WO2016199682A1

WO2016199682A1 - Infrared shielding body

Info

Publication number: WO2016199682A1
Application number: PCT/JP2016/066483
Authority: WO
Inventors: 一仁伊原
Original assignee: コニカミノルタ株式会社
Priority date: 2015-06-12
Filing date: 2016-06-02
Publication date: 2016-12-15
Also published as: JP2018124300A

Abstract

Provided is an infrared shielding body that exhibits excellent transparency, thermal shielding properties, and durability. In the infrared shielding body, which comprises an infrared shielding film, a pair of intermediate films that sandwich the infrared shielding film, and a pair of glass plate that sandwich the pair of intermediate films and the infrared shielding film, the infrared shielding film comprises a base material, an infrared reflecting layer having at least one unit in which a low refractive index layer and a high refractive index layer are alternately laminated, and an infrared absorption layer containing a binder and a tungsten oxide and/or a composite tungsten oxide. At least one different layer is present between the infrared reflecting layer and the infrared absorption layer. In the infrared absorption layer, the mass ratio of the tungsten oxide and/or the composite tungsten oxide is 15-30 mass%.

Description

Infrared shield

The present invention relates to an infrared shielding body.

As part of energy conservation measures, there is an increasing demand for laminated glass that shields infrared rays from sunlight from the viewpoint of reducing the load on cooling equipment in buildings and vehicles. Japanese Patent Application Laid-Open No. 2010-222233 (corresponding to US Patent Application Publication No. 2011/300356) discloses an infrared reflection layer in which a high refractive index layer and a low refractive index layer are alternately laminated, and ITO as an infrared absorber. An infrared shielding laminated glass having an infrared absorption layer containing conductive fine particles such as ATO and ATO is disclosed.

However, the laminated glass described in JP 2010-222233 A (corresponding to US Patent Application Publication No. 2011-300366) has high haze and low heat shielding properties (increased glass surface temperature and solar heat transmittance), It has problems such as low durability (heat cracking and cracking at high temperature).

Accordingly, the present invention has been made in view of the above-described problems, and provides an infrared shielding laminated glass (hereinafter also referred to as “infrared shielding body”) excellent in transparency, heat shielding properties, and durability. The purpose is to do.

The present inventor has intensively studied to solve the above problems. As a result, an infrared shielding body having an infrared shielding film, a pair of intermediate films sandwiching the infrared shielding film, and a pair of glass plates sandwiching the infrared shielding film and the pair of intermediate films The infrared shielding film includes a base material, an infrared reflective layer having at least one unit in which a low refractive index layer and a high refractive index layer are alternately laminated, a tungsten oxide, and a composite tungsten oxide. An infrared absorption layer containing at least one kind and a binder, and there is at least one different layer between the infrared reflection layer and the infrared absorption layer, and in the infrared absorption layer, The above-mentioned problem is solved by an infrared shielding body in which the mass proportion of at least one of the tungsten oxide and the composite tungsten oxide is 15 mass% or more and 30 mass% or less. The heading, has led to the completion of the present invention.

It is a section schematic diagram showing the infrared shielding object by one embodiment of the present invention. In FIG. 1, 10 is an infrared shielding body, 11 is an infrared shielding film, 12 is an intermediate film, and 13 is a glass plate. It is a section schematic diagram showing the infrared shielding film by one embodiment of the present invention. In FIG. 2, 11 is an infrared shielding film, 14 is a base material, 15 is an infrared reflecting layer, and 16 is an infrared absorbing layer.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited only to the following embodiment.

In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurements such as operation and physical properties are performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

According to one embodiment of the present invention, an infrared ray including an infrared shielding film, a pair of intermediate films that sandwich the infrared shielding film, and a pair of glass plates that sandwich the infrared shielding film and the pair of intermediate films. A shield is provided. In the infrared shielding body, the infrared shielding film includes an infrared reflective layer having at least one unit in which a base material, a low refractive index layer and a high refractive index layer are alternately laminated, and an infrared ray An infrared absorption layer containing at least one of tungsten oxide and composite tungsten oxide (hereinafter also referred to as “(composite) tungsten oxide” or simply “tungsten oxide”) and a binder as an absorber. In addition, there is at least one different layer between the infrared reflection layer and the infrared absorption layer, and the mass ratio of the (composite) tungsten oxide in the infrared absorption layer is 15% by mass or more and 30% by mass or less. There is a feature in a certain point.

According to the present invention, an infrared shielding body having excellent transparency, heat shielding properties, and durability is provided. The mechanism by which such effects are achieved is not completely clear, but the following mechanism has been estimated. That is, the infrared shielding material according to the present invention has less infrared absorber content than the infrared shielding material disclosed in Japanese Patent Application Laid-Open No. 2010-222233 (corresponding to US Patent Application Publication No. 2011/300356). Therefore, haze can be reduced and it has excellent crack resistance. For the same reason, the thermal conductivity of the infrared absorption layer is lowered, and the heat absorbed in the same layer is difficult to propagate to the glass plate, so that an increase in the surface temperature and thermal cracking of the glass plate can be suppressed. Furthermore, it is considered that a sufficient solar radiation shielding property can be exhibited even at a low content by using (composite) tungsten oxide having a higher infrared absorption capacity than ITO or ATO as an infrared absorber. In addition, since the infrared shielding body according to the present invention is provided with a different layer between the infrared reflection layer and the infrared absorption layer, the stress generated by the thermal expansion of the infrared absorption layer is relieved and cracks are generated. Resistance can be further improved.

FIG. 1 is a schematic cross-sectional view showing an infrared shield according to an embodiment of the present invention. As shown in FIG. 1, the infrared shielding body 10 according to the present embodiment includes an infrared shielding film 11 sandwiched between a pair of intermediate films 12, and these laminates are further sandwiched between a pair of glass plates 13. It has a configuration.

Hereinafter, the components of the infrared shielding body according to the present invention will be described in detail.

<Infrared shielding film>
FIG. 2 is a schematic cross-sectional view illustrating an infrared shielding film according to an embodiment of the present invention. As shown in FIG. 2, the infrared shielding film 11 according to this embodiment includes an infrared reflection layer 15 disposed on one surface of a base material 14 and an infrared absorption layer 16 disposed on the other surface. It has a configuration. The infrared reflecting layer 15 has a unit (not shown) in which low refractive index layers and high refractive index layers are alternately stacked. The infrared absorption layer 16 contains, for example, cesium-doped tungsten oxide and a binder as an infrared absorber. Here, the infrared shielding film is composed of a base material, an infrared reflecting layer, an infrared absorbing layer, and other optionally provided layers (such as an ultraviolet shielding layer, an adhesive layer, a heat insulating layer, a refractive index adjusting layer), There is at least one “different layer” between the infrared reflecting layer and the infrared absorbing layer. In FIG. 2, the “different layer” is the base material 14, but the “different layer” may be an optional layer other than the base material. From the viewpoint of coatability, the “different layer” is preferably a substrate.

[Base material]
The base material has a function of supporting an infrared reflection layer, an infrared absorption layer, and other optionally provided layers in the infrared shielding film.

The substrate is preferably transparent, and various resin films can be used. For example, polyolefin film (polyethylene, polypropylene, etc.), polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose triacetate, polyimide, polybutyral film, cycloolefin polymer film, transparent cellulose nanofiber film, etc. Can be used. Among these, it is preferable to use a polyester film.

Among polyester films, from the viewpoints of transparency, mechanical strength and dimensional stability, dicarboxylic acid components such as terephthalic acid and 2,6-naphthalenedicarboxylic acid, and diols such as ethylene glycol and 1,4-cyclohexanedimethanol It is preferable that it is polyester which has the film formation property which makes a component a main structural component. Among these, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.

The material and film thickness of the substrate are preferably set so that the value obtained by dividing the thermal shrinkage rate of the infrared shielding film by the thermal shrinkage rate of the substrate is within the range of 0.3 to 3. .

The film thickness of the substrate is preferably 30 to 200 μm, more preferably 30 to 150 μm, and most preferably 35 to 125 μm. It is preferable that the thickness of the substrate is 30 μm or more because wrinkles during handling are less likely to occur. On the other hand, when the film thickness of the substrate is 200 μm or less, when the infrared shielding film is bonded to the glass plate, for example, the followability to the curved glass plate is improved and wrinkles are less likely to occur. .

The substrate is preferably a biaxially oriented polyester film, but an unstretched or at least one stretched polyester film can also be used. A stretched film is preferable from the viewpoint of improving strength and suppressing thermal expansion. In particular, when it is used as a laminated glass for an automobile windshield, a stretched film is more preferable.

[Infrared reflective layer]
The infrared reflective layer according to the present invention has at least one unit in which low refractive index layers and high refractive index layers are alternately stacked.

In this specification, the terms “high refractive index layer” and “low refractive index layer” refer to a refractive index layer having a higher refractive index as “high refractive index layer” when comparing the refractive index difference between two adjacent layers. It means that a refractive index layer having a lower refractive index is a “low refractive index layer”. Therefore, the terms “high refractive index layer” and “low refractive index layer” refer to these refractive index layers when attention is paid to two adjacent refractive index layers in each refractive index layer constituting the infrared reflective layer. Includes all forms other than those having the same refractive index. Note that even an infrared reflection layer using a difference in refractive index may have an infrared absorption ability depending on the selection of a refractive index adjusting agent described later.

