JPWO2013077252A1 - Infrared shielding film and infrared shielding body - Google Patents

Abstract

An infrared shielding film having a low risk of thermal cracking, excellent storage stability and transparency, and reduced in construction cost, and an infrared shielding body including the infrared shielding film are provided.
An infrared reflective layer having at least one unit including a high refractive index layer containing a first polymer and a low refractive index layer containing a second polymer on a substrate; The infrared shielding film which has a heat insulation layer which has a space | gap on the at least one side of a base material.

Description

  The present invention relates to an infrared shielding film and an infrared shielding body.

  In recent years, many window films have been used that are bonded to the window glass surface of buildings. One of them is a film having a function of suppressing the intrusion of infrared rays and preventing the temperature inside the building from rising excessively, reducing the use of cooling and achieving energy saving.

  As a method of cutting infrared rays, there are an infrared absorption type in which an infrared absorption layer containing an infrared absorber is applied to the film, an infrared reflection type in which an infrared reflection layer is applied to the film, and a film having both functions. It is on the market.

  In particular, the infrared reflection type has a film technology for laminating dielectric layers, and a method of alternately laminating layers having different refractive indexes by a coating method in which a coating solution is coated on a substrate and laminating (Patent Documents 1 and 2), polyester A film in which a laminated thin film containing metallic silver having a three-layer structure of tungsten oxide / silver / tungsten oxide having a specific film thickness is laminated on the film surface (Patent Document 3) is disclosed.

  Patent Document 4 discloses a technique of providing an infrared reflective film between multiple glass layers.

JP-A-8-110401 JP 2007-33296 A JP-A-56-32352 US Pat. No. 7,919,158

  When the film is attached to glass, the film itself absorbs infrared rays and turns into heat energy. The heat raises the glass temperature and increases the distortion inside the glass. As a result, the phenomenon of so-called “thermal cracking” that breaks the glass becomes a problem. Since the risk of thermal cracking depends on the amount of heat generated by the film, the risk is lower in the infrared reflection type film having a smaller infrared absorption amount than in the infrared absorption type. However, even in the infrared reflection type films described in Patent Documents 1 to 4, it is difficult to completely avoid thermal cracking, and more particularly in the infrared light region than the film that reflects the visible light region in heat rays. In the case of a film that reflects light, the risk of thermal cracking is further increased because the reflective layer becomes thicker and the heat capacity increases.

  In addition, the film described in Patent Document 4 cannot solve the risk of thermal cracking as described above when the film is in contact with one side of the multilayer glass, and the film is isolated between the multilayer glass. In order to achieve this, the cost of incorporation into the double-glazed glass becomes very high, which is not practical.

  Accordingly, the present invention provides an infrared shielding film having a low risk of thermal cracking, excellent storage stability and transparency, and reduced construction costs, and an infrared shielding body including the infrared shielding film. With the goal.

  The present inventors have conducted intensive studies in view of the above problems. As a result, it was surprisingly found that an infrared shielding film having a heat insulating layer having voids reduces the risk of thermal cracking, has excellent storage stability and transparency, and further reduces the construction cost. The invention has been completed.

  That is, the above object of the present invention is achieved by the following configuration.

  1. On the substrate, an infrared reflective layer having at least one unit including a high refractive index layer containing a first polymer and a low refractive index layer containing a second polymer, and at least one of the substrates The infrared shielding film which has a heat insulation layer which has a space | gap on one side.

  2. The high refractive index layer includes a first water-soluble polymer and first metal oxide particles, and the low refractive index layer includes a second water-soluble polymer and second metal oxide particles. Above 1. An infrared shielding film according to 1.

  3. The above 1., wherein the heat insulating layer having voids contains inorganic oxide particles. Or 2. An infrared shielding film according to 1.

  4). The porosity of the heat insulating layer having the voids is 60 to 95%. ~ 3. The infrared shielding film as described in any one of these.

  5. Furthermore, it has an infrared absorption layer, 1. ~ 4. The infrared shielding film as described in any one of these.

  6). The infrared absorbing layer has an infrared absorbing agent and a hardened binder. An infrared shielding film according to 1.

  7). 4. The infrared absorption layer described above, which contains fluorine. Or 6. An infrared shielding film according to 1.

  8). 4. The infrared absorbing layer has a thickness of 1 to 20 μm, ~ 7. The infrared shielding film as described in any one of these.

  9. The thermal conductivity of the heat insulating layer having the voids is 0.001 to 0.2 W / (m · K). ~ 8. The infrared shielding film as described in any one of these.

  10. 8. The thermal conductivity of the heat insulating layer having the voids is 0.005 to 0.15 W / (m · K). An infrared shielding film according to 1.

  11. The above 1. above, wherein the lowermost layer of the infrared reflecting layer closest to the substrate and the uppermost layer of the infrared reflecting layer are both low refractive index layers. -10. The infrared shielding film as described in any one of these.

  12 Above 1. ~ 11. An infrared shielding body comprising the infrared shielding film according to any one of the above items on at least one surface of a substrate.

  13. Above 1. ~ 11. An infrared shielding glass in which the heat insulating layer having the voids according to any one of the above is disposed at a position closer to the glass than the infrared reflective layer.

  14 Above 1. ~ 11. Laminated glass in which the infrared shielding film as described in any one of these is provided between 1st glass and 2nd glass.

1 is a schematic cross-sectional view showing a layer structure of an infrared shielding film obtained in Example 1. FIG. 6 is a schematic cross-sectional view showing a layer structure of an infrared shielding film obtained in Example 12. FIG.

  The infrared shielding film of the present invention has at least one unit composed of a high refractive index layer containing a first polymer and a low refractive index layer containing a second polymer on a substrate, It has the heat insulation layer which has a space | gap on the at least one side of a base material, It is characterized by the above-mentioned. In the infrared shielding film, the high refractive index layer includes a first water-soluble polymer and first metal oxide particles, and the low refractive index layer includes a second water-soluble polymer and a second metal oxide. It is preferable that a product particle is included. By adopting such a configuration, an infrared shielding film having a low risk of thermal cracking, excellent storage stability and transparency, and reduced in construction cost, and an infrared shielding body including the infrared shielding film are provided. can get.

  As basic optical characteristics of the infrared shielding film of the present invention, the transmittance in the visible light region shown in JIS R3106: 1998 is preferably 40% or more, and more preferably 60% or more. Further, the reflectance in the wavelength region of 900 nm to 1400 nm is preferably 50% or more, and more preferably 70% or more. Furthermore, it is preferable that the transmittance in the wavelength region of 900 nm to 1400 nm is 30% or less.

  Hereinafter, the components of the infrared shielding film of the present invention will be described in detail.

[Base material (support)]
The substrate (support) used in the infrared shielding film of the present invention is preferably a film support. The film support may be transparent or opaque, and various resin films can be used. Specific examples thereof include polyolefin films (polyethylene, polypropylene, etc.), polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose triacetate, polycarbonate, polyarylate, polystyrene (PS), aromatic polyamide, poly Examples of the resin film include ether ether ketone, polysulfone, polyether sulfone, polyimide, and polyetherimide, and a resin film obtained by laminating two or more layers of the above resin films. From the viewpoint of cost and availability, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used.

  The thickness of the substrate according to the present invention is preferably 5 to 200 μm, and more preferably 15 to 150 μm. Two or more substrates may be stacked, and in this case, the types of the substrates may be the same or different.

  Further, the base material according to the present invention preferably has a visible light region transmittance of 85% or more, more preferably 90% or more, as shown in JIS R3106: 1998. If it is the range of such a transmittance | permeability, it will become advantageous for the transmittance | permeability of visible region shown by JISR3106: 1998 when it is set as an infrared shielding film to be 40% or more, and is preferable.

  The base material according to the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  As described above, the substrate may be an unstretched film or a stretched film, but a stretched film is preferable from the viewpoint of improving strength and suppressing thermal expansion.

  Moreover, the base material according to the present invention may be subjected to relaxation treatment or off-line heat treatment in terms of dimensional stability. It is preferable that the relaxation treatment is performed in a process from the heat setting in the stretching process of the polyester film to the winding in the transversely stretched tenter or after exiting the tenter. The relaxation treatment is preferably performed at a treatment temperature of 80 to 200 ° C, more preferably 100 to 180 ° C. Moreover, it is preferable that the relaxation rate is 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably, the relaxation rate is 2 to 6%. The relaxed support is subjected to the above-described off-line heat treatment to improve heat resistance and to improve dimensional stability.

In the base material according to the present invention, it is preferable to apply the undercoat layer coating solution inline on one side or both sides in the film forming process. In the present invention, undercoating during the film forming process is referred to as in-line undercoating. Examples of resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like can be used, and these can be used alone or in combination of two or more. A conventionally well-known additive can also be added to these undercoat layers. The undercoat layer can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating. The coating amount of the undercoat layer is preferably about 0.01 to ² g / m ² (dry state).

[Membrane design]
The infrared shielding film of the present invention includes at least one unit in which a high refractive index layer and a low refractive index layer are laminated. Preferably, it has a multilayer optical interference film formed by alternately laminating a high refractive index layer and a low refractive index layer on one side or both sides of a substrate. From the viewpoint of productivity, the preferred range of the total number of high refractive index layers and low refractive index layers per side of the substrate is preferably 100 layers or less, more preferably 45 layers or less. The lower limit of the range of the total number of high refractive index layers and low refractive index layers per side of the substrate is not particularly limited, but is preferably 5 layers or more. The preferred range of the total number of high refractive index layers and low refractive index layers is applicable even when laminated on only one side of the substrate, and when laminated simultaneously on both sides of the substrate. Is also applicable. When laminated on both surfaces of the substrate, the total number of high refractive index layers and low refractive index layers on one surface of the substrate and the other surface may be the same or different. In the infrared shielding film of the present invention, the lowermost layer and the uppermost layer closest to the substrate may be either a high refractive index layer or a low refractive index layer. However, by adopting a layer structure in which the low refractive index layer is located in the lowermost layer and the uppermost layer, the adhesion to the lowermost substrate, the blowing resistance of the uppermost layer, and the hard coat layer to the uppermost layer, etc. From the viewpoint of excellent coating properties and adhesion, the infrared shielding film of the present invention preferably has a layer structure in which the lowermost layer and the uppermost layer are low refractive index layers.

  In general, in an optical reflection film, it is preferable to design a large difference in refractive index between a high refractive index layer and a low refractive index layer from the viewpoint that the reflectance for a desired light beam can be increased with a small number of layers. . The same applies to the infrared shielding film.

  The refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain a near-infrared reflectance of 90% or more, if the difference in refractive index is smaller than 0.1, it is necessary to laminate 200 layers or more, which not only lowers productivity but also causes scattering at the lamination interface. Larger, less transparent, and very difficult to manufacture without failure.

  When the high refractive index layer and the low refractive index layer are alternately laminated in the infrared shielding film, the refractive index difference between the high refractive index layer and the low refractive index layer is within the range of the preferred refractive index difference. It is preferable. However, for example, when the uppermost layer is formed as a layer for protecting the film, or when the lowermost layer is formed as an adhesion improving layer with the substrate, the above-mentioned preferred refraction is performed with respect to the uppermost layer and the lowermost layer. A configuration outside the range of the rate difference may be used.

  In this specification, the terms “high refractive index layer” and “low refractive index layer” refer to the refractive index layer having a higher refractive index when the refractive index difference between two adjacent layers is compared. This means that the lower refractive index layer is the lower refractive index layer. Therefore, the terms “high refractive index layer” and “low refractive index layer” mean that each refractive index layer has the same refractive index when attention is paid to two adjacent refractive index layers. All forms other than the forms having the above are included.

  Since reflection at the interface between adjacent layers depends on the refractive index ratio between the layers, the larger the refractive index ratio, the higher the reflectance. In addition, when the optical path difference between the reflected light on the surface of the layer and the reflected light on the bottom of the layer is a relationship expressed by n · d = wavelength / 4 when viewed as a single layer film, the reflected light is controlled to be strengthened by the phase difference The reflectance can be increased. Here, n is the refractive index, d is the physical film thickness of the layer, and n · d is the optical film thickness. By utilizing this optical path difference, reflection can be controlled. Using this relationship, the refractive index and film thickness of each layer are controlled to control the reflection of visible light and near infrared light. That is, the reflectance in a specific wavelength region can be increased by the refractive index of each layer, the film thickness of each layer, the way of stacking each layer, and the like.

  The infrared shielding film of the present invention can be made into a visible light reflection film, a near infrared reflection film, or an ultraviolet reflection film by changing a specific wavelength region for increasing the reflectance. That is, if the specific wavelength region for increasing the reflectance is set to the visible light region, the visible light reflecting film is obtained, and if the specific wavelength region is set to the near infrared region, the near infrared reflecting film is obtained. Moreover, if the specific wavelength area | region which raises a reflectance is set to an ultraviolet light area | region, it will become an ultraviolet reflective film. What is necessary is just to set it as a near-infrared reflective film when using the infrared shielding film of this invention for a heat-shielding film.

