JP5314847B2 - Heat ray highly reflective exterior material, method for producing the same, and exterior finishing method - Google Patents

Description

  The present invention relates to a heat ray highly reflective exterior material, a method for producing the same, and an exterior finishing method using the heat ray highly reflective exterior material.

Conventionally, in order to protect a structure from heat rays such as sunlight, prevent a temperature rise of the structure, or reduce energy consumption due to air conditioning, etc., it has heat shielding properties and heat energy such as sunlight. A structure in which a film is formed with a coating composition containing a pigment that can efficiently reflect light (for example, see Patent Document 1), or a coating in which a film is formed with a thermal barrier coating composition containing a hollow spherical or scaly low thermal conductor Constructions and the like have been developed (see, for example, Patent Document 2).
Japanese Patent No. 2593968 JP 2006-45447 A

  The present invention is an environment-friendly, antifouling property, and has a heat ray highly reflective exterior having a film including a coating composition layer that can stably maintain the ability to reflect heat rays such as sunlight on an exterior substrate An object of the present invention is to provide a material, a manufacturing method thereof, and an exterior finishing method using the heat ray highly reflective exterior material.

In order to solve the above-mentioned problems, a heat ray high-reflection exterior material according to the present invention includes a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn, and a general formula Si (OR) ₄ ( In the formula, R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) 1 or 2 selected from the group consisting of a compound represented by the above, a partial condensate thereof, and a photocatalyst A film including a layer of a coating composition containing the above substances is provided on the exterior substrate.

Moreover, the manufacturing method of the heat ray highly reflective exterior material according to the present invention includes a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn, and a 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.), One or more substances selected from the group consisting of a compound, a partial condensate thereof, and a photocatalyst And forming a film including a layer of a coating composition containing

  Furthermore, the exterior finishing method according to the present invention is characterized by using the above-mentioned heat ray highly reflective exterior material.

  Here, the content of the composite metal oxide pigment is preferably 0.005 to 5.00 wt% with respect to the total weight when it is not necessary to contain a resin in the coating composition, When the coating composition further contains a resin, it is preferably 0.01 to 10.00 wt% with respect to the solid content of the resin. Moreover, it is preferable that the surface layer of the said film | membrane is a layer which consists of photocatalysts. The film may further include a surface impregnating material.

  According to the present invention, the heat ray height is high on the exterior substrate, which is environmentally friendly and excellent in antifouling properties, and has a film comprising a coating composition layer that can stably maintain the ability to reflect sunlight such as sunlight. A reflective exterior material, a manufacturing method thereof, an exterior finishing method using the heat ray highly reflective exterior material, and the like can be provided.

  Hereinafter, the form for implementing this invention is demonstrated in detail, giving an Example.

== Heat-reflective exterior packaging material according to the present invention ==
As shown in the Examples, a composite metal oxide pigment (hereinafter referred to as “composite pigment”) containing an oxide of Bi and / or Y and an oxide of Mn, and a 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.) Or a partial condensate thereof (hereinafter referred to as “compound A”) Since the product does not contain chromium, it has excellent environmental properties, and the coating composition layer has excellent antifouling properties and heat ray reflection performance, and stably maintains the heat ray reflection performance. Can do.

  In addition, the coating composition containing a photocatalyst instead of compound A is also excellent in environmental properties because it does not contain chromium, and the hydrophilicity of the coating composition layer is improved by the photocatalyst. Therefore, it is considered that it has excellent antifouling property and can stably maintain excellent heat ray reflection performance by the composite pigment.

