersant]
Anionic polymer dispersion ("Orotan 731 (registered trademark)", manufactured by Nippon Acrylic Chemical Co., Ltd.)

Then, the obtained monochromatic emulsion paints (E-1) to (E-4) are blended in the blending ratios shown in Table 6 below, and by stirring and mixing, the emulsion paints (F) as shown in Table 6 below are mixed. -1) to (F-5) were obtained. In Table 6 below, the unit of the blending ratio of the monochromatic emulsion paint is parts by mass.

<Preparation of gel particles>
Water-soluble consisting of 25 parts by mass of an extender pigment consisting of a 4% by mass aqueous dispersion of hydrous magnesium silicate, 5 parts by mass of a gelling agent consisting of a 5% by mass aqueous solution of ammonium diborate, and a 1% by mass aqueous solution of sodium carboxymethyl cellulose. After adding 25 parts by mass of the sex polymer compound and stirring and mixing, 45 parts by mass of water was added and diluted to obtain a dispersion medium. Next, 60 parts by mass of the emulsion paints (F-1) to (F-5) were added to 40 parts by mass of the dispersion medium, and the mixture was stirred with a dissolver to disperse the emulsion paint until the particle size became 10 mm. Gel-like particles (G-1) to (G-5) as shown in Table 7 below were obtained. Here, (GX) is a gel-like particle (X: serial number) using (FX) as an emulsion coating material. Further, in Table 7 below, the unit of the blending ratio of the emulsion paint is parts by mass.

<Adjustment of multicolored pattern paint: Examples 1 to 5>
18.5 parts by mass of resin emulsion C-1, 70 parts by mass of gel-like particles obtained by blending the above gel-like particles (G-1) to (G-5) in the blending ratio shown in Table 8 below, and increasing the alkali. 1 part by mass of thickener made of thickener ("SN Sixner 636 (registered trademark)" manufactured by Sannopco), 0.1 part by mass of 25% by mass aqueous ammonia, 6.5 parts by mass of aqueous resin B-1. And 3.9 parts by mass of water was stirred with a dissolver to obtain a colorful pattern coating material of Examples 1 to 5.

<Performance evaluation>
The multicolored pattern paints of each of the above obtained examples were evaluated as described below. The evaluation results are shown in Table 8 below. In Table 8 below, the unit of the blending ratio of the gel-like particles is parts by mass.

[Weather resistance evaluation]
First, a colorful pattern paint was applied to a slate plate to prepare a test piece for evaluation.
The above test piece was installed in the test tank of an ultraviolet irradiator (“Eye Super UV Tester W-151 (registered trademark)” manufactured by Iwasaki Electric Co., Ltd.), and the black panel temperature was 63 ° C, the humidity was 50% RH, and coating was applied. Ultraviolet rays were irradiated for 4 hours so that the irradiation intensity of the surface was 1000 mW / cm ^2. Then, the temperature in the test tank was set to about 30 ° C. and the humidity was set to 98% RH or more to cause dew condensation in the test tank, and the mixture was kept in this state for 4 hours. Then, this irradiation and dew condensation are regarded as one cycle, and after 1000 hours, that is, after 125 cycles, the test piece is taken out and the surface of the evaluation test piece is visually observed to suppress non-uniform deterioration in the evaluation test piece. Evaluated whether or not. The evaluation criteria at this time were as follows.
◯: There is almost no discoloration and the gloss has not disappeared. ×: The discoloration is large and the gloss has disappeared. In the weather resistance evaluation test, among the above evaluation criteria, those with ○ were accepted and those with × were rejected. ..

[Rain-resistant muscle contamination resistance]
An aluminum plate (size 225 x 100 x 1 mm) is bent at a position one-third from one end in the long side direction to an internal angle of 135 ° along the short side direction, and a solvent-based urethane-based undercoat paint (two liquids) is applied to the convex surface. ) Was applied and dried at room temperature for 1 day, then a water-based undercoat paint (one liquid) was applied, and the mixture was dried at room temperature for 4 hours to form an undercoat coating film. The above-mentioned multicolored pattern paint was applied onto the undercoat coating film to a thickness of 0.5 mm, and dried at room temperature for one week as a test piece. This test piece was vertically exposed to the south surface on the premises (outdoor) of Fujikura Kasei Co., Ltd. in Sakurada, Kuki City, Saitama Prefecture. Then, the rain streak stains on the test piece one year later were visually observed, and the rain streak stain resistance of the coating film was evaluated according to the following criteria.
◯: Small rain streak stain △: Medium rain streak stain ×: Large rain streak stain In the rain streak stain resistance evaluation test, among the above evaluation criteria, ○ was accepted and △ and × were rejected. ..

[water resistant]
A solvent-based urethane-based undercoat paint (two-component) is applied to one side of a slate plate (size 40 x 75 x 3 mm), dried at room temperature for one day, and then a water-based undercoat paint (one-component) is applied to room temperature. It was dried underneath for 4 hours to form an undercoat coating. Next, a multicolored pattern paint was applied onto the undercoat coating film so that the thickness after drying was 0.5 mm, and dried at room temperature for one week to form a coating film. Then, an epoxy paint (two liquids) is applied to the back surface and the side surface of the slate plate on which the coating film is formed, and after drying for one day, a fluorine paint (two liquids) is further applied on the epoxy paint. The test piece was dried for 3 days.
After immersing this test piece in pure water at 40 ° C. for 1 week, the state of the coating film of the test piece was visually observed, and the water resistance of the coating film was evaluated according to the following criteria.
◯: No abnormality Δ: Slightly blistering ×: Slightly blistering In the water resistance evaluation test, among the above evaluation criteria, those with ○ were accepted, and those with Δ and × were rejected.