  In the case of a near-infrared reflective film, a multilayer film in which films having different refractive indexes are laminated on a polymer film is formed, and the transmittance at 550 nm in the visible light region shown in JIS R3106: 1998 is 50% or more. Is preferably 70% or more, more preferably 75% or more. Further, the transmittance at 1200 nm is preferably 35% or less, more preferably 25% or less, and further preferably 20% or less. It is preferable to design the optical film thickness and unit so as to be in such a suitable range. Moreover, it is preferable to have the area | region exceeding a reflectance of 50% in the area | region of wavelength 900nm-1400nm.

[Infrared reflective layer]
The infrared shielding film of the present invention has an infrared reflective film having at least one unit comprising a high refractive index layer containing a first polymer and a low refractive index layer containing a second polymer on a substrate. In addition to the infrared reflective layer, a heat insulating layer having a gap is provided on at least one side of the substrate and the base material. In the infrared shielding film, the high refractive index layer includes the first water-soluble polymer and the first metal oxide particles, and the low refractive index layer includes the second water-soluble polymer and the second metal oxide particles. It is preferable to include. In the present specification, a layer made of this unit is also referred to as an infrared reflecting layer.

  The infrared reflective layer is preferable from the viewpoint of increasing the infrared reflectivity with a small number of stacks, as the difference in refractive index between the high refractive index layer and the low refractive index layer is large. In the present invention, in at least two or more units composed of a high refractive index layer and a low refractive index layer, the difference in refractive index between the adjacent high refractive index layer and the low refractive index layer is 0.1 or more. It is preferable that it is 0.2 or more. More preferably, it is 0.3 or more, and particularly preferably 0.4 or more. Moreover, although there is no restriction | limiting in particular in the upper limit of this refractive index difference, Usually, it is 1.4 or less.

  The number of units to be stacked is preferably 30 units or less, more preferably 20 units or less, and even more preferably 10 units or less, although it depends on the refractive index difference between the high refractive index layer and the low refractive index layer. Decreasing the number of units is preferable because haze tends to decrease.

  In the present invention, the refractive indexes of the high refractive index layer and the low refractive index layer can be determined according to the following method.

  A sample in which each refractive index layer for measuring a refractive index is coated as a single layer on a substrate is prepared, and the sample is cut into 10 cm × 10 cm, and then the refractive index is obtained according to the following method. Using a U-4000 type (manufactured by Hitachi, Ltd.) as a spectrophotometer, after roughening the back side on the measurement side of each sample, light absorption treatment is performed with a black spray to reduce the light on the back side. The reflection is prevented, the reflectance in the visible light region (400 nm to 700 nm) is measured at 25 points under the condition of regular reflection at 5 degrees, the average value is obtained, and the average refractive index is obtained from the measurement result.

  The refractive index of the high refractive index layer in the invention is preferably from 1.70 to 2.50, more preferably from 1.80 to 2.20. The refractive index of the low refractive index layer is preferably 1.10 to 1.60, more preferably 1.30 to 1.50.

  Below, the structure of a high refractive index layer and a low refractive index layer is demonstrated.

  The high refractive index layer according to the present invention includes a first polymer, and the low refractive index layer according to the present invention includes a second polymer. Preferably, the high refractive index layer includes a first water-soluble polymer and first metal oxide particles, and the low refractive index layer includes a second water-soluble polymer and a second metal oxide. Particles.

  The first polymer and the second polymer may be used alone or in combination of two or more. In addition, the first polymer and the second polymer may be synthetic products or commercially available products. Furthermore, the first polymer and the second polymer may be the same or different.

  The first polymer and the second polymer are not particularly limited. For example, polyethylene naphthalate (PEN) and its isomers (for example, 2,6-, 1,4-, 1, 5-, 2,7-, and 2,3-PEN), polyalkylene terephthalates (eg, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate), polyimides (eg, poly Acrylic imide), polyether imide, atactic polystyrene, polycarbonate, polymethacrylate (eg, polyisobutyl methacrylate, polypropyl methacrylate, polyethyl methacrylate, and polymethyl methacrylate), polyacrylate (eg, Polybutyl acrylate and polymethyl acrylate), cellulose derivatives (eg, ethyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, and cellulose nitrate), polyalkylene polymers (eg, polyethylene, polypropylene, polybutylene, polyisobutylene, and poly (4-methyl) pentene), fluorinated polymers (eg, perfluoroalkoxy resins, polytetrafluoroethylene, fluorinated ethylene-propylene copolymers, polyvinylidene fluoride, and polychlorotrifluoroethylene), chlorinated polymers (eg, poly Vinylidene chloride and polyvinyl chloride), polysulfone, polyethersulfone, polyacrylonitrile, polyamide, silicone resin, epoxy resin , Polyvinylacetate, polyether amides, ionomeric resins, elastomers (e.g., polybutadiene, polyisoprene, and neoprene), and polyurethanes. Also, copolymers, such as copolymers of PEN (eg 2,6-, 1,4-, 1,5-, 2,7- and / or 2,3-naphthalenedicarboxylic acid or esters thereof, (a ) Terephthalic acid or its ester, (b) isophthalic acid or its ester, (c) phthalic acid or its ester, (d) alkane glycol, (e) cycloalkane glycol (for example, cyclohexanedimethanol diol), (f) alkane A dicarboxylic acid and / or (g) a copolymer with a cycloalkanedicarboxylic acid (eg, cyclohexanedicarboxylic acid), a copolymer of a polyalkylene terephthalate (eg, terephthalic acid or an ester thereof, and (a) a naphthalenedicarboxylic acid or an ester thereof, (B) Isophthal Acid or ester thereof, (c) phthalic acid or ester thereof, (d) alkane glycol, (e) cycloalkane glycol (eg, cyclohexanedimethanol diol), (f) alkanedicarboxylic acid, and / or (g) cycloalkane. Dicarboxylic acids (eg, copolymers with cyclohexanedicarboxylic acid), styrene copolymers (eg, styrene-butadiene copolymers and styrene-acrylonitrile copolymers), and copolymers of 4,4′-dibenzoic acid and ethylene glycol can also be utilized. Furthermore, a blend of two or more of the above polymers or copolymers (for example, a blend of syndiotactic polystyrene and atactic polystyrene), a water-soluble polymer described later, or the like can be used for each layer. In particular, it is preferable to use water-soluble polymers as the first polymer and the second polymer.

<Water-soluble polymer>
Examples of the first water-soluble polymer and the second water-soluble polymer include gelatin, synthetic resins, thickening polysaccharides, inorganic polymers, and the like. These first water-soluble polymer and second water-soluble polymer may be used alone or in combination of two or more. The first water-soluble polymer and the second water-soluble polymer may be synthetic products or commercially available products. Furthermore, the first water-soluble polymer and the second water-soluble polymer may be the same or different. Hereinafter, the water-soluble polymer will be described.

(gelatin)
Examples of gelatin used in the present invention include various types of gelatin that have been widely used in the field of silver halide photographic materials. For example, in addition to acid-treated gelatin and alkali-treated gelatin, enzyme-treated gelatin and gelatin derivatives that undergo enzyme treatment in the gelatin production process, ie, amino groups, imino groups, hydroxyl groups, or carboxyl groups as functional groups in the molecule It may be modified by treating with a reagent having a group obtained by reacting with it. The general method for producing gelatin is well known and is described, for example, in T.W. H. James: The Theory of Photographic Process 4th. ed. Reference can be made to the descriptions of 1977 (Machillan), p. 55, Science Photo Handbook (above), p. 72-75 (Maruzen), Fundamentals of Photographic Engineering-Silver Salt Photography, p. 119-124 (Corona). Also, Research Disclosure Magazine Vol. 176, No. The gelatin described in IX page of 17643 (December, 1978) can be mentioned.

(Synthetic resin)
Examples of the synthetic resin used in the present invention include polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene oxides, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate. -Acrylic resin such as acrylic acid ester copolymer or acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer Styrene-acrylate resins such as styrene-α-methylstyrene-acrylic acid copolymer, or styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-sodium styrenesulfonate copolymer, styrene- 2-hydroxy Ethyl 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 -Vinyl acetate copolymers such as maleic acid copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer, and salts thereof. A copolymer obtained by copolymerizing two or more of the polymers exemplified above may also be used.

  Among these, polyvinyl alcohols and copolymers containing vinyl alcohol units are preferable.

  Polyvinyl alcohols preferably used in the present invention include, in addition to ordinary polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate, cation-modified polyvinyl alcohol having a cation-modified terminal, anion-modified polyvinyl alcohol having an anionic group, etc. The modified polyvinyl alcohol is also included.

  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%, more preferably 80 to 99.5%.

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

  Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride. N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamidopropyl) ammonium chloride, N- (1, 1-dimethyl-3-dimethylaminopropyl) acrylamide and the like. The ratio of the cationic group-containing ethylenically unsaturated monomer in the cation-modified polyvinyl alcohol is preferably 0.1 to 10 mol%, more preferably 0.2 to 5 mol% with respect to 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-63-330779. A copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, a modified polyvinyl alcohol having a water-soluble group, or a silanol-modified polyvinyl alcohol as described in JP-A-7-285265. Etc.

  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. Examples thereof include a block copolymer of a vinyl compound having a hydrophobic group as described and vinyl alcohol. Polyvinyl alcohol can be used in combination of two or more kinds having different degrees of polymerization and modification.

  The form of the copolymer when the synthetic resin is a copolymer may be any of a block copolymer, a random copolymer, a graft copolymer, and an alternating copolymer.

(Thickening polysaccharide)
The thickening polysaccharide used in the present invention is not particularly limited, and examples thereof include generally known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. For details of these thickening polysaccharides, reference can be made to “Biochemical Dictionary (2nd edition)” (Tokyo Kagaku Dojin), “Food Industry”, Vol. 31 (1988), p.

  The thickening polysaccharide is a polymer of saccharides and has a large number of hydrogen bonding groups in the molecule. Due to the difference in hydrogen bonding strength between molecules depending on the temperature, the viscosity at low temperature and the viscosity at high temperature are different. It is a polysaccharide with the characteristic that the difference is large, and when metal oxide particles or polyvalent metal compounds are added, the metal oxide particles or polyvalent metals react with the metal oxide particles or polyvalent metal compounds at low temperatures. It forms a hydrogen bond or ionic bond with the compound, causing an increase in viscosity or gelation. The increase in viscosity is preferably 1 mPa · s or more at 15 ° C. compared to the viscosity at 15 ° C. before the addition of the metal oxide particles or the polyvalent metal compound. The viscosity increase width is more preferably 5 mPa · s or more, and further preferably 10 mPa · s or more. In this specification, a value measured with a Brookfield viscometer is adopted as the viscosity.

  More specific examples of the thickening polysaccharide applicable to the present invention include, for example, β1-4 glucan (eg, carboxymethylcellulose, carboxyethylcellulose, etc.), galactan (eg, agarose, agaropectin, etc.), galactomannoglycan. (For example, locust bean gum, guaran, etc.), xyloglucan (for example, tamarind gum, etc.), glucomannoglycan (for example, salmon mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (for example, softwood material) Derived glycans), arabinogalactoglycans (eg, soy-derived glycans, microbial-derived glycans, etc.), glucoraminoglycans (eg, gellan gum), glycosaminoglycans (eg, hyaluronic acid, keratan sulfate, etc.), alginic acid and aglycone Gin salts, agar, .kappa.-carrageenan, lambda-carrageenan, iota-carrageenan, natural polymer and polysaccharides derived from red algae such as furcellaran.

  From the viewpoint of not lowering the dispersion stability of the metal oxide particles coexisting in the coating solution, it is preferable that the structural unit does not have a carboxylic acid group or a sulfonic acid group. Such polysaccharides include, for example, pentoses such as L-arabitose, D-ribose, 2-deoxyribose and D-xylose, and hexoses such as D-glucose, D-fructose, D-mannose and D-galactose only. It is preferable that it is a polysaccharide. Specifically, tamarind seed gum known as xyloglucan whose main chain is glucose and side chain is glucose, guar gum known as galactomannan whose main chain is mannose and side chain is glucose, cationized guar gum, Hydroxypropyl guar gum, locust bean gum, tara gum, and arabinogalactan whose main chain is galactose and whose side chain is arabinose can be preferably used. In the present invention, tamarind, guar gum, cationized guar gum, and hydroxypropyl guar gum are more preferable.

(Inorganic polymer)
The inorganic polymer used in the present invention is not particularly limited, but it is preferable to use an inorganic polymer such as a compound containing a zirconium atom or a compound containing an aluminum atom.

  The compound containing a zirconium atom applicable to the present invention excludes zirconium oxide, and specific examples thereof include, for example, zirconium difluoride, zirconium trifluoride, zirconium tetrafluoride, hexafluorozirconium salt. (For example, potassium salt), heptafluorozirconate (for example, sodium salt, potassium salt or ammonium salt), octafluorozirconate (for example, lithium salt), fluorinated zirconium oxide, zirconium dichloride, zirconium trichloride, Zirconium tetrachloride, hexachlorozirconium salt (for example, sodium salt and potassium salt), zirconium oxychloride (zirconyl chloride), zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium bromide oxide, zirconium triiodide , Four Zirconium arsenide, zirconium peroxide, zirconium hydroxide, zirconium sulfide, zirconium sulfate, zirconium p-toluenesulfonate, zirconyl sulfate, sodium zirconyl sulfate, acidic zirconyl sulfate trihydrate, potassium zirconium sulfate, zirconium selenate, zirconium nitrate , Zirconyl nitrate, zirconium phosphate, zirconyl carbonate, zirconyl ammonium carbonate, zirconium acetate, zirconyl acetate, zirconyl acetate, zirconyl lactate, zirconyl citrate, zirconyl stearate, zirconyl phosphate, zirconium oxalate, zirconium isopropylate, zirconium butyrate Rate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium stearate butyrate Over DOO, zirconium acetate, bis (acetylacetonato) dichloro zirconium and tris (acetylacetonato) chloro zirconium, and the like.

