Film-equipped glass and hard-coated film

Abstract

Disclosed are a film-attached glass and a film with a hard coat layer, the film-attached glass having a laminated film on top of a glass, the laminated film being a polyester laminated film that is composed of at least 50 layers and has reflective properties with respect to a near-infrared region, the laminated film having a hard coat layer, and the film with a hard coat layer being formed on top of the laminated film. The present invention relates to a film with a hard coating layer, which has a solar reflectance of 20% or more and a reduction in visible light transmittance of less than 8% compared to pure glass, and which is used in combination with glass and has a hard coating layer on a laminated film, the laminated film is a polyester laminated film which is composed of at least 50 layers and has reflection characteristics in the near-infrared region, and the solar reflectance of the laminated film is 20% or more.

Description

Technical Field

[0001] The present invention relates to a glass with a film and a film with a hard coating. Background Art

[0002] As a measure to save energy in buildings, residential structures, and transportation facilities like trains and cars, the development of transparent materials with heat-shielding properties has been underway. For example, a transparent material for window panels has been developed that transmits visible light from sunlight entering through the window while shielding heat rays, preventing indoor heat from escaping.

[0003] As a method for imparting a heat ray shielding function to a transparent material for a window panel, a method of uniformly forming a metal layer such as aluminum on a film or the like is widely used.

[0004] However, such a uniform metal layer generally reflects electromagnetic waves, making it difficult to use mobile phones, portable televisions, etc. indoors or in cars. Consequently, the development of glass sheets and films that shield heat rays but transmit electromagnetic waves is progressing.

[0005] Examples of such transparent materials for window panels include those that incorporate a heat-absorbing material into glass or the interlayer film used in laminated glass to shield against heat rays, and those that incorporate a polymer multilayer laminate film composed of alternating layers of polymers with different refractive indices inserted between glass panes to reflect and shield against heat rays. Methods using heat-absorbing materials convert incident sunlight into heat energy, leading to problems such as reduced heat-blocking efficiency due to radiation from this heat into the interior of the room. Heat absorption can also cause the glass temperature to rise, leading to breakage due to the temperature difference between the glass and the outside air.

[0006] On the other hand, polymer multilayer laminate films can selectively reflect near-infrared light because their layer thickness can be controlled to select the wavelength to be reflected. This allows them to improve heat shielding performance while maintaining visible light transmittance and excellent radio wave transmittance.

[0007] However, when a stretched film is used as a polymer multilayer laminate film, the refractive index of the film may be different in the three orthogonal directions of the width, length, and thickness of the film, resulting in a large phase difference. Therefore, there is a problem that when the phase difference is within a specific range, interference colors will be seen when observed through a polarizing device such as polarized sunglasses.

[0008] Therefore, Patent Document 1 reports a laminated film that suppresses interference colors and has good visibility even when observed through a polarizer, and a glass window member using the laminated film.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent No. 6225495 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] However, it is desired to further improve the heat shielding performance of transparent materials while maintaining the visible light transmittance performance.

[0014] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a glass with a film and a film with a hard coat layer that are excellent in heat shielding performance and also excellent in visible light transmittance.

[0015] Solutions for solving problems

[0016] The present inventors have discovered that heat shielding performance can be effectively improved by combining glass with a specific laminated film having a reflective property in the near-infrared region.

[0017] The present invention has been completed based on such research and has the following structure.

[0018] (1) The glass with a film of the present invention has a laminated film on glass, and is characterized in that:

[0019] The laminated film is a polyester laminated film composed of at least 50 layers and having a reflective property in the near infrared region.

[0020] The laminated film has a hard coating layer,

[0021] The glass with the film has a solar reflectivity of more than 20%, and a reduction in visible light transmittance of less than 8% compared with pure glass.

[0022] (2) Preferably, the glass is clear glass, green glass, multi-layer glass, low-e multi-layer glass, laminated glass or low-e laminated glass.

[0023] (3) Preferably, the glass is a low-emissivity multi-layer glass, wherein the low-emissivity multi-layer glass is a multi-layer glass having a hollow layer between a plurality of glass sheets, and a low-emissivity film is provided on the hollow layer side of at least one glass sheet, and the low-emissivity multi-layer glass has a reflective property for a specific wavelength.

[0024] (4) Preferably, the glass is the low-emissivity laminated glass, which is a laminated glass having a structure in which a low-emissivity film is sandwiched between a plurality of glass plates, and the low-emissivity laminated glass has a reflection characteristic for a specific wavelength.

[0025] (5) Preferably, the glass is green glass, and the green glass has absorption characteristics with respect to the infrared region.

[0026] (6) In the film-coated glass of the present invention, it is preferred that the laminated film be disposed on the indoor side.

[0027] (7) The solar reflectance of the film-coated glass of the present invention is preferably 28% or more.

