JP6853183B2 - Water-based resin paint composition, heat ray shielding film using this, and manufacturing method thereof - Google Patents

Description

The present invention relates to a water-based resin coating composition, a heat ray-shielding film using the same, and a method for producing the same (hereinafter, also simply referred to as "coating composition", "film" and "manufacturing method", respectively). The present invention relates to an aqueous resin coating composition having excellent dispersion stability of metal oxide particles and a large solid content, a heat ray-shielding film using the same, and a method for producing these.

In recent years, from the viewpoint of energy saving, for the purpose of shielding heat rays such as infrared rays and near infrared rays in sunlight, metal oxides having a heat ray shielding effect such as antimony-doped tin oxide, tin-doped indium oxide, and antimonated zinc oxide have been used. Heat ray shielding paints for paint windows containing fine particles have been developed. On the other hand, the use of organic solvents has been restricted due to environmental problems and problems of adverse effects on the human body. Therefore, the replacement of organic solvent-based paints with water-based resin paints containing almost no organic solvent is progressing, and a water-based urethane resin paint composition for heat ray shielding containing fine particles of metal oxide having a heat ray shielding effect has been proposed. (For example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2013-087228 Japanese Unexamined Patent Publication No. 2013-23613

In the conventional water-based urethane resin coating composition for heat ray shielding, the dispersion stability of the metal oxide fine particles in the urethane resin is insufficient. Therefore, 15 to 30% by mass of the metal oxide fine particles is water-based urethane. It is added to the resin. However, in order to blend a sufficient amount of metal oxide fine particles for heat ray shielding, the water content derived from the aqueous dispersion of the metal oxide fine particles becomes large, and only a coating composition having a small solid content can be obtained.

Further, since water has a large latent heat of vaporization, the water-based resin paint takes longer to dry than the solvent-based paint, and the water-based resin paint having a small solid content is further layered in order to obtain a coating film having a sufficient thickness. Painting is required, which causes problems in workability. Further, when the aqueous dispersion of the metal oxide fine particles is used, there is a problem that the transparency is insufficient because the dispersibility of the metal oxide fine particles is not sufficient.

Therefore, an object of the present invention is to provide an aqueous resin coating composition having excellent dispersion stability of metal oxide particles and a large solid content, a heat ray-shielding film using the same, and a method for producing the same.

As a result of diligent studies to solve the above problems, the present inventors have reduced the particle size of the urethane resin emulsion and the metal oxide having a heat ray-shielding property by a predetermined method to disperse the metal oxide particles. We have found that an aqueous resin coating composition having a high solid content and which can improve stability can be obtained, and have completed the present invention.

That is, the water-based resin coating composition of the present invention is the urethane resin emulsion (A) and at least one metal selected from the group consisting of antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide. A water-based resin coating composition containing oxide particles (B) and a wet pulverized product, wherein the average particle diameter of the wet pulverized product is 70 nm or less.
The urethane resin emulsion (A) is characterized by being a urethane resin which is a reaction product of a high molecular weight polyol compound having a molecular weight of 500 or more, a polyisocyanate, a hydrophilic group introducer and a chain extender. Here, the average particle size means a volume-based average particle size measured by a dynamic light scattering method.

In the coating composition of the present invention, the solid content is 15 to 45% by mass, and the content of the metal oxide particles (B) with respect to 100 parts by mass of the solid content derived from the urethane resin emulsion (A) is 18 to 80. It is preferably parts by mass. Further, in the coating composition of the present invention, the high molecular weight polyol compound is preferably a polyester polyol.

Further, the heat ray-shielding film of the present invention is characterized in that a heat ray-shielding layer made of the water-based resin coating composition of the present invention is formed on a resin base film.

Further, the method for producing the water-based resin coating composition of the present invention is at least one selected from the group consisting of the urethane resin emulsion (A) and the group consisting of antimonated tin oxide, antimonated zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide. It has a step of pulverizing and dispersing the seed metal oxide particles (B) by wet pulverization until the average particle diameter becomes 70 nm or less.
The urethane resin emulsion (A) is characterized by being a urethane resin which is a reaction product of a high molecular weight polyol compound having a molecular weight of 500 or more, a polyisocyanate, a hydrophilic group introducer and a chain extender.

In the production method of the present invention, the solid content is 15 to 45% by mass, and the content of the metal oxide particles (B) with respect to 100 parts by mass of the solid content derived from the urethane resin emulsion (A) is 18 to 80% by mass. It is preferably a part. Further, in the production method of the present invention, the high molecular weight polyol compound is preferably a polyester polyol.

Furthermore, the method for producing the heat ray shielding film of the present invention is at least one selected from the group consisting of urethane resin emulsion (A) and antimony-doped tin oxide, antimonated zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide. The metal oxide particles (B) of the above are pulverized and dispersed by wet pulverization until the average particle diameter becomes 70 nm or less to obtain an aqueous resin coating composition.
It has a step of applying the water-based resin coating composition on a resin base film.
The urethane resin emulsion (A) is characterized by being a urethane resin which is a reaction product of a high molecular weight polyol compound having a molecular weight of 500 or more, a polyisocyanate, a hydrophilic group introducer and a chain extender.

According to the present invention, it is possible to provide an aqueous resin coating composition having excellent dispersion stability of metal oxide particles and a large solid content, a heat ray-shielding film using the same, and a method for producing the same.

Hereinafter, the water-based resin coating composition of the present invention, a heat ray-shielding film using the same, and a method for producing these will be described in detail in order.

<Water-based resin paint composition>
The coating composition of the present invention is a group consisting of a urethane resin emulsion (A) (hereinafter, also simply referred to as “component (A)”), antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, and tin-doped indium oxide. It contains at least one kind of metal oxide particles (B) selected from the above (hereinafter, also simply referred to as “component (B)”) and a wet pulverized product. In the coating composition of the present invention, these wet pulverized products, that is, the average particle diameters of the components (A) and (B) are 70 nm or less.

