JP2013006898A - Heat ray highly reflective paint composition, kit for preparing heat ray highly reflective paint composition, heat ray highly reflective coated article, and production method of heat ray highly reflective coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray highly reflective paint composition which does not require use of a manganese compound, and with which a deep color type coating film with high heat ray reflection performance is obtained, a kit for preparing the composition, and a method for producing a heat ray highly reflective coated article.SOLUTION: The heat ray highly reflective paint composition contains a composite metal oxide pigment including Bi oxide and Cu oxide and a fluororesin. Furthermore, the heat ray highly reflective paint composition contains a compound represented by general formula Si(OR)(wherein Rs are optionally identical to, or different from, one another and each represent a hydrogen atom or a 1-5C alkyl group) and/or a silicon-containing compound (A) composed of a partial condensate thereof.

Description

  The present invention relates to a heat ray high reflection paint composition, a heat ray high reflection paint composition preparation kit, a heat ray high reflection paint, and a method for producing a heat ray high reflection paint.

In general, dark paints containing black pigments are often used on the roofs of buildings. However, dark color paints generally have a problem that they easily absorb solar energy, raise the temperature of buildings and the like, and increase energy consumption for air conditioning.
On the other hand, although a white coating film can be expected to have high reflection of heat rays, it has problems such as a landscape-like problem that contamination is conspicuous and a decrease in reflection of heat rays due to contamination.

In order to solve this problem, Patent Document 1 and Patent Document 2 describe a paint composition colored in black, which is an achromatic color, by mixing a chromatic pigment of red, orange, yellow, green, blue, and purple in the vehicle. Things have been proposed. However, it is difficult to adjust the color tone, and the color pigment is deteriorated by ultraviolet rays, so that there is a problem that the color is easily changed.
Further, as an example using a heat ray high reflection pigment, Patent Document 3 proposes a black fired pigment coating composition having a high solar radiation reflectance in the near infrared region. However, since chromium-based pigments are used, there is a problem that the health of workers during painting work is impaired and the environment is polluted.

Further, as dark-colored heat ray highly reflective pigments, pigments containing bismuth manganese oxide (Patent Document 4) and pigments containing rare earth manganese oxide composite oxide (Patent Document 5) have also been proposed. Further, Patent Document 6 discloses a heat ray highly reflective coating composition containing a composite metal oxide pigment containing a bismuth and / or yttrium oxide and a manganese oxide, a silicate compound, and a resin.
The coating film formed from the heat ray highly reflective coating composition of Patent Document 6 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.

Although the heat ray highly reflective coating composition of patent documents 4-6 contains a manganese compound as an essential component, there exists a problem by which a manganese compound is considered to be a substance with danger by the chemical substance management promotion method (PRTR method). .
Further, according to the heat ray highly reflective coating composition of Patent Document 6, a coating film that reflects heat rays with high reflectivity can be obtained, but the power saving requirement in summer is severe, and the coating film that reflects heat rays with higher reflectivity. Is required.

Japanese Patent No. 2593968 JP-A-5-293434 Japanese Patent No. 3468698 JP-T-2002-532379 JP 2002-38048 A JP 2008-106092 A

  The present invention has been made in view of the above circumstances, and does not require the use of a manganese compound, and can provide a dark-colored coating film having high heat ray reflection performance and its preparation. An object of the present invention is to provide a kit for manufacturing a heat-reflective coating and a method for producing a heat ray highly reflective coating. It is another object of the present invention to provide a dark-colored heat ray highly reflective coating that does not require the use of a manganese compound and has high heat ray reflection performance.

  In order to achieve the above object, the present invention employs the following configuration.

[1] A heat ray highly reflective coating composition characterized by containing a composite metal oxide pigment containing a Bi oxide and a Cu oxide and a fluororesin.
[2] Further, a compound represented by the general formula Si (OR) ₄ (wherein R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and / or a compound thereof The heat ray highly reflective coating composition according to [1], which contains a silicon-containing compound (A) comprising a partial condensate.
[3] The heat ray highly reflective coating composition according to [2], further containing a solvent.
[4] The heat ray highly reflective coating composition according to [1], further comprising a non-fluorine polymer (B) containing 10% by mass or more of repeating units having two or more hydroxy groups based on all repeating units. .
[5] The heat ray highly reflective coating composition according to [4], further containing water.
[6] The heat ray highly reflective coating composition according to any one of [1] to [5], further containing a curing agent.
[7] Composite metal oxide pigment containing Bi oxide and Cu oxide, general formula Si (OR) ₄ (wherein R may be the same as or different from each other, a hydrogen atom or a carbon number of 1 to 5) A silicon-containing compound (A) comprising a compound represented by (2) and / or a partial condensate thereof, a fluororesin, a curing agent, and a solvent. And
A heat ray highly reflective coating comprising the composite metal oxide pigment, the fluororesin, a main agent containing a part of the solvent, and the curable composition containing the silicon-containing compound (A), a curing agent, and the remainder of the solvent. A kit for preparing a composition.
[8] A composite metal oxide pigment containing an oxide of Bi and an oxide of Cu, a non-fluorine polymer (B) containing 10% by mass or more of repeating units having two or more hydroxy groups based on all repeating units ), A kit for preparing a heat ray highly reflective coating composition containing a fluororesin, a curing agent and water,
Heat ray height comprising the composite metal oxide pigment, the main component containing the fluororesin, and a part of water, and the curable composition containing the non-fluorine polymer (B), a curing agent, and the remainder of the water. A kit for preparing a reflective coating composition.
[9] A heat ray high reflection paint having a coating film formed by coating the heat ray high reflection paint composition according to any one of [1] to [6].
[10] A coated article having a coating film layer (X) and a coating film layer (Y) formed on the coating film layer (X) on the object to be coated,
The coating layer (X) contains a composite metal oxide pigment containing a Bi oxide and a Cu oxide, and a resin component (xt),
The coating layer (Y) is a compound represented by the general formula Si (OR) ₄ (wherein R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). And / or a silicon-containing compound (A) comprising a partial condensate thereof and a fluororesin (y).
[11] A coated article having a coating film layer (X) and a coating film layer (Y) formed on the coating film layer (X) on the object to be coated,
The coating layer (X) contains a composite metal oxide pigment containing a Bi oxide and a Cu oxide, and a resin component (xt),
The coating layer (Y) contains a non-fluorine polymer (B) containing 10% by mass or more of repeating units having two or more hydroxy groups with respect to all repeating units, and a fluororesin (y). A heat ray highly reflective paint characterized by this.
[12] The heat ray highly reflective coated article according to [10] or [11], wherein the coating layer (X) and / or the coating layer (Y) further contains a curing agent.
[13] On the object to be coated, a composite metal oxide pigment containing Bi oxide and Cu oxide, a composition (X1) containing a fluororesin (x) and a solvent are applied to form a coating layer ( X)
Next, a general formula Si (OR) ₄ (wherein R may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) on the coating layer (X). Applying a silicon-containing compound (A) comprising a compound represented by the present invention and / or its partial condensate, and a composition (Y1) containing a fluororesin (y) and a solvent to form a coating layer (Y). A method for producing a heat-reflective coating that is characterized.
[14] A composite metal oxide pigment containing an oxide of Bi and an oxide of Cu, a composition (X1) containing a fluororesin (x) and water is applied onto an object to be coated, and a coating layer ( X)
Next, a non-fluorine polymer (B) containing 10% by mass or more of repeating units having two or more hydroxy groups based on the total repeating units on the coating layer (X), and a fluororesin (y) And a composition (Y1) containing water and water to form a coating film layer (Y).

According to the heat ray high reflection paint composition, the heat ray high reflection paint composition preparation kit, and the method for producing the heat ray high reflection paint of the present invention, a dark color system having high heat ray reflection performance without using a manganese compound. A coating film and a coated product can be obtained.
Moreover, the heat ray highly reflective paint of the present invention does not require the use of a manganese compound, and has high heat ray reflection performance while being a dark color system.

<Coating composition (I)>
The heat ray highly reflective coating composition of the present invention (hereinafter also referred to as “coating composition (I)”) is a composite metal oxide pigment (hereinafter referred to as “composite pigment M”) containing an oxide of Bi and an oxide of Cu. And a fluororesin.
The coating composition (I) is preferably a coating composition (Ia) described later or a coating composition (Ib).

[Composite Pigment M]
The composite pigment M plays a role of imparting heat ray reflection performance to the coating film obtained from the coating composition (I). The composite pigment M is a dark pigment containing a Bi oxide and a Cu oxide. The composite pigment M is mixed and dispersed in the coating composition (I).
The content of the Cu oxide in the composite pigment M is preferably 5 to 95% by mass, and more preferably 20 to 80% by mass. If the Cu oxide content is at least the lower limit value, a black pigment with good reflection performance is easily obtained.
The content of the Bi oxide in the composite pigment M is preferably 5 to 95% by mass, and more preferably 20 to 80% by mass. If the content of Bi oxide is not less than the lower limit, a black pigment with good reflection performance can be easily obtained.
Moreover, the composite pigment M may contain the other coloring pigment mentioned later as needed.
The composite pigment M is preferably an oxide obtained by firing a mixture of Bi and Cu at a firing temperature of 700 ° C. or higher. Note that Bi and Cu 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 100 particles arbitrarily selected by 15,000 times magnified photograph observation with an electron microscope (SEM). If the average particle diameter of the composite pigment M is less than or equal to the upper limit value, it is easy to suppress a decrease in gloss of the formed coating film. Moreover, if the average particle diameter of the composite pigment M is more than a lower limit, the colorability will be good.
As a commercial item of the composite pigment M satisfying the condition of an average particle size of 0.1 μm to 30 μm, for example, Daiphiroxide Black # 9581 manufactured by Dainichi Seika Kogyo Co., Ltd. may be mentioned.

  When only the composite pigment M is used as the pigment, the content of the composite pigment M in the coating composition (I) is the fluororesin in the coating composition (I) and other resins used as required (hereinafter, These are collectively referred to as “resin component.” However, other resins do not include the non-fluorine polymer (B) described below, and the same shall apply hereinafter (in this specification, the content of various pigments and resin components). The amount is a content by dry solid content).) Is preferably 0.1% by mass or more, more preferably 0.1 to 200% by mass, and 10 to 100% by mass. Is more preferable. If the said content of the composite pigment M is more than a lower limit, sufficient heat ray reflective effect will be easy to be acquired. Moreover, if the said content of the composite pigment M is below an upper limit, it will be easy to suppress that the glossiness of the coating film formed falls.

