JPWO2014199872A1 - Infrared shielding film, infrared shielding body using the same and heat ray reflective laminated glass - Google Patents

Abstract

An infrared shielding film having excellent heat shielding performance while reducing the angle dependency of color tone is provided. A dielectric multilayer film including a high refractive index layer and a low refractive index layer, and a hard coat layer, wherein a * in the L * a * b * color system is a * ≦ −3.5. And the infrared shielding film whose b * is -12 <= b * <= 5. [Selection figure] None

Description

  The present invention relates to an infrared shielding film, an infrared shielding body using the same, and a heat ray reflective laminated glass.

  The light emitted from the sun has a wide spectrum from the ultraviolet region to the infrared light region. Among these, infrared light occupies about 50% of sunlight, and the infrared light mainly includes near infrared light having a wavelength close to visible light (wavelength of about 750 to 2500 nm) and mid-infrared light having a wavelength longer than that. (About 2500 to 4000 nm) and far infrared rays (wavelength of about 4000 nm or more). Such infrared light has a long wavelength compared to ultraviolet light, so its energy is small. On the other hand, its thermal effect is large, and when it is absorbed by a substance, it is released as heat and causes a temperature rise. For this reason, infrared light is also called heat rays, and by reflecting infrared light, for example, an increase in indoor temperature can be suppressed.

  In recent years, with the growing interest in energy conservation measures, the film that reflects infrared light is attached to the window glass of buildings and vehicles, and the load on the cooling equipment is reduced by reflecting the transmission of solar heat rays. An attempt is being made. On the other hand, if such an infrared shielding film reflects visible light having a wavelength close to that of infrared light, the transparency of the film cannot be secured and the film is colored. Therefore, it can be said that an infrared shielding film that selectively reflects infrared light and transmits visible light is preferable.

  Such an infrared shielding film capable of selectively reflecting infrared light and transmitting visible light is usually a low refractive index layer having a relatively low refractive index and a relatively high refractive index. And a high-refractive index layer having a dielectric multilayer film. At this time, for the high refractive index layer and the low refractive index layer, infrared light can be selectively reflected by controlling the optical film thickness, which is the product of the refractive index and the film thickness, to cause interference.

  By the way, as described above, since the infrared shielding film is attached to the window glass of a building or a vehicle, the hard coat layer is used for the purpose of preventing the surface from being scratched during cleaning. Sometimes formed.

As a technique related to the hard coat layer, for example, Japanese Patent Application Laid-Open No. 2010-191969 discloses a transparent hard coat film having a transparent hard coat film composed of a cured product of a coating liquid containing an ionizing radiation curable resin and a blue inorganic pigment. An invention relating to a coat film is described. According to JP 2010-191969 discloses, ^{L *} values in the material of the film thickness and the ^L * ^a * ^{b *} color system constituting the transparent hard coat film, ^{a *} value, and ^{b *} controls the value of By doing so, it is described that a desired hue can be obtained.

  The above-mentioned infrared shielding film has an optical film thickness controlled so that infrared rays can be selectively reflected. However, it has been found that the infrared shielding film in which the control of the optical film thickness is controlled may have a different color tone depending on the viewing angle.

  For such an angle dependency of the color tone, it is conceivable to adjust the color tone by providing the infrared shielding film with a hard coat layer described in JP2010-191969A. However, the technique disclosed in Japanese Patent Application Laid-Open No. 2010-191969 prevents interference fringes caused by uneven thickness of the hard coat layer, and is effective for reducing the angle dependency of the color tone based on the dielectric multilayer film. I can't say that.

  Further, from the viewpoint of preventing the angle dependency of the color tone, it is also conceivable to use an infrared shielding film that does not use a dielectric multilayer film. However, sufficient heat shielding performance cannot be obtained with such an infrared shielding film.

  Then, an object of this invention is to provide the infrared shielding film which is excellent in heat-shielding performance, reducing the angle dependency of a color tone.

As a result of intensive studies, the present inventors have found that the above problem can be solved by controlling the values of a ^* and b ^* in the L ^* a ^* b ^* color system of an infrared shielding film provided with a hard coat layer. The inventors have found that this can be solved, and have completed the present invention.

  That is, the said subject of this invention is achieved by the following means.

(1) and the dielectric multi-layer film comprising a high refractive index layer and the low refractive index layer comprises a hard coat layer, ^a, L ^* a * ^{b * a} in the color system ^* is ^{a *} ≦ -3.5, And b ^* is −12 ≦ b ^* ≦ 5;
(2) The infrared shielding film according to (1), wherein b ^* is −12 ≦ b ^* ≦ 2.
(3) The infrared shielding film according to (1) or (2), wherein at least one of the high refractive index layer and the low refractive index layer contains metal oxide particles;
(4) The infrared shielding film according to any one of (1) to (3), wherein the hard coat layer includes an infrared absorber;
(5) The infrared shielding film according to any one of (1) to (4), wherein the hard coat layer contains at least one of a pigment and a dye;
(6) An infrared shielding body comprising a base and the infrared shielding film according to any one of (1) to (5) disposed on at least one surface of the base;
(7) The infrared shielding film according to any one of (1) to (5), a pair of intermediate films that sandwich the infrared shielding film, and the infrared shielding film and the intermediate film are sandwiched. A heat ray reflective laminated glass comprising a pair of plate glasses.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

According to one aspect of the present invention, there is provided an infrared shielding film including a dielectric multilayer film including a high refractive index layer and a low refractive index layer, and a hard coat layer. In this case, ^{a *} in ^{the L} * ^a * ^{b *} color system of the infrared shielding film is ^{a *} ≦ -3.5, and wherein the ^{b *} is -12 ≦ ^{b *} ≦ 5 . According to the infrared shielding film which concerns on this form, the infrared shielding film which is excellent in heat-shielding performance can be provided, reducing the angle dependence of a color tone.

<Infrared shielding film>
The infrared shielding film includes a dielectric multilayer film and a hard coat layer. In addition, you may have a base material, an intermediate | middle layer, another functional layer, etc. as needed.

In the infrared shielding film, the value of a ^{* and} the value of b ^{* in} the L ^* a ^* b ^* color system are controlled. Here, “L ^* a ^* b ^* color system” was developed by the International Commission on Illumination (CIE). “L ^* ” is called “lightness index” and indicates lightness, and “a ^* ” and “b ^* ” are called “chromicness index” and indicate positions corresponding to hue and saturation. Is. Regarding the hue and saturation, if the value of a ^* is negative, the color is green, and if the value of a ^* is positive, the color is red. If the value of b ^* is negative, the color is blue. If the value of b ^* is positive, the color is yellow.

In this embodiment, the value of a ^* in the L ^* a ^* b ^* color system is −3.5 or less (a ^* ≦ −3.5), preferably −10 to −3.5 (−10 ≦ a ^* ≦ −3.5), more preferably −5.0 to −3.5 (−5.0 ≦ a ^* ≦ −3.5).

The value of b ^* in the L ^* a ^* b ^* color system is −12 to 5 (−12 ≦ b ^* ≦ 5), preferably −12 to 2 (−12 ≦ b ^* ≦ 2). Yes, more preferably −10 to −1.0 (−10 ≦ b ^* ≦ −1.0).

The combinations of the values of a ^* and b ^{* in} the L ^* a ^* b ^* color system are a ^* ≦ −3.5 and −12 ≦ b ^* ≦ 5, preferably a ^* ≦ −. 3.5 and −12 ≦ b ^* ≦ 2, more preferably −5.0 ≦ a ^* ≦ −3.5 and −10 ≦ b ^* ≦ −1.0.

The value of L ^* is not particularly limited, but is preferably 80 or more, and more preferably 80 to 90. It is preferable that the value of L ^* is 80 or more because the transmittance can be increased.

In this specification, the “a ^* value”, “b ^* value”, and “L ^* value” in the L ^* a ^* b ^* color system are the spectrophotometer U-4100 (manufactured by Shimadzu Corporation). The value obtained by measuring the transmittance in the visible light region (360 to 740 nm) is used.

  As described above, the optical film thickness of the infrared shielding film having the dielectric multilayer film in which the high refractive index layer and the low refractive index layer are laminated is controlled so that infrared rays can be selectively reflected. Specifically, the optical film thickness is adjusted to be ¼ of the desired wavelength. For this reason, the longer the optical film thickness, the longer the wavelength of light is reflected. When the light is incident on the dielectric multilayer film from an oblique direction, the optical film thickness is relatively increased as compared with the case where the light is incident vertically. As a result, compared with the case where the infrared shielding film is viewed from the front, a red color based on long wavelength light can be observed when viewed from an oblique direction.

In this embodiment, the color tone depending on the observation angle is controlled by controlling the a ^* value and b ^* in the L ^* a ^* b ^* color system of the infrared shielding film in which the hard coat layer is provided on the dielectric multilayer film. Changes can be prevented. Note that the value of a ^{* and} the value of b ^* tend to decrease by reducing the optical film thickness of the dielectric multilayer film. Moreover, the value of a ^* tends to decrease by adding a green pigment or dye to the hard coat layer. Furthermore, the value of b ^* tends to decrease by adding a blue pigment or dye to the hard coat layer.

  At this time, the degree of color tone change depending on the observation angle can be evaluated using the reflectance. Specifically, the change in color tone depending on the observation angle is evaluated by comparing the regular reflectance with an incident angle of 5 degrees with the regular reflectance with an incident angle of 60 degrees with respect to the normal of the dielectric multilayer film. can do. At this time, the wavelength of the irradiated light is 730 nm. In addition, in this specification, the value measured using the spectrophotometer U-4100 (made by Shimadzu Corporation) shall be employ | adopted for the value of "regular reflectance".

  It should be noted that such a reduction in the angle dependency of the color tone is only an estimation, and even if the reduction in the angle dependency of the color tone is realized by other mechanisms, it is included in the technical scope of the present invention. It is.

[Dielectric multilayer film]
The dielectric multilayer film includes a high refractive index layer and a low refractive index layer. The dielectric multilayer film includes a refractive index layer having a different refractive index, so that when infrared light is irradiated, at least part of the infrared light is reflected and an infrared shielding effect is exhibited. it can.

  In this embodiment, whether the refractive index layer constituting the dielectric multilayer film is a high refractive index layer or a low refractive index layer is determined by comparing the refractive index with the adjacent refractive index layer. Specifically, when a refractive index layer is used as a reference layer, if the refractive index layer adjacent to the reference layer has a lower refractive index than the reference layer, the reference layer is a high refractive index layer (the adjacent layer is a low refractive index layer). It is judged to be a rate layer. On the other hand, if the refractive index of the adjacent layer is higher than that of the reference layer, it is determined that the reference layer is a low refractive index layer (the adjacent layer is a high refractive index layer). Therefore, whether the refractive index layer is a high refractive index layer or a low refractive index layer is a relative one determined by the relationship with the refractive index of the adjacent layer. Depending on the relationship, it can be a high refractive index layer or a low refractive index layer.

  Although there is no restriction | limiting in particular as a refractive index layer, It is preferable to use the well-known refractive index layer used in the said technical field preferably. As a known refractive index layer, for example, a refractive index layer formed using a dry film forming method, a refractive index layer formed by extrusion molding of a resin, and a refractive index layer formed using a wet film forming method Is mentioned.

  As described above, whether the layer is a low refractive index layer or a high refractive index layer is a relative one that is determined by the relationship with the adjacent refractive index layer. The structure of a typical high refractive index layer and low refractive index layer among the refractive index layers that can be formed by the respective methods will be described below.

(Refractive index layer formed using dry film formation method)
In the dry film forming method, the refractive index layer can be formed by evaporating a dielectric material.

High Refractive Index Layer The material of the high refractive index layer in this embodiment is not particularly limited, but is preferably a transparent dielectric material. Specific examples include titanium oxide (TiO ₂ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), niobium oxide (Nb ₂ O ₅ ), aluminum oxide (Al ₂ O ₃ ), and the like. Of these, the material of the high refractive index layer is preferably titanium oxide or zinc oxide. In addition, the material of said high refractive index layer may be used independently, or may be used in combination of 2 or more type.

Low Refractive Index Layer The material of the low refractive index layer is not particularly limited, but is preferably a transparent dielectric material. Specific examples include silicon oxide (SiO ₂ ), calcium fluoride (CaF ₂ ), magnesium fluoride (MgF ₂ ), indium tin oxide (ITO), antimony tin oxide (ATO), and the like. Of these, the material of the low refractive index layer is preferably silicon oxide or magnesium fluoride. In addition, the material of said low refractive index layer may be used independently, or may be used in combination of 2 or more type.

