JP6351037B2 - Water-based thermal barrier coating for transparent substrate, method for thermal treatment of transparent substrate, and transparent substrate subjected to thermal treatment - Google Patents

Description

  The present invention relates to a water-based thermal barrier coating suitable for coating on a transparent substrate such as glass, a heat-shielding method for a transparent substrate, and a transparent substrate subjected to a thermal treatment.

  In recent years, heat-shielding paints have attracted attention as a measure to reflect and absorb sunlight and heat to suppress temperature rise inside buildings and road surfaces, reduce energy required for cooling and other facilities, and suppress global warming. .

Conventionally, a white pigment having high infrared reflection / scattering performance is used as a thermal barrier coating, and it has been applied to a building outer wall or the like which is often lightly colored. (For example, refer to Patent Document 1.)
On the other hand, there is a need for dark colors such as black for roofs, etc., but generally black pigments are said to have low infrared reflection / scattering performance. Also in this regard, thermal barrier coatings have been developed that form a dark color coating film that meets customer needs by combining a plurality of color pigments or using a specific black metal oxide. (For example, refer to Patent Document 2.)
As described above, the conventional thermal barrier coating has been designed using a coloring pigment having high concealability in either light or dark colors.

  However, it is necessary to take measures not only for walls and roofs but also for window glass in order to suppress the rise in the internal temperature of buildings. In recent years, glass walls have been erected in which the entire wall is made of glass. Therefore, it is required to impart heat shielding performance to a transparent substrate such as glass.

  Patent Document 3 discloses a composition containing an infrared shielding agent, a binder component and a polyhydric alcohol as a thermal barrier paint that can be applied to glass.

  The composition described in Patent Document 3 is coated with a coating liquid whose nozzle diameter is in a specific range, and the coating pressure of the coating liquid is adjusted to a specific range. A shielding coating film can be easily formed.

  However, the composition described in Patent Document 3 is an organic solvent type, and there is a problem that the organic solvent is diffused into the atmosphere at the odor and coating stage.

  In order to solve these problems, Patent Document 4 discloses an ultraviolet / near-infrared blocking water-based paint mainly composed of a polycarbonate polyurethane resin emulsion resin.

  The composition described in Patent Document 4 takes into consideration the working environment and safety and hygiene, and can form a coating film having an excellent ultraviolet / near-infrared blocking effect quickly and simply by simply applying it to a window glass.

  However, since the composition described in Patent Document 4 is an aqueous composition, weather resistance and durability due to poor water resistance of the coating film are insufficient.

  Thus, a water-based paint that has a heat-shielding property, has a finished appearance comparable to that of a solvent-based paint, particularly excellent in transparency, and can form a paint film having excellent film properties such as weather resistance and durability. Development of a composition and a heat-shielding method using the composition is desired.

JP 2013-147571 A JP 2009-286862 A JP 2006-334530 A JP 2013-87228 A

  An object of the present invention is to provide a water-based heat-shielding paint for a transparent substrate, which has a heat-shielding property, is transparent, and is excellent in weather resistance, a heat-shielding method for a transparent substrate, The object is to propose a transparent base material that has been subjected to a heat treatment.

  As a result of intensive studies on the above-described problems, the present inventors have determined that the combination of a fine particle metal oxide having an average particle diameter in a specific range, an aqueous resin having a specific pH in a range, and a specific amount of an alcohol compound is transparent and transparent. The inventors have found that a coating film having both feeling and weather resistance can be obtained, and have reached the present invention.

That is, the present invention
An aqueous composition comprising an aqueous resin (A), a fine metal oxide (B) having an average particle diameter of 5 to 400 nm, an alcohol compound (C) and water,
The aqueous resin (A) has an acid group, the acid value per solid content is in the range of 3 to 100 mgKOH / g, the solid content concentration is 40%, and the pH when the temperature is 23 ° C. is 6.0. In the range of ~ 10.0,
Based on 100 parts by mass of the solid content of the aqueous resin (A), the content of the particulate metal oxide (B) is in the range of 10 to 300 parts by mass, and the amount of the alcohol compound (C) is 0.5 to 250 parts by mass. Water-based heat-shielding paint for a transparent substrate, characterized in that the water-based heat-shielding paint is applied to the surface of the transparent substrate, and obtained by the treatment method The present invention relates to a heat-treated transparent base material.

  According to the water-based heat-shielding paint for a transparent substrate of the present invention, a heat-shielding pigment is homogeneously dispersed and a dense coating film is obtained, so that a transparent heat-shielding coating film can be formed, It is excellent in coating film physical properties, such as water resistance and a weather resistance, although it is a composition of this.