[Other colored pigments]
In addition to the composite pigment M, the coating composition (I) may contain other colored pigments 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, fine silica, phthalocyanine blue, phthalocyanine green, quinacridone, isoindolinone, and benzimidazolone. And organic pigments such as dioxazine.
The titanium oxide is preferably titanium oxide whose surface is coated with cerium oxide or the like. The titanium oxide is available as Ishihara Sangyo Co., Ltd., trade name “PFC-105”; Sakai Chemical Co., Ltd., trade name “D-918”. .
However, from the viewpoint of improving the heat ray reflection performance, when the coating composition is applied to the surface of the object to be coated to form a coating film, the resulting surface of the object to be painted has a dark color tone. It is preferable that Specifically, the lightness L ^* defined in JIS Z 8729 on the surface of the coated object is preferably 5 to 80, and more preferably 10 to 60.

When other colored pigments are contained in addition to the composite pigment M, the total content of the pigment in the coating composition (I) is based on the total content of the entire pigment and the resin component in the coating composition (I). 0.001 to 80% by mass is preferable, and 0.1 to 60% by mass is more preferable. If the content of the entire pigment is equal to or more than the lower limit value, it is easy to suppress the content of the composite pigment M from being excessively reduced and the heat ray reflection effect from being lowered. Moreover, if the said content of the whole pigment is below an upper limit, it will be easy to suppress that the glossiness of the coating film formed falls.
The ratio of the composite pigment M to the entire pigment when other colored pigments are contained in addition to the composite pigment M is preferably 0.1 to 100% by mass, and more preferably 20 to 100% by mass. If the ratio of the composite pigment M to the entire pigment is equal to or more than the preferable lower limit value, the excellent heat ray reflection characteristics of the composite pigment M are easily exhibited in the obtained coating film. By using the composite pigment M and other pigments, it is possible to adjust to an arbitrary color.

[Fluororesin]
The fluororesin is a polymer having a repeating unit (β1) having a fluorine atom, a resin having a clear melting point, a resin having no melting point, an elastomeric polymer exhibiting rubber elasticity, and a thermoplastic elastomeric polymer. Is included.
The fluororesin preferably has a crosslinkable group. That is, it is preferable to have a repeating unit (β2) having a crosslinkable group. The crosslinkable group is a functional group that forms a chemical bond (crosslink) by reacting with each other or with a curing agent.
As the fluororesin, a copolymer having a repeating unit (β1) having a fluorine atom and a repeating unit (β2) having a crosslinkable group is preferable.

(Repeating unit (β1))
The repeating unit (β1) is formed by polymerizing a monomer having a fluorine atom (hereinafter referred to as “monomer (b1)”).
As the monomer (b1), a monomer having a fluorine atom which is usually used as a raw material for a fluororesin can be used. Specifically, fluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), vinylidene fluoride (VdF), and vinyl fluoride (VF); fluoroalkyl groups Examples thereof include olefins and fluorovinyl ethers such as perfluoro (alkyl vinyl ether) (PAVE). Among these, fluoroolefins are preferable, TFE, HFP, CTFE, VdF, and VF are more preferable, TFE, CTFE, and VdF are more preferable, TFE and CTFE are particularly preferable, and weather resistance, chemical resistance, and permeability of the cured coating film are preferable. From the point of wetness, CTFE is most preferable.
A monomer (b1) may be used individually by 1 type, and may use 2 or more types together.

(Repeating unit (β2))
The repeating unit (β2) can be formed by polymerizing a monomer having a crosslinkable group (hereinafter referred to as “monomer (b2)”). The monomer (b2) may be any monomer having a crosslinkable group and a polymerizable unsaturated group copolymerizable with the monomer (b1). A monomer (b2) may be used individually by 1 type, and may use 2 or more types together.
Examples of the crosslinkable group in the monomer (b2) include a hydroxyl group, a carboxy group, an amino group, an epoxy group, and a hydrolyzable silyl group. Of these, a hydroxyl group, a carboxy group, and an epoxy group are preferred, and a hydroxyl group is particularly preferred from the viewpoint of crosslinking reactivity, availability, and ease of introduction into the copolymer.

The monomer having a hydroxyl group (hereinafter referred to as “monomer (b21)”) is a monomer having a hydroxyl group and a polymerizable unsaturated group.
Examples of the monomer (b21) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2. -Vinyl ethers having a hydroxyl group such as methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether; Allyl ethers having a hydroxyl group such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether A hydroxyalkyl ester of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; Of these, vinyl ethers having a hydroxyl group are preferred, and 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are more preferred from the viewpoints of availability, polymerization reactivity, and hydroxyl crosslinking.
A monomer (b21) may be used individually by 1 type, and may use 2 or more types together.

A monomer having a carboxy group (hereinafter referred to as “monomer (b22)”) is a monomer having a carboxy group and a polymerizable unsaturated group, and can be easily converted to a monomer having a carboxy group. Also included are anhydrides of unsaturated dicarboxylic acids.
Examples of the monomer (b22) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, undecylenic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, and phthalate. Unsaturated monocarboxylic acids such as vinyl acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; unsaturated dicarboxylic acid monoesters such as itaconic acid monoester, maleic acid monoester and fumaric acid monoester; Examples thereof include anhydrides of unsaturated dicarboxylic acids such as acid anhydrides. In addition to these, vinyl ethers or allyl ethers of polyvalent carboxylic acids such as vinyl pyromellitic acid are listed. Of these, crotonic acid, undecylenic acid, maleic acid, and itaconic acid are preferred from the viewpoints of availability, polymerization reactivity, and crosslinkability.
A monomer (b22) may be used individually by 1 type, and may use 2 or more types together.

The monomer having an epoxy group (hereinafter referred to as “monomer (b23)”) is a monomer having an epoxy group and a polymerizable unsaturated group. The epoxy group in the monomer (b23) is preferably a glycidyl group.
As the monomer (b23), glycidyl vinyl ether, glycidyl allyl ether, and (meth) acrylic acid glycidyl ester are preferable.
A monomer (b23) may be used individually by 1 type, and may use 2 or more types together.

The repeating unit (β2) is preferably a repeating unit formed by polymerizing the monomer (b2).
However, the repeating unit (β2) is not limited to the repeating unit formed by polymerizing the monomer (b2). For example, when a carboxy group is introduced as a crosslinkable group of the repeating unit (β2), the monomer (b21) is copolymerized, and an acid anhydride is reacted with the hydroxyl group introduced into the obtained copolymer. A carboxy group can be introduced by a method.
Examples of the acid anhydride include succinic anhydride, hexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3- Examples thereof include dicarboxylic acid anhydride and 4-methylhexahydrophthalic anhydride.
In the above description, the repeating unit (β2) not containing a fluorine atom is exemplified, but the repeating unit (β2) may have a crosslinkable group and may or may not contain a fluorine atom.

If necessary, the fluororesin may be used in addition to the repeating unit (β1) and the repeating unit (β2), in addition to the monomer (b1) and the monomer (b2) (hereinafter referred to as “single amount”). The repeating unit (β3) based on the “body (b3)”) may be included.
Examples of the monomer (b3) include olefins, alkyl vinyl ethers in which an alkyl group and a polymerizable unsaturated group are linked by an ether bond, or a carboxylic acid in which an alkyl group and a polymerizable unsaturated group are linked by an ester bond. Acid vinyl esters are preferred.

Examples of olefins include ethylene, propylene, and isobutylene.
Examples of the alkyl vinyl ethers include ethyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and the like.
Examples of the carboxylic acid vinyl esters include vinyl versatate.

The ratio of the repeating unit (β1) to the entire repeating unit (100 mol%) of the fluororesin is preferably 35 to 65 mol%, and more preferably 40 to 60 mol%. When the ratio of the repeating unit (β1) is within the above range, it is easy to achieve both the weather resistance of the formed cured coating film and the solubility in a solvent.
The ratio of the repeating unit (β2) to the entire repeating unit (100 mol%) of the fluororesin is preferably 6 to 50 mol%, and more preferably 7 to 40 mol%. If the ratio of the repeating unit (β2) is not less than the lower limit of the above range, the degree of cross-linking of the formed cured coating film is increased and the hardness and the like are improved.
If the ratio of the repeating unit (β2) is not more than the upper limit of the above range, gelation hardly occurs in the coating composition of the present invention.
The ratio of the repeating unit (β3) to the total repeating unit (100 mol%) of the fluororesin is preferably 45 mol% or less, and more preferably 35 mol% or less.
For the production of the fluororesin, a known polymerization method can be employed, and specifically, a polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization or the like can be employed.

  The number average molecular weight (Mn) of the fluororesin is preferably 5,000 to 20,000. If Mn of a fluororesin is more than a lower limit, the weather resistance of the cured coating film formed will improve. Moreover, if Mn of a fluororesin is below an upper limit, the viscosity of a coating composition will become moderate and handleability will improve. Mn of the fluororesin is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

  The fluorine content of the fluororesin is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more from the viewpoint of improving weather resistance. On the other hand, the fluorine content of the fluororesin is preferably 35% by mass or less from the viewpoint of the solubility of the fluororesin in the solvent. The fluorine content of the fluororesin is the total mass ratio of fluorine atoms of the fluororesin to the mass of the fluororesin.

  5-60 mass% is preferable and, as for content of the fluororesin in coating composition (I) (100 mass% including a solvent is included), 10-45 mass% is more preferable. If a fluororesin is more than the lower limit of the said range, a weather resistance will improve. If a fluororesin is below the upper limit of the said range, coating workability will improve.

