JP5219861B2 - Heat-reflective coating and its coating method - Google Patents

Description

  The present invention relates to a heat ray highly reflective coating and a coating method thereof.

  Dark-colored paint is often used on metal folded-plate roofs in factories, etc., and the temperature of the roof rises to 70 ° C. or more, especially in summer, which is one of the factors that cause the heat island phenomenon. In addition, as the room temperature rises in a building or the like, it becomes a factor that a large cooling load is applied. Accordingly, development of coating compositions that can form a coating film that reflects heat rays (infrared rays) derived from sunlight and suppresses temperature rise has been performed.

Patent Document 1 discloses a heat ray highly reflective coating composition containing a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn, a silicate compound, and a resin.
The coating film formed from the heat ray highly reflective coating composition of Patent Document 1 reflects heat rays with high efficiency by the composite metal oxide pigment, and can suppress an increase in temperature. In addition, since the coating film contains a silicate compound, the coating film is excellent in stain resistance, and the reflectance of the coating film is prevented from being contaminated and the reflectance is lowered. it can.

The heat ray highly reflective coating composition of Patent Document 1 is usually used as a solvent-based coating composition because it is excellent in stain resistance and weather resistance. However, since the solvent-based coating composition emits volatile organic compounds (VOC) such as toluene and xylene, there is an adverse effect on the working environment and the global environment during coating. In addition, it is difficult to recoat with a water-based paint at the time of renovation.
Accordingly, in consideration of the environment, it is conceivable to use the heat ray highly reflective coating composition of Patent Document 1 as an aqueous coating composition. In this case, the stability of the silicate compound when used as a water-based coating is low, and the coating The storage stability of the composition is reduced. Therefore, it is difficult to obtain a coated product having high heat ray reflection performance and its durability with an aqueous coating composition.

Patent Document 2 discloses a low-staining agent comprising a polymer containing one or more repeating units having two or more hydroxy groups as an aqueous coating composition capable of forming a coating film excellent in stain resistance. An aqueous fluorine-containing resin coating composition is shown.
In Patent Document 2, there is no particular description about the pigment used in the coating composition, but when a white pigment is used, it is obtained because it is white and has a certain degree of heat ray reflectivity. The coated film is also considered to have a certain degree of heat ray reflectivity. However, when a dark color pigment is used, the coating film formed from the coating composition does not have heat ray reflection performance, but rather absorbs heat rays because it is a dark color system. A rise in temperature of a coated article having a coating film formed from the coating composition is a serious problem.

JP 2008-106092 A JP 2003-55617 A

  The present invention is a coating film formed from a water-based paint composition even in a dark color paint, can reflect heat rays with a high reflectance, has excellent stain resistance, and suppresses a decrease in reflectance due to contamination. It is an object of the present invention to provide a highly heat-reflective coated product having a coating film that can maintain heat-reflecting performance for a long period of time, and a coating method thereof.

The present invention employs the following configuration in order to solve the above problems.
[1] A coated article having a coating layer (X) and a coating layer (Y) formed on the coating layer (X) on the object to be coated, the coating layer (X ) Is an oxide of bismuth (hereinafter referred to as “Bi”) and an oxide of yttrium (hereinafter referred to as “Y”) and an oxide of manganese (hereinafter referred to as “Mn”). Is a layer formed from a coating composition containing a composite metal oxide pigment containing, a resin (x), and water and no silicate compound, and two coating layers (Y) Formed from a coating composition containing a non-fluorine polymer containing 10% by mass or more of the above polymerized units having a hydroxy group, the resin (y), and water, and containing no silicate compound. Ri layer der to be, the resin (x) is a fluorine resin, an alkyd resin, Aminoa Kid resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone modified polyester resin, acrylic silicone resin, and silicone resin The resin (y) is a fluorine resin, alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone. modified polyester resins, heat ray high-reflection coated article, wherein at least one Tanedea Rukoto selected from the group consisting of acrylic silicone resin and silicone resin.
[2] The heat ray highly reflective coating according to [1], wherein a part or all of the resin (y) is a fluororesin.
[3] The heat ray highly reflective coated article according to [1], wherein a part or all of the resin (x) is a fluororesin and a part or all of the resin (y) is a fluororesin.
[ 4 ] The heat ray highly reflective coated article according to any one of [1] to [3], wherein the non-fluorine polymer further has a polymer unit having a crosslinkable functional group excluding the two or more hydroxy groups.
[ 5 ] The heat ray highly reflective coated article according to any one of [1] to [4], wherein the coating layer (Y) is crosslinked with a crosslinking agent.
[ 6 ] The heat ray highly reflective coated article according to any one of [1] to [ 5 ], wherein the coating layer (Y) further contains an ultraviolet absorber .
[ 7 ] Any of [1] to [ 6 ], wherein the content of the composite metal oxide pigment in the coating layer (X) is 0.1% by mass or more based on the solid content of the resin (x). The heat ray highly reflective paint described in Crab.
[ 8 ] A composite metal oxide pigment containing at least one of Bi oxide and Y oxide and Mn oxide, resin (x), and water on the object to be coated. Then, a coating layer (X) formed from the coating composition (X1) containing no silicate compound is formed, and polymerization units having two or more hydroxy groups are completely polymerized on the coating layer (X). Coating layer (Y) formed from a coating composition (Y1) containing a non-fluorine polymer containing 10% by mass or more based on a unit, a resin (y), and water and not containing a silicate compound forming, said resin (x) is a fluorine resin, an alkyd resin, an amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resins, polyvinyl acetate resins, acryl resins, vinyl chloride resins, phenol resins, shea The resin (y) is at least one selected from the group consisting of corn-modified polyester resin, acrylic silicone resin, and silicone resin, and the resin (y) is fluororesin, alkyd resin, aminoalkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resins, polyvinyl acetate resins, acryl resins, vinyl chloride resins, phenol resins, silicone-modified polyester resin, the heat ray high-reflection coating, wherein at least one Tanedea Rukoto selected from the group consisting of acrylic silicone resin and silicone resin How to paint things.
[9] The method for coating a heat ray highly reflective coating according to [8], wherein a part or all of the resin (y) is a fluororesin.
[10] The method for coating a heat ray highly reflective coating according to [8], wherein a part or all of the resin (x) is a fluororesin and a part or all of the resin (y) is a fluororesin.
[ 11 ] The heat ray highly reflective coating material according to any one of [ 8 ] to [10], wherein the non-fluorine polymer further has a polymer unit having a crosslinkable functional group excluding the two or more hydroxy groups. How to paint.
[ 12 ] The coating method of the heat ray highly reflective coating according to any one of [ 8 ] to [11], wherein the coating composition (Y1) further contains a crosslinking agent.
[ 13 ] The method for coating a highly heat-reflective coating according to any one of [ 8 ] to [ 12 ], wherein the coating composition (Y1) further contains an ultraviolet absorber.
[ 14 ] Any of [ 8 ] to [ 13 ], wherein the content of the composite metal oxide pigment in the coating composition (X1) is 0.1% by mass or more based on the solid content of the resin (x). A method for applying a heat-reflective coated object according to crab.

The heat ray highly reflective coating of the present invention is a coating film formed from an aqueous coating composition, which can reflect heat rays with high reflectivity, and has excellent contamination resistance and can maintain heat ray reflecting performance for a long period of time. have.
Further, since the coating method of the present invention uses an aqueous heat ray high reflection coating composition, there is almost no emission of volatile organic compounds (VOC), and the working environment and the global environment during coating are not adversely affected.
Furthermore, the coating method of the present invention is capable of reflecting heat rays with a high reflectivity, and has excellent anti-contamination properties, so that a decrease in reflectivity due to contamination is suppressed, and a heat ray height having a coating film that can maintain heat ray reflection performance for a long period of time. A reflective coating can be obtained.

<High heat reflective coating>
The heat ray highly reflective coating product of the present invention (hereinafter referred to as “the present coating product”) is a coating layer (X) and a coating layer formed on the coating layer (X). (Y).
The coating layer (X) comprises a composite metal oxide pigment (hereinafter referred to as “composite pigment M”) containing at least one of Bi oxide, Y oxide, and Mn oxide, and a resin. It is a layer formed from the coating composition containing (x).
The coating layer (Y) is made of a coating composition containing a non-fluorine polymer containing 10% by mass or more of polymerized units having two or more hydroxy groups with respect to all polymerized units, and a resin (y). It is a layer to be formed.