Therefore, a compound represented by a composite pigment and a 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), a portion thereof An exterior substrate provided with a film containing a layer of a coating composition (hereinafter simply referred to as “coating composition X”) containing one or more substances selected from the group consisting of a condensate and a photocatalyst, It is useful as a finishing material for the exterior part of a structure with excellent environmental properties (heat-reflective exterior material). By using this heat-ray highly reflective exterior material, the temperature of the structure can be prevented from rising, sunlight, etc. It is possible to prevent the deterioration of the structure and joint material due to the heat, prevent the structure from cracking due to the heat history, reduce the energy consumption by air conditioning, etc., and alleviate the heat island phenomenon. Moreover, when the film | membrane which consists of a layer of the coating composition X with little content of a composite pigment is provided in the exterior base material, the designability of an exterior base material can be ensured and aesthetics can be maintained. It becomes like this. Here, the exterior base material is not particularly limited as long as it is a base material used for an exterior part (for example, a roof or an outer wall of a structure) irradiated with heat rays such as sunlight. Tile, brick, stone, concrete, etc. can be used.

  In addition, although the heat ray highly reflective exterior material which concerns on this invention may have a film | membrane which consists of the coating composition X on an exterior base material, the film | membrane containing the layer of the coating composition X is provided on an exterior base material. You may have. For example, the film may be a film formed of the coating composition X in which a surface impregnating material is further mixed, or may be a film in which a layer made of the coating composition X is formed on the surface impregnating material. The film may be a film in which a layer made of the coating composition X is formed on the surface impregnated material, and further a layer made of a photocatalyst is formed, or the coating composition X or the coating composition in which the surface impregnated material is mixed The film | membrane which formed the layer which consists of the said photocatalyst on the layer which consists of X may be sufficient. By providing a layer made of a photocatalyst on the surface layer of the film as described above, it is possible to improve hydrophilicity and prevent contamination by a self-cleaning effect, improve designability, maintain aesthetics, and improve heat ray reflection performance. It becomes possible to prevent the decrease. Further, by including a surface impregnating material in the film, it is possible to protect the exterior material, prevent the coating composition X from penetrating into the exterior base material, and further use a large amount of the coating composition X. Can be prevented, and the film of the coating composition X can be made uniform.

  As the surface impregnating material, for example, a silane surface impregnation called a permeable water absorption preventing material, which has a monomer system (alkyl alkoxysilane, silane compound) or an oligomer system (silane oligomer, silane siloxane, silane) as a main component. Although existing materials such as materials and silicate surface impregnated materials can be used, it is preferable to use a clear surface impregnated material in that the design properties of the exterior base material are not impaired.

  The layer made of the photocatalyst is, for example, a photocatalyst particle-dispersed aqueous solution in which photocatalyst particles are dispersed in a solution of water, alcohol, acetone, n-hexane, toluene, or the like, an aqueous solution thereof and a binder (for example, silica-based binder, alumina). Mixed resin containing a photocatalytic binder), resin containing photocatalyst (for example, existing resin used for paint such as clear resin such as fluororesin, silicone resin, siloxane resin, acrylic resin, urethane resin, enamel resin) However, it is preferable to use a clear photocatalyst paint in that the design of the exterior base material is not impaired.

As the photocatalyst, there can be used, for example, an existing one such as titanium oxide or a content thereof (for example, one containing titanium oxide and a metal or metal oxide other than titanium or silica gel).
Below, each structural component of the coating composition X is demonstrated.

(Pigment)
The composite pigment M contains an oxide of Bi and / or Y and an oxide of Mn. The manganese content in the composite pigment M is preferably 5 to 65% by weight, and more preferably 10 to 50% by weight. If the manganese content is less than 5%, the heat ray reflection effect may not be sufficiently obtained.

  As the composite pigment M, it is preferable to use a mixture obtained by baking a mixture of Bi and / or Y and Mn at a baking temperature of 700 ° C. or higher. The average particle size of the composite pigment M is preferably 0.1 μm to 30 μm. If the average particle size is larger than 30 μm, the gloss may be lowered. Examples of commercially available products that satisfy these preferable conditions include Asahi Kasei Kogyo Co., Ltd. Black 6303, Black 6301, and the like.