The total number of layers of the low refractive index layer and the high refractive index layer is preferably 100 layers or less, more preferably 45 layers or less from the viewpoint of productivity. The lower limit of the total number of layers of the low refractive index layer and the high refractive index layer is not particularly limited, but is preferably 5 layers or more. In consideration of light scattering and reflection intensity, the range of the total number of low refractive index layers and high refractive index layers is more preferably 7 to 28 layers. Furthermore, from the viewpoint of further achieving the effects of the present invention, 12 to 25 layers are even more preferable, and 16 to 21 layers are particularly preferable.

The high refractive index layer preferably has a higher refractive index, preferably 1.70 to 2.50, more preferably 1.80 to 2.20, and even more preferably 1.90 to 2.20. It is. In addition, the low refractive index layer preferably has a lower refractive index, preferably 1.10 to 1.60, more preferably 1.30 to 1.55, and even more preferably 1.30 to 1. .50.

In the infrared reflection layer, it is preferable to design a large difference in refractive index between the high refractive index layer and the low refractive index layer from the viewpoint of increasing the infrared reflectance with a small number of layers. In at least one of the units composed of the low refractive index layer and the high refractive index layer, the refractive index difference between the adjacent high refractive index layer and low refractive index layer is preferably 0.1 or more, more preferably Is 0.2 or more, and more preferably 0.25 or more. When the infrared reflective layer has a plurality of units of a low refractive index layer and a high refractive index layer, the refractive index difference between the low refractive index layer and the high refractive index layer in all the units is within the preferred range. Is preferred. However, the outermost layer and the lowermost layer of the infrared reflection layer may have a configuration outside the above preferred range.

The upper limit of the film thickness of the infrared reflective layer is preferably 10 μm or less, and more preferably 9 μm or less from the viewpoint of flexibility. The lower limit of the thickness of the infrared reflective layer is not particularly limited, but is preferably 2 μm or more. Furthermore, from the viewpoint of further achieving the effects of the present invention, the thickness is preferably 2.5 to 6.0 μm, more preferably 3.0 to 5.0 μm, and particularly preferably 3.5 to 4.0 μm.

The film thickness (film thickness after drying) of the high refractive index layer is preferably 50 to 300 nm, more preferably 100 to 200 nm, and still more preferably 120 to 150 nm. The film thickness per layer of the low refractive index layer (film thickness after drying) is preferably 50 to 300 nm, and more preferably 100 to 200 nm. The film thickness of each refractive index layer can be adjusted by changing the width in the film thickness direction at the extrusion port of the die and / or by stretching conditions.

(Refractive index modifier (low refractive index layer))
As the refractive index adjusting agent used in the low refractive index layer, a metal oxide is preferable, silicon oxide is more preferable, and silicon dioxide is particularly preferable. Specific examples of silicon dioxide include synthetic amorphous silica and colloidal silica. Among these, it is more preferable to use acidic colloidal silica sol, and it is particularly preferable to use colloidal silica dispersed in water. In order to further reduce the refractive index, hollow particles having pores inside the particles may be used as the refractive index adjusting agent, and silica (silicon dioxide) hollow particles are particularly preferable. Moreover, well-known metal oxide particles other than a silica can also be used.

The metal oxide (preferably silicon dioxide) is preferably in the form of particles, and the average particle size is preferably 3 to 100 nm. The average particle diameter of primary particles of silicon dioxide dispersed in a primary particle state (particle diameter in a dispersion state before coating) is preferably 3 to 50 nm, more preferably 3 to 40 nm, and even more The thickness is preferably 4 to 20 nm, and particularly preferably 5 to 10 nm. Moreover, as an average particle diameter of secondary particle | grains, it is preferable from a viewpoint with few hazes and excellent visible light transmittance | permeability that it is 30 nm or less.

Also, the particle size of the metal oxide particles can be obtained from the volume average particle size.

The colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer. For example, JP-A-57-14091, JP-A-60-219083, JP-A-60-218904, JP-A-61-20792, JP-A-61-188183, JP-A-63-17807 (US Pat. No. 877,447), JP-A-4-93284, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142, JP-A-7-179029, JP-A-7-137431, and country Are those described in, for example, Publication No. 94/26530.

Such colloidal silica may be a synthetic product or a commercially available product. As a commercially available product, Snowtex (registered trademark, the same applies hereinafter) series (Snowtex OS, OXS, S, OS, 20, 30, 40, O, N, C, etc.) sold by Nissan Chemical Industries, Ltd. are available. Can be mentioned.

The surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.

Moreover, hollow particles can also be used as the metal oxide particles. When hollow particles are used, the average particle pore size is preferably 3 to 70 nm, more preferably 5 to 50 nm, and even more preferably 5 to 45 nm. The average particle pore diameter of the hollow particles is the average value of the inner diameters of the hollow particles. If the average particle hole diameter of the hollow particles is within the above range, the refractive index of the low refractive index layer is sufficiently lowered. The average particle diameter is 50 or more at random, which can be observed as an ellipse in a circular, elliptical or substantially circular shape by electron microscope observation, and obtains the pore diameter of each particle. Is obtained. The average particle hole diameter means the minimum distance among the distances between the two parallel lines that surround the outer edge of the hole diameter that can be observed as a circle, an ellipse, or a substantially circle or ellipse.

The content of the metal oxide particles in the low refractive index layer is preferably 20 to 90% by mass, and more preferably 30 to 85% by mass with respect to 100% by mass of the solid content of the low refractive index layer. 40 to 70% by mass is even more preferable, and 45 to 65% by mass is particularly preferable. When it is 20% by mass or more, a desired refractive index is obtained, and when it is 90% by mass or less, coating properties are good.

In the low refractive index layer, besides the metal oxide, a fluorine-containing polymer may be used as a refractive index adjusting agent. Examples of the fluorine-containing polymer include a polymer mainly containing a fluorine-containing unsaturated ethylenic monomer component.

Examples of the fluorine-containing unsaturated ethylenic monomer include a fluorine-containing alkene, a fluorine-containing acrylic acid ester, a fluorine-containing methacrylate ester, a fluorine-containing vinyl ester, a fluorine-containing vinyl ether, and the like. And fluorine-containing unsaturated ethylenic monomers described in paragraph “0181” of Japanese Patent Publication. Examples of the monomer that can be copolymerized with the fluorine-containing monomer include monomers described in paragraph “0182” of JP2013-057969A.

(Refractive index modifier (high refractive index layer))
As a refractive index adjusting agent used for the high refractive index layer, a metal oxide is preferable. Examples of metal oxides include titanium oxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, oxidation Examples thereof include magnesium, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. Among these, titanium oxide or zirconium oxide is preferable, and titanium oxide is particularly preferable because it has an advantage that light in the ultraviolet region can be absorbed.

The metal oxide (preferably titanium oxide) is preferably in the form of particles, and its primary average particle size is preferably 30 nm or less, more preferably 1 to 30 nm, and even more preferably 3 to 15 nm. A thickness of 5 to 10 nm is particularly preferable. If the primary average particle diameter is 30 nm or less, it is preferable from the viewpoint of low haze and excellent visible light transmittance.

As the titanium oxide particles according to the present invention, it is preferable to use particles in which the surface of an aqueous titanium oxide sol is modified to stabilize the dispersion state.

As a method for preparing an aqueous titanium oxide sol, any conventionally known method can be used. For example, JP-A-63-17221, JP-A-7-819 (US Pat. No. 4,786,467). Equivalent to the specification), JP-A-9-165218 (corresponding to US Pat. No. 5,840,111), JP-A-11-43327, and JP-A-63-17221. You can refer to the matter.

As for other production methods of titanium oxide particles, for example, “Titanium oxide—physical properties and applied technology”, Kiyono Manabu, p. 255-258 (2000), Gihodo Publishing Co., Ltd., or paragraph number of International Publication No. 2007/039953 The method of the step (2) described in “0011” to “0023” can be referred to.

Furthermore, as other methods for producing metal oxide particles including titanium oxide particles, reference can be made to the matters described in JP 2000-053421 A, JP 2000-063119 A, and the like.

Further, the titanium oxide particles may be coated with a silicon-containing hydrated oxide. Here, the “coating” means a state in which a silicon-containing hydrated oxide is attached to at least a part of the surface of the titanium oxide particles. That is, the surface of the titanium oxide particles used as the metal oxide particles may be completely covered with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles is a silicon-containing hydrated oxide. It may be coated. From the viewpoint that the refractive index of the coated titanium oxide particles is controlled by the coating amount of the silicon-containing hydrated oxide, it is preferable that a part of the surface of the titanium oxide particles is coated with the silicon-containing hydrated oxide. .

The titanium oxide of the titanium oxide particles coated with the silicon-containing hydrated oxide may be a rutile type or an anatase type. The titanium oxide particles coated with a silicon-containing hydrated oxide are more preferably rutile-type titanium oxide particles coated with a silicon-containing hydrated oxide. This is because the rutile type titanium oxide particles have lower photocatalytic activity than the anatase type titanium oxide particles, and therefore the weather resistance of the high refractive index layer and the adjacent low refractive index layer is increased, and the refractive index is further increased. Because.