[To be painted]
The material to be coated is not particularly limited. For example, inorganic materials such as concrete, natural stone, and glass; metals such as iron, stainless steel, aluminum, copper, brass, and titanium; wood; synthetic organic materials such as plastic and rubber The to-be-coated object is mentioned. Other coating films, adhesive layers, and the like may be formed on the surface of the object to be coated. The material of the object to be coated may be fiber reinforced plastic, resin reinforced concrete, fiber reinforced concrete or the like which is an organic-inorganic composite material. Moreover, it can be used also for the surface material and back sheet | seat for solar cell modules.

  The object to be painted may be movable or real estate. For example, industrial equipment such as automobiles, trains, aircraft and other transportation equipment, bridge members, steel towers, civil engineering members, waterproof sheets, tanks, pipes, etc. Buildings, building exteriors, doors, window gates, monuments, building components such as poles, road median strips, road components such as guardrails, communication equipment, electrical and electronic components, buildings, chemical plants, factories, warehouses , Buildings such as chimneys and bridges.

[Coating layer (X)]
The coating layer (X) is a coating composition containing a composite metal oxide pigment containing at least one of Bi oxide, Y oxide and Mn oxide, and resin (x). Formed on the object to be coated. The coating layer (X) is a layer formed on part or all of one surface of the surface of the object to be coated, and is preferably formed on the surface of the object to be irradiated with sunlight. The coating layer (X) is preferably formed on the surface of the object to be coated directly or via a layer formed by pretreatment such as primer treatment or application of a primer. More preferably. That is, it is preferable that the coating layer (X) is formed on the surface subjected to pretreatment on the surface of the object to be coated.

(Pigment)
The composite pigment M plays a role of imparting heat ray reflection performance to the coating film having the coating film layer (X) and the coating film layer (Y).
The composite pigment M contains an oxide of Bi, an oxide of Y, and an oxide of Mn. That is, the composite pigment M is an embodiment containing an oxide of Bi, an oxide of Y and an oxide of Mn, an embodiment containing an oxide of Bi and an oxide of Mn, or an oxide of Y and an oxide of Mn. It is either of the aspects containing.

The content of the Mn oxide in the composite pigment M is preferably 5 to 65% by mass, and more preferably 10 to 50% by mass. When the content of the Mn oxide is 5% by mass or more, a sufficient heat ray reflection effect is easily obtained.
The composite pigment M preferably uses an oxide obtained by firing a mixture of at least one of Bi and Y and Mn at a firing temperature of 700 ° C. or higher. Note that Bi, Y, and Mn used as raw materials for the composite pigment M are not limited to simple substances, and may be compounds such as oxides.

The average particle size of the composite pigment M is preferably 0.1 μm to 30 μm. However, the average particle diameter is a value obtained by averaging the particle diameters of arbitrarily selected particles. If the average particle diameter of the composite pigment M is 30 μm or less, it is easy to suppress a decrease in gloss of the formed coating film.
Examples of commercially available composite pigments M that satisfy the condition of an average particle size of 0.1 μm to 30 μm include black 6303 and black 6301 (above, manufactured by Asahi Kasei Kogyo Co., Ltd.).

The composite pigment M is preferably a black-colored pigment, and can be mixed and dispersed in the resin.
When only the composite pigment M is used as the pigment, the content of the composite pigment M in the coating layer (X) is preferably 0.1% by mass or more based on the solid content of the resin (x). More preferably, it is 0.1-200 mass%, and it is further more preferable that it is 10-100 mass%. When the content of the composite pigment M is 0.1% by mass or more, a sufficient heat ray reflection effect is easily obtained. Moreover, if the said content of the composite pigment M is 200 mass% or less, it will be easy to suppress that the glossiness of the coating film formed falls.

The coating layer (X) may contain other colored pigments in addition to the composite pigment M for the purpose of adjusting the color tone according to the application and purpose.
Other coloring pigments include, for example, inorganic pigments such as titanium oxide, red pepper, ocher, calcium carbonate, aluminum silicate, white carbon, finely divided silicic acid, phthalocyanine blue, phthalocyanine green, quinacridone, isoindolinone, benzimidazolone. And organic pigments such as dioxazine.
However, from the viewpoint of making better use of the heat ray reflection performance, it is preferable to adjust the pigment composition so that the surface of the present paint has a dark color tone. Specifically, it is preferable to adjust so that the lightness L ^* prescribed | regulated to JISZ8729 of this coating material surface may be set to 5-80, and it is more preferable to adjust so that it may become 10-60.

  When other colored pigments are contained in addition to the composite pigment M, the content of the entire pigment in the coating layer (X) is 0.1 to 200% by mass with respect to the solid content of the resin (x). It is preferably 10 to 100% by mass. If the said content of the whole pigment is 0.1 mass% or more, it will be easy to suppress that content of the composite pigment M decreases too much and a heat ray reflective effect falls. Moreover, if the said content of the whole pigment is 200 mass% or less, it will be easy to suppress that the glossiness of the coating film formed falls.

(Resin (x))
The coating layer (X) contains the resin (x) together with the composite pigment M.
As resin (x), it is preferable that the one part or all part is a fluororesin. By using a fluororesin, a coating film having better weather resistance can be obtained.
As the fluororesin, a fluoroolefin copolymer is preferable. The fluoroolefin copolymer is a copolymer of a fluoroolefin and another copolymerizable monomer copolymerizable with the fluoroolefin.

Examples of the fluoroolefin composing the fluoroolefin copolymer include C2-C3 fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, and vinyl fluoride.
The proportion of the polymer units based on the fluoroolefin in the fluoroolefin copolymer is preferably 20 to 70 mol% from the viewpoint of easily imparting sufficient weather resistance to the coating film.

  As another copolymerizable monomer constituting the fluoroolefin copolymer, a vinyl monomer, that is, a compound having a carbon-carbon double bond is preferable. Examples of vinyl monomers include vinyl ether, allyl ether, carboxylic acid vinyl ester, carboxylic acid allyl ester, and olefin.

Examples of vinyl ethers include cycloalkyl vinyl ethers such as cyclohexyl vinyl ether, alkyl vinyl ethers such as nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, and t-butyl vinyl ether.
Examples of the allyl ether include alkyl allyl ethers such as ethyl allyl ether and hexyl allyl ether.

Examples of the carboxylic acid vinyl ester include vinyl esters of carboxylic acids such as acetic acid, butyric acid, pivalic acid, benzoic acid, and propionic acid. Moreover, you may use the commercially available Veova-9, Veova-10 (above, Shell Chemical Co., Ltd.) etc. as a vinyl ester of the carboxylic acid which has a branched alkyl group.
Examples of the carboxylic acid allyl ester include allyl esters of the carboxylic acid.
Examples of the olefin include ethylene, propylene, and isobutylene.
Another copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

Further, the fluoroolefin copolymer preferably has a crosslinkable functional group capable of forming a crosslink by a crosslinker B described later. Examples of the crosslinkable functional group include a crosslinkable functional group generally used in a crosslinking reaction, and specifically include an aldehyde carbonyl group, a ketonic carbonyl group, a hydroxy group, a carboxy group, a sulfo group, and phosphoric acid. Residues, epoxy groups, amino groups, oxazoline residues, amide groups, alkoxy groups, hydrolyzable silyl groups, hydroxymethyl groups, zwitterionic groups, and cyano groups.
Examples of the method for introducing the crosslinkable functional group into the resin (x) include a method in which a monomer having a crosslinkable functional group is copolymerized in advance. Examples of the monomer that introduces the crosslinkable functional group into the resin (x) include the same monomers as the monomer (β1) described later.

Examples of the monomer having a hydroxymethyl group include N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N, N-bis (hydroxymethyl) acrylamide, N, N-bis (hydroxymethyl) methacrylamide, hydroxy Examples include methyl acrylate, hydroxymethyl methacrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate.
Examples of the monomer having a zwitterion include phosphorylcholine group-containing (meth) acrylate.
Examples of the monomer having a cyano group include (meth) acrylonitrile, crotonnitrile, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, and cinnamic nitrile. Is mentioned.
Moreover, as a monomer which introduce | transduces a crosslinkable functional group, in addition to the monomer quoted as the monomer (β1), vinyl ethers, allyl ethers, vinyl esters, allyl esters having a crosslinkable functional group Are also preferred.
As the monomer having a hydroxy group, for example, a monomer mentioned in the later-described monomer (β1-3), 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, Hydroxyalkyl vinyl ethers such as cyclohexanediol monovinyl ether; Hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether and 4-hydroxybutyl allyl ether; Hydroxyethyl vinyl ester, Hydroxybutyl vinyl ester, Vinyl 2-hydroxyethyl lucrotonate , Hydroxyalkyl vinyl esters such as 4-hydroxybutyl vinyl crotonate; 2-hydroxyethyl allyl ester, 4-hydroxybutyl allyl Hydroxyalkyl allyl ester such as ester and the like.
Examples of other monomers having a crosslinkable functional group include vinyl ethers such as glycidyl vinyl ether, glycidyl allyl ether, and aminopropyl ether, and allyl ethers.