[0028] (8) The hard-coated film of the present invention is a hard-coated film having a hard coat layer on a laminated film used in combination with glass, and is characterized in that:

[0029] The laminated film is a polyester laminated film composed of at least 50 layers and having a reflective property in the near infrared region.

[0030] The solar reflectivity of the laminated film is greater than 20%.

[0031] (9) The hard-coated film of the present invention preferably has a hard coat layer on at least one side of the laminated film and an adhesive layer on the hard coat layer or on the side opposite to the side where the hard coat layer is provided.

[0032] (10) The film with a hard coat layer of the present invention preferably has the hard coat layer and the adhesive layer on different surfaces.

[0033] (11) Preferably, the glass in the film with a hard coat layer of the present invention is clear glass, green glass, multiple glass, low-emissivity multiple glass, laminated glass, or low-emissivity laminated glass.

[0034] (12) It is preferred that the average reflectivity of the laminated film in the film with a hard coat layer of the present invention is 70% or more in the wavelength range of 900 nm to 1200 nm.

[0035] (13) The thickness of the laminated film in the film with a hard coat layer of the present invention is preferably 30 μm to 500 μm.

[0036] Effects of the Invention

[0037] The glass with a film and the film with a hard coat layer of the present invention are excellent in heat shielding performance and also excellent in visible light transmission performance. DETAILED DESCRIPTION

[0038] Hereinafter, embodiments of the present invention will be described. However, the embodiments of the present invention are not limited to the following embodiments.

[0039] The glass with a film according to this embodiment has a laminated film on glass and is characterized in that:

[0040] The laminated film is a polyester laminated film composed of at least 50 layers and having a reflective property in the near infrared region.

[0041] The laminated film has a hard coating layer,

[0042] The glass with the film has a solar reflectivity of more than 20%, and a reduction in visible light transmittance of less than 8% compared with pure glass.

[0043] The film with a hard coating layer of the present embodiment is used in combination with glass and has a hard coating layer on a laminated film, and is characterized in that:

[0044] The laminated film is a polyester laminated film composed of at least 50 layers and having a reflective property in the near infrared region.

[0045] The solar reflectivity of the laminated film is greater than 20%.

[0046] Alternatively, in the film with a hard coating according to this embodiment, the laminated film may have a hard coating on at least one side thereof, and an adhesive layer on the hard coating or on the side opposite to the side on which the hard coating is disposed. Alternatively, the film with a hard coating according to this embodiment may have the hard coating and the adhesive layer on different sides thereof.

[0047] Alternatively, in the film-coated glass of this embodiment, a hard coating layer may be provided on at least one side of the laminate film, and an adhesive layer may be provided on the hard coating layer or on the side opposite to the side where the hard coating layer is provided. Alternatively, in the film-coated glass of this embodiment, the hard coating layer and the adhesive layer may be provided on different sides of the laminate film. In this case, the film-coated glass of this embodiment may also have a hard coating layer on the side of the laminate film opposite to the side where the glass is provided, and an adhesive layer may be provided between the glass and the laminate film.

[0048] In this specification, heat insulation means heat ray shielding property.

[0049] (visible light, near infrared, far infrared, ultraviolet)

[0050] In this specification, visible light refers to electromagnetic waves that can be seen by the naked eye, and refers to electromagnetic waves with a wavelength of generally 380nm to 780nm. Near-infrared rays refer to electromagnetic waves with a wavelength of approximately 800nm ​​to 2500nm, with a wavelength close to that of red visible light. Near-infrared rays are included in sunlight and have the effect of heating objects. In contrast, far-infrared rays are electromagnetic waves with a wavelength of approximately 5μm to 20μm (5000nm to 20000nm), which are not included in sunlight and are close to the wavelength radiated from objects near room temperature. In addition, ultraviolet rays refer to electromagnetic waves with a wavelength of approximately 10nm to 380nm.

[0051] In this specification, heat rays refer to the range from ultraviolet rays to near infrared rays.

[0052] Hereinafter, the components constituting the glass with a film and the film with a hard coat layer will be described, and the components common to both will also be described.

[0053] (Glass)

[0054] Glass with a film and glass with a film with a hard coating is a transparent plate used to allow sunlight to irradiate the interior of buildings, vehicles, ships, etc. from the outside. Usually, so-called inorganic glass plates are used. As an inorganic glass, soda lime glass is representative. As the shape of the window glass, curved surface, plate shape, etc. can be cited. As glass, for example, transparent glass, green glass, multi-layer glass, low-emissivity multi-layer glass, laminated glass, low-emissivity laminated glass, etc. can be used. Among them, the use of low-emissivity multi-layer glass, low-emissivity laminated glass, and green glass is preferred because it can obtain higher thermal insulation performance while maintaining a high visible light transmittance, and the use of low-emissivity multi-layer glass is particularly preferred.

