Stacked body and use thereof

Abstract

An object of the present application is to provide a laminate of an acrylic resin film which is excellent in moldability and abrasion resistance. The above object is solved by providing a laminate comprising a specific acrylic resin film and a specific ultraviolet-curing hard coat layer laminated on at least one side of the acrylic resin film, the laminate having a specific crack elongation, a Δhaze of 1.0% or less in a steel wool abrasion test of 5 round trips, and a Δhaze of 1.0% or less in a steel wool abrasion test of 10 round trips. 2 , 5 round trips.

Description

Technical Field

[0001] This invention relates to laminates comprising an acrylic resin film as a substrate. Background Technology

[0002] Acrylic resin films, which are formed by processing acrylic resin compositions containing elastomers, are used and developed for various applications due to their excellent properties such as transparency, hardness, weather resistance, and re-molding ability. Applications of acrylic resin films include, for example, decorative and protective applications as lamination films on interior and exterior automotive parts instead of coatings; decorative and protective applications on the exterior of mobile electronic devices, personal computers, and home appliances; and applications as building materials.

[0003] For example, Patent Document 1 describes an acrylic resin film formed by film-forming a methacrylate resin composition (D) comprising a specific methacrylate resin (A), a rubber-grafted copolymer (B) of a four-segment polymer with an average rubber particle size of 0.2 to 0.4 μm, and a rubber-grafted copolymer (C) of a two-layer polymer with an average rubber particle size of 0.02 to 0.15 μm, as well as a laminate containing the acrylic resin film.

[0004] Patent Document 2 describes an acrylic resin film comprising graft copolymer particles (A) with an average particle size of 20 nm to 150 nm and graft copolymer particles (B) with an average particle size greater than the graft copolymer particles (A), as well as a laminated film comprising the acrylic resin film.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2013 / 051239

[0008] Patent Document 2: International Publication No. 2019 / 181752 Summary of the Invention

[0009] While the technologies described in Patent Documents 1 and 2 are excellent, there is still room for improvement in formability and wear resistance.

[0010] Therefore, the object of the present invention is to provide a laminate containing an acrylic resin film with excellent formability and wear resistance.

[0011] In order to solve the above-mentioned problems, the inventors conducted in-depth research and, for the first time, discovered that by using an acrylic resin film with specific physical properties and a specific (e.g., UV-curable) hard coating in the laminate, a laminate with excellent formability and wear resistance can be obtained. Furthermore, for the first time, it was discovered that the above-mentioned laminate can be obtained by designing the manufacturing process of the laminate, thus completing the present invention.

[0012] Therefore, one aspect of the present invention is a laminate comprising an acrylic resin film and a hard coating layer on at least one side of the acrylic resin film, wherein the acrylic resin film has a glass transition temperature (Tg) of 140°C or less, and an elongation at break of 200% or more at 120°C, and the laminate has a crack elongation at 50% or more at 120°C, and a thickness of 50 g / cm³. 2 The Δ haze of the steel wool abrasion test after 5 rounds is less than 1.0% (hereinafter referred to as "this laminate").

[0013] Another aspect of the present invention is a method for manufacturing a laminate comprising an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film. The method includes a step of curing the hard coating layer coated on at least one side of the acrylic resin film by UV irradiation on a cooling roller, wherein the cumulative UV intensity of the UV irradiation is 150–500 mJ / cm². 2 The temperature of the cooling roller is 25–70°C, the glass transition temperature of the acrylic resin film is below 140°C, and the elongation at break at 120°C is 200% or more; the crack elongation at 120°C of the laminate is 50% or more, and the thickness is 50 g / cm³. 2 The Δ haze of the steel wool abrasion test after 5 rounds is less than 1.0% (hereinafter referred to as "the manufacturing method of this laminate").

[0014] Another aspect of the present invention is a method for manufacturing a molded article, comprising a step of shaping the laminate shown below at a molding temperature of 140°C or below during pre-forming (hereinafter referred to as "the method for manufacturing this molded article"):

[0015] The laminate comprises an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film. The acrylic resin film has a glass transition temperature of 140°C or less and an elongation at break of 200% or more at 120°C. The laminate has a crack elongation at 120°C of 50% or more and a g / cm³ of 50 g / cm³. 2 The Δ haze of the steel wool abrasion test after 5 rounds was below 1.0%.

[0016] According to one aspect of the present invention, it is possible to provide a laminate containing an acrylic resin film with excellent formability and abrasion resistance. Detailed Implementation

[0017] The following provides a detailed description of one embodiment of the present invention. It should be noted that, unless otherwise specified in this specification, "A to B" indicating a numerical range means "above A and below B". Furthermore, all documents described in this specification are incorporated herein by reference.

[0018] [1. Summary of the Invention]

[0019] In recent years, the automotive display industry has seen continuous development towards larger sizes and curved surfaces. Films used in such displays require properties such as curvature, abrasion resistance (also known as scratch resistance), anti-reflective properties, and reliability. For this purpose, multilayer films consisting of polycarbonate and acrylic resins are widely used, further enhanced by coating functional layers with properties such as scratch resistance, anti-glare, anti-reflective properties, and stain resistance. However, because these films consist of two substrate layers with different heat resistances, proper secondary molding is difficult, leading to issues such as whitening, interlayer delamination, and peeling of functional layers. Furthermore, with prolonged use, they may peel off the display surface. Additionally, the inherent large phase difference of polycarbonate resin can cause issues such as rainbow patterns or reduced contrast on the display surface due to stretching during secondary molding. On the other hand, as mentioned above, acrylic resin films possess excellent optical properties such as transparency, hardness, weather resistance, small phase difference during stretching, and excellent secondary molding capabilities. Therefore, the inventors have studied the use of acrylic resin films in automotive displays.

[0020] First, the inventors attempted to improve the strength of the hard coating in a laminate comprising an acrylic resin film and a hard coating, from the viewpoint of enhancing wear resistance. However, they discovered that while improving the strength of the hard coating itself was relatively easy, a new problem arose when increasing the strength of the hard coating: the hard coating cracked during molding, making molding impossible.

[0021] Therefore, the inventors conducted in-depth research on laminates that can achieve both formability and wear resistance, and successfully obtained the following insights.

[0022] Excellent moldability can be ensured by using acrylic resin films with a glass transition temperature (Tg) of 140°C or lower and an elongation at break of 200% or higher at 120°C.

[0023] • In the manufacturing process of the hard coating, the cumulative UV light intensity is controlled to be 150–500 mJ / cm.2 Controlling the temperature of the cooling roller during UV irradiation to 25–70°C (preferably 40–70°C) can enhance the wear resistance of the laminate.

[0024] This laminate, based on the above insights, achieves both excellent formability and abrasion resistance. Such a laminate containing an acrylic resin film, exhibiting superior formability and abrasion resistance, has not been reported to date and represents an exceptionally advanced technology.

[0025] As described above, this laminate simultaneously achieves excellent formability and wear resistance. Therefore, it contributes, for example, to achieving Goal 12 of the United Nations Sustainable Development Goal (SDGs), "Ensuring sustainable consumption patterns of production." The composition of this laminate will be described in detail below.

[0026] [2. Layered structure]

[0027] This laminate comprises an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film.

[0028] (Acrylic resin film)

[0029] The acrylic resin membrane is composed of an acrylic resin composition comprising acrylic resin and graft copolymer particles containing a rubber component. Preferably, the graft copolymer particles containing the rubber component are graft copolymer particles (A) with an average particle size of 20 nm to 200 nm. In addition to graft copolymer particles (A), graft copolymer particles (B) with an average particle size larger than that of graft copolymer particles (A) may also be included. Specifically, in the acrylic resin membrane, the graft copolymer particles (A) are dispersed in the acrylic resin or a matrix containing acrylic resin and other components; or the graft copolymer particles (A) and graft copolymer particles (B) are dispersed in the acrylic resin or a matrix containing acrylic resin and other components.

[0030] <Acrylic Resin>

[0031] Acrylic resins used as acrylic resin films can be conventionally known acrylic resins. For example, from the viewpoint of hardness and formability, when the total amount of acrylic resin is set to 100% by mass, it is preferable to use a thermoplastic acrylic polymer consisting of 20% to 100% by mass of methyl methacrylate units, 50% to 100% by mass of other structural units, and 0% to 50% by mass of other structural units.

[0032] Other structural units include, for example, those derived from acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, aromatic vinyl derivatives, vinyl cyanide derivatives, and vinylidene halides. The acrylic resin may contain one or a combination of two or more of these other structural units.

[0033] Examples of acrylic acid derivatives include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, 2-(N,N-dimethylamino)ethyl acrylate, and glycidyl acrylate, among other acrylic esters.

[0034] Examples of methacrylic acid derivatives include ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, and methacrylates of methacrylic acid.

[0035] Examples of aromatic vinyl derivatives include styrene, vinyltoluene, and α-methylstyrene.

[0036] Examples of vinyl cyanide derivatives include acrylonitrile and methacrylonitrile.

[0037] Examples of vinylidene halides include vinylidene chloride and vinylidene fluoride.

[0038] To improve the heat resistance, rigidity, and surface hardness of acrylic resins, structural units with specific structures can be copolymerized and introduced into the acrylic resin through functional group modification and other methods. Examples of such specific structures include, for instance, the glutarimide structures disclosed in Japanese Patent Application Publication Nos. 62-89705, 02-178310, and WO2005 / 54311; the lactone ring structures disclosed in Japanese Patent Application Publication Nos. 2004-168882 and 2006-171464; the glutaric anhydride structures obtained by thermal condensation cyclization of (meth)acrylic acid units disclosed in Japanese Patent Application Publication No. 2004-307834; the maleic anhydride structures disclosed in Japanese Patent Application Publication No. 5-119217; and the N-substituted and unsubstituted maleimide structures disclosed in WO2009 / 84541. For example, by introducing these structures into the acrylic resin, the molecular chain becomes rigid. As a result, improvements in heat resistance, surface hardness, heat shrinkage, and chemical resistance can be expected.