  In addition, since the film made of the thermal barrier paint of the present invention is extremely excellent in adhesion and weather resistance to the base material, it can be applied to the outer surface of the window glass, both indoors and outdoors on the windows and glass walls. It can be constructed from the direction, and the internal temperature rise of the building can be further suppressed.

  The aqueous thermal barrier paint of the present invention is a multi-component composition comprising a main component (I) and a crosslinking agent component (II). The main component (I) is an aqueous resin (A) and a thermal barrier pigment (B). And an alcohol compound (C) and water.

<Aqueous resin (A)>
The aqueous resin (A) in the present invention is a resin that can be dissolved or dispersed in water, and as the resin type, any conventionally known resin can be used without particular limitation as long as it has a film-forming ability. Acrylic resins, silicone resins, polyurethane resins, fluorine resins, polyvinyl acetate resins, epoxy resins, phenol resins, polyester resins, alkyd resins, polycarbonate resins, melamine resins, etc. Can be used alone or in combination of two or more. These resins may be modified, for example, as a urethane-modified acrylic resin, may be graft-polymerized, or may be in the form of dispersed particles.

  When the aqueous resin (A) is in the form of dispersed particles, the aqueous resin (A) can have a single layer structure (homogeneous granular shape) or a multilayer structure such as a core / shell structure. Alternatively, the shell may be cross-linked.

  In the present invention, the aqueous resin (A) must have an acid group, and the acid value per solid content is in the range of 3 to 100 mgKOH / g, preferably 4.5 to 60 mgKOH / g. It should be in range.

  When the acid value per solid content of the aqueous resin (A) is outside this range, the water resistance of the coating film may be inferior.

  Examples of the acid group that gives an acid value to the aqueous resin (A) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and among them, a carboxyl group is preferable.

  These acid groups may be partially or partially selected from amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol; It may be substantially completely neutralized.

  Moreover, in this invention, pH of aqueous resin (A) exists in the range of 6.0-10.0, It is suitable for it to exist in the range of 7.0-9.0. ing.

  If the pH of the aqueous resin (A) is less than 6.0, the water-soluble resin (A) is less soluble in water and cannot be kept in a uniform mixed state. It is not preferable because the storage stability of the paint decreases, such as agglomeration in the paint system and, in some cases, sedimentation.

  In the present specification, the pH of the aqueous resin (A) is a value measured with a pH meter at a temperature of 23 ° C., diluted with water so that the solid content of the sample is 40%.

  The aqueous resin (A) is an acrylic resin having a (meth) acryloyl group-containing compound as a structural unit, and has a hydrolyzable silyl group and a polysiloxane skeleton, so that the coating film adheres to the substrate. Suitable from the viewpoint of durability, weather resistance, and durability.

  The aqueous resin (A) is obtained by, for example, hydrolyzing and condensing a hydrolyzable silyl group-containing organosilane, a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group, and a hydrolyzable silyl group. And a (meth) acryloyl group-containing compound copolymer having both acid groups and a resin obtained by dispersing or dissolving in water a resin obtained by partial neutralization or complete neutralization with a basic compound. be able to.

  Here, the hydrolyzable silyl group is an atomic group containing a silicon atom to which, for example, an alkoxy group, a substituted alkoxy group, a phenoxy group, a halogen atom, an isopropenyloxy group, an acyloxy group, or iminooxy is bonded. Examples of those that can be hydrolyzed to form silanol groups are shown. Of these, only typical ones are exemplified, but alkoxysilyl groups, phenoxysilyl groups, halosilyl groups, isopropenyloxysilyls. A group, an acyloxysilyl group or an iminooxysilyl group.

  Examples of hydrolyzable silyl group-containing organosilane compounds include dialkoxydiorganosilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane; methyltrimethoxysilane, methyltrimethoxysilane, and the like. Trialkoxymonoorganosilanes such as ethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane These can be used, and these can be used alone or in combination of two or more.