  Among these compounds, zirconyl chloride, zirconyl sulfate, zirconyl sulfate, acidic zirconyl sulfate trihydrate, zirconyl nitrate, zirconyl carbonate, zirconyl ammonium carbonate, zirconyl acetate, zirconyl ammonium acetate, zirconyl stearate are more preferable. , Zirconyl carbonate, zirconyl ammonium carbonate, zirconyl acetate, zirconyl nitrate, zirconyl chloride, and more preferably zirconyl ammonium carbonate, zirconyl chloride, zirconyl acetate.

  As the compound containing a zirconium atom, a commercially available product or a synthetic product may be used. Specific examples of commercially available products include zircosol ZA-20 (zirconyl acetate), zircozole ZC-2 (zirconyl chloride), zircozole ZN (zirconyl nitrate) (manufactured by Daiichi Rare Element Chemical Co., Ltd.).

  Structural formulas of typical compounds among the inorganic polymers containing the zirconyl atom are shown below.

  In the above formula, s and t represent an integer of 1 or more.

  A compound containing a zirconium atom may be used alone, or two or more different compounds may be used in combination.

  The compound containing an aluminum atom applicable to the present invention is one excluding aluminum oxide. Specific examples thereof include aluminum fluoride, hexafluoroaluminic acid (for example, potassium salt), aluminum chloride, Basic aluminum chloride (eg, polyaluminum chloride), tetrachloroaluminate (eg, sodium salt), aluminum bromide, tetrabromoaluminate (eg, potassium salt), aluminum iodide, aluminate (eg, Sodium salt, potassium salt, calcium salt), aluminum chlorate, aluminum perchlorate, aluminum thiocyanate, aluminum sulfate, basic aluminum sulfate, basic aluminum silicate sulfate, potassium aluminum sulfate (alum), ammonium aluminum sulfate (Ammonium alum), sodium aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum hydrogen phosphate, aluminum carbonate, aluminum polysulfate silicate, aluminum formate, aluminum acetate, aluminum lactate, aluminum oxalate, aluminum isopropylate, aluminum butyrate, ethyl acetate aluminum Examples thereof include diisopropylate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetonate) and the like.

  Among these, aluminum chloride, basic aluminum chloride, aluminum sulfate, basic aluminum sulfate, and basic aluminum sulfate silicate are preferable, and basic aluminum chloride and basic aluminum sulfate are most preferable.

  As the compound containing an aluminum atom, a commercially available product may be used, or a synthetic product may be used. Specific examples of commercially available products include TAKIBAIN (registered trademark) # 1500, which is polyaluminum chloride (PAC) manufactured by Taki Chemical Co., Ltd., polyaluminum hydroxide (Paho) manufactured by Asada Chemical Co., Ltd., and RIKEN GREEN CO., LTD. Purachem WT, etc. made by the company are mentioned.

  The structural formula of TAKIBINE (registered trademark) # 1500 is shown below.

  In the above formula, s, t and u represent an integer of 1 or more.

  The weight average molecular weight of the first water-soluble polymer and the second water-soluble polymer is preferably 1,000 to 200,000, and more preferably 3,000 to 40,000. In the present specification, a value measured by gel permeation chromatography (GPC) is adopted as the weight average molecular weight.

<Metal oxide particles>
Examples of the first metal oxide particles and the second metal oxide particles include titanium oxide, zirconium oxide, zinc oxide, silicon dioxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, Lead red, yellow lead, zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, tin oxide Etc. These may be used alone or in combination of two or more.

  Among the above, as the first metal oxide particles contained in the high refractive index layer, titanium oxide, zirconium oxide, and zinc oxide are preferable, and titanium oxide is more preferable. Furthermore, specific examples of titanium oxide include anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, strontium titanate, or these titanium oxides, tin, barium, vanadium, manganese, cobalt, nickel, gallium, Dissimilar metal atoms such as aluminum, germanium, antimony, indium, palladium, ruthenium, rhodium, niobium, zirconium, magnesium, yttrium, lanthanum, europium, zinc, lead, chromium, iron, copper, silver, gold, platinum, tungsten, cerium And the like. The doping amount is preferably 0.001% by mass to 30% by mass. Further, titanium oxide surface-treated with silica, alumina or the like is also preferable.

  The titanium oxide suitably used in the present invention is a rutile type titanium oxide having a high refractive index and a low photocatalytic ability.

  In addition, as a preferable embodiment of titanium oxide in the present invention, a titanium oxide sol in which fine particles of titanium oxide are dispersed in water or an organic solvent is preferable. Titanium oxide sol is preferable from the viewpoint of producing an infrared reflective layer, such as being easy to mix with a polymer or the like to form a coating solution.

  As a method for preparing titanium oxide, for example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327 and the like can be referred to.

  As other methods for preparing titanium oxide, see, for example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, and the like. be able to.

  The primary particle diameter of the titanium oxide particles is preferably 4 nm to 50 nm, more preferably 4 nm to 30 nm in terms of volume average particle diameter.

The volume average particle size of titanium oxide particles refers to a method of observing the particles themselves using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, or a particle image appearing on the cross section or surface of the refractive index layer. the method of observing with a microscope, 1,000 the particle size of any particles were measured, respectively _{d 1, d 2 ··· d i} ··· d each particle _n 1 having a particle size of _k, n _{In a group of 2} ... n _i ... n _k titanium oxide particles, the volume average particle size m _v = {Σ (v _i · d _i )} / {Σ (v _i )} is the average particle size weighted by the volume.

  In the high refractive index layer according to the present invention, titanium oxide and the above metal oxide may be mixed, or a plurality of types of titanium oxide may be mixed and used.

  In the low refractive index layer according to the present invention, silicon dioxide particles are preferably used as the second metal oxide particles, and acidic colloidal silica sol is more preferably used.

  The silicon dioxide particles according to the present invention preferably have an average particle size of 100 nm or less. The average particle diameter of primary particles of silicon dioxide dispersed in a primary particle state (particle diameter in a dispersion state before coating) is preferably 20 nm or less, more preferably 10 nm or less. In addition, the average particle size of the secondary particles is preferably 30 nm or less from the viewpoint of low haze and excellent visible light transmittance.

  The content of the first water-soluble polymer in the high refractive index layer is preferably 3 to 60% by mass and more preferably 10 to 45% by mass with respect to the total mass of the high refractive index layer. .

  The content of the first metal oxide particles in the high refractive index layer is preferably 30 to 95% by mass and more preferably 70 to 90% by mass with respect to the total mass of the high refractive index layer. . A higher content is preferable from the viewpoint of increasing the refractive index of the layer.

  The content of the second water-soluble polymer in the low refractive index layer is preferably 3 to 60% by mass and more preferably 10 to 45% by mass with respect to the total mass of the low refractive index layer. .

  The content of the second metal oxide particles in the low refractive index layer is preferably 30 to 95% by mass and more preferably 60 to 95% by mass with respect to the total mass of the low refractive index layer. . If the content of the metal oxide is 30% by mass or more, the refractive index can be made lower, and if the content of the metal oxide is 95% by mass or less, the flexibility of the film is improved and the infrared It becomes easier to form a shielding film.

  The thickness per layer of the high refractive index layer (thickness after drying) is preferably 20 to 1000 nm, and more preferably 50 to 500 nm.

  The thickness per layer of the low refractive index layer (thickness after drying) is preferably 20 to 800 nm, and more preferably 50 to 350 nm.

  In the infrared reflective layer according to the present invention, the lowermost layer adjacent to the substrate is a low refractive index layer from the viewpoint of adhesion to the heat insulating layer and the adhesive layer provided on the uppermost layer of the substrate and the infrared reflective layer. A layer structure in which the uppermost layer is also a low refractive index layer is preferable.

[Additive]
Various additives can be added to the high refractive index layer and the low refractive index layer according to the present invention as necessary. Hereinafter, the additive will be described.

<Curing agent>
In the present invention, a curing agent can be used to cure the water-soluble polymer as a binder.

  The curing agent applicable to the present invention is not particularly limited as long as it causes a curing reaction with a water-soluble polymer. However, when the water-soluble polymer is polyvinyl alcohol, boric acid and a salt thereof are preferable. Other known compounds can also be used, and are generally compounds having groups capable of reacting with water-soluble polymers, or compounds that promote the reaction between different groups of water-soluble polymers. It is appropriately selected according to the type of polymer. Specific examples of the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-dibutanediol diglycidyl ether, 1,6-diglycidyl cyclohexane. N, N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde-based curing agents (formaldehyde, glyoxal, etc.), active halogen-based curing Agents (2,4-dichloro-4-hydroxy-1,3,5-S-triazine, etc.), active vinyl compounds (1.3.5-tris-acryloyl-hexahydro-S-triazine, bisvinylsulfonylmethyl ester) -Tell etc.), aluminum alum and the like.

<Surfactant>
In the present invention, at least one of the high refractive index layer and the low refractive index layer may further contain a surfactant. As the surfactant, any of anionic, cationic and nonionic types can be used. More preferably, dialkylsulfosuccinate anionic surfactants, acetylene glycol nonionic surfactants, quaternary ammonium salt cationic surfactants, or fluorine based cationic surfactants are preferred.

  The addition amount of the surfactant according to the present invention is in the range of 0.005 to 0.30 mass% when the total mass of the coating liquid for high refractive index layer or the coating liquid for low refractive index layer is 100 mass%. It is preferable that it is 0.01-0.10 mass%.

<Amino acid>
In the present invention, at least one of the high refractive index layer and the low refractive index layer may further contain an amino acid. By including an amino acid, the dispersibility of the metal oxide particles in the high refractive index layer or the low refractive index layer can be improved.

  Here, the amino acid means a compound having an amino group and a carboxyl group in the same molecule, and may be any type of amino acid such as α-, β-, γ-, but has an isoelectric point of 6.5 or less. It is preferable that they are amino acids. Some amino acids have optical isomers, but in the present invention, there is no difference in effect due to optical isomers, and any isomer can be used alone or in racemic form.

  For a detailed explanation of the amino acids according to the present invention, reference can be made to the description on pages 268 to 270 of the Chemical Dictionary 1 Reprint (Kyoritsu Shuppan; issued in 1960).

  Specific examples of amino acids include, for example, glycine, alanine, valine, α-aminobutyric acid, γ-aminobutyric acid, β-alanine, serine, ε-amino-n-caproic acid, leucine, norleucine, phenylalanine, threonine, asparagine, Examples include aspartic acid, histidine, lysine, glutamine, cysteine, methionine, proline, and hydroxyproline. For use as an aqueous solution, the solubility at the isoelectric point is preferably 3 g or more with respect to 100 g of water, and glycine, alanine, serine, histidine, lysine, glutamine, cysteine, methionine, proline, hydroxyproline, etc. are preferably used. . From the viewpoint that the metal oxide particles have a gradual hydrogen bond with the binder, it is more preferable to use serine or hydroxyproline having a hydroxyl group.

  The isoelectric point of an amino acid means this pH value because an amino acid balances positive and negative charges in a molecule at a specific pH, and the overall charge becomes zero. In the present invention, it is preferable to use an amino acid having an isoelectric point of 6.5 or less. The isoelectric point of each amino acid can be determined by isoelectric focusing at a low ionic strength.

<Lithium compound>
In the present invention, at least one of the high refractive index layer and the low refractive index layer may further contain a lithium compound. The coating liquid for the high refractive index layer or the coating liquid for the low refractive index layer containing the lithium compound becomes easier to control the viscosity, and as a result, the production stability of the infrared shielding film is further improved.

The lithium compound applicable to the present invention is not particularly limited. For example, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium orotate, lithium citrate, lithium molybdate, lithium chloride, lithium hydride, water Lithium oxide, lithium bromide, lithium fluoride, lithium iodide, lithium stearate, lithium phosphate, lithium hexafluorophosphate, lithium aluminum hydride, lithium hydride triethylborate, lithium triethoxyaluminum hydride, tantalate Examples thereof include lithium, lithium hypochlorite, lithium oxide, lithium carbide, lithium nitride, lithium niobate, lithium sulfide, lithium borate, LiBF ₄ , LiClO ₄ , LiPF ₄ , LiCF ₃ SO _{3 and the} like. These lithium compounds can be used alone or in combination of two or more.

  Among these, lithium hydroxide is preferable from the viewpoint that the effects of the present invention can be sufficiently exhibited.

  The addition amount of the lithium compound is preferably in the range of 0.005 to 0.05 g, more preferably 0.01 to 0.03 g, per 1 g of the metal oxide particles present in the refractive index layer.