In the conventional water-based urethane resin coating composition for heat ray shielding, an aqueous dispersion of heat ray shielding metal oxide fine particles is added to the urethane resin emulsion, whereas in the coating composition of the present invention, the urethane resin is used. Since the emulsion and the metal oxide particles are pulverized and dispersed by wet pulverization, a composition having a high solid content can be obtained. Normally, when the metal oxide particles are stably dispersed in an aqueous solvent such as water or alcohol, a surfactant or a dispersant has been used (see, for example, Japanese Patent Application Laid-Open No. 2005-187580). In the coating composition of the present invention, the urethane resin emulsion contributes to the dispersion stability, and the metal oxide particles can be stably dispersed without using a surfactant or a dispersant. The reason for this is that it is difficult to directly specify the dispersed state of the metal oxide particles, but the urethane resin has a large number of urethane groups and urea groups, and amino groups and carboxyl groups derived from the chain extender. Alternatively, if there are sulfonic acid groups, it is considered that these groups are adsorbed on the surface of the metal oxide particles to suppress the reaggregation of the metal oxide particles.

Further, even if the solid content of the coating composition of the present invention is the same, a coating film having higher transparency than the conventional water-based urethane resin coating composition for shielding heat rays can be obtained. This is because the conventional paint composition is simply a mixture of the urethane resin emulsion and the aqueous dispersion of the metal oxide particles, and the adsorption of the urethane resin particles to the metal oxide particles is weak. In the coating composition of the present invention, the secondary particles of the metal oxide are crushed in the presence of the urethane resin emulsion, so that the urethane resin particles are strongly adsorbed or adhered to the surface of the metal oxide to improve the dispersibility. It is presumed that this is because it is improving.

In general, the smaller the particle size of the metal oxide particles, the easier it is for the particles to form secondary particles in which the particles are agglomerated with each other, and the dispersion stability in water or a solvent is lowered. However, in the coating composition of the present invention, the above effect can be satisfactorily obtained by pulverizing the secondary particles of the component (B) by wet pulverization and controlling the average particle size of the coating composition to 70 nm or less. , The dispersion stability is improved.

It is preferable that the average particle size of the coating composition of the present invention is small, but if it is made too small, it is difficult to obtain an industrial raw material, and a great deal of labor is required for production. Therefore, the average particle size of the particles of the coating composition of the present invention is preferably 30 to 65 nm, more preferably 45 to 60 nm. The average particle size of the coating composition of the present invention is not the average particle size of the secondary particles of the component (B), but the average particle size of the components (A) and (B). Hereinafter, the urethane resin emulsion (A) and the metal oxide (B) according to the coating composition of the present invention will be described in detail.

<Urethane resin emulsion (A)>
In the coating composition of the present invention, the urethane resin emulsion (A) refers to a urethane resin dispersed in water. The component (A) can be produced by a known method. For example, after synthesizing a relatively high molecular weight urethane prepolymer in a solvent that does not react with isocyanate groups, water is added little by little for phase inversion emulsification, and if necessary, the solvent is removed by reducing the pressure, or an emulsifier is added and violently. A method of dispersing in water by stirring, or a urethane prepolymer having a hydrophilic group, for example, a polyoxyethylene group or a carboxyl group introduced into the molecule, is dispersed in water, and then a chain extender is added to react. There are methods and so on. As the component (A) of the present invention, a urethane prepolymer obtained by reacting a high molecular weight polyol compound having a molecular weight of 500 or more, a polyisocyanate, and a hydrophilic group introducer is dispersed in water, and then a chain extender is added. Urethane resin is preferable.

In the coating composition of the present invention, the high molecular weight polyol compound having a molecular weight of 500 or more preferably has at least two hydroxyl groups. For example, organic acids such as phthalic acid, adipic acid, dimerized linoleic acid, maleic acid and 12-hydroxystearic acid, and glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol and 12-hydroxystearyl alcohol. , Trimethylolpropane, hexanetriol, glycerin, trimethylolethane, pentaerythritol and other polyester polyols obtained by dehydration condensation reaction; glycolide, lactide, ε-caprolactone, p-dioxanone and other polyester polyols obtained by ring-opening polymerization; ethylene Glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6 -Low molecular weight polyols such as hexanediol, bisphenol A, hydrogenated bisphenol A or addition reaction products obtained by adding ethylene oxide and / or propylene oxide to polyphenols, polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol and the like. Polyether polyol; 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1, Examples thereof include a polycarbonate polyol obtained by a condensation reaction between a diol such as 4-cyclohexanedimethanol and a carbonate compound such as dimethyl carbonate, diethyl carbonate and ethylene carbonate. Among the high molecular weight polyol compounds, polyester polyol is preferable because the component (B) has excellent dispersibility and a highly transparent coating film can be obtained.

Examples of the polyisocyanate used as the component (A) include diisocyanates and polyisocyanates having three or more isocyanate groups in one molecule. Examples of the diisocyanate include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylenediocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, and 3,3'-dimethyldiphenyl-4,4'-diisocyanate. , Aromatic diisocyanates such as dianisidine diisocyanate, tetramethylximethylene diisocyanate; alicyclic such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans and / or cis-1,4-cyclohexanediisocyanate, norbornene diisocyanate. Formula diisocyanates; aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) -trimethylhexamethylene diisocyanate, lysine diisocyanate; and mixtures thereof. Be done.

Examples of the polyisocyanate having three or more isocyanate groups in one molecule include triphenylmethane triisocyanate, 1-methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethanetetraisocyanate, and a mixture thereof. Trifunctional or higher functional isocyanates, modified products such as carbodiimide modification, isocyanurate modification, and biuret modification of these trifunctional or higher functional isocyanates, blocked isocyanates in which these are blocked by various blocking agents, and isocyanurates (trimerates) of the above-mentioned diisocyanates. ) And biuret trimeric.

Among these, aliphatic diisocyanates and alicyclic diisocyanates are preferable because they are easily available and a coating film having excellent weather resistance and strength can be obtained, and 1,6-hexamethylene diisocyanate and dicyclohexylmethane-4,4 are preferable. '-Diisocyanate and isophorone diisocyanate are more preferable.

