JP2019019269A - Multi-color coating composition - Google Patents

Abstract

To provide a multi-color coating composition from which a coated film that can keep stain resistance even when being exposed to outdoors for a long period of time is obtained.SOLUTION: A multi-color coating composition contains colored gel-like particles (A), an aqueous resin (B) and resin emulsion (C), where the aqueous resin (B) is made of constitutional units derived from a monomer (b1) having a hydrophilic group and an ethylenic unsaturated bond, a monomer (b2) having a crosslinking group and an ethylenic unsaturated bond, and a monomer (b3) having an ethylenic unsaturated bond other than the monomer (b1) and the monomer (b2) and has a weight average molecular weight of 50,000 to 150,000, a ratio of the constitutional unit derived from the monomer (b1) to the total mass of the total constitutional unit in the aqueous resin (B) is 40-95 mass%, a ratio of the constitutional unit derived from the monomer (b2) is 0.01-20 mass%, the resin emulsion (C) has a functional group that can react with a crosslinking group, and a 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.SELECTED DRAWING: None

Description

  The present invention relates to a multicolor coating composition.

  Conventionally, for the purpose of protecting a building from external stimuli such as rain, light, heat, and moisture, a method of applying a hydrophobic paint to the building is used. Furthermore, recently, paints made of various paint compositions capable of forming a coating film having a plurality of colors have attracted attention. As such paints, for example, paints of a plurality of colors in an aqueous dispersion medium. A multicolored paint containing gel-like colored particles in which is dispersed is proposed.

  Here, while the coating film formed from the hydrophobic paint as described above is excellent in water resistance, weather resistance, etc., hydrophobic dirt is likely to adhere, and the attached dirt should be washed away with water. However, there is a tendency that it does not flow down easily. For this reason, in buildings coated with hydrophobic paint, oily dirt, dirt, etc. derived from car exhaust gas, etc., adhere to the wall surface, or they move with the rain and are emphasized as rain lines. A phenomenon is seen, and rain stripes are more likely to appear depending on the shape of the building. 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 has increased. In general, a low-contamination paint often has a hydrophilic surface on the surface of the coating film formed. However, if the surface is hydrophilic, hydrophobic stains with different affinity 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 a coating film formed from the low-contamination paint as described above is exposed to the outdoors and a stimulus such as sunlight, rainfall, or temperature change is applied, generally the hydrophilicity of the coating film surface decreases. In such a case, for example, as a method for imparting stain resistance by hydrophilizing the coating film surface, a method of incorporating a colloidal silica or an aqueous polysiloxane dispersion in the paint is known. However, in this method, when exposed to the outdoors for a long period of time, the colloidal silica or the polysiloxane aqueous dispersion is washed away by rainwater or the like, and the hydrophilic effect is lost. Thus, when the hydrophilic property of the coating film surface falls, there exists a problem that stain resistance also falls.

  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 has a resistance to resistance. It is said that the contamination is good for a long time. However, in the coating film using the resin composition described in Patent Document 1, the durability of the stain resistance is not always sufficient.

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

  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 in a specific ratio is copolymerized. Water-based paints containing a specific ratio of a polymer obtained in this manner and an aqueous polymer having a carbodiimide group have been proposed. In Patent Document 3, the water-based paint film is excellent in stain resistance and water resistance, and the stain resistance is maintained for a long time. However, the coating film using the water-based paint described in Patent Document 3 still has room for improvement in the durability of stain resistance.

JP 2008-133361 A JP 2008-274242 A JP 2012-062413 A

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

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

[1] A multicolored coating composition comprising at least one colored gel particle (A) encapsulated with a gelled film, an aqueous resin (B), and a resin emulsion (C). The aqueous resin (B) is a structural unit derived from the monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, and a structural unit derived from the monomer (b2) having a crosslinking group and an ethylenically unsaturated bond; The monomer (b1) and the monomer (b2) other than the monomer (b3), and the monomer (b3) 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 molecule of the aqueous resin (B) The amount is 50,000 to 150,000, the resin emulsion (C) has a functional group capable of reacting with the crosslinking group contained in the aqueous resin (B), and the mass of the aqueous resin (B) is changed to the resin emulsion. A multicolor coating composition characterized by having a value divided by mass of (C) of 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 sulfuric acid group, a morpholino group, and a poly (oxyalkylene) group. The multicolored 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. Multicolor paint composition.
[4] The functional group capable of reacting with the crosslinking 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 multicolored paint composition according to any one of the above [1] to [3].

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

Hereinafter, the multicolored paint composition according to the present invention will be described in detail.
The “aqueous resin” described in the present embodiment means a resin that can be dispersed or dissolved in water.

  The multicolored coating composition of the present invention comprises at least one colored gel-like particle (A) (hereinafter sometimes referred to as “component (A)”) in which an emulsion coating is encapsulated with a gelled film, and an aqueous solution. Resin (B) (hereinafter sometimes referred to as “component (B)”) and resin emulsion (C) (hereinafter sometimes referred to as “component (C)”).

