JP2019019270A - Multi-color coating composition - Google Patents

Abstract

To provide a multi-color coating composition from which a coated film that prevents non-uniform degradation and can keep excellent stain resistance even when being exposed to outdoors for a long period of time is obtained.SOLUTION: In a multi-color coating composition, a difference in surface temperatures when irradiated with light of an artificial sun illumination lamp on a predetermined condition after being formed into a coated film between a dark colored emulsion coating material constituting dark colored gel-like particles (A1) and a non-dark colored emulsion coating material constituting non-dark colored gel-like particles (A2) in colored gel-like particles (A) is in a predetermined range, an 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), 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 composed of a variety of paint compositions capable of forming a coating film having a plurality of colors have attracted attention. As such paints, for example, a plurality of colors in an aqueous dispersion medium. Various pattern paints containing gel-like colored particles obtained by dispersing paints have been proposed.

  The multicolored paint as described above includes, for example, dark color gel particles such as black gel particles and non-dark gel particles such as white gel particles, thereby expressing a plurality of colors. What to do is put into practical use. On the other hand, when a coating film formed from a multicolored paint having such a composition is irradiated with light for a long time, the coating film deteriorates, such as cracks and white blur (matte), and dark gel particles The degree of occurrence of deterioration is greatly different between the periphery and the periphery of the non-dark color gel-like particles, and uneven deterioration may occur. In such a multi-color paint including such dark-colored gel particles and non-dark-colored gel particles, in order to suppress non-uniform deterioration, for example, a multi-color paint composition as described in Patent Document 1 is used. Proposed. In the multicolored paint composition described in Patent Document 1, a predetermined color after coating a dark-colored emulsion paint that forms dark-colored gel-like particles and a non-dark-colored paint that forms non-dark-colored gel-like particles. By adjusting the composition of the coating so that the difference in coating surface temperature when irradiated with artificial solar lighting under certain conditions is within the specified range, it is possible to suppress uneven degradation of the coating. Yes.

  Here, in general, a coating film formed from a hydrophobic paint is excellent in water resistance, weather resistance, etc., but hydrophobic dirt easily adheres, and even if the attached dirt is about to flow down with water. There is a tendency not to flow down. 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.

  Patent Document 2 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 stain resistance. It is said to be 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 3 discloses an aqueous coating material 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 4, 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 2014-105228 A 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 even when exposed to the outdoors for a long period of time, it is sufficiently suppressed that non-uniform deterioration occurs, and a coating film capable of maintaining excellent stain resistance. An object of the present invention is to provide a multicolor coating composition capable of obtaining

  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 colored gel particles (A) are a dark gel particle (A1) in which a dark emulsion paint is encapsulated with the gel film, and a non-dark emulsion paint is encapsulated in the gel film. A dark color comprising a non-dark colored gel-like particle (A2) and a dark-colored emulsion paint forming the dark-colored gel particle (A1) applied to the surface of the plate-like body and dried. The surface temperature T _A1 of the dark color coating film and the non-dark color gel-like particles (A2) when the light of a 100 W artificial sunlight illumination lamp is irradiated for 30 minutes from a distance of 20 cm to the system coating film Apply a non-dark color emulsion paint on the surface of the plate and dry it. The non-dark color coating film formed by the difference between the surface temperature T _A2 of the non-dark color coating when irradiated for 30 minutes with light artificial sunlight lamp of 100W at a distance of 20cm ΔT = T _A1 - The value of T _A2 is 20 ° C. or less, and the aqueous resin (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). The ratio of the structural unit derived from the monomer (b1) to the total mass of the structural unit 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 aqueous resin Weight of (B) The weight average molecular weight 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 A multi-color paint composition, wherein the value divided by the mass of the resin emulsion (C) is 0.03 or more and less than 0.11.
[2] The multicolored paint composition according to the above [1], wherein the value of ΔT is 16 ° C. or less.
[3] The above [1], wherein the dark emulsion paint includes a dark pigment containing a heat-shielding pigment, and the content of the heat-shielding pigment in the dark-colored pigment is 33% by mass or more. Or the multicolored coating composition as described in [2].
[4] 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 any one of [1] to [3], which is a seed.
[5] Any of the above [1] to [4], wherein 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 keto group, and an aldehyde group. The multicolored paint composition described in 1.
[6] 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 [1] to [5] above.