In the coating composition of the present invention, the hydrophilic group-introducing agent refers to a compound containing at least one hydrogen atom that reacts with an isocyanate group and at least one tertiary amino group, carboxyl group or sulfonic acid group. Examples of the hydrophilic group-introducing agent include trialkanolamine compounds such as triethanolamine and triisopropanolamine; N-alkyldialkanolamine compounds such as N-methyldiethanolamine, N-ethyldiethanolamine and N-butyldiethanolamine; N, N-dimethyl. N, N-dialkylalkanolamine compounds such as ethanolamine, N, N-diethylethanolamine; monool compounds having carboxyl groups such as 2-hydroxyethaneic acid and 4-hydroxybutanoic acid; 2,2-dimethylolpropionic acid , 2,2-Dimethylolbutyric acid, 2,2-Dimethylol valerate and other diol compounds having a carboxyl group; diol compounds containing a sulfonic acid group such as 1,4-butanediol-2-sulfonic acid and the like. Since the strength of the coating film is improved, the number of hydrogen atoms that react with the isocyanate group is preferably two, and the dispersion stability of the component (B) is improved, so that a diol compound containing a carboxyl group is more preferable. .. The amount of the hydrophilic group-introducing agent used is preferably 5 to 50 mol% with respect to the high molecular weight polyol compound because the water dispersibility of the component (A) is improved.

In the coating composition of the present invention, the chain extender is a low molecular weight compound having at least two hydrogen atoms that react with an isocyanate group, and refers to a compound other than the hydrophilic group introducer. Examples of the chain extender include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,12-dodecanediol, 12-hydroxystearyl alcohol, glycerin, and trimethylol. Low molecular weight polyol compounds such as ethane, trimethylolpropane, pentaerythritol, sorbitol; ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenyldimethane, diaminodicyclohexylmethane, piperazin, isophoronediamine, Polyamine compounds such as diethylenetriamine, dipropylenetriamine and melamine; hydrazine compounds such as hydrazine, monoalkylhydrazine and 1,4-hydrazinodiethylene; dihydrazide compounds such as dihydrazide such as carbohydrazide and adipic acid hydrazide, water and the like can be mentioned. Among these, polyamine compounds are preferable because they are excellent in reactivity with isocyanate, and water is preferable because they have little influence on the physical characteristics of the film.

In the case of producing a prepolymer, the compounding ratio of the high molecular weight polyol compound, polyisocyanate and the hydrophilic group introducer is such that the molar ratio of the isocyanate group to the isocyanate reactive group is 30 to 99 mol% with respect to the isocyanate group. It is preferable, and 50 to 99% is more preferable. When producing the prepolymer, a solvent may be used, and when a solvent is used, a solvent that is inert to the urethanization reaction and has a high affinity with water is preferable, and the pressure is reduced. Acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and N-methyl-2-pyrrolidone are preferable because the removal of the solvent is easy. The prepolymer is added to water and dispersed in water, and the ratio of the prepolymer to water is preferably 15 to 40% by mass of the prepolymer with respect to the total amount of the prepolymer and water.

In the coating composition of the present invention, for example, after dispersing the prepolymer in water, a chain extender may be added and reacted with the isocyanate group of the prepolymer. When a chain extender other than water is used, the amount used is preferably 10 to 200 mol% of hydrogen atoms that react with the isocyanate group of the chain extender with respect to the isocyanate group in the prepolymer, and is 50 to 200 mol%. More preferably, it is 90 mol%. If it is less than 10 mol%, the molecular weight of the component (A) may be small and the physical characteristics of the coating film may be deteriorated, while if it is more than 200 mol%, an unreacted chain extender remains. , The physical characteristics of the coating film may deteriorate.

The tertiary amino group, carboxyl group or sulfonic acid group derived from the hydrophilic group introducing agent is preferably neutralized from the viewpoint of water dispersibility of the component (A). Such neutralization may be performed before the prepolymer is dispersed in water, after the prepolymer is dispersed in water, before the addition of the chain extender, or after the reaction between the prepolymer and the chain extender. When a compound having a tertiary amino group is used as the hydrophilic group introducing agent, the neutralizing agent includes carboxylic acids such as formic acid, acetic acid and oxalic acid, organic sulfonic acids such as paratoluene sulfonic acid, sulfuric acid, phosphoric acid and the like. Examples thereof include quaternary agents such as inorganic acids, dialkylsulfuric acid, and alkyl halides. When a compound having a carboxyl group or a sulfonic acid group is used as the hydrophilic group introducing agent, the neutralizing agent includes trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, triethanolamine and the like. Examples thereof include inorganic bases such as organic amines, sodium hydroxide, potassium hydroxide and ammonia. The amount of the neutralizing agent used is sufficient to neutralize the amino group, the carboxyl group or the sulfonic acid group in the component (A).

A commercially available urethane resin emulsion may be used as the component (A) of the coating composition of the present invention. Commercially available urethane resin emulsions include, for example, the "ADEKA Bontiter" series manufactured by ADEKA Corporation, the "Orestar" series manufactured by Mitsui Toatsu Chemical Co., Ltd., and the Dainippon Ink and Chemicals Co., Ltd. "Bondic" series, "Hydran" series, Bayer "Implanil" series, Nippon Soflan Co., Ltd. "Sofranate" series, Kao Corporation "Poise" series, Sanyo Kasei Kogyo Co., Ltd. "Samplen" series, "Izelax" series manufactured by Hodogaya Chemical Industry Co., Ltd., "Superflex" series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Neolets" series manufactured by Zeneka Corporation, etc. ..

<Metal oxide particles (B)>
In the coating composition of the present invention, the metal oxide particles (B) are at least one metal oxide selected from the group consisting of antimony-doped tin oxide, antimonated zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide. It is a particle. The component (B) is a component that imparts a heat ray shielding effect such as infrared rays or near infrared rays to the coating composition. As the component (B), antimony-doped tin oxide is preferable because it has a high shielding effect of near infrared rays and the like, which has a high indoor temperature raising effect among sunlight.

In the coating composition of the present invention, in addition to the component (B) that imparts a heat ray shielding effect such as infrared rays and near infrared rays, other generally known heat ray shielding components can also be used in combination. Examples of such compounds include lanthanum compounds such as tungsten-based composite oxides and lanthanum hexaboride.