The composite pigment M is a black-colored pigment, and can be dispersed and blended in the resin.
The content of the composite pigment M relative to the resin solid content is preferably 0.01 to 200% by weight when only the composite pigment M is used as the pigment in the coating composition X. When the content of the composite pigment M is less than 0.01% by weight, the heat ray reflection effect cannot be sufficiently obtained. On the other hand, if the content is more than 200% by weight, the gloss may be lowered. The content of the composite pigment M relative to the resin solid content is more preferably 0.01 to 10.00% by weight so as not to impair the design properties of the exterior base material, and 0.02 to 4%. It is particularly preferably 0.000% by weight, and most preferably 0.20 to 2.00% by weight. When the coating composition X does not need to contain a resin, the content of the composite pigment M is set to the total weight of the coating composition X so as not to impair the design of the exterior substrate. It is preferable to set it as 0.005-5.00 weight%.

  The coating composition X may contain other coloring pigments in order to adjust the color tone according to the application and purpose. For example, inorganic pigments such as titanium oxide, bengara, ocher, calcium carbonate, aluminum silicate, white carbon, fine powder silicic acid, and organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, isoindolinone, benzimidazolone, dioxazine, etc. Can be used.

  The content of the entire pigment relative to the resin solid content is preferably 0.01 to 200% by weight, and 0.01 to 10.00% by weight in order not to impair the design properties of the exterior base material. More preferably, 0.02 to 4.00% by weight is particularly preferable, and 0.20 to 2.00% by weight is most preferable. When the content of the entire pigment is less than 0.01% by weight, the content of the composite pigment M is decreased and the heat ray reflection effect cannot be sufficiently obtained. On the other hand, if the content of the entire pigment is more than 200% by weight, the gloss may be lowered. In addition, as described above, when the coating composition X does not need to contain a resin, the total content of the coating composition X is adjusted so as not to impair the design properties of the exterior substrate. It is preferable to set it as 0.005-5.00 weight% with respect to a weight.

(Compound A)
Compound A 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) or a partial condensate thereof. It is.
The coating composition X can maintain the heat ray reflective performance of the composite pigment M stably by containing the compound A.

  When the carbon number of R in the general formula exceeds 5, the effect of maintaining the heat ray reflection performance of the layer of the coating composition X is lowered. In particular, since the layer of the coating composition X can maintain excellent heat ray reflection performance, R is preferably an alkyl group having 1 or 2 carbon atoms. Particularly preferred compound A is tetramethoxysilane, tetraethoxysilane, or a partial condensate thereof.

The silica content in Compound A is preferably 20 to 60% by weight. When the silica content is less than 20% by weight, the effect of maintaining the heat ray reflection performance is lowered, and when it is more than 60% by weight, the storage stability is impaired.
In addition, the silica content contained in the compound A is a ratio (% by weight) occupied by the silica (SiO ₂ ) obtained when the compound A undergoes 100% hydrolysis condensation with respect to the compound A.

  The content of the compound A with respect to the resin solid content is preferably 0.5 to 60% by weight, and more preferably 2 to 30% by weight. When the content of Compound A is less than 0.5% by weight, the effect of maintaining the heat ray reflective performance of the coating composition X is reduced. When the content is more than 60% by weight, when the coating composition X is applied, Leveling or the like occurs, resulting in poor paintability. As described above, when the coating composition X does not need to contain a resin, the content of the compound A is 0.1 to 80% by weight with respect to the total weight of the coating composition X. It is preferably 0.5 to 40% by weight.

  The coating composition X may contain an accelerator for proceeding the dealkoxy group reaction of the compound A and reticulating the molecule. Examples of the accelerator include conventionally known acidic catalysts such as hydrochloric acid and p-toluenesulfonic acid, and metal chelate compounds such as aluminum chelate.

  In addition, in the coating composition X, the effect of maintaining the heat ray reflection performance by the compound A is obtained because, even in the film using the composite pigment M, the film contamination causes the heat ray reflection performance to deteriorate. It is thought that.

  That is, since the heat ray reflection performance of the dark-colored film is not based on high brightness, conventionally, the relationship between dirt and a decrease in heat ray reflection performance has not been considered. However, as a result of investigation, it has been clarified that the heat ray reflection performance of the composite pigment M, which is a black pigment, is also inhibited by dirt. Therefore, it is considered that the compound A that improves the stain resistance of the film by imparting hydrophilicity to the film can prevent the heat ray reflection performance of the composite pigment M from deteriorating.

