Laminated film

Abstract

The objective is to provide a film that can be used in a wide range of applications by possessing excellent heat-cutting performance, as well as anti-fouling and water vapor barrier properties. [Solution] A laminated film in which a coating layer is laminated on one side of a base film and an inorganic thin film layer is laminated on the side of the base film opposite to the coating layer, characterized in that the laminated film satisfies the following requirements (I) to (IV). (I) The water contact angle value on the surface of the inorganic thin film layer of the laminated film is 20° or less. (II) The ratio of the solar radiation transmittance (%Ts) to the visible light transmittance (%Tv) of the laminated film ((%Ts) / (%Tv)) is 0.80 or less. (III) The maximum protrusion height Sp on the surface of the inorganic thin film layer of the laminated film is 1.0 μm or more. (IV) The water vapor transmission rate of the laminated film under a 40°C × 90%RH environment is 2 g / m² 2 It is less than or equal to d.

Description

[Technical Field]

[0001] This invention relates to a heat-cutting film with gas barrier and anti-fouling properties, which is required for decorative panels used in windows of houses, offices, vehicles, ships, etc. that have windows that allow sunlight to enter, as well as for exterior walls of houses etc. that are exposed to sunlight, and for interior finishes of furniture, walls, doors, partition materials, etc., where heat (infrared) cutting, stain resistance, and water vapor barrier properties are required. [Background technology]

[0002] During the day, sunlight enters the windows of houses, offices, vehicles, ships, etc., as well as the exterior walls of houses, etc., causing indoor and vehicle temperatures to rise and potentially leading to deterioration of exterior walls and interior furniture. Therefore, by installing this type of heat-blocking film on windows, etc., it is possible to suppress the rise in indoor and vehicle temperatures and the deterioration of exterior walls, etc.

[0003] Furthermore, windows and exterior walls of houses and other buildings become contaminated and stained over long periods by airborne dust, vehicle exhaust fumes, soot from factory buildings, and rainwater containing these substances. Therefore, by applying an anti-fouling film to exterior walls, pollutants can be naturally washed away by rainwater alone, thus reducing staining of the exterior walls.

[0004] Furthermore, decorative laminates are excellent in terms of heat resistance, abrasion resistance, chemical resistance, and stain resistance, and also have a beautiful appearance in terms of design, so they are widely used in homes, public facilities, and various businesses for furniture, doors, partitions, etc. In recent years, user needs have diversified, and there is a growing demand for decorative laminates that are not only decorative but also resistant to dirt, can be easily wiped clean, and do not absorb moisture to prevent warping of the wooden parts. In addition to design, there is a growing demand for decorative laminates with stain resistance and water vapor barrier properties.

[0005] The performance requirements for the aforementioned window glass, exterior walls of houses, decorative panels, etc. include (1) heat-cutting properties, (2) stain resistance, and (3) water vapor barrier properties.

[0006] Conventionally, as a means of achieving both the heat-shielding and stain-resistant properties described in (1) and (2) above, a method has been described in which a heat-cutting film with anti-fogging properties is provided on a base film and attached to the window glass (for example, Patent Document 1).

[0007] Furthermore, conventionally, a melamine resin decorative panel has been provided that has the stain-resistant properties of (2) and the water vapor barrier properties of (3) as described above, comprising at least a decorative layer composed of a melamine resin layer and a gas barrier layer provided on one side of the melamine resin layer (for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-173934 [Patent Document 2] Japanese Patent Publication No. 2020-97246 [Overview of the project] [Problems that the invention aims to solve]

[0009] Patent Document 1 does not address the issue of water vapor barrier properties, and Patent Document 2 does not address the issue of heat-cutting properties. Furthermore, neither Patent Document 1 nor 2 addresses means of resolving defects in appearance or processing problems during manufacturing. In other words, there has been no material that satisfies all three points (1) to (3) above.

[0010] The objective of the present invention is to provide a multi-functional film that can be used in a wide range of applications by possessing excellent heat-cutting performance, as well as anti-fouling and water vapor barrier properties, and that is less prone to appearance defects and processing problems during film processing. [Means for solving the problem]

[0011] The inventors focused on the high affinity of the inorganic thin film layer to water in a laminated film in which an inorganic thin film layer is provided on a base film, and found that by setting the water contact angle within a predetermined range, the base film can be given antifouling properties.

[0012] Furthermore, we found that by providing a heat-cutting coating layer on the side of the laminated film opposite to the inorganic thin film layer, it is possible to maintain the barrier and antifouling properties of the inorganic thin film layer while also providing heat-cutting properties.

[0013] Furthermore, we discovered that by providing a certain level of protrusion height on the surface of the inorganic thin film layer, which is the side of the laminated film opposite to the coating layer, it is possible to suppress defects in the appearance and processing of the film, thus completing the present invention.

[0014] In other words, the present invention consists of the following configuration. 1. A laminated film in which a coating layer is laminated on one side of a base film, and an inorganic thin film layer is laminated on the side of the base film opposite to the coating layer, characterized in that the laminated film satisfies the following requirements (I) to (IV). (I) The water contact angle value on the surface of the inorganic thin film layer of the laminated film is 20° or less. (II) The ratio of the solar radiation transmittance (%Ts) to the visible light transmittance (%Tv) of the laminated film ((%Ts) / (%Tv)) is 0.80 or less. (III) The maximum protrusion height Sp on the surface of the inorganic thin film layer of the laminated film is 1.0 μm or more. (IV) The water vapor transmission rate of the laminated film under a 40°C × 90%RH environment is 2 g / m² 2 It is less than or equal to d. 2. The laminated film according to 1., wherein the laminated film is transparent and has a visible light transmittance (%Tv) of 70% or more. 3. The oxygen permeability of the laminated film under a 23°C × 65%RH environment is 300 ml / m². 2 The laminated film according to 1, characterized in that it is less than or equal to d·MPa. 4. A laminated film according to any one of 1 to 3, characterized in that it is used for a window glass of a house. 5. A laminated film according to any one of 1 to 3, characterized in that it is used for a window glass of a vehicle. 6. A laminated film according to any one of 1 to 3, characterized in that it is used for an outer wall of a house. 7. A laminated film according to any one of 1 to 3, characterized in that it is used for an outer covering of a decorative board.

