JP2018124300A - Infrared shielding body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an infrared shielding body that has superior transparency, a superior heat shielding property, and superior durability.SOLUTION: An infrared shielding body comprising an infrared shielding film, a pair of intermediate layers supporting the infrared shielding film, and a pair of glass plates supporting the infrared shielding film and the pair of intermediate layers comprises: an infrared reflection layer having at least one unit in which the infrared shielding film has a base material, a low refractive index layer, and a high refractive index layer alternately laminated; and an infrared absorption layer having at least one type of tungsten oxide and composite tungsten oxide, and a binder, and there is at least one different layer between the infrared reflection layer and the infrared absorption layer, and a mass ratio of at least one type of the tungsten oxide and the composite tungsten oxide is more than or equal to 15 mass%, and is less than or equal to 30 mass% in the infrared absorption layer.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an infrared shielding body.

  As part of energy conservation measures, there is an increasing demand for laminated glass that blocks the transmission of infrared rays of sunlight from the viewpoint of reducing the load on cooling equipment in buildings and vehicles. Patent Document 1 discloses an infrared having an infrared reflection layer in which a high refractive index layer and a low refractive index layer are alternately laminated, and an infrared absorption layer containing conductive fine particles such as ITO and ATO as an infrared absorber. Shielded laminated glass is disclosed.

JP 2010-222233 A

  However, the laminated glass described in Patent Document 1 has problems such as high haze, low heat shielding properties (increased glass surface temperature and solar heat transmittance), and low durability (heat cracking and generation of cracks at high temperatures). Was.

  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.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problem can be solved by an infrared shielding body including an infrared absorption layer containing tungsten oxide in a specific ratio. We have learned and have completed the present invention.

  The above object of the present invention is achieved by the following configurations.

  1. An infrared shielding body comprising 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 low refractive index layers and high refractive index layers are alternately laminated, and at least one of tungsten oxide and composite tungsten oxide. An infrared absorption layer containing 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 tungsten The infrared shielding body whose mass ratio which at least 1 type occupies among an oxide and composite tungsten oxide is 15 to 30 mass%.

  2. The above 1. wherein the different layer is the substrate. The infrared shielding body described in 1.

  3. 1. The infrared reflective layer contains a binder resin. Or 2. The infrared shielding body described in 1.

  4). 1. The interlayer film includes polyvinyl butyral. ~ 3. The infrared shielding body in any one of.

  5. 1. The low refractive index layer and the high refractive index layer contain a metal oxide. ~ 4. The infrared shielding body in any one of.

  ADVANTAGE OF THE INVENTION According to this invention, the infrared shielding body excellent in transparency, heat insulation, and durability is provided.

It is a section schematic diagram showing the infrared shielding object by one embodiment of the present invention. It is a section schematic diagram showing the infrared shielding film by one embodiment of the present invention.

  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, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

  According to one aspect of the present invention, 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, An infrared shield is provided. In the infrared shielding body, the infrared shielding film includes a base material, an infrared reflecting layer having at least one unit in which low refractive index layers and high refractive index layers are alternately laminated, and red An infrared absorbing 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 external 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. It is characterized by a mass% or less.

  ADVANTAGE OF THE INVENTION According to this invention, the infrared shielding body excellent in transparency, heat insulation, 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, since the infrared shielding body which concerns on this invention has little content of an infrared absorber compared with the infrared shielding body of patent document 1, it can reduce a haze and has the outstanding crack tolerance. 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 illustrating an infrared shielding body 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 constituent elements of the present invention will be described in detail.

<< Constituent elements >>
<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 according to this embodiment has a configuration in which an infrared reflection layer 15 is disposed on one surface of a substrate 14 and an infrared absorption layer 16 is disposed on the other surface. Have 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 includes a base material, an infrared reflection layer, an infrared absorption layer, and other optional layers (an ultraviolet shielding layer, an adhesive layer, a heat insulating layer, a refractive index adjustment layer, etc.). At least one “different layer” exists between the infrared reflection layer and the infrared absorption 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 the polyester films, from the viewpoint of transparency, mechanical strength, dimensional stability and the like, 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. Of 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 base material are preferably set such that the value obtained by dividing the thermal shrinkage rate of the infrared shielding film by the thermal shrinkage rate of the base material is within the range of 0.3 to 3. .