The “silicon-containing hydrated oxide” in the present specification may be any of a hydrate of an inorganic silicon compound, a hydrolyzate and / or a condensate of an organosilicon compound, and in order to obtain the effects of the present invention. More preferably has a silanol group.

The coating amount of the silicon-containing hydrated oxide is preferably 3 to 30% by mass, more preferably 3 to 10% by mass, further preferably 3 to 8% by mass, and particularly preferably 4 to 7% by mass. . This is because when the coating amount is 30% by mass or less, a desired refractive index of the high refractive index layer can be obtained, and when the coating amount is 3% by mass or more, particles can be stably formed.

The volume particle diameter of the titanium oxide particles coated with the silicon-containing hydrated oxide is preferably 1 to 40 nm, more preferably 2 to 20 nm, and even more preferably 5 to 10 nm. It is particularly preferably 7 nm or more and less than 10 nm. If it is such a range, the effect of this invention will be show | played more notably.

As a method of coating the titanium oxide particles with a silicon-containing hydrated oxide, it can be produced by a conventionally known method. For example, JP-A-10-158015, JP-A-2000-204301, JP-A-2007 Reference can be made to the matters described in Japanese Patent No. 246351.

In addition, as the metal oxide of the high refractive index layer, core-shell particles produced by a known method can be used. For example, the following (i) to (v): (i) An aqueous solution containing titanium oxide particles is hydrolyzed by heating, or an aqueous solution containing titanium oxide particles is neutralized by adding an alkali, so that the average particle size is After obtaining 1 to 30 nm of titanium oxide, the titanium oxide particles and the mineral acid were mixed so that the molar ratio of titanium oxide particles / mineral acid was in the range of 1 / 0.5 to 1/2. The slurry is heat-treated at a temperature not lower than the boiling point of the slurry and not higher than the boiling point of the slurry, and then a silicon compound (for example, an aqueous sodium silicate solution) is added to the obtained slurry containing the titanium oxide particles. (Ii) Hydrous titanium oxide, wherein a hydrous oxide of silicon is precipitated and surface-treated, and then impurities are removed from the resulting slurry of the surface-treated titanium oxide particles (Japanese Patent Laid-Open No. 10-158015); A method of neutralizing a titanium oxide sol stabilized at a pH in an acidic range obtained by peptizing a titanium oxide such as monobasic acid or a salt thereof and an alkyl silicate as a dispersion stabilizer by a conventional method. (Japanese Laid-Open Patent Publication No. 2000-053421); (iii) Titanium salt (for example, titanium tetrachloride) simultaneously or alternately while maintaining hydrogen peroxide and metallic tin at a H ₂ O ₂ / Sn molar ratio of 2 to 3 A basic salt aqueous solution containing titanium, and the basic salt aqueous solution is maintained at a temperature of 50 to 100 ° C. for 0.1 to 100 hours to form a composite colloid containing titanium oxide And then removing the electrolyte in the aggregate slurry to produce a stable aqueous sol of composite colloidal particles comprising titanium oxide; silicates (e.g., sodium silicate A stable aqueous sol of composite colloidal particles containing silicon dioxide is produced by preparing an aqueous solution containing the solution) and removing cations present in the aqueous solution; the resulting composite containing titanium oxide 100 parts by mass of the aqueous sol in terms of metal oxide TiO ₂ and ₂ to 100 parts by mass of the resulting composite aqueous sol containing silicon dioxide in terms of metal oxide SiO ₂ were mixed to form an anion. (Iv) Hydrogen peroxide was added to a hydrous titanic acid gel or sol to dissolve the hydrous titanic acid. A silicon compound or the like is added to a peroxotitanic acid aqueous solution and heated to obtain a dispersion of core particles composed of a complex solid solution oxide having a rutile structure, and then a silicon compound or the like is added to the dispersion of the core particles. And then heating to form a coating layer on the surface of the core particles, obtaining a sol in which the composite oxide particles are dispersed, and further heating (Japanese Unexamined Patent Publication No. 2000-204301); To a titanium oxide hydrosol obtained by peptizing titanium, an organoalkoxysilane (R ¹ _n SiX _4-n ) as a stabilizer or a compound selected from hydrogen peroxide and an aliphatic or aromatic hydroxycarboxylic acid is added. And a core-shell particle produced by a method of performing desalting after adding and adjusting the pH of the solution to 3 or more and less than 9 for aging (Japanese Patent No. 4550753).

The core-shell particles may be those in which the entire surface of the titanium oxide particles as a core is coated with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles as a core is covered with a silicon-containing hydrated oxide. It may be coated with.

Furthermore, the metal oxide of the high refractive index layer used in the present invention is preferably monodispersed. The monodispersion here means that the monodispersity obtained by the following formula is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably 0.1 to 20%.

The content of the metal oxide in the high refractive index layer is preferably 15 to 90% by mass, more preferably 20 to 85% by mass with respect to 100% by mass of the solid content of the high refractive index layer. 30 to 85% by mass is more preferable from the viewpoint of improving the reflectance. In particular, the effect of the present invention becomes more remarkable when the content is 55 to 80% by mass.

(Binder resin)
The low refractive index layer and high refractive index layer of the infrared reflective layer according to the present invention preferably contain a binder resin in addition to the refractive index adjusting agent. The binder resin used in both layers may be the same or different. The binder resin may be water-soluble or water-insoluble. Examples of the water-insoluble binder resin include polyesters. Examples of water-soluble binder resins include polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, or acrylic. Acrylic resin such as acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic Styrene acrylic acid resins such as acid copolymers or styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymers, styrene-sodium styrenesulfonate copolymers, styrene-2-hydroxyethyl acrylate copolymers, styrene -2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, Synthetic water-soluble resins such as vinyl acetate copolymers such as vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer, and salts thereof; gelatin, thickening Examples thereof include natural water-soluble resins such as polysaccharides. Among these, particularly preferable examples include polyvinyl alcohols, polyvinylpyrrolidones and copolymers containing the same, gelatin, thickening polysaccharides (particularly celluloses) from the viewpoint of handling during production and film flexibility. Among these, from the viewpoint of optical properties, it is more preferable that the binder resin of the low refractive index layer and the high refractive index layer are both polyvinyl alcohol. These binder resins may be used alone or in combination of two or more.

As the polyvinyl alcohol used in the present invention, a synthetic product or a commercially available product may be used. Examples of commercially available products used as polyvinyl alcohol include, for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA-203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (above, manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04, JF-05, JP- 03, JP-04JP-05, JP-45 (above, manufactured by Nippon Vinegar Poval Co., Ltd.) and the like.

The polyvinyl alcohol preferably used in the present invention includes modified polyvinyl alcohol in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate. Examples of the modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, and vinyl alcohol polymers.

The polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 1,000 or more, and particularly preferably has an average degree of polymerization of 1,500 to 5,000. In particular, when used in the low refractive index layer, the average degree of polymerization is preferably 2,000 to 3,000, and when used in the high refractive index layer, it is 1,000 to 2,000. It is preferable. That is, the average degree of polymerization of polyvinyl alcohol used for the low refractive index layer is preferably higher than the average degree of polymerization of polyvinyl alcohol used for the high refractive index layer.

The average saponification degree of polyvinyl alcohol is preferably 70 to 100 mol%, particularly preferably 80 to 99.5 mol%. In particular, when used in a low refractive index layer, the average saponification degree is preferably 80 to 90 mol%, and when used in a high refractive index layer, the average saponification degree is 90 to 99.5 mol%. It is preferable that That is, the average saponification degree of polyvinyl alcohol used in the low refractive index layer is preferably lower than the saponification degree of polyvinyl alcohol used in the high refractive index layer.

Here, the degree of polymerization refers to the viscosity average degree of polymerization, and is measured according to JIS K6726: 1994. After re-saponification and purification of PVA, the intrinsic viscosity [η] (dl / G) is obtained by the following equation.

Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in, for example, JP-A-61-110483. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979. Examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.

Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group is added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795. Block copolymer of vinyl compound having a hydrophobic group and vinyl alcohol, silanol-modified polyvinyl alcohol having silanol group, reactive group modification having reactive group such as acetoacetyl group, carbonyl group, carboxyl group Polyvinyl alcohol etc. are mentioned. Examples of the vinyl alcohol polymer include EXEVAL (registered trademark) (manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (registered trademark) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.

As the gelatin applicable to the present invention, acid-processed gelatin may be used in addition to lime-processed gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used.

Examples of thickening polysaccharides that can be used in the present invention include generally known natural polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides and synthetic complex polysaccharides. For details, reference can be made to “Biochemical Dictionary (2nd edition), Tokyo Chemical Doujin Publishing”, “Food Industry”, Vol. 31 (1988), p. 21.

In the case of a water-soluble binder resin, the weight average molecular weight of the binder resin is preferably 1,000 or more and 200,000 or less, more preferably 10,000 or more and 200,000 or less, and even more preferably 40,000 or more and 150,000 or less. . In this specification, a weight average molecular weight can be measured on the following measurement conditions using a gel permeation chromatography (GPC), for example.