  As a (meth) acryloyl group containing compound, as a compound which has one (meth) acryloyl group in 1 molecule, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl, for example Linear or branched (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Alkyl group-containing (meth) acryloyl monomer; Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and other alicyclic alkyl group-containing (meth) acryloyl monomers; Benzyl (meth) acrylate and other aralkyl group-containing (meth) acrylate Royl monomer; alkoxyalkyl group-containing (meth) acryloyl monomer such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; hexafluoroisopropyl (meth) acrylate, perfluorooctylmethyl (meth) acrylate, Fluorine-containing (meth) acryloyl monomers such as fluorooctylethyl (meth) acrylate; amino group-containing (meth) acryloyl monomers such as N, N-diethylaminoethyl (meth) acrylate; (meth) acrylamide; 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and other hydroxyalkyl (meth) acrylates Hydroxyl-containing (meth) acryloyl monomer such as polyoxyethylene chain-containing (meth) acrylate having a hydroxyl group at the molecular end; (meth) acrylic acid, β-carboxyl Carboxyl group-containing (meth) acryloyl monomers such as ethyl acrylate; Carbonyl group-containing (meth) acryloyl monomers such as acetoacetoxyethyl (meth) acrylate and diacetone (meth) acrylamide; Glycidyl (meth) acrylate, β-methylglycidyl (meta ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, etc. Epoxy group-containing (meth) acryloyl monomers; isocyanato group-containing (meth) acryloyl monomers such as isocyanatoethyl (meth) acrylate; alkoxysilyl groups such as γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltriethoxysilane (Meth) acryloyl monomer; polysiloxane group-containing polymerizable unsaturated monomer; containing oxidatively curable groups such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate (Meth) acryloyl monomer, etc. are mentioned.

  Examples of the compound having at least two (meth) acryloyl groups in one molecule include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). Acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate DOO, 1,1,1-tris hydroxymethyl ethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate.

  These (meth) acryloyl group-containing compounds can be used alone or in combination of two or more.

  Moreover, you may use the other polymerizable unsaturated monomer copolymerizable with a (meth) acryloyl group containing compound. Examples of such monomers include (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; one molecule such as triallyl isocyanurate, diallyl terephthalate, and divinylbenzene. Polyvinyl compounds having at least two polymerizable unsaturated groups in the above; allyl alcohol; carboxyl group-containing polymerizable unsaturated monomers such as maleic acid and crotonic acid; (meth) acrolein, formylstyrene, vinyl having 4 to 7 carbon atoms Carbonyl group-containing polymerizable unsaturated monomers such as alkyl ketones (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyallyl ester, etc .; Epoxy group-containing polymerizable unsaturated monomers such as allyl glycidyl ether; m Isocyanato group-containing polymerizable unsaturated monomers such as isopropenyl-α, α-dimethylbenzyl isocyanate; alkoxysilyl group-containing polymerizable unsaturated monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; fluoroalkyltrifluorovinyl ether, perfluoro Fluorovinyl ethers such as alkyl trifluorovinyl ethers; and the above-mentioned epoxy group-containing polymerizable unsaturated monomers or oxidatively curable group-containing polymerizable unsaturated monomers such as reaction products of hydroxyl group-containing polymerizable unsaturated monomers and unsaturated fatty acids. These can be used alone or in combination of two or more.

  The method for polymerizing the monomer is not particularly limited, and can be performed by a known method.

  The aqueous resin (A) can have an average particle size in the range of usually 10 to 1000 nm, preferably 30 to 600 nm.

  In this specification, the average particle diameter of the aqueous resin (A) is a value measured at room temperature (about 20 ° C.) with a Coulter Counter N4 (trade name, manufactured by Beckman Coulter, Inc., particle size distribution measuring device). .

<Fine particle metal oxide (B)>
The heat-shielding water-based paint of the present invention contains a particulate metal oxide having an average particle size of 5 to 400 nm, preferably 10 to 150 nm.

  When the average particle diameter of the component (B) is within the above range, a transparent thermal barrier coating film can be obtained together with the aqueous resin (A).

  The average particle diameter of the component (B) refers to an average value of 20 particle diameters measured by observation with a transmission electron microscope.

  Preferred examples of the component (B) include particles mainly composed of an oxide of at least one metal selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Specifically, silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, antimony-doped tin oxide, tin-doped indium oxide, Examples thereof include particles such as cerium oxide, and these can be used alone or in combination of two or more. Among these, at least one compound selected from an antimony compound, a tin compound, and an indium compound, particularly an antimony compound, is preferable from the viewpoints of heat shielding properties and transparency.

  The fine particle metal oxide (B) may be dispersed in water or an organic solvent, and the dispersion may contain an amine or a surfactant.