  Especially, it is preferable that the film thickness of a base material is 30-200 micrometers, It is more preferable that it is 30-150 micrometers, It is most preferable that it is 35-125 micrometers. 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 range of the total number of low refractive index layers and high refractive index layers 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. Considering light scattering and reflection intensity, the total number of layers of the low refractive index layer and the high refractive index layer is more preferably 7 to 28 layers.

  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. is there. The lower refractive index layer preferably has a lower refractive index, preferably 1.10 to 1.60, more preferably 1.30 to 1.55, and still more preferably 1.30 to 1.5. 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 difference in refractive index 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, 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.

  The film thickness per layer of the high refractive index layer (film thickness after drying) is preferably 50 to 300 nm, and more preferably 100 to 200 nm. Further, the film thickness (film thickness after drying) of the low refractive index layer 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 size of primary particles of silicon dioxide dispersed in a primary particle state (particle size in a dispersion state before coating) is preferably 3 to 50 nm, more preferably 3 to 40 nm, and even more. Preferably it is 3-20 nm, Most preferably, it is 4-10 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.

  The particle size of the metal oxide particles can also be determined by 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-60-219084, JP-A-61-20792, JP-A-61-188183, JP-A-63-17807, JP-A-4-93284 No. 5, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142. Disclosed in JP-A-7-179029, JP-A-7-137431, and International Publication No. 94/26530. It is.

  Such colloidal silica may be a synthetic product or a commercially available product. As a commercially available product, Snowtex (registered trademark) series sold by Nissan Chemical Industries, Ltd. (Snowtex (registered trademark) OS, OXS, S, OS, 20, 30, 40, O, N, C, etc.) Is 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 using hollow particles, 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, the coatability is good, which is preferable.

  In the low refractive index layer, a fluorine-containing polymer may be used as a refractive index adjusting agent in addition to the metal oxide. 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 ester, a fluorine-containing methacrylate, 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. 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 the aqueous titanium oxide sol, any conventionally known method can be used. For example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, See the matters described in Kaihei 11-43327, JP-A 63-17221, JP-A 7-819, JP-A 9-165218, JP-A 11-43327, etc. Can do.

  As for other methods for producing titanium oxide particles, for example, “Titanium oxide—physical properties and applied technology” Manabu Seino p255-258 (2000), Gihodo Publishing Co., Ltd., or paragraph number “0011” of International Publication No. 2007/039953. The method of the step (2) described in “˜0023” can be referred to.

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

  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, still more 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.

  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 JP-A-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 (iv); (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 titanium oxide particles / mineral acid in a molar ratio ranged from 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 oxide, which is obtained by precipitating silicon hydrated oxide on the surface and then removing the impurities from the resulting slurry of the surface treated titanium oxide particles (Japanese Patent Laid-Open No. 10-158015); Titanium oxide sol stabilized at pH in the acidic range obtained by peptizing a titanium oxide such as nitrile with a monobasic acid or its salt and alkyl silicate as a dispersion stabilizer are mixed by a conventional method to neutralize. Method (Japanese Patent Laid-Open No. 2000-053421); (iii) Titanium salt (eg, titanium tetrachloride) simultaneously or alternately while maintaining hydrogen peroxide and metallic tin at a H ₂ O ₂ / Sn molar ratio of 2-3 ) And the like to form a basic salt aqueous solution containing titanium, and a composite containing titanium oxide by holding the basic salt aqueous solution at a temperature of 50 to 100 ° C. for 0.1 to 100 hours. Colloidal aggregates are formed, and then the electrolyte in the aggregate slurry is removed 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 an aqueous solution and the like 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 are mixed together to form an anion. And after aging, a method of heating and aging at 80 ° C. for 1 hour (Japanese Patent Laid-Open No. 2000-063119); (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 composite solid solution oxide having a rutile structure. Next, a silicon compound is added to the dispersion of the core particles. And the like, followed by 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); (v) water content Titanium oxide hydrosol obtained by peptizing titanium oxide, organoalkoxysilane (R ¹ _n SiX _4-n ) as a stabilizer or a compound selected from hydrogen peroxide and aliphatic or aromatic hydroxycarboxylic acid The core-shell particles produced by the method of performing desalting treatment after adjusting the pH of the solution to 3 or more and less than 9 and then aging (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%.