[0039] There are no particular limitations on the manufacturing method of acrylic resins. For example, well-known polymerization methods such as suspension polymerization, bulk polymerization, solution polymerization, emulsion polymerization, and dispersion polymerization can be used. In addition, well-known free radical polymerization, living free radical polymerization, anionic polymerization, and cationic polymerization can all be used.

[0040] <Graft copolymers containing rubber components>

[0041] As described above, the acrylic resin film preferably contains graft copolymer particles (A) as graft copolymer particles containing rubber components, and may also contain graft copolymer particles (B) in addition to graft copolymer particles (A) as needed.

[0042] The graft copolymer particles (A) preferably have a core-shell structure (multilayer structure) comprising a crosslinked elastomer (A1) as a rubber component and a graft polymer layer (A2) located on the surface side relative to the crosslinked elastomer (A1).

[0043] The crosslinked elastomer (A1) can be any known crosslinked elastomer. Preferably, the crosslinked elastomer (A1) is an acrylate-based crosslinked elastomer (a crosslinked elastomer composed of polymers with acrylate as the main component).

[0044] The particles of the acrylate-based crosslinked elastomer (A1) can have a concentric spherical multilayer structure in which a rigid or semi-rigid crosslinked resin layer is present inside the crosslinked elastomer layer. Examples of such rigid or semi-rigid crosslinked resin layers include rigid crosslinked methacrylate resin particles disclosed in Japanese Patent Publication No. 55-27576, semi-rigid crosslinked particles composed of methyl methacrylate, acrylate, and styrene disclosed in Japanese Patent Application Publication No. 4-270751, and highly crosslinked rubber particles. By having such a rigid or semi-rigid crosslinked resin layer, improvements in transparency, color tone, etc., can be expected.

[0045] The graft copolymer particles (A) preferably have a core-shell structure formed by grafting and polymerizing the graft polymer layer (A2) in the presence of the aforementioned acrylate-based crosslinked elastomer (A1) particles.

[0046] The average particle size of the graft copolymer particles (A) is 20 nm to 200 nm, more preferably 50 nm to 150 nm, and particularly preferably 50 nm to 120 nm.

[0047] If the average particle size of the graft copolymer particles (A) is too small, the impact resistance and flexural crack resistance of the acrylic resin film tend to decrease. If the average particle size of the graft copolymer particles (A) is too large, the transparency of the acrylic resin film tends to decrease, and there is a tendency for whitening due to bending.

[0048] As an acrylate-based crosslinked elastomer (A1), it is preferable to use crosslinked elastomer particles obtained by polymerizing an acrylate with a monomer mixture (a-1) containing any other vinyl monomers that can copolymerize with the acrylate and a multifunctional monomer that can copolymerize with the acrylate and has two or more non-conjugated double bonds in one molecule.

[0049] In a single-step polymerization, all acrylates, other vinyl monomers, and multifunctional monomers are mixed. Alternatively, to adjust the toughness and whitening resistance of the acrylic resin film, the composition of the acrylates, other vinyl monomers, and multifunctional monomers is appropriately changed, or the composition is kept the same, and the acrylates, other vinyl monomers, and multifunctional monomers are polymerized in two or more steps.

[0050] As for acrylates, considering factors such as providing polymers with excellent polymerizability, low price, and low Tg, aliphatic esters of acrylic acid are preferred, alkyl acrylates are more preferred, and alkyl acrylates with alkyl groups having 1 to 22 carbon atoms are particularly preferred.

[0051] Specific examples of preferred alkyl acrylates include, for instance, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dodecyl acrylate, stearyl acrylate, heptadecanyl acrylate, octadecyl acrylate, etc. They can be used individually or in combination of two or more.

[0052] The amount of acrylate is preferably 50% by mass or more in 100% by mass of the monomer mixture (a-1), more preferably 70% by mass or more, and most preferably 80% by mass or more. If the amount of acrylate is 50% by mass or more, the acrylic resin film has good impact resistance and elongation at tensile break, and is less prone to cracking during secondary molding.

[0053] Other vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; vinyl halogens such as vinyl chloride and bromovinyl; vinyl cyanide derivatives such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl formate, vinyl acetate, and vinyl propionate; aromatic vinyl derivatives such as styrene, vinyltoluene, and α-methylstyrene; and vinylidene chloride. Vinyl halides such as alkenes and vinylidene fluoride; acrylic acid; salts of acrylic acid such as sodium acrylate and calcium acrylate; acrylic acid derivatives such as β-hydroxyethyl acrylate, phenoxyethyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, acrylamide, and N-hydroxymethylacrylamide; methacrylic acid; salts of methacrylic acid such as sodium methacrylate and calcium methacrylate; methacrylic acid derivatives such as methacrylamide, β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and glycidyl methacrylate; maleic anhydride; maleic acid derivatives such as N-alkylmaleimide and N-phenylmaleimide. These can be used individually or in combination with two or more. Among them, considering weather resistance and transparency, one or more selected from methacrylates and aromatic vinyl derivatives are particularly preferred.

[0054] The amount of other vinyl monomers in 100% by mass of monomer mixture (a-1) is preferably 0% to 49.9% by mass, more preferably 0% to 30% by mass, and most preferably 0% to 20% by mass. If the amount of other vinyl monomers exceeds 49.9% by mass, the impact resistance of the acrylic resin film is easily reduced, the elongation at tensile fracture is reduced, and cracks are easily generated during secondary molding.

[0055] As multifunctional monomers, monomers commonly used as crosslinking agents and / or cross-grafting agents can be used. Examples of multifunctional monomers that can be used include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, and dipropylene glycol dimethacrylate. These multifunctional monomers can be used individually or in combination of two or more.

[0056] As these multifunctional monomers, substances that function as cross-grafting agents increase the number of graft bonds in the graft polymer layer (A2) described later relative to the crosslinked elastomer (A1). As a result, good dispersibility of the graft copolymer (A) in the acrylic resin is achieved, crack resistance to tensile and flexural deformation is improved, and stress whitening is reduced, which is therefore more preferable. As multifunctional monomers with such cross-grafting agent functions, allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, and other monomers containing allyl groups are preferred, and allyl methacrylate and allyl acrylate are particularly preferred.

[0057] The amount of the multifunctional monomer in 100% by mass of the monomer mixture (a-1) is preferably 0.1% by mass or more than 10% by mass, and more preferably 1.0% by mass or more than 4% by mass. If the amount of the multifunctional monomer is within the above range, it is preferred from the viewpoint of the acrylic resin film's resistance to flexural cracking and flexural whitening, as well as the resin's flowability during molding.

[0058] Furthermore, in the acrylate-based crosslinked elastomer (A1), to improve the grafting coverage efficiency of the graft polymer layer (A2) described later, the amount of multifunctional monomers can be varied both inside and near the surface of the crosslinked elastomer (A1). Specifically, as disclosed in Patent No. 1460364 and Patent No. 1786959, by increasing the content of multifunctional monomers that function as cross-grafting agents near the surface of the crosslinked elastomer (A1) compared to its interior, the coating of the graft polymer layer on the graft copolymer particles (A) can be improved, the dispersibility in the acrylic resin can be enhanced, or the reduction in crack resistance caused by the peeling of the graft copolymer particles (A) from the acrylic resin interface can be suppressed. Furthermore, sufficient coverage can be achieved using a relatively small amount of graft polymer layer (A2), thus reducing the amount of graft copolymer particles (A) used to introduce a specified amount of crosslinked elastomer (A1) into the acrylic resin composition. Therefore, it is expected to reduce the melt viscosity of the acrylic resin composition, improve the melt processability of the acrylic resin film, enhance the film processing precision, and increase the surface hardness.

[0059] Furthermore, in order to control the molecular weight and crosslinking density of the acrylate-based crosslinked elastomer (A1), and to control thermal stability by reducing the double bond ends of the polymer during uneven stopping of the polymerization reaction, a chain transfer agent may be added to the monomer mixture (a-1). The chain transfer agent can be selected from substances commonly used in free radical polymerization. Examples of chain transfer agents include, for instance, monofunctional or polyfunctional thiols with 2 to 20 carbon atoms such as n-octylthiol, n-dodecylthiol, and tert-dodecylthiol, mercapto acids, thiophenols, carbon tetrachloride, or mixtures thereof. The amount of chain transfer agent added relative to 100 parts by mass of the monomer mixture (a-1) is preferably 0 to 1.0 parts by mass, more preferably 0 to 0.2 parts by mass.

[0060] The particles of the crosslinked elastomer (A1) may be a single layer composed of the above-mentioned acrylate-based crosslinked elastomer (A1), or a multilayer structure composed of two or more layers of the above-mentioned acrylate-based crosslinked elastomer (A1), or at least one layer of acrylate-based crosslinked elastomer (A1) containing multilayer particles of hard or semi-hard crosslinked resin layers.

[0061] Monomers constituting rigid or semi-rigid cross-linked resin layers include methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate, as well as alkyl acrylates such as styrene and α-methylstyrene, vinyl cyanide derivatives such as acrylonitrile, maleic anhydride, maleimide and other maleic acid derivatives, and polyfunctional monomers having two or more non-conjugated double bonds in one molecule.

[0062] Of particular preference are one or more selected from methyl methacrylate, butyl methacrylate, butyl acrylate, ethyl acrylate, styrene, acrylonitrile, etc. Furthermore, as a multifunctional monomer, the same substance used in the polymerization of the acrylate-based crosslinked elastomer (A1) layer can be used. In addition, during the polymerization of rigid or semi-rigid crosslinked resin layers, in addition to these monomers, a chain transfer agent can be used for purposes such as controlling the crosslinking density and controlling thermal stability by reducing the double bond ends of the polymer. The chain transfer agent can be the same chain transfer agent used in the polymerization of the acrylate-based crosslinked elastomer (A1) layer. The amount of chain transfer agent added is 100 parts by weight relative to the total amount of the rigid or semi-rigid crosslinked resin layer, preferably 0 to 2 parts by weight, more preferably 0 to 0.5 parts by weight.