(Refractive index layer formed by resin extrusion)
Examples of a method for forming a refractive index layer formed by resin extrusion include a method in which a molten resin obtained by melting a resin is extruded onto a casting drum from a multilayer extrusion die and then rapidly cooled. At this time, after extruding and cooling the molten resin, the resin sheet may be stretched. The stretching ratio of the resin can be appropriately selected according to the resin, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

Refractive Index Layer In this embodiment, a high refractive index layer and a low refractive index layer will be described together as a refractive index layer.

  The resin constituting the refractive index layer is not particularly limited as long as it is a thermoplastic resin. For example, polyalkylene resin, polyester resin, polycarbonate resin, (meth) acrylic resin, amide resin, silicone resin And fluorine-based resins.

  Examples of the polyalkylene resin include polyethylene (PE) and polypropylene (PP).

Examples of the polyester resin include polyester resins having a dicarboxylic acid component and a diol component as main components. At this time, the dicarboxylic acid component includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexane. Examples include dicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-butanediol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4- Hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol fluorange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like. Among these, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene naphthalate (PEN) are preferable.

  Examples of the polycarbonate resin include a reaction product of bisphenol A or a bisphenol that is a derivative thereof with phosgene or phenyl dicarbonate.

  Examples of the (meth) acrylic resin include acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid-2. -Ethylhexyl, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) 2-butoxyethyl acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -Isopropyl (meth) acrylamide, N-tert-oct Le (meth) homopolymers or copolymers of acrylamide.

  Examples of the amide resins include aliphatic amide resins such as 6,6-nylon, 6-nylon, 11-nylon, 12-nylon, 4,6-nylon, 6,10-nylon, and 6,12-nylon; An aromatic polyamide such as an aromatic diamine such as phenylenediamine and an aromatic dicarboxylic acid such as terephthaloyl chloride or isophthaloyl chloride or a derivative thereof may be used.

  Examples of the silicone resin include resins containing a siloxane bond having an organic group such as an alkyl group or an aromatic group as a structural unit. The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The aromatic group is not particularly limited, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Among these, those having a methyl group and / or a phenyl group are preferable, and dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and modified products thereof are more preferable.

  Examples of the fluororesin include homopolymers or copolymers such as tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and perfluoroalkyl vinyl ether.

  The above-described resins may be used alone or in combination of two or more.

  In the formation of the refractive index layer using extrusion molding of a molten resin, a preferable material combination of a high refractive index layer and a low refractive index layer includes PET-PEN and the like.

(Refractive index layer formed by wet film formation method)
In the wet film forming method, the refractive index layer can be formed by a method of sequentially applying and drying a coating solution, a method of applying and drying a coating solution in multiple layers, or the like.

High refractive index layer The high refractive index layer includes a first water-soluble resin. In addition, the first metal oxide particles, a curing agent, a surfactant, and other additives may be included as necessary.

(1) First water-soluble resin The first water-soluble resin is not particularly limited, and polyvinyl alcohol resins, gelatin, celluloses, thickening polysaccharides, and polymers having reactive functional groups can be used. . Of these, it is preferable to use a polyvinyl alcohol-based resin. In the present specification, “water-soluble” means a G2 glass filter (maximum pores 40 to 40) when dissolved in water at a temperature at which the polymer is most dissolved at a concentration of 0.5% by mass. Means that the mass of the insoluble matter to be filtered out is within 50% by mass of the added polymer.

Polyvinyl alcohol resin As the polyvinyl alcohol resin, ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate (unmodified polyvinyl alcohol), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, vinyl alcohol Examples thereof include modified polyvinyl alcohol such as a polymer. The modified polyvinyl alcohol may improve the film adhesion, water resistance, and flexibility.

  As the polyvinyl alcohol (unmodified polyvinyl alcohol), a synthetic product or a commercially available product may be used. Commercially available products include PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA-203, PVA-205, PVA-210, PVA-217, PVA -220, PVA-224, PVA-235 (manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04, JF-05, JP-03, JP-04JP-05, JP-45 (Nippon Vinegar & Poval Co., Ltd.).

  Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A No. 61-10383 in the main chain or side chain of the polyvinyl alcohol. And polyvinyl alcohol. The cation-modified polyvinyl alcohol 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-acrylamide-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamide-3,3-dimethylpropyl). ) Ammonium chloride, N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamideamidopropyl) ammonium chloride, N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide and the like. The ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is preferably 0.1 to 10 mol%, more preferably 0.2 to 5 mol% with respect to vinyl acetate.

  Examples of the anion-modified polyvinyl alcohol include polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681, and JP-A-63-330779. And copolymers of vinyl alcohol and a vinyl compound having a water-soluble group as described in JP-A-7-285265, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.

  Further, as nonionic modified polyvinyl alcohol, 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, JP-A-8-25795 Reactive group modification having reactive groups such as block copolymers of vinyl compounds having a hydrophobic group and vinyl alcohol, silanol modified polyvinyl alcohol having silanol groups, acetoacetyl group, carbonyl group, carboxy group Polyvinyl alcohol etc. are mentioned.

  It is also preferable to use a polyvinyl alcohol-based water-soluble polymer. Examples of the polyvinyl alcohol-based water-soluble polymer include EXEVAL (registered trademark, manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (registered trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

Gelatin As the gelatin, various gelatins conventionally used widely in the field of silver halide photographic light-sensitive materials can be applied. For example, acid-treated gelatin, alkali-treated gelatin, enzyme-treated gelatin that undergoes enzyme treatment in the production process of gelatin, a group having an amino group, imino group, hydroxyl group, carboxyl group as a functional group in the molecule, and a group that can react with it And gelatin derivatives modified by treatment with a reagent having

  The general method for producing gelatin is well known, for example, see T.W. H. James: The Theory of Photographic Process 4th. ed. Reference can be made to descriptions such as 1977 (Macmillan) 55, Science Photo Handbook (above) 72-75 (Maruzen), Fundamentals of Photographic Engineering-Silver Salt Photo Hen 119-124 (Corona). Also, Research Disclosure Magazine Vol. 176, No. And gelatin described in Section IX of 17643 (December, 1978).

  When gelatin is used, a gelatin hardener can be added as necessary.

Cellulose As the cellulose, a water-soluble cellulose derivative can be preferably used. For example, water-soluble cellulose derivatives such as carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; carboxylic acid group-containing celluloses such as carboxymethyl cellulose (cellulose carboxymethyl ether) and carboxyethyl cellulose; Examples thereof include cellulose derivatives such as cellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.

Thickening polysaccharide The thickening polysaccharide is a polymer of saccharides and has many hydrogen bonding groups in the molecule. The thickening polysaccharide has a characteristic that the viscosity difference at low temperature and the viscosity at high temperature are large due to the difference in hydrogen bonding force between molecules depending on temperature. Further, when metal oxide fine particles are added to the thickening polysaccharide, the viscosity is increased due to hydrogen bonding with the metal oxide fine particles at a low temperature. As for the viscosity increase range, the viscosity at 15 ° C. is usually 1.0 mPa · s or more, preferably 5.0 mPa · s or more, more preferably 10.0 mPa · s or more.

  The thickening polysaccharide that can be used is not particularly limited and includes generally known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. For details of these polysaccharides, reference can be made to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p.

  Specific examples of thickening polysaccharides include, for example, galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, etc.), glucomanno Glycan (for example, potato mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (for example, softwood-derived glycan), arabinogalactoglycan (for example, soybean-derived glycan, microorganism-derived glycan, etc.) Derived from red algae such as glycans (eg gellan gum), glycosaminoglycans (eg hyaluronic acid, keratan sulfate, etc.), alginic acid and alginates, agar, κ-carrageenan, λ-carrageenan, ι-carrageenan Natural height Polysaccharides, and the like. Among these, in the case where the high refractive index layer contains metal oxide fine particles described later, from the viewpoint of not lowering the dispersion stability of the coating liquid for forming the high refractive index layer, a carboxylic acid group or sulfonic acid is used as the structural unit. It is preferable that it does not have a group. Examples of such thickening polysaccharides include 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. The polysaccharide which consists only of is mentioned. Specifically, tamarind seed gum known as xyloglucan whose main chain is glucose and side chain is glucose; guar gum and cationized guar gum known as galactomannan whose main chain is mannose and side chain is glucose , Hydroxypropyl guar gum, locust bean gum, tara gum; it is preferable to use arabinogalactan whose main chain is galactose and whose side chain is arabinose. Of these, it is particularly preferable to use tamarind, guar gum, cationized guar gum, or hydroxypropyl guar gum.

Polymer having reactive functional group Examples of the polymer having reactive functional group include polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic acid. Acrylic resins such as ester copolymers and acrylic acid-acrylic acid ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- Styrene acrylic resin such as α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer; styrene-sodium styrenesulfonic acid copolymer, styrene-2-hydroxyethyl Acrylate copolymer Len-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer And vinyl acetate copolymers such as vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer; and salts thereof. Of these, polyvinylpyrrolidones and copolymers containing the same are preferably used.

  The water-soluble resins described above may be used alone or in combination of two or more.

  A preferable example of the first water-soluble polymer is a polyvinyl alcohol resin.

  The polymerization degree of the polyvinyl alcohol-based resin is preferably 1000 or more, more preferably 1500 to 5000, and still more preferably 2000 to 5000. When the degree of polymerization is 1000 or more, the crack resistance of the coating film during formation of the refractive index layer is improved, which is preferable. In the present specification, “degree of polymerization” refers to the viscosity average degree of polymerization, and a value measured according to JIS-K6726 (1994) is adopted. Specifically, after the polyvinyl alcohol-based resin is completely re-saponified and purified, the intrinsic viscosity [η] (dl / g) measured in water at 30 ° C. can be obtained by the following formula.

  In the above formula, in the above formula, P represents the degree of polymerization, and η represents the intrinsic viscosity.

  Other preferable examples of the first water-soluble resin include water-soluble resins other than polyvinyl alcohol resins having a mass average molecular weight of 1,000 to 200,000, and more preferably a mass average molecular weight of 3,000 to 40,000. In this specification, the value measured by gel permeation chromatography (GPC) is adopted as the value of “mass average molecular weight”.

  The content of the first water-soluble resin is preferably 5 to 50% by mass and more preferably 10 to 40% by mass with respect to 100% by mass of the solid content of the high refractive index layer.

(2) First metal oxide particles The first metal oxide particles mean metal oxide particles that can be contained in the high refractive index layer.

  Although it does not restrict | limit especially as a 1st metal oxide particle, It is preferable that it is a metal oxide particle whose refractive index is 2.0-3.0. Specifically, titanium oxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, water Examples thereof include magnesium oxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. Among these, the first metal oxide particles are preferably titanium oxide or zirconium oxide from the viewpoint of forming a transparent and high refractive index layer having a high refractive index. From the viewpoint of improving weather resistance, the first metal oxide particles are preferably a rutile type (tetragonal type). ) Titanium oxide is more preferable.

  The titanium oxide may be in the form of core / shell particles coated with a silicon-containing hydrated oxide. The core / shell particles have a structure in which the surface of the titanium oxide particles is coated with a shell made of a silicon-containing hydrated oxide on titanium oxide serving as a core. In this case, the volume average particle size of the titanium oxide particles serving as the core portion is preferably more than 1 nm and less than 30 nm, and more preferably 4 nm or more and less than 30 nm. By including such core / shell particles, the intermixing of the high refractive index layer and the low refractive index layer can be suppressed by the interaction between the silicon-containing hydrated oxide of the shell layer and the water-soluble resin. .

  The first metal oxide particles described above may be used alone or in combination of two or more.

  The content of the first metal oxide particles is 15 to 80% by mass with respect to 100% by mass of the solid content of the high refractive index layer from the viewpoint of increasing the refractive index difference from the low refractive index layer. Preferably, it is 20-77 mass%, More preferably, it is 30-75 mass%.

