Laminated film, method for manufacturing the same, and resin molded product

Abstract

A specific laminated film according to the present invention has laminated therein a layer (layer A) containing a polycarbonate resin, a layer (layer B) containing a thermoplastic acrylic resin, an acrylic resin-mixed intermediate layer (layer C), and a layer (layer D) containing a cured product of an active energy ray-curable acrylate in this order. The laminated film is characterized by being suitable for in-mold lamination molding and exhibiting excellent wear resistance, interlayer adhesion, and flexibility.

Description

[Technical Field]

[0001] The present invention relates to a laminated film, a method for manufacturing the same, and a resin molded product. More specifically, it relates to a laminated film having a layer containing a polycarbonate resin and a layer containing a thermoplastic acrylic resin, a method for manufacturing the same, and a resin molded product. [Background technology]

[0002] Decorated resin molded products are widely used in automobiles, home appliances, and daily necessities. As a method for decorating resin molded products, a method called in-mold decoration (also called in-mold lamination) has been proposed, in which a resin film with patterns and various functions is placed inside the mold, and this resin film integrates with the injected resin at the same time as injection molding to obtain a resin molded product. Unlike conventional surface decoration methods such as painting, printing, and vapor deposition, this decoration method has the advantage of being able to handle complex shapes through mold design, performing molding and decoration simultaneously, and offering a high degree of freedom in imbuing the resin film with various designs and functions.

[0003] For example, Patent Document 1 describes a method for obtaining a resin molded product with a decorated surface by placing a decorative sheet in a mold having a cavity and injecting molten resin into the mold through the gate of the mold.

[0004] Methods for imparting functionality to resin films include coating the base film with a coating agent capable of imparting various functions. From the viewpoint of productivity, resin compositions containing active energy ray-curable polyfunctional (meth)acrylates are often used as coating agents. In this application, the term (meth)acrylate is used as a general term referring to acrylates and methacrylates.

[0005] It is known that polycarbonate resin is used as the base film for the decorative films proposed as resin films mentioned above.

[0006] For example, Patent Document 2 discloses a decorated sheet obtained by decorating one surface of a laminated film in which a layer composed of a methacrylic resin and acrylic rubber particles is laminated on the surface of a polycarbonate resin layer, and then laminating a thermoplastic resin sheet on the decorated surface.

[0007] Resin molded articles imparted with various functions by such methods have been used in various applications such as interior parts, for example.

[0008] However, when the above resin molded article is used in outdoor applications such as automobile exteriors, although the initial performance is excellent, the weather resistance cannot be said to be sufficient, and the required performance may not be maintained during the expected service life. PRIOR ART DOCUMENTS PATENT DOCUMENTS

[0009] Patent Document 1 Japanese Unexamined Patent Publication No. 2010-247493 Patent Document 2 Japanese Unexamined Patent Publication No. 2009-234184 DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0010] As described above, acrylic resin sheets are widely used for decorated sheets obtained by imparting functions to resin films. However, when an acrylic resin sheet is used on the surface, it has the disadvantage of low heat resistance and abrasion resistance applicable to outdoor use. In addition to the above properties, there is a demand for laminated films excellent in interlayer adhesion between resin films and sheets and moldability such as flexibility applicable to in-mold lamination molding.

[0011] An object of the present invention is to provide a novel laminated film.

[0012] Another object of the present invention is to provide a laminated film suitable for in-mold lamination molding, which has excellent abrasion resistance, interlayer adhesion, and flexibility.

[0013] Another object of the present invention is to provide a novel method for manufacturing the above-mentioned laminated film.

[0014] Another object of the present invention is to provide a resin molded product in which a thermoplastic resin is injection-molded onto the substrate layer side of the laminated film.

[0015] The inventors of the present invention investigated a decorative laminated film comprising a polycarbonate resin base layer, a thermoplastic acrylic resin layer on its surface, and a layer containing a cured active-energy ray-curable acrylate on that surface. In the process, they discovered that the above problems could be solved if an intermediate layer containing a specific acrylic resin was present between the thermoplastic acrylic resin layer and the cured active-energy ray-curable acrylate layer, and that the film exhibited excellent weather resistance, particularly for outdoor use, leading to the present invention. [Means for solving the problem]

[0016] The means for solving the above problems include the following embodiments. [1] A laminated film comprising a layer containing polycarbonate resin (layer A), a layer containing thermoplastic acrylic resin (layer B), an acrylic resin mixed intermediate layer (layer C), and a layer containing a cured product of active energy ray-curable acrylate (layer D), laminated in this order, and satisfying the following (a) to (d); (a) The active energy ray curable acrylate comprises at least one of a polyfunctional (meth)acrylate and a urethane (meth)acrylate, (b) Layer D comprises at least one of inorganic fine particles and a silicon compound hydrolysis condensate, (c) With respect to the total amount of the polyfunctional (meth)acrylate, the urethane (meth)acrylate, the inorganic fine particles, and the silicon compound hydrolysis condensate, the total content of the polyfunctional (meth)acrylate and the urethane acrylate is 45% to 97% by mass, and the total content of the inorganic fine particles and the silicon compound hydrolysis condensate is 3% to 55% by mass. (d) The C layer comprises the thermoplastic acrylic resin and a cured product of at least one of the polyfunctional (meth)acrylate and the urethane (meth)acrylate. [2] The laminated film according to [1] above, wherein in the C layer, when the amount of thermoplastic acrylic resin is X parts by mass and the total amount of the polyfunctional (meth)acrylate and the urethane (meth)acrylate is Y parts by mass, Y / (X+Y) is 0.2 to 0.9. [3] The laminated film according to [1] or [2] above, wherein the reaction rate of the double bonds of the (meth)acrylic groups of the polyfunctional (meth)acrylate and the urethane (meth)acrylate in the C layer is 25 to 70%. [4] The laminated film according to any one of [1] to [3] above, wherein the ratio of the thickness of the C layer to the sum of the thickness of the C layer and the thickness of the D layer is 10 to 70%. [5] The laminated film according to any of [1] to [4] above, wherein the thickness of the C layer is 0.3 to 5.0 μm. [6] The laminated film according to any one of [1] to [5] above, wherein the thickness of the D layer is 1.5 to 18 μm. [7] The laminated film according to any one of [1] to [6] above, wherein the sum of the thickness of the C layer and the thickness of the D layer is 3 to 20 μm. [8] The laminated film according to any one of [1] to [7] above, wherein the A layer contains a polyester thermoplastic elastomer, and the polyester thermoplastic elastomer comprises a hard segment consisting of polybutylene terephthalate units and a soft segment consisting of polyester units having aromatic dicarboxylic acids and aliphatic dicarboxylic acids as dicarboxylic acid components and diols having 5 to 15 carbon atoms as diol components. [9] The laminated film according to [8] above, containing 1 to 20 parts by weight of the polyester thermoplastic elastomer with respect to 100 parts by weight of the polycarbonate resin.

[10] A method for manufacturing a laminated film according to [1] above, characterized by laminating a layer containing polycarbonate resin (layer A) and a layer containing thermoplastic acrylic resin (layer B) by co-extrusion, then applying a coating liquid composition containing an organic solvent, an active energy ray curable acrylate, and at least one of inorganic fine particles and a silicon compound hydrolysis condensate onto layer B, drying the applied coating liquid composition, and then irradiating it with active energy rays to form an acrylic resin mixed intermediate layer (layer C) and an acrylate cured layer (layer D).

[11] The method for manufacturing a laminated film according to

[10] , wherein the C layer comprises the thermoplastic acrylic resin and a cured product of at least one of the polyfunctional (meth)acrylate and the urethane (meth)acrylate.

[12] A resin molded product having a thermoplastic resin layer in contact with layer A of the laminated film described in any of [1] to [9] above.

[13] A resin molded product obtained by injection molding a thermoplastic resin onto the A-layer side of the laminated film described in any of [1] to [9] above. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a laminated film that is excellent in interlayer adhesion, impact resistance, flexibility, abrasion resistance, and weather resistance. This laminated film is useful as a thermoforming film such as in-mold lamination film and as a decorative film. Resin molded products using this laminated film can be used, for example, in automotive interior materials, electrical appliances, cosmetic films, building interior and exterior parts, and its excellent weather resistance makes it particularly advantageous for use in automotive exterior materials or building exterior parts. [Best Mode for Carrying Out the Invention]

[0018] The contents of this disclosure will be described in detail below. The descriptions of the constituent elements described below may be based on representative embodiments of this disclosure, but this disclosure is not limited to such embodiments.

[0019] In this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0020] Furthermore, in the notation of groups (atomic groups) in this specification, the notation that does not specify whether they are substituted or unsubstituted includes both those with and without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0021] In this specification, "(meth)acrylic" is a term used to encompass both acrylic and methacrylic, and "(meth)acryloyl" is a term used to encompass both acryloyl and methacryloyl.

[0022] Furthermore, the term "process" as used in this specification includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0023] Furthermore, in this disclosure, "mass%" and "weight%" are synonymous, and "parts of mass" and "parts of weight" are synonymous.

[0024] Unless otherwise specified, each component in the composition or each structural unit in the polymer in this disclosure may be included alone or in combination of two or more types.

[0025] Furthermore, in this disclosure, the amount of each constituent unit in the polymer means the total amount of any multiple constituent units present in the polymer, unless otherwise specified, if there are multiple substances or constituent units corresponding to each constituent unit in the polymer.