In the coating composition of the present invention, the ratio of the component (A) to the component (B) is such that the content of the component (B) is 18 to 80 parts by mass with respect to 100 parts by mass of the solid content derived from the component (A). Is preferable. When the content of the component (B) is lower than 18 parts by mass, it is necessary to make a thick coating film in order to obtain sufficient heat ray shielding property, and the workability for painting is lowered, which is higher than 80 parts by mass. In some cases, the smoothness of the coating film and the adhesion to the substrate may be adversely affected. The content of the component (B) with respect to 100 parts by mass of the solid content derived from the component (A) is more preferably 20 to 70 parts by mass, further preferably 25 to 60 parts by mass.

The particle size of component (B) is preferably as small as possible from the viewpoint of dispersion stability and transparency of the coating film, but from the viewpoint of industrial availability, the particle size of component (B) is The average particle size of the primary particles is preferably 2 to 50 nm, more preferably 5 to 30 nm.

The coating composition of the present invention is characterized in that the component (A) and the component (B) are pulverized and dispersed by wet pulverization until the average particle size becomes 70 nm or less. In the coating composition of the present invention, the average particle size is a volume-based average particle size measured by a dynamic light scattering method. The smaller the particle size of the metal oxide particles, the easier it is for the particles to form secondary particles in which the particles are aggregated, and the dispersion stability is lowered. In the coating composition of the present invention, the dispersion stability can be improved by pulverizing the secondary particles of the metal oxide by wet pulverization and controlling the average particle size of the coating composition to 70 nm or less. It is preferable that the average particle size of the coating composition of the present invention is small, but if it is made too small, it is difficult to obtain an industrial raw material, and a great deal of labor is required for production. Therefore, the average particle size of the particles of the coating composition of the present invention is preferably 30 to 65 nm, more preferably 45 to 60 nm.

Water may be added to adjust the solid content of the coating composition of the present invention, but the solid content of the coating composition of the present invention is preferably 15 to 45% by mass. Here, the solid content is the non-volatile content measured according to the condition B (temperature: 105 ° C., heating time: 1 hour) of JIS K6828.1 (synthetic resin emulsion-Part 1: how to obtain the non-volatile content). To say. When the solid content of the coating composition of the present invention is less than 15% by mass, it may take time to dry the coating film, or recoating may be required to obtain a sufficient shielding effect, and 45% by mass. If it exceeds%, wet pulverization of the component (A) and the component (B) may become difficult, or the dispersion stability of the metal oxide particles may decrease. The solid content of the coating composition of the present invention is more preferably 20 to 43% by mass, further preferably 25 to 40% by mass.

<Other formulations>
The coating composition of the present invention can shield harmful ultraviolet rays and improves the weather resistance of the coating film. Therefore, it is preferable that the coating composition further contains an ultraviolet absorber. Examples of the ultraviolet absorber include salicylic acid derivatives such as methyl salicylate, pt-butylphenyl-salicylate, and p-octylphenyl-salicylate; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and the like. Benzophenone compounds such as 4-dodecyloxy-2-hydroxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) ) Bentotriazole compounds such as benzotriazole, 2- (2'-hydroxy-3', 5'-dit-amylphenyl) benzotriazole; 3-phenyl-7- (4'-methyl-5'-n-butoxy) Phenyl compounds such as benzotriazolyl-2-) phenyl; inorganic ultraviolet absorbers such as cerium oxide, zinc oxide, iron oxide, and titanium oxide can be mentioned. If the amount of the ultraviolet absorber is too small, the ultraviolet rays cannot be sufficiently shielded, and if the amount is too large, not only the effect of increasing the amount corresponding to the amount of the ultraviolet absorber cannot be obtained, but also the coating film obtained from the coating composition of the present invention can be obtained. The physical properties of the product may deteriorate. Therefore, the ultraviolet absorber is preferably 1 to 15 parts by mass, more preferably 5 to 10 parts by mass, based on 100 parts by mass of the solid content derived from the component (A) of the coating composition of the present invention.

Since the water-based resin coating composition of the present invention improves the weather resistance of the coating film, it may further contain a hindered amine-based light stabilizer and an antioxidant (phosphorus-based, phenol-based or sulfur-based antioxidant). preferable.

Examples of the hindered amine-based light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. , 6-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidylmethylmethacrylate, 2,2,6,6-tetra Methyl-4-piperidylmethylmethacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6) −Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3 4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl), bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2, 2,6,6-Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-dith-3-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2 6,6-Tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1, 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6) , 6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-third octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N) -Butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8 , 12-Tetrakiss [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5 8,12- Tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-ylamino ] Undecane, 1,6,11-Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-ylamino ] Undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8 , 10-Tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butyl) Carbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

Examples of phosphorus-based antioxidants include triphenylphosphite, tris (2,4-dit-butylphenyl) phosphite, tris (2,5-dit-butylphenyl) phosphite, and tris (nonylphenyl). ) Phosphite, Tris (dinonylphenyl) phosphite, Tris (mono, dimixed nonylphenyl) phosphite, diphenylacid phosphite, 2,2'-methylenebis (4,6-dit-butylphenyl) octylphosphite , Diphenyldecylphosphite, diphenyloctylphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyldiisodecylphosphite, tributylphosphite, tris (2-ethylhexyl) phosphite, tridecylphosphite, trilaurylphosphite, Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-dit-butylphenyl) pentaerythritol diphos Fight, bis (2,5-dit-butylphenyl) pentaerythritol diphosphite, bis (2,6-dit-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dikumil) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropyridendiphenylphosphite, bis [2,2'-methylenebis (4,6-dia) Milphenyl)] ・ Isopropyridene diphenyl phosphite, tetratridecyl ・ 4,4'-butylidenebis (2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl) ・ 1,1,3-tris (2-) Methyl-5-t-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-dit-butylphenyl) biphenylenediphosphonite, tris (2-[(2,4,7,9-tetrakis) t-Butyldibenzo [d, f] [1,3,2] dioxaphosfepin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-Oxide, Tris (2-[(2,4,8,10-tetrax t-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-6-a Lu) Oxy] Ethyl) amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-trax (1,1-dimethylethyl) dibenzo [d] , F] [1,3,2] dioxaphosfepin-6-yl] oxy] propyl] phenol-2-butyl-2-ethylpropanediol, 2,4,6-trit-butylphenol monophosphite, etc. Can be mentioned.