Solvent: 0.2M NaNO ₃ , NaH ₂ PO ₄ , pH 7
Column: Combination of Shodex Column Ohpak SB-802.5 HQ, 8 × 300 mm and Shodex Column Ohpak SB-805 HQ, 8 × 300 mm Column temperature: 45 ° C.
Sample concentration: 0.1% by mass
Detector: RID-10A (manufactured by Shimadzu Corporation)
Pump: LC-20AD (manufactured by Shimadzu Corporation)
Flow rate: 1 ml / min
Calibration curve: Standard for Shodex standard GFC (aqueous GPC) columns
Calibration curve using P-82 reference material pullulan is used.

The average saponification degree of polyvinyl alcohol contained in the high refractive index layer and the average saponification degree of polyvinyl alcohol contained in the low refractive index layer may be different.

Water-based coating is possible with water-soluble binder resins such as polyvinyl alcohol. In the case of aqueous coating, each coating solution that can form a low-refractive index layer and a high-refractive index layer is usually used, and each of the coating liquids is applied by sequential coating or simultaneous multilayer coating to form a high refractive index layer and a low refractive index layer. Manufactured by stacking. However, the coating film obtained by multilayer coating tends to cause mixing between adjacent layers and interface disturbance (unevenness). In the case of sequential multilayer coating, when the upper layer coating solution is applied, the lower layer formed is redissolved, the upper layer and lower layer liquids are mixed together, and mixing between adjacent layers and interface disturbance (unevenness) occur. May occur. Moreover, since the coating film obtained by simultaneous multilayer coating is stacked in an undried liquid state, mixing between adjacent layers and interface disturbance (unevenness) are more likely to occur.

By making the average saponification degree of polyvinyl alcohol contained in the high refractive index layer different from the average saponification degree of polyvinyl alcohol contained in the low refractive index layer, the reflection characteristics are further improved. Such an effect is considered to be a result of suppression of interlayer mixing. By using polyvinyl alcohol resins having different degrees of saponification, even when the high refractive index layer and the low refractive index layer are stacked in an undried liquid state, even if each layer is mixed somewhat, water that is a solvent in the drying process is used. When the volatilizes and concentrates, polyvinyl alcohol resins with different degrees of saponification undergo phase separation, and the force to minimize the area of the interface between each layer works. Is also estimated to be smaller. If interlayer mixing is suppressed, it will be excellent in the light reflectivity of a desired wavelength, and it is thought that the haze of a film also falls.

However, the above mechanism is an estimation, and the present invention is not limited to the above mechanism.

The average degree of saponification of polyvinyl alcohol in each refractive index layer is determined in consideration of the content ratio in the refractive index layer. That is, the average degree of saponification = Σ (degree of saponification of each polyvinyl alcohol (mol%) × content of each polyvinyl alcohol in each refractive index layer (%) / 100 mass (%)). For example, the refractive index layer is polyvinyl alcohol A (content mass ratio in the refractive index layer (content mass (%) of each polyvinyl alcohol in each refractive index layer / 100 mass (%)): Wa, saponification degree: Sa ( mol%)), polyvinyl alcohol B (mass ratio in the refractive index layer: Wb, saponification degree: Sb (mol%)), polyvinyl alcohol C (mass ratio in the refractive index layer: Wc, saponification degree: When Sc (mol%) is included, the average degree of saponification = (Wa × Sa + Wb × Sb + Wc × Sc / (Wa + Wb + Wc)).

The content of the water-soluble binder resin in the low refractive index layer and the high refractive index layer is not particularly limited, but is preferably 1 to 50% by mass with respect to the total mass (solid content) of each refractive index layer. More preferably, it is 10 to 50% by mass, and still more preferably 20 to 45% by mass. From the viewpoint of further achieving the effects of the present invention, the content of the low refractive index layer is preferably 35 to 45% by mass, and the content of the high refractive index layer is 20 to 30% by mass. It is preferable.

(Curing agent)
When using a water-soluble binder resin for the infrared reflective layer according to the present invention, a curing agent may be used to cure the water-soluble binder resin. The curing agent applicable to the present invention is not particularly limited as long as it causes a curing reaction with the water-soluble binder resin.

When the water-soluble binder resin is polyvinyl alcohol, the curing agent that can be used is not particularly limited as long as it causes a curing reaction with polyvinyl alcohol, but is made of boric acid, borate, and borax. Preferably it is selected from the group. Known compounds other than boric acid, borate, and borax can be used, and generally compounds having a group capable of reacting with polyvinyl alcohol or compounds that promote the reaction between different groups possessed by polyvinyl alcohol These are appropriately selected and used. Specific examples of the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3,5) , -S-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.

Boric acid or borate refers to oxyacids and salts thereof having a boron atom as a central atom, and specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaborate. Boric acid and their salts.

Borax is a mineral represented by Na ₂ B ₄ O ₅ (OH) ₄ .8H ₂ O (decahydrate of sodium tetraborate Na ₂ B ₄ O ₇ ).

Boric acid having a boron atom, borate, and borax as a curing agent may be used alone or as a mixture of two or more. An aqueous solution of boric acid or a mixed aqueous solution of boric acid and borax is preferred. The aqueous solutions of boric acid and borax can be added only as relatively dilute aqueous solutions, respectively, but by mixing them both can be made into a concentrated aqueous solution and the coating solution can be concentrated. Further, the pH of the aqueous solution to be added can be controlled relatively freely.

In the present invention, it is preferable to use boric acid and a salt thereof and / or borax in order to obtain the effects of the present invention. When using boric acid and its salts and / or borax, preferred infrared shielding properties can be achieved more. In particular, after a multilayer coating of a high refractive index layer and a low refractive index layer is applied with a coater, the film surface temperature of the coating film is once cooled to about 15 ° C. or lower (for example, 5 ° C. or lower), and then the film surface is dried. In the case of using the set coating process to be performed, the effect can be expressed more preferably.

The total amount of the curing agent used is preferably 1 to 600 mg, more preferably 20 to 200 mg, and even more preferably 20 to 100 mg per 1 g of polyvinyl alcohol resin.

(Polymer dispersant)
The low refractive index layer and the high refractive index layer may contain a polymer dispersant from the viewpoint of dispersion stability of the coating liquid. The polymer dispersant refers to a polymer dispersant having a weight average molecular weight of 10,000 or more. Preferably, the polymer has a hydroxyl group substituted at the side chain or terminal. For example, a polymer obtained by copolymerizing 2-ethylhexyl acrylate with an acrylic polymer such as sodium polyacrylate or polyacrylamide, polyethylene glycol or the like. Examples include polyethers such as polypropylene glycol, polyvinyl alcohol, and the like. Commercially available polymer dispersants may be used, and examples of such polymer dispersants include Marialim (registered trademark) AKM-0531 (manufactured by NOF Corporation). The content of the polymer dispersant is preferably 0.1 to 10% by mass in terms of solid content with respect to the refractive index layer.

(Emulsion resin)
The low refractive index layer and the high refractive index layer may further contain an emulsion resin. By including the emulsion resin, the flexibility of the film becomes higher and the workability such as sticking to glass is improved.

Specifically, as the emulsion resin, materials described in paragraphs “0121” to “0124” of JP2013-148849A can be used.

(Other additives)
The low refractive index layer and the high refractive index layer according to the present invention can contain various additives as necessary. For example, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, JP-A-57-87989, JP-A-60. -72785, 61-146591, JP-A-1-95091, and 3-13376, etc., various anionic, cationic or nonionic surfactants, 59-22993, 59-52689, 62-280069, 61-242871, and JP-A-4-219266, etc., and optical brighteners, sulfuric acid, phosphoric acid, PH adjusters such as acetic acid, citric acid, sodium hydroxide, potassium hydroxide and potassium carbonate, antifoaming agents, lubricants such as diethylene glycol Preservatives, anti-static agents may also contain various known additives such as a matting agent.

[Infrared absorbing layer]
The infrared absorption layer according to the present invention is a layer containing at least one of tungsten oxide and composite tungsten oxide ((composite) tungsten oxide) and a binder as an infrared absorber. Since the (composite) tungsten oxide has an infrared absorption capability, the infrared absorption layer formed from the coating solution has a function of blocking the transmission of infrared rays.

The thickness of the infrared absorbing layer is not particularly limited, but is preferably 1 to 10 μm, more preferably 1.5 to 8 μm. By setting the thickness to 1 μm or more, the infrared absorption layer can exhibit sufficient infrared shielding properties. On the other hand, when the thickness is 10 μm or less, cracks in the infrared absorption layer due to stress can be prevented. Among these, the thickness is particularly preferably 3 to 5 μm from the viewpoint of further achieving the effects of the present invention.

((Composite) tungsten oxide)
The (composite) tungsten oxide used in the infrared absorption layer of the present invention is represented by the general formula: W _y O _z and is described in JP2013-64042A and JP2010-215451A. Similar ones can be used. In the above general formula, W represents tungsten. O represents oxygen. y and z are compositions of tungsten and oxygen (composition of oxygen with respect to tungsten, z / y), and those satisfying the relationship of less than 3 (z / y <3) are generally used. Further, the composition of tungsten and oxygen preferably satisfies the relationship of more than 2 and less than 3 (2 <z / y <3), and 2.2 to 2.999 (2.2 ≦ z / y ≦ 2.999). It is more preferable to satisfy the relationship of With such a z / y ratio, the material is chemically stable and can exhibit a high infrared absorption ability, and a necessary amount of free electrons can be generated to provide an efficient infrared absorption material.