[0055] Preferably, low-E multi-layer glass is a type of multi-layer glass that has a hollow layer between multiple (e.g., two) glass sheets, with a low-E film applied to the surface of at least one glass sheet facing the hollow layer. This low-E multi-layer glass has reflective properties for specific wavelengths (preferably in the infrared region). Low-E multi-layer glass can be either thermally insulating or heat-isolating. Furthermore, preferably, low-E laminated glass is a type of laminated glass that has a low-E film sandwiched between multiple (e.g., two) glass sheets, and has reflective properties for specific wavelengths (preferably in the infrared region). Preferably, green glass is made by adding metal to glass raw materials and has infrared absorption properties.

[0056] Preferably, the low-emissivity film has the function of reducing the emissivity of thermal energy (such as infrared rays) and is a film containing at least one selected from the group consisting of metals, metal oxides, and metal nitrides. Examples of such low-emissivity films include single-layer films and multi-layer films formed by sputtering, CVD, powder coating, spraying, vapor deposition, etc. The film components include metals such as Ag and Al, metal oxides and metal nitrides containing Zn, Ga, Ti, Sn, Si, Ta, Al, In, Ni, Cr, and Zr, and alloys, alloy oxides, and alloy nitrides of the above metals.

[0057] (Laminated Film)

[0058] The laminated film is formed by alternately laminating 50 or more layers of two or more polyester films having different optical properties. The different optical properties here refer to the case where the difference in refractive index is greater than 0.01 in any direction selected from two orthogonal directions arbitrarily selected within a plane and a direction perpendicular to the plane. In addition, the alternate lamination mentioned here refers to the case where polyester films composed of different resins are stacked in a regular arrangement in the thickness direction. By alternately laminating polyester films with different optical properties in this way, it is possible to reflect light of a specific wavelength specified by the relationship between the difference in the refractive index of each layer and the thickness. In addition, the number of laminated layers is preferably more than 400 layers, more preferably more than 800 layers. In addition, the upper limit of the number of layers is, for example, about 1000 layers. The more the number of layers increases, the higher the reflectivity can be achieved for light in a wider wavelength band, and thus a laminated film with higher heat insulation performance can be obtained.

[0059] The average reflectivity of the laminated film at a wavelength of 900 nm to 1200 nm is desirably 70% or higher. For applications requiring high transparency, by effectively reflecting light at wavelengths slightly longer than the visible light region, such as 900 nm to 1200 nm, high thermal insulation performance can be achieved while maintaining transparency. Preferably, the average reflectivity of the laminated film at a wavelength of 900 nm to 1200 nm is 80% or higher, and more preferably, the average reflectivity of the laminated film at a wavelength of 900 nm to 1200 nm is 90% or higher.

[0060] Similarly, for coated glass, it is desirable that the average reflectivity in the wavelength range of 900nm to 1200nm on at least one surface be 60% or higher. More desirably, the average reflectivity in the wavelength range of 900nm to 1200nm on both surfaces of the coated glass be 60% or higher. Furthermore, it is preferred that the average reflectivity in the wavelength range of 900nm to 1200nm on at least one surface of the coated glass be 70% or higher. Improving thermal insulation by increasing reflectivity is preferable because it reduces the risk of thermal cracking caused by heat absorption in the glass. The shielding coefficient, commonly used to measure thermal insulation performance, reflects the effects of both increased absorptivity and increased reflectivity. However, for the reasons mentioned above, increasing reflectivity is preferred over increasing absorptivity, particularly in window glass for buildings.

[0061] The polyester resin used in the laminated film may be a copolymer or a mixture. As the polyester, a polyester obtained by polymerizing a monomer having an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid and a diol, or an ester-forming derivative of the above components as the main constituent components is preferred. Here, as aromatic dicarboxylic acids, for example, terephthalic acid, phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, etc. can be mentioned. As aliphatic dicarboxylic acids, for example, adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, and ester derivatives of the above components can be mentioned. Among them, terephthalic acid and 2,6-naphthalenedicarboxylic acid are also preferred. The above components may be used alone or in combination of two or more. Furthermore, partial copolymerization of oxygen-containing acids such as hydroxybenzoic acid may also be performed.

[0062] Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxyethoxyphenyl)propane, diethylene glycol, triethylene glycol, polyalkylene glycol, isosorbide, and spiroglycol. Among these, ethylene glycol is preferred. The above diol components may be used alone or in combination of two or more.

[0063] Preferred polyester resins used for the laminated film include polyethylene terephthalate and copolymers thereof, polyethylene naphthalate and copolymers thereof, polybutylene terephthalate and copolymers thereof, polybutylene naphthalate and copolymers thereof, polyhexamethylene terephthalate and copolymers thereof, and polyhexamethylene naphthalate and copolymers thereof.