[0063] When the graft copolymer particle (A) is a two-layer structure consisting of a crosslinked elastomer particle (A1) as the core particle and a graft polymer layer (A2), the graft copolymer particle (A) is typically obtained by graft copolymerizing a monomer mixture (a-2) containing 50% to 100% by mass of methacrylate and 0% to 50% by mass of other vinyl monomers that can copolymerize with methacrylate in the presence of the crosslinked elastomer particle (A1) to form the graft polymer layer (A2).

[0064] From the viewpoint of ensuring compatibility with the acrylic resin as the matrix and suppressing the reduction of coating toughness caused by solvent impregnation during coating on the acrylic resin film, as well as whitening and cracking caused by stretching during molding, the amount of methacrylate in the monomer mixture (a-2) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0065] The graft polymer layer (A2) is preferably obtained by graft copolymerization of 10 to 95 parts by mass of a monomer mixture (a-2) comprising 70% to 99% by mass of alkyl methacrylate, 0.5% to 30% by mass of alkyl acrylate with 2 or more carbon atoms in the alkyl group, and 0% to 19% by mass of other vinyl monomers in at least one step, in the presence of 5 to 90 parts by mass of crosslinked elastomer particles (A1). The total amount of crosslinked elastomer particles (A1) and monomer mixture (a-2) is 100 parts by mass.

[0066] In the grafted polymer layer (A2), examples of methyl methacrylates include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, phenyl methacrylate, and benzyl methacrylate, etc. Among these, alkyl methacrylates with 1 to 4 carbon atoms in the alkyl group are preferred.

[0067] In the graft polymer layer (A2), alkyl acrylates with 2 or more carbon atoms in the alkyl group can be used as other vinyl monomers. Preferably, one or more of the following are selected from ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, and stearyl acrylate; more preferably, one or more of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate; and particularly preferably, n-butyl acrylate.

[0068] Other vinyl monomers that can be used in the monomer mixture (a-2) include aromatic vinyl derivatives such as styrene and its nucleated derivatives, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid and its derivatives, acrylic acid and its derivatives, N-substituted maleimides, maleic anhydride, methacrylamide, and acrylamide.

[0069] The monomer mixture (a-2) preferably contains a reactive ultraviolet absorber as another vinyl monomer. In other words, it preferably contains a graft polymer layer (A2) derived from the structural unit of the reactive ultraviolet absorber. When the monomer mixture (a-2) contains a reactive ultraviolet absorber, it is easy to obtain an acrylic resin film with good weather resistance and chemical resistance.

[0070] As a reactive ultraviolet absorber, any known reactive ultraviolet absorber can be used, without particular limitation. Considering the molding processability and weather resistance of acrylic resin films, compounds represented by the following general formula (1) are preferred as reactive ultraviolet absorbers.

[0071]

[0072] (In general formula (1), X is a hydrogen atom or a halogen atom, R1 is a hydrogen atom, a methyl group or a tertiary alkyl group with 4 to 6 carbon atoms, R2 is a straight-chain or branched alkylene group with 2 to 10 carbon atoms, and R3 is a hydrogen atom or a methyl group.)

[0073] As reactive ultraviolet absorbers represented by general formula (1), examples include 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazoles, and more specifically, 2-(2'-hydroxy-5'-acryloyloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl-2H-benzotriazole), 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxypropylphenyl)-2H-benzotriazole, and 2-(2'-hydroxy-5'-methacryloyloxyethyl-3'-t-butylphenyl)-2H-benzotriazole. Considering cost and operability, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole is preferred.

[0074] The content of structural units from the reactive ultraviolet absorber in the grafted polymer layer (A2) is preferably 0.01% to 5% by mass, more preferably 0.1% to 3% by mass.

[0075] In the manufacture of graft copolymer particles (A), particularly during the graft copolymerization of monomer mixtures (a-2) in the presence of cross-linked elastomer particles (A1), such as acrylate-based cross-linked elastomer particles (A1), polymer components (free polymers) that are not graft-bonded to the acrylate-based cross-linked elastomer particles (A1) are sometimes produced. Such free polymers can be used as part or all of the acrylic resin constituting the matrix phase of acrylic resin compositions and acrylic resin films.

[0076] For purposes such as controlling the molecular weight of the polymer, the grafting rate on the crosslinked elastomer (A1), the amount of free polymer not bonded to the crosslinked elastomer (A1), and controlling thermal stability by reducing the double bond ends of the polymer accompanying the uneven stopping reaction during polymerization, a chain transfer agent may be added to the monomer mixture (a-2). Such a chain transfer agent can be the same as that used in the polymerization of the crosslinked elastomer (A1). The amount of chain transfer agent used is 100 parts by mass, 0 to 2 parts by mass, and preferably 0 to 0.5 parts by mass relative to the total amount of the monomer mixture (a-2).

[0077] The grafting rate of the monomer mixture (a-2) of the crosslinked elastomer particles (A1) is preferably 5% to 250%, more preferably 10% to 200%, and even more preferably 20% to 150%. If the grafting rate is less than 5%, the acrylic resin film may experience reduced flexural whitening resistance, reduced transparency, or reduced elongation at tensile fracture, and is prone to cracking during secondary molding. If the grafting rate exceeds 250%, the melt viscosity of the acrylic resin composition tends to increase during film molding, and the moldability of the acrylic resin film tends to decrease.

[0078] The average particle size d (nm) of the crosslinked elastomer particles (A1) in the acrylic resin film and the amount w (mass%) of the multifunctional monomer used in the crosslinked elastomer of the acrylic ester preferably satisfy the following relationship: 0.015d ≤ w ≤ 0.06d, more preferably 0.02d ≤ w ≤ 0.05d. If the amount of multifunctional monomer is within the range of the above relationship, the elongation of the acrylic resin film is not easily reduced during secondary molding, cracks are not easily generated during molding and cutting, transparency is excellent, and stress whitening is not easily generated during bending and tensile deformation at room temperature, high temperature above the softening temperature of the acrylic resin film, or low temperature between room temperature and Tg of the crosslinked elastomer particles (A1).

[0079] As described above, the graft copolymer particles (B) used as needed also possess a crosslinked elastomer (B1) as a rubber component, just like the graft copolymer particles (A). Typically, the graft copolymer particles (B) also possess a graft polymer layer (B2) located on the surface side relative to the crosslinked elastomer (B1), just like the graft copolymer particles (A). In other words, the graft copolymer particles (B) preferably possess both the crosslinked elastomer (B1) and the graft polymer layer (B2).

[0080] The graft copolymer particles (B) are largely the same as those (A) in terms of raw materials and manufacturing method, except that their average particle size is larger. Preferably, the acrylate-based crosslinked elastomer (B1) particles have a concentric spherical multilayer structure with a hard or semi-rigid crosslinked resin layer inside the crosslinked elastomer layer. Examples of such hard or semi-rigid crosslinked resin layers include, for instance, the hard crosslinked methacrylate resin particles disclosed in Japanese Patent Publication No. 55-27576, and the crosslinked particles disclosed in Japanese Patent Application Publication No. 4-270751 and WO2014 / 41803, which have a semi-rigid layer composed of methyl methacrylate-acrylate-styrene copolymer. By introducing such a hard or semi-rigid crosslinked resin layer, the transparency, flexural whitening resistance, and flexural crack resistance of the graft copolymer particles (B), which have a larger particle size than the graft copolymer particles (A), can be improved.

[0081] The average particle size of the graft copolymer particles (B) is preferably 150 nm to 400 nm, more preferably 200 nm to 350 nm.

[0082] The average particle size of the graft copolymer particles (B) is larger than that of the graft copolymer particles (A). The larger average particle size of the graft copolymer particles (B) more effectively induces plastic deformation (cracking) in the acrylic resin phase surrounding the graft copolymer particles relative to the external force applied to the acrylic resin material. Therefore, the graft copolymer particles (B) are highly effective in imparting impact resistance and crack resistance to the acrylic resin material. On the other hand, compared with graft copolymer particles (A), graft copolymer particles (B) have poorer resistance to flexural whitening and solvent whitening. Therefore, for example, by adding a small amount of graft copolymer particles (B) to an acrylic resin composition containing acrylic resin and graft copolymer particles (A), it is expected that the total content of the soft component relative to the acrylic resin film can be reduced without reducing the surface hardness of the acrylic resin film. This also reduces the likelihood of whitening deterioration when external stress is applied to the acrylic resin film, when coating with a coating liquid containing organic solvents, or during molding processing, and effectively improves the crack resistance and re-molding properties of the functional film.

[0083] In one or more embodiments of the present invention, the average particle size of the graft copolymer particles (A) and the graft copolymer particles (B) is measured using a laser diffraction-type particle size distribution measuring device such as the Microtrac particle size distribution measuring device MT3000 manufactured by Nikkiso Co., Ltd., and the measurement is performed using a light scattering method in the latex state.

[0084] The methods for manufacturing graft copolymer particles (A) and graft copolymer particles (B) are not particularly limited, and well-known methods such as emulsion polymerization, microemulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or dispersion polymerization can be used. Considering the wide range of resin structure adjustments, emulsion polymerization is particularly preferred.

[0085] As initiators used in the emulsion polymerization of graft copolymer particles (A) or graft copolymer particles (B), known initiators such as organic peroxides, inorganic peroxides, and azo compounds can be used. Specifically, organic peroxides such as tetramethylbutyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, tert-butyl peroxymaleate, cumene hydroperoxide, benzoyl peroxide, and lauroyl peroxide; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; and azo compounds such as azobisisobutyronitrile (AIBN) can be used. One or more of these initiators can be used individually or in combination.

[0086] These initiators can be used as thermally decomposable free radical polymerization initiators, or as redox polymerization initiator systems in combination with reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxypyruvic acid, and ferrous sulfate. It should be noted that ferrous sulfate can be used in combination with complexes such as sodium ethylenediaminetetraacetate-2-.

[0087] In terms of polymerization stability and particle size control, inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate are used, or more preferably, redox initiators that combine organic peroxides such as tert-butyl hydroperoxide and cumene hydroperoxide with inorganic reducing agents such as divalent iron salts and / or organic reducing agents such as sodium formaldehyde sulfoxylate, reducing sugars, and ascorbic acid are used.