<Adjustment of multicolored pattern paint: Examples 6 to 13, Comparative Examples 1 to 10>
The multicolored pattern paint was prepared by the same method as in Example 1 above, except that each composition was changed to the composition shown in Tables 9 to 12 below. At this time, the water-based resin B-1 and the resin emulsion C-1 used for adjusting the various patterns were changed to the water-based resins as shown in Tables 9 to 12 below, and the number of copies added was also changed.

Then, the same evaluation tests as described above were carried out for Examples 6 to 13 and Comparative Examples 1 to 10, and the results are shown in Tables 9 to 12 below.

<Evaluation result>
As shown in the results shown in Tables 1 to 10, a colorful coating composition in which the colored gel-like particles (A), the aqueous resin (B), and the resin emulsion (C) each had the composition specified in the present invention was prepared. In Examples 1 to 13 in which a coating film was formed using this composition, the evaluations of weather resistance, rain muscle stain resistance and water resistance were all "○" (pass: good).

On the other hand, in Comparative Examples 1 to 10, at least the composition of the aqueous resin (B) or the resin emulsion (C) is out of the range of the composition specified in the present invention, or these solids. This is an example in which the fraction ratio (B) / (C) is outside the specified range of the present invention.

Comparative Example 1 is particularly inferior in weather resistance and water resistance because the solid content ratio (B) / (C) exceeds the upper limit specified in the present invention.
In Comparative Example 2, since the solid content ratio (B) / (C) is less than the lower limit specified in the present invention, the rain muscle contamination resistance is inferior.
In Comparative Example 3, since the resin emulsion (C) has no functional group, the aqueous resin (B) and the resin emulsion (C) are not crosslinked, and the rain muscle contamination resistance is particularly inferior.
In Comparative Example 4, since the amount of the monomer (b1) which is a hydrophilic component is too small, the rain muscle contamination resistance is inferior.
In Comparative Example 5, since the weight average molecular weight of the aqueous resin (B) is less than the lower limit specified in the present invention, the rain muscle contamination resistance is inferior.

Since Comparative Example 6 does not contain the water-based resin (B), it is particularly inferior in rain muscle contamination resistance.
In Comparative Example 7, since the functional group of the aqueous resin (B) and the functional group of the resin emulsion (C) are not crosslinked with each other, they are not crosslinked, and in particular, the rain muscle contamination resistance is high. Inferior.
Comparative Example 8 was an example in which cracks were formed during the formation of the coating film and could not be evaluated. It is probable that this was caused by poor film formation due to too many crosslinked functional groups of the aqueous resin (B).
In Comparative Example 9, since neither the aqueous resin (B) nor the resin emulsion (C) has a functional group, they are not crosslinked, and in particular, the rain muscle contamination resistance is inferior.
Comparative Example 10 is an example in which the weight average molecular weight of the aqueous resin (B) exceeds the upper limit specified in the present invention, and although the polymer itself can be obtained and the weight average molecular weight can be measured, The polymer was not homogenized when aqueous ammonia was added, and because of its high viscosity, it could not be used as a coating composition.

From the results of the examples described above, the various coating compositions of the present invention are excellent in weather resistance, rain streak stain resistance and water resistance after coating film formation, and are excellent even when exposed to the outdoors for a long period of time. It is clear that a coating film having multiple colors can be obtained that can maintain the stain resistance.

The versatile coating composition of the present invention provides a coating film having a plurality of colors capable of maintaining excellent stain resistance even when exposed to the outdoors for a long period of time, and further, the coating film has water resistance and water resistance. It also has excellent weather resistance. Therefore, the multicolored coating composition of the present invention is very suitable for forming a coating film having a plurality of colors on various objects to be coated such as buildings.

Claims (4)

A multicolored coating composition containing at least one color of colored gel-like particles (A) in which an emulsion coating is encapsulated with a gelling film, an aqueous resin (B), and a resin emulsion (C).
The aqueous resin (B) has a structural unit derived from a monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, a structural unit derived from a monomer (b2) having a bridging group and an ethylenically unsaturated bond, and the above. It is composed of a constituent unit derived from a monomer (b1) and a monomer (b3) having an ethylenically unsaturated bond other than the monomer (b2).
The ratio of the structural unit derived from the monomer (b1) is 40 to 95% by mass, and the ratio of the structural unit derived from the monomer (b2) is 0.01 to the total mass of all the structural units in the aqueous resin (B). 20% by mass,
The water-based resin (B) has a weight average molecular weight of 50,000 to 150,000.
The resin emulsion (C) has a functional group capable of reacting with the cross-linking group contained in the aqueous resin (B).
A versatile coating composition characterized in that the value obtained by dividing the mass of the aqueous resin (B) by the mass of the resin emulsion (C) is 0.03 or more and less than 0.11. The hydrophilic group is at least one selected from the group consisting of an amino group, an amide group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, a quaternary ammonium group, a sulfate group, a morpholino group and a poly (oxyalkylene) group. The colorful coating composition according to claim 1. The colorful coating composition according to claim 1 or 2, wherein the cross-linking group is at least one selected from the group consisting of a glycidyl group, a carboxyl group, an acid anhydride group, an alkoxysilyl group, a keto group and an aldehyde group. .. Claim that the functional group capable of reacting with the cross-linking group is at least one selected from the group consisting of a glycidyl group, a carboxyl group, an acid anhydride group, an alkoxysilyl group, a hydrazide group, a carbodiimide group, an oxazoline group and an aziridine group. The colorful coating composition according to any one of 1 to 3.