  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 ( C) in a composition optimized in a specific range, and in the colored gel-like particles (A), in a predetermined condition after coating the dark-colored emulsion paint and the non-dark-colored emulsion paint. The difference of the coating film surface temperature at the time of irradiating the light with the artificial solar lighting lamp is prescribed | regulated to the predetermined range. Thereby, even when exposed to the outdoors for a long period of time, it is possible to obtain a coating film having a plurality of colors that is sufficiently suppressed from causing non-uniform deterioration and that can maintain excellent stain resistance.

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)”).

  The multicolored coating composition of the present invention is a dark-colored gel in which the component (A), the component (B), and the component (C) each have a composition described below, and are contained in the component (A). Irradiation with an artificial solar illumination lamp under a predetermined condition after forming a coating film between a dark-colored emulsion paint forming a particle-like particle (A1) and a non-dark-colored emulsion paint forming a non-dark color gel-like particle (A2) The difference of the surface temperature when performing is made into a predetermined range, and the value obtained by dividing the mass of the component (B) by the mass of the component (C) is made the predetermined range.

That is, the multicolored paint composition of the present invention comprises the above-described component (A), a dark-colored gel particle (A1) in which a dark-colored emulsion paint is encapsulated with a gelled film, and a non-dark-colored emulsion paint. Are non-dark colored gel-like particles (A2) encapsulated with a gelled film. These dark-colored gel particles (A1) and non-dark-colored gel particles (A2) are prepared by applying a dark-colored emulsion paint forming dark-colored gel-like particles (A1) to the surface of the plate-like body, The surface temperature T _A1 of the dark-colored coating film when irradiated with light of a 100 W artificial sunlight illumination lamp from a distance of 20 cm for 30 minutes to the dried dark-colored coating film, and non-dark color gel-like particles ( When the non-dark-colored coating film formed by applying the non-dark-colored emulsion paint of A2) to the surface of the plate-like body and drying is irradiated with light of a 100 W artificial sunlight illumination lamp from a distance of 20 cm for 30 minutes The difference ΔT = T _A1 −T _{A2 from} the surface temperature T _A2 of the non-dark color coating film is 20 ° C. or less.

Furthermore, 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.
As described above, the component (A) includes the dark color gel particles (A1) and the non-dark color gel particles (A2).
The component (A) further contains a color pigment, a resin emulsion, and a hydrophilic colloid-forming substance.

[Dark color gel particles (A1)]
As described above, the dark-colored gel particles (A1) are gel-like particles in which the dark-color emulsion paint is encapsulated with a gelled film, and the lightness according to the Munsell value is 4 or less.
The dark color emulsion paint includes a dark color pigment, a resin emulsion, and a hydrophilic colloid-forming substance.

(Dark color pigment)
The dark pigment may be any pigment that can reduce the Munsell value of the dark gel particles to 4 or less together with the resin emulsion and the hydrophilic colloid-forming substance. Examples of such dark pigments include non-thermal pigments such as carbon black and thermal pigments. These can be used alone or in combination of two or more. Here, the heat-shielding pigment is a pigment that does not absorb light in the near-infrared wavelength region (wavelength: 780 nm to 2500 nm) or has a small light absorption rate in the near-infrared wavelength region (wavelength: 780 nm to 2500 nm). Point to.