  The first metal oxide particles preferably have a volume average particle size of 30 nm or less, more preferably 1 to 30 nm, and even more preferably 5 to 15 nm. A volume average particle size of 30 nm or less is preferable because it has less haze and is excellent in visible light transmittance. In the present specification, the value measured by the following method is adopted as the value of “volume average particle diameter”. Specifically, arbitrary 1000 particles appearing on the cross section or surface of the refractive index layer are observed with an electron microscope to measure the particle size, and particles having particle sizes of d1, d2,. In the group of n1, n2... Ni... Nk metal oxide particles, where the volume per particle is vi, the volume average particle size (mv) is calculated by the following formula.

(3) Curing Agent The curing agent has a function of reacting with a water-soluble resin (preferably a polyvinyl alcohol-based resin) contained in the high refractive index layer to form a hydrogen bond network.

  The curing agent is not particularly limited as long as it causes a curing reaction with the first water-soluble resin, but in general, a compound having a group capable of reacting with the water-soluble resin or a different group possessed by the water-soluble resin. The compound which accelerates | stimulates mutual reaction is mentioned.

  As a specific example, when polyvinyl alcohol is used as the first water-soluble resin, it is preferable to use boric acid and its salt as a curing agent. Moreover, you may use well-known hardening | curing agents other than boric acid and its salt. Examples of the known curing agents include epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde-based curing agents (for example, formaldehyde, glioxal, etc.), active halogen-based curing agents (2,4-dichloro-4-hydroxy-1,3) , 5, -s-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.

  In addition, boric acid and its salt mean the oxygen acid which has a boron atom as a central atom, and its salt. Specific examples include orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, octaboric acid, and salts thereof.

  The content of the curing agent is preferably 1 to 10% by mass and more preferably 2 to 6% by mass with respect to 100% by mass of the solid content of the high refractive index layer.

  In particular, when polyvinyl alcohol is used as the first water-soluble binder resin, the total amount of the curing agent is preferably 1 to 600 mg per 1 g of polyvinyl alcohol, and more preferably 100 to 600 mg per 1 g of polyvinyl alcohol. preferable.

(4) Surfactant The surfactant is not particularly limited, and examples thereof include amphoteric surfactants, cationic surfactants, anionic surfactants, and nonionic surfactants. Among these, betaine-type zwitterionic surfactants, quaternary ammonium salt-type cationic surfactants, fluorine-type cationic surfactants, dialkylsulfosuccinate-type anionic surfactants, acetylene glycol-type nonionic interfaces It is preferred to use an activator.

(5) Other additives Examples of other additives include amino acids, emulsion resins, and lithium compounds. Further, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, JP-A-62-261476; JP-A-57-74192, JP-A-57-87989 Japanese Patent Laid-Open No. 60-72785, Japanese Patent Laid-Open No. 61-14659, Japanese Patent Laid-Open No. 1-95091, Japanese Patent Laid-Open No. 3-13376, etc .; Japanese Patent Laid-Open No. 59-42993 , Whitening agents described in JP-A-59-52689, JP-A-62-280069, JP-A-61-228771, JP-A-4-219266, etc .; sulfuric acid, phosphoric acid, PH adjusters such as acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate; antifoaming agents; lubricants such as diethylene glycol; antiseptics; antifungal agents; antistatic agents; matting agents; Antioxidant; flame retardants; crystal nucleating agent; inorganic particles; organic particles; viscosity reducers; lubricants; infrared absorber; dyes; known various additives such as a pigment or the like may be used as other additives.

Low refractive index layer The low refractive index layer contains a second water-soluble resin. In addition, the second metal oxide particles, a curing agent, a surfactant, other additives, and the like may be included as necessary.

(1) Second water-soluble resin The second water-soluble resin may be the same as the first water-soluble resin.

  At this time, when the high refractive index layer and the low refractive index layer both use a polyvinyl alcohol-based resin as the first water-soluble resin and the second water-soluble resin, the polyvinyl alcohol-based resins having different degrees of saponification are used. It is preferable to use a resin. Thereby, mixing of the interface is suppressed, the infrared reflectance (infrared shielding rate) becomes better, and the haze can be lowered. In the present specification, the “degree of saponification” means the ratio of hydroxy groups to the total number of acetyloxy groups (derived from vinyl acetate as a raw material) and hydroxy groups in polyvinyl alcohol.

  The difference in the absolute value of the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer and the low refractive index layer is preferably 3 mol% or more, and more preferably 5 mol% or more. When the difference between the absolute values of the saponification degree is 3 mol% or more, the interlayer mixed state of the high refractive index layer and the low refractive index layer can be brought to a preferable level. The difference in absolute value of the saponification degree is preferably as large as possible, but from the viewpoint of solubility of polyvinyl alcohol in water, the difference in absolute value of the saponification degree is preferably 20 mol% or less. .

  The saponification degree of the polyvinyl alcohol-based resin contained in the high refractive index layer and the low refractive index layer is preferably 75 mol% or more from the viewpoint of solubility in water. The saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer and the low refractive index layer is 90 mol% or more for one refractive index layer and 90 mol% for the other refractive index layer. The saponification of one refractive index layer is preferably 90 mol% or less, and the saponification degree of the refractive index layer is more preferably 95 mol% or more. It is preferable that the degree of saponification of the polyvinyl alcohol-based resin in the high refractive index layer and the low refractive index layer is in the above relationship because the intermixed state of the high refractive index layer and the low refractive index layer can be brought to a preferable level. In addition, the upper limit of the saponification degree of the polyvinyl alcohol-based resin is not particularly limited, but is preferably less than 100 mol%, and more preferably 99.9 mol% or less.

  In addition, when the high refractive index layer and / or the low refractive index layer contains two or more kinds of polyvinyl alcohol resins having different saponification degrees and polymerization degrees, the saponification degree and the polymerization degree are determined in the refractive index layer. It means the saponification degree and polymerization degree of the polyvinyl alcohol resin having the highest content.

  Here, when determining the “polyvinyl alcohol resin having the highest content in the refractive index layer”, the polyvinyl alcohol resin having a difference in saponification degree of 3 mol% or less is regarded as the same polyvinyl alcohol resin. to decide. However, a low polymerization degree polyvinyl alcohol having a polymerization degree of 1000 or less is handled as a different polyvinyl alcohol. That is, even if there is a low polymerization degree polyvinyl alcohol having a difference in saponification degree within 3 mol%, the low polymerization degree polyvinyl alcohol is not treated as the same polyvinyl alcohol. Specifically, when polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 mass%, 40 mass%, and 50 mass%, respectively. The three polyvinyl alcohols are the same polyvinyl alcohol, and the mixture of these three is the “polyvinyl alcohol resin having the highest content in the refractive index layer”.

  The “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” may be 3 mol% or less when attention is paid to any polyvinyl alcohol. For example, 90 mol%, 91 mol%, 92 mol%, 94 mol% When the polyvinyl alcohol is included, since the difference in the saponification degree of any polyvinyl alcohol is within 3 mol% when paying attention to 91 mol% of the polyvinyl alcohol, they all become the same polyvinyl alcohol.

  When polyvinyl alcohol having a saponification degree different by 3 mol% or more is contained in the same layer, it is regarded as a mixture of different polyvinyl alcohols, and the polymerization degree and the saponification degree are calculated for each. For example, PVA203: 5% by mass, PVA117: 25% by mass, PVA217: 10% by mass, PVA220: 10% by mass, PVA224: 10% by mass, PVA235: 20% by mass, PVA245: 20% by mass, most contained A large amount of PVA (polyvinyl alcohol) is a mixture of PVA 217 to 245 (the difference in the degree of saponification of PVA 217 to 245 is within 3 mol%, which is the same polyvinyl alcohol). It becomes a “polyvinyl alcohol resin having a high content”. The polymerization degree in the mixture of PVA 217 to 245 is (1700 × 0.1 + 2000 × 0.1 + 2400 × 0.1 + 3500 × 0.2 + 4500 × 0.7) /0.7=3200, and the saponification degree is 88 mol%. .

  As a water-soluble resin, when polyvinyl alcohol with a low saponification degree is used for the high refractive index layer and polyvinyl alcohol with a high saponification degree is used for the low refractive index layer, It is preferable that it is 40-100 mass% with respect to the total mass of all the polyvinyl alcohol-type resins in a high refractive index layer, and it is more preferable that it is 60-95 mass%. Further, the “polyvinyl alcohol resin having the highest content in the refractive index layer” in the low refractive index layer is 40 to 100% by mass with respect to the total mass of all polyvinyl alcohol resins in the low refractive index layer. Preferably, it is 60-95 mass%.

  On the other hand, as a water-soluble resin, when polyvinyl alcohol having a high saponification degree is used for the high refractive index layer and polyvinyl alcohol having a low saponification degree is used for the low refractive index layer, The polyvinyl alcohol resin having the highest content in the high refractive index layer is preferably 40 to 100% by mass and more preferably 60 to 95% by mass with respect to the total mass of all the polyvinyl alcohol resins in the high refractive index layer. preferable. Further, the “polyvinyl alcohol resin having the highest content in the refractive index layer” in the low refractive index layer is 40 to 100% by mass with respect to the total mass of all polyvinyl alcohol resins in the low refractive index layer. Preferably, it is 60-95 mass%.

(2) Second metal oxide particles The second metal oxide particles mean typical metal oxide particles that can be contained in the low refractive index layer.

  Although it does not restrict | limit especially as said 2nd metal oxide particle, It is preferable to use silica (silicon dioxide), such as synthetic amorphous silica and colloidal silica, and it is more preferable to use acidic colloidal silica sol. Further, from the viewpoint of further reducing the refractive index, hollow fine particles having pores inside the particles can be used as the second metal oxide particles, and it is particularly preferable to use hollow fine particles of silica (silicon dioxide). .

  The colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer. For example, JP-A-57-14091 JP, 60-219083, JP 60-219084, JP 61-20792, JP 61-188183, JP 63-17807, JP 4-194 No. 93284, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142 In Japanese Laid-Open Patent Publication No. 7-179029, No. 7-137431, and International Publication No. 94/26530. Than is.

  Such colloidal silica may be a synthetic product or a commercially available product. Examples of commercially available products include the Snowtex series (Snowtex OS, OXS, S, OS, 20, 30, 40, O, N, C, etc.) sold by Nissan Chemical Industries, Ltd.

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

  The second metal oxide particles may be surface-coated with a surface coating component.

  The first metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer of the present invention preferably have an average particle size (number average; diameter) of 3 to 100 nm, preferably 3 to 50 nm. It is more preferable. In the present specification, the “average particle diameter (number average; diameter)” of the metal oxide fine particles is 1,000 particles observed by an electron microscope on the particles themselves or on the cross section or surface of the refractive index layer. The particle size of any of the particles is measured and determined as a simple average value (number average). Here, the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.

  When hollow particles are used as the second metal oxide particles, the average particle pore size is preferably 3 to 70 nm, more preferably 5 to 50 nm, and further preferably 5 to 45 nm. . When the average particle pore diameter of the hollow particles is in the above range, the refractive index of the low refractive index layer is sufficiently lowered. In the present specification, the “average particle pore diameter of the hollow particles” is an average value of the inner diameters of the hollow particles. In addition, the value of “average particle pore diameter” is determined by observing 50 or more random pore diameters that can be observed as a circle, an ellipse, or substantially a circle or an ellipse by electron microscope observation. And the value obtained by obtaining the number average value thereof is adopted. In this case, the “average particle hole diameter” means the minimum distance among the distances between the outer edges of the hole diameter that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines. To do.

  The content of the second metal oxide particles in the low refractive index layer is preferably 0.1 to 75% by mass and 30 to 70% by mass with respect to 100% by mass of the total solid content of the low refractive index layer. It is more preferable that it is 45-65 mass%.

  The above-mentioned second metal oxide may be used alone or in combination of two or more from the viewpoint of adjusting the refractive index.

(3) Curing Agent, Surfactant, and Other Additives As the curing agent, the surfactant, and other additives, the same materials as those for the high refractive index layer can be used, and thus the description thereof is omitted here.

  In the dielectric multilayer film including the high refractive index layer and the low refractive index layer that can have the above-described configuration, at least one of the high refractive index layer and the low refractive index layer is formed by a wet film forming method. The refractive index layer is preferable, and both the high refractive index layer and the low refractive index layer are more preferably refractive index layers formed by a wet film forming method. Furthermore, it is preferable that at least one of the high refractive index layer and the low refractive index layer includes metal oxide particles, and it is more preferable that both the high refractive index layer and the low refractive index layer include metal oxide particles.