Further, the composition of the (composite) tungsten oxide is not particularly limited, but is preferably an oxide represented by the general formula: M _x W _y O _z from the viewpoint of stability. The same ones described in JP-A-664042 and JP-A-2010-215451 can be used. In the above general formula, M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, and I represent one or more elements selected from I. W represents tungsten. O represents oxygen. x, y, and z are generally compositions of tungsten and M (composition of M with respect to tungsten, x / y) satisfying 0 <x / y ≦ 1, and a composition of tungsten and oxygen (of oxygen with respect to tungsten). A composition whose z / y) satisfies 2 <z / y ≦ 3 is used. Further, the composition of tungsten and M (composition of M with respect to tungsten, x / y) satisfies the relationship of 0.001 ≦ x / y ≦ 1, and the composition of tungsten and oxygen (composition of oxygen with respect to tungsten, z / y) ) Preferably satisfies the relationship of 2.2 ≦ z / y ≦ 3, more preferably satisfies the relationship of 0.2 ≦ x / y ≦ 0.5 and 2.45 ≦ z / y ≦ 3, and 0 More preferably, the relationship of .31 ≦ x / y ≦ 0.35 and 0.27 ≦ z / y ≦ 3 is satisfied. Here, the alkali metal is a periodic table group 1 element excluding hydrogen, and is lithium, sodium, potassium, rubidium, cesium, or frangium. Alkaline earth metals are Group 2 elements of the periodic table and are calcium, strontium, barium, and radium. The rare earth elements are Sc, Y and lanthanoid elements (elements from 57th lanthanum to 71st lutetium). In particular, from the viewpoint of optical characteristics and an effect of improving weather resistance as an infrared absorbing material, M element is one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. It is preferable that the element M is Cs or Rb, and it is particularly preferable that the element is a cesium-containing composite tungsten oxide represented by Cs _x W _y O _{z in} which the element M is Cs.

The (composite) tungsten oxide that can be used in one embodiment of the present invention is not particularly limited, and examples thereof include Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . Among these, it is particularly preferable to use Cs _0.33 WO ₃ which is a cesium-containing composite tungsten oxide. That is, in the present invention, the (composite) tungsten oxide is preferably cesium-doped tungsten oxide.

The shape of (composite) tungsten oxide and the like is not particularly limited, and may take any structure such as a particulate shape, a spherical shape, a rod shape, a needle shape, a plate shape, a columnar shape, an indefinite shape, a flake shape, and a spindle shape, but preferably Is particulate. The size of the (composite) tungsten oxide is not particularly limited, but when the (composite) tungsten oxide or the like is in the form of particles, the average particle diameter (average primary particle diameter) of the (composite) tungsten oxide etc. , Diameter) is preferably 5 to 200 nm, from the viewpoint that heat ray absorption effect can be secured while suppressing reflection of visible light, and haze deterioration due to scattering does not occur and transparency can be secured. More preferably, the thickness is 20 to 50 nm. The average particle size is determined by observing particles themselves or particles appearing on the cross section or surface of the refractive index layer with an electron microscope, measuring the particle size of 1,000 arbitrary particles, and calculating the simple average value (number average). As required. Here, the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.

Specific examples of these trade names include CWO-dispersed tungsten oxide based CWO dispersion (YMF-02A, manufactured by Sumitomo Metal Mining Co., Ltd.).

From the viewpoint of achieving both transparency, durability and heat shielding properties of the infrared shielding body, the content ratio of the (composite) tungsten oxide in the infrared absorption layer is preferably 15 to 30% by mass.

(binder)
The infrared absorption layer according to the present invention contains a binder, but preferably contains an ultraviolet curable binder. Examples of the ultraviolet curable binder include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. Among these, an ultraviolet curable urethane acrylate resin and an ultraviolet curable polyol acrylate resin are preferable.

The UV curable urethane acrylate resin is generally a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer and further containing 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter, acrylate includes methacrylate). Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts Unidic (registered trademark) 17-806 (manufactured by DIC Corporation) and 1 part of Coronate (registered trademark) L (manufactured by Nippon Polyurethane Co., Ltd.) described in JP-A-59-151110 Etc. are preferably used. Commercially available products may be used as the ultraviolet curable urethane acrylate resin, and commercially available products include Beamset (registered trademark) 575 and 577 (manufactured by Arakawa Chemical Co., Ltd.), Shikou (registered trademark) UV series (Nippon Gosei). Chemical Industry Co., Ltd.).

Examples of the UV curable polyester acrylate resin include those generally formed by reacting polyester polyol with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, as disclosed in JP-A-59-151112. Those described can be used.

As the ultraviolet curable epoxy acrylate resin, an epoxy acrylate is used as an oligomer, and a reactive diluent and a photopolymerization initiator are added to the oligomer and reacted with the oligomer. JP-A-1-105738 discloses Those described can be used.

Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Examples thereof include tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and alkyl-modified dipentaerythritol penta (meth) acrylate. Commercially available products may be used as the UV curable polyol acrylate resin, and commercially available products include Sartomer SR295, SR399 (manufactured by Sartomer Japan Co., Ltd.), Aronix (registered trademark, hereinafter the same) series (Toagosei Co., Ltd. Manufactured).

In addition to the ultraviolet curable resin, a (meth) acryl-modified silicone compound may be included as an ultraviolet curable monomer. Here, the “(meth) acryl-modified silicone compound” means a (meth) acryl group at an arbitrary position (preferably terminal (one terminal or both terminals), more preferably both terminals) such as a side chain or terminal of the silicone skeleton. As a compound itself, a conventionally known compound can be appropriately used. Specific examples of the (meth) acryl-modified silicone compound include TEGORad2010 / Rad2011 (manufactured by Daicel-Evonik Co., Ltd.), SQ100 / SQ200 (manufactured by Tokushi Co., Ltd.), CN990 / CN9800 (manufactured by Sartomer), and EBECRYL (registered trademark) 350. (Daicel Ornex Co., Ltd.), X-22-2445 / X-22-1602 (both ends acrylate silicon), X-22-164 / X-22-164AS / X-22-164A / X-22-164B / X-22-164C / X-22-164E (both ends methacrylate silicon), X-22-174ASX / X-22-174BX / KF-2012 / X-22-2426 / X-22-2475 (single end methacrylate) Silicon) (Shin-Etsu Chemical Co., Ltd.) Ltd.), BYK (registered trademark, hereinafter the same) UV-3500, UV-3570 (manufactured by BYK Japan KK), and the like. Further, (meth) acryloxypropyl-terminated polydimethylsiloxane, [(meth) acryloxypropyl] methylsiloxane, a copolymer of [(meth) acryloxypropyl] methylsiloxane and dimethylsiloxane, and the like can also be used. In addition, those in which a methyl group is introduced at the terminal of the (meth) acryl group of these compounds can also be used. The number of functional groups in one molecule is preferably 2 or more, but one having 1 functional group may be used. The functional group equivalent is preferably in the range of 100 to 1000, and within this range, the tackiness of the obtained infrared absorption layer and the heat resistance of the cured product are improved.

When the (meth) acryl-modified silicone compound is contained in the infrared absorption layer, the content of the (meth) acryl-modified silicone compound in the infrared absorption layer is, for example, 0.001 to 3% by mass. When the content of the (meth) acryl-modified silicone compound is 0.001% by mass or more, the occurrence of cracks and a decrease in scratch resistance due to coating defects such as repellency and dents can be sufficiently suppressed. On the other hand, if the content of the (meth) acryl-modified silicone compound is 3% by mass or less, the infrared absorption layer is hardly broken and the occurrence of cracks can be suppressed. The content of the (meth) acryl-modified silicone compound contained in the infrared absorption layer is more preferably 0.01 to 1% by mass, and further preferably 0.03 to 0.5% by mass.

As described above, the case where the binder includes an ultraviolet curable binder has been described in detail. In the present invention, a binder other than the ultraviolet curable type (for example, a thermosetting type, a moisture curable type, a self-curing type binder, etc.) It may be contained in the infrared absorption layer.

(Polymerization initiator)
When the infrared absorption layer according to the present invention is prepared by curing by active energy ray irradiation (preferably ultraviolet irradiation), the curing reaction of the coating film can be performed in a short time by using a photopolymerization initiator.

Examples of the photopolymerization initiator include benzophenone, benzyl, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, benzyl dimethyl ketal, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropanone-1,1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (cyclopentadienyl) ) -Bis (2,6-diflu) B-3- (Pyr-1-yl) titanium, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc. These compounds may be used alone or in combination.

When a photopolymerization initiator is used, various known dyes and sensitizers can be added to improve photocurability.

Further, when the infrared absorption layer according to the present invention is cured by heating, the curing reaction of the coating film can be performed in a short time by using a thermal polymerization initiator.

The thermal polymerization initiator is not particularly limited, and includes those that decompose by heat and generate active radicals that initiate polymerization and curing. For example, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoyl, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide Di-t-butyl peroxide and the like can be used. As commercially available thermal polymerization initiators, for example, perbutyl D, perbutyl H, perbutyl P, permenta H (all manufactured by NOF Corporation) and the like are preferably used. These thermal polymerization initiators may be used individually by 1 type, and 2 or more types may be used together.

Furthermore, in order to accelerate curing, the above photopolymerization initiator and thermal polymerization initiator may be used in combination. In this case, it can be expected to further accelerate the curing of the infrared absorption layer by heating after photocuring.