[0026] Furthermore, in this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0027] The present invention uses a polycarbonate resin-containing layer (layer A) as a base layer, and in order from the base layer side, a thermoplastic acrylic resin-containing layer (layer B), an acrylic resin mixed intermediate layer (layer C), and a layer containing a cured product of an active energy ray-curable acrylate (layer D) are laminated. The invention satisfies the following conditions (a) to (d). (a) The active energy ray curable acrylate comprises at least one of a polyfunctional (meth)acrylate and a urethane (meth)acrylate. (b) Layer D comprises at least one of inorganic fine particles and a silicon compound hydrolysis condensate. (c) With respect to the total amount of the polyfunctional (meth)acrylate, the urethane (meth)acrylate, the inorganic fine particles, and the silicon compound hydrolysis condensate, the total content of the polyfunctional (meth)acrylate and the urethane acrylate is 45% to 97% by mass, and the total content of the inorganic fine particles and the silicon compound hydrolysis condensate is 3% to 55% by mass. (d) The C layer comprises the thermoplastic acrylic resin and a cured product of at least one of the polyfunctional (meth)acrylate and the urethane (meth)acrylate.

[0028] The following explains each layer. -A layer- (Layer containing polycarbonate resin (Layer A)) The polycarbonate resin used in layer A of the present invention is a polymer in which dihydroxy compounds are linked by carbonate ester bonds, and is usually obtained by reacting the dihydroxy component with a carbonate precursor by interfacial polymerization or melt polymerization.

[0029] Typical examples of dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane (bisphenol C), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, and 1,1-bis(4-hydroxyphenyl)cyclohexyl Examples include xane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, isosorbide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc. These can be homopolymers using one of these compounds alone, or copolymers obtained by copolymerizing two or more of them. Bisphenol A is preferred from a physical property and cost standpoint. In the present invention, polycarbonates in which 50 mol% or more of the bisphenol component is bisphenol A and / or bisphenol C are preferred, more preferably 70 mol% or more, and even more preferably 90 mol% or more.

[0030] Specific examples of polycarbonates include homopolymers of bisphenol A, homopolymers of bisphenol C, binary copolymers of bisphenol A and bisphenol C, binary copolymers of bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and binary copolymers of bisphenol A and 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene. Homopolymers of bisphenol A are the most preferred.

[0031] Carbonyl halides, carbonate esters, or haloformates can be used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0032] When producing polycarbonate resin by reacting the above-mentioned divalent dihydroxy compound with a carbonate precursor by interfacial polymerization or melt polymerization, catalysts, end-terminating agents, divalent phenol antioxidants, etc., may be used as needed. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic bifunctional carboxylic acid, or a mixture of two or more of the obtained polycarbonate resins.

[0033] The molecular weight of the polycarbonate resin is preferably in the range of 13,000 to 40,000, expressed as viscosity-average molecular weight. If the molecular weight is lower than 13,000, the sheet becomes brittle, and cracks and burrs may easily occur during thermoforming. If it is higher than 40,000, the melt viscosity of the resin composition with polyester thermoplastic elastomer becomes too high, making melt film formation difficult. The molecular weight is more preferably 15,000 to 35,000, even more preferably 20,000 to 32,000, and particularly preferably 22,000 to 28,000. If the polycarbonate resin is a mixture of two or more types, the molecular weight of the entire mixture is expressed. Here, viscosity-average molecular weight is the specific viscosity (η) of a solution obtained by dissolving 0.7 g of polycarbonate in 100 mL of methylene chloride at 20°C. sp The viscosity-average molecular weight (M) was calculated by measuring the viscosity and using the following formula.

[0034] η sp / c=[η]+0.45×[η] 2 c [η] = 1.23 × 10 -4 M 0.83 (However, c = 0.7 g / dL, and [η] is the intrinsic viscosity) The glass transition temperature of the polycarbonate resin-containing layer (layer A) of the present invention must be in the range of 100°C to 145°C, preferably 110°C to 140°C, and more preferably 120°C to 130°C. If the glass transition temperature is higher than the above range, it becomes necessary to raise the thermoforming temperature, and the heat exposure during thermoforming will initiate thermal decomposition reactions of the acrylic resin components contained in layers B, C, and D, as well as thermal reactions of the double bonds of unreacted acrylate monomers contained in layers C and D, resulting in appearance defects such as clouding, surface irregularities, and cracks after molding. Conversely, if the glass transition temperature is lower than the above range, the appropriate molding temperature for thermoforming layer A will fall below the glass transition temperature of the thermoplastic acrylic resin-containing layer (layer B), making thermoforming impossible. Here, the glass transition temperature refers to the value measured by differential scanning calorimetry (DSC).

[0035] The A layer preferably contains 50% by mass or more of the polycarbonate resin, more preferably 80% by mass or more, and may contain 100% of the polycarbonate resin. However, from the viewpoint of the glass transition temperature and transparency of the A layer, a polyester-based thermoplastic elastomer may be blended with the polycarbonate resin. The polyester-based thermoplastic elastomer is preferably a multiblock copolymer composed of a hard segment made of polybutylene terephthalate units and a soft segment made of polyester units in which aromatic dicarboxylic acids and aliphatic dicarboxylic acids are the dicarboxylic acid components and diols having 5 to 15 carbon atoms are the diol components.

[0036] The hard segments made of polybutylene terephthalate units have excellent compatibility with polycarbonate resin, are preferable in terms of transparency and thermoformability, and also have good properties in terms of strength and other aspects. Polybutylene terephthalate may contain other components as copolymer components as long as it does not impair the effects of the present invention. The proportion of such copolymer components is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, for both the dicarboxylic acid component and the diol component, out of 100 mol% of the total components. The intrinsic viscosity of the polymer that forms the hard segments is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5.

[0037] The soft segment, which consists of polyester units with aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component, refers to a segment in which the polymer formed from the segment has a melting point of 100°C or less, or is liquid and amorphous at 100°C. The intrinsic viscosity of the polymer that becomes the soft segment is preferably in the range of 0.2 to 2.0, more preferably in the range of 0.5 to 1.5. The soft segment used is a soft segment consisting of polyester units with aromatic dicarboxylic acids and / or aliphatic carboxylic acids as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component (hereinafter sometimes referred to as "SS-1"). SS-1 is preferred because it provides extremely good transparency.

[0038] For soft segment SS-1, it is preferable that the content of aromatic dicarboxylic acids is 60-99 mol% and the content of aliphatic dicarboxylic acids is 1-40 mol% of the total 100 mol% of dicarboxylic acid components, in order to obtain better transparency. It is more preferable that the content of aromatic dicarboxylic acids is 70-95 mol% and the content of aliphatic dicarboxylic acids is 5-30 mol%. It is even more preferable that the content of aromatic dicarboxylic acids is 85-93 mol% and the content of aliphatic dicarboxylic acids is 7-15 mol%. It is particularly preferable that the content of aromatic dicarboxylic acids is 89-92 mol% and the content of aliphatic dicarboxylic acids is 8-11 mol%.

[0039] The aromatic dicarboxylic acid of SS-1 is preferably at least one selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenylcarboxylic acid, bis(4-carboxyphenyl)methane, and bis(4-carboxyphenyl)sulfone, with terephthalic acid and isophthalic acid being more preferred, and isophthalic acid being particularly preferred in terms of reducing crystallinity.

[0040] Suitable aliphatic dicarboxylic acids for SS-1 include linear aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as succinic acid, adipic acid, and sebacic acid, with sebacic acid being particularly preferred.

[0041] As the C5-C15 diol component of SS-1, linear aliphatic diols with C6-C12 such as hexamethylene glycol, decamethylene glycol, 3-methylpentanediol, and 2-methyloctamethylenediol are more preferred, with hexamethylene glycol being particularly preferred.

[0042] SS-1 is particularly preferred because it has high compatibility with polycarbonate resin, allows for the acquisition of highly transparent materials, and also exhibits good surface properties and transparency after thermoforming. More specifically, SS-1 is preferably a polyester composed of isophthalic acid, sebaciic acid, and hexamethylene glycol.

[0043] In the present invention, the ratio of hard segments to soft segments in the polyester thermoplastic elastomer is preferably 20-70% by weight for hard segments and 80-30% by weight for soft segments, and more preferably 20-40% by weight for hard segments and 80-60% by weight for soft segments, based on 100% by weight of the elastomer. The intrinsic viscosity of the polyester thermoplastic elastomer (value measured in o-chlorophenol at 35°C) is preferably 0.6 or higher, more preferably in the range of 0.8 to 1.5, and even more preferably in the range of 0.8 to 1.2. If the intrinsic viscosity is lower than the above range, the sheet strength may decrease, which is undesirable.

[0044] In the present invention, when layer A contains a polyester-based thermoplastic elastomer, it is preferable that layer A contains 1 to 20 parts by weight of the polyester-based thermoplastic elastomer per 100 parts by weight of the polycarbonate resin. If the amount of polyester-based thermoplastic elastomer is less than 1 part by weight, the effect of improving fluidity during thermoforming is low, and if it exceeds 20 parts by weight, the rigidity of layer A tends to become insufficient.

[0045] The thickness of layer A is preferably in the range of 25 to 500 μm, more preferably in the range of 30 to 450 μm, even more preferably in the range of 40 to 400 μm, and most preferably in the range of 50 to 350 μm.

[0046] The A layer of the present invention may contain various additives commonly used in each resin. Examples include heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, dyes, etc. Furthermore, reinforcing fillers such as glass fibers may be included, to the extent that they do not impair the effects of the present invention.

[0047] The thickness of the substrate layer (layer A) containing polycarbonate resin is determined by measuring the thickness of the laminated film according to this disclosure with a micrometer and subtracting the thicknesses of layers B, C, and D, which are measured with a scanning electron microscope (SEM), from the thickness of this laminated film.