[0064] For the laminated film, it is preferred that the difference in the in-plane average refractive index of the layers composed of adjacent polyester resins having different optical properties is greater than 0.03, more preferably that the difference in the in-plane average refractive index of the above-mentioned layers is greater than 0.05, and further preferably that the difference in the in-plane average refractive index of the above-mentioned layers is greater than 0.1 and less than 0.15.

[0065] Specific examples of laminated films include those in which at least one polyester resin comprises polyethylene terephthalate or polyethylene naphthalate, and at least one polyester resin comprises spiroglycol carboxylate units. More preferably, at least one polyester resin comprises polyethylene terephthalate or polyethylene naphthalate, and at least one polyester resin is a polyester obtained using spiroglycol and cyclohexanedicarboxylic acid.

[0066] In addition, as another specific example of a laminated film, there can be cited a laminated film in which at least one polyester resin is formed by containing polyethylene terephthalate or polyethylene naphthalate, and at least one polyester resin is formed by containing cyclohexanedimethanol carboxylate units, wherein the latter at least one polyester resin may be a single component, or may be copolymerized with a small amount of other repeating units, or may be mixed with a small amount of other polyester resins.

[0067] The laminated film can be a biaxially stretched film. Stretching can be performed sequentially in two directions or simultaneously. The stretching ratio varies depending on the type of resin, but is generally preferably 2 to 15 times, more preferably 2 to 7 times. The laminated film can also be a laminated film that has been subjected to a surface treatment such as corona treatment, flame treatment, or plasma treatment as needed, and then imparted with lubricity, adhesion, antistatic properties, and other functionalities by inline coating.

[0068] As the laminated film, for example, a film described in Japanese Patent No. 6225495 can be used.

[0069] The thickness of the laminated film is not particularly limited, and is, for example, 30 μm to 500 μm, preferably 35 μm to 400 μm, and more preferably 40 μm to 300 μm.

[0070] (Hard Coating)

[0071] The hard coating layer is a layer provided on at least one surface of the laminate film. The hard coating layer can be provided on the side of the laminate film opposite to the surface on which the glass is disposed, or between the glass and the laminate film, but is preferably provided on the side of the laminate film opposite to the surface on which the glass is disposed.

[0072] The film thickness of the hard coat layer is 0.1 μm to 20 μm, preferably 0.5 μm to 10 μm, and more preferably 0.9 μm to 6 μm.

[0073] In the hard coat layer, ultraviolet curing resins are used because they can relatively easily form a high-hardness film. Examples of ultraviolet curing resins include acrylic resins, silicone resins, urethane resins, olefin resins, and ester resins. However, acrylic resins are preferred because of their ease of handling and processing.

[0074] Ultraviolet-curable acrylic resins are polymers of curable compositions composed of monomers or oligomers having an acrylic polymerizable unsaturated group. Monomers or oligomers having an acrylic polymerizable unsaturated group can be monofunctional or polyfunctional.

[0075] Specific examples of the monofunctional monomer having an acrylic polymerizable unsaturated group include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate. These components may be used alone or in combination of two or more.

[0076] Specific examples of the monofunctional oligomer having an acrylic polymerizable unsaturated group include ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, and phenoxypolyethylene glycol acrylate.

[0077] In order to make the composition composed of monomers or oligomers having an acrylic polymerizable unsaturated group curable, it is preferred that the monomers or oligomers having an acrylic polymerizable unsaturated group contain a multifunctional (meth)acrylate. Specific examples of the multifunctional (meth)acrylate include dipropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, modified bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and other difunctional (meth)acrylates, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and the like. The present invention also provides a kind of (meth)acrylate with the function of modifying the polyfunctional acrylate. The polyfunctional acrylates include trifunctional (meth)acrylates such as trimethylolpropane ethoxy tri(meth)acrylate, polyether tri(meth)acrylate, and glycerol propoxy tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. The polyfunctional acrylates may be used alone or in combination of two or more. In order to ensure the hardness of the hard coat layer, it is preferred to use a tetrafunctional (meth)acrylate.

[0078] Furthermore, it is preferred to use a fluorine-containing acrylic resin in which a part of hydrogen atoms are substituted with fluorine atoms as the monomer or oligomer having an acrylic polymerizable unsaturated group, because the scratch resistance and antifouling properties are further improved.

[0079] Ultraviolet-curable urethane-based curable resins refer to polymers of urethane acrylate monomers or oligomers. Urethane acrylate oligomers are oligomers in which a polyoxyalkylene segment or a saturated polyester segment, or both, is bonded via a urethane bond and have acryloyl groups at both terminals.