The thermal barrier pigment includes an inorganic thermal barrier pigment and an organic thermal pigment.
Examples of inorganic heat shielding pigments include titanium oxide, magnesium oxide, barium oxide, calcium oxide, zinc oxide, zirconium oxide, yttrium oxide, indium oxide, sodium titanate, silicon oxide, nickel oxide, manganese oxide, chromium oxide, Metal oxide pigments such as iron oxide, copper oxide, cerium oxide, aluminum oxide; iron oxide-manganese oxide, iron oxide-chromium oxide (for example, “Daipyroxide Side Color Black # 9595” manufactured by Dainichi Seika Co., Ltd., "Black 6350" manufactured by Asahi Kasei Kogyo Co., Ltd.), iron oxide-cobalt oxide-chromium oxide (for example, "Daipyroxide Side Color Brown # 9290" and "Daipyroxide Side Color Black # 9590" manufactured by Dainichi Seika Co., Ltd.) , Copper oxide-magnesium oxide (for example, Dainichi Seika Co., Ltd. Manufactured by “Daipyroxide Color Black # 9598”), manganese oxide-bismuth oxide (for example, “Black 6301” manufactured by Asahi Kasei Kogyo Co., Ltd.), manganese oxide-yttrium oxide (for example, “Black 6303 manufactured by Asahi Kasei Kogyo Co., Ltd.) )), Etc .; metal pigments such as silicon, aluminum, iron, magnesium, manganese, nickel, titanium, chromium and calcium; and iron-chromium, bismuth-manganese, iron-manganese, manganese-yttrium, etc. Examples include alloy pigments. These can be used alone or in combination of two or more.

  Examples of organic heat-shielding pigments include azo pigments, azomethine pigments, lake pigments, thioindigo pigments, anthraquinone pigments (antanthrone pigments, diaminoanthraquinonyl pigments, indanthrone pigments, flavanthrone pigments, anthra pigments). Pyrimidine pigments, etc.), perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine pigments, quiniphthalone pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, etc. It is done. These can be used alone or in combination of two or more.

  The dark-colored emulsion paint may contain a non-dark-colored pigment such as titanium oxide or phthalocyanine copper as long as the Munsell value of the dark-colored gel particles is 4 or less.

Here, the content of the heat shielding pigment in the dark pigment is not particularly limited, but is preferably 33% by mass or more.
In this case, since the increase in the surface temperature of the dark-colored gel-like particles due to light is particularly sufficiently suppressed, the multicolor pattern paint can particularly sufficiently suppress non-uniform deterioration in the multicolor pattern paint film.
The content of the heat-shielding pigment in the dark pigment is more preferably 50% by mass or more, still more preferably 70% by mass or more, and most preferably 100% by mass.

  The content of the dark pigment in the dark emulsion paint is not particularly limited, but is usually 10 to 200 parts by weight, preferably 50 to 150 parts by weight with respect to 100 parts by weight of the resin component. Part. Here, the resin component refers to the resin solid content in the resin emulsion.

(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 in the dark emulsion paint, an acrylic resin emulsion is particularly preferable among the above.

  Further, the content of the resin emulsion in the dark emulsion paint 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 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. As the hydrophilic colloid-forming substance in the dark emulsion paint, an aqueous solution of guar gum is particularly preferable 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 in the dark emulsion paint is not particularly limited, but usually 0.05 to 5.0 with respect to 100 parts by mass of the resin emulsion. It is a mass part, Preferably it is 0.1-3.0 mass part.

(Other ingredients)
The dark color emulsion paint further contains additives such as extender pigments such as hydrous magnesium silicate, thickeners, dispersants, antifoaming agents, preservatives, and leveling agents as necessary. May be.

(Encapsulation with gelled membrane)
In the present invention, the dark color emulsion paint is encapsulated with a gelled film. That is, the dark-colored gel particles (A1) are encapsulated by encapsulating a dark-colored emulsion paint with a gelled film.
For example, the gelled film is prepared by mixing a dark color 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 with a 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.