In the multicolor coating composition of the present invention, the component (A), the component (B) and the component (C) each have a composition described below, and the mass of the component (B) is (C). The value divided by the mass of the component is taken as the predetermined range.
That is, in the multicolor coating composition of the present invention, the component (B) has a structural unit derived from the monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, a crosslinking group and an ethylenically unsaturated bond. 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 the total of all structural units in the component (B) The proportion of the structural unit derived from the monomer (b1) to the mass is 40 to 95 mass%, the proportion of the structural unit derived from the monomer (b2) is 0.01 to 20 mass%, and the weight average of the component (B) The molecular weight is 50,000 to 150,000.
In the multicolor coating composition of the present invention, the component (C) has a functional group capable of reacting with the crosslinking group contained in the component (B).
In the multicolor 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 multicolor coating composition of the present invention usually further contains water, and typically, the (A) component, the (B) component, and the (C) component are dispersed or dissolved in water.

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

(Color pigment)
Examples of color pigments include inorganic pigments such as carbon black, titanium oxide, iron oxide, lead chromate, cadmium yellow, and cadmium red; brilliant properties such as pearl pigments, mica pigments, mica-coated pearl pigments, aluminum powder, and stainless steel powder. Pigments; organic pigments such as phthalocyanine blue, phthalocyanine green, and quinacridone red. Moreover, these color pigments may be used individually by 1 type, and may use 2 or more types together.

  The content of the color pigment in the emulsion paint of component (A) is preferably 0.01 to 50 parts by weight, more preferably 100 parts by weight of the solid content of all resin emulsions contained in the emulsion paint. Is 0.1-30 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 emulsion of copolymers of these resins. Moreover, these resin emulsions may be used individually by 1 type, and may use 2 or more types together.

As the resin emulsion contained in the component (A) emulsion paint, an acrylic resin emulsion is particularly preferable among the above.
Moreover, the content rate of the resin emulsion in the emulsion paint of (A) component is although it does not specifically limit, Usually, it is 20-70 mass%, Preferably it is 30-50 mass%.

(Hydrophilic colloid-forming substance)
Examples of the hydrophilic colloid-forming substance include aqueous solutions containing natural polymers such as cellulose derivatives, polyethylene oxide, polyvinyl alcohol, casein, starch, galactomannone, guar gum, locust bean gum and the like. These hydrophilic colloid-forming substances may be used alone or in combination of two or more.

The hydrophilic colloid-forming substance contained in the component (A) emulsion paint is particularly preferably an aqueous solution of guar gum among the above aqueous solutions.
Moreover, the density | concentration of these aqueous solution is not specifically limited, For example, what is necessary is just 0.5-5.0 mass%.
Further, the content of the hydrophilic colloid-forming substance in the emulsion paint of the component (A) is 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. Preferably, it is 0.1-3.0 mass parts.

(Other ingredients)
The emulsion paint of component (A) further contains additives such as extender pigments such as hydrous magnesium silicate, thickeners, dispersants, antifoaming agents, preservatives, and leveling agents as necessary. It may be.

(Encapsulation with gelled membrane)
In the present invention, the emulsion paint of component (A) is encapsulated with a gelled film. That is, the component (A) is obtained by encapsulating and encapsulating an emulsion paint with a gelled film.
The gelled film is prepared by, for example, mixing a dark-colored emulsion paint containing a hydrophilic colloid-forming substance and a dispersion medium containing a gelling agent and dispersing the paint while stirring with a disperser such as a dissolver. It is obtained by reacting the gelling agent therein and the hydrophilic colloid-forming substance.

  As the dispersion medium, an aqueous dispersion medium containing a gelling agent is used. Examples of the gelling agent include aqueous solutions containing magnesium montmorillonite clay, sodium pentachlorophenol, borate salts such as ammonium biborate, 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 agent. Among these, it is particularly preferable to use a borate such as ammonium biborate as a dispersion medium. Further, the dispersion medium may further contain a extender pigment such as hydrous magnesium silicate and a water-soluble polymer compound such as sodium carboxymethyl cellulose, if necessary.

  The dispersion medium as described above can be obtained, for example, by stirring and mixing 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 content rate of the gelatinizer in a dispersion medium is not specifically limited, For example, it is 0.05-5.0 mass% in 100 mass% of dispersion media.

<Water-based resin (B)>
In the present invention, the component (B) (aqueous resin (B)) comprises a structural unit derived from the monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, a monomer having a crosslinking group and an ethylenically unsaturated bond ( It is a copolymer composed of a structural unit derived from b2) and a structural unit derived from a monomer (b3) having an ethylenically unsaturated bond other than the monomer (b1) and 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 sulfuric acid group, a morpholino group, and a poly (oxyalkylene) group. At least one is preferred.
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 (wherein R ¹ and R ² each independently represents a hydrogen atom or an alkyl group). ) Is preferred.
The poly (oxyalkylene) group is preferably a poly (oxyethylene) group.