Effect of the Invention

[0015] By such a technique, the inventors have provided a film that, in addition to excellent heat ray cutting performance, has all the performances of an antifouling function and a water vapor barrier property, and can be used in a wide range of applications. Moreover, during film processing, it is a multifunctional film that is unlikely to cause appearance defects or processing failures.

Mode for Carrying Out the Invention

[0016] Hereinafter, the present invention will be described in detail. A laminated film in which a coating layer is laminated on one surface of a base film, and an inorganic thin film layer is laminated on the surface of the base film opposite to the coating layer, wherein the laminated film satisfies the following requirements (I) to (IV). (I) The contact angle value of water on the surface of the inorganic thin film layer of the laminated film is 20° or less. (II) The ratio ((%Ts) / (%Tv)) of the solar transmittance (%Ts) to the visible light transmittance (%Tv) of the laminated film is 0.80 or less. (III) The maximum protrusion height Sp on the surface of the inorganic thin film layer of the laminated film is 1.0 μm or more. (IV) The water vapor permeability of the laminated film in an environment of 40°C × 90% RH is 2 g / m 2 ·d or less.

[0017] Hereinafter, each layer of the laminated film will be described. [Base Film Layer] The plastic base film used in the present invention (hereinafter referred to as "base film") can be, for example, a film obtained by melt-extruding plastic and, if necessary, stretching, cooling, and heat-setting it in the longitudinal and / or widthwise directions. Examples of plastics include polyamides represented by nylon 4-6, nylon 6, nylon 6-6, nylon 12, etc.; polyesters represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, etc.; polyolefins represented by polyethylene, polypropylene, polybutene, etc.; as well as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, fully aromatic polyamide, polyamide-imide, polyimide, polyetherimide, polysulfone, polystyrene, polylactic acid, etc. Among these, polyester is preferred in terms of heat resistance, dimensional stability, and transparency, and polyethylene terephthalate and copolymers obtained by copolymerizing polyethylene terephthalate with other components are particularly preferred.

[0018] As the base film, any thickness can be used depending on the desired purpose and application, such as mechanical strength and transparency. While the thickness is not particularly limited, it is generally recommended to be between 5 and 250 μm, and preferably between 10 and 60 μm when used as a packaging material. The transparency of the base film is not particularly limited, but when used as a packaging material where transparency is required, a light transmittance of 50% or more is desirable. Furthermore, for films with excellent mechanical strength, stretched films such as biaxially oriented polyester film and biaxially oriented nylon film are preferred.

[0019] In this invention, the antiblocking agent added to the resin can be appropriately selected from inorganic particles such as silica, calcium carbonate, kaolin, and zeolite, or organic particles such as acrylic, polymethacrylic, and polystyrene. Among these, silica and polymethacrylic particles are particularly preferred. The preferred average particle size of the antiblocking agent is not particularly limited as long as the maximum protrusion height (Sp) on the surface of the inorganic thin film layer is within a specified range, but is preferably 1.0 to 3.0 μm, and more preferably 1.0 to 2.7 μm. The method for measuring the average particle size here is to take a photograph with a scanning electron microscope, measure the horizontal Ferret diameter using an image analyzer, and display the average value.

[0020] The inorganic thin film layer surface of the laminated film of the present invention preferably has a maximum peak height (Sp) of 1.0 μm or more. More preferably, it is 1.1 μm or more, and even more preferably, 1.2 μm or more. If the maximum peak height (Sp) is less than 1.0 μm, the surface irregularities are small, which worsens the slipperiness of the film and the time it takes for air to escape between films. This makes it easier for cosmetic defects such as wrinkles and bubbles to occur when winding the film onto a roll, and the winding performance tends to deteriorate. In addition, in the present invention, since the coating layer is laminated on the side opposite to the inorganic thin film layer of the base film, blocking is more likely to occur. By keeping the maximum peak height (Sp) within the specified range, blocking problems can be suppressed. Furthermore, the upper limit of the maximum peak height (Sp) is preferably 5 μm or less. More preferably, it is 4 μm or less, and even more preferably, 3 μm or less. If it exceeds 5 μm, the surface protrusions are large, which may cause voids during inorganic thin film formation, raising concerns about poor barrier properties and other issues.

[0021] The base film may be a single-layer film made of one type of plastic, or a laminated film made by laminating two or more types of plastic films. In the case of a laminated film, the type of laminate, the number of layers, the lamination method, etc., are not particularly limited and can be arbitrarily selected from known methods depending on the purpose. Furthermore, the base film may be subjected to surface treatments such as corona discharge treatment, glow discharge treatment, flame treatment, surface roughening treatment, etc., as long as it does not impair the purpose of the present invention, and may also be subjected to known anchor coating treatments, printing, decoration, etc.

[0022] [Inorganic thin film layer] The laminated film of the present invention has an inorganic thin film layer laminated on the side opposite to the coating layer described later. The inorganic thin film layer is a thin film made of a metal or an inorganic oxide. There are no particular restrictions on the material that forms the inorganic thin film layer as long as it can be made into a thin film, but from the viewpoint of gas barrier properties and affinity with water, inorganic oxides such as aluminum, silicon dioxide (silica), aluminum oxide (alumina), and mixtures of silicon dioxide and aluminum oxide are preferred. In this composite oxide, the mixing ratio of silicon dioxide and aluminum oxide is preferably in the range of 20 to 70% by mass of Al in terms of the mass ratio of the metal content. If the Al concentration is less than 20% by mass, the water vapor barrier properties may be low. On the other hand, if it exceeds 70% by mass, the inorganic thin film layer tends to harden, and there is a risk that the film will be destroyed during secondary processing such as printing or lamination, reducing the gas barrier properties. Also, when the Al concentration is 100% by mass, the water vapor barrier performance is good, but because it is a single material, the surface tends to be smooth, resulting in poor slipperiness and making it prone to processing defects (wrinkles, blemishes, etc.). In this context, silicon oxide refers to various silicon oxides such as SiO and SiO2, or mixtures thereof, while aluminum oxide refers to various aluminum oxides such as AlO and Al2O3, or mixtures thereof.