  In general, in an infrared shielding film, it is preferable to design a large difference in refractive index between a low refractive index layer and a high refractive index layer from the viewpoint that the infrared reflectance can be increased with a small number of layers. In this embodiment, in at least one of the laminates composed of the low refractive index layer and the high refractive index layer, the difference in refractive index between the adjacent low refractive index layer and high refractive index layer may be 0.1 or more. Preferably, it is 0.3 or more, more preferably 0.35 or more, and particularly preferably 0.4 or more. In the case of having a plurality of laminated bodies of high refractive index layers and low refractive index layers, it is preferable that the refractive index difference between the high refractive index layer and the low refractive index layer in all the laminated bodies is within the above-mentioned preferable range. However, even in this case, the refractive index layers constituting the uppermost layer and the lowermost layer of the dielectric multilayer film may have a configuration outside the above preferred range.

  The reflectance in the specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of stacked layers, and the larger the difference in refractive index, the same reflectance can be obtained with a smaller number of layers. 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 an infrared reflectance of 90% or more, if the refractive index difference is smaller than 0.1, it is necessary to stack 200 layers or more. In such cases, productivity loss, increased scattering at the stack interface, reduced transparency, and manufacturing failures can occur.

  The refractive index of the high refractive index layer is preferably 1.80 to 2.50, and more preferably 1.90 to 2.20.

  Further, the refractive index of the low refractive index layer is preferably 1.10 to 1.60, and more preferably 1.30 to 1.50.

  The number of refractive index layers of the dielectric multilayer film (total number of high refractive index layers and low refractive index layers) is preferably 6 to 50 layers, and preferably 8 to 40 layers from the above viewpoint. Are more preferable, 9 to 30 layers are more preferable, and 11 to 31 layers are particularly preferable. It is preferable that the number of refractive index layers in the dielectric multilayer film be in the above range because excellent heat shielding performance and transparency, suppression of film peeling and cracking, and the like can be realized. When the dielectric multilayer film has a plurality of high refractive index layers and / or low refractive index layers, each high refractive index layer and / or each low refractive index layer is the same or different. It may be.

  As long as the effect of the present invention is obtained, the dielectric multilayer film may be provided only on one side of the base material, or may be provided on both sides of the base material. Whether the dielectric multilayer film is provided on one side or both sides can be appropriately determined from the viewpoint of film properties. For example, when another layer is provided on one side of the substrate, depending on the physical properties of the other layer, it may be possible to solve problems such as curling by providing a dielectric multilayer film on the opposite side. Moreover, these problems may be solved by providing the dielectric multilayer film on both sides.

  The thickness per layer of the high refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm.

  Further, the thickness per layer of the low refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 500 nm.

  Here, when measuring the thickness per layer, the composition may change continuously without having a clear interface at the boundary between the high refractive index layer and the low refractive index layer. In such an interface region where the composition changes continuously, when the maximum refractive index−minimum refractive index = Δn, the point where the minimum refractive index between two layers + Δn / 2 is regarded as the layer interface.

  In addition, when the high refractive index layer and the low refractive index layer contain metal oxide particles, the above composition can be observed from the concentration profile of the metal oxide particles. The metal oxide concentration profile is formed by etching from the surface to the depth direction using a sputtering method, and using an XPS surface analyzer, sputtering is performed at a rate of 0.5 nm / min, with the outermost surface being 0 nm. It can be seen by measuring the ratio. Further, the laminated film may be cut and the cut surface may be confirmed by measuring the atomic composition ratio with an XPS surface analyzer.

  The XPS surface analyzer is not particularly limited, and any model can be used. As the XPS surface analyzer, for example, ESCALAB-200R manufactured by VG Scientific, Inc. can be used. Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

[Hard coat layer]
The hard coat layer has a function of preventing scratches on the infrared shielding film.

  The hard coat layer includes a hard coat material. In addition, infrared absorbers, pigments and dyes, surfactants, inorganic particles and the like may be included as necessary.

  The film thickness of the hard coat layer is preferably 0.1 to 50 μm, and more preferably 1 to 20 μm. A film thickness of 0.1 μm or more is preferable because hard coat properties can be improved. On the other hand, the film thickness of 50 μm or less is preferable because the transparency of the infrared shielding film can be improved.

  The hardness of the hard coat layer is preferably a pencil hardness of at least 2H because the moldability is easy.

(Hard coat material)
The hard coat material is not particularly limited, and examples thereof include a cured resin.

  The curable resin is not particularly limited, and examples thereof include a thermosetting resin and an active energy ray curable resin. In the present specification, the “active energy ray” represents an active ray such as an ultraviolet ray or an electron beam, and preferably means an ultraviolet ray.

  Although it does not restrict | limit especially as said thermosetting resin, The cured resin obtained from the polysiloxane precursor represented by a following formula is mentioned.

In the above formula, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms. M and n are integers satisfying the relationship m + n = 4.

  Specific examples of the polysiloxane precursor include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-poropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, Tetra-tert-butoxysilane, terapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropyl Pokishishiran, dimethyl-butoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, hexyl trimethoxy silane and the like.

  Other polysiloxane precursors include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, N-β- (N-aminobenzylaminoethyl) -γ-aminopropylmethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyl Examples include trimethoxysilane, γ-chloropropyltrilimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, and the like.

  In addition, as a polysiloxane precursor, you may use commercially available products, such as Sarkote series (made by the motion dynamics), SR2441 (Toray Dow Corning), Perma-New 6000 (California Hardcoating Company).

  The active energy ray curable resin is not particularly limited, but is an ultraviolet curable urethane (meth) acrylate resin, an ultraviolet curable polyester (meth) acrylate resin, an ultraviolet curable epoxy (meth) acrylate resin, an ultraviolet curable polyol (meth) acrylate resin, or the like. Is mentioned. Among these, it is preferable to use an ultraviolet curable (meth) acrylate resin.

  The active energy ray-curable resin can be usually obtained by curing a resin precursor with active energy rays.

  The resin precursor of the ultraviolet curable urethane (meth) acrylate resin is obtained by reacting the polyester polyol with an isocyanate monomer or a prepolymer, and further with 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth). It can be easily obtained by reacting a (meth) acrylate monomer having a hydroxyl group such as acrylate or 2-hydroxypropyl (meth) acrylate. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) described in JP-A-59-151110 is preferably used.

  The resin precursor of the UV curable polyester (meth) acrylate resin is obtained by reacting 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid or the like with the hydroxyl group or carboxy group of the polyester terminal. Can be easily obtained (for example, JP-A-59-151112).

  A resin precursor of an ultraviolet curable epoxy (meth) acrylate resin is obtained by reacting a monomer such as (meth) acrylic acid, (meth) acrylic acid chloride, or glycidyl (meth) acrylate with a hydroxyl group at the terminal of the epoxy resin. Can do. For example, Unidic V-5500 (manufactured by DIC Corporation) can be used.

  The resin precursor of the UV curable polyol (meth) acrylate resin is not particularly limited, but ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) Examples include acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and alkyl-modified dipentaerythritol penta (meth) acrylate. .

  The above resin precursors may be used alone or in combination of two or more.

  The hard coat material can be usually obtained by curing the polysiloxane precursor, the resin precursor and the like. For example, by irradiating an active energy ray curable resin precursor with an active energy ray, the resin precursor is cured through a crosslinking reaction or the like, and becomes an active energy ray curable resin as a hard coat material. Examples of the curing method include heating and active energy ray irradiation, but active energy ray irradiation is preferable from the viewpoint of curing temperature, curing time, cost, and the like.

(Infrared absorber)
The infrared absorbing agent has a function of imparting a certain infrared absorbing ability to the hard coat layer. In one Embodiment of this invention, it is preferable that a hard-coat layer contains an infrared absorber.

  Although it does not restrict | limit especially as an infrared absorber, An inorganic infrared absorber and an organic infrared absorber are mentioned.

  Inorganic infrared absorbers include zinc oxide, aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), gallium-doped zinc oxide (GZO), tin oxide, antimony-doped tin oxide (ATO), indium-doped tin oxide ( ITO), lanthanum boride, and nickel complex compounds. Among these, the infrared absorber is preferably a zinc oxide-based infrared absorber from the viewpoints of visible light transmittance, infrared absorptivity, dispersibility in the resin, and the like, and is AZO, ATO, ITO, zinc antimonate. It is more preferable that

  Examples of the organic infrared absorber include imonium compounds, phthalocyanine compounds, aminium compounds, and the like.

  A commercially available product may be used as the infrared absorber. Although it does not restrict | limit especially as a commercial item of an inorganic infrared absorber, Cellnax series (Nissan Chemical Industry Co., Ltd.), Passetto series (Hakusitek Co., Ltd.), ATO dispersion, ITO dispersion (Mitsubishi Materials), KH series (Made by Sumitomo Metal Mining). Moreover, as a commercial item of an organic infrared absorber, NIR-IM1, NIR-AM1 (made by Nagase Chemitex), Lumogen series (made by BASF), etc. are mentioned.

  The above infrared absorbers may be used alone or in combination of two or more.

  As content of an infrared absorber, although it changes also with kinds of infrared absorber to be used, it is preferable that it is 25 mass% or more with respect to the total mass of a hard-coat layer, and it is 25-65 mass%. Preferably, it is 45-65 mass%. It is preferable for the content of the infrared absorber to be 25% by mass or more because the hard coat layer can suitably absorb infrared rays.

(Pigments and dyes)
The pigment and the dye have a function of adjusting the color tone of the infrared shielding film. In one embodiment of the present invention, the hard coat layer preferably contains at least one of a pigment and a dye.

  Although it does not restrict | limit especially as a pigment and dye, Cadmium red, Molybdenum red, Chromium permillion, Chromium oxide, Viridian, Titanium cobalt green, Cobalt green, Cobalt chrome green, Victoria green, ultramarine blue, ultramarine blue, bitumen, Berlin blue , Miroli Blue, Cobalt Blue, Cerulean Blue, Cobalt Silica Blue, Cobalt Zinc Blue, Manganese Violet, Mineral Bio Red, Cobalt Violet and other colored inorganic pigments, azo, condensed azo, phthalocyanine, anthraquinone, indigo, Perinone, perylene, dioxazine, quinacridone, methine, isoindolinone, quinophthalone, pyrrole, thioindigo, metal complex organic pigments and organic dyes Etc. The. Among these, it is preferable to use an anthraquinone as the pigment and the dye from the viewpoint of controlling the red color observed when the infrared shielding film is viewed from an oblique direction.

  Commercially available pigments and dyes may be used. As the said commercial item, Ceres Blue RR-J Gran. (Bayer Chemicals AG) Savinyl Blue RS (CLARIANT) and the like.

These pigments and dyes may be used singly or in combination of two or more, but control the value of a ^* and b ^* of L ^* a ^* b ^* of the infrared shielding film. From the viewpoint, it is preferable to adjust the color tone by mixing two or more pigments and / or dyes.

  The content of at least one of the pigment and the dye varies depending on the pigment / dye to be used, but is preferably 0.002% by mass or more based on the total mass of the hard coat layer. It is more preferable that it is mass%, and it is further more preferable that it is 0.002-0.01 mass%. It is preferable that the content of at least one of the pigment and the dye is 0.002% by mass or more because the hue of the hard coat layer can be changed. When the hard coat layer contains an infrared absorber, the pigment and The content of at least one of the dyes varies depending on the pigment / dye used, but is preferably 0.001 to 0.01% by mass, and 0.001 to 0.005% by mass with respect to the mass of the infrared absorber. % Is more preferable.

(Surfactant)
The surfactant has a function of imparting leveling properties, water repellency, slipperiness, and the like.

  The surfactant is not particularly limited, and examples thereof include acrylic surfactants, silicon surfactants, and fluorine surfactants. Among these, it is preferable to use a fluorochemical surfactant.

  A commercially available product may be used as the surfactant. The commercial products include F series (Megafax F-430, F-477, F-552, F-559, F-561, F-562, etc., manufactured by DIC Corporation), RS-76-E (DIC stock) Company-made), Surflon series (manufactured by AGC Seimi Chemical Co., Ltd.), POLYFOX series (manufactured by OMNOVA SOLUTIONS), ZX series (manufactured by T & K TOKA), OPTOOL series (manufactured by Daikin) and the like.

(Inorganic particles)
Although it does not restrict | limit especially as an inorganic particle, The microparticles | fine-particles of an inorganic compound containing metals, such as titanium, a silica, zirconium, aluminum, magnesium, antimony, zinc, tin, are mentioned.