[0080] In order to form an ultraviolet curable resin, it is necessary to add a polymerization initiator to the above-mentioned monomer or oligomer having a polymerizable unsaturated group as needed to form an ultraviolet curable composition.

[0081] As the ultraviolet polymerization initiator, various known polymerization initiators can be used. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, α-hydroxyacetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 4-[ ... -(2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, propiophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoate, etc. The above-mentioned ultraviolet polymerization initiators can be used alone or in combination of two or more. Preferably, the amount of ultraviolet polymerization initiator added is 1% to 10% by mass relative to the monomer or oligomer having a polymerizable unsaturated group.

[0082] In addition, hard coat layer can also contain the component other than the above-mentioned in the scope of not damaging the effect of the present embodiment as needed.As the component that can be added to hard coat layer, for example, can enumerate ultraviolet light absorber, light stabilizer (hindered amine light stabilizer (HALS) etc.), fluorine type antifouling agent etc.

[0083] (Adhesive layer)

[0084] The adhesive layer is a layer that bonds the laminated film to the glass. Adhesives and adhesives commonly used for glass bonding, etc., can be used as materials for the adhesive layer. Examples of materials used for the adhesive layer include various resins such as acrylic resins, rubber resins (natural rubber, polybutadiene, etc.), silicone resins, urethane resins, polyvinyl butyral resins, polyvinyl acetal resins, and ethylene-vinyl acetate resins. Among the above materials, from the perspective of durability, it is preferred that at least one of an acrylic resin, a rubber resin, and a silicone resin be contained.

[0085] (Method for producing a film with a hard coat layer)

[0086] Next, a method for producing the film with a hard coat layer according to this embodiment will be described.

[0087] The film with a hard coat layer of the present embodiment can be produced by forming a hard coat layer on a laminated film.

[0088] The method for forming a hard coat layer is described below. An appropriate amount of a UV-curable resin is mixed with a solvent to prepare a solution of appropriate viscosity. This solution is applied to the laminate film. After drying, the hard coat layer can be formed by a curing reaction using ultraviolet light.

[0089] The method for forming the adhesive layer is described below. First, an appropriate amount of solvent is mixed with an adhesive or binder to prepare a coating composition solution of appropriate viscosity. The resulting solution is then applied to the laminated film. The solution is then dried to form the adhesive layer. Alternatively, the adhesive layer may be formed by applying the resulting solution to another sheet, and then the adhesive layer may be attached to the laminated film.

[0090] The film-coated glass of the present embodiment can be produced by using a film with a hard coating layer having an adhesive layer and bonding the film with a hard coating layer to glass via the adhesive layer.

[0091] In the film-coated glass of this embodiment, the laminated film may be attached to either the indoor side or the outdoor side, but it is preferable to arrange the laminated film on the indoor side.

[0092] [Performance of Glass with Film and Performance of Film with Hard Coat]

[0093] Hereinafter, various properties of the glass with a film and the film with a hard coat layer will be described.

[0094] (Visible light transmittance)

[0095] The coated glass and the hard-coated film transmit visible light with a wavelength of 380 nm to 780 nm. Preferably, the visible light transmittance of the coated glass and the hard-coated film is 60% or higher. A visible light transmittance of 60% or higher provides excellent visibility. A more preferred value is 70% or higher. Furthermore, the coated glass preferably exhibits a reduction in visible light transmittance of less than 8%, and more preferably less than 5%, compared to pure glass. Visible light transmittance can be measured using a spectrophotometer in accordance with JIS S3107:2013.

[0096] (Solar reflectivity)

[0097] Preferably, the solar reflectance of the filmed glass and the hard-coated film is 20% or higher. A solar reflectance of 20% or higher provides excellent thermal insulation. A solar reflectance of 28% or higher is more preferred, and 30% or higher is even more preferred. Solar reflectance can be measured using a spectrophotometer in accordance with JIS S3107:2013.

[0098] The film with a hard coating layer of the present embodiment has excellent visible light transmission performance and excellent heat insulation performance, so it can be attached to glass such as windows of buildings, windows of vehicles such as automobiles, etc. In addition, the glass with a film of the present embodiment can also be used as window glass.

[0099] Example

[0100] This embodiment will be described in more detail with reference to the following examples.

[0101] (Example 1)

[0102] (Preparation of thermoplastic resin)

[0103] As thermoplastic resin A, [Toray F20S] (polyethylene terephthalate, intrinsic viscosity 0.65, melting point 255°C, in-plane refractive index of a film obtained by stretching and heat treating the resin: 1.66) was prepared. As thermoplastic resin B, a copolymer having an intrinsic viscosity of 0.72 and being amorphous, obtained by copolymerizing 80 mol% of polyethylene terephthalate and 20 mol% of spiroglycol (in-plane refractive index of a film obtained by stretching and heat treating the resin: 1.55) was prepared.