[0088] The aforementioned inorganic or organic peroxides can be added using known methods such as direct addition to the polymer, addition in combination with monomers, or addition by dispersing in an aqueous emulsifier solution. From the viewpoint of the transparency of acrylic resin films, addition in combination with monomers and addition by dispersing in an aqueous emulsifier solution are preferred.

[0089] The surfactant (also called emulsifier) ​​used in the emulsion polymerization of graft copolymer particles (A) or graft copolymer particles (B) is not particularly limited. Well-known surfactants are widely used in emulsion polymerization. Preferred surfactants include, for example, anionic surfactants such as sodium, potassium, and ammonium salts of alkyl sulfonic acids, alkylbenzene sulfonic acids, dioctyl sulfosuccinic acid, alkyl sulfates, sodium fatty acids, polyoxyethylene alkyl ether acetic acid, alkyl phosphates, alkyl ether phosphates, alkyl phenyl ether phosphates, and surfactants such as sodium, potassium, and ammonium salts of surfactants; and nonionic surfactants such as reaction products of alkylphenols, aliphatic alcohols, and propylene oxide and ethylene oxide. For example, polyoxyethylene lauryl ether phosphate and its sodium salt are preferred as alkyl ether phosphates. These surfactants can be used alone or in combination of two or more.

[0090] The latex containing graft copolymer particles (A) or graft copolymer particles (B) obtained from emulsion polymerization can be separated and recovered using known methods. For example, water-soluble electrolytes such as calcium chloride or magnesium sulfate can be added to the latex to cause it to solidify, or it can be solidified by freezing. The graft copolymer particles (A) or graft copolymer particles (B) can then be separated and recovered through filtration, washing, and drying of the solid components. Alternatively, the latex can be treated with spray drying, freeze drying, or other methods to separate and recover the graft copolymer particles (A) or graft copolymer particles (B).

[0091] In order to reduce appearance defects and internal foreign matter in acrylic resin films, the latex of graft copolymer particles (A) or graft copolymer particles (B) is filtered with a filter or screen before separation and recycling to remove environmental foreign matter, polymer scale and other substances that cause defects.

[0092] As a filter or screen, a known filter or screen used for filtering liquid media can be used. The type of filter or screen, the pore size, the filtration accuracy, and the filtration capacity can be appropriately selected according to the application, the type, size, and quantity of foreign matter to be removed. For example, the pore size and filtration accuracy of the filter or screen are preferably more than twice the average particle size of the graft copolymer particles (A) or (B).

[0093] In acrylic resin films, the content of graft copolymer particles (A) is not particularly limited, but is preferably 1% to 70% by mass, more preferably 5% to 65% by mass, and even more preferably 10% to 60% by mass.

[0094] In acrylic resin films, the content of graft copolymer particles (B) is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. The lower limit is not particularly limited, for example, it is 1% by mass or more.

[0095] In acrylic resin films, the total content of crosslinked elastomer (A1) and crosslinked elastomer (B1) is not particularly limited, but is preferably 15% by mass or less, more preferably 13% by mass or less, and most preferably 12% by mass or less.

[0096] <Other Ingredients>

[0097] Acrylic resin films (acrylic resin compositions constituting acrylic resin films) may, as needed, contain thermoplastic resins that are at least partially compatible with acrylic resins, without prejudice to the purpose of this invention. Examples of such thermoplastic resins include, for example, styrene-based resins, polyvinyl chloride resins, polycarbonate resins, amorphous saturated polyester resins, polyamide resins, phenoxy resins, polyarylate resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, cellulose derivatives (cellulose acylates, etc.), vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polylactic acid resins, and PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) resin). Examples of styrene-based resins include, for example, styrene-acrylonitrile resins, benzene... Ethylene-methacrylic acid resin, styrene-acrylic acid resin, styrene-maleic anhydride resin, styrene-N-substituted maleimide resin, styrene-unsubstituted maleimide resin, styrene-acrylonitrile-butadiene resin, and styrene-acrylonitrile-acrylate resin, etc. Among these, considering excellent compatibility with acrylic resins, the ability to improve the flexural crack resistance, solvent resistance, low moisture absorption, and glass shatter resistance of acrylic resin films, one or more thermoplastic resins selected from styrene-based resins, polycarbonate resins, and cellulose acylated resins are preferred.

[0098] Acrylic resin films (acrylic resin compositions constituting acrylic resin films) may also contain, as needed and without prejudice to the purposes of this invention, conventionally known additives used in acrylic resin films. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusing agents, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, anti-blocking agents composed of organic or inorganic particles, infrared reflectors composed of metals or metal oxides, plasticizers, and antistatic agents. Additives are not limited to these. These additives may be used in any amount, depending on the type of additive, without prejudice to the purposes of this invention or to enhance the effects of this invention.

[0099] <Physical Properties>

[0100] The glass transition temperature (Tg) of the acrylic resin film is 140°C or lower, preferably 135°C or lower, and more preferably 130°C or lower. When the glass transition temperature of the acrylic resin film is 140°C or lower, it has the advantage of allowing molding without increasing the molding temperature and suppressing crack formation during molding. Furthermore, the lower limit is not particularly limited, but from the viewpoint of preventing printing misalignment during printing drying and improving reliability, it is preferred, for example, to be 100°C or higher. It should be noted that the glass transition temperature of the acrylic resin film was measured using the method described in the examples.

[0101] The elongation at break at 120°C of the acrylic resin film is 200% or more, preferably 210% or more, and more preferably 220% or more. When the elongation at break at 120°C of the acrylic resin film is 200% or more, it has the advantage of excellent shape conformability during molding. It should be noted that the elongation at break at 120°C of the acrylic resin film was measured using the method described in the examples.

[0102] The elongation at break at 23°C of the acrylic resin film is preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more. When the elongation at break at 23°C of the acrylic resin film is 20% or more, cracking is less likely to occur during handling, cutting, and other operations of the acrylic resin film or the laminate at room temperature, making operation easier. It should be noted that the elongation at break at 23°C of the acrylic resin film can be measured by the method described in the examples.

[0103] The thickness of the acrylic resin membrane is not particularly limited, but is, for example, 75–500 μm, preferably 75–300 μm, and more preferably 100–250 μm. An acrylic resin membrane with a thickness of 75–500 μm has the advantages of being elastic and having excellent operability. It should be noted that the thickness of the acrylic resin membrane can be measured using the method described in the examples.

[0104] From the viewpoint of being less prone to scratches, the pencil hardness of the surface of the acrylic resin film without the hard coating is preferably B or higher, and more preferably HB or higher. It should be noted that the pencil hardness of the surface of the acrylic resin film without the hard coating is measured according to the method described in the examples of JIS K5600-5-4.

[0105] <Method for Manufacturing Acrylic Resin Films>

[0106] Acrylic resin films can be manufactured using known processing methods. Specific examples of known processing methods include melt processing, calendering, pressure molding, and solvent casting. Examples of melt processing include blow molding and T-die extrusion. In solvent casting, after dissolving and dispersing the acrylic resin composition in a solvent, the resulting dispersion (coating) is flowed onto a strip substrate in sheet form. Then, the solvent is evaporated from the flowing sheet-like coating to obtain an acrylic resin film.

[0107] Among these methods, solvent-free melt processing is preferred, and T-die extrusion is particularly preferred. Melt processing offers fewer limitations on the thickness of the manufactured film, enables the production of films with excellent surface properties at high productivity, and reduces the environmental and operational burden of solvents, thereby lowering manufacturing costs.

[0108] When an acrylic resin composition is molded into a film by melt processing or solvent casting, in order to improve the appearance quality of the acrylic resin film, it is preferable to use a filter or screen to remove environmental foreign matter, polymer scale, degraded resin, etc. in the acrylic resin composition that cause appearance defects, internal foreign matter, etc. of the acrylic resin film.

[0109] When manufacturing membranes via melt processing, filtration can be performed at one or more of the following times: during the preparation of the acrylic resin composition by melt mixing, during the granulation of the molten acrylic resin composition, and during the membrane forming process using a T-mold. In the solvent casting method, filtration can be performed after mixing the acrylic resin, graft copolymer particles (A), (B), and other components with the solvent, and before casting the membrane.

[0110] As such a filter or screen, any known filter or screen can be used without particular restrictions, as long as it has heat resistance, weather resistance, and resistance to solvents, coatings, etc., corresponding to the melting processing conditions.

[0111] When manufacturing acrylic resin membranes through melt processing, especially to obtain high-quality acrylic resin membranes, filters with large filtration capacity and low retention of molten resin from resin deteriorators and crosslinking products that could damage membrane quality are preferred. For example, considering filtration efficiency and productivity, disc filters and pleated filters are preferred.

[0112] When manufacturing acrylic resin films using T-die extrusion, to improve film thickness accuracy, an automatic die head device can be used, for example, to online measure the film thickness distribution along the TD direction (perpendicular to the extrusion direction) of the extruded film and automatically adjust the die lip gap of the T-die during film extrusion. By using an automatic die with appropriate control methods, the thickness accuracy of acrylic resin films can be improved.

[0113] In the manufacture of acrylic resin films, depending on the requirements, during the film forming process, the molten film is simultaneously brought into contact (clamped) with both sides of a cooling roller or cooling belt to obtain a film with superior surface properties. In this case, it is preferable to simultaneously bring the molten film into contact with a roller or cooling belt maintained at a temperature of at least -80°C, preferably at least -70°C, the glass transition temperature of the acrylic resin composition.

[0114] More preferably, as at least one of the rollers used for such clamping, such as the roller with an elastic metal sleeve disclosed in Japanese Patent Application Publication No. 2000-153547 and Japanese Patent Application Publication No. 11-235747, a roller with an elastic metal sleeve can be used to transfer the roller mirror surface or a specific surface shape using low clamping pressure, thereby obtaining a film with excellent smoothness or moderate surface roughness, excellent film surface lubricity, suppression of film adhesion, and less internal strain.