[Non-dark color gel particles (A2)]
The non-dark color gel particles (A2) are non-dark color emulsion paints encapsulated with a gelled film as described above, and are gel-like particles having a lightness by Munsell value greater than 4. .
The non-dark color emulsion paint includes a non-dark color pigment, a resin emulsion, and a hydrophilic colloid-forming substance.

(Non-dark pigment)
The non-dark color pigment may be any one that makes the Munsell value of the non-dark color gel-like particles (A2) larger than 4 together with the resin emulsion and the hydrophilic colloid-forming substance. Examples of such non-dark color pigments include white pigments such as titanium oxide and blue pigments such as phthalocyanine copper. These can be used alone or in combination of two or more. The content of the non-dark color pigment in the dark color emulsion paint is not particularly limited, but is usually 10 to 200 parts by weight, preferably 50 to 100 parts by weight with respect to 100 parts by weight of the resin component. 150 parts by mass. Here, the resin component refers to the resin solid content in the resin emulsion.

(Resin emulsion)
In the non-dark color emulsion paint, the same resin emulsion as that contained in the dark color emulsion paint can be used as the resin emulsion. Although the content rate of the resin emulsion in a non-dark color emulsion coating material is not specifically limited, Usually, it is 20-70 mass%, Preferably it is 30-50 mass%.

(Hydrophilic colloid-forming substance)
In the non-dark color emulsion paint, the same hydrophilic colloid-forming substance as the hydrophilic colloid-forming substance contained in the dark color emulsion paint can be used. The content of the hydrophilic colloid-forming substance in the non-dark color emulsion paint is not particularly limited and may be, for example, 0.5 to 5.0% by mass.

(Other ingredients)
In the above non-dark color emulsion paint, as in the case of the dark color emulsion paint, if necessary, further extender pigments such as hydrous magnesium silicate, thickener, dispersant, antifoaming agent, preservative And additives such as leveling agents may be included.

(Encapsulation with gelled membrane)
In the present invention, the non-dark color emulsion paint is encapsulated with a gelled film as in the case of the dark color emulsion paint. That is, the non-dark color gel particles (A2) are encapsulated by encapsulating a dark color emulsion paint with a gelled film.
For example, the gelled film is a mixture of a non-dark emulsion paint containing a hydrophilic colloid-forming substance and a dispersion medium containing a gelling agent as described above, and the paint is dispersed while stirring with a disperser such as a dissolver. And the gelling agent in the dispersion medium and the hydrophilic colloid-forming substance are reacted with each other.

<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 multicolored coating composition of the present invention comprises the component (A) as described above (colored gel particles (A): dark color gel particles (A1) and non-dark color gel particles (A2)), It can adjust by stirring (B) component (aqueous resin (B)) and (C) component (resin emulsion (C)) using dispersers, such as a dissolver, for example. 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 coating composition of the present invention, at least one or more colored gel particles (A) in which an emulsion coating is encapsulated with a gelled film, an aqueous resin (B), and a resin emulsion (C) is included in a composition optimized in a specific range, and in the colored gel particles (A), predetermined conditions after the coating of the dark emulsion paint and the non-dark emulsion paint are applied. The difference in the coating film surface temperature when irradiating with the light from the artificial solar illumination lamp is defined within a predetermined range. Thereby, even when exposed to the outdoors for a long period of time, it is possible to obtain a coating film having a plurality of colors that is sufficiently suppressed from causing non-uniform deterioration and that can maintain excellent stain resistance.