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-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, sodium alkylallylsulfosuccinate, allylsulfonic acid, sulfoethoxy (meth) acrylate, sodium styrenesulfonate, 2- (meth) acryloyloxyethyl acid Examples include phosphate, N, N-dimethylaminoethyl (meth) acrylate methyl chloride salt, N, N-dimethylaminopropyl (meth) acrylamide methyl chloride salt, N, N-dimethylaminoethyl (meth) acrylate benzyl chloride salt, and the like. .
“(Meth) acrylate” is a generic term for acrylate and methacrylate, “(meth) acryl” is a generic term for acrylic and methacrylic, and “(meth) acryloyl” is a generic term for acryloyl and methacryloyl.

  The crosslinking group in the monomer (b2) is preferably 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.

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- (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, 3- ( Examples include meth) acryloxypropylmethyl dipropoxysilane, acrolein, crotonaldehyde, 2-acetoacetoxyethyl (meth) acrylate, diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone.
The keto group of diacetone acrylamide functions as a crosslinking 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 (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth ) Acrylate, methoxy polyethylene glycol (meth) acrylate, (meth) acrylic acid esters and the like;
Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, vinylnaphthalene, vinylpyridine;
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;
Other vinyl compounds such as (meth) acrylonitrile;

  In the component (B), 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) may each be one kind or two or more kinds.

  (B) 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 is 40 to 95% by mass, and preferably 50 to 90% by mass. When the proportion of the structural unit derived from the monomer (b1) is not less than the lower limit of the above range, the hydrophilic effect is sufficiently exhibited, the coating film is excellent in stain resistance, and the storage stability of the various coating compositions is improved. 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 coating film is excellent in water resistance and weather resistance.

  The ratio of the structural unit derived from the monomer (b2) to the total mass of all structural units in the component (B) is 0.01 to 20% by mass, and preferably 0.1 to 10% by mass. When the proportion of the structural unit derived from the monomer (b2) is not less than the lower limit of the above range, the hydrophilicity of the coating film surface hardly deteriorates with time under outdoor exposure, and stain resistance is maintained over a long period of time. When the proportion of the structural unit derived from the monomer (b2) is less than or equal to the upper limit of the above range, the coating film has excellent film forming properties 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 structural units in the component (B) is preferably 5.0 to 59.99% by mass, and more preferably 5.0 to 49.9% by mass.
In addition, 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) with respect to the total mass of all the structural units in the component (B) is 100. % By mass.

(B) The weight average molecular weights of a component are 50000-150,000, and 80000-120000 are preferable. When the weight average molecular weight of the component (B) is not less than the lower limit of the above range, the hydrophilicity of the coating film surface is unlikely to deteriorate with time under outdoor exposure, and the stain resistance is maintained over a long period of time. When the weight average molecular weight of (B) component exceeds the upper limit of the said range, when manufacturing (B) component by solvent polymerization, a viscosity will rise too much and a synthesis | combination will become difficult.
In addition, the weight average molecular weight of (B) component demonstrated by this embodiment is the value of standard polystyrene conversion measured by gel permeation chromatography (GPC).

(B) A component is typically mix | blended with a various coating composition in the state of an aqueous dispersion or aqueous solution.
The solid content of the aqueous dispersion of component (B) or the aqueous solution (content in terms of solid content of 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 mass% is preferable. If the solid content is less than the lower limit of the above range, the viscosity of the paint when converted into a paint is too low, and the coating workability may be reduced. Moreover, when solid content exceeds the upper limit of the said range, there exists a possibility that an aqueous dispersion may become unstable and gelatinize.

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

(Production method of component (B))
(B) A component is obtained by superposing | polymerizing the monomer mixture which consists of a monomer (b1), a monomer (b2), and a monomer (b3).
The ratio (mass%) of each monomer with respect to the total mass of the monomer mixture is the same as the ratio of the structural unit derived from each monomer to the total mass of all the structural units constituting the component (B).
The polymerization method is not particularly limited, and a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, or the like can be used.

(B) As an example of the manufacturing method of a component, the monomer mixture which consists of a monomer (b1), a monomer (b2), and a monomer (b3) is melt | dissolved in an organic solvent, it heats, and it reacts using a polymerization initiator ( Polymerization reaction), cooling, neutralizing as necessary, adding water, and removing the organic solvent. As a result, a translucent liquid aqueous dispersion in which fine (B) component particles are uniformly dispersed in water is obtained. This aqueous dispersion can be used as it is for the preparation of various coating compositions.
The temperature at the time of making the said monomer mixture react can be 60-90 degreeC, for example. Moreover, the time to make it react can be 3 to 10 hours, for example.

  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, di- Examples include propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol. (B) In manufacture of a component, said organic solvent may be used individually by 1 type, and may use 2 or more types together. In addition, as an organic solvent, 1-propanol or 2-propanol is preferable from the point of superposition | polymerization stability, the water substitution property of a solvent, and solvent removability.