[0104] (Production of Laminated Body)

[0105] After the thermoplastic resins A and B were melted at 280°C using a vented twin-screw extruder, they were alternately layered and combined in a feed zone to produce a laminate. The thickness of each layer was adjusted to be identical. The outermost layers on both the front and back sides of the laminate were made of thermoplastic resin A. After the laminate was discharged from a T-die and formed into a sheet, it was placed in contact with a casting drum and cooled to produce a laminate.

[0106] (Stretching treatment)

[0107] The laminate was heated with a roller set to a surface temperature of 80° C., and then further heated with a radiation heater to a temperature of 90° C., stretched 4 times in the longitudinal direction, and then cooled to obtain a uniaxially stretched film.

[0108] (Surface Treatment)

[0109] After corona discharge treatment was applied to both sides of the uniaxially stretched film in air, a dispersion of a composition containing 2% by mass of silica particles (trade name: Seahoster KE, manufactured by Nippon Shokubai Co., Ltd.) and 98% by mass of a polyester resin (trade name: TP294, manufactured by Mitsubishi Chemical Corporation) was applied to form a 200 nm thick easy-adhesion layer.

[0110] The uniaxially stretched film was heated to 100° C. using a heater and stretched 4 times in the transverse direction using a tenter. The film was then slowly cooled to room temperature and wound up.

[0111] The resulting laminated film has a thickness of 75 μm. Furthermore, while reflecting light from 900 to 1200 nm, it maintains high transparency and exhibits a nearly flat reflectance distribution within the visible light region of 400 to 700 nm. The average reflectance within the 900 to 1200 nm wavelength range for a single laminated film is 90% or higher. The laminated film comprises at least 50 layers.

[0112] (Formation of Hard Coat Layer)

[0113] A coating material composed of 100 parts by mass of Aronix (trademark) M-940 (hexafunctional acrylate, solid content 100% by mass) manufactured by Toagosei Co., Ltd., 4 parts by mass of Irgacure 184 (photoinitiator, solid content 100% by mass) manufactured by BASF, 0.5 parts by mass of Optool DAC-HP (fluorinated antifouling material, solid content 20% by mass) manufactured by Daikin Industries, Ltd., and 1300 parts by mass of PGM (solvent, solid content 0% by mass) was applied to one side of the obtained laminated film using a Meyer bar to a thickness of 2.0 μm after drying, and dried at 80° C. for 1 minute. Subsequently, the coating material was heated under a high-pressure mercury lamp (illuminance 400 mW / cm 2 ) According to the light intensity, it becomes 150mJ / cm 2 The coating is cured by irradiating ultraviolet light to form a hard coating.

[0114] (Formation of Adhesive Layer)

[0115] A coating consisting of 100 parts by mass of SK1429DT (acrylic adhesive, 30% solid content) manufactured by Soken Chemical Co., Ltd., 3 parts by mass of AD-5A (aluminum complex curing agent, 5% solid content) manufactured by Soken Chemical Co., Ltd., and 3 parts by mass of Tinuvin (trademark) 928 (benzotriazole ultraviolet absorber, 100% solid content) manufactured by BASF was applied to the silicone-treated surface of a diaphragm sheet (manufactured by Mitsubishi Chemical Corporation, MRQ#38, 38 μm thickness) and dried in a hot air oven at 100°C for two minutes to form an adhesive layer with a thickness of approximately 12 μm.

[0116] The PET surface of the film and the adhesive surface of the separator sheet were laminated and aged for 7 days to prepare a film with an adhesive layer.

[0117] (Production of Glass with Film)

[0118] The separator sheet of the film with the adhesive layer was peeled off, and the adhesive surface was laminated on a Low-E multi-layer glass (heat-insulating type) transparent type (neutral) manufactured by YKK AP Co., Ltd., to produce a film-coated glass of Example 1.

[0119] (Example 2)

[0120] A glass with a film was produced in the same manner as in Example 1, except that float glass with a nominal thickness of 3 mm was used as the laminated glass.

[0121] (Example 3)

[0122] A glass with a film was produced in the same manner as in Example 1 except that green glass (manufactured by AGC Corporation, trade name: Sungreen, nominal thickness 5 mm) was used as the laminated glass.

[0123] (Example 4)

[0124] A film-coated glass was produced in the same manner as in Example 1 except that the thermoplastic resin A and the thermoplastic resin B were laminated so that the average reflectivity at 900 nm to 1200 nm in a single laminated film was 80% or more and formed to 108 μm.

[0125] (Example 5)

[0126] A glass with a film was produced in the same manner as in Example 4 except that float glass with a nominal thickness of 3 mm was used as the laminated glass.

[0127] (Example 6)

[0128] A glass with a film was produced in the same manner as in Example 4 except that green glass (manufactured by AGC Corporation, trade name: Sungreen, nominal thickness 5 mm) was used as the laminated glass.