Examples of the phenolic antioxidant include 2,6-dit-butyl-p-cresol, 2,6-diphenyl-4-octadesiloxyphenol, and stearyl (3,5-dit-butyl-4-). Hydroxyphenyl) propionate, distearyl (3,5-dit-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-dit-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5) -Di t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-m-cresol), 2-octylthio-4,6-di (3,5-dit-butyl) -4-Hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-t-butylphenol), bis [3,3-bis (4-hydroxy-3-t-butylphenyl) butyl Acid] Glycolester, 4,4'-butylidenebis (2,6-dit-butylphenol), 4,4'-butylidenebis (6-t-butyl-3-methylphenol), 2,2'-ethylidenebis (4) , 6-dit-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2) -Hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3 5-Tris (3,5-dit-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris (3,5-dit-butyl-4-hydroxybenzyl) -2,4,6- Trimethylbenzene, 1,3,5-tris [(3,5-dit-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3', 5'-dit-butyl) -4'-Hydroxyphenyl) propionate] methane, 2-t-butyl-4-methyl-6- (2-acroyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis [2 -(3-t-Butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol Bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) pro Pionate], tocophenol and the like.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl ester of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Β-alkyl mercaptopropionic acid esters of.

If the blending amount of the hindered amine light stabilizer and the antioxidant is too small, a sufficient blending effect cannot be obtained, and if the blending amount is too large, not only the amount increasing effect commensurate with the blending amount cannot be obtained, but also the blending effect of the present invention cannot be obtained. The physical properties of the coating film obtained from the coating composition may deteriorate. Therefore, the blending amount of the hindered amine-based light stabilizer and the antioxidant is preferably 0.001 to 5 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the solid content derived from the component (A) of the coating composition of the present invention. ~ 3 parts by mass is more preferable.

The coating composition of the present invention preferably contains a silane coupling agent because the adhesion to glass is improved. Examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy group-containing silane coupling agents; p-styryltrimethoxysilane and other styryl Group-containing silane coupling agent; 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropylmethyldiethoxysilane, 3- (meth) acry (Meta) acrylic group-containing silane coupling agent such as loxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Amino group-containing silane coupling agent such as N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl; isocyanurate-containing silane coupling agent such as tris- (trimethoxysilylpropyl) isocyanurate; 3-ureidopropyl Urea group-containing silane coupling agent such as trialkoxysilane; mercapto group-containing silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; sulfide such as bis (triethoxysilylpropyl) tetrasulfide. Group-containing silane coupling agent; Examples thereof include isocyanate group-containing silane coupling agent such as 3-isocyanuppropyltriethoxysilane. If the blending amount of the silane coupling agent is too small, the effect of adhesion to the glass is not sufficient, and if it is too large, not only the effect of increasing the blending amount cannot be obtained, but also the coating composition of the present invention cannot be obtained. The physical properties of the coating film obtained from the above may be deteriorated. Therefore, the blending amount of the silane coupling agent is preferably 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass derived from the solid content of the component (A) of the coating composition of the present invention. Is more preferable.

In addition to this, various known additives may be further used in the coating composition of the present invention, if necessary. Examples of such additives include inorganic ultraviolet absorbers, film-forming aids, curing agents, blocking inhibitors, leveling agents, antigelling agents, dispersion stabilizers, epoxy compounds, plasticizers, lubricants, and antistatic agents. Examples thereof include agents, catalysts, antibacterial agents, antifungal agents, anticorrosion agents, antifoaming agents, viscosity modifiers, thickeners, organic solvents, antisettling agents and the like.

When an ultraviolet absorber, a hindered amine-based light stabilizer, an antioxidant, a silane coupling agent, or the like is added to the coating composition of the present invention, these compounds are difficult to disperse in water, and therefore a urethane resin emulsion is produced. It is preferable to add it to a high molecular weight polyol or a prepolymer at the stage.

Since the coating film obtained by the coating composition of the present invention is excellent in heat ray shielding property, the coating composition can be suitably used as a heat ray shielding property for window glass. The method of applying the coating composition to the window glass is not particularly limited, but when it is applied to the existing window glass, it can be easily applied, so a sponge coat or a spray coat is preferable. Further, when applied on the production line of a factory, a sponge coat, a spray coat, and a curtain coat (flow coat) are preferable. If the thickness of the coating film is too thin, the effect of shielding heat rays is insufficient, and if it is too thick, the cost may increase and the transmittance of visible light may decrease. Therefore, the thickness of the coating film after drying is preferably 2 to 50 μm, more preferably 5 to 40 μm, and even more preferably 10 to 30 μm. When applying to glass, either one side or both sides of the glass may be used, but when applying to the existing window glass, since contamination of the coating film from the outside of the facility can be reduced, it should be applied only to the inner surface (indoor surface). Is preferable. Applying only to the inner surface is preferable in the case of window glass on the second floor or higher from the viewpoint of ease of construction.

By applying the coating composition of the present invention to the window glass, heat rays from the outside are shielded, and as a result, a rapid rise in the indoor air temperature is suppressed, and the electric power required for cooling in the summer can be saved. Further, when the coating composition of the present invention is used for a windshield, a side glass, a sunroof, etc. of a vehicle, it is possible to suppress an increase in temperature inside the vehicle. The coating composition of the present invention can be applied not only to inorganic glass but also to transparent resin plates and resin sheets.

<Heat ray shielding film>
Next, the heat ray shielding film of the present invention will be described. The film of the present invention is formed by forming a heat ray-shielding layer made of the above-mentioned coating composition of the present invention on a resin base film.

As the resin base film used in the film of the present invention, a resin film having weather resistance such as a polyester film, an acrylic film, a polycarbonate film, a fluorine film, and a polyimide film is preferable. A film obtained by forming a coating film of the coating composition of the present invention on these resin-based base film and adhesively processing the film is useful as a heat ray-shielding sheet used by adhering it to a window glass, a vehicle windshield, or the like. .. The thickness of the resin base film is preferably 50 to 200 μm from the viewpoint of sheet handleability. The thickness of the coating film after drying is preferably 2 to 50 μm, more preferably 5 to 40 μm, and even more preferably 10 to 30 μm.

<Manufacturing method of water-based resin paint composition>
Next, a method for producing the water-based resin coating composition of the present invention will be described. The production method of the present invention comprises a urethane resin emulsion (A) and at least one metal oxide particle (B) selected from the group consisting of antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide. ) And a step of pulverizing and dispersing until the average particle size becomes 70 nm or less. Here, in the production method of the present invention, wet pulverization is used as a means of pulverization and dispersion. The reason for this is as follows.