[0048] The thicknesses of layers B, C, and D mentioned above are determined by measuring the cross-section of the laminated film according to this disclosure using a scanning electron microscope (SEM). -B layer- (Layer containing thermoplastic acrylic resin (Layer B)) In the present invention, the thermoplastic acrylic resin used in layer B is preferably mainly composed of a polymer of methacrylate ester or acrylic acid ester. If a resin other than thermoplastic acrylic resin is used for layer B, for example, polycarbonate resin results in low surface hardness of the laminated film, making the molded article prone to scratches, which is undesirable. Also, PET resin is undesirable because it is prone to appearance defects due to uneven thickness. The thermoplastic acrylic resin is preferably a copolymer containing methyl methacrylate in an amount of 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0049] Other copolymer components besides methyl methacrylate include ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Other copolymer components include other ethylenically unsaturated monomers. Specifically, these include vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene; diene compounds such as 1,3-butadiene and isoprene; alkenyl cyanide compounds such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide. These may be used individually or in combination of two or more. The copolymer content is preferably 0 to 50% by weight, more preferably 0 to 30% by weight, and even more preferably 0 to 20% by weight. Methods for producing thermoplastic acrylic resins are generally broadly classified into emulsion polymerization, suspension polymerization, and continuous polymerization, but the thermoplastic acrylic resin used in the present invention may be produced by any of these polymerization methods. Furthermore, various additives such as general heat stabilizers, colorants, mold release agents, lubricants, antistatic agents, and matting agents may be added to layer B.

[0050] While rubber particles may be added to layer B of the present invention, it is preferable that it is substantially free of rubber particles. Although the addition of rubber particles to thermoplastic acrylic resin to improve toughness is a known and widely used technique, it is preferable to omit them from the viewpoint of ensuring transparency and surface hardness.

[0051] The thickness of layer B is preferably in the range of 10 to 200 μm, more preferably in the range of 20 to 150 μm, and most preferably in the range of 30 to 100 μm. By designing the thickness of layer B within this range, more stable film formation becomes possible, and various properties such as weather resistance can be achieved by adding various additives. Furthermore, it is possible to realize a laminated film with appropriate flexibility and excellent weather resistance and other properties. -C layer- (Acrylic resin mixed intermediate layer (C layer)) Layer C is an intermediate layer located between layers B and D, containing a mixture of acrylic resins, and comprising a thermoplastic acrylic resin that constitutes layer B and a cured product of an active energy ray-curable acrylate that constitutes layer D (described later).

[0052] Regarding the composition of layer C, when the amount of thermoplastic acrylic resin is X parts by mass, and the total amount of the polyfunctional (meth)acrylate and the urethane (meth)acrylate is Y parts by mass, Y / (X+Y) is preferably 0.2 to 0.9. By keeping it within this range, the difference in linear expansion coefficients between layer B and layer C, and between layer C and layer D can be kept below 100 ppm / K. This suppresses thermal shock caused by the difference in linear expansion coefficients at the interface between layer B and layer C and the interface between layer C and layer D, resulting in a laminated film with excellent adhesion and weather resistance. More preferably, it is 0.3 to 0.8, and most preferably 0.4 to 0.75.

[0053] The value of Y / (X+Y) above can be appropriately adjusted by changing the film formation conditions for the C and D layers, such as the type and composition of the solvent used for forming the D layer, and the heat drying temperature and time.

[0054] Layer C contains two types of acrylic resins that form layer B and layer D described later: a thermoplastic acrylic resin and a cured product of an active energy ray-curable acrylate. The state of layer C, which contains these two types of acrylic resins, greatly affects interlayer adhesion, various durability properties, and flexibility. When performing in-mold lamination molding using the laminated film of the present invention, the laminated film is placed and mounted in a mold, which may have a three-dimensional shape, and high-temperature molten resin is injected into this mold. For this reason, the mounted laminated film needs to conform to the shape of the mold (it can also accommodate complex shapes), and various deformation stresses act on it, such as strain caused by linear expansion due to direct contact with the high-temperature molten resin. Therefore, the flexibility of the mounted laminated film greatly affects the moldability of in-mold lamination molding.

[0055] Before the formation of layer C, unreacted polyfunctional (meth)acrylate and / or urethane (meth)acrylate are present around the polymer chains of the thermoplastic acrylic resin. After curing, these reactions are thought to form a three-dimensional crosslinked structure in which the long-chain polymer chains of the thermoplastic acrylic resin become entangled. It is believed that this structure reduces the flexibility and weather resistance of the laminated film itself, as well as the stress and shearing between layers B and D during in-mold lamination. As a result, not only is adhesion improved, but flexibility is also improved, and weather resistance, which is strongly affected by interlayer stress (especially between layers B and D), can be significantly improved.

[0056] The thermoplastic acrylic resin contained in layer C, and the crosslinked reaction cured product of the polyfunctional (meth)acrylate contained in layer C and layer D (described later) and the urethane (meth)acrylate can be confirmed by micro-infrared spectroscopy (micro-FT-IR method).

[0057] Specifically, the laminated film relating to this disclosure is cut before UV irradiation, and the cross-sections of each layer B, C, and D are analyzed using a micro-FT-IR measuring device. For example, if the C layer contains a polyfunctional acrylate, a peak (810 cm²) originating from the C=CH structure of the polyfunctional acrylate is detected. -1 ) and a peak (1740 cm²) originating from the OC=O structure of thermoplastic acrylic resins and polyfunctional acrylates. -1 From the ratios of the surrounding areas, it can be confirmed that the components constituting layer B and some of the components constituting layer D are mixed together. Similarly, even if polyfunctional acrylate is not present in layers C and D, it can be confirmed that layer C contains both the acrylic components of layers B and D by focusing on specific peaks derived from the components of layer B.

[0058] As described above, the thermoplastic acrylic resin can be the same as that which constitutes layer B.

[0059] Examples of active energy ray curable acrylates constituting the C layer include polyfunctional (meth)acrylate and urethane (meth)acrylate. Here, the C layer contains a cured product of at least one of polyfunctional (meth)acrylate and urethane (meth)acrylate. That is, it contains a crosslinked reaction cured product of polyfunctional (meth)acrylate, a crosslinked reaction cured product of urethane (meth)acrylate, a crosslinked reaction cured product (copolymer) of polyfunctional (meth)acrylate and urethane (meth)acrylate, or a mixture thereof. Here, the cured product refers to a three-dimensional crosslinked body or a three-dimensional crosslinked copolymer produced by active energy ray irradiation. In the case of a three-dimensional crosslinked copolymer, the copolymerization ratio of polyfunctional (meth)acrylate to urethane (meth)acrylate is, for example, 20 to 95 mol%, preferably 50 to 85 mol%, of the total of polyfunctional (meth)acrylate and urethane (meth)acrylate.

[0060] In the crosslinking reaction of polyfunctional (meth)acrylates, urethane (meth)acrylates, and copolymers thereof, the double bonds of the (meth)acryl groups contained in the polyfunctional (meth)acrylates and urethane (meth)acrylates react to form a crosslinked structure, which becomes a cured product to constitute a cured layer. In this case, the reaction ratio (reaction rate) of the double bonds of the (meth)acryl groups (when the state where all acrylic groups completely react is defined as 100%) is preferably 25 to 70%, more preferably 40 to 65%. The reaction rate can be obtained from the peak derived from the C=C-H structure of the unreacted polyfunctional acrylate (810 cm -1 ) and the peak derived from the O-C=O structure of the thermoplastic acrylic resin and the polyfunctional acrylate (1740 cm -1 nearby), and can be calculated by comparing the ratio of the peak derived from the C=C-H structure of the polyfunctional acrylate in the C layer after curing (810 cm -1 ) and the peak derived from the O-C=O structure of the thermoplastic acrylic resin and the polyfunctional acrylate (1740 cm -1 nearby).

[0061] Specific compounds of the polyfunctional (meth)acrylates and urethane (meth)acrylates are the same as those for forming the D layer. The D layer will be described later.

[0062] The thickness of the C layer is preferably 0.3 to 5.0 μm. Setting the thickness of the C layer to 0.3 to 5.0 μm provides excellent weather resistance and impact resistance. It is more preferably 0.5 to 4.5 μm, and most preferably 1.0 to 4.0 μm. -Layer D- (Layer containing a cured product of active energy ray-curable acrylate (Layer D)) Layer D is a layer containing a cured product of an active energy ray-curable acrylate. Here, the active energy ray-curable acrylate includes polyfunctional (meth)acrylate, urethane (meth)acrylate, or both. The cured product of the active energy ray-curable acrylate refers to a three-dimensional crosslinked body with polyfunctional (meth)acrylate as the monomer, a three-dimensional crosslinked body with urethane (meth)acrylate as the monomer, or a three-dimensional crosslinked copolymer with polyfunctional (meth)acrylate and urethane (meth)acrylate as monomers. In the case of a three-dimensional crosslinked copolymer, the copolymerization ratio of polyfunctional (meth)acrylate to urethane (meth)acrylate is such that the proportion of polyfunctional (meth)acrylate is, for example, 20 to 95 mol%, preferably 50 to 85 mol%, relative to the total of polyfunctional (meth)acrylate and urethane (meth)acrylate. [Multifunctional acrylate] The polyfunctional (meth)acrylate monomers used to form the D layer are not particularly limited as long as they have two or more ((meth)acrylate groups) in one molecule. Examples include bifunctional (meth)acrylate monomers such as trimethylolpropanedi(meth)acrylate, ethylene oxide-modified trimethylolpropanedi(meth)acrylate, propylene oxide-modified trimethylolpropanedi(meth)acrylate, glycerin di(meth)acrylate, and bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate; trifunctional (meth)acrylate monomers such as pentaerythritol tri(meth)acrylate and ditrimethylolpropanetri(meth)acrylate; and tetrafunctional or more (meth)acrylate monomers such as pentaerythritol tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate.