[0023] The water contact angle of the inorganic thin film layer is preferably 20° or less. More preferably 17° or less, and even more preferably 15° or less. By setting the water contact angle of the inorganic thin film layer within the above range, antifouling properties can be provided. If the water contact angle of the inorganic thin film layer is high, there are problems such as dirt adhering to the surface of the inorganic thin film layer not being easily wiped away, and pollutants not being naturally washed away by rainwater alone. There is no particular lower limit to the water contact angle, but 5° or more is preferred. More preferably 8° or less, and even more preferably 10° or less. There is a concern that inorganic thin film layers with a water contact angle of 5° or less have low water resistance.

[0024] The thickness of the inorganic thin film layer is typically 1 to 100 nm, preferably 5 to 50 nm. If the thickness of the inorganic thin film layer is less than 1 nm, it may be difficult to obtain satisfactory gas barrier properties. On the other hand, if the thickness is excessively increased beyond 100 nm, the corresponding improvement in gas barrier properties cannot be obtained, and it may even be disadvantageous in terms of flexibility and manufacturing costs.

[0025] There are no particular restrictions on the method for forming an inorganic thin film layer; for example, any known deposition method such as vacuum deposition, sputtering, ion plating (physical vapor deposition methods (PVD)), or chemical vapor deposition (CVD) can be used as appropriate. Below, a typical method for forming an inorganic thin film layer will be described using a silicon oxide / aluminum oxide thin film as an example. For example, when using vacuum deposition, silicon oxide, aluminum oxide, aluminum, a mixture of silicon oxide and aluminum oxide, or a mixture of silicon oxide and aluminum are preferably used as deposition raw materials. These deposition raw materials are usually used in the form of particles, and it is desirable that the size of each particle is such that the pressure during deposition does not change, with a preferred particle size of 1 mm to 5 mm. For heating, methods such as resistance heating, high-frequency induction heating, electron beam heating, and laser heating can be used. It is also possible to use reactive deposition by introducing oxygen, nitrogen, hydrogen, argon, carbon dioxide, water vapor, etc. as a reaction gas, or by using means such as ozone addition or ion assistance. Furthermore, the film deposition conditions can be arbitrarily changed, such as by applying a bias to the substrate (the laminated film used for deposition) or by heating or cooling the substrate. These deposition materials, reaction gases, bias, heating / cooling of the substrate can also be similarly modified when using sputtering or CVD methods.

[0026] [Coating layer] In this invention, the base film has a coating layer to impart heat-cutting properties. The presence of the coating layer makes it possible to shield from infrared and near-infrared heat rays in particular.

[0027] The amount of coating layer applied is not particularly limited as long as the desired heat-cutting properties can be achieved, but 3.00 g / m is a good guideline. 2 It is preferable that it be greater than or equal to ~. There is no particular upper limit, but 10.00 g / m³ is not particularly limited. 2 The following is preferable. This allows for uniform control of the coating layer during the coating process, resulting in a film with fewer coating inconsistencies and defects. A more preferable range is 8.00 g / m². 2The following. A more preferable range is 7.00 g / m 2 or less. When the coating amount of the coating layer exceeds 10.00 g / m 2 , the heat ray cutting property is improved, but in terms of processability, blocking may occur due to the thick film thickness, and there is also a possibility of increasing the manufacturing cost. On the other hand, when the coating amount of the coating layer is less than 3.00 g / m 2 , there is a risk that sufficient heat ray cutting property cannot be obtained.

[0028] A preferable resin composition used for the coating layer is an aqueous resin coating composition, which contains a polyurethane resin emulsion (A) (hereinafter also referred to as the “component (A)”), at least one metal oxide particle (B) (hereinafter also referred to as the “component (B)”) selected from the group consisting of antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, and tin-doped indium oxide, and at least one leveling agent (C) (hereinafter also referred to as the “component (C)”) selected from the group consisting of saccharides and sugar alcohols.

[0029] <(A) Polyurethane resin emulsion>[ In a water-based paint composition, component (A) refers to a urethane resin dispersed or emulsified in water. The method for producing component (A) is not particularly limited and can be produced by known methods. For example, one method involves reacting a polyol with a polyisocyanate using a solvent as needed to synthesize a relatively high molecular weight urethane prepolymer, then adding an emulsifier, and then gradually adding water to perform phase inversion emulsification (if a low boiling point solvent of 100°C or less is used, it is removed under reduced pressure after the emulsification step; the same applies to the following methods). In the above phase inversion emulsification method, if polyethylene glycol residues or hydrophilic groups such as carboxyl groups are incorporated into the backbone of the urethane prepolymer, an emulsifier may not be used. Another method besides phase inversion emulsification is to gradually add the urethane prepolymer to water containing an emulsifier to disperse and emulsify it (prepolymer mixing method). In the prepolymer mixing method, if polyethylene glycol residues or hydrophilic groups such as carboxyl groups are incorporated into the backbone of the urethane prepolymer, an emulsifier may not be used, similar to the phase inversion emulsification method.

[0030] The polyol is not particularly limited as long as it is a compound having at least two hydroxyl groups. For example, (a1) polyester diols, (a2) polycarbonate diols, (a3) ​​polyether polyols, and (a4) polyols with a number average molecular weight of less than 500 can be used as (a) polyol components.

[0031] (a1) As the polyester polyol, for example, compounds obtained by esterifying a low molecular weight polyol with a polycarboxylic acid, compounds obtained by ring-opening polymerization of cyclic ester compounds such as ε-caprolactone and γ-valerolactone, and copolymer polyesters thereof can be used.

[0032] Examples of low molecular weight polyols that can be used include aliphatic polyols such as ethylene glycol, diethylene glycol, triethylene glycol, and neopentyl glycol; polyols containing aliphatic cyclic structures such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; and bisphenol-type polyols such as bisphenol A, alkylene oxide adducts of bisphenol A, bisphenol S, and alkylene oxide adducts of bisphenol S. Among these, aliphatic polyols are preferred from the viewpoint of balancing the viscosity of the urethane prepolymer with the physical properties of the urethane resin when it forms a film.

[0033] Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, and hydroxystearic acid; alicyclic polycarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and cyclohexanetricarboxylic acid; aromatic polycarboxylic acids such as orthophthalic acid, isophthalic acid, and terephthalic acid; and their anhydrides or ester derivatives, which can be used individually or in combination of two or more. Among these, aromatic polycarboxylic acids are preferred, and aromatic dicarboxylic acids are more preferred, in order to improve the strength and solvent resistance when formed into a urethane resin film.