[Other resins]
Moreover, coating composition (I) may contain other resin other than a fluororesin. Other resins include 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 resin, A silicone resin etc. are mentioned. Among these, an acrylic resin is preferable.
Moreover, it is preferable that other resin has the said crosslinkable group, it is more preferable that it has a hydroxyl group, and the acrylic resin which has a hydroxyl group from a viewpoint of a weather resistance is especially preferable.
It is particularly preferable that the resin component of the coating composition (I) is composed only of a fluororesin. Moreover, when other resin is contained as a resin component, it is preferable that a fluororesin is 5-98 mass% with respect to the whole resin component, and it is more preferable that it is 30-98 mass%.
5-80 mass% is preferable and, as for content of the resin component in coating composition (I) (it is set as 100 mass% including a solvent), 10-60 mass% is more preferable. When the resin component is at least the lower limit of the above range, the coating film thickness can be secured. If the resin component is not more than the upper limit of the above range, the coating workability is improved.
Moreover, it is preferable that content of the fluororesin in a resin component is 5-100 mass%, and it is more preferable that it is 30-100 mass%. The higher the content of the fluororesin in the resin component, the higher the weather resistance.

[Curing agent]
The coating composition (I) can contain a curing agent. The curing agent reacts with the resin component to form a crosslinked structure. A hardening | curing agent is suitably selected according to the kind of crosslinkable group which the resin component contained in coating composition (I) has. In coating composition (I), it is preferable that the crosslinkable group which a fluororesin and the other resin used as needed are a hydroxyl group, and a hardening | curing agent is a polyisocyanate type hardening | curing agent (C).

As the polyisocyanate curing agent (C), the following curing agent (C1) is preferable from the viewpoint of excellent solubility in a solvent. However, the polyisocyanate curing agent is not limited to the following curing agent (C1), and general polyisocyanate curing agents such as hexamethylene diisocyanate and isophorone diisocyanate may be used.
Curing agent (C1): Allophanate group (All) and isocyanate obtained by reacting one or more diisocyanates selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates with monoalcohols having 1 to 20 carbon atoms. A polyisocyanate curing agent having a molar ratio (All / Iso) of nurate groups (Iso) of 81/19 to 90/10.
An aliphatic diisocyanate is a diisocyanate compound having an aliphatic group in the molecule. On the other hand, alicyclic diisocyanate is a diisocyanate compound having a cyclic aliphatic group in the molecule.

Examples of the aliphatic diisocyanate include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 1,6-diisocyanato-2,2,4- Examples include trimethylhexane and methyl 2,6-diisocyanatohexanoate (lysine diisocyanate). Of these, HDI is preferred from the viewpoint of industrial availability.
Examples of the alicyclic diisocyanate include 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane (also known as isophorone diisocyanate) and 1,3-bis (isocyanatomethyl) cyclohexane (also known as hydrogenated). Xylylene diisocyanate), bis (4-isocyanatocyclohexyl) methane (also known as hydrogenated diphenylmethane diisocyanate), 1,4-diisocyanatocyclohexane and the like. Of these, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are preferred from the viewpoint of industrial availability.
As the diisocyanate, an aliphatic diisocyanate is preferable to an alicyclic diisocyanate from the viewpoint that the curing agent (C1) has a low viscosity, and HDI is particularly preferable from the viewpoint of the weather resistance and flexibility of the formed cured coating film. preferable.

  The lower limit of the carbon number of the monoalcohol having 1 to 20 carbon atoms is 1, from the viewpoint of solubility in a solvent, 2 is preferable, 3 is more preferable, 4 is more preferable, and 6 is particularly preferable. The upper limit of the carbon number of the monoalcohol is 20 from the viewpoint of the hardness of the cured coating film to be formed, 16 is preferable, 12 is more preferable, and 9 is more preferable.

The monoalcohol is preferably composed only of a saturated hydrocarbon group and a hydroxyl group. Moreover, it is preferable that the monoalcohol has a branch.
Examples of the monoalcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, and 2-hexanol. 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1,3,5-trimethylcyclohexanol, 3,3,5-trimethyl-1-hexanol, tridecanol, pentadecanol, pal Examples include methyl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, methylcyclohexanol, trimethylcyclohexanol, and the like.

Monoalcohol is isobutanol, 1-butanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1- in terms of solubility in a solvent. Hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol, 1,3,5-trimethylcyclohexanol, 3,3,5-trimethyl-1-hexanol are preferred, isobutanol, 2-hexanol, 2-octanol, 2-Ethyl-1-hexanol and 3,3,5-trimethyl-1-hexanol are more preferred.
In addition, monoalcohol has a lower viscosity such as 1-propanol, isobutanol, 1-butanol, isoamyl alcohol, 1-pentanol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2 -Octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol are preferred.
The monoalcohol is not limited to those described above, and may be a monoalcohol having an ether group, an ester group, or a carbonyl group in the molecule.
Monoalcohol may use only 1 type and may use 2 or more types together.

The molar ratio (All / Iso) of allophanate groups (All) and isocyanurate groups (Iso) in the curing agent (C1) is preferably 81/19 to 90/10. When the molar ratio (All / Iso) is within the above range, curability and solubility in a solvent are excellent. The lower limit of the molar ratio (All / Iso) is more preferably 83/17. The upper limit of the molar ratio (All / Iso) is preferably 88/12, more preferably 86/14.
The molar ratio (All / Iso) is determined by the ¹ H-NMR method described in International Publication No. 2008/047761 pamphlet.

  The content of the isocyanate group in the curing agent (C1) (100% by mass) (hereinafter referred to as “NCO content”) is preferably 10 to 22% by mass from the viewpoint of solubility in a solvent and crosslinkability. 13-21 mass% is more preferable, and 16-20 mass% is further more preferable.

  The lower limit of the viscosity of the curing agent (C1) is preferably 50 mPa · s, more preferably 75 mPa · s, further preferably 100 mPa · s, and 120 mPa · s from the viewpoint of crosslinkability. s is particularly preferred. The upper limit of the viscosity of the curing agent (C1) is preferably 500 mPa · s, more preferably 450 mPa · s, further preferably 400 mPa · s, and particularly preferably 350 mPa · s from the viewpoint of reducing the volatile organic compound (VOC). 300 mPa · s is most preferable.

The average number of isocyanate groups in the curing agent (C1) is preferably 2.10 to 2.50, more preferably 2.15 to 2.40, from the viewpoint of curability and solubility in a solvent, and 2.20. ~ 2.35 is more preferred.
The average number of the isocyanate groups is determined by the following formula as described in International Publication No. 2008/047761.
(Average number of isocyanate groups) = (Number average molecular weight) × (NCO content) / 4200
The number average molecular weight of the curing agent (C1) can be measured by GPC.

When the polyisocyanate curing agent (C) is used as a curing agent, it may be a blocked polyisocyanate curing agent in which the isocyanate group is protected, and a non-blocking polyisocyanate curing agent in which the isocyanate group is not protected. It may be. When an unblocked polyisocyanate curing agent is used as the curing agent, the curing agent is blended immediately before the coating composition is applied. On the other hand, when a blocked polyisocyanate curing agent is used as the curing agent, the blending time of the curing agent is not particularly limited.
As the blocked polyisocyanate curing agent, a curing agent in which an isocyanate group in an isocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate is blocked with methyl ethyl ketone oxime or the like is preferable.

When the crosslinkable group of the resin component is a hydroxyl group and the curing agent is a polyisocyanate curing agent (C), the hydroxyl group of the resin component contained in the coating composition, that is, a fluororesin, and if necessary 0.3-2.0 are preferable and, as for the molar ratio (OH / NCO) of the isocyanate group of a hardening | curing agent, and the sum total of the hydroxyl group which the other resin to use has, 0.7-1.3 are more preferable. When the molar ratio (OH / NCO) is not less than the lower limit, the solvent resistance is improved. When the molar ratio (OH / NCO) is equal to or less than the upper limit, weather resistance is improved, and it is easy to suppress the occurrence of poor curing (remaining tack).
A polyisocyanate type hardening | curing agent (C) may be used individually by 1 type, and may use 2 or more types together.

What is necessary is just to select suitably the hardening | curing agent in case the crosslinkable group which the resin component contained in coating composition (I) has other than a hydroxyl group according to the kind of this crosslinkable group.
When the crosslinkable group of the resin component contained in the coating composition (I) is a carboxy group, examples of the curing agent include known amino curing agents and epoxy curing agents.
When the crosslinkable group of the resin component fat contained in the coating composition (I) is an amino group, as the curing agent, known curing agents having a carbonyl group, epoxy curing agents, acid anhydride curing agents Etc.
When the crosslinkable group of the fluororesin contained in the coating composition (I) and other resin used as necessary is an epoxy group, the curing agent may be a known curing agent having a carboxy group, acid An anhydride type hardening | curing agent, an amino type hardening | curing agent, etc. are mentioned.
A hardening | curing agent may be used individually by 1 type, and may use 2 or more types together.

[Other ingredients]
As long as the coating composition (I) I is within the range not impairing the effects of the present invention, a curing catalyst, a light stabilizer, an ultraviolet absorber, a matting agent, a surfactant, a leveling agent, an antifoaming agent, a dispersing agent, and the like. Other components may also be included.
Examples of the curing catalyst include dibutyltin dilaurate when a polyisocyanate-based curing agent (C) is used as the curing agent.

Examples of the light stabilizer include hindered amine light stabilizers. As the hindered amine light stabilizer, for example, trade names “MARX LA62” and “MARX LA67” manufactured by Adeka Argus Chemical Co., Ltd .; trade names “TINUVIN 292”, “TINUVIN 144”, “TINUVIN 123” manufactured by BASF Japan, “Tinuvin 440” and the like.
Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, triazine compounds, and cyanoacrylate compounds. Specifically, “Viosorb130”, “Viosorb582”, “Viosorb583”, “Viosorb910” (trade name, manufactured by Kyodo Pharmaceutical Co., Ltd.), “Ubinar 3039”, “Tinuvin 320”, “Tinuvin 384-2”, “Tinubin 982” ”,“ Tinubin 1130 ”,“ Tinubin 400 ”,“ Tinubin 379 ”(above, trade name, manufactured by BASF Japan Ltd.), and the like. Examples of matting agents include ultra fine powder synthetic silica. When a matting agent is used, it is possible to form a cured film with an elegant semi-glossy and matte finish.