(photocatalyst)
As a photocatalyst, existing things, such as a titanium oxide or its content (For example, a thing containing a metal other than titanium, a metal oxide other than titanium, or a silica gel), can be used, for example.

  Since the coating composition X contains a photocatalyst, it can improve hydrophilicity and prevent stains by a self-cleaning effect, so that it can exhibit excellent antifouling properties and stabilize the heat ray reflection performance of the composite pigment M. Can be maintained.

(resin)
As described above, for example, when the coating composition X contains a silicate-based surface impregnating material that is a permeable water absorption preventing material, the coating composition X does not need to contain a resin, but as necessary. The coating composition X may contain a resin. When the coating composition X contains a resin, part or all of the resin is preferably a fluororesin. This is because a film having good weather resistance can be obtained by using a fluororesin.

  As the fluororesin, a fluoroolefin copolymer is preferable. The fluoroolefin copolymer is a copolymer of a fluoroolefin and another copolymerizable monomer copolymerizable with the fluoroolefin.

  Examples of the fluoroolefin composing the fluoroolefin copolymer include C2-C3 fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, and vinyl fluoride.

  The proportion of the polymer units based on the fluoroolefin in the fluoroolefin copolymer is preferably 20 to 70 mol% in order to give the film sufficient weather resistance.

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

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

  Examples of the carboxylic acid vinyl ester or the carboxylic acid allyl ester include vinyl esters or allyl esters of carboxylic acids such as acetic acid, butyric acid, pivalic acid, benzoic acid, and propionic acid. Moreover, as a vinyl ester of a carboxylic acid having a branched alkyl group, commercially available Veova-9, Veova-10 (both manufactured by Shell Chemical Co., Ltd., trade names) and the like may be used. Examples of olefins include ethylene, propylene, and isobutylene.

Another copolymerizable monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
Further, the fluoroolefin copolymer preferably has a functional group capable of reacting with a curing agent described later to form a crosslink. The type of the functional group can be appropriately selected depending on the combination with the curing agent. Representative examples include a hydroxyl group, a carboxyl group, a hydrolyzable silyl group, an epoxy group, and an amino group.

  Examples of such a method for introducing a functional group include a method in which a monomer having a functional group is copolymerized in advance. Examples of the monomer having a functional group include the following. 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, hydroxyalkyl vinyl ethers such as cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, vinyl esters of hydroxyl-containing carboxylic acids such as hydroxyalkyl vinyl crotonate, or Monomers having a hydroxyl group such as allyl ester. Monomers having a carboxyl group such as crotonic acid and undecenoic acid. Monomers having hydrolyzable silyl groups such as triethoxyvinylsilane. Monomers having an epoxy group such as glycidyl vinyl ether and glycidyl allyl ether. Monomers having an amino group such as aminopropyl vinyl ether and aminopropyl vinyl ether.

  Moreover, you may introduce | transduce a functional group after superposition | polymerization of a monomer. As this method, a method in which a hydroxyl group is introduced by saponifying a polymer obtained by copolymerization of a vinyl carboxylate ester, a carboxyl group is introduced by reacting a polymer having a hydroxyl group with a polyvalent carboxylic acid or its anhydride. Examples thereof include a method of reacting an isocyanate alkylalkoxysilane with a hydroxyl group-containing polymer to introduce a hydrolyzable silyl group, a method of reacting a polymer having a hydroxyl group with a polyvalent isocyanate compound to introduce an isocyanate group, and the like. The

  Preferable specific examples of the fluoroolefin copolymer include, for example, a copolymer of chlorotrifluoroethylene, cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether, a copolymer of chlorotrifluoroethylene, alkyl vinyl ether and allyl alcohol, chloro Examples thereof include a copolymer of trifluoroethylene, an aliphatic carboxylic acid vinyl ester and a hydroxyalkyl vinyl ether, or a copolymer using tetrafluoroethylene in place of chlorotrifluoroethylene in these copolymers. These are commercially available under trade names such as Lumiflon (Asahi Glass) and Cefral Coat (Central Glass).