[0034] (a2) As the polycarbonate diol, for example, one obtained by reacting a carbonate ester and / or phosgene with a polyol described later can be used. As the carbonate ester, for example, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, etc. can be used.

[0035] Examples of polyols that can be used include low molecular weight dihydroxy compounds such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and 1,2-propanediol; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone.

[0036] (a3) As the polyether polyol, for example, one obtained by addition polymerization of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as initiators can be used.

[0037] Examples of initiators that can be used include water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, phosphoric acid, and acidic phosphate esters.

[0038] Examples of alkylene oxides include ethylene oxide, propylene oxide, and tetrahydrofuran.

[0039] Examples of polyols with a number-average molecular weight of less than 500 (a4) above include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and diethylene glycol; trivalent or higher polyols such as glycerin and pentaerythritol; aliphatic cyclic structure-containing polyols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; and bisphenol-type polyols such as bisphenol A, alkylene oxide adducts of bisphenol A, bisphenol S, and alkylene oxide adducts of bisphenol S. Among these, aliphatic diols, trivalent or higher polyols, and bisphenol-type polyols are preferred in terms of improving the physical properties of the urethane resin film, and alkylene oxide adducts of bisphenol A are more preferred.

[0040] In the paint composition, any of the above-mentioned polyols (a1), (a2), (a3), and (a4) may be used. Furthermore, as the above (a) polyol component, polyols (a1), (a2), (a3), and (a4) may be used individually, or two or more of them may be used in combination.

[0041] To obtain a highly strong urethane resin film using a polyurethane resin emulsion as a paint, (a1) polyester polyol is preferred as the (a) polyol component, and polyester polyol obtained by reacting an aliphatic polyol with an aromatic polycarboxylic acid is more preferred. When one or more of (a1), (a2), and (a3) ​​are used as the (a) polyol component, the number average molecular weight of the (a) polyol component is preferably 700 to 5000, and more preferably 1000 to 3000. To balance the workability during the production of the urethane prepolymer with the physical properties of the urethane resin film when the paint composition is used as a paint, it is preferable that the (a) polyol component contains (a4) polyol. In this case, the ratio of (a4) polyol to the total amount of the (a) polyol component is preferably 1 to 30% by mass, and more preferably 3 to 15% by mass.

[0042] As the polyisocyanate for obtaining the polyurethane resin emulsion, any known compound having at least two isocyanate groups can be used without particular limitation. For example, aromatic diisocyanates such as phenylenediisocyanate, tolylenediisocyanate, and diphenylmethanediisocyanate, aliphatic or alicyclic structure-containing diisocyanates such as 1,6-hexamethylenediisocyanate, lysinediisocyanate, cyclohexanediisocyanate, and isophoronediisocyanate, and compounds obtained by trimerizing these aromatic diisocyanates or aliphatic or alicyclic structure-containing diisocyanates can be used. These may be used alone or in combination of two or more. Among these other isocyanate compounds, 1,3-bis(isocyanatemethyl)cyclohexane, tolylenediisocyanate, and isophoronediisocyanate are preferred because they are inexpensive and readily available.

[0043] When a hydrophilic group is introduced into the molecular skeleton to obtain a polyurethane resin emulsion, the urethane prepolymer can be dispersed and emulsified without the use of an emulsifier. Examples of such hydrophilic groups include acidic groups such as carboxyl groups and sulfonic acid groups, basic groups such as amino groups, and nonionic groups such as amide groups and polyoxyethylene groups.

[0044] Compounds for introducing acidic groups into the urethane resin skeleton include hydroxycarboxylic acids such as dimethylolpropionic acid and glycolic acid, amino acids (aminocarboxylic acids) such as aminobenzoic acid, glycine, and alanine, hydroxysulfonic acids such as 2-hydroxyethanesulfonic acid, and aminosulfonic acids such as aminoethylsulfonic acid. By using these compounds in combination with the polyol components mentioned above, acidic groups can be introduced into the urethane resin skeleton. Furthermore, by neutralizing these acidic groups with monovalent metal hydroxides such as potassium hydroxide, sodium hydroxide, and calcium hydroxide, or amine compounds such as ammonia, trimethylamine, and triethylamine, the dispersibility and emulsification properties of the urethane prepolymer in water can be improved.

[0045] Compounds used to introduce basic groups into the urethane resin skeleton include tertiary amine compounds such as N-methylpyrrolidone, N,N-dimethylethanolamine, N-methyldimethanolamine, and N-methyldiethanolamine. By using these compounds in combination with the polyol components mentioned above, basic groups can be introduced into the urethane resin skeleton. Furthermore, by neutralizing these basic groups with organic acids such as formic acid, acetic acid, and propionic acid, or inorganic acids such as hydrochloric acid, phosphoric acid, and nitric acid, the dispersibility and emulsification properties of the urethane prepolymer in water can be improved.

[0046] Examples of compounds for introducing nonionic groups into the urethane resin skeleton include polyoxyethylene glycol, polyoxyethylene monool in which one of the hydroxyl groups of polyoxyethylene glycol is replaced with an alkyl group such as a methyl or ethyl group, and compounds having a polyoxyethylene group and at least two hydroxyl groups as described in Japanese Patent No. 5869893, etc. By using these compounds in combination with the above-mentioned polyol component, nonionic groups can be introduced into the urethane resin skeleton.

[0047] Examples of solvents that can be optionally used in the production of polyurethane resin emulsions include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. When using a solvent with a boiling point of 100°C or lower, it is preferable to remove the solvent by vacuum distillation or the like after synthesizing the polyurethane resin emulsion. There are no particular restrictions on the amount of solvent used, but 3 to 200 parts by mass per 100 parts by mass of the total amount of raw materials for the urethane prepolymer is preferred.

[0048] In the production of urethane prepolymers, a crosslinked structure can be introduced into the urethane prepolymer using a crosslinking agent. Any crosslinking agent commonly used in the synthesis of urethane prepolymers can be used without limitation. Examples of such crosslinking agents include melamine, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, methylated methylolmelamine, butylated methylolmelamine, and melamine resin. Melamine is preferred as the crosslinking agent due to its excellent dispersibility in polyurethane and low cost. The amount of crosslinking agent used is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the polyol component.