  Moreover, a functional group can also be introduce | transduced by post reaction after superposition | polymerization. Examples of post-reaction introduction methods include, for example, a method of introducing a hydroxy group by saponifying a polymer copolymerized with a carboxylic acid vinyl ester, and reacting a polyvalent carboxylic acid or its anhydride with a polymer having a hydroxy group. A method of introducing a carboxy group, a method of introducing a hydrolyzable silyl group by reacting an isocyanate alkylalkoxysilane with a polymer having a hydroxy group, and a reaction of a polyvalent isocyanate compound with a polymer having a hydroxy group. And a method of introducing an isocyanate group.

  Preferable specific examples of the fluoroolefin copolymer include, for example, chlorotrifluoroethylene, cyclohexyl vinyl ether, copolymers of alkyl vinyl ether and hydroxyalkyl vinyl ether, copolymers of chlorotrifluoroethylene, alkyl vinyl ether and allyl alcohol, Examples thereof include a copolymer of chlorotrifluoroethylene, an aliphatic carboxylic acid vinyl ester and a hydroxyalkyl vinyl ether, or a copolymer using tetrafluoroethylene in place of chlorotrifluoroethylene in these copolymers. Moreover, these are marketed with brand names, such as Lumiflon (made by Asahi Glass Co., Ltd.), cefral coat (made by Central Glass Co., Ltd.), and zaffle (made by Daikin Industries, Ltd.).

  A fluoroolefin type copolymer may be used individually by 1 type, and may use 2 or more types together. The number average molecular weight of the fluoroolefin copolymer is preferably 2,000 to 100,000, more preferably 6,000 to 30,000.

  As the resin (x), in addition to the fluoroolefin copolymer, other fluororesin may be used alone or together with the fluoroolefin copolymer. In addition to fluororesin, alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone modified polyester resin, acrylic silicone A resin, a silicone resin, or the like may be used alone or in combination with a fluororesin.

(Other ingredients)
The coating layer (X) may contain fine particle fillers, additives, and the like as necessary.
As the additive, additives commonly used in water-based paints can be used. For example, colorants, film-forming aids, thickeners, plasticizers, antifoaming agents, ultraviolet absorbers, leveling agents, repellency inhibitors And conventional additives such as an anti-burr agent, a pigment dispersant, and a silane coupling agent.
As the fine particle filler, a hollow sphere that can impart heat insulation is generally used.
As the hollow sphere, an inorganic balloon, a resin balloon or the like is known depending on the material. Specific examples include glass balloons, shirasu balloons, alumina balloons, zirconia balloons, and aluminosilicate balloons.

The thickness of the coating layer (X) is preferably 5 to 100 μm, and more preferably 20 to 50 μm.
When the thickness of the coating layer (X) is 5 μm or more, the concealability and weather resistance are improved. In addition, when the thickness of the coating layer (X) is 100 μm or less, it is difficult for adverse effects on construction such as sagging to occur.

[Coating layer (Y)]
The coating layer (Y) is a layer formed on the coating layer (X). The coating layer (Y) is a non-fluorine polymer (hereinafter referred to as “a”) containing at least 10% by mass of polymer units having two or more hydroxy groups (hereinafter referred to as units (a)) based on the total polymerization units. It is formed from a coating composition containing non-fluorinated polymer A ”) and resin (y). A non-fluorine resin is a polymer having no fluorine atom.
(Non-fluorine polymer A)
The non-fluorinated polymer A plays a role of imparting stain resistance to the coating film having the coating film layer (X) and the coating film layer (Y).
The non-fluorinated polymer A has a unit (a) and may have a polymer unit other than the unit (a) (hereinafter referred to as “unit (b)”) as necessary.

  The unit (a) can be introduced into the polymer by polymerizing a polymerizable monomer having two or more hydroxy groups (hereinafter referred to as “monomer (α)”), for example. The unit (a) can also be introduced into the polymer by various modification methods such as introducing two or more hydroxy groups into the polymer having a reactive site. Hereinafter, the monomer (α) will be described as a typical example.

  Moreover, what was described as (meth) acrylate in the specific compound name of this specification means an acrylate or a methacrylate. Similarly, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylamide means acrylamide or methacrylamide.

As the monomer (α), for example, CH ₂ = CHCOOR ¹ , CH ₂ = C (CH ₃ ) COOR ¹ , CH ₂ = CHOCOR ¹ , CH ₂ = C (CH ₃ ) OCOR ¹ , CH ₂ = CHOR ¹ , CH ₂ = C (CH ₃ ) OR ¹ , CH ₂ = CHCH ₂ OR ¹ , CH ₂ = CHCH ₂ OCOR ¹ , CH ₂ = CHCONHR ¹ , CH ₂ = C (CH ₃ ) CONHR ¹ , CH ₂ = CHCON ( ^{_{R 1) 2, CH 2 =}} C (CH 3) CON (R 1) 2, CH 2 = CHNHCOR 1, CH 2 = C (CH 3) NHCOR 1 may be mentioned. However, R ¹ is an organic group having two or more hydroxy groups.
R ¹ is preferably an organic group having 1 to 100 carbon atoms, and more preferably an organic group having 1 to 20 carbon atoms, from the viewpoint of excellent contamination resistance. When two or more R ¹ are contained, they may be the same or different. Furthermore, R ¹ may contain a functional group other than a hydroxy group, or other atoms such as a nitrogen atom, a chlorine atom, or a fluorine atom.

Specific examples of the monomer (α) include the following monomers.
Monomer (α-1): an ester of a trifunctional or higher functional polyol compound or saccharide with (meth) acrylic acid or the like.
Monomer (α-2): an amide of a bifunctional or higher functional polyol compound having an amino group or a saccharide having an amino group and (meth) acrylic acid or the like.

Examples of the trifunctional or higher functional polyol compound include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, pentaerythritol, 1,2,6-hexanetriol, and 2-hydroxymethyl-2-methyl-1. , 3-propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol.
Examples of the saccharide include monosaccharides such as glucose, mannose, galactose, growth, fructose, D-ribose, glucosides derived from the monosaccharide, galactosides or fructosides, and dimers and trimers thereof. The body is mentioned.
Examples of the bifunctional or higher functional polyol compound having an amino group include 3-amino-1,2-propanediol.
Examples of the saccharide having an amino group include D-glucosamine.
The unit (a) may be one type or two or more types.

  The content of the unit (a) in the non-fluorinated polymer A is 10 to 100% by mass and preferably 30 to 100% by mass with respect to all the polymerized units. When the content of the unit (a) is 10% by mass or more, a coating film having excellent stain resistance is formed.

The unit (b) is a polymer unit other than the unit (a), that is, a polymer unit having one hydroxy group or no hydroxy group.
At least one of the units (b) is preferably a polymerized unit having a crosslinkable functional group (hereinafter referred to as “unit (b1)”) excluding two or more hydroxy groups. In addition, as the unit other than the unit (b1) in the unit (b), a unit other than the unit (a) and a unit other than the unit (b1), that is, a polymer unit having no hydroxy group or crosslinkable functional group (hereinafter, "Unit (b2)"). The unit (b) may be either one of the unit (b1) or the unit (b2), or a combination of the unit (b1) and the unit (b2).

Examples of the crosslinkable functional group possessed by the unit (b1) include crosslinkable functional groups generally used in a crosslinking reaction. Specifically, an aldehyde carbonyl group, a ketonic carbonyl group, one hydroxy group, Examples thereof include a carboxy group, a sulfo group, a phosphoric acid residue, an epoxy group, an amino group, an oxazoline residue, an amide group, an alkoxy group, and a hydrolyzable silyl group.
Examples of the polymerizable monomer that gives the unit (b1) (hereinafter referred to as “monomer (β1)”) include monomers having a crosslinkable functional group that are generally used in a crosslinking reaction. Specific examples of the monomer (β1) include the following monomers.
Monomer (β1-1): A monomer having an aldehyde carbonyl group.
Monomer (β1-2): A monomer having a ketonic carbonyl group.
Monomer (β1-3): A monomer having one hydroxy group.
Monomer (β1-4): A monomer having a carboxy group or a salt thereof.
Monomer (β1-5): A monomer having a sulfo group or a salt thereof.
Monomer (β1-6): A monomer having a phosphate residue or a salt thereof.
Monomer (β1-7): A monomer having an epoxy group.
Monomer (β1-8): A monomer having an amino group or a salt thereof.
Monomer (β1-9): A monomer having an oxazoline residue.
Monomer (β1-10): A monomer having an amide group.
Monomer (β1-11): Monomer having an alkoxy group.
Monomer (β1-12): A monomer having a hydrolyzable silyl group.
However, carbonyl in the monomer (β1-1) and the monomer (β1-2) represents aldehyde and ketone, respectively, and excludes ester, amide, and carboxy.