[0115] Alternatively, depending on the purpose, uniaxial or biaxial stretching can be performed after the membrane is formed. Uniaxial or biaxial stretching can be carried out using known stretching apparatus. Biaxial stretching can be performed using known methods such as sequential biaxial stretching, simultaneous biaxial stretching, or longitudinal stretching followed by transverse stretching to reduce membrane curvature.

[0116] Furthermore, depending on the application, any surface shape can be applied to one or both sides of the acrylic resin film, such as hairline, prism, embossed shapes, three-dimensional decoration, matte surface, rough surface with a certain surface roughness, or knurling at the film ends. Such surface shapes can be applied using known methods. For example, one method involves clamping both sides of the molten film after extrusion or the formed film fed from a feeding device with at least two rollers or belts whose surfaces have surface shapes, thereby transferring the surface shape of the transfer rollers.

[0117] (Hard coating)

[0118] The hard coating layer of this laminate is a functional layer laminated on at least one side of the acrylic resin film. The hard coating layer may be laminated on one side or both sides of the acrylic resin film.

[0119] The hard coating of this laminate is preferably a cured product of a resin composition comprising a polyfunctional (meth)acrylate and a photopolymerization initiator. The hard coating is preferably obtained by curing using known curing methods such as thermosetting or active energy radiation curing. More preferably, it is obtained by curing using active energy radiation such as ultraviolet light.

[0120] As a hard coating, various UV-curable hard coatings conventionally used in functional films, resin molded products, etc., can be used without particular limitation. For example, the hard coating can be formed by curing monomers, oligomers, resins, or compositions containing mixtures thereof that have free radical reactive functional groups, such as polyfunctional (meth)acrylates, epoxy acrylates, polyurethane acrylates, polyester acrylates, silicone acrylates, polycarbonate acrylates, and polyacrylates. Alternatively, a hard coating can be formed, for example, by curing monomers, oligomers, resins, or compositions containing mixtures thereof that have cationic or anionic curable functional groups such as epoxy groups and oxetyl groups. Furthermore, a hard coating can be formed by thermally curing a polysiloxane-based resin obtained by hydrolyzing and partially condensing an alkoxy-substituted silyl compound. Alternatively, a hard coating can be formed by introducing reactive functional groups into a silyl compound and reacting it to cure it. The above-mentioned components used in forming the hard coating can be used alone or in combination, depending on the circumstances.

[0121] It should be noted that, for ease of explanation, the examples of hard coatings described above are categorized as "polyfunctional (meth)acrylates," "epoxy acrylates," and "polyurethane acrylates," etc. However, "polyfunctional (meth)acrylates" is a general term for compounds such as monomers, oligomers, and polymers that contain two or more (meth)acryloyl functional groups. It encompasses epoxy acrylates, polyurethane acrylates, and compounds containing any main chain or skeleton structure such as alkyl, alkenyl, aryl, ester, amide, ether, fluoroalkyl, or siloxy groups, and two or more (meth)acryloyl functional groups. That is, when described as "polyfunctional (meth)acrylates," as commonly understood by those skilled in the art, it is intended to include epoxy acrylates, polyurethane acrylates, and poly(meth)acrylate compounds having any of the aforementioned structures.

[0122] There are no particular limitations on polyfunctional (meth)acrylates as long as they have at least two (meth)acryloyl groups. Specifically, examples include dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, hexanediol di(meth)acrylate, and diethylene glycol di(meth)acrylate. They can be used alone or in combination of two or more. Furthermore, commercially available substances as UV-curable hard coatings are also examples. In this specification, (meth)acrylate means including both methacrylate and acrylate. In this specification, (meth)acryloyl group means including both methacryloyl and acryloyl groups.

[0123] There are no particular limitations on the monomers used in epoxy acrylate systems. Specifically, examples include glycidyl methacrylate, β-methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, and vinyl cyclohexene oxide (i.e., 1,2-epoxy-4-vinylcyclohexane).

[0124] Polyurethane acrylate resins can be obtained, for example, by mixing polyols, polyisocyanates and hydroxyl-containing (meth)acrylates, and generating polyurethane bonds through the reaction of isocyanate groups with hydroxyl groups.

[0125] The various properties of polyurethane acrylate resins can be appropriately adjusted by the structure of the polyol, the type of polyisocyanate, and the number of acryloyl groups or methacryloyl groups (CH2=CH-CO- or CH2=C(CH3)-CO-) derived from hydroxyl-containing (meth)acrylates, without particular limitations. Furthermore, examples include commercially available polyurethane acrylate resins as UV-curable hard coatings.

[0126] There are no particular limitations on hydroxyl-containing (meth)acrylates. For example, in addition to 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, compounds with at least one olefinic unsaturated bond having a hydroxyl group may be added as needed, such as 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, trimethylpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, allyl alcohol, ethylene glycol allyl ether, glycerol (mono, die)allyl ether, N-hydroxymethyl(meth)acrylamide, etc., or mixtures thereof.

[0127] There are no particular limitations on what constitutes a polyisocyanate. Examples of polyisocyanate compounds containing two or more isocyanate groups include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, isophenylene diisocyanate, terephthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane triisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenyl diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2- Ethyl isocyanate fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, toluidine diisocyanate, hydrohydrated diphenylmethane diisocyanate, hydroxylenide diisocyanate, tetramethylxylenide diisocyanate, 2,5-bis(methyl isocyanate)-bicyclo[2.2.1]heptane, 2,6-bis(methyl isocyanate)-bicyclo[2.2.1]heptane, trimethylolpropane adduct of triethylene diisocyanate, isocyanurate of triethylene diisocyanate, oligomer of diphenylmethane-4,4'-diisocyanate, biuret of hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, urea diketone of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, etc. In addition, these polyisocyanates can be used alone or in combination of two or more.

[0128] Specific examples of polyols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, neopentanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanediol, and polybutanediol. These polyols can be used individually or in combination of two or more.

[0129] To promote the reaction with the isocyanate group of the isocyanate component, an organotin-based carbamate catalyst is used. As an organotin-based carbamate catalyst, it can be a substance commonly used in carbamate reactions, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkylmalate, tin stearate, tin octoate, etc. There is no particular limitation on the amount of these organotin-based carbamate catalysts used, and they are appropriately used in the range of 0.005% to 3% by mass. If the lower limit is not reached, the carbamate reaction will not proceed sufficiently; if the upper limit is exceeded, the reaction will be difficult to control due to the heat generated during the carbamate reaction.

[0130] The composition for hard coating forming, which is composed of a polysiloxane resin composition, is preferably a curable composition containing a condensate (A) obtained by hydrolyzing and condensing a silane compound (Z) having hydrolyzable silanes represented by the following general formula (2) and a catalyst or curing agent (B) that reacts the reactive substituents.

[0131] R 4 -(SiR 5 a (OR 6 ) 3－a (2)

[0132] (In general formula (2), R) 4 R is a monovalent hydrocarbon group selected from at least a portion of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, whose terminal portion is substituted by a reactive substituent selected from an epoxy group, an oxetyl group, a (meth)acryloyl group, a vinyl group, a hydroxyl group, a carboxyl group, an amino group, or an amino group protected by a functional group. 5 Each is independently a monovalent hydrocarbon group selected from hydrogen, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 25 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms. R 6 Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. (a is an integer from 0 to 2.)

[0133] Preferably, the weight-average molecular weight of the condensate (A) is 30,000 or less. Furthermore, it is preferable that the proportion of the silane compound having reactive substituents used is 10% by mass or more. In this case, the cured product as a hard coating exhibits excellent hardness, chemical resistance, and weather resistance.

[0134] From the perspective of the photocurability of the composition, the catalyst or curing agent (B) is preferably selected from one or more of the following: photoradical generators, photocation generators, and photoanion generators.

[0135] Considering the minimal curing shrinkage during hard coating formation, the ease of obtaining functional films with excellent weather resistance and anti-curling properties, the reactive substituents in general formula (2) are preferably epoxy groups or oxocyclic butyl groups.

[0136] Neutral salt catalysts are preferred as catalysts for the hydrolysis-condensation reaction of silane compounds (Z). This is because when the reactive substituents are epoxy or oxetyl, the decomposition of the reactive substituents during hydrolysis-condensation is easily suppressed.

[0137] More preferably, the ratio Q of the number of OR 6 groups directly bonded to silicon atoms in the condensate (A) to the number of OR 6 groups directly bonded to silicon atoms in the silane compound (Z) that is the raw material for the condensate (A) is 0.2 or less. This is because the cured product exhibits excellent hardness, chemical resistance, and weather resistance.

[0138] Known methods can be used to cure the resin composition when forming a hard coating. As a curing method, irradiation with active energy rays, such as ultraviolet light, is preferred. When curing by irradiation with active energy rays, photopolymerization initiators, photoanionizers, and photocationizers are typically added to the composition used for forming the hard coating.

[0139] Specific examples of photopolymerization initiators include acetophenone, benzophenone, benzoyl methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diarylethane, 1-hydroxy-cyclohexyl-phenyl-one, 2,2-dimethoxy-2-phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one compounds. Among these, 1-hydroxy-cyclohexyl-phenyl-one, which has excellent compatibility with resins, is preferred.

[0140] Specific examples of photocation generators include CPI-100P, CPI-101A, CPI-200K, and CPI-200S manufactured by San-Apro; WPI-124, WPI-113, WPI-116, WPI-169, WPI-170, and WPI-124 manufactured by Hikari Pure Chemical Industries Co., Ltd.; and RHODORSIL 2074 manufactured by Rhodia.

[0141] Specific examples of photoion generators include acetylbenzyl oxime, nifedipine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene salt of 2-(9-oxazanol-2-yl)propionate, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidine of 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidine, and n-butyl triphenylborate.

[0142] When a coating film composed of a curable composition is cured to form a hard coating, various known leveling agents can be incorporated into the curable composition for purposes such as improving the scratch resistance and stain resistance after curing. Fluorine-based leveling agents, acrylic-based leveling agents, silicone-based leveling agents, and their adducts or mixtures can be used as leveling agents. The amount of leveling agent incorporated is not particularly limited, for example, in the range of 0.03 parts by weight to 3.0 parts by weight relative to 100 parts by weight of the curable composition.