As described above, in general, the smaller the particle size of the metal oxide particles, the easier it is for the particles to form secondary particles in which the particles are aggregated, and the dispersion stability in water or a solvent is lowered. Therefore, in the production method of the present invention, the secondary particles of the component (B) are pulverized by wet pulverization, and the average particle size of the coating composition is controlled to 70 nm or less to improve the dispersion stability. However, it is preferable that the average particle size of the coating composition of the present invention is small, but if it is made too small, it is difficult to obtain an industrial raw material, and a great deal of labor is required for production. Therefore, the average particle size of the particles of the coating composition of the present invention is preferably 30 to 65 nm, more preferably 45 to 60 nm. The average particle size of the production method of the present invention is not the average particle size of the secondary particles of the component (B), but the average particle size of the components (A) and (B).

As a method of wet pulverization, there is a method using a cylinder or a cylinder such as a rod or a roll; a sphere such as a ball or a bead, but a method using a sphere is preferable because fine pulverization is possible. Preferred wet pulverizers include a hammer mill, a rotary mill, a vibration mill, a planetary mill, an attritor, a bead mill, and the like, and a bead mill is preferable because a dispersion having good dispersion stability and a small particle size can be obtained. .. Examples of the material of the beads that can be used include metal, glass, and ceramics, but ceramics are preferable because of their excellent wear resistance. The smaller the particle size of the beads, the smaller the particle size of the dispersion can be obtained. However, if the particle size of the beads is too small, the operability is poor. Therefore, the particle size of the beads is preferably 30 to 300 μm, and 50. ~ 100 μm is more preferable.

As described above, the method for producing the component (A) is not particularly limited, and a known method can be applied. However, from the viewpoint of ease of production and dispersion stability of the resin, a prepolymer is synthesized by reacting in a solvent. Then, the prepolymer method in which the feed is dispersed in water and the prepolymer method in which the prepolymer is dispersed in water are preferable, and the prepolymer method in which the prepolymer is dispersed in water is more preferable. The blending ratio of the polyester polyol compound, the polyisocyanate and the chain extender in producing the prepolymer is such that the molar ratio of the isocyanate group to the isocyanate-reactive group is 30 to 99 mol% with respect to the isocyanate group. Preferably, 50-99 mol% is more preferred. As the solvent used in the prepolymer method, a solvent that is inert to the urethanization reaction and has a high affinity with water is preferable, and removal under reduced pressure is easy. Therefore, acetone, methyl ethyl ketone, dioxane, and tetrahydrofuran can be used. , N-Methyl-2-pyrrolidone is preferred. The ratio of prepolymer to water is preferably 15 to 40% by mass of prepolymer with respect to the total amount of prepolymer and water.

When an amino alcohol compound or a low molecular weight polyol compound having a carboxyl group or a sulfonic acid group is used as the chain extender, from the viewpoint of water dispersibility of the component (A), it is after the production of the prepolymer. It is preferable to neutralize with a neutralizing agent before adding the prepolymer to water or after adding water. When an amino alcohol compound is used as the chain extender, the neutralizing agent includes carboxylic acids such as formic acid, acetic acid and oxalic acid, organic sulfonic acids such as paratoluene sulfonic acid, inorganic acids such as hydrochloric acid and phosphoric acid, and dialkyl. Examples thereof include quaternary agents such as sulfuric acid and alkyl halides. When a low molecular weight polyol compound having a carboxyl group or a sulfonic acid group is used as the chain extender, the neutralizing agent includes trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, triethanolamine and the like. Examples thereof include organic amines, sodium hydroxide, potassium hydroxide, ammonia and other inorganic bases. The amount of the neutralizing agent used is sufficient to neutralize the amino group, carboxyl group or sulfonic acid group of the prepolymer.

In the production method of the present invention, when an ultraviolet absorber, a hindered amine-based light stabilizer, an antioxidant, a silane coupling agent, or the like is added, these compounds are difficult to disperse in water. It is not preferable to add it later, and it is preferable to add it to a high molecular weight polyol or a prepolymer at the stage of producing a urethane resin emulsion.

In order to adjust the solid content of the coating composition of the present invention, water may be added, but when water is added, it may be before wet pulverization or after dispersion.

<Manufacturing method of heat ray shielding film>
The method for producing a heat ray-shielding film of the present invention includes a step of applying the coating composition of the present invention on a resin base film. That is, the urethane resin emulsion (A) and at least one metal oxide particle (B) selected from the group consisting of antimony-doped zinc oxide, antimony-doped zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide are wetted. It includes a step of crushing and dispersing until the average particle size becomes 70 nm or less by pulverization to obtain an aqueous resin coating composition, and a step of applying the aqueous resin coating composition on a resin base film.

As described above, as the resin base film, a resin film having weather resistance such as a polyester film, an acrylic film, a polycarbonate film, a fluorine film, and a polyimide film is preferable. Further, as a coating method, a sponge coat, a spray coat, and a curtain coat (flow coat) are preferable. If the thickness of the coating film is too thin, the effect of shielding heat rays is insufficient, and if it is too thick, the cost may increase and the transmittance of visible light may decrease. Therefore, the thickness of the coating film after drying is preferably 2 to 50 μm, more preferably 5 to 40 μm, and even more preferably 10 to 30 μm.

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

<High molecular weight polyol compound>
A1: Neopentyl glycol / 12-hydroxystearic acid / adipic acid = 10/9/6 (molar ratio) reaction product number average molecular weight 1030
A2: Neopentyl glycol / 12-hydroxystearyl alcohol / adipic acid = 3/7/7 (molar ratio) reaction product number average molecular weight 1020
A3: 1,6-Hexanediol-based polycarbonate diol (manufactured by Asahi Kasei Chemicals, product name T6002) Number average molecular weight 2000
A4: Polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, product name PTMG2000) Number average molecular weight 2000

<Production Example 1: Emulsion B1>
Take 222 parts by mass of high molecular weight polyol compound A1, 78 parts by mass of hexamethylene diisocyanate (HDI), 22 parts by mass of dimethylolpropionic acid, and 83 parts by mass of N-methyl-2-pyrrolidone in a reaction vessel and keep the temperature at 80 to 100 ° C. The reaction was carried out to produce a prepolymer. After neutralizing by adding 17.8 parts by mass of triethylamine to this prepolymer, 8.3 parts by mass of hexamethylenediamine was added, and a cross-linking reaction was carried out at 35 ° C. or lower while adding water to bring the solid content to 30%. Water was added until the emulsion B1 was produced.