Examples of the monomer (β1-1) include (meth) acrolein, crotonaldehyde, β-formylstyrene, β-formyl-α-methylstyrene, β- (meth) acryloyloxy-α, α-dialkylpropanal. Kind.
Examples of β- (meth) acryloyloxy-α, α-dialkylpropanals include β- (meth) acryloyloxy-α, α-dimethylpropanal, β- (meth) acryloyloxy-α, α-diethyl. Propanal, β- (meth) acryloyloxy-α, α-dipropylpropanal, β- (meth) acryloyloxy-α-methyl-α-butylpropanal, β- (meth) acryloyloxy-α, α, β-trimethylpropanal is mentioned.

Examples of the monomer (β1-2) include diacetone acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl propyl ketone, and vinyl isopropyl ketone. , Vinyl butyl ketone, vinyl isobutyl ketone, vinyl tert-butyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone, and (1,1-dimethyl-3-oxobutyl) (meth) acrylate.
Furthermore, the monomer (β1-2) may be a monomer having an active methylene moiety. Examples of the monomer include allyl acetoacetate, 2-acetoacetoxyethyl (meth) acrylate, 2- (acetoacetoxy) propyl (meth) acrylate, 3- (acetoacetoxy) propyl (meth) acrylate, 2- ( Examples include acetoacetoxy) butyl (meth) acrylate, 3- (acetoacetoxy) butyl (meth) acrylate, and 4- (acetoacetoxy) butyl (meth) acrylate.

Examples of the monomer (β1-3) include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, neopentyl glycol mono (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, N-hydroxymethyl (meth) acrylamide, and hydroxymethyl (meth) acrylate. In addition, a vinyl ester or an allyl ester of a hydroxy group-containing carboxylic acid such as vinyl hydroxyalkylcrotonate can be used.
The monomer (β1-3) may be a monomer having a polyoxyalkylene chain (hereinafter referred to as “POA chain”) and having a terminal hydroxyl group. For example, CH _{2 = CHOCH 2 C 6 H 10 CH} 2 O (C 2 H 4 O) k H (k is an integer from 1 to 100. hereinafter the _{same.), CH 2 = CHOC 4} H 8 O (C 2 H 4 O) _{k H, CH 2 = CHCOOC 2} H 4 O (C 2 H 4 O) k H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) k H, CH 2 = CHCOOC 2 H ₄ O (C ₂ H ₄ O) _m (C ₃ H ₆ O) _n H (m is 0 or an integer of 1 to 100, n is an integer of 1 to 100, and m + n is 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 _{) M (C 3 H 6 O} ) n H and the like.
Examples of commercially available monomers (β1-3) having a POA chain and having a hydroxyl group at the end include, for example, PE-90, PE-200, PE-350, AE-400, PP-500, PP-800, PP-1000, AP-400, 50PEP-300, 70PEP-350B (above, manufactured by NOF Corporation) may be mentioned.

Examples of the monomer (β1-4) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid, and salts thereof. .
Examples of the monomer (β1-5) include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, 2-hydroxyallyloxy-1-propane sulfonic acid, sulfoethoxy acrylate, sulfoethoxy methacrylate, 2- Acrylamide-2-methylpropanesulfonic acid, or a salt thereof.
Examples of the monomer (β1-6) include phosphoric acid 2-acryloyloxyethyl ester, phosphoric acid 2-methacryloyloxyethyl ester, and salts thereof.

Examples of the monomer (β1-7) include glycidyl (meth) acrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, and 3,4-epoxy-1-butene.
Examples of the monomer (β1-8) include 2-N-methylaminoethyl (meth) acrylate, 2-N-ethylaminoethyl (meth) acrylate, 3-amino-2-hydroxypropyl (meth) acrylate, Examples include allylamine or a salt thereof.
Examples of the monomer (β1-9) include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl- Examples include 2-oxazoline and 2-isopropenyl-4-methyl-2-oxazoline.
Examples of the monomer (β1-10) include (meth) acrylamide, N-vinylformamide, and N-vinylacetamide.

Examples of the monomer (β1-11) include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, N-methoxymethyl (meth) acrylamide, N, N-bis (methoxymethyl) ( (Meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N, N-bis (ethoxymethyl) (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N, N-bis (propoxymethyl) (meth) acrylamide, Examples thereof include N-butoxymethyl (meth) acrylamide, N, N-bis (butoxymethyl) (meth) acrylamide, and N- (2,2-dimethoxy-1-hydroxyethyl) (meth) acrylamide.
The monomer (β1-11) may be a monomer having a POA chain and having an alkoxy group at the end. For _example, CH 2 = CHOCH (where k is an integer from 1 to 100. Hereinafter the _{same.) 2 C 6 H 10 CH} 2 O (C 2 H 4 O) k CH 3, CH 2 = CHOC 4 H 8 O (C _{2 H 4 O) k CH 3} , CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) k CH 3, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) k CH ₃ , CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _m (C ₃ H ₆ O) _n CH ₃ (m is 0 or an integer from 1 to 100, and n is an integer from 1 to 100 , m + n is 1-100. hereinafter the _{same.) include CH 2 = C (CH 3)} COOC 2 H 4 O (C 2 H 4 O) m (C 3 H 6 O) n CH 3.
Examples of commercially available monomers (β1-11) having a POA chain and having an alkoxy group at the end include, for example, M-20G, M-40G, M-90G, M-230G, and AM-90G (above , Shin-Nakamura Chemical Co., Ltd.), PME-100, PME-200, PME-400 (manufactured by Nippon Oil & Fats Co., Ltd.).

  Examples of the monomer (β1-12) include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 2 -(Meth) acryloyloxyethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, 3-trimethoxysilylpropyl vinyl ether, 3-methyldimethoxysilyl And propyl vinyl ether.

The unit (b1) is a polymerized unit obtained from at least one monomer selected from the group consisting of the monomer (β1-1), the monomer (β1-2) and the monomer (β1-9). It is preferable that
The unit (b1) contained in the non-fluorinated polymer A may be one type or two or more types.

  The content of the unit (b1) in the non-fluorinated polymer A is preferably 0.01% by mass or more and less than 90% by mass, and particularly preferably 1 to 50% by mass. When the content is 0.01% by mass or more, the stain resistance and the durability of the formed coating film are better. When the content is less than 90% by mass, the storage stability of the coating composition is better.

Examples of the polymerizable monomer (β2) that gives the unit (b2) include the following monomers.
Monomer (β2-1): hydrocarbon-based olefins.
Monomer (β2-2): Vinyl ethers.
Monomer (β2-3): Isopropenyl ethers.
Monomer (β2-4): allyl ethers.
Monomer (β2-5): Vinyl esters.
Monomer (β2-6): allyl esters.
Monomer (β2-7): alkyl (meth) acrylic acid esters.
Monomer (β2-8): Aromatic vinyl compound.
Monomer (β2-9): Chloroolefins.
Monomer (β2-10): Conjugated dienes.
Monomer (β2-11): a compound having a polyfunctional polymerizable double bond.

Examples of the monomer (β2-1) include ethylene, propylene, and isobutylene.
Examples of the monomer (β2-2) include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, and isohexyl vinyl ether. , Chain alkyl vinyl ethers such as n-octyl vinyl ether and 4-methyl-1-pentyl vinyl ether, alicyclic alkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, and aromatic group-containing vinyl ethers such as phenyl vinyl ether and benzyl vinyl ether. .

Examples of the monomer (β2-3) include methyl isopropenyl ether, ethyl isopropenyl ether, n-propyl isopropenyl ether, and n-butyl isopropenyl ether.
Examples of the monomer (β2-4) include ethyl allyl ether and cyclohexyl allyl ether.
Examples of the monomer (β2-5) include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl octoate, vinyl versatate, and vinyl octadecanoate.