  As content of the metal oxide in a high refractive index layer, it is preferable that it is 15-90 mass% with respect to 100 mass% of solid content of a high refractive index layer, and it is more preferable that it is 20-85 mass%. 30 to 85% by mass is more preferable from the viewpoint of improving the reflectance. Especially, 55-80 mass% is especially preferable.

(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 resin such as acid copolymer or styrene-α-methylstyrene-acrylic acid-acrylic ester copolymer, styrene-sodium styrenesulfonate copolymer, styrene-2-hydroxyethyl acrylate copolymer, 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 flexibility of the film. 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. The degree of saponification is preferably 70 to 100 mol%, particularly preferably 80 to 99.5 mol%.

  Here, the degree of polymerization refers to the viscosity average degree of polymerization, which is measured according to JIS K6726: 1994. After the PVA is completely re-saponified and purified, 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, as described in JP-A No. 61-10383, in the main chain or side chain of the polyvinyl alcohol. 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 as described in JP-A-7-9758 is added to a part of vinyl alcohol, 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 vinyl alcohol polymers include Exeval (trade name: manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (trade name: 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.

  In addition to lime-processed gelatin, acid-processed gelatin may be used as gelatin applicable to the present invention, 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 Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p. 21.

  In the case of a water-soluble binder resin, the mass 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 mass 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 P-82 standard material pullulan for Shodex standard GFC (aqueous GPC) column is used. Average saponification degree of polyvinyl alcohol contained in high refractive index layer and polyvinyl contained in low refractive index layer The average saponification degree of alcohol may be different.

  A water-based coating is possible with a water-soluble binder resin 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. 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 said mechanism is estimation and this invention is not restrict | limited to the said mechanism at all.

  The average saponification degree 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 10-50 mass%, More preferably, it is 20-45 mass%.

(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 as a curing agent, borate, and borax may be used as a single aqueous solution or in combination 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, when 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., and then the set surface coating process is used to dry the film surface. Can express an effect more preferably.

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

(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 mass average molecular weight of 10,000 or more. Preferred is a polymer having a hydroxyl group substituted at the side chain or terminal, for example, an acrylic polymer such as poly (sodium acrylate) or polyacrylamide and 2-ethylhexyl acrylate copolymerized, polyethylene glycol or the like. Examples include polyethers such as polypropylene glycol, polyvinyl alcohol, and the like. A commercially available polymer dispersant may be used, and examples of such a polymer dispersant 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 JP-A-3-13376, various surfactants of anion, cation or nonion, 59-42993, 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 absorption 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.

((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 or 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. 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 in general 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. In particular, it is more preferable that the M element is Cs or Rb, and it is particularly preferable to be a cesium-containing composite tungsten oxide represented by Cs _x W _y O _z where the M element 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 because it can ensure the heat ray absorption effect while suppressing the reflection of visible light, and it can ensure transparency without causing haze deterioration due to scattering. It is more preferable that 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.

  Moreover, as these specific brand names, CWO dispersion liquid (YMF-02A, manufactured by Sumitomo Metal Mining Co., Ltd.) and the like are listed as a cesium-doped tungsten oxide system.

  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 17-806 (manufactured by Dainippon Ink Co., Ltd.) and 1 part of Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. It is done. 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 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers with polyester polyol, and 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 them. 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 triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol. Examples include pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate. Commercially available products may be used as the UV curable polyol acrylate resin, and examples of commercially available products include Sartomer SR295, SR399 (manufactured by Sartomer), Aronix (registered trademark) series (manufactured by Toagosei Co., Ltd.), and the like. Can do.