<Emulsion resin>
In the present invention, the high refractive index layer or the low refractive index layer may further contain an emulsion resin. By including the emulsion resin, the flexibility of the film is increased and the workability such as sticking to glass is improved.

  Here, the emulsion resin is a resin (preferably resin fine particles) obtained by emulsion-polymerizing an oil-soluble monomer in an aqueous solution containing a dispersant and using a polymerization initiator.

  Examples of the dispersant used in the polymerization of the emulsion include polyoxyethylene nonyl phenyl ether, in addition to low molecular weight dispersants such as alkyl sulfonate, alkyl benzene sulfonate, diethylamine, ethylenediamine, and quaternary ammonium salt. Examples thereof include polymer dispersants such as polyethylene ethylene laurate, hydroxyethyl cellulose, and polyvinyl pyrrolidone.

  The emulsion resin used in the present invention is preferably a resin in which fine, for example, resin particles having an average particle size of about 0.01 to 2 μm are dispersed in an emulsion state in an aqueous medium. It can be obtained by emulsion polymerization using a polymer dispersant having There is no fundamental difference in the polymer component of the resulting emulsion resin depending on the type of dispersant used, but when emulsion polymerization is performed using a polymer dispersant having a hydroxyl group, the presence of hydroxyl groups is present on at least the surface of fine particles. It is presumed that the chemical and physical properties of the emulsion differ from the emulsion resin polymerized using other dispersants.

  The polymer dispersant containing a hydroxyl group is a polymer dispersant having a weight average molecular weight of 10,000 or more, and has a hydroxyl group substituted at the side chain or terminal. For example, an acrylic polymer such as sodium polyacrylate or polyacrylamide is used. Examples of such a polymer include those obtained by copolymerization of 2-ethylhexyl acrylate, polyethers such as polyethylene glycol and polypropylene glycol, and polyvinyl alcohol. Polyvinyl alcohol is particularly preferable.

  Polyvinyl alcohol used as a polymer dispersant is an anion-modified polyvinyl alcohol having an anionic group such as a cation-modified polyvinyl alcohol or a carboxyl group in addition to ordinary polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate. Further, modified polyvinyl alcohol such as silyl-modified polyvinyl alcohol having a silyl group is also included. Polyvinyl alcohol has a higher effect of suppressing the occurrence of cracks when forming the ink absorbing layer when the average degree of polymerization is higher, but when the average degree of polymerization is within 5000, the viscosity of the emulsion resin is not high, and at the time of production Easy to handle. Accordingly, the average degree of polymerization is preferably 300 to 5000, more preferably 1500 to 5000, and particularly preferably 3000 to 4500. The saponification degree of polyvinyl alcohol is preferably 70 to 100 mol%, more preferably 80 to 99.5 mol%.

  Examples of the resin that is emulsion-polymerized with the above polymer dispersant include homopolymers or copolymers of ethylene monomers such as acrylic acid esters, methacrylic acid esters, vinyl compounds, and styrene compounds, and diene compounds such as butadiene and isoprene. Examples of the polymer include acrylic resins, styrene-butadiene resins, and ethylene-vinyl acetate resins.

<Other additives>
Various additives applicable to the high refractive index layer and the low refractive index layer according to the present invention are listed below. For example, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, and JP-A-57-87989. , JP-A-60-72785, JP-A-61-14659, JP-A-1-95091, JP-A-3-13376, etc. Nonionic surfactants, JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-228771, and JP-A-4-219266 Fluorescent brighteners, sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, etc. Agents, lubricants such as diethylene glycol, preservatives, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared rays Examples include various known additives such as absorbents, dyes, and pigments.

<Infrared reflective layer forming method>
The method for forming the infrared reflective layer according to the present invention is not particularly limited, but usually, several tens or hundreds of layers are coextruded to obtain a multilayer extrudate, and then the multilayer extrudate is 1 if necessary. It can be made by passing one or more co-extruding dies to further stack the layers, and then stretching or orienting the extrudate to form a film. In another method, a coating solution for a high refractive index layer containing a first water-soluble polymer and first metal oxide particles on a substrate, a second water-soluble polymer and a second metal Although the manufacturing method including the process of apply | coating the coating liquid for low refractive index layers containing an oxide particle can be mentioned, In this invention, the manufacturing method including this application | coating process is preferable.

  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 U.S. Pat. No. 2,761,419, U.S. Pat. Examples thereof include a slide hopper coating method and an extrusion coating method described in Japanese Patent No. 2,761,791. In addition, as a method of applying a plurality of layers in a multilayer manner, sequential multilayer coating or simultaneous multilayer coating may be used.

  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 high refractive index layer and the coating solution for the low 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>
The concentration of the first water-soluble polymer in the coating solution for the high refractive index layer is preferably 30 to 80% by mass. Moreover, it is preferable that the density | concentration of the 1st metal oxide particle in the coating liquid for high refractive index layers is 2-50 mass%.

  It is preferable that the density | concentration of the 2nd water-soluble polymer in the coating liquid for low refractive index layers is 1-10 mass%. Moreover, it is preferable that the density | concentration of the 2nd metal oxide particle in the coating liquid for low refractive index layers is 2-50 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 water-soluble polymer, metal oxide particles, and other additives added as necessary. The method of adding and stirring and mixing is mentioned. At this time, the order of addition of the water-soluble polymer, metal oxide particles, and other additives used as necessary is not particularly limited, and each component may be added and mixed sequentially while stirring. However, they may be added and mixed at once. If necessary, it is further adjusted to an appropriate viscosity using a solvent.

<Viscosity of coating liquid>
The viscosity at 40 ° 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 100 mPa · s, and is preferably 10 to 50 mPa · s. A range is more preferred. The viscosity at 40 ° C. of the coating solution for high refractive index layer and the coating solution for low refractive index layer at the time of simultaneous multilayer coating by the slide curtain coating method is preferably in the range of 5 to 1200 mPa · s, and 25 to 500 mPa · s. -The range of 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.

<Application 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. More preferable drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. 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 thickness at the time of preferable drying as shown above.

  Here, the set refers to increasing the viscosity of the coating composition by reducing the temperature by applying cold air or the like to the coating film, or lowering the fluidity of each layer and the substance in each layer, or first And a second compound are reacted to form a gel, that is, to form an intermediate layer. A state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.

  After application, the time from application of cold air to completion of setting (setting time) is preferably within 5 minutes, and preferably within 2 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. If the set time is too short, mixing of the components in the layer may be insufficient. On the other hand, if the set time is too long, the interlayer diffusion of the metal oxide particles proceeds, and the refractive index difference between the high refractive index layer and the low refractive index layer may be insufficient. If the intermediate layer between the high-refractive index layer and the low-refractive index layer is highly elastic, the setting step may not be provided.

  The set time can be adjusted by adjusting the concentration of water-soluble polymer and metal oxide particles, and adding other components such as gelatin, pectin, agar, carrageenan, gellan gum and other known gelling agents. It can be adjusted by doing.

  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.

[Insulation layer]
In this invention, it has the heat insulation layer which has a space | gap in any one side of a base material. The heat insulating layer of the present invention is provided separately from the above-described infrared reflecting layer. By having such a heat insulating layer, the risk of so-called thermal cracking can be reduced.

  The heat insulating layer having voids according to the present invention preferably has a thermal conductivity of 0.001 to 0.2 W / (m · K), more preferably 0.005 to 0.15 W / (m · K). is there. When the thermal conductivity is 0.001 W / (m · K) or more, slight heat transfer and thermal diffusion occur, and damage such as swelling, peeling, and discoloration of the film hardly occurs. In the case of 0.2 W / (m · K) or less, heat transfer and thermal diffusion can be suppressed, heat conduction to the glass can be effectively suppressed, and glass thermal cracking hardly occurs.

  The thermal conductivity of the heat insulating layer of the present invention can be adjusted by selecting the type of members constituting the heat insulating layer, and appropriately selecting the spatial structure, the size of the void, the abundance of the void, and the like. As a method for increasing the porosity, (1) selection of a porous material, (2) a material that volatilizes by applying heat is mixed with a constituent material of the heat insulating layer, and the volatilizing material is volatilized by applying heat. (3) A method such as adjusting the aggregation of the material constituting the voids with a surfactant or the like can be appropriately employed.

  The thermal conductivity can be measured using, for example, a hot wire probe type thermal conductivity measuring device (manufactured by Kyoto Electronics Industry Co., Ltd., QTM-500).

  Moreover, if the material and spatial structure which comprise a heat insulation layer can be specified, it can simulate by a well-known method. If the members of each constituent layer such as the infrared reflecting layer constituting the infrared shielding film are known, the thermal conductivity obtained by the simulation and the measured value are in good agreement. For example, if the thermal conductivity of the entire film is obtained by actual measurement, and the members and configuration other than the heat insulation layer are known, the thermal conductivity of the heat insulation layer can be obtained by actual measurement value-simulation value.

  The porosity of the heat insulating layer having voids according to the present invention is preferably 30 to 95%, more preferably 60 to 95%. If the porosity is 30% or more, the heat insulating performance is exhibited and glass thermal cracking hardly occurs. Moreover, if the porosity is 95% or less, the layer structure strength can be maintained to such an extent that the structure does not collapse even during handling.

  The porosity (A) can be calculated by the following formula from the density (B) obtained from the volume and mass of the heat insulating layer and the density (C) of the material itself constituting the heat insulating layer.

  In addition, when the material which comprises a heat insulation layer is 2 or more types, the density (C) of material itself is computed by a weighted average from the compounding ratio and density of each material.

  Although the material which forms the heat insulation layer which has a space | gap is not restrict | limited in particular, For example, the combination of an inorganic oxide particle and a polymer binder, or foamed resin etc. are mentioned.

A known material can be used as the inorganic oxide particles. Specifically, for example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), zeolite, titanium oxide (TiO ₂ ), barium titanate (BaTiO ₃ ), strontium titanate (SrTiO ₃ ). ₃ ), calcium titanate (CaTiO ₃ ), aluminum borate, iron oxide, calcium carbonate, barium carbonate, lead oxide, tin oxide, cerium oxide, calcium oxide, trimanganese tetroxide, magnesium oxide, niobium oxide, tantalum oxide, Tungsten oxide, antimony oxide, aluminum phosphate, calcium silicate, zirconium silicate, ITO, titanium silicate, FSM16, MCM41, montmorillonite, saponite, vermiculite, hydrotalcite, kaolinite, kanemite, eye Lalite, magadiite, and kenyaite are listed. These may be used alone or in combination of two or more. Furthermore, these composite oxides can also be preferably used. Among these, neutral to acidic inorganic oxide particles are preferable from the viewpoint of the strength of the heat insulating layer. Specifically, zirconium oxide, montmorillonite, saponite, vermiculite, hydrotalcite, kaolinite, kanemite, tin oxide, tungsten oxide, titanium oxide, aluminum phosphate, silica, zinc oxide, or alumina are preferable, and more preferable. Are silica particles or alumina particles. This is because silica particles and alumina particles are industrially inexpensive and can be easily obtained, and since the surface has a reactive hydroxyl group, it is relatively easy to modify the surface with a crosslinkable functional group.

The inorganic oxide particles may be porous particles. The porous inorganic oxide particles are inorganic oxide particles having innumerable fine holes in the particle surface or inside, and the specific surface area is preferably 500 to 1000 m ² / g. If the specific surface area is 500 m ² / g or more, the porosity can be increased, and the heat insulation tends to be improved. Moreover, if it is 1000 m < ² > / g or less, it exists in the tendency for the film | membrane intensity | strength of a heat insulation layer to improve. The specific surface area can be measured by a conventional mercury intrusion method or gas adsorption method (BET method), and the BET method can be suitably used in the present invention. The BET method is a method in which a molecule (for example, N ₂ ) whose adsorption occupation area is known is adsorbed on the particle surface at the temperature of liquid nitrogen and the specific surface area of the sample is obtained from the amount. In addition, as a pore diameter that is another index of porosity, it is preferable to have a pore diameter in the meso region. The meso region is a region of 2 to 50 nm to which Kelvin's capillary condensation theory can be applied. The pore diameter can be measured by the median diameter of the pore distribution calculated by analyzing the hysteresis pattern of the adsorption / desorption isotherm obtained by the gas adsorption method with a pore diameter distribution measuring device, or by a transmission electron microscope (TEM). ) Can also be measured by observation.

  As such inorganic oxide machine particles having porosity, for example, as described in JP-A-7-133105, the surface of porous inorganic oxide particles is coated with silica or the like, low refraction Nanometer-size composite oxide fine particles, and, as described in JP-A-2001-233611, a low-refractive-index nanometer size comprising silica and an inorganic oxide other than silica and having a cavity inside Also suitable are silica-based fine particles.

  The average particle size of the inorganic oxide particles of the present invention is preferably 1 nm to 200 nm. If the average particle size is 1 nm or more, the porosity tends to increase and the heat insulating property tends to be improved, and if the average particle size is 200 nm or less, the film strength of the heat insulating layer tends to improve.