Examples of the monomer (β2-6) include allyl acetate and allyl propionate.
Examples of the monomer (β2-7) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl-n-hexyl (Meth) acrylate, n-octyl (meth) acrylate, and cyclohexyl (meth) acrylate may be mentioned.

Examples of the monomer (β2-8) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 3,4 -Dimethylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 4-chloro-3-methyl Examples include styrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylpyridine, and 4-vinylpyridine.
Examples of the monomer (β2-9) include vinyl chloride, vinylidene chloride, isopropenyl chloride, and allyl chloride.

Examples of the monomer (β2-10) include 1,3-butadiene, isoprene, chloroprene, and 2,3-dimethyl-1,3-butadiene.
Examples of the monomer (β2-11) include divinylbenzene, divinyl ether, allyl (meth) acrylate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol (meth) diacrylate, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate.
The unit (b2) may be one type or two or more types.

  The content of the unit (b2) in the non-fluorinated polymer A is preferably less than 89.99% by mass from the viewpoint of stain resistance of the coating film to be formed and its durability, and is 0 to 30% by mass. It is particularly preferred that

  The molecular weight of the non-fluorinated polymer A is preferably 160 to 1,000,000 and more preferably 320 to 100,000 in terms of number average molecular weight. When the number average molecular weight is within this range, the stain resistance of the formed coating film is better.

The non-fluorinated polymer A can be synthesized by, for example, a method in which the monomer (α) is dissolved in a solvent together with the monomer (β) as necessary, heated, and reacted by adding a polymerization initiator.
As the solvent in the synthesis, water or a water-soluble solvent is preferable. For example, water, methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-methyl-1-propanol, ethylene glycol, polypropylene glycol, 1,3-butanediol, glycerol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2- (2-methoxyethoxy) ethanol, methyl acetate, ethyl acetate, 2,2-dichlorodiethyl ether, chloropropanol, acetone, Examples include methyl ethyl ketone, 1,4-dioxane, dimethylformamide, formamide, and acetonitrile.
The solvent may be used alone or in combination of two or more. The solvent is preferably methanol or acetone from the viewpoint of polymerization stability and ease of solvent replacement.

  As the polymerization initiator, known organic peroxides, inorganic peroxides, azo compounds and the like can be used. Organic peroxides and inorganic peroxides may be used as a redox catalyst in combination with a reducing agent. The polymerization initiator may be used alone or in combination of two or more.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, tert-butyl hydroperoxide, and tert-butyl-α-cumyl peroxide.
Examples of inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonate.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), Examples include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, and 2,2′-azobis (2-amidinopropane) dihydrochloride.

Furthermore, in order to adjust the molecular weight of the non-fluorinated polymer A, mercaptans, alkyl halides and the like can be used as known chain transfer agents.
Examples of mercaptans include n-butyl mercaptan, n-dodecyl mercaptan, tert-butyl mercaptan, ethyl thioglycolate, and 2-ethylhexyl thioglycolate.
Examples of the alkyl halides include chloroform, carbon tetrachloride, and carbon tetrabromide.
The chain transfer agent may be used alone or in combination of two or more.

  The content of the non-fluorinated polymer A in the coating layer (Y) is preferably 0.1 to 100% by mass, and 0.5 to 50% by mass with respect to the solid content of the resin (y). More preferably, it is more preferably 1 to 30% by mass. If the said content is 0.1 mass% or more, the coating-film layer (Y) which has the outstanding stain resistance will be easy to be formed, and the effect of maintaining heat ray reflective performance will be easy to be acquired. Moreover, if the said content of the non-fluorine-type polymer A is 100 mass% or less, it will be easy to improve the weather resistance of the coating film formed.

The non-fluorinated polymer A in the coating layer (Y) is preferably cross-linked by a cross-linking agent (cross-linking agent B) that can cross-link the non-fluorinated polymer A. Although the crosslinking agent B is demonstrated below, this crosslinking agent B can also be used as a crosslinking agent which bridge | crosslinks resin (x) and resin (y).
A particularly preferred coating layer (Y) is a layer in which the non-fluorinated polymer A and the resin (y) are both crosslinked by a crosslinking agent B.

The crosslinking agent B is not particularly limited as long as it is a crosslinking agent that can react with the crosslinkable functional group, and various known crosslinking agents can be used. Examples of the crosslinking agent B include the following crosslinking agents.
Crosslinking agent B1: amino resin.
Cross-linking agent B2: polyisocyanate compound.
Crosslinking agent B3: A compound having two or more hydrazino groups.
Cross-linking agent B4: polycarbodiimide compound.
Crosslinking agent B5: A compound having two or more epoxy groups.
Cross-linking agent B6: a compound having two or more oxazoline residues.
Cross-linking agent B7: A compound having two or more aziridine residues.
Cross-linking agent B8: polyvalent metals.
Crosslinking agent B9: A compound having two or more amino groups.
Cross-linking agent B10: polyketimine.
Cross-linking agent B11: A compound having two or more carboxy groups.
Cross-linking agent B12: acid anhydride.
Cross-linking agent B13: a compound having two or more mercapto groups.
Crosslinking agent B may be used individually by 1 type, and may use 2 or more types together.

As the crosslinking agent B1, for example, a compound obtained by hydroxymethylating a part or all of an amino group such as a melamine compound, a guanamine compound or a urea compound, or a part or all of a hydroxy group of the hydroxymethylated compound The compound (for example, hexamethoxymethyl melamine) which etherified with methanol, ethanol, n-butyl alcohol, 2-methyl-1-propanol etc. is mentioned.
Examples of the crosslinking agent B2 include polyisocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate, isocyanate silane compounds such as methyltriisocyanate silane, condensates or multimers thereof, and water thereof. Examples thereof include blocked polyisocyanate compounds in which isocyanate groups are blocked with a dispersing agent such as a dispersion type or phenol. In particular, a non-yellowing type polyisocyanate compound is preferred.

Examples of the crosslinking agent B3 include dihydrazide, polyfunctional hydrazide, and polyfunctional semicarbazide.
Examples of the dihydrazide include carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, heptanedioic acid dihydrazide, octanedioic acid dihydrazide, nonanedioic acid dihydrazide, dodecanediode Diacid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 2,6-pyridinedihydrazide, 1, Examples include 4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, and itaconic acid dihydrazide.
Examples of the polyfunctional hydrazide include ethylenediaminetetraacetic acid tetrahydrazide, citric acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, trimellitic acid trihydrazide, pyromellitic acid trihydrazide, pyromellitic acid tetrahydrazide, 1, 4, 5, 8 -Reaction products of oligomers containing alkyloxycarbonyl groups such as naphthoic acid tetrahydrazide and alkyl (meth) acrylate oligomers with hydrazine.
Examples of the polyfunctional semicarbazide include a reaction product of polyisocyanate and hydrazine.

Examples of the crosslinking agent B4 include compounds obtained by a known carbon dioxide condensation reaction of organic diisocyanates. In the reaction, a phosphoric acid compound such as trimethyl phosphate or triethyl phosphate can be used as a known catalyst. Further, nonionic hydrophilic polycarbodiimide compounds obtained using a mixture of an organic diisocyanate and a hydroxy group-containing polyethylene glycol can be mentioned. Of these, nonionic hydrophilic polycarbodiimide compounds are preferred from the viewpoint of water dispersibility and stability.
Examples of the crosslinking agent B5 include a glycerol polyglycidyl ether compound.
Examples of the crosslinking agent B6 include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2 -A copolymer of polymerizable monomers such as isopropenyl-4-methyl-2-oxazoline can be mentioned.

Examples of the crosslinking agent B7 include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 2,2,2-trishydroxymethylethanol-tris [3- (1-aziridinyl) propionate. ].
Examples of the crosslinking agent B8 include zinc chloride, zinc chloride ammonium, zinc nitrate, zinc carbonate, zinc sulfate, chromic acid and its salt, dichromic acid and its salt, diisopropoxytitanium bisacetylacetone, aluminum sulfate, and triacetylaluminum. , Zirconyl nitrate, zirconyl acetate, zirconyl ammonium carbonate, potassium zirconium fluoride, and zirconium ammonium fluoride.

Examples of the crosslinking agent B9 include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and heterocyclic polyamines.
Aliphatic polyamines include, for example, ethylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, diethylenediamine. And cyan diamine.
Examples of the alicyclic polyamines include 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, N-3-aminopropylcyclohexylamine, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, and bis. (3-methyl-4-aminocyclohexyl) methane, 1,4-bis (ethylamino) cyclohexane.
Examples of aromatic polyamines include m-xylylenediamine, p-xylylenediamine, 4- (1-aminoethyl) aniline, metaphenylenediamine, and diaminodiphenylmethane.
Examples of the heterocyclic polyamines include N-aminoethylpiperazine and 1,4-bis (3-aminopropyl) piperazine.