[0063] Among these, the polyfunctional (meth)acrylate monomer used for forming the D layer is preferably a bifunctional to tetrafunctional (meth)acrylate monomer, and more preferably a bifunctional or trifunctional (meth)acrylate monomer.

[0064] In this specification, a polyfunctional (meth)acrylate monomer means a polyfunctional (meth)acrylate having a molecular weight of less than 2,000.

[0065] The D layer may be formed using a monofunctional (meth)acrylate monomer to balance wear resistance and flexibility. In that case, the polyfunctional (meth)acrylate monomer is preferably 90% by mass or more, more preferably 93% by mass or more, and particularly preferably 96% by mass or more, based on the total mass of the (meth)acrylate monomer. [Di(meth)acrylate compounds] The bifunctional (meth)acrylate monomer used to form the D layer may be an aliphatic or aromatic di(meth)acrylate compound, but an aliphatic di(meth)acrylate compound is preferred.

[0066] The aliphatic di(meth)acrylate compound is preferably a compound obtained by esterifying and bonding an alkyl diol with acrylic acid or methacrylic acid.

[0067] Preferred structures of aliphatic di(meth)acrylate compounds include 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate.

[0068] Aliphatic di(meth)acrylate compounds may be synthesized or commercially available. Commercially available products include HDDA (manufactured by Daicel Ornex), A-HD-N, A-NOD-N, A-DOD-N (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and 1,9-DA (manufactured by Kyoei Chemical Industry Co., Ltd.).

[0069] Aliphatic di(meth)acrylate monomers may be used individually or in combination of two or more.

[0070] When the polyfunctional (meth)acrylate monomer contains an aliphatic di(meth)acrylate compound, the blending ratio of the aliphatic di(meth)acrylate compound is preferably 10% to 80% by mass, more preferably 20% to 70% by mass, and even more preferably 25% to 60% by mass, based on the total mass of the polyfunctional (meth)acrylate monomer. [Tri(meth)acrylate compounds] The trifunctional (meth)acrylate monomer used to form the D layer may be an aliphatic tri(meth)acrylate monomer or an aromatic tri(meth)acrylate monomer, but it is preferably an aliphatic tri(meth)acrylate monomer or an aromatic ring tri(meth)acrylate monomer which may contain heteroatoms, and more preferably an aliphatic tri(meth)acrylate compound or a tri(meth)acrylate monomer having an isocyanuric ring.

[0071] The aliphatic tri(meth)acrylate monomer is preferably pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, or dipentaerythritol penta(meth)acrylate, and more preferably pentaerythritol tri(meth)acrylate or pentaerythritol tetra(meth)acrylate. [Urethane (meth)acrylate] The urethane (meth)acrylate used to form the D layer is an acrylate oligomer with urethane bonds in its molecule. These urethane bonds impart properties such as abrasion resistance to the laminated film, and by adjusting the proportion of acrylate, a layer with excellent flexibility and abrasion resistance can be formed. Urethane (meth)acrylate can be prepared by reacting a polyisocyanate compound, which has multiple isocyanate groups in its molecule, with an acrylate that has a hydroxyl group in its molecule, and various products are commercially available. Examples of commercially available urethane (meth)acrylates include 8BR-600, 8UV-085A, and 8UX-116A from Taisei Fine Chemical Co., Ltd. [Isocyanuric ring-containing tri(meth)acrylate monomer] The isocyanuric ring-containing tri(meth)acrylate monomer used to form the C layer is preferably a compound represented by the following general formula (5).

[0072] [ka]

[0073] In the above general formula (5), R 9 , R 10 and R 11 Each of these independently represents a group expressed by the following formula (5-a).

[0074] [ka]

[0075] In the above equation (5-a), n² represents an integer from 2 to 4, and R 8 Q represents a hydrogen atom or a methyl group. 3 and Q 4 Each element in the repeating unit independently represents either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0076] Preferred structures of isocyanuric ring-containing tri(meth)acrylate monomers include compounds having the structure represented by (5A) below.

[0077] [ka]

[0078] Isocyanuric ring-containing tri(meth)acrylate monomers may be synthesized or commercially available. Commercially available products include M-315 (manufactured by Toagosei Co., Ltd.), A9300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), FA-731A (manufactured by Hitachi Chemical Co., Ltd.), SR368 (manufactured by Sartomer Co., Ltd.), and M-370 (manufactured by MIWON Co., Ltd.). [Concentration of isocyanuric ring-containing tri(meth)acrylate compound monomers] The proportion of isocyanuric ring-containing tri(meth)acrylate monomer used to form the C layer is preferably 20% to 70% by mass, more preferably 30% to 69% by mass, and even more preferably 35% to 68% by mass, based on the total mass of the polyfunctional (meth)acrylate monomer.

[0079] From the viewpoint of balance between hardness and flexibility, abrasion resistance, adhesion, etc., the polyfunctional (meth)acrylate monomer used to form the D layer is preferably a bifunctional (meth)acrylate (preferably an aliphatic di(meth)acrylate monomer, more preferably a compound obtained by esterifying and bonding an alkyldiol with acrylic acid or methacrylic acid), and a trifunctional (meth)acrylate monomer (preferably an aliphatic tri(meth)acrylate monomer or a tri(meth)acrylate monomer having an isocyanuric ring, more preferably pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, or a compound represented by the above general formula (5), even more preferably pentaerythritol tri(meth)acrylate, or a compound having the structure represented by the above (5A).

[0080] The polyfunctional (meth)acrylate contained in the D layer is preferably a polymer of the above-mentioned polyfunctional (meth)acrylate monomer (polyfunctional (meth)acrylate polymer).

[0081] The above-mentioned polyfunctional (meth)acrylate polymer may contain oligomers from the viewpoint of balancing abrasion resistance and adhesiveness.

[0082] In this specification, a polyfunctional (meth)acrylate oligomer means a polymer of polyfunctional (meth)acrylate having a weight-average molecular weight of 2,000 or more and less than 50,000. In this specification, a polyfunctional (meth)acrylate polymer means a polymer of polyfunctional (meth)acrylate having a weight-average molecular weight of 50,000 or more.

[0083] The weight-average molecular weight of the polymer of the polyfunctional (meth)acrylate monomer is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 200,000 or more, from the viewpoint of abrasion resistance and thermal flexibility.

[0084] The polyfunctional (meth)acrylate polymer may be a homopolymer or a copolymer, but it is more preferable to be a copolymer. [Content of polyfunctional (meth)acrylate and / or urethane (meth)acrylate] The polyfunctional (meth)acrylate (preferably a polyfunctional (meth)acrylate polymer) contained in the D layer may be used alone or in combination of two or more types.

[0085] The content of polyfunctional (meth)acrylate in layer D is 35% to 95% by mass, preferably 40% to 90% by mass, and more preferably 50% to 90% by mass, based on the total amount of polyfunctional (meth)acrylate, inorganic fine particles, and silicon compound hydrolysis condensate.

[0086] When the content of polyfunctional (meth)acrylate in the D layer is within the above range, it exhibits excellent wear resistance, adhesion, and other properties.

[0087] The polyfunctional (meth)acrylate content (mass%) in layer D was determined by removing a portion of layer D, performing pyrolysis gas chromatography on the removed layer, identifying the compounds contained in layer D, and further measuring the 650 cm³ of layer D. -1 From 4000cm -1 The composition of the D layer can be determined by combining the results of characteristic absorption measurements performed using infrared spectroscopy in the wavenumber region with the results of these measurements. [Reaction rates of polyfunctional (meth)acrylates and / or urethane (meth)acrylates] The addition polymerization reaction rate of the (meth)acrylic group of polyfunctional (meth)acrylate and / or urethane (meth)acrylate (hereinafter sometimes simply referred to as "reaction rate") is preferably 30% to 70%, more preferably 40% to 68%, and even more preferably 45% to 65%, from the viewpoint of abrasion resistance, adhesion, etc.

[0088] The reaction rate of the polyfunctional (meth)acrylate and / or urethane (meth)acrylate in layer D is determined by the method described above for measuring the relative abundance of the polyfunctional (meth)acrylate in layer D, and at least one of the inorganic fine particles and silicon compound hydrolysis condensates, thereby determining the composition of the inorganic fine particle dispersion. Furthermore, infrared spectroscopy (ATR-IR) analysis is performed on the surface of layer D using attenuated total reflectance measurement, and a peak (1740 cm) originating from the (meth)acrylic ester is observed. -1 (Near) and peaks originating from (meth)acrylic monomer and urethane (meth)acrylate monomer (810 cm) -1 It can be obtained from the vicinity using the following formulas (1) to (4) or (5).

[0089] (1) The surface of layer D is 650 cm -1 From 2000cm -1 ATR-IR measurements were performed in the wavenumber region, and in each of the obtained measurement results, 1900 cm -1 and 2000cm -1 The background infrared absorptive αb is calculated from the measured infrared absorptive αm using the following formula (1) and formula (2).