  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 multicolored paint composition of the present invention, even when exposed to the outdoors for a long period of time, the occurrence of non-uniform deterioration is sufficiently suppressed, and excellent stain resistance can be maintained. Possible coatings with multiple colors are obtained.
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-7), the dispersing agent shown below, and water are mix | blended in the compounding 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-7) 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) Thermal barrier pigment black ("Daipyroxide Color Black 9595 (registered trademark)", manufactured by Dainichi Seika Co., Ltd., iron-chromium composite oxide)
(D-2) Thermal barrier pigment brown ("Daipyroxide Side Color Brown 9290 (registered trademark)", manufactured by Dainichi Seika Co., Ltd., iron-cobalt-chromium composite oxide)
(D-3) Black (“Mitsubishi Carbon Black MA-100 (registered trademark)”, manufactured by Mitsubishi Chemical Corporation, carbon black)
(D-4) Brown ("T-10", manufactured by Titanium Industry Co., Ltd., iron-zinc composite oxide)
(D-5) Blue ("Cyanine Blue 5187 (registered trademark)", manufactured by Dainichi Seika Co., Ltd., phthalocyanine copper)
(D-6) Yellow (“LLXLO”, manufactured by Titanium Industry Co., Ltd., iron oxide)
(D-7) 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-7) were blended at the blending ratios shown in Table 6 and Table 7 below, and stirred and mixed, as shown in Table 6 and Table 7 below. Emulsion paints (F-1) to (F-19) were obtained. In Tables 6 and 7 below, the unit of the blending ratio of the monochromatic emulsion paint is parts by mass.

(Surface temperature measurement)
The dark-colored emulsion paints (F-1) to (F-16) obtained as described above were used to form a transparent polycrystal having a thickness of 5 mm so that the thickness of the coating film became 50 μm with a doctor blade. A test specimen was prepared by applying onto a vinyl chloride plate and drying. And this test body was arrange | positioned in the distance of 20 cm from the 100W artificial solar illuminating lamp ("XC-100A", the product made from Celic), and light was irradiated for 30 minutes in this state. And the temperature of the surface in a test body was measured with the thermometer ("IT-540", Horiba, Ltd. make), and this value was made into _TA1 (degreeC). On the other hand, the surface temperature of the test specimens prepared by the same method as described above using (F-17) to (F-19), which are non-dark color emulsion paints, was measured as described above. This value was _designated as T _A2 (° C.). These results are shown in Table 6 and Table 7 below.

<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-19) are added to 40 parts by mass of the dispersion medium, and stirred with a dissolver. The emulsion paint is dispersed until the particle size becomes 10 mm. Gel-like particles (G-1) to (G-19) were obtained. Here, (GX) is gel particles (X: serial number) using (FX) as an emulsion paint.
In Tables 6 and 7, the lightness (Munsell value) of the gel particles (G-1) to (G-19) is described in the columns of emulsion paints (F-1) to (F-19), respectively. doing.

<Adjustment of multicolored paint: Examples 1-13, Comparative Examples 1-3>
18.5 parts by mass of the resin emulsion C-1 in the blending ratios shown in Table 8 and Table 9 below, the dark-colored gel particles (G-1) to (G-16) and non-dark-colored gel particles ( 70 parts by mass of gel particles formed by blending G-17) to (G-19) and 1 part by mass of a thickener consisting of an alkali thickener ("SN thickener 636 (registered trademark)" manufactured by San Nopco) By stirring 0.1 parts by mass of 25% by mass ammonia water, 6.5 parts by mass of aqueous resin B-1 and 3.9 parts by mass of water with a dissolver, Examples 1 to 13 and Comparative Examples 1 to 1 were stirred. 3 colorful pattern paints were obtained.

<Performance evaluation>
The multicolor pattern paints of the respective examples obtained above were evaluated as described below. These evaluation results are shown in Table 8 and Table 9 below. In Tables 8 and 9 below, the unit of the blending ratio of the gel-like particles is part by mass.

[Heat insulation evaluation]
Based on the following formula {ΔT _A = T _A1 −T _A2 } from the surface temperatures T _A1 (° C.) and T _A2 (° C.) shown in Tables 6 and 7 for the colorful pattern paints of the examples and comparative examples. calculates a difference [Delta] T _a of the surface temperature, the results are shown in Table 8 and Table 9. At this time, when there are a plurality of T _A1 and T _A2 , a value that maximizes ΔT _A was used.