Examples of the crosslinking agent B11 include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic carboxylic acids, and tri- or higher functional polycarboxylic acids.
Examples of the aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, tartaric acid, malic acid, and iminodiacetic acid.
Examples of the alicyclic dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
Examples of the aromatic carboxylic acids include phthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.
Examples of the tri- or more functional polycarboxylic acids include citric acid, 1,3,5-cyclohexanetricarboxylic acid, ethylenediaminetetraacetic acid, trimellitic acid, pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid. Examples include acids.

Examples of the crosslinking agent B12 include acetic anhydride, propionic anhydride, butyric anhydride, citraconic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′- A benzophenone tetracarboxylic dianhydride is mentioned.
Examples of the crosslinking agent B13 include aliphatic dimercapto compounds and aromatic dimercapto compounds.
Examples of the aliphatic dimercapto compound include aliphatic dimercapto compounds such as 1,6-dimercaptohexane, dimercaptodiethyl ether, triglycol dimercaptan, and bis- (2-mercaptoethyl) sulfide.
Examples of the aromatic dimercapto compound include 3,4-dimercaptotoluene, bis (4-mercaptophenyl) sulfide, 2,5-dimercapto-1,3,4-thiadiazole, 4-tert-butyl-1,2- Examples thereof include benzenedithiol, 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine, and 2,4,6-trimercapto-1,3,5-triazine.

  Table 1 shows an example of a combination of the crosslinkable functional group and the crosslinking agent B in the non-fluorinated polymer A. “◯” in Table 1 means a combination.

In the crosslinking reaction of the non-fluorinated polymer A, a curing accelerator can be used.
For example, when the crosslinking agent B2 is used as the crosslinking agent B, a tin compound or the like can be used as the curing accelerator. Examples of the tin compound include dibutyltin dilaurate, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltin di (maleic acid monoester), and dibutyltin diacetate.
When the crosslinking agent B1 is used as the crosslinking agent B, N, N-dimethylethylsulfamate can be used.
In the crosslinking reaction between the oxazoline group and the crosslinking agent B11, diammonium hydrogen phosphate can be used.

  In the combination of the crosslinkable functional group and the crosslinking agent B, a combination capable of one-component room temperature crosslinking is preferable. For example, a combination of an oxazoline group and a crosslinking agent B11, a combination of an oxazoline group and a crosslinking agent B13, a combination of a carboxy group and a crosslinking agent B6, a combination of a carbonyl group and a crosslinking agent B3, an active methylene group and a crosslinking agent B9, The combination of is mentioned.

  The blending amount of the crosslinking agent B is preferably 0.01 to 1000 parts by mass, more preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer A, and 0 More preferably, it is 5-200 mass parts. If the said compounding quantity is 0.01 mass part or more, the stain resistance of the coating film formed and its durability will become more favorable. Moreover, if the said compounding quantity is 1000 mass parts or less, the storage stability of a coating composition will become more favorable.

(Resin (y))
The coating layer (Y) contains the resin (y) together with the non-fluorinated polymer A. Examples of the resin (y) include the same resins as those mentioned for the resin (x), and preferred embodiments are also the same.
That is, part or all of the resin (y) is preferably a fluororesin. By using the fluororesin, a coating layer (Y) having better weather resistance is formed. The resin (y) may be the same resin as the resin (x), a different resin, or the same resin, whether a fluororesin or a resin other than the fluororesin is used. Is preferably used.

(UV absorber)
The coating layer (Y) preferably further contains an ultraviolet absorber. The ultraviolet absorber suppresses deterioration of the composite pigment M due to ultraviolet rays, and suppresses a decrease in heat ray reflection performance.
Examples of the ultraviolet absorber include benzotriazole-based, cyanoacrylate-based, benzophenone-based, hydroxyphenyltriazine-based, and oxalic anilide-based ultraviolet absorbers.

0.1-20 mass% is preferable with respect to the total amount of a coating-film layer (Y), and, as for content of the ultraviolet absorber in a coating-film layer (Y), 0.5-10 mass% is more preferable.
When the content of the ultraviolet absorber is 0.1% by mass or more, the effect of preventing the composite pigment M from being deteriorated is easily obtained. Moreover, if content of an ultraviolet absorber is 20 mass% or less, it will be easy to suppress that a coating film colors or a coating film softens.

  Moreover, the coating-film layer (Y) may contain the particulate filler, additive, etc. which were mentioned by the coating-film layer (X) as needed.

The thickness of the coating layer (Y) is preferably 5 to 100 μm, and more preferably 10 to 40 μm.
If the thickness of the coating layer (Y) is 5 μm or more, concealability and weather resistance are easily obtained. In addition, when the thickness of the coating layer (Y) is 100 μm or less, adverse effects on construction such as sagging are unlikely to occur.

The octane desorption work calculated from the contact angle of octane in water of the coating film in the present coated product is preferably less than 2.0 × 10 ⁻² J / m ² . The octane desorption work is determined by measuring the contact angle of octane with the coating film in water.

Octane desorption work (W _A ′) can be expressed by the following equation.
_{W A '= γ SW + γ} WO -γ SO
(Where γ _SW is the interfacial tension between the coating surface and water (J / m ² ), γ _WO is the interfacial tension between water and octane (J / m ² ), and γ _SO is the interfacial tension between the coating surface and octane. Represents tension (J / m ² ).

Substitute the Young's formula γ _SW = γ _SO + γ _WO = cos θ (where θ is the contact angle of octane with the coating film in water) into the above formula, and use the extended Fowkes formula to determine the surface of water and octane. Noting that the tension dispersion components are equal, the following equation can be derived.
W _A '= C (1 + cos θ)
(However, C is a polar component of the surface tension of water, and C = 0.051 (J / m ² ).)
Since θ may vary 0~180 °, _{W A} 'varies from ^{0~10.2 × 10 -2 (J / m} 2). This means that the smaller W _A ′ means that less energy is required to separate octane from the surface of the coating film in water, so that the contamination resistance is considered to be better. In order to exert the stain resistance, the desorption work of octane in water is preferably less than 2.0 × 10 ⁻² J / m ^{2 and} less than 1.5 × 10 ⁻² J / m ^2. Is more preferable.

  The mechanism by which the stain resistance is improved by the non-fluorinated polymer A of the coating layer (Y) is not necessarily clear, but is considered as follows. The coating film containing the non-fluorinated polymer A having one or more units (a) has a small octane desorption work in water. This means that even if the oily component contained in the soiling substance once adheres to the surface of the coating film, it is easily washed away by rain or the like, which means that the stain resistance is excellent. Furthermore, by introducing a crosslinkable functional group into the non-fluorinated polymer A and blending a suitable crosslinking agent B, the hydrophilic component is immobilized on the surface of the coating film from the beginning of the coating film formation. Contamination can last longer. In addition, a coating film formed from a coating composition (Y) containing a fluorine resin (resin (y)) having a fluorine content of 5% by mass or more and a non-fluorinated polymer A is obtained with a resin other than the fluorine resin. Anti-static properties and dust resistance can also be achieved.

  In the present coated product, it is preferable that the coating layer (Y) is formed as the uppermost layer. If it is inside, another layer may be provided on the coating film layer (Y). If the coating film layer (Y) is the uppermost layer, the non-fluorinated polymer A exhibits the effect of preventing the surface contamination and maintaining the aesthetic appearance.

  This coated product is within the range that does not impede the effect of maintaining the reflective performance of the heat ray of the coated product and the reflective performance between the coated layer (X) and the coated layer (Y) and maintaining the aesthetic appearance. Another intermediate layer (Z) may be provided. However, it is preferable not to provide the intermediate layer (Z) from the viewpoint of the heat ray reflection performance and its maintenance effect.

Since the present coated product described above has the coating layer (X) containing the composite pigment M and the coating layer (Y) containing the non-fluorinated polymer A, the heat ray has a high reflectance. The heat ray reflection performance is maintained for a long time because the temperature rise is suppressed by reflecting and the anti-contamination property is excellent.
In addition, since the present coated material achieves high heat ray reflection performance without using chromium oxide by using the composite pigment M, environmental pollution is further reduced.