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

  As the resin contained in the coating composition X, in addition to the fluoroolefin copolymer, other fluororesin may be used alone or in combination with the fluoroolefin copolymer. In addition to fluororesin, alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinyl acetate resin, acrylic resin, vinyl chloride resin, phenol resin, silicone modified polyester resin, acrylic silicone A resin, a silicone resin, or the like may be used alone or in combination with a fluororesin. When the content of the composite pigment contained in the coating composition X is small, a clear resin is added to the coating composition X in order to ensure the design of the exterior base material or maintain the aesthetics. It is preferable to provide a film composed of the coating composition X layer on the exterior base material.

(Curing agent)
The coating composition X may contain a curing agent. As the curing agent, various curing agents known as coating curing agents can be used. Specific examples of the curing agent include amino-based curing agents such as aminoplasts and urea resins, polyvalent isocyanate-based curing agents, and block polyvalent isocyanate-based curing agents.
A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type. Note that when a self-curing resin is used, a curing agent is not essential.
In addition, there is no limitation on the curing method of the coating composition X, 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.

(Other ingredients)
The coating composition X may contain a fine particle filler, an additive, a solvent and the like as necessary.
As the fine particle filler, a hollow sphere that can impart heat insulation is generally used. As the hollow sphere, an inorganic balloon, a resin balloon or the like is known depending on the material. Specific examples include glass balloons, shirasu balloons, alumina balloons, zirconia balloons, and aluminosilicate balloons.
Additives are not particularly limited, for example, matting agents such as silica and alumina, antifoaming agents, leveling agents, anti-sagging agents, surface conditioners, viscosity modifiers, dispersants, ultraviolet absorbers, light stabilizers, Conventional additives such as a curing catalyst can be exemplified.
The coating composition X may be any of a non-aqueous solvent type paint, a water-based paint, a non-water emulsion type paint, and the like.

Therefore, the solvent is not particularly limited as long as it is generally used for paints. For example, petroleum, mixed solvents such as toluene, xylene, ExxonMobil Solvesso 100, ExxonMobil Solvesso 150 and the like, minerals Aromatic hydrocarbons such as spirit; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and water. These may be used alone or in combination of two or more.
When a solvent is used, it is preferable to use the resin solution by dissolving or dispersing the resin in the solvent.

(Manufacturing method of coating composition X)
The coating composition X is obtained by mixing the above components. The order of mixing is not particularly limited, but when the coating composition X contains a resin, a pigment is mixed in advance with the resin solution, and this is added to the general formula Si (OR) ₄ (wherein R may be the same as each other). 1 or 2 or more substances selected from the group consisting of a compound represented by a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a partial condensate thereof, and a photocatalyst. A method of adding a curing agent or the like is preferable.

  In addition, when the coating composition X contains the compound A, it is preferable to add the accelerator of the compound A to the compound A in advance. However, when the time from mixing the compound A into the pigment to coating is long, it is preferable that the accelerator for promoting reticulation of the compound A is blended immediately before the coating composition X is coated.

  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.

== Method for producing heat ray highly reflective exterior material according to the present invention ==
Next, the manufacturing method of the heat ray highly reflective exterior material which concerns on this invention is demonstrated.
The heat ray highly reflective exterior material according to the present invention can be produced by forming a film made of the coating composition X or a film including a layer of the coating composition X on the exterior substrate.

  Here, the film formed of the coating composition X can be formed by coating the coating composition X on the exterior substrate. In addition, the film including the layer of the coating composition X is formed by, for example, coating the surface impregnating material, coating the coating composition X, or coating the coating composition X, and then coating the above-described photocatalytic coating. Or after coating the surface impregnating material, the coating composition X is applied, and the above-mentioned photocatalyst coating is further applied. After coating the object X, coating the surface impregnating material, coating the coating composition X, or coating the coating composition X mixed with the surface impregnating material, the above-mentioned photocatalyst coating may be applied. preferable. The coating can be performed by various methods such as brush coating, spray coating, dipping method, roll coater or flow coater.