<Production Example 2: Emulsion B2>
Reaction of high molecular weight polyol compound A2 by 166 parts by mass, isophorone diisocyanate (IPDI) by 108 parts by mass, 1,4-butanediol by 5 parts by mass, N-methyldiethanolamine by 25 parts by mass, and N-methyl-2-pyrrolidone by 75 parts by mass. It was placed in a container and reacted at 80 to 100 ° C. to produce a prepolymer. After neutralizing this prepolymer by adding 15 parts by mass of acetic acid, water was added until the solid content became 30% to prepare emulsion B2.

<Production Example 3: Emulsion B3>
Reaction vessel containing 490 parts by mass of high molecular weight polyol compound A3, 120 parts by mass of 1,12-dodecanediol, 519 parts by mass of isophorone diisocyanate, 71.7 parts by mass of dimethylolpropionic acid, and 246 parts by mass of N-methyl-2-pyrrolidone. To produce a prepolymer, the reaction was carried out while maintaining the temperature at 100 to 110 ° C. After neutralizing by adding 60 parts by mass of triethylamine to this prepolymer, water was added until the solid content became 30% to prepare emulsion B3.

<Production Example 4: Emulsion B4>
818 parts by mass of high molecular weight polyol compound A3, 24 parts by mass of 12-hydroxystearyl alcohol, 319 parts by mass of 4,4'-diphenylmethane diisocyanate (hydrogenated MDI), 43 parts by mass of dimethylol propionic acid and N-methyl-2- 26 parts by mass of pyrrolidone was placed in a reaction vessel and reacted while maintaining the temperature at 100 to 110 ° C. to produce a prepolymer. After neutralizing by adding 39 parts by mass of triethylamine to this prepolymer, water was added until the solid content became 30% to prepare an emulsion B4.

<Production Example 5: Emulsion B5>
Take 222 parts by mass of high molecular weight polyol compound A1, 78 parts by mass of hexamethylene diisocyanate (HDI), 22 parts by mass of dimethylolpropionic acid, and 83 parts by mass of N-methyl-2-pyrrolidone in a reaction vessel and keep the temperature at 80 to 100 ° C. The reaction was carried out to produce a prepolymer. After neutralizing by adding 17.8 parts by mass of triethylamine to this prepolymer, 8.3 parts by mass of hexamethylenediamine and 20 parts by mass of aminopropyltriethoxysilane (silane coupling agent) are added, and water is added. The cross-linking reaction was carried out at 35 ° C. or lower, and water was added until the solid content became 30% to prepare emulsion B5.

<Production Example 6: Emulsion B6>
Take 222 parts by mass of high molecular weight polyol compound A1, 78 parts by mass of hexamethylene diisocyanate (HDI), 22 parts by mass of dimethylolpropionic acid, and 83 parts by mass of N-methyl-2-pyrrolidone in a reaction vessel and keep the temperature at 80 to 100 ° C. The reaction was carried out to produce a prepolymer. After neutralizing by adding 17.8 parts by mass of triethylamine to this prepolymer, 8.3 parts by mass of hexamethylenediamine was added, and a cross-linking reaction was carried out at 35 ° C. or lower while adding water to bring the solid content to 35%. Water was added until the emulsion B6 was produced.

<Production Example 7: Emulsion B7>
Reaction vessel containing 490 parts by mass of high molecular weight polyol compound A4, 120 parts by mass of 1,12-dodecanediol, 519 parts by mass of isophorone diisocyanate, 71.7 parts by mass of dimethylolpropionic acid, and 246 parts by mass of N-methyl-2-pyrrolidone. To produce a prepolymer, the reaction was carried out while maintaining the temperature at 100 to 110 ° C. After neutralizing by adding 60 parts by mass of triethylamine to this prepolymer, water was added until the solid content became 30% to prepare emulsion B7.

<Metal oxide particles>
C1: Antimony-doped tin oxide powder with a primary particle size of 20 nm C2: An aqueous dispersion of antimony-doped tin oxide powder with an average of 62 nm (manufactured by Mitsubishi Materials Corporation, trade name TDL-S, solid content 17.5% by mass)

<Example 1>
90 parts by mass of emulsion B1 and 10 parts by mass of metal oxide particles C1 and a bead mill (manufactured by Kotobuki Kogyo, model UAM-015) were used to grind, disperse, and carry out until the change in average particle size became constant. The water-based resin coating composition of Example 1 was prepared. The beads used were zirconia beads having a particle size of 0.1 mm, and the space filling rate of the beads in the crushing tank of the bead mill was set to 50%.

<Example 2>
The water-based resin coating composition of Example 2 was prepared by performing the same operation as in Example 1 except that 90 parts by mass of emulsion B2 was used instead of emulsion B1.

<Example 3>
The water-based resin coating composition of Example 3 was prepared by performing the same operation as in Example 1 except that 90 parts by mass of emulsion B3 was used instead of emulsion B1.

<Example 4>
The water-based resin coating composition of Example 4 was prepared by performing the same operation as in Example 1 except that 90 parts by mass of emulsion B4 was used instead of emulsion B1.

<Example 5>
The water-based resin coating composition of Example 5 was prepared by performing the same operation as in Example 1 except that 60 parts by mass of emulsion B1 and 30 parts by mass of water were used instead of 90 parts by mass of emulsion B1.

<Example 6>
The same operation as in Example 1 was carried out except that the emulsion B1 was changed from 90 parts by mass to 87 parts by mass and the metal oxide particles C1 were changed from 10 parts by mass to 13 parts by mass. Prepared.

<Example 7>
The same operation as in Example 1 was carried out except that the emulsion B1 was changed from 90 parts by mass to 93 parts by mass and the metal oxide particles C1 were changed from 10 parts by mass to 7 parts by mass. Prepared.