<Coating method>
The coating method of this coating object forms the coating-film layer (X) formed from coating composition (X1) on a to-be-coated article, and then, coating composition (Y1) on coating-film layer (X). ) To form a coating layer (Y).
The coating composition (X1) is a coating composition for forming the coating layer (X), and the coating composition (Y1) is a composition for forming the coating layer (Y). And a coating composition containing each essential component contained in the coating layer (Y).

  The coating composition (X1) and the coating composition (Y1) are water-based coating compositions containing water. That is, the coating composition (X1) is a coating composition containing the composite pigment M, the resin (x), and water. The coating composition (Y1) is a coating composition containing the non-fluorine polymer A, the resin (y), and water.

However, in the coating composition (X1) and the coating composition (Y1), the heat ray reflection performance of the coating film to be formed and its maintenance effect, and the work environment at the time of painting, etc. are within a range that does not deteriorate too much, A solvent may be included.
Examples of the solvent include those that can be generally used as a solvent for paints, for example, petroleum mixed solvents such as toluene, xylene, Exubemobil's Solvesso 100, ExxonMobil's Solvesso 150; and aromatic carbonization such as mineral spirits. Examples include hydrogens; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These may be used alone or in combination of two or more.

There is no limitation on the blending order of each component of the coating composition (X1). When adding the crosslinking agent B, a method of adding the crosslinking agent B after previously mixing the pigment and the resin (x) in water is preferable. In addition, when adding additives such as colorants, film-forming aids, thickeners, plasticizers, antifoaming agents, UV absorbers, leveling agents, repellency inhibitors, anti-burr agents, pigment dispersants, It is preferable to mix with water together with the pigment.
There is no limitation on the blending order of each component of the coating composition (Y1), and when adding the curing accelerator of the non-fluorinated polymer A, the curing accelerator is added to the non-fluorinated polymer A in advance. It is preferable. Further, when the time from application of the resin (y) and the non-fluorine polymer A to mixing with water is long, it is preferable to add a curing accelerator immediately before applying the coating composition (Y1). .
Further, there is no particular limitation on the curing method of the coating composition (X1) and the coating composition (Y1), and various curing methods such as a thermosetting type, a thermoplastic type, a room temperature drying type, and a room temperature curing type are used. Can do.

  When applying the coating composition (X1) to the object to be coated, the pre-treatment used when applying normal paint such as surface polishing, sanding treatment, sealing treatment, primer treatment, primer coating, etc. Preferably it is done. The kind of pre-treatment may be one kind or two or more kinds, and the number of times of each treatment may be once or twice or more. There are no particular limitations on the sealing agent, primer, and primer used, and examples include organic solvent solutions, non-aqueous dispersions, aqueous solutions, and aqueous dispersions.

  Examples of the primer or primer include epoxy resin-based, modified epoxy ester resin-based, vinyl resin-based, and chlorinated rubber-based paints. If necessary, the coating is zinc phosphate, red lead, zinc powder, lead oxide, calcium leadate, cyanamide lead, basic lead chromate, basic lead sulfate and other anticorrosive pigments, iron oxide, mica, aluminum, glass It may contain scaly pigments such as flakes. Moreover, in order to improve rust prevention power, a zinc rich primer may be used, and two or more types of the above-mentioned primer can be applied.

  Various methods can be applied to the coating composition (X1) and the coating composition (Y1). For example, brush coating, spray coating, immersion coating, roll coater or flow coater coating can be applied. The coating composition (X1) and the coating composition (Y1) are applied, for example, after the coating composition (X1) is applied and dried to form the coating layer (X), then the coating composition (Y1) It is performed by applying. Moreover, when forming an intermediate | middle layer (Z), intermediate | middle layer (Z) is formed by methods, such as application | coating, as needed before application | coating of coating composition (Y1). The coating composition (Y1) may be applied before the coating composition (X1) (intermediate layer (Z)) is completely dried. The coating composition (X1) and the coating composition (Y1) may be applied one or more times. The method of performing coating a plurality of times is preferable as a method of increasing the film thickness without causing sagging.

By the coating method of the present invention described above, the present coated product having the coating layer (X) and the coating layer (Y) is obtained.
In addition, since the coating method of the present invention can be formed using an aqueous coating composition, adverse effects on the work environment and the global environment due to VOC emission are reduced. In addition, since the water-based coating composition uses the non-fluorinated polymer A in place of the silicate compound that reacts with water to reduce the storage stability, it is excellent in storage stability even when it is aqueous. In addition, overcoating with other water-based paints can be easily performed at the time of renovation.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
[Base material]
In this example, as a base material, a chromate-treated aluminum plate having a length of 140 mm × width of 240 mm × thickness of 0.5 mm was coated with an undercoat (coating amount 0.15 kg / m ² ) and an intermediate coating (coating amount 0.13 kg). / M ² ) and a substrate coated sequentially.
As the undercoat, Bon Epocoat 55MP, white (manufactured by AGC Co-Tech, epoxy resin paint) was used. As an intermediate coating agent, Bonflon aqueous W # 1500 intermediate coating white (acrylic resin emulsion paint, manufactured by AGC Co-Tech) was used.

[Production Example 1] Enamel paint 1 (coating composition (X1))
Aqueous fluororesin emulsion FE-4200 (made by Asahi Glass Co., Ltd., hydroxy group-containing fluoroolefin copolymer, 60.0 g), which is a copolymer of chlorotrifluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether and hydroxyalkyl vinyl ether, SN deformer 381 (manufactured by San Nopco, 0.48 g), water (11.34 g), and EHG (manufactured by Nippon Emulsifier Co., Ltd., 4.52 g) were added as a film-forming aid.
Next, AQ-E1990 (manufactured by Resino Color Industry Co., Ltd., pigment concentration) 60 mass%, 21.8 g) was added, and the mixture was sufficiently stirred using a disper to obtain an enamel paint 1.
The average particle diameter of the pigment was measured by a laser diffraction particle size distribution measuring device (HORIBA LA-920).

[Production Example 2] Enamel Paint 2
To the aqueous fluororesin emulsion FE-4200 (60.0 g), the SN deformer 381 (0.20 g), water (14.4 g) as an antifoaming agent, and the EHG (5.16 g) as a film increasing aid are added. It was. Next, PSM black C (manufactured by Mikuni Dye Co., Ltd .: pigment concentration: 25% by mass, 8.2 g) was added as an aqueous dispersion of carbon black and sufficiently stirred using a disper to obtain an enamel paint 2.

[Production Example 3] Clear paint 1 (paint composition (Y1))
In the aqueous fluororesin emulsion FE-4200 (60.0 g), the SN deformer 381 (0.48 g), water (11.34 g) as an antifoaming agent, the EHG (4.52 g) as a film increasing aid, ultraviolet rays Uvinul 3039 (manufactured by BASF, 1.60 g) was added as an absorbent. Further, non-fluorine polymer A comprising 75% by mass of GLM (glycerin monomethacrylate), 15% by mass of PME-400 (methoxypolyethylene glycol monomethacrylate), and 10% by mass of DAAM (diacetone acrylamide). Polymer a, 6.61 g and a 10% by mass aqueous solution (2.45 g) of adipine sanhydrazide (manufactured by Otsuka Chemical Co., Ltd.) as crosslinking agent B were added, and the mixture was sufficiently stirred using a disper to obtain clear coating 1 It was.

[Production Example 4] Clear paint 2
In the aqueous fluororesin emulsion FE-4200 (60.0 g), the SN deformer 381 (0.48 g), water (11.34 g) as an antifoaming agent, the EHG (4.52 g) as a film increasing aid, ultraviolet rays The Uvinul 3039 (1.60 g) was added as an absorbent. Further, MKC silicate MS56S (manufactured by Mitsubishi Chemical Co., Ltd., 8.65 g) was added as a low-contaminating agent, and a clear paint 2 was obtained by sufficiently stirring with a disper.

The storage stability of the clear paints 1 and 2 obtained in Production Examples 3 and 4 was evaluated.
[Storage stability]
The clear paint obtained in Production Examples 3 and 4 is collected in a sealable glass bottle, and the state of the paint is confirmed with a stirring bar after 3 days. Storage stability was evaluated according to the following criteria.
○: The paint did not gel.
X: The paint gelled.
Table 1 shows the evaluation of storage stability.

  As shown in Table 2, the clear coating 1 obtained in Production Example 3 did not gel even after 3 days. On the other hand, the clear coating obtained in Production Example 4 gelled after 3 days.