[0049] Known surfactants can be used as emulsifiers for emulsifying urethane prepolymers. For example, common anionic and nonionic surfactants, cationic surfactants such as primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, and pyridinium salts, and amphoteric surfactants such as betaine type, sulfate ester type, and sulfonic acid type can be used.

[0050] As anionic surfactants, alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate, polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate, alkyl sulfonates such as sodium sulfolicinolate, fatty acid salts such as sodium laurate, and alkylaryl sulfonates such as sodium benzenesulfonate and alkali metal sulfates of alkali phenol hydroxyethylene can be used. Furthermore, high alkylnaphthalene sulfonates and naphthalene sulfonic acid formalin condensates can also be used.

[0051] As nonionic surfactants, fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate, polyoxyethylene glycol fatty acid esters, and polyglycerin fatty acid esters can be used. Furthermore, ethylene oxide and / or propylene oxide adducts of alcohols having 1 to 18 carbon atoms, ethylene oxide and / or propylene oxide adducts of alkylphenols, ethylene oxide and / or propylene oxide adducts of alkylene glycols and / or alkylenediamines can also be used.

[0052] Nonionic surfactants are composed of alcohols with 1 to 18 carbon atoms, such as methanol, ethanol, propanol, and 2-propanol.

[0053] Alkylenediamines are compounds in which the alcoholic hydroxyl group of an alkylene glycol, as described earlier, is replaced with an amino group. Both random adducts and block adducts can be used as ethylene oxide and propylene oxide adducts.

[0054] Examples of cationic surfactants that can be used include lauryltrimethylammonium chloride and stearyltrimethylammonium chloride.

[0055] For example, lauryldimethylamino acid betaine, sulfate ester-type amphoteric surfactants, and sulfonic acid-type amphoteric surfactants can be used as amphoteric surfactants.

[0056] Polyurethane resin emulsions can be further increased in molecular weight by dispersing and emulsifying a urethane prepolymer in water and then reacting it with a chain extender. Polyurethane resins with increased molecular weight exhibit improved physical properties, chemical resistance, water resistance, and other characteristics when used as coating films.

[0057] As chain extenders, for example, aliphatic diols such as ethylene glycol, 1,2-propanediol, and 1,3-propanediol can be used. Furthermore, polyamines such as low molecular weight diamines such as alicyclic diols such as cyclohexanedimethanol and cyclohexanediol, polyether diamines such as polyoxypropylenediamine and polyoxyethylenediamine, alicyclic diamines such as mensendiamine and isophoronediamine, and aromatic diamines such as m-xylenediamine and α-(m / p-aminophenyl)ethylamine can also be used. In addition, hydrazines such as succinate dihydrazide and adipic acid dihydrazide, hydrazine hydrate, and water can also be used.

[0058] While there are no particular restrictions on the amount of chain extender used, from the viewpoint of balancing the physical properties of the coating film made of polyurethane resin emulsion with the workability during the reaction, it is preferable to use an amount such that the ratio of the isocyanate reaction group equivalent in the chain extender to the isocyanate group equivalent in the urethane prepolymer before the chain extension reaction is in the range of 0.1 to 1.0.

[0059] In polyurethane resin emulsions, the solid content derived from urethane resin is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and even more preferably 10 to 30% by mass, relative to the total amount of the paint composition. If it is less than 5% by mass, the strength of the urethane resin film and the heat shielding effect tend to be inferior, and if it is more than 50% by mass, the viscosity of the paint composition becomes significantly higher, which tends to adversely affect workability.

[0060] Furthermore, when a polyurethane resin emulsion is obtained by reacting a polyol, polyisocyanate, and a chain extender, and the resulting polyurethane resin is dispersed or emulsified in water, the repeating units of the polyurethane resin are not uniform, and their structure and number of repeats vary considerably. Therefore, the structure of the polyurethane resin according to the present invention is complex and cannot be uniformly represented by any kind of general formula.

[0061] As component (A) of the paint composition, a commercially available polyurethane resin emulsion may be used. Examples of commercially available polyurethane resin emulsions include the "ADEKA Bonditer" series from ADEKA Corporation, the "Orestar" series from Mitsui Toatsu Chemicals, Inc., and the "Bondic" series and "Hydran" series from Dainippon Ink and Chemicals, Inc.

[0062] <Metal oxide particles (B)> In the paint composition, component (B) is at least one metal oxide particle selected from the group consisting of antimond-doped tin oxide, antimond-doped zinc oxide, gallium-doped zinc oxide, and tin-doped indium oxide. Component (B) is a component that imparts a heat shielding effect, such as infrared and near-infrared rays, to the paint composition. Antimond-doped tin oxide is preferred as component (B) because it has a high shielding effect against near-infrared rays, which have a high effect on raising indoor temperature among sunlight.

[0063] In paint compositions, in addition to component (B) which provides heat shielding effects such as infrared and near-infrared rays, other commonly known heat shielding components can also be used in combination. Examples of such compounds include tungsten-based composite oxides and lanthanum-based compounds such as lanthanum hexaboride.

[0064] In the paint composition, the ratio of component (A) to component (B) is preferably such that the content of component (B) is 18 to 80 parts by mass per 100 parts by mass of solid content derived from component (A). If the content of component (B) is lower than 18 parts by mass, a thick coating film is required to obtain sufficient heat shielding, which reduces the workability for painting. If it is higher than 80 parts by mass, it may adversely affect the smoothness of the coating film and its adhesion to the substrate. The content of component (B) per 100 parts by mass of solid content derived from component (A) is more preferably 20 to 70 parts by mass, and even more preferably 25 to 60 parts by mass.

[0065] The particle size of component (B) in the paint composition is preferably as small as possible from the viewpoint of dispersion stability and transparency of the paint film. Methods for obtaining metal oxide particles with a small particle size include dry grinding or wet grinding of the metal oxide particles.

[0066] Examples of dry grinders used for dry grinding include flake crushers, hammer mills, pin mills, bantam mills, jet mills, flute mills, pan mills, edge runners, roller mills, mix mallers, and vibratory mills. One or more of these can be used in combination, or the same equipment can be used to repeatedly perform the fine grinding process.