  The average particle diameter of the inorganic particles is preferably 1000 nm or less, and more preferably 10 to 500 nm, from the viewpoint of ensuring visible light transmittance.

  In addition, inorganic particles have a higher bonding force with the hard coat material, and can be prevented from falling off the hard coat layer. Therefore, a photosensitive group having photopolymerization reactivity such as monofunctional or polyfunctional acrylate is introduced on the surface. What is doing is preferable.

  When the hard coat layer is formed on the substrate, the refractive index of the substrate and the hard coat layer is preferably a close value from the viewpoint of uneven interference. For example, when a polyethylene terephthalate film having a refractive index of 1.65 is used as the substrate, the refractive index of the hard coat layer is preferably 1.50 to 1.65.

[Base material]
The substrate has a function of supporting the dielectric multilayer film.

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

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

  The material and film thickness of the base material are preferably set so that the value obtained by dividing the thermal shrinkage rate of the infrared shielding film by the thermal shrinkage rate of the base material falls within the range of 1 to 3.

  Especially, it is preferable that the film thickness of a base material is 30-200 micrometers, It is more preferable that it is 30-150 micrometers, It is most preferable that it is 35-125 micrometers. It is preferable that the thickness of the substrate is 30 μm or more because wrinkles during handling are less likely to occur. On the other hand, when the thickness of the substrate is 200 μm or less, for example, when the substrate is bonded to the transparent substrate, the followability to the curved transparent substrate is improved and wrinkles are less likely to occur.

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

  The refractive index of the substrate is preferably a value close to the refractive index of the layer adjacent to the substrate. For example, since the material used for the adjacent layer is likely to be a general resin, the refractive index of the base material is 1.50 to 1.70 from the relationship with the refractive index of a general resin. Is preferred.

[Middle layer]
The intermediate layer has a function of improving the adhesion between adjacent layers. The intermediate layer is usually disposed between the dielectric multilayer film and the hard coat layer.

  Moreover, in one Embodiment, it is a lamination | stacking form which has arrange | positioned the hard-coat layer on the intermediate | middle layer, and can implement | achieve a big film thickness as a laminated body of the said intermediate | middle layer-hard-coat layer. Specifically, the film thickness of the intermediate layer-hard coat layer laminate is preferably 10 μm or more, and more preferably 16 μm or more. It is preferable that the thickness of the laminate is 10 μm or more because rainbow unevenness due to optical interference can be prevented.

  Although it does not restrict | limit especially as a material of an intermediate | middle layer, Resins, such as a polyvinyl acetal resin, an acrylic resin, a urethane resin, are mentioned.

  The polyvinyl acetal resin is a resin obtained by acetalizing polyvinyl alcohol with at least one aldehyde. Specific examples of the polyvinyl acetal include copolymer acetals such as polyvinyl acetal, polyvinyl formal, polyvinyl butyral, polyvinyl butyral containing a partially formalized part, and polyvinyl butyral acetal. In addition, the said polyvinyl acetal resin may have another repeating unit.

  A commercial item may be used for these polyvinyl acetal resins. Examples of the commercially available products include Denka Butyral # 2000L, # 3000-1, # 3000-K, # 4000-1, # 5000-A, # 6000-C, Denka Formal # 20, # 100, # 200 (Electric Manufactured by Chemical Industry Co., Ltd.), ESREC B Series BL-1, BL-2, BL-S, BM-1, BM-2, BH-1, BX-1, BX-10, BL-1, BL-SH, Examples include BX-L, ESREC K series KS-10, ESREC KW series KW-1, KW-3, KW-10, ESREC KX series KX-1, KX-5 (manufactured by Sekisui Chemical Co., Ltd.).

  The degree of acetalization of the polyvinyl acetal resin is preferably 5 to 65 mol%, and more preferably 15 to 50 mol% from the viewpoints of water solubility and adhesion effects. When the degree of acetalization is 5 mol% or more, the adhesion with the hard coat layer is preferable. On the other hand, when the degree of acetalization is 65 mol% or less, the adhesion with the dielectric multilayer film is preferable.

  Although it does not restrict | limit especially as said acrylic resin, Resin which uses acrylic monomers, such as methacrylic acid, acrylic acid, these esters or salts, acrylamide, and methacrylamide, as a polymer structural component is mentioned. Specifically, acrylic acid; methacrylic acid; alkyl acrylate (methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl Acrylate, benzyl acrylate, phenylethyl acrylate, etc.), acrylic esters such as hydroxy-containing alkyl acrylates (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc.); alkyl methacrylates (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , T-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenylethyl methacrylate, etc.), methacrylic acid esters such as hydroxy-containing alkyl methacrylates (2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc.); Acrylamide; substituted acrylamides such as N-methylacrylamide, N-methylolacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide; methacrylamide; N-methylmethacrylamide, N-methylolmethacrylamide, N, N-di Substituted methacrylamide such as methylol methacrylamide and N-methoxymethyl methacrylamide; N, N-di Amino group-substituted alkyl acrylate such as tilaminoethyl acrylate; amino group-substituted alkyl methacrylate such as N, N-diethylamimethacrylate; epoxy group-containing acrylate such as glycidyl acrylate; epoxy group-containing methacrylate such as glycidyl methacrylate; sodium salt of acrylic acid And salts of acrylic acid such as potassium salt of acrylic acid and ammonium salt of acrylic acid; salts of methacrylic acid such as sodium salt of methacrylic acid, potassium salt of methacrylic acid and ammonium salt of methacrylic acid.

  The above monomers may be used alone or in combination of two or more.

  Among the acrylic resins described above, methyl methacrylate-ethyl acrylate-ammonium acrylate-acrylamide copolymer, methacrylamide-butyl acrylate-sodium acrylate-methyl methacrylate-N-methylol acrylamide copolymer, etc. are used. It is preferable.

  The acrylic resin may contain isocyanate as a crosslinking agent. Examples of the isocyanate include cyclic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and 4,4-diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate. And organic diisocyanate compounds. When the acrylic resin is used in an aqueous system, a blocked isocyanate, for example, product number 214 manufactured by Baxenden can be used.

  The urethane resin is a general term for polymers having a urethane bond in the main chain, and is usually obtained by reaction of polyisocyanate and polyol.

  Although it does not restrict | limit especially as said polyisocyanate, TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthylene diisocyanate), TODI (toluidine diisocyanate), HDI (hexamethylene dicyanate), IPDI (isophorone diisocyanate) Etc.

  On the other hand, the polyol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, glycerin, hexanetriol and the like.

  The urethane resin may be a urethane resin obtained by subjecting a polyurethane polymer obtained by the reaction of polyisocyanate and polyol to chain extension treatment to increase the molecular weight.

  A commercially available product may be used as the polyurethane resin. Although it does not restrict | limit especially as the said commercial item, Superflex 150HS, Superflex 470 etc. (made by Daiichi Kogyo Seiyaku Co., Ltd.), Hydran AP-20, Hydran WLS-210, Hydran HW-161 etc. (made by DIC Corporation) 8UA series (Taisei Fine Chemical).

  The above-mentioned polyvinyl acetal resin, acrylic resin, and urethane resin may be used alone or in combination of two or more.

  The glass transition temperature (Tg) of the resin is preferably -30 to 60 ° C, and more preferably -20 to 40 ° C. A glass transition temperature (Tg) of −30 ° C. or higher is preferable because stability is improved. On the other hand, it is preferable that the glass transition temperature (Tg) is 60 ° C. or less because good adhesion can be obtained.

  The thickness of the intermediate layer is preferably 4.0 μm or more, more preferably 6.0 μm or more, and further preferably 6.0 to 30 μm.

  Moreover, when the dielectric multilayer film is disposed on the intermediate layer, the total film thickness of the intermediate layer-dielectric multilayer film laminate is preferably 10 μm or more.

The refractive index of the intermediate layer is preferably a value between the refractive index of the dielectric multilayer film and the refractive index of the hard coat layer from the relationship of the refractive index with the adjacent dielectric multilayer film and the hard coat layer. For example, when the uppermost layer of the dielectric multilayer film is a SiO ₂ film and has a refractive index of 1.48, and the hard coat layer has a refractive index of 1.58, the refractive index of the intermediate layer is 1.48 to 1.58. It is preferable that

[Other functional layers]
As other functional layers, an infrared absorbing layer, a heat insulating layer, an adhesive layer, a transparent resin layer, and the like may be provided as long as the object and effects of the present invention are not impaired. Among these, when attaching an infrared shielding film to a building member, a window glass, etc., it is preferable to provide an adhesive layer.

  The material of the adhesive layer is not particularly limited, but is a dry laminating agent, a wet laminating agent, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, an adhesive such as nitrile rubber, a heat seal agent, A hot melt agent etc. are mentioned.

  In addition, it is preferable that the thickness of the adhesion layer is 1-100 micrometers from viewpoints, such as an adhesion effect and a drying rate.

<Method for producing infrared shielding film>
The manufacturing method of an infrared shielding film includes the process of forming a dielectric multilayer film, and the process of forming a hard-coat layer. In addition, the process of forming an intermediate | middle layer etc. may be included as needed.

[Step of forming dielectric multilayer film]
The method of forming the dielectric multilayer film can be roughly classified into a dry film forming method and a wet film forming method according to the above-described refractive index layer forming method.

(Dry film forming method)
In the dry film forming method, for example, an infrared shielding film can be manufactured by sequentially forming a refractive index layer by vapor-depositing two or more dielectric materials on a substrate.

  Examples of the vapor deposition method include physical vapor deposition and chemical vapor deposition. Of these, it is preferable to use physical vapor deposition, and it is more preferable to use vacuum vapor deposition or sputtering. The vacuum deposition method is a method in which a dielectric material is heated and evaporated by resistance heating or electron gun irradiation to form a thin film on a substrate. Sputtering, on the other hand, generates plasma between a substrate and a target using a plasma generator, bombards the dielectric material with ions using an electric potential gradient, and strikes the dielectric material on the substrate. It is the method of forming into a film. For these methods, known methods can be referred to as appropriate.

(Wet deposition method)
In the wet film forming method, for example, a refractive index layer is formed by applying a coating solution on a substrate and drying to form a refractive index layer sequentially, applying a coating solution in layers, drying, or a combination thereof. By doing so, an infrared shielding film can be manufactured.

  The coating solution can usually contain a solvent in addition to the water-soluble resin and / or metal oxide particles and other additives. The solvent may be water, an organic solvent, or a mixed solvent thereof.

  The component that can be contained in the coating solution can be appropriately selected depending on whether the coating solution is a coating solution for a high refractive index layer or a coating solution for a low refractive index layer. At this time, a water-soluble resin (first water-soluble resin and second water-soluble resin) and metal oxide particles (first metal oxide particles and second metal oxide particles) that can be used in the coating liquid, About the component of another additive, the thing similar to what was mentioned above may be used.

  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 admixture of two or more.

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

  The concentration of the water-soluble resin in the coating solution is preferably 1 to 10% by mass. Moreover, when a coating liquid contains a metal oxide particle, it is preferable that the density | concentration of a metal oxide particle is 1-50 mass%. By changing the concentration of each of these materials, the thermal shrinkage rate of the optical film can be changed, and the value obtained by dividing the thermal shrinkage rate of the optical film by the thermal shrinkage rate of the transparent resin film is within a range of 1 to 3. Can be adjusted.

  The method for preparing the coating solution is not particularly limited, and examples thereof include a method in which a water-soluble resin, metal oxide particles added as necessary, and other additives are added and stirred and mixed. At this time, the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring. If necessary, it may be adjusted to an appropriate viscosity using a solvent.

  When preparing a coating liquid containing metal oxide particles in the form of core / shell particles (for example, titanium oxide coated with silicon-containing hydrated oxide), the pH is 5.0 to 7.0. In addition, it is preferable to prepare a coating solution by adding a sol of metal oxide particles having a negative zeta potential to the solvent.

  As a coating method of the coating liquid, for example, a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a slide curtain coating method, a slide hopper coating method and the like are preferably used.

  When the coating method is simultaneous multi-layer coating using a slide hopper coating method, the viscosity of the coating solution at 40 to 45 ° C. is preferably 5 to 300 mPa · s, and 10 to 250 mPa · s. Is more preferable. In the case of simultaneous multilayer coating using the slide curtain coating method, the viscosity of the coating solution at 40 to 45 ° C. is preferably 5 to 1200 mPa · s, and more preferably 25 to 500 mPa · s. preferable.