The surfactant may be any of nonionic type, cationic type, anionic type, ROLEX ASE (Daiichi Kogyo Co., Ltd., trade name), Fluorosurfactant "Surflon" (Asahi Glass Co., Ltd., trade name) In addition, “Modaflow” (trade name) manufactured by Monsanto Co., Ltd., “Leo Fat” series (trade name, manufactured by Kao Corporation), and the like are available.
If a leveling agent is mix | blended, the uniformity of the thickness of the cured coating film to form will improve. As the leveling agent, BYK-300 (manufactured by BYK-Chemie, trade name), Floren No. 3 (manufactured by Kyoeisha Chemical Co., Ltd., trade name), Disparon LF 1985 (manufactured by Enomoto Kasei Co., Ltd., trade name) and the like.

<Coating composition (Ia)>
The coating composition (Ia) is the coating composition (I) and further contains a silicon-containing compound (A).

[Silicon-containing compound (A)]
The silicon-containing compound (A) is a compound represented by the general formula Si (OR) ₄ (wherein R may be the same as or different from each other, and represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and The silicon-containing compound (A), which is a partial condensate thereof, is a component that contributes to the stable maintenance of the heat ray reflection performance of the composite pigment M by preventing contamination of the coating film surface obtained by the coating composition (Ia). .

If the carbon number of R in the general formula exceeds 5, the effect of maintaining the heat ray reflection performance tends to decrease, so the carbon number of R is 1-5. R is preferably an alkyl group having 1 or 2 carbon atoms because a particularly excellent heat ray reflection performance maintaining effect is obtained. A particularly preferable silicon-containing compound (A) is tetramethoxysilane, tetraethoxysilane, or a partial condensate thereof.
The silicon-containing compound (A) preferably has a SiO ₂ content of 20 to 60% by mass. When the SiO ₂ content is 20% by mass or more, the effect of maintaining the heat ray reflection performance is excellent, and when it is 60% by mass or less, the storage stability is excellent.
“SiO ₂ component” means a silicon-containing compound (A before mixing with other components of the coating composition) before the hydrolysis and condensation reaction of the alkoxy group occurs in the coating composition. ) Is the value indicating the silica content in terms of SiO ₂ when the total mass is 100 mass%.

The content of the silicon-containing compound (A) with respect to the resin component is preferably 0.5 to 60% by mass, and more preferably 2 to 30% by mass. If the content of the silicon-containing compound (A) is too small, the effect of maintaining the heat ray reflection performance is lowered, and if it is too large, foam, sagging, leveling, etc. may occur and the paintability may be inferior.
Moreover, it is preferable to contain a hydrophilization promoter for promoting dealkoxy group reaction of the silicon-containing compound (A) and reticulation of molecules. Examples of the hydrophilization accelerator include conventionally known acidic catalysts such as hydrochloric acid and p-toluenesulfonic acid, and metal chelate compounds such as aluminum chelate.
It is preferable that content of the hydrophilization promoter of a silicon containing compound (A) is 0.1-50 mass% with respect to solid content of a silicon containing compound (A).

  The silicon-containing compound (A) improves the stain resistance of the coating film by imparting hydrophilicity to the coating film surface obtained by the coating composition (Ia). And it is thought that an improvement in stain resistance prevents a decrease in the heat ray reflection performance of the composite pigment M contained in the coating composition (Ia).

[solvent]
The coating composition (Ia) is preferably a liquid composition, and examples thereof include a non-aqueous solvent-type paint, a water-based paint, and a non-water emulsion-type paint, and a non-aqueous solvent-type paint containing a solvent is preferred. .
Examples of the solvent when the coating composition (1a) is a non-aqueous solvent-type coating material include those that can be generally used as a solvent for coating materials. Petroleum-based mixed solvents such as: aromatic hydrocarbons such as mineral spirits; 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.

[Production method]
The coating composition (Ia) is obtained by mixing the above-described components. The order of mixing is not particularly limited, but a pigment such as composite pigment M is mixed in advance with a solvent solution of the resin component, and a silicon-containing compound (A) or silicon-containing compound (A) and a solvent solution of a curing agent are added thereto. Is preferred.
The hydrophilization accelerator for the silicon-containing compound (A) is preferably added in advance to the silicon-containing compound (A). However, when the time from the mixing of the silicon-containing compound (A) into the resin solution and the pigment to the coating is long, the hydrophilization accelerator for promoting the reticulation of the silicon-containing compound (A) is a coating composition. It is preferable to blend immediately before painting.
Additives such as matting agents, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, UV absorbers, light stabilizers, curing catalysts, etc., are mixed into the resin solution together with the pigment. It is preferable.
The coating composition (Ia) can be easily prepared by using the heat ray high reflection coating composition preparation kit (IIa) described later and mixing the main agent and the curing composition.

<Coating composition (Ib)>
The coating composition (Ib) is the coating composition (I) and further contains a non-fluorine polymer (B).

[Non-fluorine polymer (B)]
The non-fluorine polymer (B) is a non-fluorine polymer containing 10% by mass or more of repeating units having two or more hydroxy groups (hereinafter referred to as “repeating units (α1)”) based on all repeating units. It is. The non-fluorine polymer is a polymer having no fluorine atom.
The non-fluorine polymer (B) plays a role of imparting stain resistance to the formed coating film.
The non-fluorine polymer (B) has a repeating unit (α1) and, if necessary, has a repeating unit other than the repeating unit (α1) (hereinafter referred to as “repeating unit (α2)”). May be.
The repeating unit (α1) can be introduced into the polymer by polymerizing a polymerizable monomer having two or more hydroxy groups (hereinafter referred to as “monomer (a1)”), for example. The repeating unit (α1) 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 (a1) 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 (a1), 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. Further, R ¹ may contain a functional group other than a hydroxy group, and other atoms such as a nitrogen atom and a chlorine atom.

Specific examples of the monomer (a1) include the following monomers.
Monomer (a1-1): an ester of a trifunctional or higher functional polyol compound or saccharide with (meth) acrylic acid or the like.
Monomer (a1-2): 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, and 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 repeating unit (α1) contained in the non-fluorine polymer (B) may be one type or two or more types.
Content of the repeating unit ((alpha) 1) in a non-fluorine-type polymer (B) is 10-100 mass% with respect to all the repeating units, and it is preferable that it is 30-100 mass%. If content of a repeating unit ((alpha) 1) is more than a lower limit, the coating film which has the outstanding stain | pollution resistance will be formed.

The repeating unit (α2) is a repeating unit other than the repeating unit (α1), that is, a repeating unit having one hydroxy group or no hydroxy group.
At least one of the repeating units (α2) is preferably a repeating unit having a crosslinkable functional group excluding two or more hydroxy groups (hereinafter referred to as “repeating unit (α21)”). Moreover, as a repeating unit other than the repeating unit (α21) in the repeating unit (α2), the repeating unit other than the repeating unit (α1) and a repeating unit other than the repeating unit (α21), ie, having no hydroxy group or crosslinkable functional group. And a repeating unit (hereinafter referred to as “repeating unit (α22)”). The repeating unit (α2) may be either one of the repeating unit (α21) or the repeating unit (α22), or a combination of the repeating unit (α21) and the repeating unit (α22).

Examples of the crosslinkable functional group that the repeating unit (α21) has include crosslinkable functional groups that are generally used in a crosslinking reaction. Specifically, an aldehyde carbonyl group, a ketonic carbonyl group, and one hydroxy group. Carboxy group, sulfo group, phosphoric acid residue, epoxy group, amino group, oxazoline residue, amide group, alkoxy group, hydrolyzable silyl group.
Examples of the polymerizable monomer that gives the repeating unit (α21) (hereinafter referred to as “monomer (a21)”) include monomers having a crosslinkable functional group. Specific examples of the monomer (a21) include the following monomers.
Monomer (a21-1): A monomer having an aldehyde carbonyl group.
Monomer (a21-2): A monomer having a ketonic carbonyl group.
Monomer (a21-3): A monomer having one hydroxy group.
Monomer (a21-4): A monomer having a carboxy group or a salt thereof.
Monomer (a21-5): A monomer having a sulfo group or a salt thereof.
Monomer (a21-6): A monomer having a phosphate residue or a salt thereof.
Monomer (a21-7): A monomer having an epoxy group.
Monomer (a21-8): A monomer having an amino group or a salt thereof.
Monomer (a21-9): A monomer having an oxazoline residue.
Monomer (a21-10): A monomer having an amide group.
Monomer (a21-11): Monomer having an alkoxy group.
Monomer (a21-12): A monomer having a hydrolyzable silyl group.
However, carbonyl in the monomer (a21-1) and the monomer (a21-2) represents aldehyde and ketone, respectively, and excludes ester, amide, and carboxy.

Examples of the monomer (a21-1) 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 (a21-2) 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 (a21-2) 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 (a21-3) 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 (a21-3) may be a monomer having a polyoxyalkylene chain (hereinafter referred to as “POA chain”) and having a hydroxy group at the end. 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 _{O) m (C 3 H 6} O) n H and the like.
Examples of commercially available monomers (a21-3) having a POA chain and having a terminal hydroxyl group include 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 (a21-4) 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 (a21-5) 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 (a21-6) include phosphoric acid 2-acryloyloxyethyl ester, phosphoric acid 2-methacryloyloxyethyl ester, and salts thereof.

Examples of the monomer (a21-7) include glycidyl (meth) acrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, and 3,4-epoxy-1-butene.
Examples of the monomer (a21-8) 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 (a21-9) 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 (a21-10) include (meth) acrylamide, N-vinylformamide, and N-vinylacetamide.

  Examples of the monomer (a21-11) 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 (a21-11) 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 (a21-12) 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 repeating unit (α21) is a repeating unit obtained from at least one monomer selected from the group consisting of monomer (a21-1), monomer (a21-2) and monomer (a21-9). Preferably it is a unit.
1 type may be sufficient as the repeating unit ((alpha) 21) which a non-fluorine-type polymer (B) has, and 2 or more types may be sufficient as it.

  The content of the repeating unit (α21) in the non-fluorinated polymer (B) is preferably 0.01% by mass or more and less than 90% by mass, and particularly preferably 1 to 50% by mass. If the said content is more than a lower limit, the stain resistance of the coating film formed and its durability are better. If the content is less than the upper limit, the storage stability of the coating composition is better.