  The inorganic oxide particles contained in the heat insulating layer of the present invention may be hollow particles from the viewpoint of easily controlling the pore diameter of the voids and the thickness of the outer casing of the heat insulating layer structure. As hollow particles to be used, the template surface is coated with an inorganic oxide using a sol-gel solution such as a metal alkoxide or a silane coupling agent in which a template of inorganic nanoparticles having a predetermined particle size is dispersed, or a reactive resin monomer solution. After that, it can be obtained by a method of dissolving the template inside and making it hollow. The hollow particles may have a structure in which a part of the outer casing is not only closed but also partially open. In addition, as materials used for the outer casing, silica, metal oxide, organic resin material, etc. can be used without limitation, but in order to ensure the mechanical strength of the heat insulating layer, silica or organic modified silica is formed. It is preferable to use a silane coupling agent.

  The average pore diameter of the hollow particles is preferably 80 nm or less, and more preferably 50 nm or less in order to ensure heat insulation and transparency. Moreover, 1-7 nm is preferable and, as for the average thickness of an outer casing, 1-5 nm is more preferable. If the thickness of the outer sheath is 7 nm or less, the transparency of the heat insulating layer tends to be improved, and if it is 1 nm or more, the mechanical strength of the heat insulating layer tends to be increased.

  The average particle diameter of these inorganic oxide particles is the volume average value of the diameter (sphere converted particle diameter) when each particle is converted to a sphere having the same volume, and this value can be determined by observation with an electron microscope. That is, from observation of the inorganic oxide particles with an electron microscope, 200 or more inorganic oxide fine particles in a certain visual field were measured, the spherical equivalent particle diameter of each particle was obtained, and the average value was obtained. is there.

  As the inorganic oxide particles of the present invention, particles whose surface is modified with a silane coupling agent or the like can be used. The surface modifying group is not particularly limited, but a crosslinkable functional group capable of crosslinking with a nitrogen-containing aromatic polymer having a crosslinkable functional group at the terminal is preferably used. Here, as the crosslinkable functional group, a group having a carbon-carbon unsaturated bond such as vinyl group, acrylic group, methacryl group or allyl group, cyclic ether group such as epoxy group or oxetane group, isocyanate group, hydroxyl group, carboxyl group Etc.

  As a method of providing a crosslinkable functional group on the surface of the inorganic oxide particle (surface modification method), a method of reacting the silane compound having the crosslinkable functional group with the surface of the inorganic oxide particle is preferably used. Examples of the silane compound having a crosslinkable functional group include a 1-3 functional alkoxysilane, a chlorosilane compound having a crosslinkable functional group, a disilazane compound having a crosslinkable functional group, and the like.

  More specifically, as a surface modification method, a dry method in which the silane compound having a crosslinkable functional group is directly sprayed onto the inorganic oxide particles to heat-fix, or the inorganic oxide particles are dispersed in a solution. A wet method in which a surface treatment is performed by adding a silane compound having a crosslinkable functional group is preferable, but a wet method in which inorganic oxide particles are more uniformly dispersed is preferable. For example, when the method described in Japanese Patent Application Laid-Open No. 2007-264581 is performed, the inorganic oxide particles have high dispersibility, which is preferable for the present invention. In both the dry method and the wet method, the reaction with the silane compound having an overforced functional group can be promoted by previously subjecting the inorganic oxide particles to hydrothermal treatment.

  Although content in particular of the inorganic oxide particle in a heat insulation layer is not restrict | limited, It is preferable that it is 10-95 mass% with respect to the total mass of a heat insulation layer, and it is more preferable that it is 50-90 mass%. When it is 10% by mass or more, the porosity tends to increase and the heat insulation tends to be improved, and when it is 95% by mass or less, the mechanical strength of the heat insulation layer tends to improve.

  When the heat insulating layer having voids contains inorganic oxide particles, it is preferable to contain a small amount of a polymer binder from the viewpoints of coating film flexibility and void formation.

  Examples of the polymer binder include thermoplastic resins and polymers having rubber elasticity. Specifically, for example, starch, carboxymethyl cellulose, cellulose, diacetyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium alginate, poly Water-soluble polymers such as acrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer, polyvinyl chloride , Polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene (Meth) acrylic such as fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate (Meth) acrylic acid ester copolymer containing acid ester, (meth) acrylic acid ester-acrylonitrile copolymer, polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene-butadiene copolymer, acrylonitrile -Butadiene copolymer, polybutadiene, neoprene rubber, fluoro rubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polymer Urethane resins, polyester resins, phenol resins, an emulsion (latex) or suspension such as epoxy resins. Of these, water-soluble polymers are preferable, and polyvinyl alcohol is more preferably used.

  Although content in particular of these polymer binders is not restrict | limited, 5-90 mass% is preferable with respect to the total mass of a heat insulation layer, and 10-50 mass% is more preferable. If it is 5 mass% or more, it exists in the tendency for the softness | flexibility of a heat insulation layer to increase, If it is 90 mass% or less, porosity will be obtained and a heat insulation layer with higher heat insulation can be formed.

  Examples of the foamed resin used as the material for the heat insulating layer include foams such as polyolefins such as polyurethane, polystyrene, polyethylene, and polypropylene, phenol resins, polyvinyl chloride, urea resins, polyimides, and melamine resins. These may be used alone or in combination of two or more. Among these, foamed polystyrene or foamed polyurethane is preferable from the viewpoint of moldability.

  Moreover, you may use a crosslinking agent for the heat insulation layer of this invention from a viewpoint of raising film | membrane intensity | strength more. The crosslinking agent is roughly classified into an inorganic type and an organic type. In the present invention, either of them can provide a sufficient effect. These crosslinking agents can be used alone or in combination of two or more.

  Examples of inorganic crosslinking agents used in the present invention include, for example, acids having boron atoms (boric acid, orthoboric acid, 2 boric acid, metaboric acid, 4 boric acid, 5 boric acid, etc.) or salts thereof, zinc salts (Such as zinc sulfate), copper salts (such as copper sulfate), zirconium salts and the like (such as zirconyl nitrate and zirconyl acetate), aluminum salts (such as aluminum sulfate salts), titanium salts (such as titanium lactate salts) and the like. Among these, preferred inorganic crosslinking agents are acids having a boron atom or salts thereof, aluminum salts, and zirconium salts, more preferably zirconium salts.

  Examples of the organic crosslinking agent include aldehyde crosslinking agents (formalin, glyoxal, dialdehyde starch, polyacrolein, N-methylol urea, N-methylol melamine, N-hydroxylmethylphthalimide, etc.), active vinyl crosslinking agents. (Bisvinylsulfonylmethylmethane, tetrakisvinylsulfonylmethylmethane, N, N, N-trisacryloyl-1,3,5-hexahydrotriazine, etc.), an epoxy-based crosslinking agent, and a polyisocyanate-based crosslinking agent. Of these, polyisocyanate crosslinking agents, epoxy crosslinking agents, and aldehyde crosslinking agents are preferred, and polyisocyanate crosslinking agents and epoxy curing agents that exhibit a good reaction with hydroxyl groups are more preferred.

  The epoxy-based crosslinking agent is a compound having at least two glycidyl groups in the molecule. For example, many crosslinking agents are commercially available from Nagase Chemtech Co., Ltd. under the trade name Denacol (registered trademark).

  A polyisocyanate-based crosslinking agent is a compound having at least two isocyanate groups in the molecule and has high reactivity with a hydroxyl group or the like. Examples of main isocyanate crosslinking agents include toluylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and modified products and prepolymers thereof, polyfunctional aromatic isocyanates, aromatic polyisocyanates, polyfunctional aliphatic isocyanates. , Block polyisocyanate, polyisocyanate prepolymer, and the like. The details of these polyiasocyanate-based crosslinking agents are described in, for example, the crosslinking agent handbook (published by Taiseisha, published in October 1981).

  In any case of the above-mentioned inorganic crosslinking agent and organic crosslinking agent, it is preferably used in a range of approximately 1 to 50% by mass, more preferably 2 to 2%, based on the polymer binder from the viewpoints of heat insulating layer film strength and flexibility. It is used in the range of 40% by mass.

  The method for supplying these crosslinking agents to the heat insulating layer is not particularly limited. For example, the crosslinking agent may be added to a coating solution for forming a heat insulating layer, or after the heat insulating layer is provided, the crosslinking agent is overcoated. You may supply. The overcoating may be performed at the same time as or after the coating of the heat insulating layer forming coating solution. At this time, the coating method of the crosslinking agent may be a coating method using a coater or the like, a spraying method, or a method in which the coating agent is immersed in a crosslinking agent solution.

  Subsequently, the formation method of the space | gap heat insulation layer of this invention is demonstrated.

  The method for forming the heat insulating layer having voids according to the present invention is not particularly limited. However, when the heat insulating layer includes inorganic oxide particles and a polymer binder, a wet coating method is preferable. Specifically, it can be formed by mixing inorganic oxide particles, a polymer binder, and, if necessary, a crosslinking agent with a solvent to prepare a coating solution, and then coating and drying on a substrate.

  The solvent may be any solvent that can uniformly disperse the inorganic oxide particles, the polymer binder, and the crosslinking agent. Specifically, one or more of water, methanol, ethanol, 2-propanol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, N-dimethylformamide and the like can be used. At this time, various additives may be added to stabilize the coating solution (dispersion). Even if these additives are materials that can be removed by heating, there is no particular limitation as long as the materials do not crush the voids of the void heat insulating layer of the present invention.

  As a coating method using a coating liquid, the method is not particularly limited as long as it is a method that can be applied substantially uniformly to a desired thickness. For example, a screen printing method, a bar coating method, a roll coating method, a reverse coating method, a gravure printing method, a doctor blade method, a die coating method, and the like can be given. The coating method can be properly used as necessary, such as continuous coating, intermittent coating, and stripe coating. Furthermore, it is also possible to apply multiple layers simultaneously with the above-described infrared reflective layer.

  The drying method after coating is not particularly limited as long as the solvent contained in the coating solution can be removed. Hot air drying, infrared drying, far infrared drying, microwave drying, electron beam drying, vacuum drying, supercritical drying. Various methods such as these can be selected and used as appropriate. The drying temperature is not particularly limited, but is preferably 50 to 400 ° C, and more preferably 70 to 150 ° C.

  Further, when using a UV curable crosslinking agent, it is possible to form a heat insulating layer by further irradiating and curing UV after coating.

  The formation method of the heat insulation layer when the heat insulation layer contains a foamed resin is not particularly limited, and examples thereof include chemical foaming and physical foaming. For example, in the case of expanded polystyrene, polystyrene and an inert gas in a supercritical state such as carbon dioxide as a blowing agent are injected into a supercritical extruder, and a polystyrene sheet having fine bubbles at high density is red. A method of extruding on the outer reflection layer to form a heat insulating layer can be employed.

  Although the thickness in particular of the heat insulation layer formed by the said method is not restrict | limited, 100 nm-200 micrometers are preferable and 100 nm-20 micrometers are more preferable. Furthermore, it is preferable that it is 1.5 micrometers or more as thickness of a heat insulation layer, and it is especially preferable to set it as 10 times or more of the average optical thickness in each layer of an infrared reflection layer. If it is this range, it will hardly influence the transparency of a film, and also heat insulation can be expressed.

  The heat insulating layer having voids according to the present invention may be provided on at least one side of the base material, but in consideration of the mechanism of thermal cracking, heat transfer is blocked between the glass and the heat generation site. For this purpose, it is preferable to provide a heat insulating layer, and it is preferable to provide it at a position closer to the glass. Specifically, an arrangement located between the base material and the glass is preferable, and an arrangement located between the infrared reflection layer and the glass is more preferable. Moreover, if it is an infrared shielding film provided with an infrared absorption layer, arrangement | positioning that this heat insulation layer is located between an infrared absorption layer and glass is preferable.

  In addition, the porosity of the heat insulation layer which has a space | gap can be controlled by adjusting content in each heat insulation layer, when a heat insulation layer contains an inorganic oxide particle and a polymer binder. Moreover, when a heat insulation layer contains foaming resin, the porosity of the heat insulation layer which has a space | gap can be controlled by controlling the foaming conditions of resin.

[Infrared shielding film]
The total thickness of the infrared shielding film of the present invention is preferably 12 μm to 315 μm, more preferably 15 μm to 200 μm, and still more preferably 20 μm to 100 μm. Thus, the infrared shielding film of the present invention can obtain a high infrared reflectance with a thinner film thickness than the conventional infrared shielding film.

  The infrared shielding film of the present invention has a conductive layer, an antistatic layer, a gas barrier layer, an easy-adhesion layer (for the purpose of adding further functions under the base material or on the outermost surface layer opposite to the base material). Adhesive layer), antifouling layer, deodorant layer, droplet layer, slippery layer, hard coat layer, wear-resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorption layer, infrared absorption layer, printing layer, fluorescence Light emitting layer, hologram layer, release layer, adhesive layer, adhesive layer, infrared cut layer (metal layer, liquid crystal layer) other than the high refractive index layer and low refractive index layer of the present invention (colored layer (visible light absorbing layer)), combination One or more functional layers such as an intermediate film layer used for glass may be included. Hereinafter, the adhesive layer, the infrared absorption layer, and the hard coat layer which are preferable functional layers will be described.

<Adhesive layer>
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, silicon-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, polyvinyl butyral pressure-sensitive adhesives, and ethylene-vinyl acetate pressure-sensitive adhesives. Can do.