== Exterior finishing method according to the present invention ==
The exterior finishing method according to the present invention is not particularly limited as long as it is a construction method for finishing an exterior using the above-mentioned heat ray high reflection exterior material. For example, the above-mentioned heat ray high reflection exterior material is applied to an exterior part of a structure. Can be applied using an adhesive (for example, mortar, adhesive, etc.) or fixed with a fixture (for example, nail, wire, etc.).

Hereinafter, the present invention will be specifically described by way of examples. In addition, these Examples demonstrate the heat ray reflective performance of the composite pigment M and the antifouling effect of the compound A among the present invention, and do not limit the scope of the present invention.
The base material, main agent, and curing agent composition used in this example are as follows.

(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 Epo Coat 55MP-S, gray (Asahi Glass Co., Ltd., epoxy paint) was used. As an intermediate coating agent, Bonflon # 1000 white (Asahi Glass Coat and Resin Co., Ltd., fluorine paint) was used.

(Main agent 1)
Fluororesin Lumiflon LF-200, 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) 60% by weight 15.0 g of xylene was added to 63.0 g. Next, 22.0 g of black 6301 (Mn, Bi composite oxide pigment manufactured by Asahi Kasei Kogyo Co., Ltd.) was added, dispersed with a sand mill, 0.0005 g of dibutyltin dilaurate was added, and the mixture was stirred to obtain main ingredient 1.

(Main agent 2)
16.0 g of xylene was added to 63.0 g of fluororesin Lumiflon LF-200. Next, 21.0 g of black 6303 (manufactured by Asahi Kasei Kogyo Co., Ltd., Mn, Y composite oxide pigment) was added and dispersed with a sand mill, and 0.0005 g of dibutyltin dilaurate was further added and stirred to obtain main agent 2. .

(Main agent 3)
Xylene 34.0g was added to 63.0g of fluororesin Lumiflon LF-200. Next, 3.0 g of Mitsubishi Carbon Black MA-11 (manufactured by Mitsubishi Chemical Corporation) was added and dispersed with a sand mill, and 0.0005 g of dibutyltin dilaurate was further added and stirred to obtain Main Agent 3.

(Main agent 4)
10.0 g of fluororesin Lumiflon LF-200 and 3.0 g of xylene were added to 83.4 g of the main agent 3 (34.03 g as a solid content). Next, 3.6 g of titanium oxide (trade name CR-90, manufactured by Ishihara Sangyo Co., Ltd.) treated so that photocatalysis does not easily occur is added and dispersed by a sand mill, and 0.000083 g of dibutyltin dilaurate is added and stirred. The resulting product was designated as Main Agent 4.

(Curing agent composition 1)
1.7 g of aluminum chelate D (produced by Kawaken Fine Chemical Co., Ltd., aluminum chelate compound) is added to 30.0 g of coronate HX (manufactured by Nippon Polyurethane, non-yellowing type isocyanate curing agent) and mixed, and MKC silicate is used as compound A. Curing agent composition 1 was prepared by adding 17.0 g of MS56S [Mitsubishi Chemical Co., Ltd., methyl silicate condensate having a silica content of 56 wt%] and mixing them.

(Curing agent composition 2)
Curing agent composition 2 was prepared by adding 18.7 g of xylene to 30.0 g of coronate HX.

Example 1
A coating composition obtained by mixing 12 g of the curing agent 1 with 100 g of the main agent 1 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. 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)
A coating composition obtained by mixing 12 g of the curing agent 1 with 100 g of the main agent 2 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. 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.

(Comparative Example 1)
A coating composition obtained by mixing 12 g of the curing agent 2 with 100 g of the main agent 3 (40.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. 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 the curing agent 1 with 100 g of the main agent 4 (43.3 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. 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 of the curing agent 2 with 100 g of the main agent 1 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. 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.