  Examples of commercially available products of the particulate metal oxide (B) include, for example, “IPA-ST”, “MEK-ST”, “NBA-ST”, “XBA-ST”, “DMAC-ST”, “ST- UP "," ST-OUP "," ST-20 "," ST-40 "," ST-C "," ST-N "," ST-O "," ST-50 "," ST-OL " “Alumina sol-100”, “Alumina sol-200”, “Alumina sol-520”, “Selnax” (all trade names, manufactured by Nissan Chemical Industries, Ltd.); “Aerosil 130”, “Aerosil 300”, “Aerosil 380”, “Aerosil TT600”, “Aerosil OX50” (all trade names, manufactured by Nippon Aerosil Co., Ltd.), “Sealdex H31”, “Sealdex H32”, “Sealdex H51”, “Sealdex H5” ”,“ Shielddex H121 ”,“ Shielddex H122 ”(all trade names, manufactured by Asahi Glass Co., Ltd.),“ E220A ”,“ E220 ”(all trade names, manufactured by Nippon Silica Kogyo),“ SYLYSIA470 ”( "AS-150I", "AS-150T", "HXU-110JC" (all trade names, Sumitomo, etc.), such as "trade name, manufactured by Fuji Silysia Co., Ltd.", "SG Flakes" (trade name, manufactured by Nippon Sheet Glass Co., Ltd.) (Osaka Cement Co., Ltd.), “Nanotech” (trade name, manufactured by CI Kasei Co., Ltd.), “SN-100D” (produced by Ishihara Sangyo Co., Ltd.), “ATO series”, “ITO series” (all trade names, manufactured by Mitsubishi Materials Corporation) ), “Nidoral” (trade name, manufactured by Taki Chemical Co., Ltd.) and the like.

<Alcohol compound (C)>
The water-based thermal barrier paint of the present invention contains the alcohol compound (C), so that the stability of the fine metal oxide (B) particles in water is improved. There is an effect to spread easily.

  The alcohol compound (C) may be any of primary alcohol, secondary alcohol, and tertiary alcohol. Specifically, methyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl Alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol Monoalcohols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol Polyhydric alcohols such as neopentyl glycol, glycerin, trimethylolpropane and pentaerythritol; a compound having at least one epoxy group and at least one hydroxyl group, carboxyl group, primary amino group, secondary amino group, Alternatively, polyhydric alcohols such as a compound having two or more secondary hydroxyl groups in one molecule obtained by reaction with a compound having a thiol group can be mentioned.

  The water-based heat-shielding paint of the present invention comprises the water-based resin (A), the particulate metal oxide (B), the alcohol compound (C) and water, and based on 100 parts by mass of the solid content of the water-based resin (A), The solid metal oxide (B) solid content is in the range of 10 to 300 parts by mass, preferably 20 to 200 parts by mass, and the alcohol compound (C) is based on 100 parts by mass of the aqueous resin (A) solid content. It is suitable to be in the range of 0.5 to 250 parts by mass, preferably 1 to 150 parts by mass.

  Here, if the content of the particulate metal oxide (B) is less than 10 parts by mass, the heat shielding property is insufficient. On the other hand, if it exceeds 300 parts by mass, the transparency of the coating film is poor, and water whitening resistance is also achieved. Is worse, not preferable. When the content of the alcohol compound (C) is less than 0.5 parts, the water-based heat-shielding paint becomes difficult to drip on the transparent substrate, while when it exceeds 250 parts, the water-based heat-shielding paint is in the form of fine particles when stored. Since the metal oxide (B) aggregates and a transparent film cannot be obtained, it is not preferable.

  Further, from the viewpoint of film forming property and heat shielding property of the water-based heat-shielding paint, the solid content of the water-based resin (A) is 1 to 60% by weight, preferably in the range of 3 to 40% by weight with respect to the total weight of the water-based heat-shielding paint. It is suitable to be in

<Crosslinking agent component (II)>
The aqueous thermal barrier paint of the present invention can contain, as a crosslinking agent component (II), a compound (D) having a functional group capable of reacting with a functional group contained in the aqueous resin (A).

  Such a compound (D) can be, for example, a compound that reacts with a group such as a hydroxyl group, a carboxyl group, an amino group, or an alkoxysilyl group to form a crosslinked structure.

  Specific examples include compounds having a plurality of at least one group selected from an isocyanato group, an epoxy group, an amino group, and an alkoxysilyl group in one molecule.

  In the present invention, since the aqueous resin (A) has an acid group, the compound is preferably a compound containing a functional group capable of reacting with an acid group. Further, the aqueous resin (A) is a hydrolyzable silyl group. In the case of having a compound, it is desirable that the compound (D) is a compound having both an epoxy group and an alkoxysilyl group from the viewpoints of compatibility with the aqueous resin (A), adhesion to a transparent substrate and coating water resistance. .

  Examples of the compound having both the epoxy group and the alkoxysilyl group include a vinyl polymer having both types of reactive groups, a silane coupling agent having an epoxy group, or both types of reactive groups. A silicone resin having both is particularly representative.