The content of the polymerization initiator is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 0.3 to 10% by mass, and still more preferably based on the total amount of the curable component. 0.4-3 mass%. When the content is 0.1% by mass or more and 30% by mass or less, an infrared absorption layer having an appropriate hardness can be formed.

(Other additives)
The infrared absorbing layer coating liquid may contain an optional component such as an infrared shielding metal compound other than the (composite) tungsten oxide and various additives, if necessary. Additives include hydrogen ion scavengers, metal soaps, leveling properties, water repellency, surfactants for imparting slipperiness, etc., dyes, pigments, sensitizers for improving curability by UV irradiation, Examples include a dispersant for stabilizing the (composite) tungsten oxide.

Infrared shielding metal oxides other than (composite) tungsten oxide are not particularly limited, but include zinc oxide, antimony-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), gallium-doped zinc oxide (GZO), Examples thereof include aluminum-doped zinc oxide, tin oxide, antimony-doped tin oxide (ATO), and indium-doped tin oxide (ITO). Moreover, as these specific brand names, for example, as a zinc oxide system, the Celnax (registered trademark) series (manufactured by Nissan Chemical Industries, Ltd.), the passette series (manufactured by Hakusui Tech Co., Ltd.); ATO dispersion liquid (SR35M Advanced Nano Products, Inc.), ITO dispersion liquid (Mitsubishi Materials Electronics Kasei Co., Ltd.), KH series (Sumitomo Metal Mining Co., Ltd.), etc. are mentioned.

The hydrogen ion scavenger captures hydrogen ions generated by hydrolysis of carboxylic acid or carboxylate present in the binder, thereby suppressing the rise of hydrogen ions in the infrared absorption layer and passing through the haze of the infrared shielding body. Suppresses persistent rise. The type of hydrogen ion scavenger is not particularly limited, but is preferably a basic nitrogen-containing compound. The basic nitrogen-containing compound is not particularly limited, and examples thereof include heterocyclic compounds such as 2,4,6-trimethylpyridine and pyridine, amine compounds, oxime compounds, and imine compounds. Of these, amine compounds, oxime compounds, and imine compounds are preferred. That is, the basic nitrogen-containing compound is preferably at least one compound selected from the group consisting of amine compounds, oxime compounds, and imine compounds. In addition, the said basic nitrogen-containing compound may be used individually or may be used in combination of 2 or more types as appropriate.

Also, metal soap functions as a coating liquid desiccant. There is no restriction | limiting in particular as a kind of metal soap, For example, an octylic acid metal soap, a fatty-acid metal soap, etc. are mentioned. In addition, specific trade names of these include, for example, 8% hexoate cobalt, 15% hexoate zinc, 12% hexoate zirconium, 6% hexoate manganese, hexoate cobalt 8 manufactured by Toei Chemical Co., Ltd. % Etc. are mentioned. The metal soap is preferably contained in an amount of 0.1% by mass or more and 10% by mass or less based on the total mass of the components excluding the solvent of the coating solution for the infrared absorption layer.

Further, the type of the surfactant is not particularly limited, and a fluorosurfactant, an acrylic surfactant, a silicone surfactant, and the like can be used. In particular, a fluorosurfactant is preferably used from the viewpoint of leveling properties, water repellency, and slipperiness of the coating solution. Examples of the fluorosurfactant include, for example, Megafac (registered trademark) F series (F-430, F-477, F-552 to F-559, F-561, F-562, etc., manufactured by DIC Corporation. ), Megafuck (registered trademark) RS series (RS-76-E, etc.) manufactured by DIC Corporation, Surflon (registered trademark) series manufactured by AGC Seimi Chemical Co., Ltd., POLYFOX series manufactured by OMNOVA SOLUTIONS Corporation, T & K TOKA Corporation Commercially available products such as ZX series, Optool (registered trademark) series manufactured by Daikin Industries, Ltd., and Footgent (registered trademark) series (602A, 650A, etc.) manufactured by Neos Corporation can be used. Examples of the acrylic surfactant include Polyflow Series (manufactured by Kyoeisha Chemical Co., Ltd.), New Coal Series (manufactured by Nippon Emulsifier Co., Ltd.), and BYK 354 (manufactured by Big Chemie Japan Co., Ltd.). Examples of the silicone surfactant include BYK345, 347, 348, and 349 (manufactured by Big Chemie Japan Co., Ltd.). Surfactants may be used alone or in admixture of two or more. The surfactant is preferably contained in an amount of 0.01% by mass or more and 1% by mass or less based on the total mass of the components excluding the solvent of the coating solution for the infrared absorption layer.

<Intermediate film>
In the present invention, as the pair of intermediate films sandwiching the infrared shielding film, any film can be used as long as it has a bonding performance for bonding the infrared shielding film and the glass plate. It is preferable to contain. The pair of intermediate films may be the same type or different types. Examples of the thermoplastic resin include ethylene-vinyl acetate copolymer (EVA) and polyvinyl butyral (PVB), and PVB is preferable from the viewpoint of improving transparency and suppressing the rise in surface temperature and thermal cracking. Further, in each intermediate film, in the range that does not inhibit the visible light transmittance, various kinds of infrared absorbing fine particles or ultraviolet absorbers are included, or coloring is performed by mixing pigments, so that the solar transmittance is 75. % Or more is more preferable.

Examples of the fine particles that absorb infrared rays include fine metal particles such as Ag, Al, and Ti, fine metal nitride, and fine metal oxide particles, ITO, ATO, aluminum zinc composite oxide (AZO), and gallium-doped zinc oxide ( There are conductive transparent metal oxide fine particles such as GZO) and indium zinc composite oxide (IZO), and one or more of them can be selected and contained in the intermediate film to improve the heat insulation performance. In particular, conductive transparent metal oxide fine particles such as ITO, ATO, AZO, GZO, and IZO are preferable.

<Glass plate>
In the present invention, the kind of the pair of glass plates sandwiching the infrared shielding film and the pair of intermediate films is not particularly limited, and may be selected depending on the light transmission performance and heat insulation performance required for the application. Any of a board, an organic glass board, and an organic-inorganic hybrid glass board may be sufficient. The inorganic glass plate is not particularly limited, and various inorganic glass plates such as a float glass plate, a polished glass plate, a mold glass plate, a netted glass plate, a lined glass plate, a heat ray absorbing glass plate and a colored glass plate Is mentioned. Examples of the organic glass plate include glass plates made of polycarbonate resin, polystyrene resin, polymethyl methacrylate resin, and the like. These organic glass plates may be a laminate formed by laminating a plurality of sheet-shaped ones made of the resin. Examples of the organic / inorganic hybrid glass plate include a hybrid glass plate in which silica is dispersed in a resin such as an epoxy resin. The color of the glass plate is not limited to a transparent glass plate, and various color glass plates such as general-purpose green, brown, and blue used in vehicles can be used. The glass plate may be of the same type or in combination of two or more.

The thickness of the glass plate is preferably about 1 to 10 mm in consideration of the strength and the transmittance of infrared light in the visible light region. The curved glass plate preferably has a radius of curvature of 0.5 to 2.0 m. When the radius of curvature of the glass plate is within this range, the infrared shielding film can follow the curved shape of the glass.

<Method for producing infrared shielding film>
As an example of the method for producing an infrared shielding film according to the present invention, an infrared reflective layer is produced by directly applying and drying an infrared reflective layer coating solution on one surface of a substrate, and then the other surface of the substrate. The method for producing the infrared absorbing layer by directly applying and curing the coating solution for the infrared absorbing layer is shown below, but is not particularly limited thereto.

[Infrared reflective layer manufacturing method]
The infrared reflective layer may be prepared by any of a wet method, a dry method (such as sputtering and vapor deposition), and a combination thereof, but is preferably prepared by a wet method from the viewpoint of manufacturing cost and area increase. .

In the case of the wet method, the coating method is not particularly limited, and for example, roll coating method, rod bar coating method, air knife coating method, spray coating method, slide curtain coating method, or US Pat. No. 2,761,419 And a slide hopper coating method and an extrusion coating method described in U.S. Pat. No. 2,761,791. In addition, as a method of applying a plurality of layers in layers, sequential multilayer coating or simultaneous multilayer coating may be used, but simultaneous multilayer coating is preferable because productivity is improved.

Hereinafter, the simultaneous multilayer coating by the slide hopper coating method, which is a preferable manufacturing method (coating method) of the present invention, will be described in detail.

(solvent)
The solvent for preparing the coating solution for the low refractive index layer and the coating solution for the high refractive index layer is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable.

Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether, Examples thereof include ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more.

From the viewpoint of environment and ease of operation, the solvent for the coating solution is particularly preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate.

(Concentration of coating solution)
The concentration of the binder resin in the coating solution for the high refractive index layer is preferably 1 to 10% by mass. The concentration of the refractive index adjusting agent in the coating solution for the high refractive index layer is preferably 1 to 50% by mass.

The concentration of the binder resin in the coating solution for the low refractive index layer is preferably 1 to 10% by mass. The concentration of the refractive index adjusting agent in the coating solution for the low refractive index layer is preferably 1 to 50% by mass.