[0143] When a hard coating is formed by coating a curable composition, various additives such as UV absorbers, light stabilizers, defoamers, antioxidants, light diffusing agents, matting agents, antifouling agents, lubricants, pigments, dyes, organic particles, inorganic particles, and antistatic agents may be added to the curable composition as needed. Additives are not limited to these.

[0144] To impart suitable coatability to the curable composition, an organic solvent is typically used. As an organic solvent, the desired coatability can be imparted to the curable composition, and there are no particular limitations as long as a hard coating with the desired film thickness and properties can be formed. From the perspective of coatability and the drying properties of the formed coating film, it is preferable that the boiling point of the organic solvent is between 50°C and 150°C.

[0145] Specific examples of organic solvents include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; alcohols such as methanol, ethanol, isopropanol, and butanol; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and tetrahydrofuran, dichloromethane ... Ethers such as alkanes, propylene glycol monoethyl ether, methyl cellosolve, and ethyl cellosolve; amides such as N-methylpyrrolidone and dimethylformamide, etc. Organic solvents can be used alone or in combination of two or more.

[0146] When the curable composition is applied to the main surface of the aforementioned acrylic resin film, which serves as the substrate film, any coating method can be used without particular limitation. Examples of coating methods include reverse coating, gravure coating, bar coating, mold coating, spray coating, kiss coating, wire bar coating, and curtain coating. These coating methods can be implemented individually or in combination.

[0147] After applying the curable composition for forming a hard coating as described above to the surface of the aforementioned acrylic resin film, which serves as a substrate film, the organic solvent is removed from the coated film by drying, and then cured by irradiation with ultraviolet light, thereby forming a hard coating.

[0148] The drying temperature for removing organic solvents from the coated film is preferably 60°C to 120°C, more preferably 70°C to 100°C. If the drying temperature is too low, organic solvents may remain in the coated film. In addition, if the drying temperature is too high, the flatness of the functional film (hard coating) may be damaged due to thermal deformation of the substrate film.

[0149] The wavelength of the ultraviolet light irradiated during the curing of the coating film is preferably in the range of 200 nm to 400 nm. The cumulative amount of ultraviolet (UV) light is preferably achieved using the conditions described later in [4. Method for manufacturing the laminate]. As the irradiation device for UV exposure, for example, an irradiation device equipped with a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, and an excimer lamp, or a pulsed or continuous laser source such as an argon ion laser and a helium-neon laser can be used.

[0150] Because ultraviolet radiation generates heat and causes the temperature to rise, it is preferable to cool the rollers while simultaneously irradiating them with ultraviolet light. The cooling roller temperature at this time is preferably set according to the conditions described later in [4. Manufacturing Method of Laminated Body].

[0151] As a composition for forming a hard coating, commercially available products such as "Z-879" manufactured by Aica Industries, Ltd., "UNIDIC ESS108" manufactured by DIC Corporation, "NSC-7312" manufactured by Daihatsu Seika Industries, Ltd., "Beamset 575" manufactured by Arakawa Chemical Industries, Ltd., "UV-1700B" manufactured by Nippon Synthetic Chemical Industries, Ltd., "8BR-600" manufactured by Taisei Precision Chemicals, Ltd., and "FA-3280H" manufactured by Nippon Haku Coatings, Ltd. can be used. After curing, it also exhibits elongation, thus further improving the 120°C crack elongation of this laminate.

[0152] The thickness of the hard coating is not particularly limited, but is, for example, 0.6 to 10.0 μm, preferably 0.7 to 7.0 μm, and more preferably 0.8 to 5.0 μm. If the hard coating thickness is 0.6 to 10.0 μm, it offers the advantage of combining wear resistance and formability. It should be noted that the hard coating thickness was determined using the method described in the examples.

[0153] In another embodiment of the present invention, inorganic particles or metal particles may be added to improve the wear resistance of the hard coating. The inorganic or metal particles are not particularly limited; examples include silicon dioxide, aluminum oxide, titanium dioxide, zinc oxide, zirconium oxide, graphene, nano-carbon, carbon black, nano-diamond, mica, barium titanate, boron nitride, metallic silver, and metallic copper. These particles can be used directly without surface treatment. Alternatively, to control the dispersion state, surface treatment can be performed beforehand using known methods to appropriately control their affinity with the hard coating.

[0154] <Other Functional Layers>

[0155] In addition to the hard coating layer, this laminate may also have other functional layers. There are no particular limitations on these other functional layers; for example, various conventionally known functional layers can be used. Specific examples of functional layers include anti-reflective layers, anti-glare layers, anti-fouling layers, anti-fingerprint layers, anti-scratch layers, antistatic layers, ultraviolet shielding layers, infrared shielding layers, textured layers, light diffusion layers, matte layers, polarizing layers, coloring layers, design layers, embossed layers, conductive layers, gas barrier layers, and gas absorption layers. Two or more of these functional layers can be combined. Furthermore, a single functional layer can possess two or more functions. The anti-reflective layer can be composed of a low-refractive-index layer, or both a high-refractive-index layer and a low-refractive-index layer. Additionally, it can be constructed by forming surface irregularities smaller than the wavelength of visible light on the surface of the functional layer.

[0156] (Layered structure)

[0157] As described above, this laminate is composed of a specific acrylic resin film and a hard coating, exhibiting excellent formability and wear resistance.

[0158] The crack elongation at 120°C of this laminate is 50% or more, preferably 52% or more, and more preferably 54% or more. If the crack elongation at 120°C of this laminate is 50% or more, it has the advantage of preventing crack formation during molding. It should be noted that the crack elongation at 120°C of this laminate was measured using the method described in the examples.

[0159] 50g / cm of this laminate 2 The Δhaze of the steel wool abrasion test after 5 rounds is 1.0% or less, preferably 0.8% or less, and more preferably 0.6% or less. If 50 g / cm 2 If the Δhaze of the steel wool abrasion test after 5 rounds is below 1.0%, it has the advantage of not being scratched even when wiped. It should be noted that 50g / cm 2 The Δhaze of the steel wool abrasion test after 5 round trips was determined by the method described in the examples.

[0160] 50g / cm of this laminate 2 The Δhaze of a steel wool abrasion test after 10 rounds is, for example, 1.0% or less, preferably 0.9% or less, and more preferably 0.8% or less. If 50 g / cm³ 2 If the Δhaze of a steel wool abrasion test conducted after 10 rounds is below 1.0%, it has the advantage of not being scratched even when wiped. It should be noted that 50g / cm 2 The Δhaze of the steel wool abrasion test after 10 round trips was determined by the method described in the examples.

[0161] From the viewpoint of scratch resistance, the pencil hardness of this laminate is preferably H or higher, more preferably 2H or higher. It should be noted that the pencil hardness of this laminate was determined by the method described in the examples.

[0162] The aforementioned "steel wool abrasion test" and "pencil hardness" are both indicators of abrasion resistance. The "steel wool abrasion test" evaluates abrasion resistance by the scratches caused during wiping, while the "pencil hardness" evaluates abrasion resistance by the scratches caused during scraping. This laminate is preferred as it performs well in both indicators.

[0163] The phase difference (Re) of this laminate is, for example, 38 nm or less, preferably 30 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 8 nm or less. If the phase difference (Re) is 38 nm or less, the reduction in contrast can be suppressed in the liquid crystal display device. It should be noted that the phase difference (Re) is measured by the method described in the examples.

[0164] The phase difference (Rth) of this laminate is, for example, |30| nm or less, preferably |20| nm or less, and more preferably |10| nm or less. If the phase difference (Rth) is |30| nm or less, the reduction in contrast can be suppressed in the liquid crystal display device. It should be noted that the phase difference (Rth) is measured by the method described in the embodiments.

[0165] The ΔE (color difference) of this laminate after weathering resistance testing is preferably 5.2% or less, more preferably 4.0% or less, and even more preferably 3.0% or less. If the ΔE after weathering resistance testing is 5.2% or less, it has the advantage of excellent long-term weather resistance. It should be noted that the ΔE after weathering resistance testing was measured using the method described in the examples.

[0166] The formable radius of curvature of this laminate is, for example, 1 mm or less, preferably 0.8 mm or less, and more preferably 0.6 mm or less. If the formable radius of curvature is 1 mm or less, it has the advantage that even complex shapes can be formed. Furthermore, it should be noted that the formable radius of curvature is determined by the method described in the examples.

[0167] This laminate may have a primer layer on the back side relative to the side with the hard coating. The primer layer may consist of inks used in post-processing printing, metal vapor deposition, or resins with good adhesion. Examples include polyurethane resins, acrylic resins, polyester resins, polycarbonate resins, epoxy resins, melamine resins, and copolymers of vinyl acetate and vinyl chloride. By providing a primer layer, adhesion to injection-molded resins, inks, etc., can be enhanced.

[0168] The thickness of the primer layer is preferably 0.5–10 μm, more preferably 0.5–5 μm, and most preferably 0.5–3 μm. If it is 0.5 μm or more, adhesion can be guaranteed, and if it is less than 10 μm, productivity is better.

[0169] [3. Molded body]

[0170] In one embodiment of the present invention, a molded body having the present laminate (hereinafter referred to as "the molded body") is provided.

[0171] Specific examples of applications for this molded body include: interior applications such as dashboards, front panels of in-vehicle displays, consoles, instrument covers, door lock pedals, steering wheels, power window switch bases, center consoles, and instrument panels; exterior applications such as weatherstripping, bumpers, bumper guards, side mudguards, body panels, spoilers, front longitudinal beams, pillar supports, wheel covers, center pillars, door mirrors, center trim pieces, side trim strips, door trim strips, windshield trim strips, windows, headlight covers, taillight covers, and windshield components; and applications for portable electronic devices such as smartphones, mobile phones, or tablets, including mobile phone housings, display windows, buttons, televisions, DVD players, and audio systems. Applications include: equipment, rice cookers, washing machines, refrigerators, air conditioners, humidifiers, dehumidifiers, electric fans, and other household electronic and electrical appliances; housings, front panels, buttons, badges, surface decoration materials, and furniture exterior materials; interior building materials such as walls, ceilings, floors, bathtubs, and toilet seats; exterior building materials such as wall panels, fences, roofs, doors, and gable panels; surface decoration materials for furniture such as window frames, doors, handrails, thresholds, and lintels; optical components such as various displays, lenses, mirrors, goggles, and window glass; and interior and exterior applications for various vehicles other than automobiles, including trains, airplanes, and ships.