[0067] Examples of wet grinders for wet grinding include bead-type wet grinders (OB mill, Ultra Apex mill, etc.), roller mills such as roller-rolling mills (Roche mill, etc.), centrifugal roller mills (Raymond mill, etc.), high-speed rotary mills such as turbo mills (Turbo mill, etc.), fixed impact plate types (Wetco mill, etc.), media-agitating mills such as flow-through-tube mills (Sand grinder), agitated-tank mills (Atrier, etc.), jet mills such as jet-flow impact type (Majac pulperizer, etc.), impact plate type composite type (Super Single Track Jet Mill, etc.), and other colloidal mills. One or more of these types may be used in combination, or the same equipment may be used to repeatedly perform the micronization process.

[0068] In paint compositions, among the grinding methods listed above, a method of obtaining metal oxide particles with a small particle size by wet grinding is preferred. By performing wet grinding in a mixed solution of urethane resin emulsion and metal oxide particles, the metal oxide particles can exist more stably. Furthermore, wet grinding using a bead-type wet grinder is even more preferred in that it can produce a composition with better storage stability.

[0069] When using a bead-type wet grinder, examples of beads include metal, glass, and ceramics, but ceramics are preferred due to their excellent wear resistance. Smaller bead particle sizes result in smaller dispersions, but if the bead particle size is too small, the handling becomes poor. Therefore, a bead particle size of 30 to 300 μm is preferred, and 50 to 100 μm is more preferred.

[0070] The particle size of the metal oxide particles wet-milled by the above method is preferably such that the average particle size of the urethane resin particles and metal particles, measured by dynamic light scattering in a mixed solution of polyurethane resin emulsion and metal oxide particles, is 1 to 70 nm, more preferably 2 to 50 nm, and even more preferably 5 to 30 nm, from the viewpoint of ease of obtaining industrial raw materials and workability.

[0071] [(C) Leveling agent] The (C) component used in the paint composition is a sugar or a sugar alcohol. By further adding a sugar or sugar alcohol to a mixture of polyurethane resin emulsion and metal oxide particles, the drying properties of the paint film can be reduced, thereby reducing surface irregularities caused by rapid drying. Furthermore, the paint is less likely to drip when applied to vertical surfaces, resulting in a paint with good workability.

[0072] Sugars include monosaccharides, disaccharides, trisaccharides, and polysaccharides, specifically including glucose, mannose, and fructose.

[0073] Examples of sugar alcohols include glycerin, erythritol, and treitol.

[0074] The above-mentioned sugars and sugar alcohols may be used individually or in combination of two or more. Among these sugars and sugar alcohols, ribose, xylose, melibiose, xylitol, and sorbitol are particularly preferred, and sorbitol is more preferred, in that they provide good aesthetic appeal when used in paints.

[0075] The amount of component (C) used in the paint composition is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, even more preferably 2.5 to 70 parts by mass, and particularly preferably 30 to 70 parts by mass, based on 100 parts by mass of solid content in the combined components of (A) and (B).

[0076] Methods for adding component (C) include adding it before increasing the molecular weight of the urethane prepolymer with a chain extender, or adding it after manufacturing the polyurethane resin emulsion. However, from the viewpoint of being able to control the molecular weight of the urethane resin, the method of adding it after manufacturing the polyurethane resin emulsion is preferred. Furthermore, component (C) may be added directly as is, or it may be added in the form of a solution diluted with a solvent such as water.

[0077] [Other additives] Additives can be added to the water-based resin coating composition as long as they do not impair the effects of the present invention. Various general resin additives can be used without limitation as additives. Examples of such additives include crosslinking agents, various weathering agents (hindered amine-based light stabilizers, ultraviolet absorbers and antioxidants), silane coupling agents that particularly strengthen adhesion to the substrate, inorganic colloidal sols such as colloidal silica or colloidal alumina, tetraalkoxysilanes and their condensed polymers, chelating agents, epoxy compounds, pigments, dyes, film-forming aids, curing agents, external crosslinking agents, viscosity modifiers, leveling agents other than sugars and sugar alcohols, defoaming agents, anticoagulants, radical scavengers, heat-resistant agents, inorganic or organic fillers, plasticizers, lubricants, antistatic agents such as fluorine-based or siloxane-based agents, reinforcing agents and rust inhibitors.

[0078] Examples of crosslinking agents include amino resins composed of adducts of urea, melamine, benzoguanamine, etc., with formaldehyde, alkyl ether compounds containing the above adducts and alcohol units having 1 to 6 carbon atoms, polyfunctional epoxy compounds, polyfunctional isocyanate compounds, blocked isocyanate compounds, and polyfunctional aziridine compounds. Specific examples of these include, for example, oxazoline compounds, epoxy compounds, carbodiimide compounds, aziridine compounds, melamine compounds, and zinc complexes.

[0079] Examples of UV absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; 2-(2-hydroxyphenyl)-4,6-diaryl-1,3,5-triazines such as 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-5-3rd octylphenyl)benzotriazole; benzoates such as phenyl salicylate and resorcinol monobenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and various metal salts or metal chelates, such as nickel or chromium salts or chelates.

[0080] The amount of weather-resistant agents (hindered amine-based light stabilizers, ultraviolet absorbers, and antioxidants) used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the solid content of component (A). If the amount of weather-resistant agent is less than 0.001 parts by mass per 100 parts by mass of the solid content, a sufficient additive effect may not be obtained. If the amount of weather-resistant agent is more than 10 parts by mass per 100 parts by mass of the solid content, it may adversely affect the water dispersion stability and the properties of the coating film.

[0081] These weather-resistant agents can be added in any of the following ways: to the polyol raw material for urethane, to the urethane prepolymer, to the aqueous phase during aqueous dispersion of the urethane prepolymer, or to the urethane prepolymer after aqueous dispersion. In terms of ease of operation, the methods of adding to the polyol raw material and adding to the urethane prepolymer are preferred. [Laminated film]

[0082] The overall thickness of the laminated film of the present invention is preferably 9 μm or more and 200 μm or less, more preferably 10 μm or more and 150 μm or less, even more preferably 12 μm or more and 100 μm or less, and particularly preferably 15 μm or more and 80 μm or less.