  The viscosity at 15 ° C. of the coating solution is preferably 10 mPa · s or more, more preferably 15 to 30000 mPa · s, still more preferably 20 to 20000 mPa · s, and further preferably 20 to 18000 mPa · s. It is particularly preferred that

  Although the coating film obtained by application | coating of a coating liquid changes also with the components of the coating liquid to be used, preferably a refractive index layer can be formed by drying at 60-120 degreeC, Preferably it is 80-95 degreeC.

  The drying temperature is preferably 30 ° C. or higher. For example, it is preferable to dry at a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 30 to 100 ° C. (preferably 10 to 50 ° C.). As a drying method, warm air drying, infrared drying, and microwave drying are used. As a specific drying method, a method of blowing warm air of 40 to 60 ° C. for 1 to 5 seconds can be mentioned. Moreover, although drying may be performed by a single process or a multistage process, drying is preferably performed by a multistage process. In this case, it is more preferable that the temperature of the constant rate drying unit is smaller than the temperature of the reduction rate drying unit. The temperature range of the constant rate drying unit is preferably 30 to 60 ° C, and the temperature range of the decreasing rate drying unit is preferably 50 to 100 ° C.

  In addition, you may perform a setting process after application | coating and before drying. A setting process means the process of cooling the coating film obtained by application | coating once before drying. By performing the setting step, the viscosity of the coating film is improved, or the fluidity of the substances in each layer and in each layer can be reduced by gelation. Thereby, mixing between layers can be prevented and coating film uniformity can be improved.

  The temperature of the cold air in the setting step is preferably 1 to 15 ° C, and more preferably 5 to 10 ° C.

  The time for which the coating film is exposed to cold air is preferably 10 to 360 seconds, more preferably 10 to 300 seconds, and still more preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.

  The time until the setting step is completed (setting time) is preferably within 5 minutes, and more preferably within 2 minutes. When the set time is within 5 minutes, interlayer diffusion of the refractive index layer components (metal oxide particles, etc.) is suppressed, and the value of the refractive index difference between the high refractive index layer and the low refractive index layer can increase. preferable. In addition, although there is no restriction | limiting in particular about the minimum of setting time, From a viewpoint of mixing the component in a layer suitably, it is preferable that it is 45 second or more. The set time can be controlled by adjusting the concentration of the water-soluble resin and metal oxide particles in the coating solution and adding additives such as gelatin pectin, agar, carrageenan, gellan gum and the like. The set time can be controlled by appropriately adjusting the type and concentration of the water-soluble resin and the metal oxide particles added as necessary. The “completion of the setting process” means a state in which the coating film component does not adhere to the finger when the finger is pressed against the surface of the coating film.

[Step of forming a hard coat layer]
The hard coat layer can usually be formed by a wet film forming method in which a hard coat layer coating solution is applied and dried, followed by heating and / or irradiation with active energy rays, a dry film forming method in which vapor deposition is performed, or the like. Among these, it is preferable to carry out by a hard coat layer wet film forming method.

(Coating solution for hard coat layer)
The coating liquid for hard coat layers contains a hard coat material and a solvent. If necessary, an infrared absorber, a pigment and a dye, a surfactant, inorganic particles, and the like may be included.

  Since hard coat materials, infrared absorbers, pigments and dyes, surfactants, inorganic particles and the like can be the same as those described above, description thereof will be omitted here.

  The solvent is not particularly limited, and methyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, ethyl acetate and the like can be used.

  The concentration of the hard coat material that can be contained in the hard coat layer coating solution is preferably 10 to 50% by mass, and more preferably 10 to 20% by mass.

(Coating, drying)
The coating is not particularly limited, but can be performed by continuous coating using a die coater, gravure coater, comma coater, or the like, in addition to coating by wire bar, spin coating, dip coating.

  Although it does not restrict | limit especially as a drying method, Heating, ventilation of a warm air, etc. are mentioned.

  Although it does not restrict | limit especially as drying temperature, It is preferable that it is 30-150 degreeC.

(Heating, irradiation of active energy rays)
When the thermosetting resin in the coating liquid for hard coat layer is heated, the thermosetting resin undergoes crosslinking or the like, and can become a hard coat agent. In addition, the active energy ray-curable resin in the hard coat layer coating solution can be used as a hard coat agent by irradiating an active energy ray (for example, an ultraviolet lamp) to cause crosslinking or the like of the active energy ray-curable resin. .

  When a specific example is given, when the coating liquid for hard-coat layers contains a polysiloxane precursor, it is preferable to heat-process for 30 minutes-several days at 50-150 degreeC, and the heat resistance of a base material or a laminated roll shape From the viewpoint of the stability of the base material when it is made, it is more preferable to perform heat treatment at 40 to 80 ° C. for 2 days or more.

  In some cases, the temperature in the drying step may be adjusted, and drying and heating may be performed simultaneously.

[Step of forming intermediate layer]
The intermediate layer can usually be formed by applying and drying an intermediate layer coating solution.

(Coating liquid for intermediate layer)
The intermediate layer coating solution contains an intermediate layer forming monomer and a solvent. Other additives may be included as necessary.

  As the monomer for forming the intermediate layer, since the above-described monomers can be used, description thereof is omitted here.

  The solvent is not particularly limited as long as it does not interact with the monomer.

(Coating, drying)
The coating and drying methods are not particularly limited, and the intermediate layer can be formed by appropriately taking into account known techniques.

<Infrared shield and laminated glass>
The above-described infrared shielding film can be applied to a wide range of fields. For example, a film for window pasting such as a heat ray reflecting film that gives a heat ray reflecting effect, a film for an agricultural greenhouse, etc. As, it is mainly used for the purpose of improving the weather resistance.

  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. For example, pasting to windows exposed to sunlight such as outdoor windows of buildings and automobile windows, film for window pasting that gives infrared reflection effect to suppress excessive rise in indoor temperature, film for agricultural greenhouse, etc. As, it is mainly used for the purpose of an agricultural film provided with an infrared shielding effect for suppressing an excessive increase in the temperature in the house.

  In addition, like the laminated glass for automobiles, the infrared shielding film of the present invention is sandwiched between glasses and used as an infrared shielding film for automobiles. In this case, the infrared shielding film can be sealed from outside air gas. From the viewpoint of durability, it is preferable.

  That is, according to one form of this invention, the infrared shielding body containing a base | substrate and the above-mentioned infrared shielding film arrange | positioned at the at least one surface of the said base | substrate is provided.

  According to another embodiment of the present invention, the infrared shielding film described above, a pair of intermediate films sandwiching the infrared shielding film, and a pair of plate glasses sandwiching the infrared shielding film and the intermediate film. A heat ray reflective laminated glass is provided.

  The infrared shielding body of the present invention means an embodiment in which the infrared shielding film of the present invention is provided on at least one surface of the substrate. The infrared shielding film of the present invention is provided on a plurality of surfaces of the substrate. A plurality of substrates may be provided on the substrate.

  Among these, in particular, the laminated glass has a structure in which an infrared shielding film is sandwiched between two sheet glasses using two intermediate films.

  In the infrared shielding body, 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 Examples thereof include resins, melamine resins, phenol resins, diallyl phthalate resins, polyimide resins, urethane resins, polyvinyl acetate resins, polyvinyl alcohol resins, styrene resins, vinyl chloride resins, metal plates, ceramics, and cloths. The type of the resin may be any of a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin, or two or more of these may be used in combination.

  Further, the substrate may be in various forms such as a film shape, a plate shape, a spherical shape, a cubic shape, and a rectangular parallelepiped shape.

  Among these, the infrared shielding body which provided the infrared shielding film of this invention in the plate-shaped ceramic base | substrate or glass base | substrate is preferable.

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

  As an example of a glass base | substrate, it is preferable that they are the float plate glass described in JISR3202: 2011, and polished plate glass, for example. Further, the glass thickness is preferably 0.01 mm to 20 mm.

  As a method of providing the infrared shielding film of the present invention on the substrate, as described above, an adhesive layer (adhesive layer) such as an adhesive (adhesive) is coated on the infrared shielding film, and the substrate is interposed via the adhesive layer. The method of affixing to is used suitably.

  Examples of the adhesive applicable to the present invention include an adhesive mainly composed of a photo-curable or thermosetting resin. The adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic adhesive or a silicone adhesive. Furthermore, an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost. In particular, solvent-based and emulsion-based acrylic adhesives are preferable, and solvent-based acrylic adhesives are more preferable because the peel strength can be easily controlled. When a solution polymerization polymer is used as the solvent-based acrylic adhesive, known monomers can be used as the monomer.

  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.

  Polyvinyl butyral resin or ethylene-vinyl acetate copolymer resin may be used as the adhesive. Specific examples thereof include 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), 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.

  A laminated glass similar to the above can also be used.

  In addition, about plate glass, inorganic glass and organic glass, such as the above-mentioned glass base | substrate, are mentioned.

  The inorganic glass is not particularly limited, and examples thereof include various types of inorganic glass such as float plate glass, polished plate glass, mold plate glass, netted plate glass, lined plate glass, heat ray absorbing plate glass, and colored plate glass.

  Examples of the organic glass include glass plates made of resins such as polycarbonates, polystyrenes, and polymethyl methacrylates. These organic glass plates may be a laminate formed by laminating a plurality of sheet-shaped ones made of the resin. Regarding the color, not only the transparent glass plate but also glass plates of various colors such as general-purpose green, brown and blue used for vehicles and the like can be used.

  The same type may be sufficient as plate glass, and may use 2 or more types together.

  The thickness of the plate glass is preferably about 1 to 10 mm in consideration of strength and infrared light transmittance in the visible light region.

  The curved plate glass preferably has a radius of curvature of 0.5 to 2.0 m. If the radius of curvature of the plate glass is within this range, the infrared shielding film can follow the curved shape of the glass.

  Moreover, about the intermediate | middle layer which comprises laminated glass, any film | membrane can be used if it is a film | membrane which has the adhesive performance which bonds an infrared shielding film and glass.

  Preferable interlayer films include polyvinyl butyral resins that can also be used as adhesives, ethylene-vinyl acetate copolymer resins, and the like.

  The intermediate film may be composed of a single layer of the resin film, or may be used in a state where two or more layers are laminated. The two intermediate films may be made of the same type of resin, or may be made of different types of resin.

  Moreover, it is preferable that an intermediate film contains the heat ray shielding fine particle with an average particle diameter of 0.2 micrometer or less which has a heat ray shielding absorptivity from the point of a heat ray shielding effect. When an intermediate film containing heat ray shielding fine particles is used, color unevenness due to reflection of visible light when the film is applied to curved glass is also reduced. This is considered to be because the reflection of visible light becomes inconspicuous due to scattering and absorption by the heat ray shielding fine particles.

  The functional fine particles include Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, and Mo metals, oxidation In particular, from the viewpoint of the heat ray shielding effect, antimony-doped tin oxide ( ATO) or indium tin oxide (ITO) is preferred.

  The average particle size of the heat ray-shielding fine particles is 0.2 μm or less because the heat ray shielding effect can be secured while suppressing the reflection of visible light, and haze deterioration due to scattering does not occur and transparency can be secured. Is more preferable, and 0.15 μm or less is more preferable. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.10 μm or more. The average particle size is determined by observing particles themselves or particles appearing on the cross section or surface of the refractive index layer with an electron microscope, measuring the particle size of 1,000 arbitrary particles, and calculating the simple average value (number average). As required. Here, the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.

  The content of the heat ray shielding fine particles is not particularly limited, but is preferably 0.5 to 10% by mass with respect to the total mass of the interlayer film from the viewpoint of the heat ray shielding effect, More preferably, it is 5 mass%.

  In addition, you may add and mix | blend an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, coloring, an adhesion regulator etc. suitably in an intermediate | middle layer.

  The film thickness of the intermediate layer is usually about 0.1 to 2 mm.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

<Example 1>
[Dielectric multilayer film]
(Coating solution for low refractive index layer)
First, a coating solution for a low refractive index layer was prepared. Specifically, 430 parts of colloidal silica (10% by mass) (Snowtex OXS; manufactured by Nissan Chemical Industries, Ltd.), 150 parts of boric acid aqueous solution (3% by mass), 85 parts of water, 300 parts of polyvinyl alcohol (4% by mass) (JP-45; degree of polymerization: 4500; degree of saponification: 88 mol%; manufactured by Nihon Acetate / Poval) 3 parts surfactant (5% by mass) (softazoline LSB-R; river Were added in this order at 45 ° C. And it finished to 1000 parts with pure water, and prepared the coating liquid for low refractive index layers.