The following monomers are mentioned as a polymerizable monomer (a22) which gives a repeating unit ((alpha) 22).
Monomer (a22-1): hydrocarbon-based olefins.
Monomer (a22-2): Vinyl ethers.
Monomer (a22-3): Isopropenyl ethers.
Monomer (a22-4): Allyl ethers.
Monomer (a22-5): Vinyl esters.
Monomer (a22-6): Allyl esters.
Monomer (a22-7): alkyl (meth) acrylic acid ester.
Monomer (a22-8): Aromatic vinyl compound.
Monomer (a22-9): Chloroolefins.
Monomer (a22-10): Conjugated dienes.
Monomer (a22-11): a compound having a polyfunctional polymerizable double bond.

Examples of the monomer (a22-1) include ethylene, propylene, and isobutylene.
Examples of the monomer (a22-2) 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 (a22-3) include methyl isopropenyl ether, ethyl isopropenyl ether, n-propyl isopropenyl ether, and n-butyl isopropenyl ether.
Examples of the monomer (a22-4) include ethyl allyl ether and cyclohexyl allyl ether.
Examples of the monomer (a22-5) include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl octoate, vinyl versatate, and vinyl octadecanoate.

Examples of the monomer (a22-6) include allyl acetate and allyl propionate.
Examples of the monomer (a22-7) 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.

As the monomer (a22-8), for example, 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 (a22-9) include vinyl chloride, vinylidene chloride, isopropenyl chloride, and allyl chloride.

Examples of the monomer (a22-10) include 1,3-butadiene, isoprene, chloroprene, and 2,3-dimethyl-1,3-butadiene.
Examples of the monomer (a22-11) 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 repeating unit (α22) may be one type or two or more types.

  The content of the repeating unit (α22) in the non-fluorinated polymer (B) is preferably less than 89.99% by mass from the viewpoint of the stain resistance of the coating film to be formed and its durability. It is especially preferable that it is 30 mass%.

  The molecular weight of the non-fluorinated polymer (B) is preferably 160 to 1,000,000, 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-fluorine polymer (B) is synthesized by, for example, a method in which the monomer (a1) is dissolved in a solvent together with the monomer (a2) as necessary and heated, and a polymerization initiator is added to react. it can.
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 (B), 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-fluorine polymer (B) in the coating composition (Ib) is preferably 0.1 to 100% by mass, more preferably 0.5 to 50% by mass with respect to the resin component. Preferably, it is 1-30 mass%, and it is still more preferable. If the said content is more than a lower limit, the coating film which has the outstanding stain resistance will be easy to be formed. Moreover, if the said content is below an upper limit, it will be easy to improve the weather resistance of the coating film formed.

[solvent]
The coating composition (Ib) is preferably an aqueous coating composition containing water. However, a solvent may be included as long as it is within a range in which the heat ray reflection performance and the maintenance effect of the coating film to be formed and the working environment at the time of painting are not deteriorated excessively.
Solvents that can be used with water generally include solvents that can be used as paint solvents, such as toluene, xylene, ExxonMobil Solvesso 100, ExxonMobil Solvesso 150, and other petroleum-based mixed solvents; Group hydrocarbons; esters such as ethyl acetate and butyl acetate; and ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. These may be used alone or in combination with water, or two or more thereof may be used in combination with water.

[Production method]
The coating composition (Ib) is obtained by mixing the above-described components. The order of mixing is not particularly limited, but a pigment such as the composite pigment M is mixed in advance with an aqueous solution of a fluororesin and other resin to be used as necessary, and this is mixed with the non-fluorine polymer (B) or non-polymer. A method of adding an aqueous solution of the fluoropolymer (B) and the curing agent is preferred.
Additives such as matting agents, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, UV absorbers, light stabilizers, curing catalysts, etc., are mixed into the resin solution together with the pigment. It is preferable.
The coating composition (Ib) can be easily prepared by using the heat ray high reflection coating composition preparation kit (IIb) described later and mixing the main agent and the curing composition.

<Heat Ray High Reflective Coating Composition Preparation Kit (IIa)>
The heat ray highly reflective coating composition preparation kit (IIa) is a two-component curing type kit for preparing the coating composition (Ia) described above. The kit for preparing a heat ray highly reflective coating composition of the present invention comprises the main component containing the composite pigment M, the fluororesin, and a part of the solvent, the silicon-containing compound (A), the curing agent, and the remainder of the solvent. A curing composition is provided.
When the coating composition (Ia) is prepared by the kit for preparing the heat ray highly reflective coating composition of the present invention (IIa), the curing agent is preferably a non-blocked polyisocyanate curing agent not protected by a protective group. .
When using other resins than the fluororesin, the other resins are preferably contained in the main agent. . When a pigment other than the composite pigment M is used, the other pigment is also preferably contained in the main agent. The hydrophilization accelerator of the silicon-containing compound (A) is preferably added to the curable composition. Additives such as matting agents, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, UV absorbers, light stabilizers, curing catalysts, etc. are included in the main agent together with the composite pigment M It is preferable to make it.

The composition of the main agent and the curing composition in the heat ray highly reflective coating composition preparation kit (IIa) may be any composition that becomes the coating composition (Ia) described above when they are mixed.
The content of the composite pigment M in the main agent in the heat ray high reflection coating composition preparation kit (IIa) is preferably 0.1% by mass or more based on the total content of the composite pigment M and the resin component.
10-90 mass parts is preferable with respect to 100 mass parts of resin components for the solvent in the main ingredient in the heat ray highly reflective coating composition preparation kit (IIa).
10-90 mass parts is preferable with respect to 100 mass parts of silicon-containing compound (A), as for the solvent in the hardening composition in the heat ray highly reflective coating composition preparation kit (IIa).

<Heat Ray High Reflective Coating Composition Preparation Kit (IIb)>
The heat ray highly reflective coating composition preparation kit (IIb) is a two-component curing type kit for preparing the coating composition (Ib) described above. The kit for preparing a heat ray highly reflective coating composition of the present invention comprises a main agent containing the composite pigment M, the fluororesin, and a part of water, and a non-fluorine polymer (B), a curing agent, and water. A curable composition containing the remainder is provided.
When preparing the coating composition (Ib) with the kit for preparing a high heat-reflective coating composition of the present invention (IIb), the curing agent is preferably a non-blocked polyisocyanate curing agent that is not protected by a protective group. .
When using other resins than the fluororesin, the other resins are preferably contained in the main agent. When a pigment other than the composite pigment M is used, the other pigment is also preferably contained in the main agent. Additives such as matting agents, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, UV absorbers, light stabilizers, curing catalysts, etc. are included in the main agent together with the composite pigment M It is preferable to make it.

The composition of the main agent and the curing composition in the heat ray high reflection coating composition preparation kit (IIb) may be any composition that becomes the coating composition (Ib) described above when they are mixed.
The content of the composite pigment M in the main agent in the heat ray high reflection coating composition preparation kit (IIb) is preferably 0.1% by mass or more based on the total content of the composite pigment M and the resin component.
10-90 mass parts is preferable with respect to 100 mass parts of resin components for the solvent in the main ingredient in the heat ray highly reflective coating composition preparation kit (IIb).
The solvent in the curable composition in the heat ray highly reflective coating composition preparation kit (IIb) is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer (B).

<High heat reflective coating>
The heat ray highly reflective coated product of the present invention has a coated article obtained from the coating composition (I) on the article to be coated (heat ray highly reflective coated article IIIs), or the article to be coated has the composite pigment M and the resin component. (Xt) (however, the resin component (xt) does not include the non-fluorine polymer (B); the same shall apply hereinafter) and the silicon-containing compound (A) to the non-fluorine-based material. A polymer (B) and a coating layer (Y) containing a fluororesin (y) are sequentially provided (heat ray high reflection paint IIIa, heat ray high reflection paint IIIb).

[Coated article]
There is no particular limitation on the material of the article to be coated. For example, there are inorganic materials such as concrete, natural stone, and glass, metals such as iron, stainless steel, aluminum, copper, brass, and titanium, or wood. Moreover, fiber reinforced plastic, resin reinforced concrete, fiber reinforced concrete, etc. which are organic-inorganic composite materials may be used.
Further, it may be an article having another coating film or adhesive layer already formed on the surface, or a layer of plastic, rubber or the like.

  Articles to be painted include transportation equipment such as automobiles, trains and aircraft, civil engineering members such as bridge members and steel towers, waterproof materials such as sheets and asphalt, industrial equipment such as tanks and pipes, building exteriors, doors and windows. Examples include gate members, monuments, building members such as poles, road median strips, road members such as guardrails, communication equipment, electrical and electronic parts, and the like.

[Heat ray highly reflective coating (IIIs)]
The heat ray highly reflective coating (IIIs) is an article having a coating film formed by coating the article to be coated with the coating composition (I). Although the thickness of a coating film is not specifically limited, 5-100 micrometers is preferable and 20-50 micrometers is more preferable. When the film thickness is reduced, the concealability and weather resistance tend to be reduced, and when it is increased, construction problems such as sagging tend to occur.
The method of coating the coating composition (I) on the article to be coated can be performed by various methods. For example, brush coating, spray coating, dipping method, roll coater or flow coater can be applied.

  When coating the coating composition (I) on the article to be coated, the pre-treatment used when applying the normal coating such as surface polishing, sanding, sealing, primer treatment, primer coating, etc. Preferably it is done. The sealing agent, primer, and undercoat used here are not particularly limited and include organic solvent solutions, non-aqueous dispersions, aqueous solutions, and aqueous dispersions.

Examples of the primer or primer include epoxy resin-based, modified epoxy resin-based, polyester resin-based, epoxy-modified polyester resin-based, vinyl resin-based, and chlorinated rubber-based paints. If necessary, zinc phosphate, lead Including rust preventive pigments such as red powder, zinc dust, lead oxide, calcium lead acid, cyanamide lead, basic lead chromate, basic lead sulfate, and scaly pigments such as iron oxide, mica, aluminum, glass flakes, etc. Good. Moreover, in order to improve rust prevention power, the zinc rich primer described in JIS K5552 may be used, and two or more kinds of the above-described solvent-based undercoat materials can be applied repeatedly.
There is no limitation on the curing method of the coating composition (I), and various curing methods such as a thermosetting type, a thermoplastic type, a room temperature drying type, and a room temperature curing type can be used.

[Heat ray highly reflective coating (IIIa)]
The heat ray highly reflective coating (IIIa) is an article in which a coating layer (X) and a coating layer (Y) are sequentially provided on the article to be coated. The coating layer (Y) of the heat ray highly reflective coating (IIIa) is a coating layer (Ya) containing the silicon-containing compound (A).