(Method for preparing coating solution)
The method for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited. For example, a binder resin, a refractive index adjusting agent, and other additives that are added as necessary are added. And a method of stirring and mixing. At this time, the order of addition of the binder resin, the refractive index adjuster, and other additives used as necessary is not particularly limited, and each component may be added and mixed sequentially while stirring, or while stirring. They may be added and mixed at once. If necessary, it is further adjusted to an appropriate viscosity using a solvent.

(Viscosity of coating solution)
The viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer when performing simultaneous multilayer coating by the slide hopper coating method is preferably in the range of 5 to 150 mPa · s, and 10 to 100 mPa · s. The range of s is more preferable. Further, the viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer when performing simultaneous multilayer coating by the slide curtain coating method is preferably in the range of 5 to 1200 mPa · s, 25 A range of ˜500 mPa · s is more preferable.

The viscosity at 15 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably 100 mPa · s or more, more preferably 100 to 30,000 mPa · s, and more preferably 3,000 to 30,000 mPa · s. s is more preferable, and 10,000 to 30,000 mPa · s is particularly preferable.

(Coating and drying method)
The coating and drying method is not particularly limited, but the high refractive index layer coating solution and the low refractive index layer coating solution are heated to 30 ° C. or higher, and the high refractive index layer coating solution and the low refractive index are coated on the substrate. After the simultaneous application of the rate layer coating solution, the temperature of the formed coating film is preferably cooled (set) preferably to 1 to 15 ° C. and then dried at 10 ° C. or higher. Preferably, the wet bulb temperature is in the range of 5 to 50 ° C. and the film surface temperature is in the range of 10 to 50 ° C. For example, hot air of 40 to 85 ° C. is blown to dry. Moreover, as a cooling method immediately after application | coating, it is preferable to carry out by a horizontal set system from a viewpoint of the uniformity improvement of the formed coating film.

What is necessary is just to apply | coat so that the coating thickness of the coating liquid for high refractive index layers and the coating liquid for low refractive index layers may become the film thickness at the time of preferable drying shown by the term of the said infrared reflection layer.

Here, the set means a step of increasing the viscosity of the coating composition and reducing the fluidity of the substances in each layer and in each layer by means such as applying cold air to the coating film to lower the temperature. To do. A state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.

After applying, it is preferable that the time (setting time) from application of cold air to completion of setting is within 5 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. When the set time is in the above range, the components in the layer are sufficiently mixed, and the refractive index difference between the high refractive index layer and the low refractive index layer is sufficient.

To adjust the set time, adjust the concentration of the binder resin and the refractive index adjuster, or add other components such as various known gelling agents such as gelatin, pectin, agar, carrageenan and gellan gum. Can be adjusted.

The temperature of the cold air is preferably 0 to 25 ° C, more preferably 5 to 10 ° C. Further, the time during which the coating film is exposed to the cold air is preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.

[Production method of infrared absorption layer]
The infrared absorbing layer is formed by applying an infrared absorbing layer coating liquid containing the above-described constituent components to the surface of a substrate or the like. In addition, when the binder contained in the coating solution contains a curable resin that is cured by light or heat, the coating film is formed by irradiation with active energy rays such as ultraviolet rays and electron beams, heating, catalyst, etc., preferably by ultraviolet rays. By curing, an infrared absorption layer is formed. Hereinafter, a method for producing an infrared absorption layer will be described by taking as an example a case where a coating film is cured by ultraviolet irradiation.

(solvent)
The solvent for preparing the coating solution for the infrared absorbing layer is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable.

Examples of the organic solvent include hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, 2-propanol, 1-butanol and cyclohexanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and methyl acetate. , Esters such as ethyl acetate and butyl acetate, and glycol ethers. These organic solvents may be used alone or in combination of two or more.

The content of the solvent in the coating solution for the infrared absorbing layer is not particularly limited, but is generally about 10 to 80% by mass, more preferably 15 to 60% by mass with respect to the total mass of the coating solution. More preferably, it is 20 to 40% by mass.

(Method for preparing coating solution)
The coating liquid for infrared absorption layers is adjusted by mixing each said component. The order of addition and the addition method are not particularly limited, and each component may be added and mixed sequentially while stirring, or may be added and mixed all at once while stirring.

In preparing the infrared absorbing layer coating solution, by adjusting the compounding ratio (mass ratio) of the (composite) tungsten oxide solids and the solids of the other components, in the infrared absorbing layer after curing The content ratio (mass%) of the (composite) tungsten oxide in can be easily controlled. For example, in order to control the (composite) tungsten oxide content in the infrared absorption layer after curing to a range of 15 to 30% by mass, the solid content of the (composite) tungsten oxide and the other solid content Each component is preferably blended so that the mass ratio is 1: 6.0 to 1: 2.6.

(Coating and curing method)
There is no restriction | limiting in particular about the method of apply | coating the coating liquid for infrared rays absorption layers, Well-known methods, for example, methods, such as coating by a wire bar, spin coating, dip coating, can be employ | adopted. Further, it can be applied by a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.

The drying conditions after application are not particularly limited. For example, the drying temperature is preferably 70 to 110 ° C., more preferably 80 to 90 ° C. The drying time is preferably 30 seconds to 5 minutes, more preferably 1 to 2 minutes.

Thereafter, the coating film obtained by applying the coating solution for the infrared absorption layer on the substrate is irradiated with ultraviolet rays from the side of the coating film far from the substrate to cure the coating film. In this case, the conditions such as the irradiation wavelength of ultraviolet rays, the illuminance, and the amount of light vary depending on the type of the binder resin monomer and the polymerization initiator to be used. For example, when an ultraviolet lamp is used, the illuminance is preferably 50 to 1500 mW / cm ² , more preferably 50 to 1000 mW / cm ² , and even more preferably 100 to 500 mW / cm ² . Further, the amount of irradiation energy is preferably 50 ~ 1500mJ / cm ^2, more preferably 100 ~ 1000mJ / cm ^2, still more preferably 200 ~ 500mJ / cm ^2.

<Infrared shield manufacturing method>
There is no restriction | limiting in particular in the manufacturing method of the infrared shielding body which concerns on this invention, The manufacturing method of the conventional laminated glass can be used. For example, an intermediate film, an infrared shielding film, and an intermediate film are sandwiched between a pair of glass plates in this order, and the stacked ones are passed through a pressing roll, or preferably placed in a rubber bag and sucked under reduced pressure, and glass The air remaining between the plate and the intermediate film is deaerated, and if necessary, pre-adhered at 70 to 110 ° C. to form a laminated body. Then, the deaerated laminated body is put in an autoclave or pressed, and 120 to It can be produced by performing the main bonding at 150 ° C. and a pressure of 0.5 to 1.5 MPa.

<Application>
The infrared shielding body according to this embodiment can be applied to a wide range of fields. For example, it is used for the purpose of reducing indoor temperature rise due to the transmission of sunlight (infrared rays) as laminated glass installed in buildings and vehicles.

The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively.

[Example 1]
<Preparation of infrared shielding film>
[Preparation of infrared reflection layer]
(Preparation of coating solution for low refractive index layer)
A 10% by mass acidic colloidal silica aqueous solution (Snowtex OXS, primary particle size: 5.4 nm, manufactured by Nissan Chemical Industries, Ltd.) is heated to 40 ° C., and 3% by mass of a 3% by mass boric acid aqueous solution is added. Further, 39 parts by mass of a 6% by mass aqueous polyvinyl alcohol solution (PVA-224, polymerization degree: 2400, average saponification degree: 87 mol%, manufactured by Kuraray Co., Ltd.), and 5% by mass aqueous solution of surfactant (SOFTAZOLINE (registered trademark)) LSB-R, manufactured by Kawaken Fine Chemical Co., Ltd.) 1 part by mass was added in this order at 40 ° C. to prepare a coating solution for a low refractive index layer.

(Preparation of coating solution for high refractive index layer)
After adding 2 parts by mass of pure water to 0.5 parts by mass of 15.0% by mass of titanium oxide sol (SRD-W, volume average particle diameter: 5 nm, rutile titanium dioxide particles, manufactured by Sakai Chemical Industry Co., Ltd.), 90 Heated to ° C. Next, 0.5 parts by mass of an aqueous silicic acid solution (sodium silicate 4 (manufactured by Nippon Chemical Industry Co., Ltd.) diluted with pure water so that the SiO ₂ concentration becomes 0.5 mass%) was gradually added. Then, heat treatment was performed at 175 ° C. for 18 hours in an autoclave, and after cooling, the resultant was concentrated with an ultrafiltration membrane, whereby a titanium dioxide sol (hereinafter referred to as “SiO _2”) having a solid content concentration of 6 mass% adhered to the surface. Silica-attached titanium dioxide sol) (volume average particle size: 9 nm) was obtained.

48 parts by mass of an aqueous citric acid solution (1.92% by mass) is added to 113 parts by mass of the 20 mass% silica-attached titanium dioxide sol thus obtained, and an 8% by mass polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd.). , PVA-117, polymerization degree 1700, average degree of saponification: 97.5 to 99 mol%) was added and stirred, and finally a 5% by weight aqueous solution of surfactant (SOFTAZOLINE LSB-R, Kawaken Fine Chemical Co., Ltd.) 0.4 parts by mass (made by company) was added to prepare a coating solution for a high refractive index layer.