[0090] Measured infrared absorption αm (wavelength) = -Log(R (wavelength) / 100) ... (1) In the above formula, R represents the reflectance of the attenuated total reflection at the measurement wavelength in the measurement sample. Background infrared absorptivity αb (wavelength p) = 1900 cm -1 αm in (1900) +(Wavelength p-1900)×(2000cm -1 αm in (2000) -1900cm -1 αm in (1900) ) / 100···(2) (2) From the background infrared absorption value obtained above, the converted infrared absorption αc is calculated using the following formula (3). (波長p) Calculate. αc (波長p) =αm (波長p) -αb (波長p) ...(3) (3) The reaction rate r between the polyfunctional (meth)acrylate and the double bond in the urethane (meth)acrylate is calculated from the ATR-IR measurement results before and after the curing reaction of layer D using the following formula (4) or (5).

[0091] Reaction rate of polyfunctional (meth)acrylates and double bond r in urethane methacrylates = [1-(αc1] (810) / αc1 (1740) ) / (αc0 (810) / αc0 (1740) )〕×100···(4) In other words r = [1 - (αc1)] (810) ×αc0 (1740) ) / (αc0 (810) ×αc1 (1740) )〕×100···(5) It is calculated as follows.

[0092] In the above formulas (3) or (4), αc0 (wavelength) represents the converted infrared absorptivity before the curing reaction of the D layer, and αc1 (波長) This represents the converted infrared absorptivity after ATR-IR measurement.

[0093] Note that the wavelength 810 refers to the peak originating from the (meth)acrylate functional group contained in the double bond in polyfunctional (meth)acrylate and urethane (meth)acrylate, with a wavenumber of 1740 cm⁻¹. -1 This refers to the peaks originating from the (meth)acrylic ester groups contained in polyfunctional (meth)acrylates and urethane (meth)acrylates.

[0094] From the viewpoint of excellent abrasion resistance and adhesion, the combined content of the polyfunctional (meth)acrylate and the urethane acrylate relative to the total amount of the polyfunctional (meth)acrylate, the urethane (meth)acrylate, the inorganic fine particles and the silicon compound hydrolysis condensate is preferably 45% to 97% by mass, and more preferably 65% ​​to 92% by mass. The blending ratio of the polyfunctional (meth)acrylate monomer is preferably 40% to 98% by mass, more preferably 45% to 96% by mass, and more preferably 60% to 70% by mass. [Inorganic microparticles (D3)] The D layer contains at least one of inorganic fine particles and a silicon compound hydrolysis condensate. Inorganic oxide fine particles are preferred as the inorganic fine particles. Examples of inorganic oxide fine particles include titanium dioxide, zinc oxide, cerium oxide, and silicon dioxide (silica). Among these, silica fine particles such as colloidal silica are preferred.

[0095] Examples of commercially available colloidal silica include the following products manufactured by Nissan Chemical Industries, Ltd.: methyl silica sol, IPA-ST, PGM-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL (all product names).

[0096] Furthermore, silica nanoparticles may be used that have been improved in terms of dispersibility by known methods. Examples of silica nanoparticles with improved dispersibility include those surface-treated with a reactive silane coupling agent having hydrophobic groups, and those modified with a compound having a (meth)acryloyl group. Examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, MIBK-AC, MEK-AC, and PGM-AC (all product names) manufactured by Nissan Chemical Industries, Ltd.

[0097] The shape of the silica nanoparticles is not particularly limited; spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped nanoparticles can be used. For example, commercially available hollow silica nanoparticles include Silinax® manufactured by Nippon Steel Mining Co., Ltd.

[0098] The primary average particle size of the inorganic oxide fine particles is preferably 1 nm to 200 nm, and more preferably 1 nm to 100 nm. By setting the primary average particle size of the inorganic oxide fine particles within the above range, a laminated film with excellent abrasion resistance, adhesion, etc., can be obtained.

[0099] From the viewpoint of dispersibility in the D layer, the average primary particle size of the inorganic oxide fine particles is preferably 3 nm to 500 nm, more preferably 5 nm to 300 nm, and even more preferably 10 nm to 100 nm.

[0100] From the viewpoint of dispersibility in the D layer, the inorganic oxide fine particles are preferably spherical colloidal silica with an average primary particle diameter of 5 nm to 100 nm, and more preferably colloidal silica with an average primary particle diameter of 20 nm to 60 nm.

[0101] The average primary particle size of inorganic oxide fine particles is measured by observing the D layer in the cross-section of the laminated film according to this disclosure using a transmission electron microscope (TEM). [Inorganic microparticle content] Inorganic fine particles may be used individually or in combination of two or more types.

[0102] The blending ratio of inorganic fine particles is preferably 5% to 40% by mass, relative to the total mass of the polyfunctional (meth)acrylate compound, urethane (meth)acrylate, silicon compound hydrolysis condensate, and inorganic fine particles. From the viewpoint of wear resistance, adhesion, etc., it is preferably 8% to 35% by mass, and more preferably 12% to 30% by mass. [Silicon compound hydrolysis condensate] Hydrolyzable silane compounds are preferred as silicon compound hydrolysis condensates.

[0103] Examples of hydrolyzable silane compounds include hydrolysis condensates of alkoxysilane compounds.

[0104] Specifically, examples include alkyltrialkoxysilanes such as methylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; 3-(meth)acryloyloxypropyltrialkoxysilanes such as 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyltriethoxysilane; vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; and hydrolysis condensates of alkoxysilane compounds such as aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

[0105] Hydrolysis condensates of alkoxysilane compounds are obtained by hydrolysis condensation of alkoxysilane compounds. In the hydrolysis condensation reaction, it is preferable that the condensation reaction proceeds along with the hydrolysis, and that most of the Si-OR groups, which are hydrolyzable groups of the hydrolyzable silane compound, are hydrolyzed to 100%. From the viewpoint of liquid stability, it is preferable that most of the OH groups formed by hydrolysis, preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more, are condensed with hydroxyl groups formed by the hydrolysis of other alkoxysilane compounds.

[0106] The silicon compound hydrolysis condensate may be obtained by hydrolyzing an alkoxysilane compound alone, or by hydrolyzing it in the presence of the inorganic oxide fine particles mentioned above. However, from the viewpoint of the dispersibility of the inorganic oxide fine particles, it is preferable to obtain the product by hydrolyzing it in the presence of the inorganic oxide fine particles mentioned above.

[0107] Furthermore, to improve the dispersibility of inorganic fine particles, the silicon compound hydrolysis condensate may be obtained by reacting an (meth)acrylic resin having an alkoxysilyl group in its side chain or an (meth)acrylic resin having a highly polar hydroxyl group, amine group, or carboxyl group in its side chain with inorganic oxide fine particles and / or a hydrolyzable silane compound. [Triazine-based UV absorber (D4)] The layer (D layer) containing the cured product of the active energy ray-curable acrylate according to this disclosure preferably contains a triazine-based ultraviolet absorber (D4).

[0108] Examples of triazine-based UV absorbers (D4) include UV absorbers that have a triazine skeleton within their molecular framework.

[0109] Because the triazine-based UV absorber (D4) has the above structure, it has excellent UV absorption capabilities. As a result, the D layer according to this disclosure also has excellent light resistance.

[0110] Specific examples of triazine-based UV absorbers (D4) include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-[4-[(2-hydroxy-3-(2 Examples include -ethylhexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyroxyphenyl)-6-(2,4-bis-butyroxyphenyl)-1,3,5-triazine, and 2-(2-hydroxy-4-[1-octyroxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine.

[0111] Triazine-based UV absorbers (C4) may be synthesized or commercially available. Commercially available options include TINUVIN400 (BASF), TINUVIN405 (BASF), and TINUVIN479 (BASF).

[0112] In triazine-based UV absorbers (D4), the preferred materials are 2-[4-(octyl-2-methylethanoate)oxy-2-hydroxyphenyl]-4,6-[bis(2,4-dimethylphenyl)]-1,3,5-triazine and 2-[4-(2-hydroxy-3-dodecyloxypropyl)oxy-2-hydroxyphenyl]-4,6-[bis(2,4-dimethylphenyl)-1,3,5-triazine].

[0113] Triazine-based UV absorbers (D4) may be used alone or in combination of two or more types.

[0114] The amount of triazine-based ultraviolet absorber (D4) is preferably 3% to 5% by mass per 100 parts by mass of the total of polyfunctional (meth)acrylate and / or urethane (meth)acrylate and at least one of inorganic fine particles and silicon compound hydrolysis condensate, and more preferably 3.5% to 4.5% by mass from the viewpoint of abrasion resistance, adhesion after heat bending and weather resistance. [Hindered amine (light stabilizer (D5))] The layer (D layer) containing the cured product of the active energy ray curable acrylate according to this disclosure preferably contains a hindered amine light stabilizer (D5). Examples of hindered amine light stabilizers (D5) include compounds in which two of the three substituents on the nitrogen atom in the amine compound (including compounds that form a cyclic structure with the two substituents and the nitrogen atom) have a structure with high steric hindrance.

[0115] Because the hindered amine light stabilizer (D5) has the above structure, it can react with and deactivate reactive species (radicals) generated in the coating layer.

[0116] Specific examples of hindered amine light stabilizers (D5) include alkyl-type hindered amines such as bis(1,2,2,6,6-pentamethylpiperidine-4-yl)=3,4-bis{[(1,2,2,6,6-pentamethylpiperidine-4-yl)oxy]carbonyl}hexanediate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)=decanediate, and 1,2,2,6,6-pentamethyl-4-piperidyl=methacrylate, as well as bis(2,2,6,6-tetramethylpiperidine Examples of hydrogen-type hindered amines include bis[2,2,6,6-tetramethyl-4-piperidyl-4-yl]oxycarbonyl]hexanediate and 2,2,6,6-tetramethyl-4-piperidyl=methacrylate, as well as alkoxy-type hindered amines such as bis[2,2,6,6-tetramethyl-1-(undecyloxy)piperidine-4-yl]carbonate and 1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl=octanediate.