  In addition, only typical examples of the epoxy group-containing silane coupling agent described above are exemplified. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycid Xypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- ( Various epoxy silane compounds such as 3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyltriisopropenyloxysilane or γ-glycidoxypropyltriiminooxysilane; γ-isocyanate Propyl triisopropenyloxy Adducts of various isocyanate silane compounds such as lan or γ-isocyanatopropyltrimethoxysilane and glycidyl; or various aminosilane compounds such as γ-aminopropyltrimethoxysilane and diepoxy compounds Additives; or compounds having two or more epoxy groups and hydrolyzable silyl groups in one molecule, obtained by partially hydrolyzing and condensing various epoxysilane compounds as described above.

  The amount of the compound (D) used is 0.3 to 2 equivalents of the functional group contained in the compound (D) capable of reacting with the functional group with respect to 1 equivalent of the functional group contained in the aqueous resin (A). It is good to set it as the ratio which becomes.

  In the present invention, the crosslinking agent component (II) may be one kind of crosslinking agent or a combination of two or more kinds of crosslinking agents, and the addition method is not particularly limited.

  The water-based heat-shielding paint of the present invention can be made into a two-pack paint form comprising a main component (I) containing a water-based resin (A) and a crosslinking agent component (II), and both can be mixed immediately before use. .

  The above-mentioned water-based heat-shielding paint includes an antifoaming agent, a surface conditioner, a film-forming aid, a curing catalyst, a dispersant, a preservative, a thickener, an ultraviolet absorber, a light stabilizer, an organic solvent, and an aqueous resin (A). Other modifying resins and the like can be included in the main component (I) and / or the crosslinking agent component (II) according to the purpose.

  Among these, as the antifoaming agent, for example, “Surfinol 104”, “Surfinol 104E”, “Surfinol 104H”, “Surfinol 104A”, “Surfinol 104BC”, “Surfinol 104DPM”, “Surfinol 104PA” "Surfinol 104PG-50", "Surfinol 104S", "Surfinol 420", "Surfinol DF-110D", "Surfinol 82" (all trade names, manufactured by Air Products Chemicals), "BYK −011 ”,“ BYK-012 ”,“ BYK015 ”,“ BYK-017 ”,“ BYK-018 ”,“ BYK-019 ”,“ BYK-020 ”,“ BYK-021 ”,“ BYK-022 ”, "BYK-023", "BYK-024", "BYK-025" “BYK-028”, “BYK-038”, “BYK-044”, “BYK-080A”, “BYK-094”, “BYK-1610”, “BYK-1615”, “BYK-1650”, “BYK” -1710 "," BYK-1730 "," BYK-1770 "(all trade names, manufactured by Big Chemie Japan)," TEGO FORAMEX 800 "," TEGO FORAMEX 825 "," TEGO FORAMEX 855 "," TEGO FAMEX 1495 "," TEGO " "FOAMEX 8030" (all trade names, manufactured by Evonik Japan Co., Ltd.) and the like.

  Examples of the surface conditioner include “polyflow KL-100”, “polyflow KL-400HF”, “polyflow KL-401”, “polyflow KL-402”, “polyflow KL-403”, “polyflow KL-404”, and the like. (All trade names, manufactured by Kyoeisha), “BYK-300”, “BYK-302”, “BYK-306”, “BYK-307”, “BYK-320”, “BYK-325”, “BYK-330” ”,“ BYK-331 ”,“ BYK-333 ”,“ BYK-337 ”,“ BYK-341 ”,“ BYK-344 ”,“ BYK-345 ”,“ BYK-346 ”,“ BYK-347 ”, “BYK-348”, “BYK-349”, “BYK-375”, “BYK-377”, “BYK-378”, “BYK-3441”, “BYK-UV3” "00", "BYK-UV3510" (all trade names, manufactured by Big Chemie Japan), "TEGO Flow-425", "TEGO Glide-100", "TEGO Glide-110", "TEGO Glide-410", " TEGO Glide-440, TEGO Glide-450, TEGO Glide-ZG400, TEGO Wet-240, TEGO Wet-KL245, TEGO Wet-250, TEGO Wet-260, TEGO "Wet-270", "TEGO Wet-280" (all trade names are manufactured by Evonik Japan).

<Method of heat-shielding transparent substrate using water-based heat-shielding paint>
In the present invention, it is possible to impart heat shielding properties to the transparent substrate by coating the surface of the transparent substrate with the water-based thermal barrier coating.

  The base material capable of maximizing the performance of the water-based thermal barrier paint of the present invention may be any base material having transparency, or may be colored within a range having transparency. Specific examples of such transparent substrates include, for example, plastic plates and plastic sheets made of glass plates, acrylic resins, vinyl chloride, polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, etc., and have rigidity and size. The degree and shape are not particularly limited, and it may be already heat-shielded.