[0172] When this laminated body is used, it can easily produce a molded body with excellent appearance, where the surface hardness, scratch resistance, chemical resistance, stain resistance, reflective properties, and anti-glare properties are well controlled, even with complex three-dimensional shapes. Therefore, this molded body is preferably used, for example, for applications such as automotive display front panels having planar, curved, or three-dimensional shapes. Therefore, in one embodiment of the present invention, an automotive display front panel equipped with this molded body is provided.

[0173] [4. Manufacturing method of laminated body]

[0174] In one embodiment of the present invention, a method for manufacturing a laminate comprising an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film is provided. The method for manufacturing this laminate includes a step of curing the hard coating layer coated on at least one side of the acrylic resin film by UV irradiation on a cooling roller, wherein the cumulative UV intensity of the UV irradiation is 150–500 mJ / cm². 2 The cooling roller temperature is 25–70°C, the glass transition temperature of the acrylic resin film is below 140°C, and the elongation at break at 120°C is 200% or more; the crack elongation at 120°C of the laminate is 50% or more, and 50 g / cm³ 2 The Δ haze of the steel wool abrasion test after 5 rounds was below 1.0%.

[0175] In the manufacturing method of this laminate, the cumulative ultraviolet (UV) light intensity is, for example, 150–500 mJ / cm. 2 The preferred value is 160–480 mJ / cm³. 2 More preferably, it is 170–460 mJ / cm². 2 The cumulative UV light intensity is 150–500 mJ / cm². 2 This ensures formability and achieves a suitable hardness for the hard coating.

[0176] In the manufacturing method of this laminate, the temperature of the cooling roller is, for example, 25–70°C, preferably 30–70°C, more preferably 35–70°C, even more preferably 40–70°C, particularly preferably 42–68°C, and especially preferably 45–65°C. If the cooling roller temperature is 25–70°C, the temperature rise during ultraviolet irradiation can be suppressed, and the hard coating can be cured, enabling the manufacture of a laminate with the desired physical properties.

[0177] The manufacturing method of this laminate may include the following steps: before the step of curing the above-mentioned hard coating, a step of applying a curable composition for forming a hard coating to the surface of an acrylic resin film as a substrate film; and a step of removing organic solvents from the above-formed coating film by drying, etc.

[0178] It should be noted that matters other than the above-mentioned conditions in the manufacturing method of this laminate are referred to in [2. Laminated Body].

[0179] [5. Manufacturing method of molded body]

[0180] One embodiment of the present invention provides a method for manufacturing a molded article, comprising a step of shaping a laminated article as shown below at a molding temperature of 140°C or below during pre-forming:

[0181] The aforementioned laminate is a laminate comprising an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film.

[0182] The glass transition temperature of the aforementioned acrylic resin film is below 140°C, and the elongation at break at 120°C is above 200%.

[0183] The crack elongation at 120°C of the above-mentioned laminate is more than 50%, and 50 g / cm³. 2 The Δ haze of the steel wool abrasion test after 5 rounds was below 1.0%.

[0184] In the manufacturing method of this molded body, the film is shaped by pre-forming at a temperature below 140°C. This laminate contains the aforementioned specific acrylic resin film, therefore, low-temperature molding can be performed when the resin is laminated onto this laminate.

[0185] In the manufacturing method of this molded article, the pre-forming temperature is, for example, 140°C or below, preferably 130°C or below, and more preferably 120°C or below. If the pre-forming temperature is 140°C or below, it has the advantage that the hard coating is less prone to cracking. In addition, there is no particular limitation on the lower limit, but from the viewpoint of shape imparting, it is, for example, 100°C or above, preferably 105°C or above.

[0186] There are no particular limitations on the resins used in injection molding; for example, thermoplastic resins and curable resins can be cited. Examples of thermoplastic resins include polycarbonate resins, acrylic resins, styrene resins (AS resin, ABS resin, MAS resin, styrene-maleimide resin, styrene-maleic anhydride resin, etc.) having a bisphenol-based, fluorene-based, or isosorbide-based backbone, saturated polyester resins, polyvinyl chloride resins, polyarylate resins, PPS-based resins, POM-based resins, polyamide resins, polylactic acid resins, cellulose acylate-based resins, and polyolefin-based resins. Examples of curable resins include epoxy resins, vinyl ester resins, unsaturated polyester resins, phenolic resins, melamine resins, and benzo[a]benzene resins. Resins such as aziridine resins. Among them, transparent resins such as polycarbonate resins, acrylic resins, styrene resins, polyarylate resins, and polyolefin resins are preferred.

[0187] In one embodiment of the present invention, the molded body can be manufactured by pre-forming (curved surface forming) the printed laminate at a temperature below 140°C, trimming it, placing it in a metal mold, and then integrating it with resin injection molding.

[0188] It should be noted that matters other than the above-mentioned conditions in the manufacturing method of this molded body refer to the matters described in [2. Laminated Body] above.

[0189] This invention is not limited to the embodiments described above, and various modifications can be made within the scope of the claims. Embodiments obtained by appropriately combining the means of the techniques disclosed in different embodiments are also included within the scope of the technology of this invention.

[0190] That is, one embodiment of the present invention is as follows.

[0191] <1> A laminate comprising an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film,

[0192] The glass transition temperature of the aforementioned acrylic resin film is below 140°C, and the elongation at break at 120°C is above 200%.

[0193] The crack elongation at 120°C of the above-mentioned laminate is more than 50%, and 50 g / cm³. 2 The Δ haze of the steel wool abrasion test after 5 round trips was below 1.0%.

[0194] <2> The laminated body according to <1>, wherein it has at least one of the following physical properties:

[0195] The phase difference (Re) is below 38 nm.

[0196] The ΔE after the weathering test is less than 5.2%.

[0197] <3> The laminate according to <1> or <2>, wherein the hard coating is a cured product of a resin composition comprising a polyfunctional (meth)acrylate and a photopolymerization initiator.

[0198] <4> The laminate according to any one of <1> to <3>, wherein the acrylic resin film comprises 1 to 70% by mass of graft copolymer particles (A) with an average particle size of 20 nm to 200 nm and less than 20% by mass of graft copolymer particles (B) with an average particle size larger than the graft copolymer particles (A), and the total content of crosslinked elastomer (A1) and crosslinked elastomer (B1) in the acrylic resin film is less than 15% by mass.

[0199] <5> The laminate according to <4>, wherein the average particle size of the above-mentioned graft copolymer particles (B) is 150 nm or more, and the laminate contains 1 to 10% by mass of the graft copolymer particles (B).

[0200] <6> The laminate according to any one of <1> to <5>, wherein the surface of the acrylic resin film without the hard coating layer has a pencil hardness of B or higher, and the elongation at break at 23°C is 20% or higher.

[0201] <7> The laminate according to any one of <4> to <6>, wherein the above-mentioned graft copolymer particles (A) contain 0.01 to 5% by mass of a reactive ultraviolet absorber.

[0202] <8> A molded body comprising any one of <1> to <7> of the laminated body.

[0203] <9> A vehicle display front panel comprising the molded body described in <8>.

[0204] <10> A method for manufacturing a laminate comprising an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film.

[0205] The process includes curing the hard coating layer, which is applied to at least one side of the acrylic resin film, by UV irradiation on a cooling roller.

[0206] The cumulative UV light intensity of the above-mentioned UV irradiation is 150–500 mJ / cm. 2 ,

[0207] The temperature of the aforementioned cooling rollers is 25–70°C.

[0208] The glass transition temperature of the aforementioned acrylic resin film is below 140°C, and the elongation at break at 120°C is above 200%.

[0209] The crack elongation at 120°C of the above-mentioned laminate is more than 50%, and 50 g / cm³. 2 The Δ haze of the steel wool abrasion test after 5 rounds was below 1.0%.

[0210] <11> A method for manufacturing a molded article, comprising a step of shaping the laminate shown below at a molding temperature of 140°C or below during preforming:

[0211] The laminate is a laminate comprising an acrylic resin film and a hard coating layer on at least one side of the acrylic resin film.

[0212] The glass transition temperature of the aforementioned acrylic resin film is below 140°C, and the elongation at break at 120°C is above 200%.

[0213] The crack elongation at 120°C of the above-mentioned laminate is more than 50%, and 50 g / cm³. 2 The Δ haze of the steel wool abrasion test after 5 round trips was below 1.0%.

[0214] Example

[0215] The present invention will now be described in detail based on embodiments, but the present invention is not limited to these embodiments.

[0216] [Measurement and Evaluation Methods]

[0217] The examples and comparative examples were measured and evaluated according to the following methods.

[0218] (glass transition temperature (Tg))

[0219] A Seiko Instruments SSC-5200 differential scanning calorimeter (DSC) was used. After a preliminary adjustment, the sample was temporarily heated to 200°C at a rate of 25°C / min, held for 10 minutes, and then cooled to 50°C at a rate of 25°C / min. Measurements were then taken during the period of heating to 200°C at a rate of 10°C / min. The differential value (SSDC) was obtained from the resulting DSC curve, and the glass transition temperature was determined from its maximum point.

[0220] (Elongation at break)

[0221] The laminated film was cut into 10mm (width) × 100mm (length) pieces and tested using a Tensilon tensile testing machine (Shimadzu Corporation, AG-2000D) equipped with a high-temperature bath set to 120°C, under the conditions of a preheating time of 2 minutes, a clamp spacing of 50mm, and a tensile speed of 200mm / min. The elongation at the point of fracture of the laminated film was taken as the elongation at the point of tensile fracture.