  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 EVONIC), SQ100 / SQ200 (manufactured by Tokushiki), CN990 / CN9800 (manufactured by Sartomer), EBECRYL350 (manufactured by Daicel Ornex), X -22-2445 / X-22-1602 (Both-terminal 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) (above, manufactured by Shin-Etsu Chemical Co., Ltd.) ), BYK UV-3500 / BYK UV -3570 (manufactured by Big Chemie Japan). 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. Within this range, the tackiness of the obtained infrared absorption layer and the heat resistance of the cured product are improved.

  The content of the (meth) acryl-modified silicone compound contained 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, benzyldimethyl 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-difluo) -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 using a photoinitiator, it is also possible to add various well-known dyes and sensitizers in order to improve photocurability.

  In addition, 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 independently and 2 or more types may be used together.

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

  Although content in particular of a polymerization initiator is not restrict | limited, Preferably it is 0.1-30 mass% with respect to the total amount of a sclerosing | hardenable component, More preferably, it is 0.3-10 mass%, More preferably 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, surfactants for imparting leveling properties, water repellency, slipperiness, etc .; dyes, pigments, sensitizers, etc. for improving curability by UV irradiation Is mentioned.

  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 (manufactured by SR35M Advanced Nano Products), ITO dispersion liquid (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), KH series (manufactured by Sumitomo Metal Mining Co., Ltd.) and the like can be 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.

  Further, the metal soap functions as a coating solution 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.

  Moreover, there is no restriction | limiting in particular as a kind of said surfactant, A fluorine-type surfactant, an acrylic surfactant, a silicone type surfactant, etc. 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, 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 Co., Ltd. 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 (registered trademark) -354 (manufactured by Big Chemie Japan Co., Ltd.). Examples of the silicone-based surfactant include BYK (registered trademark) -345, BYK (registered trademark) -347, BYK (registered trademark) -348, and BYK (registered trademark) -349 (manufactured by Big Chemie Japan). 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 particularly preferable. 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, a colored glass plate, etc. 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 the transparent glass plate, and various color glass plates such as general-purpose green, brown, and blue used in vehicles and the like 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 strength and infrared light transmittance in the visible light region. The curved glass plate preferably has a radius of curvature of 0.5 to 2.0 m. If the curvature radius of a glass plate is this range, an infrared shielding film can follow the curved-surface shape of glass.

<< Manufacturing method >>
<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 preferred production 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 simplicity 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)
It is preferable that the density | concentration of the binder resin in the coating liquid for high refractive index layers is 1-10 mass%. Moreover, it is preferable that the density | concentration of the refractive index regulator in the coating liquid for high refractive index layers is 1-50 mass%.

  It is preferable that the density | concentration of the binder resin in the coating liquid for low refractive index layers is 1-10 mass%. Moreover, it is preferable that the density | concentration of the refractive index regulator in the coating liquid for low refractive index layers is 1-50 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. The viscosity at 40 to 45 ° C. of the coating solution for high refractive index layer and the coating solution for 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.

  Further, 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 simultaneous multi-layer coating 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 and dried. 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.

  It is preferable that the time (setting time) from application of cold air to completion of setting after application 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, and more preferably 5 to 10 ° C. Moreover, although the time for which a coating film is exposed to cold wind also depends on the conveyance speed of a coating film, it is preferable that it is 10 to 120 seconds.

[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 absorption 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. Yes, more preferably 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 absorption layer coating solution, by adjusting the compounding ratio (weight ratio) between the (composite) tungsten oxide solids and the solids of other components, in the infrared absorption 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. The drying time is preferably 30 seconds to 5 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 used, and therefore the conditions can be appropriately adjusted by those skilled in the art. For example, when an ultraviolet lamp is used, the illuminance is preferably 50 to 1500 mW / cm ² and the irradiation energy amount is preferably 50 to 1500 mJ / 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 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, and then the degassed laminated body is put in an autoclave or pressed, and 120 to It can manufacture by performing this adhesion | attachment at the pressure of 0.5-1.5 MPa at 150 degreeC.