  The water-based thermal barrier paint of the present invention can be applied by using a coating means known per se. It can be appropriately selected and used according to the type of material, application and the like. Moreover, the water-based coating composition of this invention can also be reapplied several times in the range which does not impair the coating-film external appearance.

  Although the formed coating film can be dried at room temperature, it may be dried by heating or forcedly depending on the composition of the coating composition used and the coating environment.

  Although a dry film thickness can be suitably adjusted with an application base material and a coating environment, generally 0.2-80 micrometers, Preferably 0.5-50 micrometers is good.

  Since the water-based thermal barrier paint of the present invention is extremely excellent in adhesion and weather resistance to the base material, it can be applied not only to the indoor side of windows and wall surfaces, such as in buildings and vehicles, but also to the outdoor side surface. It is also possible to paint.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to only these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively. Moreover, the pH of the aqueous resin described in Examples is measured by the method described in the specification.

<Manufacture of water-based thermal barrier paint>
Example 1
The main ingredients and the curing agent were obtained by mixing the following materials for 15 minutes using a stirrer. And the main ingredient and the hardening | curing agent were well mixed by main ingredient / hardening agent mass ratio = 30/1 just before coating, and the water-based heat-shielding coating material (A-1) was obtained.

<Main ingredient formulation>
“Ceranate WSA-1050” (Note 1) 100 parts Texanol 5 parts “ATO aqueous dispersion T-1” (Note 2) 180 parts Isopropyl alcohol 15 parts <Containing curing agent>
Isopropyl alcohol 5 parts “KBM-403” (Note 3) 5 parts.

(Note 1) “Ceranate WSA-1050”: trade name, manufactured by DIC Corporation, hydrolyzable silyl group-containing polysiloxane acrylic composite aqueous resin, solid content 40%, pH 7.5, solid content acid value 18 mgKOH / g,
(Note 2) “ATO aqueous dispersion T-1”: trade name, manufactured by Mitsubishi Materials Corporation, antimony-doped tin oxide aqueous dispersion, solid content 30%, average particle size 30 nm,
(Note 3) “KBM-403”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane.

Example 2
In Example 1, the water-based heat-shielding paint ((A-2)) was obtained in the same manner as in Example 1 except that the blending composition was as follows.

<Main ingredient formulation>
“Ceranate WSA-1050” (Note 1) 100 parts Texanol 5 parts “ITO aqueous dispersion IR5-DE” (Note 4) 180 parts Isopropyl alcohol 15 parts <Containing curing agent>
Isopropyl alcohol 5 parts “KBM-403” (Note 3) 5 parts.

  (Note 4) “ITO aqueous dispersion IR5-DE”: trade name, manufactured by Evonik Japan KK, tin-doped indium oxide aqueous dispersion, solid content 30%, average particle diameter 40 nm.

Example 3
In Example 1, the water-based heat-shielding paint ((A-3)) was obtained in the same manner as in Example 1 except that the composition was changed as follows.

<Main ingredient formulation>
"Polydurex H-7100" (Note 5) 100 parts Texanol 5 parts "ATO aqueous dispersion T-1" (Note 2) 180 parts Isopropyl alcohol 15 parts <Containing curing agent>
None.

  (Note 5) “Polydurex H-7100”: trade name, manufactured by Asahi Kasei Chemicals Corporation, hydrolyzable silyl group-containing polysiloxane acrylic composite aqueous resin, pH = 8.4, solid content 42%, solid content acid value 16 0.0 mg KOH / g.

Example 4
In Example 1, the water-based heat-shielding paint ((A-4)) was obtained in the same manner as in Example 1 except that the blending composition was as follows.

<Main ingredient formulation>
“Ceranate WSA-1050” (Note 1) 100 parts Texanol 5 parts “ATO aqueous dispersion SNS-100S” (Note 6) 240 parts Isopropyl alcohol 15 parts <Containing curing agent>
Isopropyl alcohol 5 parts “KBM-403” (Note 3) 5 parts.

  (Note 6) “ATO aqueous dispersion SNS-100S”: trade name, manufactured by Ishihara Sangyo Co., Ltd., antimony-doped tin oxide aqueous dispersion, solid content 18%, average particle size 45 nm.

Example 5
In Example 1, the water-based heat-shielding paint ((A-5)) was obtained in the same manner as in Example 1 except that the blending composition was as follows.

<Main ingredient formulation>
"WD-551" (Note 7) 100 parts Texanol 5 parts "ATO aqueous dispersion T-1" 180 parts Isopropyl alcohol 120 parts <Containing curing agent>
“Burnock DNW-6000” (Note 8) 5 parts.