[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.
◎: No cracks are observed around the dark-colored gel particles and the gloss is not lost ○: No cracks are observed around the dark-colored gel particles, but the gloss is slightly disappeared △: Dark Very fine cracks are observed around the color gel particles. ×: Large cracks are scattered along the dark gel particles. In the weather resistance evaluation test, among the above evaluation criteria, ◎, ○, △. Was accepted 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. .

[Heat insulation function after contamination]
Based on the surface temperature measurement method described above, the surface temperature of the coated plate used in the above-described rain-strip stain resistance evaluation was measured. This measurement is performed before and after the rain-resistant stain resistance evaluation test, where the surface temperature before contamination is T _B0 (° C.) and the surface temperature after contamination is T _B1 (° C.), and the following equation {ΔT _B = T _B1 −T Based on _B0 }, the difference ΔT _{B in} surface temperature was calculated.

[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.

<Evaluation results of Examples 1 to 13 and Comparative Examples 1 to 3>
As shown in the results shown in Table 8 and Table 9, the colored gel particles (A), the aqueous resin (B), and the resin emulsion (C) are respectively contained in compositions optimized in specific ranges, and colored. In the gel-like particles (A), the difference in the coating surface temperature between the dark-colored emulsion paint and the non-dark-colored emulsion paint when the film is irradiated with light from an artificial solar illuminating lamp under predetermined conditions after the coating is formed is within a predetermined range. In Examples 1 to 13 in which the multicolor coating composition was prepared and a coating film was formed using this composition, the rain-stain stain resistance and the water resistance evaluation were “◯” (pass), and In addition, the evaluation of weather resistance (inhibition effect of uneven degradation) was）, ○, or Δ (pass). That is, all the multicolored paint films formed using the multicolored paints of Examples 1 to 13 reached the acceptance criteria in all the evaluation items.

On the other hand, the multicolored pattern coating film formed using the multicolored pattern paints of Comparative Examples 1 to 3 was evaluated as “○” (passed) in terms of rain-stain stain resistance and water resistance, but it was converted into a coating film. Since the difference in the surface temperature of the coating film was too great when the artificial solar illumination light was irradiated under certain conditions later, all evaluations of weather resistance (inhibition effect of non-uniform degradation) were all “x” (failed). , Did not reach the acceptance criteria.
From the above results, according to the multicolored paints of Examples 1 to 13 that satisfy the provisions of the present invention, in the coating film formed from the multicolored paint including dark gel particles and non-dark gel particles. It was confirmed that the non-uniform deterioration could be sufficiently suppressed and the weather resistance was excellent.

<Adjustment of multicolored paint: Examples 14-21, Comparative Examples 4-13>
A multicolored paint was prepared by the same method as in Example 12 except that each composition was changed to the composition shown in Tables 10 to 13 below. At this time, the water-based resin B-1 and the resin emulsion C-1 used for adjusting the colorful pattern were changed to water-based resins as shown in Tables 10 to 13 below, and the number of added parts was also changed.

  And also about Examples 14-21 and Comparative Examples 4-13, the same evaluation test was done above, and the results are shown in Tables 10-13 below.

<Evaluation results of Examples 14 to 21 and Comparative Examples 4 to 13>
As shown in the results shown in Tables 10 to 13, each of the colored gel particles (A), the aqueous resin (B), and the resin emulsion (C) is optimized in a specific range, and the colored gel In the particle-like particles (A), the difference in the coating surface temperature between the dark emulsion paint and the non-dark emulsion paint when irradiated with light from an artificial solar illumination lamp under a predetermined condition after forming the coating film is within a predetermined range. In Examples 14 to 21 in which the prepared multicolor coating composition was prepared and a coating film was formed using this composition, the evaluation of the weather resistance (the effect of suppressing non-uniform deterioration) was ◎ (pass), In addition, the rain-stain stain resistance and water resistance were evaluated as “◯” (passed). That is, all the multicolored paint films formed using the multicolored paints of Examples 1 to 13 reached the acceptance criteria in all the evaluation items.