  As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Azo compounds such as valeronitrile), organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, tert-butyl-α-cumyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, Examples include inorganic peroxides such as sodium persulfate. (B) In manufacture of a component, said polymerization initiator may be used individually by 1 type, and may use 2 or more types together. Moreover, reaction can also be accelerated | stimulated by combining the said polymerization initiator and a reducing agent.

  Examples of the neutralizing agent include ammonia, sodium hydroxide, potassium hydroxide, triethylamine, triethanolamine, aminomethylpropanol, and the like. The neutralizing agent is preferably ammonia from the viewpoint of the water resistance and stain resistance of the coating film.

<Resin emulsion (C)>
In this invention, (C) component (resin emulsion (C)) has a functional group which can react with the crosslinking group of the structural unit (b2) which said (B) component has.
Such a functional group is preferably at least one selected from the group consisting of glycidyl group, carboxyl group, acid anhydride group, alkoxysilyl group, hydrazide group, carbodiimide group, oxazoline group and aziridine group.

The functional group which (C) component has is suitably selected according to the crosslinking group which (B) component has.
When the crosslinking group which (B) component has is a glycidyl group, the functional group which (C) component has has any one or both of a carboxyl group and an acid anhydride group.
(B) When the crosslinking group which component has is either one or both of carboxyl group and acid anhydride group, the functional group which component (C) has is a group consisting of glycidyl group, carbodiimide group, oxazoline group and aziridine group At least one selected from the above is preferred.
When the crosslinking group which (B) component has is an alkoxysilyl group, the functional group which (C) component has is preferably an alkoxysilyl group.
When the crosslinking group which (B) component has is either one or both of keto group and aldehyde group, the functional group which (C) component has is preferably a hydrazide group.

(C) As a component, what is necessary is just to have the said functional group, and the aqueous resin which has various resin frame | skeleton composition 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 silicone copolymer resin, an aqueous acrylic urethane copolymer resin, an aqueous fluoroacrylic copolymer resin, and an aqueous fluorovinyl copolymer. Examples thereof include resins. As the component (C), any one of the above may be used alone, or two or more may be used in combination.
In addition, content of the said functional group in (C) component is prescribed | regulated suitably by the structure of a functional group.

(C) 0-50 degreeC is preferable and the glass transition temperature (Tg) of a component has more preferable 20-30 degreeC. If Tg of (C) component is the said temperature range, rain-stain stain | pollution | contamination resistance will become favorable.
In addition, the glass transition temperature (Tg) demonstrated by this embodiment is measured with 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 viewpoints of the stability of the multicolor coating composition, the water resistance of the coating film and the accelerated weather resistance.
In addition, the particle diameter of (C) component demonstrated by this embodiment is an average particle diameter measured by the Otsuka Electronics Co., Ltd. make and a thick type particle size analyzer, for example.

(Production method of component (C))
(C) As a manufacturing method of a component, the method of superposing | polymerizing the monomer component containing the monomer which has the said functional group is mentioned, for example. In order to introduce a hydrazide group, usually, a step of polymerizing a monomer having a keto group capable of reacting with a hydrazide group and reacting with this a compound having a hydrazide group is performed. Examples of the monomer having a keto group include diacetone acrylamide, and examples of the compound having a hydrazide group include adipic acid dihydrazide.

As a monomer which has the said functional group, the monomer which has the said functional group and an ethylenically unsaturated bond, such as the monomer which has the said functional group among the said monomers (b2), is mentioned, for example.
At this time, the monomer component may further include a monomer other than the monomer having the functional group. The other monomer may be any monomer that can be copolymerized with the monomer having the functional group, and is selected from monomers known in the art for use in paint resins, depending on the desired resin skeleton composition of component (C). It can be selected as appropriate.
Moreover, the polymerization method of a monomer component is not specifically limited, Well-known polymerization methods, such as solution polymerization, emulsion polymerization, and suspension polymerization, can be used.

<Solid content ratio of (B) component and (C) component>
In the multicolor 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.
If the solid content ratio (B) / (C) in the multicolored paint composition is equal to or higher than the lower limit of the above range, the hydrophilizing effect by the component (B) is sufficiently exerted, and the resulting coating film is resistant to contamination. Excellent. Moreover, it is excellent in the stain resistance of the coating film obtained, water resistance, and a weather resistance because solid content ratio (B) / (C) is below the upper limit of the said range.
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.

<Optional components in various paint compositions>
In addition to the above-mentioned components, the multi-color paint composition of the present invention is, as necessary, a range that does not impair the effects of the present invention, and further, resin emulsions other than those described above, and extender pigments such as hydrous magnesium silicate, Additives such as thickeners, dispersants, antifoaming agents, preservatives and leveling agents may be included. As these components, known components can be used, respectively.

<Manufacturing method of multicolored paint composition>
The multicolor coating composition of the present invention comprises the above component (A) (colored gel particles (A)), component (B) (aqueous resin (B)), component (C) (resin emulsion (C) )) Can be adjusted, for example, by stirring using a disperser such as a dissolver. Under the present circumstances, in addition to said (A) component, (B) component, and (C) component, the other arbitrary component mentioned above can further be mixed as needed. At this time, the total content of the component (A), the component (B) and the component (C) in the multicolored paint composition is appropriately determined depending on the use of the multicolored paint composition.