<Example 8>
The water-based resin coating composition of Example 8 was prepared by performing the same operation as in Example 1 except that 90 parts by mass of emulsion B5 was used instead of emulsion B1.

<Example 9>
The water-based resin coating composition of Example 9 was prepared by performing the same operation as in Example 1 except that 90 parts by mass of emulsion B6 was used instead of emulsion B1.

<Example 10>
The water-based resin coating composition of Example 10 was prepared by performing the same operation as in Example 1 except that 90 parts by mass of emulsion B7 was used instead of emulsion B1.

<Comparative example 1>
90 parts by mass of emulsion B1 and 10 parts by mass of metal oxide particles C1 are stirred for 60 minutes at a rotation speed of 3000 rpm using a high-speed disperser (manufactured by Primix Corporation, model: Homo Disper 2.5 type), and the aqueous system of Comparative Example 1 A resin coating composition was prepared.

<Comparative example 2>
The aqueous resin coating composition of Comparative Example 2 was prepared by stirring 43 parts by mass of the emulsion B1 and 57 parts by mass of the metal oxide particles C2 under the same conditions as in Comparative Example 1.

<Comparative example 3>
The aqueous resin coating composition of Comparative Example 3 was prepared by stirring 61 parts by mass of the emulsion B1 and 39 parts by mass of the metal oxide particles C2 under the same conditions as in Comparative Example 1.

Regarding the water-based resin coating compositions of Examples 1 to 10 and Comparative Examples 1 to 3, the content (B) of the component (B) with respect to the average particle size, the solid content and 100 parts by mass of the solid content derived from the component (A) by the following method. / (A) was measured or calculated. The results are shown in Table 2.

<Average particle size>
The water-based resin coating composition was diluted with distilled water, and the particle size was measured using a dynamic light scattering particle size distribution meter (manufactured by Otsuka Electronics Co., Ltd., model: ELSZ-1000).

<Solid content>
The measurement was performed in accordance with the condition B (temperature: 105 ° C., heating time: 1 hour) of JIS K6828-1 (synthetic resin emulsion-Part 1: how to determine the non-volatile content).

<(B) / (A)>
The content of the component (B) with respect to 100 parts by mass of the solid content derived from the component (A) was calculated from the charged amounts of the component (A) and the component (B).

<Storage stability>
The water-based resin coating composition was placed in a 100 mL glass storage container and stored in a constant temperature bath at 50 ° C. for 1 week, and the storage stability was judged according to the following criteria based on the presence or absence of precipitation.
◯: No precipitation was observed and storage stability was good.
X: No precipitation is observed and storage stability is poor.

<Preparation of test piece>
Using the water-based resin coating compositions of Examples 1 to 10 and Comparative Examples 2 to 3, which had good storage stability, the dry film thickness was 20 μm on a glass plate surface of 100 mm in length × 70 mm in width × 2 mm in thickness. And air-dried at 25 ° C. for 3 days to prepare a test piece. Using this test piece, the transmittance of haze and visible light and infrared rays was measured by the following method. The results are shown in Table 2.

<Measurement of haze>
The haze was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., model NHD2000) in accordance with JIS K7136 (Plastic-How to obtain haze of transparent material).

<Measurement of transmittance>
The transmittance at wavelengths of 550 nm (visible light) and 950 nm (infrared light) was measured using a spectrophotometer (manufactured by JASCO Corporation, model V-670).

※：Ｂ１が６０質量部と水が３０質量部

*: 60 parts by mass of B1 and 30 parts by mass of water

※２：（Ａ）成分由来の固形分１００質量部に対する（Ｂ）成分の含量

* 2: Content of component (B) with respect to 100 parts by mass of solid content derived from component (A)

From the above, it can be seen that the coating composition according to the present invention is excellent in the dispersion stability of the metal oxide particles in the coating composition even if the solid content is increased.

Claims (8)

Wet ground product of urethane resin emulsion (A) and at least one metal oxide particle (B) selected from the group consisting of antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide. a water-based resin coating composition containing a Ri mean der particle diameter 70nm or less of the wet ground product,
A water-based resin coating composition, wherein the urethane resin emulsion (A) is a urethane resin which is a reaction product of a high molecular weight polyol compound having a molecular weight of 500 or more, a polyisocyanate, a hydrophilic group introducer, and a chain extender. The first aspect of claim 1, wherein the solid content is 15 to 45% by mass, and the content of the metal oxide particles (B) with respect to 100 parts by mass of the solid content derived from the urethane resin emulsion (A) is 18 to 80 parts by mass. Water-based resin paint composition. Before Symbol high molecular weight polyol compound, water-based resin coating composition of claim 1 wherein the polyester polyol. A heat ray-shielding film characterized in that a heat ray-shielding layer made of the water-based resin coating composition according to claim 1 is formed on a resin base film. The urethane resin emulsion (A) and at least one metal oxide particle (B) selected from the group consisting of antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide are wet-pulverized. , possess ground to an average particle size of the 70nm or less, a step of dispersing,
A water-based resin coating composition, wherein the urethane resin emulsion (A) is a urethane resin which is a reaction product of a high molecular weight polyol compound having a molecular weight of 500 or more, a polyisocyanate, a hydrophilic group introducer, and a chain extender. Production method. The fifth aspect of claim 5, wherein the solid content is 15 to 45% by mass, and the content of the metal oxide particles (B) with respect to 100 parts by mass of the solid content derived from the urethane resin emulsion (A) is 18 to 80 parts by mass. A method for producing a water-based resin paint composition. Manufacturing method of the preceding Symbol high molecular weight polyol compound, water-based resin coating composition of claim 5 wherein the polyester polyol. The urethane resin emulsion (A) and at least one metal oxide particle (B) selected from the group consisting of antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide and tin-doped indium oxide are wet-pulverized. , A step of crushing and dispersing until the average particle size becomes 70 nm or less to obtain an aqueous resin coating composition, and
The water-based resin coating composition possess a step of applying the resin base film, a
A method for producing a heat ray-shielding film, wherein the urethane resin emulsion (A) is a urethane resin which is a reaction product of a high molecular weight polyol compound having a molecular weight of 500 or more, a polyisocyanate, a hydrophilic group introducer and a chain extender. ..