The coating layer (X) contains the composite pigment M and the resin component (xt). The composite pigment M is equivalent to the composite pigment M in the coating composition (I), and may contain other pigments as in the coating composition (I). Further, the resin component (xt) can contain a fluororesin (x) equivalent to the fluororesin in the coating composition (I) and / or another resin similar to the coating composition (I).
The coating layer (X) can contain a curing agent equivalent to the curing agent in the coating composition (I). Moreover, you may contain other components, such as a curing catalyst, a light stabilizer, a ultraviolet absorber, a matting agent, surfactant, a leveling agent, an antifoamer, a dispersing agent similarly to coating composition (I).

A desirable ratio of each component in the coating layer (X) is a coating composition (Ia) except that it does not contain a silicon-containing compound (A), does not necessarily contain a fluororesin, and does not contain a solvent. It is the same.
For example, the content of the composite pigment M in the coating layer (X) is preferably 0.1% by mass or more based on the total content of the composite pigment M and the resin component (xt). More preferably, it is -200 mass%, and it is further more preferable that it is 10-100 mass%.
Moreover, it is preferable that content of the whole pigment in coating-film layer (X) is 0.1 mass% or more with respect to the total content of the whole pigment and the resin component (xt), and 0.1-200 It is more preferable that it is mass%, and it is further more preferable that it is 10-100 mass%.

Moreover, it is preferable that it is 30-99 mass%, and, as for content of the resin component (xt) in coating-film layer (X) (100 mass%), it is more preferable that it is 50-99 mass%.
Moreover, it is preferable that it is 0-100 mass%, and, as for content of the fluororesin (x) in the resin component (xt), it is more preferable that it is 30-100 mass%. The higher the content of the fluororesin (x) in the resin component (xt), the higher the weather resistance. However, since the coating layer (X) is covered with the coating layer (Y), the fluororesin (x) The content of may be low or zero.
The molar ratio (OH / NCO) of the total hydroxyl groups of the resin component (xt) and the isocyanate groups of the curing agent when the curing agent is a polyisocyanate curing agent (C) is 0.3-2. 0 is preferable, and 0.7 to 1.3 is more preferable.
Although the thickness of coating-film layer (X) is not specifically limited, 5-100 micrometers is preferable and 20-50 micrometers is more preferable. When the film thickness is reduced, the concealability and weather resistance tend to be reduced, and when it is increased, construction problems such as sagging tend to occur.

The coating layer (Ya) contains a silicon-containing compound (A) and a fluororesin (y).
The silicon-containing compound (A) is the same as the silicon-containing compound (A) in the coating composition (Ia). The fluororesin (y) is equivalent to the fluororesin in the coating composition (I), and may contain other resins as in the coating composition (I).
The coating layer (Ya) can contain a curing agent equivalent to the curing agent in the coating composition (I). Moreover, you may contain other components, such as a curing catalyst, a light stabilizer, a ultraviolet absorber, a matting agent, surfactant, a leveling agent, an antifoamer, a dispersing agent similarly to coating composition (I).

A desirable ratio of each component in the coating layer (Ya) is the same as that of the coating composition (Ia) except that the composite pigment M is not contained and a solvent is not contained.
For example, the content of the silicon-containing compound (A) in the coating layer (Ya) is a fluororesin and other resins used as necessary (hereinafter collectively referred to as “resin component (yt)”, provided that The other resin does not contain the non-fluorinated polymer (B), the same shall apply hereinafter) and the total content of 100 parts by mass of the curing agent is preferably 1.5 to 90 parts by mass. -30 mass parts is more preferable.

The content of the resin component (yt) in the coating layer (Ya) (100% by mass) is preferably 30 to 99% by mass, and more preferably 50 to 99% by mass.
Moreover, 5-100 mass% is preferable and, as for content of the fluororesin (y) in a coating-film layer (Ya) (100 mass%), 30-100 mass% is more preferable.
The molar ratio (OH / NCO) of the total hydroxyl groups of the resin component (yt) and the isocyanate groups of the curing agent when the curing agent is a polyisocyanate curing agent (C) is 0.3-2. 0 is preferable, and 0.7 to 1.3 is more preferable.
Although the thickness of a coating-film layer (Ya) is not specifically limited, 5-100 micrometers is preferable and 20-50 micrometers is more preferable. When the film thickness is reduced, the concealability and weather resistance tend to be reduced, and when it is increased, construction problems such as sagging tend to occur.

  The heat ray highly reflective coated product (IIIa) has a reflection performance of the heat ray highly reflective coated product (IIIa) between the coating layer (X) and the coating layer (Ya), an effect of maintaining the reflecting performance, and an aesthetic appearance. Another intermediate layer may be provided within a range that does not hinder the effect of maintaining. However, it is preferable that the coating layer (Ya) is formed on the surface of the coating layer (X) and no intermediate layer is provided.

The heat ray highly reflective coating (IIIa) has a coating layer (X) containing the composite pigment M and a coating layer (Ya) containing the silicon-containing compound (A), so that contamination is not noticeable. The heat ray reflection performance can be stably maintained.
The composite pigment M is contained in the coating layer (X) and the silicon-containing compound (A) is separately contained in the coating layer (Ya), and the coating layer (Ya) is placed on the coating layer (X). Prepare. Therefore, the surface contamination prevention effect by the silicon-containing compound (A) is further improved, and the deterioration of the composite pigment M is further suppressed. In addition, the heat ray highly reflective coating (IIIa) is provided with the coating layer (Y) as the uppermost layer, so that the effect of maintaining the aesthetics by preventing the surface contamination and the effect of maintaining the heat ray reflection performance are particularly high. .

[Heat ray highly reflective coating (IIIb)]
The heat ray highly reflective coating (IIIb) is an article in which a coating film layer (X) and a coating film layer (Y) are sequentially provided on the article to be coated. The coating layer (Y) of the heat ray highly reflective coating (IIIb) is a coating layer (Yb) containing the non-fluorinated polymer (B).

The coating layer (X) contains the composite pigment M and the resin component (xt). The composite pigment M is equivalent to the composite pigment M in the coating composition (I), and may contain other pigments as in the coating composition (I). Further, the resin component (xt) can contain a fluororesin (x) equivalent to the fluororesin in the coating composition (I) and / or another resin similar to the coating composition (I).
The coating layer (X) can contain a curing agent equivalent to the curing agent in the coating composition (I). Moreover, you may contain other components, such as a curing catalyst, a light stabilizer, a ultraviolet absorber, a matting agent, surfactant, a leveling agent, an antifoamer, a dispersing agent similarly to coating composition (I).

A desirable ratio of each component in the coating layer (X) is a coating composition (except for a point not containing the non-fluorine polymer (B), a point not containing a fluororesin, and a point not containing a solvent). Same as Ib).
For example, the content of the composite pigment M in the coating layer (X) is preferably 0.1% by mass or more based on the total content of the composite pigment M and the resin component (xt). More preferably, it is -200 mass%, and it is further more preferable that it is 10-100 mass%.
Moreover, it is preferable that content of the whole pigment in coating-film layer (X) is 0.1 mass% or more with respect to the total content of the whole pigment and the resin component (xt), and 0.1-200 It is more preferable that it is mass%, and it is further more preferable that it is 10-100 mass%.

Moreover, it is preferable that it is 30-99 mass%, and, as for content of the resin component (xt) in coating-film layer (X) (100 mass%), it is more preferable that it is 50-99 mass%.
In addition, the content of the fluororesin (x) in the resin component (xt) is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, in the resin component (xt). The higher the content of (x), the higher the weather resistance, but since the coating layer (X) is covered with the coating layer (Y), the content of the fluororesin (x) may be low, Zero is acceptable.
The molar ratio (OH / NCO) of the total hydroxyl groups of the resin component (xt) and the isocyanate groups of the curing agent when the curing agent is a polyisocyanate curing agent (C) is 0.3-2. 0 is preferable, and 0.7 to 1.3 is more preferable.
Although the thickness of coating-film layer (X) is not specifically limited, 5-100 micrometers is preferable and 20-50 micrometers is more preferable. When the film thickness is reduced, the concealability and weather resistance tend to be reduced, and when it is increased, construction problems such as sagging tend to occur.

The coating layer (Yb) contains a non-fluorine polymer (B) and a fluororesin (y).
The non-fluorine polymer (B) is equivalent to the non-fluorine polymer (B) in the coating composition (Ib). The fluororesin (y) is equivalent to the fluororesin in the coating composition (I), and may contain other resins as in the coating composition (I).
The coating layer (Yb) can contain a curing agent equivalent to the curing agent in the coating composition (I). Moreover, you may contain other components, such as a curing catalyst, a light stabilizer, a ultraviolet absorber, a matting agent, surfactant, a leveling agent, an antifoamer, a dispersing agent similarly to coating composition (I).

A desirable ratio of each component in the coating layer (Yb) is the same as that of the coating composition (Ib) except that the composite pigment M is not contained and a solvent is not contained.
For example, the content of the non-fluorine polymer (B) in the coating layer (Yb) is preferably 0.1 to 100% by mass, and 0.5 to 50% by mass with respect to the resin component (yt). % Is more preferable, and 1 to 30% by mass is even more preferable.

Moreover, it is preferable that it is 30-99 mass%, and, as for content of the resin component (yt) in a coating-film layer (Yb) (100 mass%), it is more preferable that it is 50-99 mass%.
Moreover, 5-100 mass% is preferable and, as for content of the fluororesin (y) in a coating-film layer (Yb) (100 mass%), 30-100 mass% is more preferable.
Moreover, since the non-fluorine polymer (B) acts as a curing agent, the coating layer (Yb) may not contain other curing agents. That is, the molar ratio (OH / NCO) of the total hydroxyl groups of the resin component (yt) and the isocyanate groups of the curing agent when the curing agent is a polyisocyanate curing agent (C) is 0.0-2. 0 is preferable and 0.0 to 1.3 is more preferable.
Although the thickness of a coating-film layer (Yb) is not specifically limited, 5-100 micrometers is preferable and 20-50 micrometers is more preferable. When the film thickness is reduced, the concealability and weather resistance tend to be reduced, and when it is increased, construction problems such as sagging tend to occur.