[0117] Hindered amines may be synthesized or commercially available.

[0118] Commercially available options include TINUVIN123 (BASF), LA-52 (ADEKA), LA-57 (ADEKA), LA-68 (ADEKA), LA-72 (ADEKA), LA-77 (ADEKA), LA-81 (ADEKA), LA-82 (ADEKA), and LA-87 (ADEKA).

[0119] Hindered amines may be used individually or in combination of two or more.

[0120] The amount of hindered amine is preferably 0.5% to 30% by mass per 100 parts by mass of the total of the polyfunctional (meth)acrylate and / or urethane (meth)acrylate and at least one of the inorganic fine particles and the silicon compound hydrolysis condensate, and more preferably 3% to 20% by mass from the viewpoint of abrasion resistance, adhesion and weather resistance. [Other ingredients] The layer (D layer) containing the cured product of the active energy ray-curable acrylate according to this disclosure may contain components other than those described above as necessary. Examples of other components include surface modifiers, colorants, and dispersion media for adjusting the solid content and viscosity of the dispersion.

[0121] Any liquid medium that does not impair the effects of the present disclosure may be used as the dispersion medium, and examples include various organic solvents.

[0122] When the curing means for the layer (D layer) containing the cured product of the active energy ray-curable acrylate according to this disclosure is ultraviolet light, it is preferable to further include a photopolymerization initiator. Any known photopolymerization initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. Examples of acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone. Examples of benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone and benzyldimethyl ketal.

[0123] Examples of benzophenones include benzophenone and methyl o-benzoylbenzoate.

[0124] Examples of benzoins include benzoin, benzoin methyl ether, and benzoin isopropyl ether.

[0125] The photopolymerization initiator may be used alone or in combination of two or more types.

[0126] The amount of photopolymerization initiator used is polyfunctional (meth)acrylate and / or urethane (meth)acrylate, inorganicThe amount is preferably 1% to 15% by mass, and more preferably 2% to 10% by mass, based on 100 parts by mass of the total of at least one of the fine particles and the silicon compound hydrolysis condensate.

[0127] Methods for measuring the relative abundance of at least one of the cured polyfunctional (meth)acrylate and urethane (meth)acrylate constituting the D layer, and at least one of the inorganic fine particles and silicon compound hydrolysis condensates include scraping off the D layer of the laminated film and analyzing the types of compounds present by pyrolysis gas chromatography, determining the composition by elemental analysis, or infrared spectroscopy (ATR-IR) by attenuated total reflectance measurement of the D layer surface, or cutting the laminated film in the thickness direction and using transmission IR on the D layer cross-section. in By measuring, peaks originating from polyfunctional (meth)acrylates and urethane (meth)acrylates (1740 cm) can be detected. -1 (Near) and a peak originating from at least one of inorganic fine particles and silicon compound hydrolysis condensates (1100 cm in the case of silica) -1 Methods that combine methods such as comparing the relative abundance of nearby areas are examples of such methods.

[0128] While there are no particular restrictions on the thickness of the D layer, from the viewpoint of wear resistance, thermal flexibility, and adhesion after thermal bending, it is preferably in the range of 1.5 μm to 18 μm, more preferably in the range of 3 μm to 15 μm, and even more preferably in the range of 5 μm to 12 μm.

[0129] The thickness of layer D is determined by the same method as described above, as is the thickness of layers B and C.

[0130] Furthermore, the combined thickness of the C layer and the D layer is preferably 3 to 20 μm, and more preferably 4 to 15 μm, from the viewpoint of abrasion resistance and weather resistance.

[0131] The ratio of the thickness of the C layer to the sum of the thicknesses of the C layer and the D layer is preferably 10% to 70%, and more preferably 25% to 60%, from the viewpoint of transparency (initial haze) and flexibility. [Method for manufacturing laminated film] There are no particular limitations on the method for manufacturing the laminated film of the present invention, but one method is to first form a layer containing a thermoplastic acrylic resin (layer B) on a layer made of polycarbonate resin (layer A), and then form an acrylic resin mixed intermediate layer (layer C) and a layer containing a cured product of an active energy ray curable acrylate (layer D) on layer B.

[0132] There are no particular limitations on the method for forming a layer (B layer) containing thermoplastic acrylic resin on a layer (A layer) made of polycarbonate resin, and known methods can be used. For example, a method in which each layer is separately made into a sheet or film and then heated and pressed together; a method in which an adhesive is applied to at least one of the surfaces in advance and then bonded together; a co-extrusion method in which the polycarbonate resin and thermoplastic acrylic resin are laminated in an extruder die to obtain a sheet or sheet-like material; an in-mold molding method in which the thermoplastic acrylic resin is vacuum-formed in advance and then the polycarbonate resin that will serve as the base material is injection-molded; and a method in which a coating solution in which the thermoplastic acrylic resin is dissolved in a solvent is applied to the A layer, and then dried to remove the solvent. For cost reduction and productivity improvement, the co-extrusion method and the in-mold molding method are preferred. In particular, the co-extrusion method is preferred in terms of cost and productivity. -Method for forming layers C and D- There are no particular restrictions on the method for forming layers C and D; layers C and D may be formed separately, or they may be formed simultaneously. For example, a composition containing a polyfunctional (meth)acrylate and / or urethane (meth)acrylate and a thermoplastic acrylic resin for forming layer B may be applied to the surface of layer B and cured to form layer C, and a coating liquid composition containing at least one of a polyfunctional (meth)acrylate and urethane (meth)acrylate for forming layer D, and at least one of inorganic fine particles and a silicon compound hydrolysis condensate, and containing an organic solvent may be applied to the surface of layer B and heat-treated to allow a portion of the components of layer D to penetrate into layer B, thereby simultaneously forming layers C and D. Alternatively, a coating liquid composition containing at least one of a polyfunctional (meth)acrylate and urethane (meth)acrylate for forming layer D, and at least one of inorganic fine particles and a silicon compound hydrolysis condensate, and containing an organic solvent may be applied to the surface of layer B, and a portion of the components of layer D may be permeated into layer B, thereby simultaneously forming layers C and D.

[0133] The latter method, which forms layers C and D simultaneously, is preferable to the former method because it requires fewer steps and offers higher productivity. This method will be explained below.

[0134] In the method of simultaneously forming layers C and D, the difference between the solubility parameter of the thermoplastic (meth)acrylic resin constituting layer B and the value obtained from the weighted average of the solubility parameters of the components forming layer D is 10 MPa. 1 / 2 It is preferable that it be less than or equal to the following:

[0135] If the difference in solubility parameters is within the above range, a mixed intermediate layer (layer C) can be formed at the contact surface after coating layer D onto layer B, where both components of the acrylic resin forming layers B and D are mixed together by diffusion due to molecular motion.

[0136] In this method, predetermined amounts of each component that ultimately constitutes layer D (polyfunctional (meth)acrylate, urethane (meth)acrylate, inorganic fine particles, silicon compound hydrolysis condensate) are dissolved and dispersed in a solvent such as an organic solvent to prepare a coating liquid composition. At this time, the predetermined amounts of each component are adjusted to the desired amounts of polyfunctional (meth)acrylate and urethane (meth)acrylate that will form layer C. Next, the coating liquid composition is applied to the side of layer B opposite to layer A, and then dried for a certain period of time to remove the solvent and form a film. After that, the film is irradiated with active energy rays such as ultraviolet light and electron beams to react and cure the polyfunctional (meth)acrylate and urethane (meth)acrylate, thereby forming layer D on layer B via layer C.

[0137] There are no particular restrictions on the method of applying the coating composition, but examples of known and conventional coating methods include brush coating, roller coating, spray coating, dipping, flow coater coating, roll coater coating, or electrodeposition coating.

[0138] In a method that simultaneously forms both the C and D layers, the thickness of the C layer can be appropriately adjusted by changing the drying temperature and drying time.

[0139] The method for drying the coating film of the above-mentioned coating composition is not limited to natural drying, air drying, and heating.

[0140] The drying temperature is preferably 65°C to 95°C, and more preferably 70°C to 85°C.

[0141] Furthermore, regarding the drying time, from the viewpoint of the thickness required to effectively exhibit weather resistance, it is preferably 5 to 20 minutes, more preferably 5 to 15 minutes, and even more preferably 5 to 13 minutes.

[0142] As the solvent mentioned above, an organic solvent capable of dissolving polyfunctional (meth)acrylates, urethane (meth)acrylates, etc., and dissolving or dispersing inorganic fine particles and silicon compound hydrolysis condensates is preferred. For example, from the viewpoint of being able to adjust the thickness of the acrylic resin mixed intermediate layer (C layer) to a suitable range, examples of organic solvents include alcohols such as methanol, ethanol, propanol, and butanol; ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, methyl butyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), and cyclohexanone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, and ethyl valerate; ether alcohols such as methoxyethanol, ethoxyethanol, butoxyethanol, and methoxypropanol (hereinafter sometimes referred to as "propylene glycol monomethyl ether (PGM)"), ethoxypropanol, and butoxypropanol; aliphatic hydrocarbons such as hexane, heptane, and octane; and aromatic hydrocarbons such as toluene, xylene, (ethylbenzene), styrene, and stilbene.

[0143] Organic solvents can be used individually or in combination.

[0144] When using an organic solvent alone, ether alcohols such as methoxyethanol, ethoxyethanol, butoxyethanol, methoxypropanol, ethoxypropanol, and butoxypropanol are preferred from the viewpoint of solubility of the acrylate monomer contained in the layer (D layer) that contains the cured product of the active energy ray-curable acrylate, and permeability into the thermoplastic acrylic resin layer (B layer). Among these, methoxypropanol is particularly preferred from the viewpoint of balance between volatility, solubility of acrylic resin, permeability into the thermoplastic acrylic resin layer (B layer), and low toxicity.