(Note 7) “WD-551”: trade name, manufactured by DIC Corporation, aqueous acrylic polyol resin, solid content 42%, pH 7.5, solid content acid value 12 mgKOH / g,
(Note 8) “Bernock DNW-6000”: trade name, manufactured by DIC Corporation, water-dispersible polyisocyanate.

Comparative Example 1
In Example 1, water-based heat-shielding paint (A-6) was obtained in the same manner as in Example 1 except that the composition was as follows.

<Main ingredient formulation>
“Boncoat CE-6400” (Note 9) 70 parts Texanol 5 parts “ATO aqueous dispersion T-1” (Note 2) 180 parts Isopropyl alcohol 15 parts <Containing curing agent>
None.

  (Note 9) “Boncoat CE-6400”: trade name, aqueous resin manufactured by DIC Corporation, solid content 60%, pH = 3.5, solid content acid value 5 mgKOH / g.

Comparative Example 2
In Example 1, a water-based thermal barrier paint ((A-7)) was obtained in the same manner as in Example 1 except that the blending composition was as follows.

<Main ingredient formulation>
“Boncoat 520S-EF” (Note 10) 210 parts Texanol 5 parts “ATO aqueous dispersion T-1” (Note 2) 180 parts Isopropyl alcohol 15 parts <Containing curing agent>
None.

  (Note 10) “Boncoat 520S-EF”: trade name, aqueous resin manufactured by DIC Corporation, solid content 18%, pH 11.0, solid content acid value 16 mgKOH / g.

Comparative Example 3
In Example 1, instead of using 180 parts of “ATO aqueous dispersion T-1” (Note 2), 180 parts of a dispersion of antimony-doped tin oxide having a solid content of 30% and an average particle size of 430 nm is used. In the same manner as in Example 1, a water-based thermal barrier paint (A-8) was obtained.

Comparative Example 4
In Example 1, water-based heat-shielding paint (A-9) was obtained in the same manner as in Example 1 except that the composition was as follows.

<Main ingredient formulation>
"Ceranate WSA-1050" (Note 1) 100 parts Texanol 5 parts "ATO aqueous dispersion T-1" (Note 2) 10 parts Isopropyl alcohol 15 parts <Containing curing agent>
Isopropyl alcohol 5 parts “KBM-403” (Note 3) 5 parts.

Comparative Example 5
In Example 1, water-based heat-shielding paint (A-10) was obtained in the same manner as in Example 1 except that the composition was as follows.

<Main ingredient formulation>
"Ceranate WSA-1050" (Note 1) 100 parts Texanol 5 parts "ATO aqueous dispersion T-1" (Note 2) 450 parts Isopropyl alcohol 15 parts <Containing curing agent>
Isopropyl alcohol 5 parts “KBM-403” (Note 3) 5 parts.

Comparative Example 6
In Example 1, a water-based thermal barrier paint (A-11) was obtained in the same manner as in Example 1 except that the blending composition was as follows.

<Main ingredient formulation>
“Ceranate WSA-1050” (Note 1) 100 parts Texanol 0 part “ATO aqueous dispersion T-1” (Note 2) 180 parts Isopropyl alcohol 0 part <Containing curing agent>
Isopropyl alcohol 0.1 part “KBM-403” (Note 3) 5 parts.

Comparative Example 7
In Example 1, water-based heat-shielding paint (A-12) was obtained in the same manner as in Example 1 except that the composition was as follows.
<Main ingredient formulation>
"Ceranate WSA-1050" (Note 1) 100 parts Texanol 5 parts "ATO aqueous dispersion T-1" (Note 2) 180 parts Isopropyl alcohol 120 parts <Containing curing agent>
Isopropyl alcohol 5 parts “KBM-403” (Note 3) 5 parts.

<Performance evaluation>
Evaluation items, evaluation methods, and evaluation criteria for paint properties and coating film performance of the water-based thermal barrier paints obtained in the above Examples and Comparative Examples are as follows. Moreover, the same evaluation was performed also about the following solvent-dilution type window thermal-insulation paint (B-1)-(B-2) as a reference example.

Solvent dilution type thermal barrier paint for windows (B-1): trade name “ST-IR21” manufactured by Ishihara Sangyo Co., Ltd.
Solvent dilution type thermal barrier paint for windows (B-2): Product name “Humin Coat” manufactured by Humin Industry Co., Ltd.

1. Paint condition Each paint immediately after mixing of the main agent curing agent was confirmed to have no uniform and coarse gelled product or the like and to have a viscosity suitable for coating by visual observation and stirring with a spatula.
○ / No abnormality, Δ / Slightly high viscosity, X / Part of coating liquid separated and non-uniform.