  The heat ray high reflection coating product (IIIb) has a reflection performance of the heat ray high reflection coating material (IIIb) between the coating layer (X) and the coating layer (Yb), an effect of maintaining the reflection performance, and an aesthetic appearance. Another intermediate layer may be provided within a range that does not hinder the effect of maintaining. However, it is preferable that the coating layer (Yb) is formed on the surface of the coating layer (X) and no intermediate layer is provided.

The heat ray highly reflective coating (IIIb) has a coating layer (X) containing the composite pigment M and a coating layer (Yb) containing the non-fluorine polymer (B), so that the contamination is conspicuous. It is difficult to maintain the heat ray reflection performance stably.
Further, the composite pigment M is contained in the coating layer (X) and the non-fluorine polymer (B) is separately contained in the coating layer (Yb), and the coating layer (Yb) is contained in the coating layer (X). Prepare for the top. Therefore, the surface contamination prevention effect by the non-fluorinated polymer (B) is further improved, and the deterioration of the composite pigment M is further suppressed. In addition, the heat ray highly reflective coating (IIIb) is provided with the coating layer (Y) as the uppermost layer, so that the effect of maintaining the aesthetics by preventing the surface contamination and the effect of maintaining the heat ray reflection performance are particularly high. .

<Manufacturing method of heat ray highly reflective coating>
The manufacturing method of the heat ray highly reflective coated product of the present invention is a method for producing the heat ray highly reflective coated product (IIIa) or the heat ray highly reflective coated product (IIIb). A coating layer (X) is formed, and then the composition (Y1) is applied onto the coating layer (X) to form the coating layer (Y).

[Production method of heat ray highly reflective coating (IVa)]
The manufacturing method (IVa) of the heat ray high reflection coating product is a manufacturing method of the heat ray high reflection coating material (IIIa). The composition (X1) in the production method (IIIa) of the heat ray highly reflective coating is a composition (X1a) containing a solvent, and the composition (Y1) is a composition (Y1a) containing a silicon-containing compound (A) and a solvent. The coating layer (Y) is a coating layer (Ya) containing the silicon-containing compound (A).

The composition (X1a) is a coating composition for forming the coating layer (X), and the composition (Y1a) is a coating composition for forming the coating layer (Ya). Or it is the composition for application | coating containing each essential component contained in a coating-film layer (Ya), an arbitrary component, and a solvent.
That is, the composition (X1a) contains the composite pigment M, the fluororesin (x), and a solvent as essential components, and may include an optional component in the coating layer (X). The composition (Y1a) may contain the silicon-containing compound (A), the fluororesin (y), and a solvent as essential components, and may include an optional component of the coating layer (Ya).
As the solvent in the composition (X1a) and the composition (Y1a), the same solvent as that in the coating composition (Ia) is used. The composition (X1a) and the composition (Y1a) are each a solvent composition obtained by dissolving or dispersing each essential component and optional component contained in the coating layer (X) or the coating layer (Ya) in a solvent.

  There is no limitation on the blending order of each component of the composition (X1a). However, when adding a curing agent, a pigment such as the composite pigment M is mixed in advance with a solvent solution of the resin component (xt), and a curing agent is added thereto. The method of adding is preferable. In addition, when adding additives such as matting agents, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, light stabilizers, and curing catalysts, resin components ( xt) is preferably mixed with the solvent solution.

  There is no limitation on the blending order of each component of the composition (Y1a), but when adding the hydrophilization promoter of the silicon-containing compound (A), the hydrophilization promoter is added to the silicon-containing compound (A) in advance. It is preferable to keep it. Moreover, when the time from mixing the composition (Y1a) into the solvent composition to application is long, it is preferable to add a hydrophilization accelerator immediately before applying the composition (Y1a).

  There is no limitation on the curing method of the composition (X1a) and the composition (Y1a), and various curing methods such as a thermosetting type, a thermoplastic type, a room temperature drying type, and a room temperature curing type can be used.

  When the composition (X1a) is applied to an object to be coated, pre-treatment that is usually used when applying a paint such as polishing of the surface, sanding, sealing, primer treatment, and application of a primer is performed. It is preferable. 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. The sealing agent, primer, and undercoat used here are not particularly limited and 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, zinc phosphate, red lead, zinc dust, lead oxide , Anticorrosive pigments such as calcium leadate, lead cyanamide, basic lead chromate, and basic lead sulfate, and scaly pigments such as iron oxide, mica, aluminum, and glass flakes. Moreover, in order to improve rust prevention power, a zinc rich primer may be used, and two or more kinds of the above-mentioned undercoat materials can be applied repeatedly.

  Various methods can be applied to the method of applying the composition (X1a) and the composition (Y1a). For example, brush coating, spray coating, dipping method, roll coater or flow coater can be applied. The composition (X1a) and the composition (Y1a) are applied by applying the composition (Y1a) after the composition (X1a) is applied and dried to form the coating layer (X). It is preferable. Moreover, when forming an intermediate | middle layer, before application | coating of a composition (Y1a), formation of an intermediate | middle layer is performed by methods, such as application | coating as needed.

  Application of the composition (Y1a) may be performed before the composition (X1a) (and the intermediate layer) is completely dried. The application of the composition (X1a) and the composition (Y1a) may be performed once or more. The method of performing coating a plurality of times is preferable as a method of increasing the film thickness without causing sagging.

[Production method of heat ray highly reflective coating (IVb)]
The manufacturing method (IVb) of the heat ray high reflection coating product is a manufacturing method of the heat ray high reflection coating material (IIIb). The composition (X1) in the production method (IIIb) of the heat ray highly reflective coating is a composition (X1b) containing water, and the composition (Y1) is a composition containing a non-fluorine polymer (B) and water ( Y1b), and the coating layer (Y) is a coating layer (Yb) containing the non-fluorinated polymer (B).

The composition (X1b) is a coating composition for forming the coating layer (X), and the composition (Y1b) is a coating composition for forming the coating layer (Yb). Or it is the composition for application | coating containing each essential component contained in a coating-film layer (Yb), arbitrary components, and water.
That is, the composition (X1b) contains the composite pigment M, the fluororesin (x), and water as essential components, and may include an optional component in the coating layer (X). The composition (Y1b) contains the non-fluorine polymer (B), the fluororesin (y) and water as essential components, and may contain an optional component of the coating layer (Yb).
As the solvent in the composition (X1b) and the composition (Y1b), the same solvent as the solvent in the coating composition (Ib) can be used in addition to water. The composition (X1b) and the composition (Y1b) are each an aqueous composition obtained by dissolving or dispersing each essential component and optional component contained in the coating layer (X) or the coating layer (Yb) in a solvent containing water. And

  There is no limitation on the blending order of each component of the composition (X1b), but when adding a curing agent, a pigment such as composite pigment M is mixed in advance with an aqueous solution of the resin component (xt), and a curing agent is added thereto. Is preferred. In addition, when adding additives such as matting agents, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, light stabilizers, and curing catalysts, resin components ( xt) is preferably mixed with an aqueous solution.

  There is no limitation on the curing method of the composition (X1b) and the composition (Y1b), and various curing methods such as a thermosetting type, a thermoplastic type, a room temperature drying type, and a room temperature curing type can be used.

When the composition (X1b) is coated on the object to be coated, it is preferable to perform the same pretreatment as in the coating of the composition (X1a) in the production method (IIIb) of the heat ray highly reflective coated object.
Moreover, the method similar to apply | coating a composition (X1a) and a composition (Y1a) is employable as the method of apply | coating a composition (X1b) and a composition (Y1b). Moreover, when forming an intermediate | middle layer, before application | coating of a composition (Y1b), an intermediate | middle layer is formed by methods, such as application | coating as needed.
Application of the composition (Y1b) may be performed before the composition (X1b) (and the intermediate layer) is completely dried. The application of the composition (X1b) and the composition (Y1b) may be performed once or more. The method of performing coating a plurality of times is preferable as a method of increasing the film thickness without causing sagging.

The present invention is described in detail below, but the present invention is not limited thereto.
The base material, the main agent, and the curing agent composition used in Examples and Comparative Examples are as follows. The main agent containing a pigment is called an enamel main agent, and the main agent not containing a pigment is called a clear main agent.

[Prescription]
(Base material)
As the base material, an aluminum plate 140 mm × 240 mm × 0.5 mm subjected to a chromate treatment and an undercoating agent and an intermediate coating agent were sequentially applied.
As the undercoat, Bon Epocoat 55MP and white (manufactured by AGC Co-Tech, epoxy paint) were used. Bonflon # 1000 white (manufactured by AGC Co-Tech, fluorine paint) was used as the intermediate coating agent.

(Enamel main ingredient 1)
16.0 g of xylene was added to 69.0 g of fluororesin Lumiflon LF-200. Next, 13.0 g of dipyroxide black # 9581 (Cu, Bi composite oxide pigment manufactured by Dainichi Seika Kogyo Co., Ltd.) was added and dispersed with a sand mill. Further, 0.0005 g of dibutyltin dilaurate was added and stirred to make an enamel main ingredient 1.

(Enamel main ingredient 2)
16.0 g of xylene was added to 69.0 g of fluororesin Lumiflon LF-200. Next, 13.0 g of black 6301 (manufactured by Asahi Kasei Kogyo Co., Ltd., Mn, Bi composite oxide pigment, manganese content 29% by mass) was added and dispersed by a sand mill. Further, 0.0005 g of dibutyltin dilaurate was added and stirred, and enamel main ingredient 2 was obtained.

(Enamel main ingredient 3)
Xylene 28.0g was added to 69.0g of fluororesin Lumiflon LF-200. Next, 3.0 g of Mitsubishi Carbon Black MA-11 (Mitsubishi Chemical Corporation) was added and dispersed with a sand mill. Further, 0.0005 g of dibutyltin dilaurate was added and stirred to obtain an enamel main ingredient 3.

(Enamel main ingredient 4)
Weak solvent-soluble fluororesin Lumiflon LF-800S, a copolymer of chlorotrifluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether and hydroxyalkyl vinyl ether [manufactured by Asahi Glass Co., Ltd., hydroxyl group-containing fluoroolefin copolymer (hydroxyl value: 52 mgKOH / g 2) 72.72 g of mineral spirit A (manufactured by Nippon Petrochemical Co., Ltd.) was added to 64.28 g of the organic solvent solution containing 60% by mass.
Next, 13.0 g of dipyroxide black # 9581 (Cu, Bi composite oxide pigment manufactured by Dainichi Seika Kogyo Co., Ltd.) was added and dispersed with a sand mill. Further, 0.0005 g of dibutyltin dilaurate was added and stirred to obtain an enamel main agent 4.