[0145] When using a mixture of organic solvents, from the viewpoint of easily forming a C layer, the ether alcohols listed above as organic solvents for use alone are further mixed with at least one organic solvent selected from the group consisting of ketones such as acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), and cyclohexanone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, and ethyl valerate; and aromatic hydrocarbons such as toluene, xylene, (ethylbenzene), styrene, and stilbene. It is preferable to use a mixed solvent which has a boiling point in the range of 70 to 140°C and can delay the evaporation of the solvent and the formation of an excessively thick penetration layer when the substrate is heat-dried after hard coat application. It is more preferable to use a mixed solvent which is an ether alcohol to which at least one organic solvent selected from the group consisting of methyl ethyl ketone, ethyl acetate, butyl acetate, and toluene has been added, and it is particularly preferable to use a mixed solvent which is a methoxypropanol to which at least one organic solvent selected from the group consisting of methyl ethyl ketone, ethyl acetate, butyl acetate, and toluene has been added.

[0146] From the standpoint of volatility during coating and solvent recovery, methyl ethyl ketone (MEK) or methoxypropanol (propylene glycol monomethyl ether) is preferred.

[0147] The content of the above-mentioned organic solvent is preferably 40 to 70 parts by mass, and more preferably 45 to 65 parts by mass, per 100 parts by mass of the inorganic fine particle dispersion.

[0148] According to the present invention, it is possible to provide a laminated film that is excellent in adhesion between layers, impact resistance, flexibility, abrasion resistance, and weather resistance. Therefore, this laminated film is useful as a thermoforming film such as in-mold lamination film or a decorative film. For example, when using the laminated film of the present invention for in-mold lamination filming, first, the D layer of the laminated film is placed in contact with the mold, and then a thermoplastic resin (e.g., polycarbonate resin) that has been molten by injection molding is discharged into the mold to obtain a polycarbonate resin molded product decorated with the laminated film. In such a resin molded product, a thermoplastic resin layer (e.g., a polycarbonate layer) is formed in contact with the A layer side surface of the laminated film. [Examples]

[0149] The present disclosure will be described in detail below with reference to examples, but the disclosure is not limited to these examples. In these examples, unless otherwise specified, "%" and "parts" mean "mass%" and "parts by mass," respectively. [Evaluation Method] <Total light transmittance (TT)> Measurements were taken using an NDH-300A manufactured by Nippon Denshoku Co., Ltd., in accordance with JIS K7361-1 (1997). <Initial haze (H)> The haze meter NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd., was used for the measurement. The haze value (H) is expressed as H = Td / Tt × 100 (Td: scattered light transmittance, Tt: total light transmittance). <Abrasion resistance (△H)> The surface of an abrasive wheel (product name: CS-10F, manufactured by Taber) was polished 25 times with a Taber ST-11 abrasive stone before the Taber abrasion test to prepare the wheel. Using the prepared abrasive wheel, a Taber abrasion test was performed on the D layer surface of a laminated film under a load of 500g and 500 rotations, in accordance with ASTM D1044, and the change in haze value (ΔH) of the laminated film surface before and after the Taber abrasion test was measured.

[0150] The change in haze value (ΔH) was measured using a haze meter (product name: NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) under measurement method 2, light source A. The haze value (H) is the value shown by H = Td / Tt × 100 (Td: scattered light transmittance, Tt: total light transmittance).

[0151] The haze value (H) was measured on three test pieces with the same polishing specifications, and the average value of ΔH was evaluated according to the evaluation criteria below. A smaller value of ΔH indicates better wear resistance, and a ΔH of less than 9.0 is preferable.

[0152] The abrasion wheels used in the Taber abrasion test were those whose change in haze value (ΔH) was in the range of 0.6 to 1.0 when a Taber abrasion test was performed on commercially available float glass (plate glass) under the same conditions as described above, with a load of 500g and 1,000 rotations. Abrasion wheels whose ΔH fell outside this range were not used in the test. <Boiling water resistance (adhesion)> The laminated film was immersed in boiling water for 3 hours, then removed, any adhering water droplets were wiped off, and the film was allowed to rest for 15 minutes in an environment of 25°C and 50% RH. 100 grid lines were made on the surface of the D layer of the removed laminated film at 1 mm intervals using a utility knife, and Nichiban adhesive tape (product name "Sellotape (registered trademark)") was pressed onto the grid and peeled off firmly in a vertical direction (according to JIS K5400). A × indicated that part of the coating peeled off during the first peeling operation, a △ indicated that no coating was formed during the first peeling operation but part of the coating peeled off during the second peeling operation, and a ○ indicated that no coating peeling occurred during either of the two peeling operations. <Flexibility> Laminated films were wrapped around cylinders with diameters of 18 mm and 36 mm, with the D layer facing outwards. Films that showed no abnormalities in appearance when wrapped around an 18 mm diameter cylinder were marked with ○, films that cracked when wrapped around an 18 mm cylinder but showed no abnormalities in appearance when wrapped around a 36 mm cylinder were marked with △, and films that cracked even when wrapped around a 36 mm cylinder were marked with ×. <Impact Resistance> A DuPont impact resistance tester (DuPont Impact Resistance Tester No. 451, manufactured by Toyo Seiki Co., Ltd.) equipped with a flat support base was used. The laminated film was placed on the support base with the D layer facing upwards, and a striking mold with a cone tip radius of 12.7 mm was placed on top of it. A 300 g drop weight was then dropped from a height of 20 cm. After the test, the laminated film was observed. A ○ was used if there was a depression of 1 mm or less in depth on the surface of the test area, but no delamination or cracking of the D layer. A △ was used if there was a depression of more than 1 mm in depth on the surface of the test area, but no delamination or cracking of the D layer. A × was used if delamination or cracking occurred in the D layer. <Weather resistance> The laminated film was placed in a Suga Test Instruments Co., Ltd. Super Xenon Weather Meter SX-75 with the D layer facing the light source, and the UV irradiation intensity was 180 W / m². 2 The samples were exposed to a black panel at a temperature of 63°C for 2000 and 4000 hours under conditions of 18 minutes of rain during a 120-minute period. After removing the laminated film and observing its appearance, the surface was lightly scrubbed clean with a sponge soaked in neutral detergent. Then, 100 grid lines were made on the surface of the D layer at 1 mm intervals using a utility knife. Nichiban adhesive tape (product name "Sellotape®") was pressed onto the grid and peeled off twice with strong vertical force. Samples showing cracks or delamination at 2000 hours were marked with ×, samples with good appearance and adhesion at 2000 hours but showing cracks or delamination at 4000 hours were marked with △, and samples with good appearance and adhesion even after 4000 hours were marked with ○. [Preparation Example 1] (Production of polyester-based thermoplastic elastomer) With respect to 100 parts by mass of dimethyl isophthalate, 13 parts by mass of dimethyl sebacate and 80 parts by mass of hexamethylene glycol are subjected to transesterification reaction using a dibutyltin diacetate catalyst, followed by polycondensation under reduced pressure, whereby an amorphous polyester (soft segment) having an intrinsic viscosity of 1.06 and exhibiting no endothermic peak attributable to crystal melting as measured by DSC is obtained. 32 parts by mass of polybutylene terephthalate pellets (hard segment) having an intrinsic viscosity of 0.98 are added to 100 parts by mass of the above polyester, the mixture is further reacted at 240°C for 45 minutes, and then 0.03 parts by mass of phenylphosphonic acid is added to terminate the reaction, whereby a polyester-based thermoplastic elastomer (X1) is obtained. The obtained polymer had a melting point of 190°C and an intrinsic viscosity of 0.93. [Preparation Example 2] (Synthesis of Silicon Compound Hydrolysis Condensate C1) 100 parts by weight of 2-propanol, 40 parts by weight of 0.1 mol / L hydrochloric acid, and 101 parts by weight of methyltrimethoxysilane are added to a reaction vessel, the mixture is stirred at 30°C for 1 hour and 30 minutes, while stirring is continued, the liquid temperature is raised to 80°C, and a part of the contained solvent is distilled off to obtain CH3SiO 3 / 2 124.5 parts by weight of a silicon compound hydrolysis condensate (C1) having a solid content concentration of 30% by weight in terms of conversion is obtained. <Preparation of Coating Agent for D Layer Formation (HC-1)> As polyfunctional (meth)acrylates, 420 parts by mass of Aronix M-350 (trimethylolpropane ethylene oxide-modified triacrylate) manufactured by Toagosei Co., Ltd., and 1820 parts by mass of 1,9-DA (1,9-nonanediol diacrylate) manufactured by Kyoeisha Chemical Co., Ltd. were used; as urethane acrylate, 31.5 parts by mass of 8UX-116A (solid content concentration: 63.5 mass% MEK solution) manufactured by Taisei Fine Chemical Co., Ltd. was used; as inorganic fine particles (D3), 50 parts by mass of organic solvent-dispersed surface-modified colloidal silica (MEK-AC-2140Z, manufactured by Nissan Chemical Corporation, solid content concentration 40%) was used; as (D4), 4 parts by mass of Tinuvin 405 (hydroxyphenyltriazine-based ultraviolet absorber) manufactured by BASF Japan Ltd. was used; as hindered amine light stabilizer (D5), 2 parts by mass of LA-52 (manufactured by ADEKA Corporation) was used; as photopolymerization initiator (D6), 1 part by mass of phenyl 1-hydroxyethyl ketone (Irgacure 184, manufactured by BASF Japan Ltd.), 2050 parts by mass of methyl ethyl ketone (MEK), 10050 parts by mass of methoxypropanol (MIBK), and 4010 parts by mass of isopropanol (IPA) were added to prepare a coating agent for forming D layer (HC-1). The composition of (HC-1) is shown in Table 1 below. <Preparation of Coating Agents for Forming D Layer (HC-2 to HC-10)> (HC-2) to (HC-10) were prepared in the same manner as the preparation of (HC-1), except that the compositions were as shown in Table 1.