[0083] In the laminated film of the present invention, the water contact angle of the inorganic thin film layer is preferably 20° or less. More preferably 17° or less, and even more preferably 15° or less. If the water contact angle of the inorganic thin film layer is high, there are problems such as the inability to easily wipe away dirt adhering to the surface of the inorganic thin film layer, and the inability of pollutants to be naturally washed away by rainwater alone.

[0084] The preferred range for the water vapor transmission of the laminated film of the present invention under 23°C × 65%RH conditions is 0.1 g / m². 2 / d or more, 10g / m 2 It is less than or equal to / d. More preferably 5g / m 2 / d or less, more preferably 3g / m 2 It is less than or equal to / d.

[0085] [Print layer] Furthermore, the laminated film of the present invention may have at least one printed layer or other plastic substrate and / or paper substrate laminated on the coating layer.

[0086] Water-based and solvent-based resin-containing printing inks are preferably used as the printing ink for forming the printed layer. Examples of resins used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. The printing ink may contain known additives such as antistatic agents, light-blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, defoaming agents, crosslinking agents, anti-blocking agents, and antioxidants. The printing method for forming the printed layer is not particularly limited, and known printing methods such as offset printing, gravure printing, and screen printing can be used. For drying the solvent after printing, known drying methods such as hot air drying, hot roll drying, and infrared drying can be used.

[0087] The laminated film of the present invention exhibits the following film properties. Each of these properties is measured and evaluated by the method described later in the examples.

[0088] The laminated film of the present invention has a ratio ((%Ts) / (%Tv)) of solar radiation transmittance (%Ts) from 300nm to 2500nm to visible light transmittance (%Tv) from 380nm to 780nm, measured by a spectrophotometer, of 0.8 or less. More preferably, it is 0.78 or less. There is no particular lower limit to ((%Ts) / (%Tv)), but as ((%Ts) / (%Tv)) decreases, the haze tends to increase, which may reduce transparency and indoor visibility.

[0089] The laminated film of the present invention has a visible light transmittance (%Tv) of 70% or more in the 380nm to 780nm range, as measured by a spectrophotometer. More preferably, it is 73% or more. Even more preferably, it is 75% or more. If the visible light transmittance (%Tv) is less than 70%, the transparency of the film and the visibility inside the room may decrease. There is no particular upper limit to the visible light transmittance (%Tv), but as the visible light transmittance (%Tv) increases, ((%Ts) / (%Tv)) increases, which may reduce the heat-blocking performance.

[0090] The overall thickness of the laminated film of the present invention is preferably 9 μm or more and 200 μm or less, more preferably 10 μm or more and 150 μm or less, and particularly preferably 12 μm or more and 100 μm or less.

[0091] The preferred range for the oxygen permeability of the laminated film of the present invention under 23°C × 65%RH conditions is 1 ml / m². 2 / d / MPa or more, 200ml / m 2 It is less than or equal to / d / MPa. More preferably 150 ml / m 2 / d / MPa or less, more preferably 100 ml / m 2 It is less than / d / MPa. [Examples]

[0092] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. The evaluation methods and physical property measurement methods used in each example and comparative example are as follows.

[0093] (1) Method for evaluating contact angle Each laminated film obtained in each example and comparative example was measured in an atmosphere of 23°C and 65% relative humidity using a contact angle measuring device (KRUSSDSA100, manufactured by Sanyo Trading Co., Ltd.) with a contact angle measuring method of the inorganic thin film layer surface of the laminated film. 2 μl of water was dropped onto the surface of the coating layer, and the contact angle value was measured 1 second after dropping.

[0094] (2) Heat-blocking properties (visible light transmittance (%Tv) and solar radiation transmittance (%Ts)) For each laminated film obtained in each example and comparative example, the visible light transmittance (%Tv) from 380nm to 780nm was measured using a spectrophotometer (Shimadzu UV-3600 iPlus) in accordance with the standard (JIS R 3106-2019), and the solar radiation transmittance (%Ts) from 300nm to 2500nm was also measured.

[0095] (3) [Maximum height Sp] For each laminated film obtained in each example and comparative example, an area of ​​10 cm in the longitudinal direction × 10 cm in the width direction was cut out in accordance with ISO 25178, and the maximum protrusion height Sp (μm) was measured by scanning with a Zygo white laser interferometer (NEWVIEW8000) under the observation conditions described below. The measurement was performed on the surface excluding foreign matter such as unmelted material and dust. Measurements were taken at 10 arbitrary points on the 10 cm × 10 cm sample, and the average value was defined as the maximum protrusion height Sp. (Observation conditions) • Objective lens: 10x • Zoom lens: 1x • Field of view: 0.82 x 0.82 mm • Estimated measurement time: 4 seconds Type: Surface Mode: CSI • Z resolution: High • Scan length: 20 μm Camera mode: 1024×1024@100Hz Shutter speed: 100% • Light intensity: 1.3% • Options: SureScan Off, SmartPsi Averages 4, Noise Reduction • Signal processing options: Fringe order analysis Advanced Fringe removal ON

[0096] (4) Method for evaluating water vapor transmission For each laminated film obtained in each example and comparative example, the water vapor transmission rate was measured in accordance with the JIS-K7129B method using a water vapor transmission rate measuring device (MOCON "PERMATRAN-W 3 / 33MG") under an atmosphere of 40°C and 90% RH humidity. The water vapor transmission rate was measured in the direction in which water vapor permeates from the inorganic thin film layer side.

[0097] (5) Method for evaluating dirt-wiping ability For each laminated film obtained in each example and comparative example, a 10 mm line was drawn on the opposite side of the coating layer with oil-based ink, and a wet paper wiper (Kimwipes S-200, manufactured by Nippon Paper Crecia Co., Ltd.) was used to wipe the line back and forth parallel to the line. The number of back-and-forth movements of the paper wiper when the line was completely wiped off was measured. The above wiping process was repeated five times, and the average value was taken as the number of back-and-forth movements.