  In addition, the mixing method of each said component will not be restrict | limited especially if each material can be mixed uniformly. Also, the mixing order when mixing the above components is not particularly limited.

<Various paint composition coatings>
The coating film obtained from the multi-color coating composition of the present invention can be formed by applying the multi-color coating composition to an object to be coated and drying it.
The material to be coated with the multicolored paint composition of the present invention is not particularly limited, and examples thereof include siding boards and flexible boards. In addition, an undercoat coating film may be formed in advance on these objects before the multicolor coating composition is applied. This undercoat coating film can be formed using a known undercoat paint.

The application method of the multicolor coating composition is not particularly limited, and examples thereof include a method using a brush, a roller, a gun, and the like.
Moreover, as a drying condition of the various coating composition after application | coating, the conditions left to stand at 23 degreeC for 14 days are mentioned, for example.
Moreover, the thickness of the coating film of a multicolor coating composition is not specifically limited, For example, the thickness after drying can be 50-500 micrometers.

<Effect>
As described above, according to the multicolored paint composition of the present invention, at least one or more colored gel particles (A) (component (A)) in which an emulsion paint is encapsulated with a gelled film, an aqueous resin ( B) (component (B)) and resin emulsion (C) (component (C)) are included with compositions optimized within specific ranges. 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 multicolored paint composition is 0.03 or more and less than 0.11. As a result, it is possible to form a coating film that is not easily contaminated even when exposed outdoors for a long period of time.

  Moreover, 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 crosslinking group. When the component (B) has a hydrophilic group, the surface of the coating film has hydrophilicity, and the resulting coating film has excellent stain resistance. Moreover, (B) component has a crosslinking group, (C) component has a functional group which can react with the said crosslinking group, (B) component and (C) component react in a coating film. Due to the strong chemical bond, the hydrophilicity of the coating film surface is not easily lost, and the stain resistance of the coating film lasts for a long time.

Therefore, according to the multicolor coating composition of the present invention, a coating film having a plurality of colors can be obtained which can maintain excellent stain resistance even when exposed outdoors for a long period of time.
Moreover, the coating film formed from the multicolored coating composition of this invention is excellent also in water resistance and a weather resistance.

  EXAMPLES Hereinafter, the multicolor coating composition 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, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified.

<Production of water-based resin (B)>
Below, the synthesis example of aqueous resin (B) in manufacture example B1-B13 is shown.

[Production Example B1]
A 3-L round bottom flask equipped with a stirrer was charged with 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. 2,2′-Azobisisobutyronitrile (2 g) was charged and the reaction was started. The mixture was reacted at an internal temperature of 75 ° C. for 5 hours and cooled, and at 40 ° C. or lower, 15% ammonia water 15 g and water 1800 g were charged and stirred until uniform to obtain a liquid having a solid content of 8%. And 2-propanol was distilled off from this liquid using the rotary evaporator, and solid content 10% and the weight average molecular weight 110,000 aqueous resin (B1) were obtained.

[Production Examples B2 to B13]
Aqueous resins (B2) to (B13) were produced in the same manner as in Production Example B1, except that the amount (g) of the raw material used was changed as shown in Tables 1 to 3 by the same method as in Production Example B1. ) It shows to following Tables 1-3 about solid content in each manufacture example B1-B13, a particle diameter, and a weight average molecular weight.

  In addition, about water-based resin (B11) obtained by manufacture example B11 (*), since the copolymer was not homogenized at the time of ammonia water addition and it was in the state of high viscosity, solid content and particle diameter cannot be measured. It was. However, the weight average molecular weight could be measured at the time of non-neutralization before adding ammonia water.

<Manufacture of resin emulsion (C)>
The synthesis example of the resin emulsion (C) of manufacture example C1 to C5 is shown below.

[Production Example C1]
In a 3 L separable round bottom flask equipped with a stirrer, 520 parts of water and 10 parts of ADEKA rear soap (registered trademark) SR10 (manufactured by ADEKA) were charged, and the temperature was raised to 60 ° C. while stirring.
Next, 210 parts of water was charged into a beaker having an internal volume of 2 L, and 10 parts of ADEKA rear soap SR10 (manufactured by ADEKA) was added and dissolved, and while stirring, 520 parts of methyl methacrylate, 400 parts of 2-ethylhexyl acrylate, 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 the total amount of each of the monomer emulsion and the initiator aqueous solution is 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. Next, after confirming heat generation and color tone change (blue-white), each of the monomer emulsion and the initiator aqueous solution was dropped into the separable round bottom flask over 4 hours. The reaction temperature at this time was maintained at 65 ° C. Next, after completion of the dropwise addition, the mixture was reacted for 2 hours, cooled, and at 40 ° C. or lower, an aqueous dispersion obtained by adding 60 parts of ammonia and 20 parts of adipic acid dihydrazide to 150 parts of water and 5 parts of preservative were added and evaporated. A residual 50% acrylic polymer emulsion 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., minimum film forming temperature of 0 ° C., particle size of 0.10 μm, and pH of 8.
In addition, ADEKA rear soap SR10 (made by ADEKA) is a compound represented by the following chemical formula, and R shows an alkyl group in the following formula.