(Clear base 1)
To 69.00 g of fluororesin Lumiflon LF-200, 3.0 g of UV absorber (manufactured by Kyodo Pharmaceutical Co., Ltd .: Viosorb 910) and 28.00 g of xylene were added, and 0.0005 g of dibutyltin dilaurate was further added and stirred. Was defined as Clear Main Agent 1.

(Curing agent composition 1)
To 20.9 g of Duranate A2400-100 (a weak solvent-soluble non-yellowing type isocyanate curing agent manufactured by Asahi Kasei Chemicals Corporation), 10 of ethyl silicate 48 (COLCOT Co., Ltd., SiO ₂ 48% by weight ethyl silicate condensate). Curing agent composition 1 was prepared by adding 18.3 g of .8 g and mineral spirit A (manufactured by Nippon Petrochemical Co., Ltd.) and mixing them.

(Curing agent composition 2)
22.9 g of Duranate A2400-100 (a weak solvent soluble non-yellowing type isocyanate curing agent manufactured by Asahi Kasei Chemicals Co., Ltd.) and 29.1 g of mineral spirit A (manufactured by Shin Nippon Petrochemical Co., Ltd.) were added and mixed. Was designated as a curing agent composition 2.

(Curing agent composition 3)
1.8 g of aluminum chelate D (produced by Kawaken Fine Chemical Co., Ltd., aluminum chelate compound) was added to 30.8 g of Coronate HX (Nippon Polyurethane, non-yellowing type isocyanate curing agent) and mixed, and MKC silicate MS56S [Mitsubishi 17.4 g of a methyl silicate condensate made by Kagaku Co., SiO ₂ min 56% by weight] was added and mixed to obtain a curing agent composition 3.

(Curing agent composition 4)
Curing agent composition 4 was prepared by adding 19.2 g of xylene to 30.8 g of coronate HX.

Example 1
A coating composition obtained by mixing 12 g (9.7 g as dry solid content) of the hardener composition 3 with 100 g (54 g as dry solid content) of the enamel main ingredient 1 was coated on a substrate with a bar coater. It apply | coated so that it might become a film thickness of 30 micrometers. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60%, and the test body of Example 1 was obtained.

(Example 2)
The coating composition obtained by mixing 100 g of enamel main ingredient 1 (54 g as a dry solid content) and 12 g (7.4 g as a dry solid content) of the curing agent composition 4 on a substrate with a bar coater, It apply | coated so that it might become a film thickness of 30 micrometers, and it cured for 24 hours under the temperature of 23 degreeC and 60% of relative humidity, and formed the coating layer (X).
Next, a coating composition obtained by mixing 12 g of the curing agent composition 3 (9.7 g as the dry solid content) with 100 g of the clear main agent 1 (45 g as the dry solid content) was used as the coating layer (X). The coating was applied on the top with a bar coater to a thickness of 30 μm to form a coating layer (Y).
Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test body of Example 2.

(Example 3)
The coating composition obtained by mixing 100 g of enamel main ingredient 1 (54 g as a dry solid content) and 12 g (7.4 g as a dry solid content) of the curing agent composition 4 on a substrate with a bar coater, It apply | coated so that it might become a film thickness of 30 micrometers. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test body of Example 3.

Example 4
The coating composition obtained by mixing 100 g of enamel main ingredient 1 (54 g as a dry solid content) and 12 g (7.4 g as a dry solid content) of the curing agent composition 4 on a substrate with a bar coater, It apply | coated so that it might become a film thickness of 30 micrometers, and it cured for 24 hours under the temperature of 23 degreeC and 60% of relative humidity, and formed the coating layer (X).
Next, a coating composition obtained by mixing 12 g (7.4 g as dry solid content) of the curing agent composition 4 with 100 g (45 g as dry solid content) of the clear main agent 1 was used as the coating layer (X). The coating was applied on the top with a bar coater to a thickness of 30 μm to form a coating layer (Y).
Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test body of Example 4.

(Example 5)
A coating composition obtained by mixing 15 g of curing agent composition 2 (6.3 g as dry solids) with 100 g of enamel main ingredient 4 (52 g as dry solids) was placed on a substrate with a bar coater. It apply | coated so that it might become a film thickness of 30 micrometers. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test body of Example 5.

(Comparative Example 1)
A coating composition obtained by mixing 12 g (9.7 g as dry solids) of the hardener composition 3 with 100 g (54 g as dry solids) of the enamel main ingredient 2 was placed on a substrate with a bar coater. It apply | coated so that it might become a film thickness of 30 micrometers. Thereafter, curing was performed at a temperature of 23 ° C. and a relative humidity of 60% for 7 days to obtain a specimen of Comparative Example 1.

(Comparative Example 2)
A coating composition obtained by mixing 12 g of curing agent composition 4 (7.4 g as dry solids) with 100 g of enamel main ingredient 2 (54 g as dry solids) was coated on a substrate with a bar coater. It apply | coated so that it might become a film thickness of 30 micrometers. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60% to obtain a test sample of Comparative Example 2.

(Comparative Example 3)
A coating composition obtained by mixing 12 g (9.7 g as dry solids) of the hardener composition 3 with 100 g (44 g as dry solids) of the enamel main ingredient 3 was placed on a substrate with a bar coater. It apply | coated so that it might become a film thickness of 30 micrometers. Thereafter, curing was performed for 7 days at a temperature of 23 ° C. and a relative humidity of 60%, to obtain a specimen of Comparative Example 3.

[Evaluation]
(Initial adhesion test)
About each test body, the adhesiveness of the coating film was evaluated according to JISK5600-5-6 (adhesiveness: cross-cut method). The results are shown in Table 1.

(Initial solar reflectance measurement)
For each test specimen, the spectral reflectance was measured with an ultraviolet-visible near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation), and near red according to JIS K5602 (how to determine the solar reflectance of the coating film). The solar reflectance of the outer area was calculated. The results are shown in Table 1.

(Measurement of water contact angle of coating film)
After curing of each specimen, the surface hydrostatic contact angle after 1 day of immersion in ion-exchanged water was measured with a contact angle measuring device DropMaster (manufactured by Kyowa Interface Science) to evaluate hydrophilicity. The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 5 containing the composite pigment M, the solar reflectance in the near infrared region was higher than those of Comparative Examples 1 to 3 using pigments other than the composite pigment M.

Claims (14)

 A heat ray highly reflective coating composition comprising a composite metal oxide pigment containing an oxide of Bi and an oxide of Cu and a fluororesin. Further, a compound represented by the general formula Si (OR) ₄ (wherein R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and / or a partial condensate thereof. The heat ray highly reflective coating composition according to claim 1, comprising a silicon-containing compound (A) comprising:   Furthermore, the heat ray highly reflective coating composition of Claim 2 containing a solvent.   Furthermore, the heat ray highly reflective coating composition of Claim 1 containing the non-fluorine-type polymer (B) which contains 10 mass% or more of repeating units which have a 2 or more hydroxy group with respect to all the repeating units.   Furthermore, the heat ray highly reflective coating composition of Claim 4 containing water.   Furthermore, the heat ray highly reflective coating composition as described in any one of Claims 1-5 containing a hardening | curing agent. A composite metal oxide pigment containing a Bi oxide and a Cu oxide, having a general formula Si (OR) ₄ (wherein R may be the same as or different from each other, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); A kit for preparing a highly heat-reflective coating composition containing a silicon-containing compound (A) comprising a compound represented by (2) and / or a partial condensate thereof, a fluororesin, a curing agent, and a solvent,
A heat ray highly reflective coating comprising the composite metal oxide pigment, the fluororesin, a main agent containing a part of the solvent, and the curable composition containing the silicon-containing compound (A), a curing agent, and the remainder of the solvent. A kit for preparing a composition. A composite metal oxide pigment containing an oxide of Bi and an oxide of Cu, a non-fluorine polymer (B) containing 10% by mass or more of a repeating unit having two or more hydroxy groups based on all repeating units, fluorine A kit for preparing a heat ray highly reflective coating composition containing a resin, a curing agent and water,
Heat ray height comprising the composite metal oxide pigment, the main component containing the fluororesin, and a part of water, and the curable composition containing the non-fluorine polymer (B), a curing agent, and the remainder of the water. A kit for preparing a reflective coating composition.   A heat ray high reflection paint having a coating film formed by coating the heat ray high reflection paint composition according to any one of claims 1 to 6. 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 a Bi oxide and a Cu oxide, and a resin component (xt),
The coating layer (Y) is a compound represented by the general formula Si (OR) ₄ (wherein R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). And / or a silicon-containing compound (A) comprising a partial condensate thereof and a fluororesin (y). 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 a Bi oxide and a Cu oxide, and a resin component (xt),
The coating layer (Y) contains a non-fluorine polymer (B) containing 10% by mass or more of repeating units having two or more hydroxy groups with respect to all repeating units, and a fluororesin (y). A heat ray highly reflective paint characterized by this.   The heat ray highly reflective coated article according to claim 10 or 11, wherein the coating layer (X) and / or the coating layer (Y) further contains a curing agent. On the object to be coated, a composite metal oxide pigment containing Bi oxide and Cu oxide, and a composition (X1) containing a resin component (xt) and a solvent are applied to form a coating layer (X). Form,
Next, a general formula Si (OR) ₄ (wherein R may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) on the coating layer (X). Applying a silicon-containing compound (A) comprising a compound represented by the present invention and / or its partial condensate, and a composition (Y1) containing a fluororesin (y) and a solvent to form a coating layer (Y). A method for producing a heat-reflective coating that is characterized. On the object to be coated, a composite metal oxide pigment containing Bi oxide and Cu oxide, and a composition (X1) containing a resin component (xt) and water are applied to form a coating layer (X). Formed,
Next, a non-fluorine polymer (B) containing 10% by mass or more of repeating units having two or more hydroxy groups based on the total repeating units on the coating layer (X), and a fluororesin (y) And a composition (Y1) containing water and water to form a coating film layer (Y).