[0129] (Comparative Example 1)

[0130] A polyethylene terephthalate film (highly adhesive biaxially oriented PET film, Cosmoshine (trademark) A4360 manufactured by Toyobo Co., Ltd., thickness 38 μm) was used instead of the laminate film, and a coating material consisting of 100 parts by mass of Aronix M-940 manufactured by Toagosei Co., Ltd. (hexafunctional acrylate, solid content 100 mass%), 4 parts by mass of Irgacure 184 manufactured by BASF, 0.5 parts by mass of Optool DAC-HP manufactured by Daikin Industries, Ltd. (fluorinated antifouling material, solid content 20 mass%), 1300 parts by mass of PGM (solvent, solid content 0 mass%), and 90 parts by mass of YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd. (near-infrared absorbing material, solid content 18.5 mass%) was used to form a hard coat layer. Except for the above, a glass with a film was produced in the same manner as in Example 1.

[0131] (Comparative Example 2)

[0132] A glass with a film was produced in the same manner as in Comparative Example 1, except that float glass having a nominal thickness of 3 mm was used as the laminated glass.

[0133] (Comparative Example 3)

[0134] A glass with a film was produced in the same manner as in Comparative Example 1, except that green glass (manufactured by AGC Corporation, trade name: Sungreen, nominal thickness 5 mm) was used as the laminated glass.

[0135] (Comparative Example 4)

[0136] Instead of a laminated film, a film comprising three metal oxide layers was formed by sputtering the following: a first metal oxide layer 1, a first silver alloy layer 2, a second metal oxide layer 3, a second silver alloy layer 4, and a third metal oxide layer 5, sequentially laminated onto one surface of a polyethylene terephthalate film (highly adhesive biaxially oriented PET film, Cosmoshine (trademark) A4360 manufactured by Toyobo Co., Ltd., thickness 38 μm). A glass film with the film was produced in the same manner as in Example 1, except for the above details. The sputtering was performed under a vacuum of 0.4 Pa. The composition and thickness of each layer are as follows. Furthermore, an adhesive layer was formed on the metal oxide layer surface of the obtained film, and a hard coating layer was formed on the PET surface.

[0137] 1st metal oxide layer 1: ITO, 27nm

[0138] First silver alloy layer 2: AgPd (silver alloy containing 1 atomic % palladium), 10 nm

[0139] Second metal oxide layer 3: ITO, 55nm

[0140] Second silver alloy layer 4: AgPd (silver alloy containing 1 atomic % of palladium), 10 nm

[0141] Third metal oxide layer 5: ITO, 27nm

[0142] (Comparative Example 5)

[0143] A glass with a film was produced in the same manner as in Comparative Example 4, except that float glass having a nominal thickness of 3 mm was used as the laminated glass.

[0144] (Comparative Example 6)

[0145] A glass with a film was produced in the same manner as in Comparative Example 4 except that green glass (manufactured by AGC Corporation, trade name: Sungreen, nominal thickness 5 mm) was used as the laminated glass.

[0146] <Evaluation Items>

[0147] (visible light transmittance, visible light reflectance, sunlight transmittance, sunlight reflectance, sunlight absorptivity)

[0148] The measurement was performed using a spectrophotometer (SolidSpec-3700i DUV manufactured by Shimadzu Corporation) within a wavelength range of 300 nm to 2500 nm in accordance with JIS S3107: 2013. The solar absorption rate was determined using the following formula.

[0149] (Solar absorption rate) = 100% - (Solar transmittance) - (Solar reflectance)

[0150] Evaluation criteria for visible light transmittance: For the reduction in visible light transmittance, "A" is set when it is less than 5% compared to pure glass, "B" is set when it is 5% or more and less than 7% compared to pure glass, "C" is set when it is 7% or more and less than 8% compared to pure glass, and "D" is set when it is 8% or more compared to pure glass.

[0151] Evaluation criteria for solar reflectance: For solar reflectance, a solar reflectance of 30% or more is designated as "A", a solar reflectance of 28% or more and less than 30% is designated as "B", a solar reflectance of 20% or more and less than 28% is designated as "C", and a solar reflectance of less than 20% is designated as "D".

[0152] Evaluation criteria for comprehensive evaluation: The lower one of the evaluation of visible light transmittance and the evaluation of solar reflectance was used.

[0153] (Shielding coefficient)

[0154] Spectral reflectance was measured using a Fourier transform infrared spectrophotometer (IRTracer-100, manufactured by Shimadzu Corporation) within the wavelength range of 5.5 μm to 25 μm. Normal emissivity was determined according to the calculation method for normal emissivity in Annex JB, JB.2, of JIS R 3106 (Test methods for transmittance, reflectance, and emissivity of sheet glass and calculation method for solar heat gain of sheet glass for architectural use). The normal emissivity was calculated using the spectral reflectance at a wavelength of 23.3 μm for the wavelength range of 25.2 μm to 50.0 μm. The shielding coefficient was calculated using the obtained normal emissivity in accordance with JIS S3107:2013.