[Production Example C2]
Into a 3 L separable round bottom flask equipped with a stirrer, 670 g of water and 10 g of Adeka Soap SR10 (manufactured by ADEKA) were charged, and the temperature was raised to 60 ° C. while stirring.
Next, 105 g of water is charged into a beaker having an internal volume of 1 L, and 5 g of ADEKA rear soap SR10 (manufactured by ADEKA) is added and dissolved, and 270 g of methyl methacrylate, 205 g of 2-ethylhexyl acrylate, and 25 g of glycidyl methacrylate are stirred. The monomer emulsion I was obtained by charging and emulsifying. Next, 50 g of water was charged 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 aqueous initiator solution are added to the separable round bottom flask at 60 ° C., and further dissolved in 30 g of water. 1 g of sodium bisulfite was added. Next, after confirming heat generation and color change (blue white), the remaining total amount of the monomer emulsion I and 45% of the remaining initiator aqueous solution were dropped into the separable round bottom flask over 2 hours. did. The reaction temperature at this time was maintained at 65 ° C. And it was made to react for 1 hour after completion | finish of dripping.
Next, 105 g of water was charged into a beaker having an internal volume of 1 L, and 5 g of ADEKA rear soap SR10 (manufactured by ADEKA) was added and dissolved, and while stirring, methyl methacrylate 270 g, 2-ethylhexyl acrylate 205 g, methacrylic acid 25 g And emulsified to obtain monomer emulsion II. Next, the total amount of the monomer emulsion II and 45% of the remaining aqueous initiator solution were dropped into 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 dropwise addition, the mixture was reacted for 2 hours and cooled, and 30 g of ammonia and 5 g of an antiseptic 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., minimum film forming temperature of 0 ° C., particle size of 0.20 μm, and pH of 8.

[Production Example C3]
Into a 3 L separable round bottom flask equipped with a stirrer, 670 g of water and 5 g of Adekaria soap SR10 (manufactured by ADEKA) were charged, and the temperature was raised to 60 ° C. while stirring.
Next, 210 g of water was charged into a 2 L beaker, and 15 g of ADEKA rear soap SR10 (manufactured by ADEKA) was added and dissolved, and while stirring, methyl methacrylate 580 g, 2-ethylhexyl acrylate 360 g, Z6030 (Toray Industries, Inc.) 10 g of Dow Corning) and 50 g of methacrylic acid were charged and emulsified to obtain a monomer emulsion. Next, 100 g of water was charged into a 200 mL beaker, 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 (blue white), the monomer emulsion and the remaining initiator aqueous solution were dropped into the separable round bottom flask over 3 hours. The reaction temperature at this time was maintained at 65 ° C. After completion of the dropwise addition, the mixture was reacted for 2 hours and cooled, and 60 g of ammonia and 5 g of an antiseptic were added at 40 ° C. or lower to obtain an acrylic silicon polymer emulsion having an evaporation residue of 50%. To this was added 120 g of texanol and 180 g of water to obtain a resin emulsion (C3) having an evaporation residue of 50%, Tg of 30 ° C., minimum film-forming temperature of 0 ° C., particle size of 0.15 μm and pH of 8.
Z6030 (manufactured by Toray Dow Corning) is a compound represented by the following chemical formula.

[Production Example C4]
Into a 3 L separable round bottom flask equipped with a stirrer, 670 g of water and 5 g of Adekaria soap SR10 (manufactured by ADEKA) were charged, and the temperature was raised to 60 ° C. while stirring.
Next, 210 g of water is charged into a 2 L beaker, and 15 g of Adeka Soap SR10 (made by ADEKA) is added and dissolved, and 540 g of methyl methacrylate, 410 g of 2-ethylhexyl acrylate, and 50 g of methacrylic acid are charged while stirring. Emulsified to obtain a monomer emulsion. Then, 50 g of water was charged into 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. . Subsequently, after confirming heat generation and color tone change (blue white), the monomer emulsion and the remainder of the initiator aqueous solution were dropped into the separable round bottom flask over 4 hours. The reaction temperature at this time was maintained at 65 ° C. After completion of the dropwise addition, the reaction was allowed to proceed for 2 hours, and the mixture was cooled. At 40 ° C. or lower, 60 g of ammonia and 5 g of preservative were added to obtain an acrylic polymer emulsion having an evaporation residue of 50%. To this was added 100 g of texanol and 100 g of water to obtain a resin emulsion (C4) having an evaporation residue of 50%, Tg of 20 ° C., minimum film forming temperature of 0 ° C., particle size of 0.20 μm and pH of 8.