  When the infrared shielding film of the present invention is pasted on a window glass, water is sprayed on the window, and the pasting method of matching the adhesive layer of the infrared shielding film on the wet glass surface, the so-called water pasting method is re-stretched, It is preferably used from the viewpoint of repositioning and the like. For this reason, an acrylic pressure-sensitive adhesive that has a weak adhesive force in the presence of water is preferably used.

  The acrylic pressure-sensitive adhesive used may be either solvent-based or emulsion-based, but is preferably a solvent-based pressure-sensitive adhesive because it is easy to increase the adhesive strength and the like, and among them, those obtained by solution polymerization are preferable. As a raw material when producing such a solvent-based acrylic pressure-sensitive adhesive by solution polymerization, for example, as a main monomer serving as a skeleton, an acrylic ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acryl acrylate, As a comonomer to improve cohesive strength, vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc., to further promote crosslinking, to give stable adhesive strength, and to maintain a certain level of adhesive strength even in the presence of water Examples of the functional group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, and glycidyl methacrylate. Since the adhesive layer of the laminated film requires a particularly high tack as the main polymer, those having a low glass transition temperature (Tg) such as butyl acrylate are particularly useful.

  This adhesive layer contains additives such as stabilizers, surfactants, UV absorbers, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion modifiers, etc. It can also be made. In particular, when used as a window sticker as in the present invention, the addition of an ultraviolet absorber is also effective for suppressing deterioration of the infrared shielding film due to ultraviolet rays.

  The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 3 to 50 μm. If it is 1 micrometer or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is acquired. On the other hand, if the thickness is 100 μm or less, not only the transparency of the infrared shielding film is improved, but also after the infrared shielding film is attached to the window glass, when it is peeled off, cohesive failure does not occur between the adhesive layers. There is a tendency for the remaining adhesive to disappear.

  The method for forming the pressure-sensitive adhesive layer is not particularly limited. For example, after preparing a pressure-sensitive adhesive coating solution containing the pressure-sensitive adhesive, it is coated on a separator film using a wire bar or the like and dried to produce a film with a pressure-sensitive adhesive layer. To do. Then, the method of bonding the adhesion layer surface of a film with an adhesion layer to the surface of a heat insulation layer with a bonding machine, etc. are mentioned.

<Infrared absorbing layer>
The infrared reflective film of the present invention can have an infrared absorption layer at an arbitrary position. Conventionally, an infrared reflective film having an infrared absorption layer has a problem that the risk of thermal cracking is increased. However, the infrared shielding film provided with the heat insulating layer having voids of the present invention reduces the risk of thermal cracking even if it has an infrared absorption layer, and further has excellent storage stability and transparency. Become.

  Although it does not restrict | limit especially as a material contained in an infrared absorption layer, For example, the ultraviolet curable resin which is a binder component, a photoinitiator, an infrared absorber, etc. are mentioned. In the infrared absorption layer of the present invention, the contained binder component is preferably cured. Here, the curing means that the reaction proceeds and cures by active energy rays such as ultraviolet rays or heat.

  The ultraviolet curable resin is more excellent in hardness and smoothness than other resins, and is also advantageous from the viewpoint of dispersibility of ITO, ATO, and thermally conductive metal oxide. The ultraviolet curable resin can be used without particular limitation as long as it forms a transparent layer by curing, and examples thereof include silicone resins, epoxy resins, vinyl ester resins, acrylic resins, and allyl ester resins. More preferred is an acrylic resin from the viewpoint of hardness, smoothness and transparency.

  From the viewpoint of hardness, smoothness, and transparency, the acrylic resin is a reactive silica particle having a photosensitive group having photopolymerization reactivity introduced on its surface as described in International Publication No. 2008/035669 ( In the following, it is preferable to simply include “reactive silica particles”. Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The ultraviolet curable resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an organic compound having a polymerizable unsaturated group. There may be. In addition, a polymerizable unsaturated group-modified hydrolyzable silane reacts with a silica particle that forms a silyloxy group and is chemically bonded to the silica particle by a hydrolysis reaction of the hydrolyzable silyl group. Can be used as conductive silica particles. Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle diameter in such a range, transparency, smoothness, and hardness can be satisfied in a well-balanced manner.

  The acrylic resin preferably contains fluorine from the viewpoint of adjusting the refractive index. That is, the infrared absorption layer preferably contains fluorine. Examples of such an acrylic resin include an acrylic resin containing a structural unit derived from a fluorine-containing vinyl monomer. Fluorine-containing vinyl monomers include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (eg, Biscoat 6FM (commodity) Name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), R-2020 (trade name, manufactured by Daikin Industries, Ltd.), and the like, and fully or partially fluorinated vinyl ethers.

  As a photoinitiator, a well-known thing can be used, It can use individually or in combination of 2 or more types.

Inorganic infrared absorbers that can be included in the infrared absorption layer include tin-doped indium oxide (ITO), antimony-doped tin oxide (from the viewpoint of visible light transmittance, infrared absorptivity, dispersibility in the resin, etc. ATO), zinc antimonate, lanthanum hexaboride (LaB ₆ ), cesium-containing tungsten oxide (Cs _0.33 WO ₃ ) and the like are preferable. These may be used alone or in combination of two or more. 5-100 nm is preferable and, as for the average particle diameter of an inorganic infrared absorber, 10-50 nm is more preferable. If it is less than 5 nm, the dispersibility in the resin and the infrared absorptivity may be lowered. On the other hand, if it is larger than 100 nm, the visible light transmittance may decrease. The average particle size is measured by taking an image with a transmission electron microscope, randomly extracting, for example, 50 particles, measuring the particle size, and averaging the results. Moreover, when the shape of particle | grains is not spherical, it defines as what was calculated by measuring a major axis.

  The content of the inorganic infrared absorber in the infrared absorption layer is preferably 1 to 80% by mass and more preferably 5 to 50% by mass with respect to the total mass of the infrared absorption layer. If the content is 1% or more, a sufficient infrared absorption effect appears, and if it is 80% or less, a sufficient amount of visible light can be transmitted.

  In the infrared absorption layer, other infrared absorbers such as metal oxides other than those described above, organic infrared absorbers, metal complexes, and the like may be included within the scope of the effects of the present invention. Specific examples of such other infrared absorbers include, for example, diimonium compounds, aluminum compounds, phthalocyanine compounds, organometallic complexes, cyanine compounds, azo compounds, polymethine compounds, quinone compounds, diphenylmethane compounds. Compounds, triphenylmethane compounds, and the like.

  The thickness of the infrared absorption layer is preferably 0.1 μm to 50 μm, and more preferably 1 to 20 μm. If it is 0.1 μm or more, the infrared absorption ability tends to be improved. On the other hand, if it is 50 μm or less, the crack resistance of the coating film is improved.

  The method for forming the infrared absorbing layer is not particularly limited. For example, the infrared absorbing layer coating liquid containing the above components is prepared, and then the coating liquid is applied using a wire bar and dried. And the like.

<Hard coat layer>
The infrared shielding film of the present invention is a hard coat containing a resin that is cured by heat, ultraviolet rays, or the like, as a surface protective layer for enhancing scratch resistance, on the uppermost layer opposite to the side having the adhesive layer of the substrate. It is preferable to laminate the layers.

  Examples of the curable resin used in the hard coat layer include a thermosetting resin and an ultraviolet curable resin. However, an ultraviolet curable resin is preferable because it is easy to mold, and among them, those having a pencil hardness of at least 2H. More preferred. Such cured resins can be used singly or in combination of two or more.

  As such an ultraviolet curable resin, it is synthesized from, for example, a polyfunctional acrylate resin such as acrylic acid or methacrylic acid ester having a polyhydric alcohol, and acrylic acid or methacrylic acid having a diisocyanate and a polyhydric alcohol. Such polyfunctional urethane acrylate resins can be mentioned. Furthermore, polyether resins, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins or polythiol polyene resins having an acrylate-based functional group can also be suitably used.

  Moreover, as reactive diluents for these resins, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (meta) having relatively low viscosity are used. ) Bifunctional or higher functional monomers and oligomers such as acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentylglycol di (meth) acrylate, and Acrylic esters such as N-vinylpyrrolidone, ethyl acrylate, propyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate Methacrylic acid esters such as acrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, and nonylphenyl methacrylate, derivatives such as tetrahydrofurfuryl methacrylate and its caprolactone modified products, styrene, α-methylstyrene, acrylic acid, etc. A monofunctional monomer or the like can be used. These reactive diluents can be used alone or in combination of two or more.

  Furthermore, as photosensitizers (radical polymerization initiators) for these resins, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl methyl ketal and the like Alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone; anthraquinones such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone, 2,4 -Thioxanthones such as diethylthioxanthone and 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenone and 4,4-bismethyl Minobe benzophenone benzophenone such as and can be used azo compounds. These may be used alone or in combination of two or more. In addition, tertiary amines such as triethanolamine and methyldiethanolamine; photoinitiators such as benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate can be used in combination. it can. The usage-amount of these radical polymerization initiators is 0.5-20 mass parts with respect to 100 mass parts of polymeric components of resin, Preferably it is 1-15 mass parts.

  In addition, you may mix | blend a well-known general paint additive with the above-mentioned cured resin as needed. For example, a silicone-based or fluorine-based paint additive that imparts leveling or surface slip properties is effective in preventing scratches on the surface of a cured film, and in the case of using ultraviolet rays as active energy rays, When the additive bleeds to the air interface, the inhibition of curing of the resin by oxygen can be reduced, and an effective degree of curing can be obtained even under low irradiation intensity conditions.

  The hard coat layer preferably contains inorganic fine particles. Preferable inorganic fine particles include fine particles of an inorganic compound containing a metal such as titanium, silica, zirconium, aluminum, magnesium, antimony, zinc or tin. The average particle size of the inorganic fine particles is preferably 1000 nm or less, and more preferably in the range of 10 to 500 nm, in order to ensure visible light transmittance. In addition, the inorganic fine particles have a higher bond strength with the cured resin forming the hard coat layer, and can be prevented from falling off the hard coat layer. Therefore, a photosensitive group having photopolymerization reactivity such as monofunctional or polyfunctional acrylate. Those in which is introduced into the surface are preferred.

  The thickness of the hard coat layer is preferably 0.1 μm to 50 μm, and more preferably 1 to 20 μm. If it is 0.1 μm or more, the hard coat property tends to be improved. Conversely, if it is 50 μm or less, the transparency of the infrared shielding film tends to be improved.

  The hard coat layer may also serve as the above-described infrared absorption layer.

  The method for forming the hard coat layer is not particularly limited. For example, after preparing a coating liquid for hard coat layer containing the above components, the coating liquid is applied with a wire bar or the like, and the coating liquid is cured with heat and / or UV. And a method of forming a hard coat layer.

[Infrared shield]
The infrared shielding film of the present invention can be applied to a wide range of fields. For example, as a film for window pasting such as heat ray reflective film that gives heat ray reflection effect, film for agricultural greenhouses, etc. It is mainly used for the purpose of improving weather resistance. Moreover, it is used suitably also as an infrared shielding film for motor vehicles pinched | interposed between glass, such as laminated glass for motor vehicles. In this case, since the infrared shielding film can be sealed from outside air gas, it is preferable from the viewpoint of durability.

  Especially the infrared shielding film which concerns on this invention is used suitably for the member bonded by base | substrates, such as glass or glass substitute resin, directly or through an adhesive agent.

  That is, this invention also provides the infrared shielding body which provides the infrared shielding film of this invention in the at least one surface of a base | substrate.

  Specific examples of the substrate include, for example, glass, polycarbonate resin, polysulfone resin, acrylic resin, polyolefin resin, polyether resin, polyester resin, polyamide resin, polysulfide resin, unsaturated polyester resin, epoxy resin, melamine resin, Examples thereof include phenol resin, diallyl phthalate resin, polyimide resin, urethane resin, polyvinyl acetate resin, polyvinyl alcohol resin, styrene resin, vinyl chloride resin, metal plate, ceramic and the like. The type of the resin may be any of a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin, and these may be used alone or in combination of two or more. The substrate that can be used in the present invention can be produced by a known method such as extrusion molding, calendar molding, injection molding, hollow molding, compression molding and the like.

  The thickness of the substrate is not particularly limited, but is usually 0.1 mm to 5 cm.

  The adhesive layer for bonding the infrared shielding film and the substrate of the present invention is preferably installed so that the infrared shielding film is on the sunlight (heat ray) incident surface side. Further, it is preferable to sandwich the infrared shielding film of the present invention between a window glass and a substrate because it can be sealed from surrounding gas such as moisture and has excellent durability. Even if the infrared shielding film of the present invention is installed outdoors or on the outside of a vehicle (for external application), it is preferable because of environmental durability.

  Moreover, you may use the polyvinyl butyral resin used as an intermediate | middle layer of a laminated glass, or ethylene-vinyl acetate copolymer type | system | group resin as said adhesive layer or an adhesion layer. Specific examples thereof include, for example, plastic polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.), ethylene-vinyl acetate copolymer (manufactured by DuPont, manufactured by Takeda Pharmaceutical Company Limited, duramin), and modified ethylene-acetic acid. Vinyl copolymer (manufactured by Tosoh Corporation, Mersen G). In the adhesive layer or the adhesive layer, an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, a colorant, an adhesion (adhesion) adjusting agent, and the like may be appropriately added and blended.