  On the other hand, in Comparative Examples 4 to 13, the composition of at least one of the aqueous resin (B) or the resin emulsion (C) is outside the range defined by the present invention, or the solid content ratio ( Examples where B) / (C) is outside the specified range of the present invention, or the difference in coating film surface temperature when irradiated with light from an artificial solar illuminating lamp under predetermined conditions after coating is defined by the present invention. This is an example that is out of range.

Comparative Example 4 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 5, although the weather resistance and water resistance were good, the solid content ratio (B) / (C) was less than the lower limit prescribed in the present invention, so that the rain-stain stain resistance was poor. .
In Comparative Example 6, although the weather resistance was good, 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, rain-stain stain resistance. Is inferior.
Although the comparative example 7 had favorable weather resistance, since the monomer (b1) which is a hydrophilic component is too few, it is especially inferior in rain-stain stain resistance.
Although the comparative example 8 had favorable weather resistance, since the weight average molecular weight of aqueous resin (B) is less than the minimum prescribed | regulated by this invention, rain-stain stain | pollution | contamination property is especially inferior.

Although the comparative example 9 had good weather resistance and water resistance, it did not contain the water-based resin (B), and therefore the rain-stain stain resistance was particularly poor.
In Comparative Example 10, although the weather resistance and water resistance were good, the functional group possessed by the aqueous resin (B) and the functional group possessed by the resin emulsion (C) were not cross-linked with each other. Does not crosslink, and in particular, the rain-stain stain resistance is poor.
Comparative Example 11 is an example in which cracking occurred during the formation of the coating film and evaluation was impossible, but this is considered to be because film formation failure occurred because the aqueous resin (B) had too many cross-linking functional groups.
In Comparative Example 12, although the weather resistance was good, since neither the aqueous resin (B) nor the resin emulsion (C) has a functional group, they do not crosslink, and in particular, rain-stain stain resistance. Is inferior.
Comparative Example 13 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 paint composition of the present invention is excellent in weather resistance after film formation, rain-stain stain resistance and water resistance, and even when exposed outdoors for a long period of time, It is apparent that a coating film having a plurality of colors can be obtained, in which the occurrence of non-uniform deterioration is sufficiently suppressed and excellent stain resistance can be maintained.

  The multi-color coating composition of the present invention can provide a coating film having a plurality of colors, which is capable of suppressing uneven deterioration even when exposed outdoors for a long period of time and maintaining excellent stain resistance. Furthermore, this coating film is also excellent in water resistance and 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 (6)

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 colored gel particles (A) are dark gel emulsion particles (A1) in which a dark emulsion paint is encapsulated with the gel film, and non-dark emulsion paints are encapsulated in the gel film. Non-dark colored gel-like particles (A2),
The dark-colored emulsion paint that forms the dark-colored gel particles (A1) is applied to the surface of the plate-like body and dried. and a surface temperature T _A1 of the dark color coating when irradiated for 30 minutes, coated with a non-dark color emulsion paint which forms the non-dark color gelling particles (A2) on the surface of the plate, dried The difference ΔT = T _A1 − from the surface temperature T _A2 of the non-dark color coating film when the non-dark color coating film is irradiated with light of a 100 W artificial sunlight illumination lamp from a distance of 20 cm for 30 minutes. The value of T _A2 is 20 ° C. or less,
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 multi-colored paint composition according to claim 1, wherein the value of ΔT is 16 ° C. or less. The dark color emulsion paint comprises a dark color pigment containing a heat shielding pigment,
The multi-color paint composition according to claim 1 or 2, wherein a content of the heat shielding pigment in the dark pigment is 33% by mass or more.   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 as described in any one of Claims 1-3.   The said bridge | crosslinking group is at least 1 sort (s) chosen from the group which consists of a glycidyl group, a carboxyl group, an acid anhydride group, an alkoxy silyl group, a keto group, and an aldehyde group. Multicolor paint composition.   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-color paint composition according to any one of claims 1 to 5.