<< Usage >>
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 effects 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. In the following examples, the operation was performed at room temperature (25 ° C.) unless otherwise specified. 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, saponification degree: 87 mol%, manufactured by Kuraray Co., Ltd.), and 5% by mass aqueous solution of surfactant (SOFTAZOLINE LSB-R, 1 part by mass of Kawaken Fine Chemical Co., Ltd.) 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 Co., Ltd.), Heated. Subsequently, 0.5 parts by mass of an aqueous silicic acid solution (sodium silicate 4 (manufactured by Nippon Chemical Co., Ltd.) diluted with pure water so that the SiO ₂ concentration becomes 0.5% by mass) was gradually added. Titanium dioxide sol (hereinafter referred to as silica) with SiO ₂ having a solid content concentration of 6 mass% adhered to the surface by heat treatment at 175 ° C. for 18 hours in an autoclave, cooling, and concentrating with an ultrafiltration membrane. Adhesive 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% by mass silica-attached titanium dioxide sol thus obtained, and an 8% by mass polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., 113 parts by mass of PVA-117, polymerization degree 1700, saponification degree: 97.5 to 99 mol%) was added and stirred, and finally a 5% by mass aqueous solution of surfactant (SOFTAZOLINE LSB-R, manufactured by Kawaken Fine Chemical Co., Ltd.) 0.4 parts by mass 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 and 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, warm air of 80 ° C. was blown and dried to prepare a multilayer coating product having an infrared reflection layer consisting of 21 layers (total film thickness of 21 layers: 3.0 μm).

[Preparation of infrared absorption layer]
(Preparation of coating solution for infrared absorption layer)
Aronix M-305 (pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd.) 200 parts by mass, (composite) cesium-doped tungsten oxide (CWO) dispersion (YMF-02A, total solid concentration 28 mass% (cesium) as tungsten oxide Doped tungsten oxide concentration 18.5% by mass), composition: Cs _0.33 WO ₃ , average primary particle size: 50 nm, manufactured by Sumitomo Metal Mining Co., Ltd.) 315 parts by mass, and methyl ethyl ketone 150 parts by mass as a solvent were added. Furthermore, 3 parts by mass of Irgacure 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. ~ 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, the residue was dissolved in an aqueous sodium hydroxide solution, and the mass of tungsten was measured using ICP-AES (manufactured by SII Nano Technology, 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]
The infrared shielding body 2 was produced by the same method as Example 1 except having changed the coating liquid for infrared absorption layers into 180 mass parts of Aronix M-305, and 222 mass parts of CWO dispersion liquid. In addition, the content rate of CWO in the obtained infrared absorption layer was 16.7 mass%.

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

[Comparative Example 1]
The infrared shielding body 4 was produced by the method similar to Example 1 except having changed Aronix M-305 to 190 mass parts and the CWO dispersion liquid to 122 mass parts about the coating liquid for infrared absorption layers. In addition, the content rate of CWO in the obtained infrared absorption layer was 9.09 mass%.

[Comparative Example 2]
The infrared shielding body 5 was produced by the method similar to Example 1 except having changed Aronix M-305 to 160 mass parts and the CWO dispersion liquid to 444 mass parts about the coating liquid for infrared absorption layers. 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]
An infrared shielding body 7 was produced 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) instead of CWO fine particles. .

<Performance evaluation of infrared shield>
The following performance evaluation was performed about the infrared shielding bodies 1-7 produced 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]
Based on JIS S3107: 2013, using a spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type), the transmittance in the region of 380 to 780 nm of the infrared shield is measured, and the average 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 shielding body. 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 the 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 loupe is 10% or less △: 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.

10: Infrared shielding body 11: Infrared shielding film 12: Intermediate film 13: Glass plate 14: Base material 15: Infrared reflecting layer 16: Infrared absorbing layer

Claims (5)

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, wherein the infrared reflection layer contains a binder resin.   The infrared shielding body in any one of Claims 1-3 in which the said intermediate film contains polyvinyl butyral.   The infrared shielding body according to claim 1, wherein the low refractive index layer and the high refractive index layer contain a metal oxide.