[Production Example C5]
670 g of water was charged into a 3 L separable round bottom flask equipped with a stirrer, and the temperature was raised to 60 ° C. while stirring.
In addition, 210 g of water is charged into a beaker having an internal volume of 2 L, 20 g of ADEKA rear soap SR10 (manufactured by ADEKA) is charged into the beaker, dissolved, stirred and stirred with methyl methacrylate 520 g, 2-ethylhexyl acrylate 380 g, and BLEMMER (registered trademark) PE350. 100 g (manufactured by NOF Corporation) was charged and emulsified to obtain a monomer emulsion.
Next, 100 g of water was charged into a 200 mL beaker, 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. Subsequently, after confirming heat generation and color tone change (blue white), the monomer emulsion and the remainder of the initiator aqueous solution were dropped into the separable round bottom flask for 3 hours. The reaction temperature at this time was maintained at 65 ° C. After completion of the dropwise addition, the mixture was reacted for 2 hours and cooled, and 20 g of ammonia and 5 g of an antiseptic 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., minimum film-forming temperature of 0 ° C., particle size of 0.25 μm and 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 diameter, pH, and functional group types of the resin emulsions (C1) to (C5).

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

[Acrylic resin emulsion]
Anionic polymer 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 gum 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 Titanium Industry Co., Ltd., iron-zinc composite oxide)
(D-3) Yellow (“LLXLO”, manufactured by Titanium Industry Co., 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) were blended at the blending ratios shown in Table 6 below, and stirred and mixed, whereby emulsion paints (F -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>
An aqueous solution composed of 5 parts by mass of a gelling agent consisting of a 5% by mass aqueous solution of ammonium biborate and 25% by mass of an extender pigment consisting of a dispersion of 4% by mass hydrous magnesium silicate in water, and a 1% by mass aqueous solution of sodium carboxymethylcellulose. After adding 25 parts by mass of the conductive 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) are added to 40 parts by mass of the dispersion medium, stirred with a dissolver, and the emulsion paint is dispersed until the particle size becomes 10 mm. Gel-like particles (G-1) to (G-5) as shown in Table 7 below were obtained. Here, (GX) is gel particles (X: serial number) using (FX) as an emulsion paint. In Table 7 below, the unit of the blending ratio of the emulsion paint is parts by mass.

<Adjustment of multicolored paint: Examples 1 to 5>
18.5 parts by mass of resin emulsion C-1 and 70 parts by mass of gel particles obtained by blending the gel particles (G-1) to (G-5) at a blending ratio shown in Table 8 below, increase in alkali. 1 part by weight of a thickener ("SN thickener 636 (registered trademark)" manufactured by San Nopco), 0.1 part by weight of 25% by weight ammonia water, 6.5 parts by weight of aqueous resin B-1, And 3.9 mass parts of water was stirred with the dissolver, and the multicolored paint of Examples 1-5 was obtained.

<Performance evaluation>
The multicolor pattern paints of the respective examples obtained above 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 part by mass.

[Weather resistance evaluation]
First, a colorful pattern paint was applied to a slate plate to prepare a test specimen for evaluation.
The above test specimen is placed in a test tank of an ultraviolet irradiation machine (“I Super UV Tester W-151 (registered trademark)” manufactured by Iwasaki Electric Co., Ltd.), the black panel temperature is 63 ° C., the humidity is 50% RH, and the coating is performed. Ultraviolet rays were irradiated over 4 hours so that the irradiation intensity of the surface was 1000 mW / cm ² . Thereafter, the temperature in the test tank was set to about 30 ° C. and the humidity was set to 98% RH or more, the inside of the test tank was condensed, and this state was maintained for 4 hours. Then, this irradiation and condensation are defined as one cycle, and after 1000 hours, that is, after 125 cycles, the test specimen is taken out, and the surface of the evaluation test specimen is visually observed to suppress uneven degradation in the evaluation test specimen. Evaluated whether or not. The evaluation criteria at this time were as follows.
○: Almost no discoloration and gloss has not disappeared ×: Large discoloration and gloss has disappeared In the weather resistance evaluation test, among the above evaluation criteria, ○ was acceptable and x was rejected. .

[Rain-stain stain resistance]
An aluminum plate (size: 225 × 100 × 1 mm) is bent at an inner angle of 135 ° along the short side direction at one third of the long side direction, and a solvent-type urethane base coat (two-component) is formed on the convex surface. ) And dried at room temperature for 1 day, and then an aqueous base coating (one liquid) was applied and dried at room temperature for 4 hours to form a base coating film. On this undercoat coating film, the above-mentioned multicolor pattern paint was applied to a thickness of 0.5 mm and dried at room temperature for 1 week to obtain a test specimen. This test specimen was vertically exposed on the south surface within the premises (outdoor) of Fujikura Kasei Co., Ltd. in Sakurada, Kuki City, Saitama Prefecture. And the rain-stain stain | pollution | contamination in the test body after one year was observed visually, and the rain-resistant stain | pollution | contamination resistance of the coating film was evaluated on the following references | standards.
○: Small rain-stain stain △: Rain-stain stain is large ×: Rain-stain stain is large In the rain-stain stain evaluation test, among the above evaluation criteria, ○ is acceptable and △, × is unacceptable. .