2. Storage stability The main component of each coating material was sealed in a 70 cc glass bottle and stored at 40 ° C. for one month, and the state of the coating material was confirmed visually and stirred with a spatula.
○ / No abnormality, Δ / Slightly high viscosity, X / Part of the coating liquid is separated and is in a non-uniform state or significantly solidified.

3. Film-forming property The following criteria evaluated the film-forming property when each coating material was apply | coated to glass using the short-haired roller brush.
○ / Can be applied evenly to the glass plate substrate, and the smoothness of the surface of the coating film is maintained. No abnormality, △ / Repelled dents can be observed, × / Wet to glass Bad and completely repelled.

4). Transparency Each paint is applied to a glass plate with a roller brush and cured at 23 ° C. for 14 days to form a test plate. Each specimen was measured using a spectrophotometer (SolidSpec-3700 manufactured by Shimadzu Corporation), and the visible light transmittance calculated by the method shown in JIS-A-5602 and the presence or absence of cloudiness of the coating film were used as evaluation criteria.
○ / Visible light transmittance of 80% or more and no turbidity, Δ / Visible light transmittance of 75% or more and less than 80%, or slightly cloudy, × / obviously white turbidity, and visible light transmittance of less than 75%.

5. Water whitening resistance Each sample was coated on a glass plate with a roller brush and cured at 23 ° C. for 14 days. Each test specimen was immersed in hot water of 80 ° C. and pulled up after 3 hours. The surface moisture was immediately removed, the surface was observed, and the state of the coating film was confirmed.
○ / No coating film abnormality, Δ / whitening is slightly observed, but no swelling or the like, x / whitening is remarkable, and peeling is also observed.

6). Base Material Adhesion Each paint was applied to a glass plate using a roller brush, and a sample cured at 23 ° C. for 14 days was used as a test specimen. Each test specimen is immersed in hot water at 80 ° C and pulled up after 3 hours. The surface moisture is immediately removed, and then a 2mm wide crosscut is used with a cutter knife (10 squares x 10 squares). Adhesive tape A peel test was conducted. In the table, the number of peeled cells is shown. The smaller the value, the better.

7). Thermal barrier properties Each paint was applied to a glass plate using a roller brush, and a sample cured at 23 ° C. for 14 days was used as a test specimen. Measurement was performed using a spectrophotometer (SolidSpec-3700 manufactured by Shimadzu Corporation), and the infrared light transmittance value calculated by the method described in JIS-A-5602 was used as the evaluation result of the heat shielding property. The infrared transmittance of the glass plate blank is 92%, and the existing product Humin Coat (Humin Industry) has an infrared transmittance of 69%.

8). Weather resistance Each paint was applied to a glass plate using a roller brush, and a sample cured at 23 ° C. for 14 days was used as a test specimen. Each specimen was accelerated and deteriorated with an accelerated weathering tester xenon weather meter (manufactured by Suga Test Instruments), and the state of the coating film at the time of 2000 hours was visually evaluated.
○ / Almost no change, Δ / Gloss deterioration is recognized, × / Gloss deterioration, cracks, and whitening are remarkable.

Claims (7)

An aqueous composition comprising an aqueous resin (A), a fine metal oxide (B) having an average particle diameter of 5 to 400 nm, an alcohol compound (C) and water,
The aqueous resin (A) has an acid group, the acid value per solid content is in the range of 3 to 100 mgKOH / g , the solid content concentration is 40%, and the pH when the temperature is 23 ° C. is 6.0.
In the range of ~ 10.0,
Based on 100 parts by mass of the solid content of the aqueous resin (A), the content of the particulate metal oxide (B) is in the range of 10 to 300 parts by mass, and the amount of the alcohol compound (C) is 0.5 to 250 parts by mass. A water-based thermal barrier coating for a transparent substrate, characterized by being in the range of parts.   The aqueous thermal barrier paint according to claim 1, wherein the aqueous resin (A) is an acrylic resin having a (meth) acryloyl group-containing compound as a constituent unit and having a hydrolyzable silyl group and a polysiloxane skeleton. .   The water-based thermal barrier paint according to claim 1 or 2, wherein the particulate metal oxide (B) is an antimony compound.   The aqueous thermal barrier paint according to any one of claims 1 to 3, further comprising a compound (D) having a functional group capable of reacting with the functional group contained in the aqueous resin (A) as the crosslinking agent component (II). .   The water-based thermal barrier paint according to claim 4, wherein the compound (D) is a compound having both an epoxy group and an alkoxysilyl group.   A heat-shielding method comprising applying the water-based heat-shielding paint according to any one of claims 1 to 5 to the surface of a transparent substrate.   A heat-shielded transparent substrate obtained by the treatment method according to claim 6.