[0153] In addition, in Table 1, M-315 refers to Aronix M-315 (isocyanuric acid ethylene oxide-modified di- and triacrylate mixture) manufactured by Toagosei Co., Ltd., and MIBK-ST refers to MIBK-ST (manufactured by Nissan Chemical Corporation, solid content concentration 30%). [Example 1] (Molding Material A) Polycarbonate resin pellets (Teijin Limited's Panlite L1250WP (bisphenol A homopolycarbonate resin (PC-A, viscosity-average molecular weight 23,900)) and the thermoplastic elastomer (X1) obtained in [Preparation Example 1] above) were pre-dried beforehand. 92.93 parts by weight of polycarbonate resin pellets were mixed with 7 parts by weight of the thermoplastic elastomer (X1) polymerized in Preparation Example 1 and 0.07 parts by weight of tetrakis-2,4-t-butylphenyl 4,4'-biphenylenediphosphonate (BASF's Irgaphos PEP-Q) as a heat stabilizer using a V-type blender. The mixture was then extruded using a twin-screw extruder at a cylinder temperature of 260°C to obtain molding material A for layer A. The glass transition temperature of molding material A was 145°C. (Molding material B) For the B layer, we prepared an acrylic resin (Acrypet VH-001 manufactured by Mitsubishi Rayon Co., Ltd., a thermoplastic acrylic resin copolymerized with 95 mol% methyl methacrylate and 5 mol% methyl acrylate). (Co-extrusion) Molding material A and molding material B were extruded from a 650 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 40 mm, under the conditions of cylinder temperature of 260°C (molding material A) and 250°C (molding material B), screw rotation speed of 109 rpm (molding material A) and 11 rpm (molding material B). The molten resin was then compressed and cooled using a metal roll and a metal sleeve roll, and after edge trimming, it was wound at a winding speed of 10.3 m / min to create a 400 mm wide laminated sheet with a two-layer structure of A layer / B layer (A layer 240 μm, B layer 60 μm). (Coating) Next, the coating agent for forming the D layer (HC-1) was applied to the B layer side of the laminated sheet using a bar coater (#8), and then dried with hot air in a 100°C drying oven for 5 minutes. A laminated film with a four-layer structure (A layer 240 μm, B layer 59 μm, C layer 1.5 μm, D layer 3.5 μm) was obtained (however, the C and D layers were in an uncured state).

[0154] The resulting laminated film was irradiated with a high-pressure mercury lamp at an intensity of 250 wW / cm². 2, irradiation amount 2000mJ / cm 2 The C and D layers were cured by irradiation with ultraviolet light to obtain a laminated film. [Examples 2-17] Each laminated film was obtained in the same manner as in Example 1, except that the coating agent prepared with the composition described in Table 1 was used as described in Table 2 and prepared under the conditions described in Tables 2 and 3. [Example 18] First, the laminated film obtained in Example 1 was placed on the female mold (lower mold) of a 15 cm square molding die with a gently curved surface shape and a radius of curvature of 1 m, with the D layer facing downwards, i.e., towards contact with the mold. Then, the laminated film was pressed tightly against the mold by suction from a suction port provided on the surface of the female mold (lower mold). Next, after closing the molding die, polycarbonate resin pellets (Teijin Limited, Panlite L1250WP) were injection molded into the cavity of the molding die under conditions of a mold temperature of 90°C and a resin temperature of 290°C to obtain a polycarbonate resin molded product decorated with the laminated film. The obtained resin molded product had no defects such as cracks or wrinkles in its appearance and had a beautiful appearance.

[0155] The weather resistance of the obtained molded product was evaluated using the same method as in Example 1, and it was found to be good (〇). [Comparative Examples 1-3] Each laminated film was obtained in the same manner as in Example 1, except that the coating agent prepared with the composition described in Table 1 was used as described in Table 2 and prepared under the conditions described in Table 3. [Comparative Example 4] A polycarbonate resin molded product was obtained in the same manner as in Example 18, except that the laminated sheet obtained in Comparative Example 1 was used. The obtained resin molded product had no defects such as cracks or wrinkles in its appearance and had a beautiful appearance. When its weather resistance was evaluated, it was found to be poor (×).

[0156] [Table 1]

[0157] [Table 2]

[0158] [Table 3]

[0159] P1: Teijin Limited Panlight L1250WP X1: Polyester-based thermoplastic elastomer obtained in Preparation Example 1 T1: 4,4'-biphenylenediphosphonate tetrakis-2,4-t-butylphenyl P2: Acrypet VH-001 manufactured by Mitsubishi Rayon Co., Ltd. UV1: BASF Corporation's Chinuvin 360 (benzotriazole-based UV absorber) C1: Silicon compound hydrolysis condensate synthesized in Preparation Example 2 UV2: BASF Corporation's Chinuvin 405 (hydroxyphenyltriazine-based UV absorber) HA1: LA-52 (hindered amine light stabilizer) manufactured by ADEKA Corporation [Industrial applicability]

[0160] The laminated film of the present invention is excellent in adhesion, impact resistance, flexibility, abrasion resistance, and weather resistance, making it useful as a thermoforming film or decorative film for in-mold lamination molding, for example. Therefore, resin molded products using this laminated film can be used for, for example, automotive interior materials, electrical appliances, cosmetic films, building interior and exterior parts, and are particularly suitable as automotive exterior materials or building exterior parts due to their excellent weather resistance.

Claims

1. A laminated film comprising a layer containing polycarbonate resin (layer A), a layer containing thermoplastic acrylic resin (layer B), an acrylic resin mixed intermediate layer (layer C), and a layer containing a cured product of active energy ray-curable acrylate (layer D), laminated in this order, and satisfying the following conditions (a) to (e); (a) The active energy ray curable acrylate comprises at least one of a polyfunctional (meth)acrylate and a urethane (meth)acrylate, (b) Layer D comprises at least one of inorganic fine particles and a silicon compound hydrolysis condensate, (c) With respect to the total amount of the polyfunctional (meth)acrylate, the urethane (meth)acrylate, the inorganic fine particles, and the silicon compound hydrolysis condensate, the total content of the polyfunctional (meth)acrylate and the urethane acrylate is 45% to 97% by mass, and the total content of the inorganic fine particles and the silicon compound hydrolysis condensate is 3% to 55% by mass. (d) The C layer comprises the thermoplastic acrylic resin and a cured product of at least one of the polyfunctional (meth)acrylate and the urethane (meth)acrylate, wherein when the amount of the thermoplastic acrylic resin is X parts by mass and the total amount of the polyfunctional (meth)acrylate and the urethane (meth)acrylate is Y parts by mass, Y / (X+Y) is in the range of 0.2 to 0.

75. (e) The thickness of layer B is in the range of 10 to 200 μm, the thickness of layer C is in the range of 0.3 to 5.0 μm, the thickness of layer D is in the range of 1.5 μm to 18 μm, the sum of the thicknesses of layer C and layer D is 3 to 20 μm, and the ratio of the thickness of layer C to the sum of the thicknesses of layer C and layer D is 10% to 70%.

2. The laminated film according to claim 1, wherein in the C layer, when the amount of the thermoplastic acrylic resin is X parts by mass and the total amount of the polyfunctional (meth)acrylate and the urethane (meth)acrylate is Y parts by mass, Y / (X+Y) is 0.28 to 0.

35.

3. The laminated film according to claim 1 or 2, wherein the reaction rate of the double bonds of the (meth)acrylic groups of the polyfunctional (meth)acrylate and the urethane (meth)acrylate in the C layer is 25 to 70%.

4. The laminated film according to claim 1 or 2, wherein the A layer contains a polyester thermoplastic elastomer, and the polyester thermoplastic elastomer comprises a hard segment made of polybutylene terephthalate units and a soft segment made of polyester units having aromatic dicarboxylic acids and aliphatic dicarboxylic acids as dicarboxylic acid components and C5 to C15 diols as diol components.

5. The laminated film according to claim 4, wherein the polycarbonate resin is present in an amount of 1 to 20 parts by weight of the polyester thermoplastic elastomer per 100 parts by weight of the polycarbonate resin.

6. A method for manufacturing a laminated film according to claim 1, characterized by laminating a layer containing polycarbonate resin (layer A) and a layer containing thermoplastic acrylic resin (layer B) by co-extrusion, then applying a coating liquid composition containing an organic solvent, an active energy ray-curable acrylate, and at least one of inorganic fine particles and a silicon compound hydrolysis condensate onto layer B, drying the applied coating liquid composition, and then irradiating it with active energy rays to form an acrylic resin mixed intermediate layer (layer C) and an acrylate cured layer (layer D).

7. The method for manufacturing a laminated film according to claim 6, wherein the C layer comprises the thermoplastic acrylic resin and a cured product of at least one of the polyfunctional (meth)acrylate and the urethane (meth)acrylate.

8. A resin molded article having a thermoplastic resin layer in contact with layer A of the laminated film described in claim 1.

9. A resin molded product obtained by injection molding a thermoplastic resin onto the A-layer side surface of the laminated film according to claim 1.

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