  Preferable substrates include plastic substrates, metal substrates, ceramic substrates, cloth substrates, etc., and the infrared shielding film of the present invention is applied to substrates of various forms such as film, plate, sphere, cube, and cuboid. Can be provided. Among these, a plate-shaped ceramic substrate is preferable, and an infrared shielding body in which the infrared shielding film of the present invention is provided on a glass plate is more preferable. As an example of a glass plate, the float plate glass described in JISR3202: 1996 and polished plate glass are mentioned, for example, As glass thickness, 0.01 mm-20 mm are preferable.

  As a method for providing the infrared shielding film of the present invention on the substrate, a method in which an adhesive layer is coated on the infrared shielding film as described above, and is attached to the substrate via the adhesive layer is suitably used. As a pasting method, a dry pasting method in which a film is pasted on a substrate as it is, and a water pasting method as described above can be applied, but in order to prevent air from entering between the substrate and the infrared shielding film, From the viewpoint of ease of construction, such as positioning of the infrared shielding film on the substrate, it is more preferable to bond by a water bonding method.

  Further, the infrared shielding body of the present invention may be, for example, a form in which the infrared shielding film of the present invention is provided on both surfaces of glass, or an adhesive layer is coated on both surfaces of the infrared shielding film of the present invention, A laminated glass-like form in which glass is bonded to both sides of the outer shielding film may be used.

  Moreover, the form which bonded the infrared shielding film of this invention on the glass surface of the multilayer glass may be sufficient as the infrared shielding body of this invention. The laminated surface of the infrared shielding film may be the surface on either side of the multilayer glass.

  The present invention provides an infrared shielding film and an infrared shielding body, but an optical film in which the infrared reflection layer according to the present invention is replaced with a configuration that reflects a wavelength region other than infrared (ultraviolet, visible light). This configuration can also be used.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples at all. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

Example 1
(Preparation of coating solution for low refractive index layer)
To 500 parts by mass of pure water, 10.0 parts by mass of water-soluble resin PVA224 (manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 1000) is added, and further water-soluble resin R1130 (manufactured by Kuraray Co., Ltd., Silanol-modified polyvinyl alcohol) 5.0 parts by mass, and then 2.0 parts by mass of water-soluble resin AZF8035 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) are added and dissolved at a temperature of 70 ° C. while mixing. An aqueous solution of was obtained.

  Subsequently, the entire amount of the water-soluble resin aqueous solution was added and mixed in 350 parts by mass of 10% by mass acidic silica sol (Snowtex (registered trademark) OXS, manufactured by Nissan Chemical Industries, Ltd.) containing silica fine particles having an average particle diameter of 5 nm. Furthermore, 0.3 parts by mass of Lapisol A30 (manufactured by Nippon Oil & Fats Co., Ltd.) was added as an anionic activator, and after stirring for 1 hour, a coating solution for low refractive index layer was prepared by finishing to 1000.0 g with pure water. .

<Preparation of aqueous dispersion of titanium oxide sol>
Sodium hydroxide aqueous solution (concentration 10 mol / L) was added to 10 L of an aqueous suspension (TiO ₂ concentration 100 g / L) in which titanium oxide hydrate was suspended in water with stirring, and the temperature was raised to 90 ° C. After warming and aging for 5 hours, it was neutralized with hydrochloric acid, filtered and washed with water. In the above reaction (treatment), titanium oxide hydrate was obtained by thermal hydrolysis of an aqueous titanium sulfate solution according to a known method.

The titanium oxide hydrate treated with the base was suspended in pure water so that the TiO ₂ concentration was 20 g / L, and 0.4 mol% of citric acid was added to the amount of TiO ₂ with stirring to raise the temperature. When the liquid temperature reached 95 ° C., concentrated hydrochloric acid was added to a hydrochloric acid concentration of 30 g / L, and the mixture was stirred for 3 hours while maintaining the liquid temperature.

  When the pH and zeta potential of the obtained titanium oxide sol solution were measured, the pH was 1.4 and the zeta potential was +40 mV. Furthermore, when the particle size was measured with a Zetasizer Nano manufactured by Malvern, the average particle size was 35 nm, and the monodispersity was 16%. Further, the titanium oxide sol solution was dried at 105 ° C. for 3 hours to obtain a particle powder, and X-ray diffraction measurement was performed using JDX-3530 type manufactured by JEOL Datum Co., Ltd. to confirm that the particles were rutile type particles. did. Moreover, the volume average particle diameter was 10 nm.

  1 kg of pure water was added to 1 kg of a 20.0 mass% titanium dioxide sol aqueous dispersion containing rutile-type titanium oxide fine particles having a volume average particle size of 10 nm to obtain a 10.0 mass% titanium oxide sol aqueous dispersion.

<Preparation of silicic acid aqueous solution>
An aqueous silicic acid solution having a SiO ₂ concentration of 2.0 mass% was prepared.

<Preparation of silica-modified titanium oxide sol aqueous dispersion>
2 kg of pure water was added to 0.5 kg of the 10.0 mass% titanium oxide sol aqueous dispersion, and the mixture was heated to 90 ° C. Next, 1.3 kg of the above silicic acid aqueous solution was gradually added, and heat treatment was performed at 175 ° C. for 18 hours in an autoclave. Thereafter, further concentration was performed to obtain a silica-modified titanium dioxide sol aqueous dispersion containing a silica-modified titanium dioxide sol having a rutile structure and a coating layer of SiO ₂ at a concentration of 20.0% by mass.

(Preparation of coating solution for high refractive index layer)
20.0% by mass of silica-modified titanium oxide particle sol aqueous dispersion obtained above 289 parts by mass, 1.92% by mass of citric acid aqueous solution 105 parts by mass, 10% by mass of allyl ether copolymer (AKM-0531, JP (Oil Co., Ltd.) 20 parts by mass of an aqueous solution and 90 parts by mass of a 3% by mass boric acid aqueous solution were mixed to prepare a silica-modified titanium oxide sol dispersion H2.

  Next, while stirring the silica-modified titanium oxide sol dispersion H2, 20 parts by mass of pure water and 335 parts by mass of a 5.0% by mass aqueous solution of polyvinyl alcohol (PVA217, manufactured by Kuraray Co., Ltd.) were added. Furthermore, 20 parts by mass of a 1% by mass aqueous solution of an anionic surfactant (Lapisol A30, manufactured by NOF Corporation) was added, and finally the total amount was 1000 parts by mass with pure water. Prepared.

(Formation of infrared reflection layer)
As the coating apparatus, a slide hopper coating apparatus capable of simultaneously coating 21 layers was used. On the 30 cm × 30 cm polyethylene terephthalate (PET) film (A4300: double-sided easy-adhesive layer, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm, the coating liquid H2 for the low refractive index layer and the coating liquid H2 for the high refractive index layer prepared above. While keeping the temperature at 45 ° C., simultaneous multilayer coating was performed, and the uppermost layer was a low refractive index layer, the low refractive index layer was 11 layers, and the high refractive index layer was 10 layers, for a total of 21 layers. Immediately thereafter, cold air was blown for 1 minute under conditions where the film surface was 15 ° C. or lower, and then dried by blowing hot air of 80 ° C. to form an infrared reflective layer 1 composed of 21 layers. When the cross section of the coating film was observed by SEM, the film thickness of the low refractive index layer was 170 nm, and the film thickness of the high refractive index layer was 130 nm. The refractive index of the low refractive index layer was 1.44, and the refractive index of the high refractive index layer was 1.92.

(Formation of heat insulation layer)
Polystyrene was introduced into a single screw screw type supercritical extruder. A supercritical carbon dioxide gas at a temperature of 200 ° C. and a pressure of 90 MPa is introduced from a material supply port that is a gas at room temperature in a supercritical extruder, and polystyrene is impregnated with carbon dioxide over 15 minutes to obtain an impregnated composition. It was. This impregnation composition was discharged from the discharge port of the supercritical extruder, and further introduced into the foam forming extruder through the introduction port of the foam forming extruder having a single screw. After passing through the die of the extruder, the impregnated composition was extruded as a sheet so that the thickness after foaming was 10 μm on the infrared reflective layer, and then cooled to room temperature (25 ° C.) over 4 hours and the pressure was increased. It reduced to normal pressure and made it foam, and the heat insulation layer which consists of expanded polystyrene was formed.

(Formation of adhesive layer)
60 parts by mass of ethyl acetate and 20 parts by mass of toluene were mixed, 20 g of an acrylic adhesive (Arontack M-300, manufactured by Toagosei Co., Ltd.) was further added, and the mixture was stirred and mixed to prepare an adhesive coating solution.

  As a separator film, a 25 μm thick polyester film (Therapy, manufactured by Toyo Metallizing Co., Ltd.) is used. On this separator film, an adhesive coating solution is applied with a wire bar, and dried at 80 ° C. for 2 minutes. An attached film was produced.

  The pressure-sensitive adhesive layer surface of the film with the pressure-sensitive adhesive layer was bonded to the surface of the heat insulating layer by a bonding machine. At this time, the tension | tensile_strength by the side of a heat insulation layer was 10 kg / m, and the tension | tensile_strength of the film with an adhesion layer was 30 kg / m. Thereby, the adhesion layer was formed on the heat insulation layer. As a result of observation by SEM, the thickness of the adhesive layer was 20 μm.

  In this way, an infrared shielding film was produced.

  FIG. 1 is a schematic cross-sectional view showing the layer structure of the infrared shielding film of this example.

(Example 2)
An infrared shielding film was produced in the same manner as in Example 1 except that the cooling time after extruding the polystyrene impregnated with carbon dioxide gas from the supercritical extruder was 1 hour 30 minutes when forming the heat insulating layer. did.

(Example 3)
An infrared shielding film was produced in the same manner as in Example 1 except that the cooling time after extruding the polystyrene impregnated with carbon dioxide gas from the supercritical extruder was 30 minutes when forming the heat insulating layer.

Example 4
The heat insulation layer was formed as follows.

  13.5 parts by mass of Alu-C (non-porous alumina, average particle size 13 nm, manufactured by Nippon Aerosil Co., Ltd.) as inorganic oxide particles was added to 40 g of water, and 1.0 part by mass of acetic acid was further added, and 5000 rpm, 30 with a homogenizer. Dispersion mixed for minutes. Furthermore, 5.5 parts by mass of PVA217 (polyvinyl alcohol, polymerization degree 1700, manufactured by Kuraray Co., Ltd.) is added as a water-soluble resin, and finally 40 g of water is added and stirred to apply a heat insulation layer with a nonvolatile content ratio of 20% by mass. A liquid was prepared. The obtained heat insulating layer coating solution was applied on the infrared reflective layer with a die coater so that the dry film thickness was 10 μm, and dried under conditions of 70 ° C. and 90 seconds to form a heat insulating layer.

  Except this, the infrared shielding film was manufactured by the same method as Example 1.

(Example 5)
In place of 5.5 parts by mass of PVA217, an infrared shielding film was formed in the same manner as in Example 4 except that 3.0 parts by mass of PVA235 (polyvinyl alcohol, polymerization degree 3500, manufactured by Kuraray Co., Ltd.) was used. Manufactured.

(Example 6)
An infrared shielding film was produced in the same manner as in Example 5 except that 3.0 parts by mass of PVA235 was changed to 1.8 parts by mass.

(Example 7)
An infrared shielding film was produced in the same manner as in Example 4 except that silica particles A200 (manufactured by Nippon Aerosil Co., Ltd., average particle size 5 nm) were used instead of Alu-C.

(Example 8)
An infrared shielding film was produced in the same manner as in Example 7 except that the amount of the silica particles A200 was 16.0 parts by mass.

Example 9
The heat insulation layer was formed as follows.

  To 170 parts by mass of a 10% by mass calcium carbonate aqueous dispersion prepared using calcium carbonate having an average particle diameter of 50 nm, 8 parts by mass of 28% by mass of aqueous ammonia was added and stirred for 10 minutes. Tetraethoxysilane: methyltriethoxysilane = 40 parts by mass of 1: 1 (mass ratio) was added, and the mixture was stirred at room temperature (25 ° C.) for 1 hour. Thereafter, the temperature was raised to 60 ° C., the mixture was stirred for 3 hours, and cooled to room temperature (25 ° C.) to obtain a silica-coated calcium carbonate dispersion.

  190 parts by mass of methanol was added to 200 parts by mass of the obtained silica-coated calcium carbonate dispersion, and 180 parts by mass of a 10% by mass nitric acid aqueous solution was added to elute calcium carbonate. Next, 200 parts by mass of distilled water was added, and 200 parts by mass of the aqueous solution was discharged using an ultrafiltration membrane. This operation is repeated three times, and an organic material having an outer shell with a number average thickness of 3 nm and a number average inner diameter of 50 nm formed from tetraethoxysilane: methyltriethoxysilane = 1: 1 (mass ratio) Inorganic hybrid silica hollow particles were obtained. Next, after 1.5 parts by mass of tetraethoxysilane and 70 parts by mass of methanol were mixed, 3 parts by mass of an aqueous ammonia solution (3N) was added and stirred at room temperature (25 ° C.) for 15 hours to obtain a tetraethoxysilane sol ( After preparing a solid content of 2% by mass, the hollow particles were added thereto so as to be 17% by volume to prepare a hollow particle-containing sol. On the infrared reflecting layer, the hollow particle-containing sol is coated with a die coater so as to have a dry film thickness of 10 μm, and then moisture is dried by a supercritical drying method to form silica hollow particles. A heat insulating layer was formed.