[0098] [Preparation of the coating layer] The methods for preparing the coating layers used in each example and comparative example are described below. [Polymerization of water-based urethane resin with heat-cutting properties] In a four-necked flask equipped with a stirrer, a Liebig condenser, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 64.93 parts of 1,3-bis(isocyanatemethyl)cyclohexane, 11.21 parts of dimethylolpropionic acid, 10.45 parts of neopentyl glycol, 100.3 parts of polyester diol with a number average molecular weight of 2000, and 85.00 parts of acetonitrile and 4.45 parts of N-methylpyrrolidone as solvents were added. The mixture was stirred at 75°C for 3 hours under a nitrogen atmosphere, and it was confirmed that the reaction solution reached the predetermined amine equivalent. Next, the reaction solution was cooled to 40°C, and 8.04 parts of triethylamine were added to obtain a polyurethane prepolymer solution (isocyanate-terminated prepolymer). Next, 450 parts of water were added to a reaction vessel equipped with a homodisperser capable of high-speed stirring. The temperature was adjusted to 25°C, and the entire amount of the polyurethane prepolymer solution (isocyanate-terminated prepolymer) obtained above was added and dispersed in water while stirring for 2000 min⁻¹. A urethane resin emulsion (D) was prepared.

[0099] 69.4 g of urethane resin emulsion (D), 11.2 g of antimond-doped tin oxide powder (primary particle size 20 nm), 54.4 g of water, and 10.2 g of sorbitol were added to a 500 mL glass beaker and stirred at 25°C for 5 minutes. Then, the mixture was ground and dispersed using a bead mill wet grinder (model UAM-015, manufactured by Hiroshima Metal & Machinery Co., Ltd.) until the change in average particle size became constant, thereby preparing a water-based urethane resin (E). Zirconia beads with a particle size of 0.1 mm were used, and the bead filling rate in the grinding chamber of the bead mill was set to 50%.

[0100] [Coating liquid 1] Water was added to a water-based urethane resin (E) to obtain the desired coating solution 1. The mixing ratio is shown below. Water-based urethane resin (E) 73.03% by mass Water 26.97% by mass

[0101] [Coating liquid 2] Water was added to a water-based urethane resin (E) to obtain the desired coating solution 2. The mixing ratio is shown below. Water-based urethane resin (E) 18.73% by mass Water 81.27% by mass

[0102] [Coating Liquid 3] Water was added to a water-based urethane resin (E) to obtain the desired coating solution 3. The mixing ratio is shown below. Water-based urethane resin (E) 41.57% by mass Water 58.43% by mass

[0103] [Coating liquid 4] The water-based urethane resin (E) was used as coating liquid 4 without adding any water.

[0104] [Fabrication of laminated films] (Example 1) As a deposition source, particulate Al (99.9% purity) of approximately 7 mm to 9 mm and SiO2 (99.9% purity) of approximately 4 mm to 7 mm were used to form a composite oxide thin film on the corona-treated surface of a 12 μm thick PET film (Toyobo Co., Ltd.: UV516) using the vacuum deposition apparatus shown in Figure 1. Furthermore, on the opposite side of the substrate film from the side with the inorganic thin film layer, coating solution 1 was used as the coating layer and applied to the opposite side of the inorganic thin film layer by gravure roll coating, and dried in a dry oven at 130°C for 10 seconds. The amount of coating layer attached at this time was 3.50 g / m². 2 Subsequently, a post-heat treatment was performed at 40°C for two days to obtain the desired laminated film. (Example 2) As the coating layer, coating liquid 4 was used, and the adhesion amount of the coating layer was 4.80 g / m². 2 The desired laminated film was obtained under the same conditions as in Example 1, except for the difference in the other conditions. (Comparative Example 1) The desired laminated film was obtained under the same conditions as in Example 1, except that a coating layer was not provided. (Comparative Example 2) Coating liquid 2 was used as the coating layer, and the adhesion amount of the coating layer was 0.90 g / m². 2 The desired laminated film was obtained under the same conditions as in Example 1, except for the difference in the other conditions. (Comparative Example 3) Coating liquid 3 was used as the coating layer, and the amount of coating layer adhered was 2.00 g / m². 2 The desired laminated film was obtained under the same conditions as in Example 1, except for the difference in the other conditions. (Comparative Example 4) The desired laminated film was obtained under the same conditions as in Example 2, except that an inorganic thin film layer was not provided, and a coating layer was provided on the corona-treated surface of the substrate film. (Comparative Example 5) The desired laminated film was obtained under the same conditions as in Comparative Example 2, except that an inorganic thin film layer was not provided, and a coating layer was provided on the non-corona treated surface of the substrate film.

[0105] The laminated film was prepared as described above. The results of various evaluations conducted on the obtained laminated film are shown in Table 1.

[0106] [Table 1] [Industrial applicability]

[0107] According to the present invention, in addition to having excellent heat-cutting performance, the film possesses all the properties of anti-fouling and water vapor barrier properties, making it usable in a wide range of applications. Furthermore, it provides a multi-functional film that is less prone to appearance defects and processing problems during film processing.

Claims

1. A laminated film comprising a base film with a coating layer laminated on one side and an inorganic thin film layer laminated on the side of the base film opposite to the coating layer, characterized in that the laminated film satisfies the following requirements (I) to (IV). (I) The water contact angle value on the surface of the inorganic thin film layer of the laminated film is 20° or less. (II) The ratio of the solar radiation transmittance (%Ts) to the visible light transmittance (%Tv) of the laminated film ((%Ts) / (%Tv)) is 0.80 or less. (III) The maximum protrusion height Sp on the inorganic thin film layer surface of the laminated film is 1.0 μm or more. (IV) The water vapor transmission rate of the laminated film under a 40°C × 90% RH environment is 2 g / m². ２ ・It is less than or equal to d.

2. The laminated film according to claim 1, wherein the laminated film is transparent and has a visible light transmittance (%Tv) of 70% or more.

3. The aforementioned laminated film has an oxygen permeability of 300 ml / m² under a 23°C × 65% RH environment. ２ The laminated film according to claim 1, characterized in that it is d·MPa or less.

4. A laminated film according to any one of claims 1 to 3, characterized in that it is used for window glass in a house.

5. A laminated film according to any one of claims 1 to 3, characterized in that it is used for vehicle window glass.

6. A laminated film according to any one of claims 1 to 3, characterized in that it is used for the exterior walls of a house.

7. A laminated film according to any one of claims 1 to 3, characterized in that it is used for exterior application of decorative panels.

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