(Coating liquid for high refractive index layer)
Next, a coating solution for a high refractive index layer was prepared. Specifically, a dispersion of silica-modified titanium oxide particles was prepared in advance, and a solvent or the like was added thereto.

  A dispersion of silica-modified titanium oxide particles was prepared as follows.

An aqueous titanium sulfate solution was thermally hydrolyzed by a known method to obtain titanium oxide hydrate. The obtained titanium oxide hydrate was suspended in water to obtain 10 L of an aqueous suspension (TiO ₂ concentration: 100 g / L). To this was added 30 L of an aqueous sodium hydroxide solution (concentration: 10 mol / L) with stirring, the temperature was raised to 90 ° C., and the mixture was aged for 5 hours. The obtained solution was neutralized with hydrochloric acid, filtered and washed with water to obtain a base-treated titanium compound.

Next, the base-treated titanium compound was suspended in pure water and stirred so that the TiO ₂ concentration was 20 g / L. Under stirring, it was added citric acid in an amount of 0.4 mol% with respect to TiO ₂ weight. The temperature was raised to 95 ° C., concentrated hydrochloric acid was added to a hydrochloric acid concentration of 30 g / L, and the liquid temperature was maintained, followed by stirring for 3 hours. Here, when the pH and zeta potential of the obtained mixed solution were measured, the pH was 1.4 and the zeta potential was +40 mV. Further, when the particle size was measured with Zetasizer Nano (manufactured by Malvern), the volume average particle size was 35 nm and the monodispersity was 16%.

  1 kg of pure water was added to 1 kg of a 20.0 mass% titanium oxide sol aqueous dispersion containing rutile-type titanium oxide particles to prepare a 10.0 mass% 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 described above, and then heated to 90 ° C. Thereafter, 1.3 kg of an aqueous silicic acid solution having a SiO ₂ concentration of 2.0 mass% was gradually added. The obtained dispersion is subjected to a heat treatment at 175 ° C. for 18 hours in an autoclave, and further concentrated to thereby contain 20% by mass of silica-modified titanium oxide particles containing titanium oxide having a rutile structure coated with SiO _2. A dispersion (sol aqueous dispersion) was obtained.

  A solvent or the like was added to the sol aqueous dispersion of silica-modified titanium oxide particles thus prepared to prepare a coating solution for a high refractive index layer. Specifically, 320 parts of silica-modified titanium oxide particle sol aqueous dispersion (20.0% by mass), 120 parts of citric acid aqueous solution (1.92% by mass), 20 parts of polyvinyl alcohol (10% by mass) (PVA-103, polymerization degree: 300, saponification degree: 99 mol%, manufactured by Kuraray Co., Ltd.), 100 parts boric acid aqueous solution (3 mass%), 350 parts polyvinyl alcohol (4 mass%) (PVA-124, Degree of polymerization: 2400, degree of saponification: 99 mol%, manufactured by Kuraray Co., Ltd.) 1 part of a surfactant (5% by mass) (Softazolin LSB-R, manufactured by Kawaken Fine Chemical Co., Ltd.) was added in this order at 45 ° C. . And it finished to 1000 parts with pure water, and prepared the coating liquid for high refractive index layers.

(Coating, drying)
A polyethylene terephthalate film (A4300, double-sided easy-adhesion layer, thickness: 50 μm, length: 200 m × width 210 mm, refractive index: 1.58, manufactured by Toyobo Co., Ltd.) was prepared as a substrate.

Using a slide hopper coating apparatus that can coat 9 layers, 9 layers are laminated on a substrate heated to 45 ° C. while keeping the coating solution for low refractive index layer and the coating solution for high refractive index layer at 45 ° C. Application was performed. At this time, the lowermost layer and the uppermost layer were low refractive index layers, and other than that, the low refractive index layers and the high refractive index layers were alternately laminated. The coating amount was adjusted such that the film thickness during drying was 150 nm for each low refractive index layer and 130 nm for each high refractive index layer. The film thickness was confirmed by cutting the manufactured infrared shielding film and observing the cut surface with an electron microscope. At this time, when the interface between the two layers could not be clearly observed, the interface was determined by the XPS profile in the thickness direction of TiO ₂ contained in the layer obtained by the XPS surface analyzer.

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

  After completion of the setting, warm air of 80 ° C. was blown and dried to prepare a multi-layer coated product consisting of 9 layers.

  On the back surface of the 9-layer multilayer coated product (base material surface (back surface) opposite to the base material surface on which the 9-layer multilayer coating was applied), 9-layer multilayer coating was further performed.

  This obtained the 1st film which consists of dielectric multilayer film (9 layer lamination | stacking)-base material-dielectric multilayer film (9 layer lamination | stacking).

  The formed high refractive index layer had a refractive index of 1.95, and the low refractive index layer had a refractive index of 1.45.

[Middle layer]
(Coating liquid for intermediate layer)
EMB498 (high molecular weight type of high acid value acrylic resin, Tg: 60 ° C., manufactured by Mitsubishi Rayon Co., Ltd.) was dissolved in ethanol so as to have a concentration of 20% by mass to prepare an intermediate layer coating solution.

(Coating, drying)
On the one dielectric multilayer film of the first film produced above, the intermediate layer coating solution is applied and dried using a wire bar so that the dry film thickness is 6.0 μm. Formed.

  This obtained the 2nd film which consists of dielectric multilayer film (9 layer lamination | stacking)-base material-dielectric multilayer film (9 layer lamination | stacking)-intermediate | middle layer.

  The refractive index of the intermediate layer was 1.49.

[Hard coat layer]
(Coating solution 1 for hard coat layer)
Cellulax CX-Z410K (aluminum-doped zinc oxide (AZO) methyl isobutyl ketone dispersion sol, manufactured by Nissan Chemical Industries, Ltd.), pentaerythritol triacrylate (manufactured by Daicel-Cytech), and solvent, methyl ethyl ketone. Next, 0.1 wt% of a fluorosurfactant (Megafax F-552, manufactured by DIC Corporation) was added to prepare a coating solution 1 for hard coat layer. Under the present circumstances, it adjusted so that the total solid of the coating liquid 1 for hard-coat layers might be 37 mass%. Moreover, it adjusted so that the density | concentration of AZO might be 65 mass% with respect to solid content.

(Coating, drying)
On the intermediate film of the second film produced above, the hard coat layer coating solution 1 is applied using a wire bar so that the dry film thickness is 6.0 μm, and dried at a drying section temperature of 90 ° C. By doing so, a coating film was formed.

(Irradiation of active energy rays)
The coating film obtained above was irradiated with ultraviolet rays using an ultraviolet lamp as an active energy ray to form a hard coat layer. At this time, the illuminance of the irradiation part of the ultraviolet lamp was 100 mW / cm ² and the irradiation amount was 0.5 J / cm ² .

  This obtained the infrared shielding film which consists of a dielectric multilayer film (9 layer lamination | stacking)-base material-dielectric multilayer film (9 layer lamination | stacking)-intermediate | middle layer-hard-coat layer.

  The refractive index of the hard coat layer was 1.59.

Moreover, in the manufactured infrared shielding film, L of an infrared shielding film is measured by measuring the transmittance | permeability of visible region (360-740 nm) using the spectrophotometer U-4100 (made by Shimadzu Corporation). ^{* A *} b ^{* When} the a ^* value and b ^* value in the color system were measured, the a ^* value was -4.1 and the b ^* value was 3.3.

<Example 2>
In the same manner as in Example 1, a second film comprising a dielectric multilayer film (9-layer laminate) -base material-dielectric multilayer film (9-layer laminate) -intermediate layer was obtained.

[Hard coat layer]
(Coating solution 2 for hard coat layer)
Infrared absorber (antimony-doped tin oxide (ATO) methyl isobutyl ketone dispersion sol, manufactured by ANP), pentaerythritol triacrylate (manufactured by Daicel Cytec), and methyl ethyl ketone as a solvent are mixed, and then a fluorosurfactant (Megafax F-552, manufactured by DIC Corporation) was added in an amount of 0.1% by mass to prepare a coating solution 2 for hard coat layer. Under the present circumstances, it adjusted so that the total solid of the coating liquid 2 for hard-coat layers might be 30 mass%. Moreover, it adjusted so that the density | concentration of ATO might be 50 mass% with respect to solid content.

(Coating, drying)
On the intermediate film of the second film produced above, the hard coat layer coating solution 2 is applied using a wire bar so that the dry film thickness is 4.0 μm, and dried at a drying section temperature of 90 ° C. By doing so, a coating film was formed.

(Irradiation of active energy rays)
The coating film obtained above was irradiated with ultraviolet rays using an ultraviolet lamp as an active energy ray to form a hard coat layer. At this time, the illuminance of the irradiation part of the ultraviolet lamp was 100 mW / cm ² and the irradiation amount was 0.5 J / cm ² .

  This obtained the infrared shielding film which consists of a dielectric multilayer film (9 layer lamination | stacking)-base material-dielectric multilayer film (9 layer lamination | stacking)-intermediate | middle layer-hard-coat layer.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −3.5. Yes, the value of b ^* was 0.4.

<Example 3>
Except that 0.001% by mass of Savinyl Blue RS (manufactured by CLARIANT) with respect to the mass of AZO was added to the coating solution 1 for hard coat layer of Example 1, except that the coating solution for hard coat layer was used. In the same manner as in Example 1, an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −4.4. Yes, the value of b ^* was 1.5.

<Example 4>
Except that 0.008% by mass of Savinyl Blue RS (manufactured by CLARIANT) with respect to the mass of AZO was added to the coating solution 1 for hard coat layer of Example 1, except that the coating solution for hard coat layer was used. In the same manner as in Example 1, an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −5.0. Yes, and the value of b ^* was -6.4.

<Example 5>
Except for using the hard coat layer coating solution obtained by adding 0.01% by weight of Savinyl Blue RS (manufactured by CLARIANT) to the hard coat layer coating solution 1 of Example 1 In the same manner as in Example 1, an infrared shielding film composed of a dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9 layers laminated) -intermediate layer-hard coat layer was produced.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −6.3. Yes, the value of b ^* was -10.0.

<Example 6>
In the hard coat layer coating solution 1 of Example 1, 0.002% by mass of Ceres Blue RR-J Gran. Dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9) in the same manner as in Example 1 except that the coating liquid for hard coat layer added with (Bayer Chemicals AG) was used. An infrared shielding film composed of (layer lamination) -intermediate layer-hard coat layer was produced.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −7.5. Yes, and the value of b ^* was -5.2.

<Example 7>
In the hard coat layer coating solution 1 of Example 1, 0.005% by mass of Ceres Blue RR-J Gran. Dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9) in the same manner as in Example 1 except that the coating liquid for hard coat layer added with (Bayer Chemicals AG) was used. An infrared shielding film composed of (layer lamination) -intermediate layer-hard coat layer was produced.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −9.0. Yes, the value of b ^* was -10.0.

<Example 8>
In the hard coat layer coating solution 1 of Example 1, 0.007% by mass of Ceres Blue RR-J Gran. Dielectric multilayer film (9 layers laminated) -base material-dielectric multilayer film (9) in the same manner as in Example 1 except that the coating liquid for hard coat layer added with (Bayer Chemicals AG) was used. An infrared shielding film composed of (layer lamination) -intermediate layer-hard coat layer was produced.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −9.3. Yes, the value of b ^* was −11.3.

<Example 9>
In the same manner as in Example 1, a second film comprising a dielectric multilayer film (9-layer laminate) -base material-dielectric multilayer film (9-layer laminate) -intermediate layer was obtained.

[Hard coat layer]
(Coating liquid 3 for hard coat layer)
Infrared absorbent (gallium-doped zinc oxide (GZO) methyl ethyl ketone dispersion sol, manufactured by Hakusui Tech Co., Ltd.), pentaerythritol triacrylate (Daicel Cytec Co., Ltd.) and solvent methyl ethyl ketone are mixed, and then a fluorosurfactant (mega 0.1 wt% of Fax F-552 (manufactured by DIC Corporation) was added to prepare a coating solution 3 for hard coat layer. Under the present circumstances, it adjusted so that the total solid content of the coating liquid 3 for hard-coat layers might be 37 mass%. Moreover, it adjusted so that the density | concentration of GZO might be 65 mass% with respect to solid content.