(Preparation of infrared reflection layer)
Using a slide hopper coating apparatus (slide coater) capable of multi-layer coating, the above-mentioned coating solution for low refractive index layer and coating solution for high refractive index layer are kept at 45 ° C. and heated to 45 ° C. A low refractive index layer on a polyethylene terephthalate film (Diafoil (registered trademark) T900E50, manufactured by Mitsubishi Plastics, Inc.) so that the high refractive index layer and the low refractive index layer have a dry film thickness of 150 nm and 200 nm, respectively. Eleven layers and 10 high refractive index layers were alternately applied in a total of 21 layers simultaneously.

Immediately after application, 5 ° C. cold air was blown to set. At this time, even if the surface was touched with a finger, the time until the finger was lost (set time) was 5 minutes.

After completion of the setting, hot air of 80 ° C. was blown and dried to prepare a multilayer coating product having an infrared reflective layer composed of 21 layers (total thickness of 21 layers: 3.65 μm).

[Preparation of infrared absorption layer]
(Preparation of coating solution for infrared absorption layer)
200 parts by mass of Aronix M-305 (pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd.), cesium-doped tungsten oxide (CWO) dispersion (YMF-02A, total solid concentration of 28.5% by mass) as (composite) tungsten oxide (Cesium-doped tungsten oxide 18.5 mass%, dispersant 10 mass%), composition: Cs _0.33 WO ₃ , average primary particle size: 50 nm, manufactured by Sumitomo Metal Mining Co., Ltd.) 315 mass parts, methyl ethyl ketone 150 mass as solvent Part was added. Furthermore, 3 parts by mass of Irgacure (registered trademark) 819 (manufactured by BASF Japan Ltd.) was added as a polymerization initiator to prepare a coating solution for an infrared absorption layer.

(Preparation of infrared absorption layer)
On the opposite surface of the substrate on which the infrared reflective layer was applied, the infrared absorbing layer coating solution was applied with a gravure coater under the condition that the dry film thickness was 5 μm, and dried at 90 ° C. for 1 minute. . Next, using a UV lamp, the coating film is cured by irradiating with UV light from the side of the coating film that is far from the substrate under the conditions of an illuminance of 100 mW / cm ² and an irradiation amount of 0.5 J / cm ^2. An absorption layer was formed to produce an infrared shielding film.

(Calculation of mass ratio of CWO in infrared absorption layer)
A. To c. In the infrared absorption layer obtained above, the mass ratio occupied by CWO was calculated by the method shown in FIG.

<< a. Infrared absorption layer mass measurement >>
The film before and after application of the infrared absorption layer was cut into 10 cm × 10 cm, mass measurement was performed, and the mass of the infrared absorption layer was calculated from the mass difference between the two films.

<< b. Mass measurement of CWO in infrared absorbing layer >>
The film after application of the infrared absorption layer was heated at 800 ° C. for 3 hours, and the residue was dissolved in an aqueous sodium hydroxide solution, and the mass of tungsten was measured using ICP-AES (manufactured by Hitachi High-Tech Science Co., Ltd., SPS3520UV). . The mass of obtained tungsten × 1.5 was defined as the mass of CWO. Here, 1.5 times is based on the mass ratio of CWO to tungsten. For other cesium-containing (composite) tungsten oxides and (composite) tungsten oxides containing elements other than cesium, the mass of the (composite) tungsten oxide can be calculated from the mass ratio to tungsten. .

<< c. Calculation of mass ratio of CWO in infrared absorbing layer >>
A. And b. As a result of calculation from the above, the content ratio of CWO in the infrared absorption layer produced was 23.1% by mass.

<Production of infrared shielding body>
Next, a 3 mm thick green glass (visible light transmittance Tv: 81%, solar radiation transmittance Te: 63%) serving as an indoor side glass, a film made of polyvinyl butyral having a thickness of 380 μm serving as an indoor intermediate film, The infrared shielding film produced above, a film made of polyvinyl butyral having a thickness of 380 μm serving as an intermediate film on the outdoor side, a clear glass having a thickness of 3 mm serving as the outdoor glass (visible light transmittance Tv: 91%, solar radiation transmittance) (Te: 86%) are laminated in this order, and after removing the excess portion protruding from the edge portion of the glass, heating is performed for 30 minutes, pressure deaeration is performed at a temperature of 140 ° C. and a pressure of 1 MPa, and a combination treatment is performed. A shield 1 was produced.

[Example 2]
An infrared shielding body 2 was produced in the same manner as in Example 1 except that the coating liquid for the infrared absorbing layer was changed to 180 parts by mass of Aronix M-305 and 222 parts by mass of the CWO dispersion. In addition, the content rate of CWO in the obtained infrared absorption layer was 16.7 mass%.

Example 3
An infrared shielding body 3 was produced in the same manner as in Example 1 except that the coating liquid for the infrared absorbing layer was changed to 160 parts by mass of Aronix M-305 and 380 parts by mass of the CWO dispersion. In addition, the content rate of CWO in the obtained infrared absorption layer was 28.6 mass%.

[Comparative Example 1]
An infrared shielding body 4 was produced in the same manner as in Example 1 except that the coating liquid for the infrared absorbing layer was changed to 190 parts by mass of Aronix M-305 and 122 parts by mass of the CWO dispersion. In addition, the content rate of CWO in the obtained infrared absorption layer was 9.09 mass%.

[Comparative Example 2]
An infrared shielding body 5 was produced in the same manner as in Example 1 except that the coating liquid for infrared absorbing layer was changed to 160 parts by mass of Aronix M-305 and 444 parts by mass of the CWO dispersion. In addition, the content rate of CWO in the obtained infrared absorption layer was 33.3 mass%.

Example 4
An infrared shielding body 6 was produced in the same manner as in Example 1 except that the intermediate film was changed to ethylene vinyl alcohol (EVA).

[Comparative Example 3]
The infrared shielding layer 7 was coated in the same manner as in Example 1 except that the coating liquid for infrared absorbing layer was replaced with ITO fine particles (ultrafine particle tin-doped indium oxide, manufactured by Sakai Seisakusho Co., Ltd.) instead of CWO fine particles. Produced.

<Performance evaluation of infrared shield>
The following performance evaluation was performed on the infrared shielding bodies 1 to 7 manufactured as described above.

[Measurement of haze]
Based on JIS K7136: 2000, the haze of the infrared shielding body produced above was measured using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH7000).

[Measurement of visible light transmittance]
In accordance with JIS S3107: 2013, the transmittance in the region of 380 to 780 nm of the infrared shielding body was measured using a spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type), and the average was measured. The value was determined and this was taken as the visible light transmittance (%).

[Measurement of solar heat gain rate]
In accordance with JIS S3107: 2013, using a spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type), transmittance / reflectance every 5 nm in the region of 300 to 2500 nm of the infrared shield. Was measured. Next, in accordance with the method described in JIS R3106: 1998, calculation processing of the measured value and the solar reflection weight coefficient was performed to calculate the solar heat gain rate (TTS). It represents that infrared shielding property is so high that this value is low.

[Measurement of glass surface temperature]
A 15 cm square infrared shield is set on an artificial solar lighting device (XC-100AFSS, manufactured by Celic Co., Ltd.) with the surface provided with an infrared reflective layer facing upward, and is 3 hours from a height of 30 cm. After the irradiation, the glass surface temperature of the surface of the infrared shield not provided with the infrared reflection layer was measured using a thermocouple.

[Durability test (hot water test)]
In accordance with JIS R3212: 1998, a 30 cm × 30 cm infrared shielding body was immersed in boiling water at 100 ° C. for 2 hours, and the presence or absence of cracks was confirmed visually and with a loupe. In addition, the following percentage represents the ratio of the area by which the crack was recognized when the area of the whole infrared shielding body is 100%.

◎: No crack ○: Level that can be confirmed with a loupe is 10% or less Δ: Level that can be visually confirmed is 10% or less ×: Level that can be visually confirmed is 10% or more.

From the results of Table 1, the infrared shielding body of the present invention has high transparency, good heat shielding properties (solar heat acquisition rate and glass surface temperature), and durability (crack resistance at high temperatures). It was confirmed that it was excellent.

This application is based on Japanese Patent Application No. 2015-119659 filed on June 12, 2015, the disclosure of which is incorporated by reference as a whole.

Claims

An infrared shielding film;
A pair of intermediate films sandwiching the infrared shielding film;
A pair of glass plates sandwiching the infrared shielding film and the pair of intermediate films;
An infrared shield having
The infrared shielding film is
A substrate;
An infrared reflective layer having at least one unit in which low refractive index layers and high refractive index layers are alternately laminated; and
An infrared absorption layer containing at least one of tungsten oxide and composite tungsten oxide and a binder,
There is at least one different layer between the infrared reflective layer and the infrared absorbing layer;
The infrared shielding body whose mass ratio which at least 1 type occupies among the said tungsten oxide and composite tungsten oxide in the said infrared absorption layer is 15 mass% or more and 30 mass% or less.
The infrared shielding body according to claim 1, wherein the different layer is the base material.
The infrared shielding body according to claim 1 or 2, wherein the infrared reflection layer contains a binder resin.
The infrared shielding body according to any one of claims 1 to 3, wherein the intermediate film contains polyvinyl butyral.
The infrared shielding body according to any one of claims 1 to 4, wherein the low refractive index layer and the high refractive index layer contain a metal oxide.