  Except this, the infrared shielding film was manufactured by the same method as Example 1.

(Example 10)
An infrared shielding film was produced in the same manner as in Example 9 except that the amount of tetraethoxysilane: methyltriethoxysilane = 1: 1 (mass ratio) was 25 parts by mass.

(Example 11)
An infrared shielding film was produced in the same manner as in Example 9 except that the amount of tetraethoxysilane: methyltriethoxysilane = 1: 1 (mass ratio) was 19 parts by mass.

(Example 12)
After obtaining an infrared absorption film by the same method as in Example 3, an infrared absorber-containing hard coat layer was further formed by the method as described below to obtain an infrared shielding film of this example.

(Formation of an infrared absorber-containing hard coat layer)
7.5 parts by mass of UV curable hard coat material (UV-7600B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is added to 90 parts by mass of methyl ethyl ketone solvent, and then a photopolymerization initiator (Irgacure (registered trademark) 184, Ciba Specialty) (Chemicals Co., Ltd.) 0.5 parts by mass was added and stirred and mixed. Next, 2 parts by mass of ATO powder (ultrafine particle ATO, manufactured by Sumitomo Metal Mining Co., Ltd.) was added and stirred at high speed with a homogenizer to prepare a coating solution for a hard coat layer.

The said coating liquid for hard-coat layers was apply | coated with the wire bar to the PET film surface on the opposite side to the side with the infrared reflective layer of PET film, and it dried with hot air at 70 degreeC for 3 minutes. Then, the infrared absorptive hard coat layer was formed in the atmosphere by curing with an irradiation amount of 400 mJ / cm ² using a UV curing apparatus (using a high-pressure mercury lamp) manufactured by iGraphics. As a result of observation by SEM, the thickness of the infrared absorbent-containing hard coat layer was 3 μm.

  FIG. 2 is a schematic cross-sectional view showing the layer structure of the infrared shielding film of this example.

(Example 13)
An infrared absorbent hard coat layer was further formed on the infrared shielding film of Example 6 by the same method as in Example 12 to obtain an infrared shielding film of this example.

(Example 14)
An infrared absorbent hard coat layer was further formed on the infrared shielding film of Example 11 by the same method as in Example 12 to obtain an infrared shielding film of this example.

(Example 15)
According to the melt extrusion method described in US Pat. No. 6,049,419, polyethylene naphthalate (PEN) TN8065S (manufactured by Teijin Chemicals Ltd.) and polymethyl methacrylate (PMMA) resin acripet (registered trademark) VH (manufactured by Mitsubishi Rayon Co., Ltd.) Are melted at 300 ° C. and laminated by extrusion, and (PMMA (152 nm) / PEN (137 nm)) 64 / (PMMA (164 nm) / PEN (148 nm)) 64 / (PMMA (177 nm) / PEN (160 nm) ) 64 / (PMMA (191 m) / PEN (173 nm)) 64 Infrared reflecting film (infrared reflecting) which was stretched about 3 times in length and width and then heat-fixed and cooled, and a total of 256 layers were alternately laminated. Layer 2) was obtained. This infrared reflective film was bonded with an adhesive onto a polyethylene terephthalate (PET) film (A4300: double-sided easy-adhesive layer, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm. Here, in the above layer structure, “(PMMA (152 nm) / PEN (137 nm)) 64” means that 64 units each having a PMMA having a thickness of 152 nm and a PEN having a thickness of 137 nm stacked in this order are stacked. It is. On the infrared reflective layer 2, the impregnated composition similar to that of Example 1 was extruded as a sheet so that the thickness after foaming was 10 μm, and then cooled to room temperature (25 ° C.) over 4 hours. The pressure was reduced to normal pressure and foamed to form a heat insulating layer made of expanded polystyrene.

(Example 16)
After obtaining an infrared reflective film (infrared reflective layer 2) by the same method as in Example 15, the PET film surface opposite to the side having the infrared reflective layer of the PET film is subjected to the following method. Then, an infrared absorber-containing hard coat layer was formed to obtain an infrared shielding film of this example.

(Formation of an infrared absorber-containing hard coat layer)
7.5 parts by mass of UV curable hard coat material (UV-7600B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is added to 90 parts by mass of methyl ethyl ketone solvent, and then a photopolymerization initiator (Irgacure (registered trademark) 184, Ciba Specialty) -0.5 parts by mass of Chemicals) and 0.1 parts by mass of Surflon (registered trademark) S-651 (manufactured by AGC Sey Chemical Co., Ltd.) were added and mixed with stirring. Next, 2 parts by mass of ATO powder (ultrafine particle ATO, manufactured by Sumitomo Metal Mining Co., Ltd.) was added and stirred at high speed with a homogenizer to prepare a coating solution for a hard coat layer.

The hard coat layer coating solution was applied with a wire bar and dried with hot air at 70 ° C. for 3 minutes. Then, the infrared absorptive hard coat layer was formed in the air | atmosphere by hardening with the irradiation amount of 400 mJ / cm < ² > with the UV hardening apparatus (uses a high pressure mercury lamp) by an i-graphics company. As a result of observation by SEM, the thickness of the infrared absorbent-containing hard coat layer was 3 μm.

(Comparative Example 1)
An infrared shielding film was produced in the same manner as in Example 1 except that the heat insulating layer was not formed. The adhesive layer was formed on the infrared reflective layer surface.

(Comparative Example 2)
The infrared shielding film was manufactured by the method similar to Example 3 except having formed the infrared reflective layer by the following method.

A polyethylene terephthalate (PET) film (A4300: double-sided easy-adhesion layer, manufactured by Toyobo Co., Ltd.) having a size of 30 cm × 30 cm and a thickness of 50 μm is placed in a vacuum tank of a vacuum deposition apparatus, and the inside of the tank is up to 10 ⁻⁵ torr (0.0013 Pa). The pressure was reduced and the film temperature was maintained at 50 ° C. Two evaporation boards were installed in the vacuum chamber, and a silver bar and indium oxide powder were placed in each of them. First, indium oxide was heated to 1200 ° C., and an indium oxide film having a thickness of 350 Å was formed at a deposition rate of 10 Å / sec. Next, the silver was heated to 1400 ° C. to form a 100 銀 silver coating on the indium oxide coating at a rate of 20 Å / sec. After forming an indium oxide film with the same film thickness again under the same conditions as above, form a silver film with the same film thickness under the same conditions as above, and finally form an indium oxide film with the same film thickness under the same conditions as above. Infrared reflective layer 2 was obtained.

(Comparative Example 3)
An infrared shielding film was produced by the same method as in Example 6 except that the infrared reflective layer was formed by the method described in Comparative Example 2 above.

(Comparative Example 4)
The amount of PVA271 to be added was changed from 5.5 parts by mass to 22.0 parts by mass, and the dry film thickness was changed from 10 μm to 20 μm. Produced. And except this heat insulation layer, it carried out similarly to Example 1, and manufactured the infrared shielding film. When the porosity of this heat insulating layer was confirmed, it was 0%.

(Evaluation)
(Porosity of thermal insulation layer, thermal conductivity)
The porosity and thermal conductivity of the heat insulating layer were measured by the above-described apparatus and method.

(Measurement of glass temperature)
The infrared shielding film obtained in each Example and each Comparative Example was attached to a 5 mm thick float plate glass and left outdoors on a sunny day of April. In that case, the glass plate was installed so that sunlight might enter from the glass side instead of the film side. At noon, the glass surface was measured at 10 points with a contact thermometer, and the average value was obtained. If it exceeds 70 ° C, the risk of thermal cracking increases.

(Evaluation of haze value)
It measured according to JISK7136: 2000 using the haze meter (HM-150, Murakami Color Research Laboratory make). A haze value of 2.0 or less is practical.

(Evaluation of infrared reflectance)
The reflectance in the region of 850 to 1150 nm was measured using a spectrophotometer (using an integrating sphere, V-670, manufactured by JASCO Corporation) for the infrared shielding film attached to a 3 mm thick float plate glass. The sample was placed so that light intrusion during the measurement came from the glass surface. The measurement was performed 3 times, the average value was calculated | required, and it was set as the infrared reflectance.

  In addition, as a forced deterioration promotion, a sunshine weather meter manufactured by Suga Test Instruments Co., Ltd. was used, and after 2000 hours exposure under the irradiation conditions and rain conditions described in JIS A5759: 1982, the infrared reflectance was similarly measured. . A film having a lower reflectivity before and after forced deterioration is a more durable infrared shielding film, and practical if the difference in reflectivity before and after forced deterioration is 5 or less.

  Table 1 shows the structures and evaluation results of the infrared shielding films obtained in each Example and each Comparative Example.

  As is clear from the results in Table 1 above, the infrared shielding film of the present invention having a heat insulating layer having voids is excellent in storage stability and transparency, has a low glass surface temperature, and has a risk of so-called thermal cracking. It turned out to be lower. In particular, the infrared shielding films of Examples 8 to 11 and 14 having a heat insulating layer having a porosity of 60 to 95% have a lower glass surface temperature. In addition, when a heat insulating layer having a porosity of 0% is provided as in Comparative Example 4, it must be provided with a considerable thickness in order to obtain a predetermined heat insulating rate, and as a result, haze only deteriorates. In addition, the infrared reflectance also decreases.

  Moreover, even if it uses the infrared shielding film which has an infrared absorption layer like Examples 12-14, it turns out that the glass surface temperature is kept low.

(Production of laminated glass)
Using the produced infrared shielding films 1 to 15, laminated glasses 1 to 15 and laminated glasses 16 to 18 using Comparative Examples 1 to 3 were respectively produced by the following methods.

  2 mm thick first glass plate, polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., ESREC (registered trademark) B) intermediate film (0.4 mm) (hereinafter referred to as PVB intermediate film), infrared shielding film, PVB An interlayer film and a second glass plate having a thickness of 2 mm were stacked, and the stacked layers were put in a vacuum bag and depressurized with a vacuum pump. The vacuum bag in a reduced pressure state was placed in an autoclave and subjected to heat and pressure treatment at 90 ° C. for 30 minutes. The inside of the autoclave is returned to atmospheric pressure and room temperature, the laminated body is taken out from the vacuum bag, heated and pressurized to 130 ° C for 30 minutes in the autoclave again, and then returned to room temperature and normal pressure to produce laminated glass. did. In the laminated glass, similar to the results obtained in Examples 12 to 14, the glass surface temperature of the sample satisfying the present invention was kept low.

  In addition, this application is based on the JP Patent application 2011-254285 for which it applied on November 21, 2011, The content of an indication is quoted as a whole by reference.

10, 20 Infrared shielding film,
11 substrate,
12 Infrared reflective layer,
13 Insulation layer,
14 Adhesive layer,
15 Separate film,
16 Infrared absorber-containing hard coat layer.

Claims (14)

An infrared reflective layer having at least one unit comprising a high refractive index layer containing a first polymer and a low refractive index layer containing a second polymer on a substrate;
A heat insulating layer having a void on at least one side of the substrate;
An infrared shielding film having: The high refractive index layer includes a first water-soluble polymer and first metal oxide particles,
The infrared shielding film according to claim 1, wherein the low refractive index layer includes a second water-soluble polymer and second metal oxide particles.   The infrared shielding film of Claim 1 or 2 in which the heat insulation layer which has the said space | gap contains an inorganic oxide particle.   The infrared shielding film of any one of Claims 1-3 whose porosity of the heat insulation layer which has the said space | gap is 60 to 95%.   Furthermore, the infrared shielding film of any one of Claims 1-4 which has an infrared absorption layer.   The infrared shielding film according to claim 5, wherein the infrared absorption layer includes an infrared absorber and a cured binder.   The infrared shielding film according to claim 5 or 6, wherein the infrared absorption layer contains fluorine.   The infrared shielding film according to claim 5, wherein the infrared absorption layer has a thickness of 1 to 20 μm.   The infrared shielding film of any one of Claims 1-8 whose heat conductivity of the heat insulation layer which has the said space | gap is 0.001-0.2 W / (m * K).   The infrared shielding film according to claim 9, wherein the heat conductivity of the heat insulating layer having voids is 0.005 to 0.15 W / (m · K).   The infrared shielding according to any one of claims 1 to 10, wherein a lowermost layer of the infrared reflecting layer closest to the base material and an uppermost layer of the infrared reflecting layer are both low refractive index layers. the film.   The infrared shielding body which provides the infrared shielding film of any one of Claims 1-11 in the at least one surface of a base | substrate.   The infrared shielding glass in which the heat insulation layer which has the said space | gap of any one of Claims 1-11 is arrange | positioned in the position close | similar to glass rather than the said infrared reflective layer.   The laminated glass in which the infrared shielding film of any one of Claims 1-11 is provided between 1st glass and 2nd glass.

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