[water resistant]
Apply a solvent-type urethane base coat (two liquids) on one side of a slate plate (size 40 x 75 x 3 mm), dry at room temperature for 1 day, and then apply a water base coat (one liquid). Undercoat was dried for 4 hours to form an undercoat film. Next, a multicolor paint was applied onto the undercoat coating film so that the thickness after drying was 0.5 mm, and dried at room temperature for 1 week to form a coating film. Then, after applying an epoxy paint (two liquids) to the back and sides of the slate plate on which the coating film was formed and drying for one day, further applying a fluorine paint (two liquids) on the epoxy paint, A test specimen was dried for 3 days.
After immersing this test body in 40 degreeC pure water for 1 week, the state of the coating film of the test body was observed visually, and the water resistance of the coating film was evaluated on the following reference | standard.
○: No abnormality Δ: Slightly swelled ×: Swelled In the water resistance evaluation test, among the above evaluation criteria, ◯ was accepted and △, x was rejected.

<Adjustment of multicolored paint: Examples 6-13, Comparative Examples 1-10>
A multicolor paint was prepared in the same manner as in Example 1 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 when adjusting the colorful pattern were changed to water-based resins as shown in Tables 9 to 12 below, and the number of added parts was also changed.

  And about Examples 6-13 and Comparative Examples 1-10, the above-mentioned evaluation test was done and the result was shown to the following Tables 9-12.

<Evaluation results>
As in the results shown in Tables 1 to 10, the colored gel particles (A), the aqueous resin (B), and the resin emulsion (C) were each adjusted to have a composition defined in the present invention, and the various coating compositions were prepared. In Examples 1 to 13 in which a coating film was formed using this composition, the weather resistance, rain-stain stain resistance, and water resistance were all evaluated as “◯” (pass: good).

  On the other hand, in Comparative Examples 1 to 10, the composition of at least one of the aqueous resin (B) or the resin emulsion (C) is out of the range defined by 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 defined in the present invention.
In Comparative Example 2, the solid content ratio (B) / (C) is less than the lower limit defined in the present invention, and therefore the rain-stain stain 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 cross-linked, and in particular, the rain-stain stain resistance is inferior.
Since the comparative example 4 has too little monomer (b1) which is a hydrophilic component, it has inferior rain-strip stain resistance.
Since the weight average molecular weight of the aqueous resin (B) is less than the lower limit prescribed | regulated by this invention, the comparative example 5 is inferior in rain-stain stain resistance.

Since Comparative Example 6 does not contain the aqueous resin (B), the rain-stain stain resistance is particularly inferior.
In Comparative Example 7, since the functional group of the aqueous resin (B) and the functional group of the resin emulsion (C) are not cross-linked with each other, they are not cross-linked. Inferior.
Comparative Example 8 is an example in which cracks occurred during the formation of the coating film and the evaluation was impossible, but this is considered to be caused by poor film formation because the aqueous resin (B) had too many cross-linking functional groups.
In Comparative Example 9, since neither the water-based resin (B) nor the resin emulsion (C) has a functional group, they are not crosslinked, and in particular, the rain-stain stain 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 the polymer itself was obtained, and the weight average molecular weight could be measured. When the ammonia water was added, the polymer was not homogenized and could not be used as a coating composition because of its high viscosity state.

  From the results of the examples described above, the multicolored coating composition of the present invention is excellent in weather resistance after film formation, rain-stain stain resistance and water resistance, and is excellent even when exposed outdoors for a long period of time. It is clear that a coating film having a plurality of colors can be obtained, which can maintain the stain resistance.

  The multi-color coating composition of the present invention provides a coating film having a plurality of colors that can maintain excellent stain resistance even when exposed outdoors for a long period of time. It also has excellent weather resistance. Therefore, the multi-color coating composition of the present invention is very suitable for use in forming a coating film having a plurality of colors on various objects to be coated such as buildings.

Claims (4)

A multicolored coating composition comprising at least one colored gel particle (A) encapsulated with a gelled film, an aqueous resin (B), and a resin emulsion (C),
The aqueous resin (B) is a structural unit derived from the monomer (b1) having a hydrophilic group and an ethylenically unsaturated bond, a structural unit derived from the monomer (b2) having a crosslinking group and an ethylenically unsaturated bond, and Consists of a structural unit derived from the monomer (b3) having an ethylenically unsaturated bond other than the monomer (b1) and the monomer (b2),
The proportion of the structural unit derived from the monomer (b1) is 40 to 95% by mass, and the proportion 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 weight,
The aqueous 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 multi-color paint composition, wherein a 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 sulfuric acid group, a morpholino group, and a poly (oxyalkylene) group. The multicolored paint composition according to claim 1.   The multi-color paint 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. .   The functional group capable of reacting with the crosslinking 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 multi-colored paint composition according to any one of claims 1 to 3.