[0155] Table 1 shows the evaluation results of the hard coat layers of Examples 1 to 6 and Comparative Examples 1 to 6, as well as the laminated films with adhesive layers and the film-coated glasses.

[0156] [Table 1]

[0157]

[0158] The shielding coefficients of the films used in Examples 1-3 and Comparative Examples 1-6 were comparable, ranging from 0.73 to 0.76. In Examples 1-6, the reduction in visible light transmittance compared to pure glass was within 4%. In Comparative Examples 1-6, the visible light transmittance was reduced by at least 8% compared to pure glass.

[0159] Solar reflectivity increased in Examples 1-6 and Comparative Examples 4-6 compared to that of pure glass. The Examples exhibited higher solar reflectivity than the Comparative Examples. Specifically, the solar reflectivity was 30% or higher in Example 1, Example 3, Example 4, and Comparative Example 4; 28% or higher in Example 6 and Comparative Example 1; 20% or higher in Example 2, Example 5, Comparative Example 5, and Comparative Example 6; and less than 20% in Comparative Examples 2 and 3.

[0160] In Example 3, Example 6, and Comparative Example 6, the sunlight absorption rate is greatly reduced compared to pure Sungreen.

[0161] From the results of visible light transmittance and solar reflectance, Examples 1 to 6 have excellent heat shielding performance while maintaining transparency.

[0162] Furthermore, the increase in solar reflectance obtained by comparison with pure glass is shown in Table 2. The ratios of the increase in solar reflectance of Film a and Film b relative to the increase in solar reflectance of Film d are 1.8 and 2.4 only when Low-E multilayer glass is used, which are higher values ​​than the values ​​of 1.0 to 1.3 for the other two types of glass.

[0163] [Table 2]

[0164]

[0165] Based on the above results, the present invention provides a glass with a film and a film with a hard coat layer that are excellent in both heat shielding performance and visible light transmittance performance.

Claims

1. A glass with a film, comprising a laminated film on the glass, wherein: The laminated film is a polyester laminated film composed of at least 50 layers and having a reflective property in the near infrared region. The laminated film has a hard coating layer, The glass with the film has a solar reflectivity of more than 20%, and a reduction in visible light transmittance of less than 8% compared with pure glass.

2. The glass with a film according to claim 1, wherein: The glass is clear glass, green glass, multi-layer glass, low-e multi-layer glass, laminated glass or low-e laminated glass.

3. The glass with a film according to claim 1, wherein: The glass is low-e multi-layer glass, The low-e multi-layer glass is a multi-layer glass having a hollow layer between a plurality of glass sheets, and a low-e film is provided on a hollow layer side surface of at least one glass sheet. The low-e multi-layer glass has a reflection characteristic for a specific wavelength.

4. The glass with a film according to claim 1, wherein The glass is low-e laminated glass, The low-emissivity laminated glass is a laminated glass having a structure in which a low-emissivity film is sandwiched between a plurality of glass plates, and the low-emissivity laminated glass has a reflection characteristic for a specific wavelength.

5. The glass with a film according to claim 1, wherein The glass is green glass, The green glass has absorption properties in the infrared region.

6. The glass with a film according to any one of claims 1 to 5, wherein The laminated film is arranged on the indoor side.

7. The glass with a film according to any one of claims 1 to 5, wherein The solar reflectivity of the film-coated glass is greater than 28%.

8. A film with a hard coating layer, the film being used in combination with glass and comprising a hard coating layer on a laminated film, wherein: The laminated film is a polyester laminated film composed of at least 50 layers and having a reflective property in the near infrared region. The solar reflectivity of the laminated film is greater than 20%.

9. The film with a hard coat according to claim 8, wherein The laminate film has a hard coat layer on at least one side thereof, and has an adhesive layer on the hard coat layer or on the side opposite to the side where the hard coat layer is provided.

10. The film with a hard coating according to claim 9, wherein The hard coating layer and the adhesive layer are provided on different surfaces.

11. The film with a hard coat layer according to any one of claims 8 to 10, wherein The glass is clear glass, green glass, multi-layer glass, low-e multi-layer glass, laminated glass or low-e laminated glass.

12. The film with a hard coat layer according to any one of claims 8 to 10, wherein The laminated film has an average reflectivity of 70% or more in a wavelength range of 900 nm to 1200 nm.

13. The film with a hard coat layer according to any one of claims 8 to 10, wherein The thickness of the laminated film is 30 μm to 500 μm.

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