(Coating, drying)
On the intermediate film of the second film produced above, the hard coat layer coating solution 3 is applied using a wire bar so that the dry film thickness is 7 μm, and dried at a drying section temperature of 90 ° C. A coating film was formed.

(Irradiation of active energy rays)
The coating film obtained above was irradiated with ultraviolet rays using an ultraviolet lamp as an active energy ray to form a hard coat layer. At this time, the illuminance of the irradiation part of the ultraviolet lamp was 100 mW / cm ² and the irradiation amount was 0.5 J / cm ² .

  This obtained the infrared shielding film which consists of a dielectric multilayer film (9 layer lamination | stacking)-base material-dielectric multilayer film (9 layer lamination | stacking)-intermediate | middle layer-hard-coat layer.

  The refractive index of the hard coat layer was 1.58.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −3.7. Yes, the value of b ^* was 3.1.

<Example 10>
[Dielectric multilayer film]
Based on the description in paragraphs “0046” to “0049” of JP-T-2008-528313, coPEN / PETG is alternately laminated on the base material used in Example 1 by resin extrusion (coextrusion method). A dielectric multilayer film was formed. At this time, the total number of refractive index layers including the coPEN layer and the PETG layer is 50 layers.

  This obtained the 3rd film which consists of a base material-dielectric multilayer film (50 layer lamination | stacking).

  The film thickness of the formed low refractive index layer (PETG layer) was 170 nm for each layer, and the film thickness of the high refractive index layer (coPEN layer) was 170 nm for each layer. The refractive index of the high refractive index layer was 1.64, and the refractive index of the low refractive index layer was 1.57.

[Middle layer]
In the same manner as in Example 1, an intermediate layer was formed on the dielectric multilayer film of the third film.

  This obtained the 4th film which consists of a base material-dielectric multilayer film (50 layer lamination | stacking) -intermediate layer.

  The refractive index of the intermediate layer was 1.49.

[Hard coat layer]
On the intermediate layer of the fourth film produced above, a hard coat layer is formed in the same manner as in Example 1, and consists of a base material-dielectric multilayer film (50 layers laminated) -intermediate layer-hard coat layer. An infrared shielding film was produced.

  The refractive index of the hard coat layer was 1.59.

Further, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −4.5. Yes, the value of b ^* was 2.5.

<Example 11>
In the same manner as in Example 10, a fourth film composed of a base material-dielectric multilayer film (laminated 50 layers) -intermediate layer was obtained.

[Hard coat layer]
(Coating solution 4 for hard coat layer)
Infrared absorber (antimony-doped tin oxide (ATO) methyl isobutyl ketone dispersion sol, manufactured by ANP), pentaerythritol triacrylate (manufactured by Daicel Cytec), and methyl ethyl ketone as a solvent are mixed, and then a fluorosurfactant 0.1% by mass (Megafax F-552, manufactured by DIC Corporation) was added. And the coating liquid 4 for hard-coat layers was prepared by adding 0.004 mass% Savinyl Blue RS (made by CLARIANT) with respect to the mass of AZO. Under the present circumstances, it adjusted so that the total solid content of the coating liquid 4 for hard-coat layers might be 30 mass%. Moreover, it adjusted so that the density | concentration of ATO might be 50 mass% with respect to solid content.

(Coating, drying, irradiation of active energy rays)
A hard coat layer was formed on the intermediate layer of the fourth film by the same method as in Example 2 using the coating liquid 4 for hard coat layer.

  This obtained the infrared shielding film which consists of a base material-dielectric multilayer film (50 layer lamination | stacking)-intermediate | middle layer-hard-coat layer.

  The refractive index of the hard coat layer was 1.59.

Further, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −4.5. Yes, the value of b ^* was -2.3.

<Comparative Example 1>
Substrate-dielectric multilayer film (50 layers) in the same manner as in Example 11 except that Savinyl Blue RS (manufactured by CLARIANT) was not added to the coating liquid 4 for hard coat layer of Example 11. An infrared shielding film comprising a laminate) -intermediate layer-hard coat layer was produced.

  The refractive index of the hard coat layer was 1.59.

Further, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −2.3. Yes, the value of b ^* was -1.0.

<Comparative Example 2>
On the base material used in Example 1, an infrared shielding film composed of a base material-hard coat layer was produced in the same manner as in Example 1 using the hard coat layer coating solution used in Comparative Example 1. .

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −2.6. Yes, the value of b ^* was 4.3.

<Comparative Example 3>
[Hard coat layer]
(Coating solution 5 for hard coat layer)
Infrared absorbent (gallium-doped zinc oxide (GZO) methyl ethyl ketone dispersion sol, manufactured by Hakusui Tech Co., Ltd.), pentaerythritol triacrylate (Daicel Cytec Co., Ltd.) and solvent methyl ethyl ketone are mixed, and then a fluorosurfactant (mega 0.1% by mass of Fax F-552, manufactured by DIC Corporation) was added. And the coating liquid 5 for hard-coat layers was prepared by adding 0.004 mass% cadmium red with respect to the mass of GZO. Under the present circumstances, it adjusted so that the total solid of the coating liquid 5 for hard-coat layers might be 37 mass%. Moreover, it adjusted so that the density | concentration of GZO might be 65 mass% with respect to solid content.

(Coating, drying, irradiation of active energy rays)
On the base material used in Example 1, a hard coat layer is formed by the same method as in Example 9 using the coating liquid 5 for hard coat layer, and an infrared shielding film comprising the base material-hard coat layer is produced. did.

  The refractive index of the hard coat layer was 1.58.

Further, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was 6.0. , B ^* was 3.3.

<Comparative example 4>
Similar to Example 1 except that the hard coat layer coating solution 1 of Example 1 with 0.004% by mass of cadmium red added to the mass of AZO was used. The infrared shielding film which consists of a dielectric multilayer film (9 layer lamination | stacking) -base material-dielectric multilayer film (9 layer lamination | stacking) -intermediate layer-hardcoat layer was manufactured by the method of this.

  The refractive index of the hard coat layer was 1.59.

Further, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was 3.9. , B ^* was 5.9.

<Comparative Example 5>
Similar to Example 1 except that the hard coat layer coating solution 1 of Example 1 was added with 0.001% by mass of cadmium red based on the mass of AZO. The infrared shielding film which consists of a dielectric multilayer film (9 layer lamination | stacking) -base material-dielectric multilayer film (9 layer lamination | stacking) -intermediate layer-hardcoat layer was manufactured by the method of this.

  The refractive index of the hard coat layer was 1.59.

Further, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was 0.5. , B ^* was 4.9.

<Comparative Example 6>
Example 1 is the same as Example 1 except that the hard coat layer coating solution 1 is obtained by adding 0.01% by weight of a phthalocyanine pigment to the AZO weight to the hard coat layer coating solution 1 of Example 1. The infrared shielding film which consists of a dielectric multilayer film (9 layer lamination | stacking)-base material-dielectric multilayer film (9 layer lamination | stacking)-intermediate | middle layer-hard-coat layer was manufactured by the same method.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −3.5. Yes, the value of b ^* was -13.0.

<Comparative Example 7>
Except for using hard coat layer coating solution in which 0.01% by mass of cobalt green was added to the AZO mass to hard coat layer coating solution 1 of Example 1, the same as Example 1 was used. The infrared shielding film which consists of a dielectric multilayer film (9 layer lamination | stacking) -base material-dielectric multilayer film (9 layer lamination | stacking) -intermediate layer-hardcoat layer was manufactured by the method of this.

  The refractive index of the hard coat layer was 1.59.

Moreover, when the value of a ^{* and} the value of b ^* in the L ^* a ^* b ^* color system of the infrared shielding film were measured by the same method as in Example 1, the value of a ^* was −3.5. Yes, the value of b ^* was 5.9.

<Performance evaluation>
Various performance evaluation was performed about the infrared shielding film manufactured in Examples 1-11 and Comparative Examples 1-7.

[Heat insulation performance]
The transmittance and reflectance were measured by irradiating light having a wavelength of 250 nm to 2500 nm from the opposite direction to the surface on which the hard coat layer of the infrared shielding film was formed. The solar radiation acquisition rate (Tts) was calculated | required by performing calculation processing with the solar reflection weight coefficient using these values. At this time, a spectrophotometer U-4100 (manufactured by Shimadzu Corporation) was used for measurement of transmittance and reflectance.

  The heat shielding performance was evaluated according to the following criteria.

A: The value of solar radiation acquisition rate (Tts) is less than 55%. ○: The value of solar radiation acquisition rate (Tts) is 55% or more and less than 57%. X: The value of solar radiation acquisition rate (Tts) is 59% or more.

[Color change]
A three-wavelength fluorescent lamp (white light, FHF32EXNH-10P Mellow Line 32W, manufactured by Toshiba Corporation) is lit from the surface on which the hard coat layer is formed in an environment of 25 ° C. and 55% RH. Irradiated. At this time, the color tone of the infrared shielding film was visually observed while sequentially changing the observation angle of the infrared shielding film, and the color tone change was evaluated according to the following criteria.

5: Little appearance of angle dependency of color tone is observed, and appearance is good 4: Angle dependency of color tone is slightly recognized, but it is very weak angle dependency and almost good appearance 3: Appearance that the angle dependency of the color tone is recognized and is a little concerned in practical use 2: The angle dependency of the color tone is recognized relatively strongly and the appearance that is concerned in practical use 1: The angle dependency of the color tone is strongly recognized The appearance is unbearable.

[Reflection intensity ratio]
Irradiation of light with a wavelength of 730 nm from the opposite direction to the surface on which the hard coat layer of the infrared shielding film is formed, a regular reflectance with an incident angle of 5 degrees with respect to the normal of the dielectric multilayer film, and an incident angle And the regular reflectance at which the angle becomes 60 degrees. At this time, a spectrophotometer U-4100 (manufactured by Shimadzu Corporation) was used for measuring the regular reflectance. And the reflection intensity (reflection intensity ratio) of 60 degree | times regular reflectance when the reflection intensity of 5 degree | times regular reflectance was set to 1 was computed.

  The obtained results are shown in Table 1 below.

  As is clear from the results in Table 1, it can be seen that the infrared shielding films according to the examples have excellent heat shielding performance. In addition, the infrared shielding films according to the examples show good results in the color tone change depending on the observation angle, and since the reflection intensity ratio is close to 1, regular reflectances of 5 degrees and 60 degrees with respect to the normal of the film surface There was no difference. That is, it turns out that the infrared shielding film which concerns on an Example has low angle dependence of a color tone.

  On the other hand, it turns out that the infrared shielding film which concerns on a comparative example has not implement | achieved both thermal insulation performance and the reduction of the angle dependence of a color tone. For example, in Comparative Examples 2 and 3, since there is no dielectric multilayer film, the angle dependency of the color tone is low, but it is understood that the heat shielding performance is insufficient. Further, for example, in Comparative Examples 4 to 7, it can be seen that although the thermal insulation performance is obtained by the dielectric multilayer film, the angle dependency of the color tone is high.

  This application is based on Japanese Patent Application No. 2013-125802 filed on June 14, 2013, the disclosure of which is incorporated by reference in its entirety.

Claims (7)

A dielectric multilayer film including a high refractive index layer and the low refractive index layer comprises a hard coat layer, a, ^{a *} in ^{the L} * ^a * ^{b *} color system is ^{a *} ≦ -3.5, and, b ^An infrared shielding film in which ^* is −12 ≦ b ^* ≦ 5. The infrared shielding film according to claim 1, wherein the b ^* is −12 ≦ b ^* ≦ 2.   The infrared shielding film according to claim 1 or 2, wherein at least one of the high refractive index layer and the low refractive index layer contains metal oxide particles.   The infrared shielding film of any one of Claims 1-3 in which the said hard-coat layer contains an infrared absorber.   The infrared shielding film according to claim 1, wherein the hard coat layer includes at least one of a pigment and a dye.   The infrared shielding body containing a base | substrate and the infrared shielding film of any one of Claims 1-5 arrange | positioned at the at least one surface of the said base | substrate.   The infrared shielding film according to any one of claims 1 to 5, a pair of intermediate films sandwiching the infrared shielding film, a pair of plate glasses sandwiching the infrared shielding film and the intermediate film, Including heat ray reflective laminated glass.