(Comparative Example 4)
A coating composition obtained by mixing 12 g of the curing agent 2 with 100 g of the main agent 2 (59.8 g as a solid content) was applied on a substrate with a bar coater so as to have a film thickness of 30 μm. 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 4.

(Measurement of brightness)
About the surface of each test body, the lightness L ^* prescribed | regulated to JISZ8729 was measured using the spectrocolorimeter CM-2002 type | mold (Minolta company make). The results are shown in Table 1.

(Measurement of water contact angle)
A FACE contact angle meter CA-A type (manufactured by Kyowa Interface Chemical Co., Ltd.) was used to measure the contact angle of 0.005 ml of ion-exchanged water droplets. The results are shown in Table 1.

(Measurement of the initial temperature _{T 1)}
About each test body, the temperature of the film | membrane when an infrared lamp was irradiated for 10 minutes was measured in the following procedures.
First, the thermocouple was installed in the center part of the test body surface. In addition, an infrared lamp was installed 60 cm from the surface of the test body. The infrared lamp was turned on for 10 minutes and then turned off.
The surface temperature of the specimen was continuously measured with a thermocouple for 15 minutes from the start of lighting of the infrared lamp to 5 minutes after the light was turned off. The highest temperature obtained in the course of the 15 minutes was the initial temperature T _1. The results are shown in Table 1.

(Measurement of pollution after the temperature _{T 2)}
For each specimen, as shown in the procedure below, after carrying out accelerated soil adhesion in accordance with the antifouling test of the Civil Engineering Research Center method (antifouling material evaluation accelerated test method I), the post-contamination temperature T ₂ Was measured. The results are shown in Table 1.
(1) As a soiling substance, 95% by weight of deionized water was mixed well with 5% by weight of carbon black for pigment (manufactured by Deggsa, particle size 0.002-0.028 μm) to prepare a suspension.
(2) About 1/3 of the suspension volume was added to the suspension, and glass beads (2 mmφ) were added and stirred at 2500 rpm using a stirrer. Thereafter, the glass beads were removed to separate the carbon black suspension.
(3) About 200 g / m ² of the carbon black suspension was sprayed on the surface of the test body. After spraying, it was baked and dried with a dryer at 60 ° C. for 1 hour.
(4) After cooling to room temperature, the gauze was moved in the vertical, horizontal and vertical order on the surface of the test specimen under running tap water, and the soiled substances were washed off lightly.
(5) Then, it dried at room temperature and obtained the soil test body.
(6) Test body, except that instead of the dirty specimen, in the same manner as in the measurement of the initial temperature T _1, obtains the highest temperature obtained in the course of 15 minutes, was contaminated after temperature T _2.

As shown in Table 1, in Examples 1 and 2 in which the coating composition contains both the composite pigment M (containing Mn and an oxide of Bi or Y) and the compound A, the initial temperature T ₁ , the post-contamination temperature T ₂ was low, and the difference between the two was small. That is, the test bodies of Example 1 and Example 2 were able to stably maintain good heat ray reflection performance.

On the other hand, in Comparative Example 1 in which the coating composition does not contain both the composite pigment M and the compound A, the initial temperature T ₁ and the post-contamination temperature T ₂ are both high, and the difference between the _two is also compared with Examples 1 and 2. It was big.

Further, in Comparative Example 2 in which the coating composition does not contain the composite pigment M, the initial temperature T ₁ and the post-contamination temperature T ₂ are both high, and the initial temperature T ₁ the difference of pollution after the temperature T ₂ was also very large.

Further, in Comparative Examples 3 and 4 in which the coating composition contains the composite pigment M (containing Mn and an oxide of Bi or Y) but does not contain the compound A, the initial temperature T ₁ is low, but the post-contamination temperature. T ₂ is high, the test bodies were those reflecting the performance of good heat ray can not be maintained.

From the above, the composite metal oxide pigment containing the oxide of Bi and / or Y and the oxide of Mn, and the general formula Si (OR) ₄ (wherein R may be the same as or different from each other, hydrogen An exterior material in which a film including a layer of a coating composition containing a compound represented by an atom or an alkyl group having 1 to 5 carbon atoms or a partial condensate thereof is formed on an exterior substrate is contaminated. It was found that it was excellent in antifouling property because it was inconspicuous. Moreover, it turned out that the said exterior material has the outstanding heat ray reflective performance, and can maintain the said performance stably.