Hereinafter, the Example and comparative example which form a coating film using the coating material obtained by manufacture examples 1-4 are demonstrated.
[Example 1]
By spray coating, the enamel paint 1 obtained in Production Example 1 is applied on the base material so as to have a film thickness of 30 ± 10 μm, cured at a temperature of 23 ° C. and a relative humidity of 60% for 1 day, and further sprayed By coating, the clear paint 1 obtained in Production Example 3 was applied to a film thickness of 25 ± 10 μm and cured for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test specimen.

[Comparative Example 1]
By spray coating, the enamel paint 1 obtained in Production Example 1 is applied on the base material so as to have a film thickness of 30 ± 10 μm, followed by curing for 7 days at a temperature of 23 ° C. and a relative humidity of 60%. Got.

[Comparative Example 2]
By spray coating, the enamel paint 2 obtained in Production Example 2 is applied on the base material so as to have a film thickness of 30 ± 10 μm, cured at a temperature of 23 ° C. and a relative humidity of 60% for 1 day, and further sprayed. By coating, the clear paint 1 obtained in Production Example 3 was applied to a film thickness of 25 ± 10 μm and cured for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test specimen.

[Comparative Example 3]
The enamel paint 1 obtained in Production Example 1 was applied onto the base material by spray coating so as to have a film thickness of 30 ± 10 μm, followed by curing at a temperature of 23 ° C. and a relative humidity of 60% for 1 day. Furthermore, spray coating of the clear paint 2 obtained in Production Example 4 was attempted.

In the examples and comparative examples, the paintability of the clear paint was evaluated. Further, with respect to the test body obtained in Examples and Comparative Examples, the initial temperature T _1, to evaluate the temperature T _2, and weather resistance after contamination.
(Paintability)
The paintability of the clear paint was evaluated according to the following criteria.
○: The clear paint did not gel and could be easily applied.
X: The clear paint gelled and could not be applied.

(Initial temperature T ₁ )
The coating composition obtained in Examples and Comparative Examples was applied by spray coating so as to have a film thickness of 30 ± 10 μm and cured for 7 days at a temperature of 23 ° C. and a relative humidity of 60%. Got. Next, the temperature of the coating film when the test piece was irradiated with an infrared lamp for 10 minutes was measured according to the following procedure.
First, the thermocouple was installed in the center part of the test body surface. In addition, an infrared lamp was installed 60 cm from the surface of the test body. The infrared lamp was turned on for 10 minutes and then turned off. And the temperature of the test body surface was continuously measured using the thermocouple for 15 minutes from the lighting start of an infrared lamp to 5 minutes after light extinction. The highest temperature in the measurement results of 15 minutes to a temperature T _1, if T ₁ is 45 ° C. or less "○", and a "×" if exceed 45 ° C..

(Post-contamination temperature T ₂ )
For each the test body performs accelerated fouling in accordance with the antifouling test, measuring contamination after temperature T ₂ by the following procedure.
(1) As a soiling substance, a suspension was prepared by thoroughly mixing 95% by mass of deionized water with 5% by mass of carbon black for pigment (Degusa, particle size 0.002-0.028 μm).
(2) Add about 1/3 of glass beads (diameter 2 mm) to the suspension, stir at 2500 rpm using a stirrer, remove the glass beads and suspend carbon black The liquid was separated.
(3) The carbon black suspension is sprayed on the surface of the test specimen at about 200 g / m ² , and the gauze is moved in the vertical, horizontal and vertical order on the surface of the test specimen while flowing tap water on the surface of the specimen. And lightly wash off the soiled material to obtain a soiled specimen.
(4) except for replacing the specimen stain test specimens in the measurement of the initial temperatures T ₁ is the temperature of the contamination test surface in a manner similar to the measurement of the initial temperatures T ₁ measured continuously measured for 15 minutes The highest temperature in is taken as post-contamination temperature T ₂ , “T” when T ₂ is 45 ° C. or less, and “X” when 45 ° C. or more.

(Weatherability)
An accelerated weather resistance test based on Type 1 UVB313 described in JIS K5600-7-8 accelerated weather resistance test (ultraviolet fluorescent lamp method) was carried out, and the appearance was evaluated based on the following criteria by visual observation.
○: No change in appearance.
Δ: Some discoloration was observed in appearance.
X: Significant discoloration was observed in appearance.
Table 3 shows the evaluation of the initial temperature T ₁ , the post-contamination temperature T ₂ and the weather resistance.

As shown in Table 3, enamel paint 1 (resin composition (X1)) and clear coating 1 (resin composition (Y1)) In Example 1 using a low initial temperature T ₁ of the formed coating film The heat ray reflection performance was excellent, and the weather resistance was also excellent. Also, the clear paint 1 could be easily applied.

On the other hand, in Comparative Example 1 was coated only enamel paint 1, but coating film formed in the initial temperature T ₁ is superior heat ray reflective performance low, the coating film is inferior in its maintenance effect and is easily contaminated. Moreover, it was inferior also in the weather resistance.
In Comparative Example 2 not using the composite pigment M, the initial temperatures T ₁ had inferior heat reflecting performance low.
Further, in Comparative Example 3 using the clear coating material 2 using a silicate compound instead of the non-fluorinated polymer A, the coating material was gelled and it was difficult to apply.

Claims (14)

A coated article having a coating layer (X) and a coating layer (Y) formed on the coating layer (X) on the object to be coated,
The coating layer (X) contains a composite metal oxide pigment containing at least one of a bismuth oxide, an yttrium oxide, and a manganese oxide, a resin (x), and water. And a layer formed from a coating composition not containing a silicate compound,
The coating layer (Y) contains a non-fluorine polymer containing 10% by mass or more of polymer units having two or more hydroxy groups, the resin (y), and water. , the layer der formed from the coating composition containing no silicate compound is,
The resin (x) is fluorine resin, alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone modified polyester resin, Is at least one selected from the group consisting of acrylic silicone resins and silicone resins,
The resin (y) is fluorine resin, alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone modified polyester resin, heat ray high reflection coated article, wherein at least one Tanedea Rukoto selected from the group consisting of acrylic silicone resin and silicone resin. The heat ray highly reflective coated article according to claim 1, wherein a part or all of the resin (y) is a fluororesin. The heat ray highly reflective coated article according to claim 1, wherein a part or all of the resin (x) is a fluororesin and a part or all of the resin (y) is a fluororesin. The heat ray highly reflective coating product according to any one of claims 1 to 3, wherein the non-fluorinated polymer further has a polymerized unit having a crosslinkable functional group excluding the two or more hydroxy groups. The heat ray highly reflective coated product according to any one of claims 1 to 4, wherein the coating layer (Y) is crosslinked by a crosslinking agent. The heat ray highly reflective coated product according to any one of claims 1 to 5 , wherein the coating layer (Y) further contains an ultraviolet absorber. According to any one of the coating layers according to claim 1 to 6 wherein the content of the composite metal oxide pigment in (X) is 0.1 mass% or more based on the solid content of the resin (x) Heat ray highly reflective paint. A silicate containing a composite metal oxide pigment containing at least one of a bismuth oxide, an yttrium oxide, and a manganese oxide, a resin (x), and water. Forming a coating layer (X) formed from the coating composition (X1) containing no compound;
On the coating layer (X), a non-fluorinated polymer containing 10% by mass or more of polymer units having two or more hydroxy groups, the resin (y) and water are contained. And forming a coating layer (Y) formed from the coating composition (Y1) containing no silicate compound ,
The resin (x) is fluorine resin, alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone modified polyester resin, Is at least one selected from the group consisting of acrylic silicone resins and silicone resins,
The resin (y) is fluorine resin, alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone modified polyester resin, At least Tanedea coating method of the heat ray high-reflection coated article, characterized in Rukoto selected from the group consisting of acrylic silicone resin and silicone resin. The coating method of the heat ray highly reflective coating according to claim 8, wherein a part or all of the resin (y) is a fluororesin. The coating method of the heat ray highly reflective coating according to claim 8, wherein a part or all of the resin (x) is a fluororesin and a part or all of the resin (y) is a fluororesin. The coating method of the heat ray highly reflective coating material as described in any one of Claims 8-10 in which the said non-fluorine-type polymer further has a polymerization unit which has a crosslinkable functional group except the said 2 or more hydroxy group. The coating method of the heat ray highly reflective coating according to any one of claims 8 to 11, wherein the coating composition (Y1) further contains a crosslinking agent. The coating method of the heat ray highly reflective coating according to any one of claims 8 to 12 , wherein the coating composition (Y1) further contains an ultraviolet absorber. According to any one of the coating composition (X1) the mixed metal oxide pigments content the resin is 0.1 mass% or more with respect to the solid content of the (x) claims 8 to 13 in How to apply high-reflective heat-reflective coatings.