Claims (15)

A composite metal oxide pigment comprising an oxide of Bi and / or Y and an oxide of Mn;
A photocatalyst or a photocatalyst and a compound represented by the general formula Si (OR) ₄ (wherein R may be the same as or different from each other and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and / or The partial condensate ,
A heat ray highly reflective exterior material comprising a film including a layer of a coating composition containing a mixture thereof on an exterior substrate. A composite metal oxide pigment comprising an oxide of Bi and / or Y and an oxide of Mn;
General formula Si (OR) ₄ (Wherein R may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), 1 selected from the group consisting of a compound represented by the formula: Two or more substances,
Having a film containing a layer of a coating composition containing a mixture on an exterior substrate,
A heat ray highly reflective exterior material, wherein the surface layer of the film is a layer made of a photocatalyst. The coating composition contains a mixture of the compound represented by the general formula Si (OR) ₄ or a partial condensate thereof,
Formula Si (OR) compound represented by the ₄ or a partial condensate is silica obtained by 100% hydrolysis condensation, the formula Si (OR) compound or its partial condensation product represented by the ₄ heat ray highly reflective exterior material according to claim 1 or 2, characterized in that it comprises 20 to 60 wt% with respect to. The content of the composite metal oxide pigment is 0.005 to 5.00 wt% with respect to the total weight, The heat ray highly reflective exterior material according to any one of claims 1 to 3 . The heat ray highly reflective exterior material according to any one of claims 1 to 3, wherein the coating composition further contains a resin. The heat ray highly reflective exterior material according to claim 5 , wherein the content of the composite metal oxide pigment is 0.01 to 10.00 wt% with respect to the solid content of the resin.   The heat ray highly reflective exterior material according to claim 1, wherein the film further includes a surface impregnating material. A composite metal oxide pigment comprising an oxide of Bi and / or Y and an oxide of Mn;
A photocatalyst or a photocatalyst and a compound represented by the general formula Si (OR) ₄ (wherein R may be the same as or different from each other and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and / or The partial condensate ,
A method for producing a heat ray highly reflective exterior material, comprising a step of forming a film including a layer of a coating composition containing a mixture of the composition on an exterior substrate. A composite metal oxide pigment comprising an oxide of Bi and / or Y and an oxide of Mn;
General formula Si (OR) ₄ (Wherein R may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), 1 selected from the group consisting of a compound represented by the formula: Two or more substances,
Including a step of forming a film including a layer of a coating composition containing a mixture on an exterior substrate,
The method for producing a highly heat-resistant exterior packaging material, wherein the surface layer of the film is a layer made of a photocatalyst. The coating composition contains a mixture of the compound represented by the general formula Si (OR) ₄ or a partial condensate thereof,
Formula Si (OR) compound represented by the ₄ or a partial condensate is silica obtained by 100% hydrolysis condensation, the formula Si (OR) compound or its partial condensation product represented by the ₄ The manufacturing method of the heat ray highly reflective exterior material of Claim 8 or 9 characterized by including 20-60 weight% with respect to this. The method for producing a highly heat-resistant exterior packaging material according to any one of claims 8 to 10, wherein the content of the composite metal oxide pigment is 0.005 to 5.00 wt% with respect to the total weight. . The said coating composition contains resin further, The manufacturing method of the heat ray highly reflective exterior material in any one of Claims 8-10 characterized by the above-mentioned. The method for producing a highly heat-resistant exterior packaging material according to claim 12 , wherein the content of the composite metal oxide pigment is 0.01 to 10.00 wt% with respect to the solid content of the resin.   The method for producing a highly heat-resistant exterior packaging material according to any one of claims 8 to 13, wherein the film further contains a surface-impregnated material.   An exterior finishing method using the heat ray highly reflective exterior material according to any one of claims 1 to 7.