[0222] The elongation at tensile fracture point is the average of the results obtained from 5 specimens after removing the highest and lowest values.

[0223] (Crack elongation)

[0224] Crack elongation was measured on laminated films (HC layer formation) with a hard coating on one side. Specifically, a 10 mm (width) × 100 mm (length) section of the laminated film was cut and measured using a Tensilon tensile testing machine (Shimadzu Corporation, AG-2000D) equipped with a high-temperature bath set to 120°C, under the conditions of a preheating time of 2 minutes, a clamping distance of 50 mm, and a tensile speed of 200 mm / min. The elongation at which cracks formed in the hard coating was measured was taken as the crack elongation at 120°C. The average values ​​of the test results obtained from the measurements of the three samples are recorded in Tables 5 and 6.

[0225] (Formable radius of curvature)

[0226] A vacuum air-pressurized molding machine (manufactured by Fuse Vacuum Co., Ltd., NGF-0406-S) was used. The molding machine consists of an upper and a lower part. The lower part is equipped with multiple raised metal molds with radius of curvature R: 0.3, 0.5, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0 and a height of 3 mm. The upper part is equipped with a laminated film. Subsequently, the pressure in both the upper and lower parts is reduced to -100 kPa, and an infrared heater located in the upper part heats the laminated film. In Examples 1-12, Comparative Examples 1-4, and Comparative Examples 8-12, the temperature is heated to 120°C, and in Comparative Examples 5-7, the temperature is heated to 160°C. The laminated film is pressed onto the metal mold, and then pressurized air is introduced into the upper part at 300 kPa for molding. 〇: No cracks in the raised portion; △: Cracks are present in a portion of the circumference of the raised portion; ×: Cracks are present on the entire circumference of the raised portion.

[0227] (Friction test)

[0228] A HEIDON Type 14DR surface properties tester (manufactured by Shin-Tō Science Co., Ltd.) was used. Steel wool #0000 was mounted on a 1mm diameter probe, and a 50g weight was placed on it. The steel wool was placed on the hard-coated surface of the laminated film, and 5 and 10 round trip tests were performed at a stroke of 50mm and a speed of 6000mm / min. The haze was measured before and after the test. The haze was measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) according to ISO 14782.

[0229] (Phase difference)

[0230] A 40mm × 40mm specimen was cut from the membrane. The in-plane phase difference Re and the thickness direction phase difference Rth were measured on the specimen using an automatic birefringence meter (KOBRA-WR manufactured by Oji Keise Co., Ltd.) at a temperature of 23±2℃ and a humidity of 50±5% at a wavelength of 590nm and an incident angle of 0°.

[0231] (Weather resistance test)

[0232] A Suga SX2D-75 spectrophotometer (manufactured by Suga Testing Equipment Co., Ltd.) was used. Irradiance was 180 (W / m², 300–400 nm), black panel temperature was 83±3℃, and relative humidity was 50±5%. The glass filter was constructed with quartz on the inner side and polysilicate #275 on the outer side. A 500-hour test was conducted. Color difference (ΔE) was measured before and after the test. ΔE was measured using a spectrophotometer SE7700 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).

[0233] Mode: Transmission, Light source: D65, Field of view: 2°, Measurement diameter: 28mm.

[0234] (film thickness)

[0235] The film thickness of the acrylic resin film was measured using a PEACOCK micrometer No25 (manufactured by Ozaki Seisakusho Co., Ltd.).

[0236] The film thickness of the hard coat was measured using an F20 film thickness measurement system (manufactured by Filmetrics, Inc.). The back side of the hard coat was painted black with a felt tip pen, and the refractive index of the acrylic resin film was measured to be 1.49 and that of the hard coat was 1.50.

[0237] (Pencil hardness)

[0238] The pencil hardness was measured in accordance with JIS K5600-5-4. Using an electric pencil hardness testing machine (manufactured by Beige Testing Machine Co., Ltd.), five tests were carried out at a load of 750 g and a speed of 60 mm / min. If the number of scratches was 1 or less, it was judged as qualified.

[0239] The pencil hardness was measured for the hard coat of the functional film.

[0240] [Production Example 1: Graft copolymer particles (A)]

[0241] The following substances were charged into an 8 L polymerization apparatus equipped with a stirrer.

[0242] · Deionized water: 200 parts

[0243] · Sodium dioctyl sulfosuccinate: 0.24 parts

[0244] · Sodium formaldehyde sulfoxylate: 0.15 parts

[0245] · Ethylenediaminetetraacetic acid disodium salt: 0.001 part

[0246] · Ferrous sulfate: 0.00025 part

[0247] The inside of the polymerization apparatus was thoroughly purged with nitrogen to make it substantially oxygen-free. Thereafter, the internal temperature of the polymerization apparatus was set to 60°C. Next, 30 parts of the following monomer mixture was continuously added to the polymerization apparatus at a rate of 10 mass parts / hour. After the addition was completed, polymerization was continued for an additional 0.5 hour to obtain particles of a crosslinked elastomer (A1) (average particle diameter 90 nm). The polymerization conversion rate was 99.5%.

[0248] Monomer mixture:

[0249] · Vinyl monomer mixture (90% n-butyl acrylate (BA) and 10% methyl methacrylate (MMA)): 30 parts

[0250] · Allyl methacrylate (AlMA): 1 part

[0251] · Cumene hydroperoxide (CHP): 0.2 part

[0252] Subsequently, 0.05 parts by weight of sodium dioctyl sulfosuccinate were added to the polymerization apparatus. Next, the internal temperature of the polymerization apparatus was set to 60°C, and 70 parts of a monomer mixture consisting of 98% MMA, 1% BA, and 1% RUVA for forming the graft polymer layer (A2), and 0.5 parts of a monomer mixture consisting of 0.5 parts tert-dodecyl mercaptan (t-DM) and 0.5 parts CHP were continuously added to the polymerization apparatus at a ratio of 10 parts / hour. Polymerization was continued for another hour to obtain graft copolymer particles (average particle size 90 nm). The polymerization conversion rate was 98.2%. The obtained latex was salted out with calcium chloride and solidified. The solidified solid components were washed with water and dried to obtain graft copolymer particle (A) powder. It should be noted that the proportions of each component are shown in Table 1.

[0253] In addition, RUVA is a reactive ultraviolet absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2-H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., RUVA-93)).

[0254] [Manufacturing Example 2: Graft copolymer particles (A)]

[0255] The following substances were loaded into an 8L polymerization apparatus equipped with a mixer.

[0256]

[0257] After completely purging the polymer with nitrogen to create a virtually oxygen-free environment, and setting the internal temperature to 60°C, a mixture of monomers consisting of 27 parts n-butyl acrylate, 3 parts methyl methacrylate, and 0.9 parts allyl methacrylate, along with 0.2 parts cumene hydroperoxide, was continuously added over 3 hours. After the addition was complete, polymerization continued for another 0.5 hours to obtain rubber particles. The polymerization conversion rate was 99.5%.

[0258] Subsequently, 0.05 parts of sodium dioctyl sulfosuccinate were added, and the internal temperature was set to 60°C. After 5 hours, a mixture of monomers consisting of 7 parts of n-butyl acrylate, 63 parts of methyl methacrylate, and 0.2 parts of cumene hydroperoxide was continuously added, and polymerization continued for another hour to obtain graft copolymer particle latex. The polymerization conversion rate was 98.5%. The obtained latex was precipitated with calcium chloride, coagulated, washed with water, and dried to obtain white powdery graft copolymer particles (A). It should be noted that the proportions of each component are shown in Table 1.

[0259] The average particle size of the rubber particles in the graft copolymer particles (A) is 80 nm.

[0260] (Table 1)

[0261]

[0262] [Manufacturing Example 3: Grafted Copolymer Particles (B)]

[0263] The following substances were loaded into an 8L polymerization apparatus equipped with a mixer.

[0264] 180 portions of deionized water

[0265] · 0.002 parts of polyoxyethylene lauryl ether phosphate

[0266] 0.4725 parts of boric acid

[0267] Sodium carbonate 0.04725 parts

[0268] 0.0098 parts of sodium hydroxide

[0269] After completely purging the polymer with nitrogen to create a substantially oxygen-free environment, the internal temperature of the polymerization apparatus was then set to 80°C. 0.027 parts of potassium persulfate were added to the polymerization apparatus as a 2% aqueous solution, followed by the continuous addition of a mixture consisting of 27 parts of a vinyl monomer mixture (MMA 97% and BA 3%) and 0.036 parts of allyl methacrylate over 81 minutes.

[0270] Polymerization continued for another 60 minutes to obtain polymer particles that form the first layer of the core (crosslinked elastomer (B1)). The polymerization conversion rate was 99.0%.

[0271] Subsequently, 0.0267 parts of sodium hydroxide were added to the polymerization apparatus in the form of a 2% aqueous solution. Next, 0.08 parts of potassium persulfate were added to the polymerization apparatus in the form of a 2% aqueous solution. Then, a mixture consisting of 50 parts of a vinyl monomer mixture (BA 83% and styrene (St) 17%) and 0.375 parts of allyl methacrylate was continuously added to the polymerization apparatus over 150 minutes. After the addition was complete, 0.015 parts of potassium persulfate were added to the polymerization apparatus in the form of a 2% aqueous solution. Polymerization was then continued for 120 minutes to obtain a core (crosslinked elastomer (B1)) consisting of a first and second layer. The polymerization conversion rate was 99.0%, and the average particle size was 230 nm.

[0272] Subsequently, 0.023 parts of potassium persulfate were added to the polymerization apparatus in the form of a 2% aqueous solution. Next, 23 parts of a vinyl monomer mixture (80% MMA and 20% BA) were continuously added to the polymerization apparatus over 45 minutes. Polymerization continued for another 30 minutes to obtain a latex of graft copolymer particles (B1) consisting of a two-layer structure: a core (crosslinked elastomer (B1)) and a shell (graft polymer layer (B2)). The polymerization conversion rate was 100.0%. The obtained latex was salted out with magnesium sulfate, coagulated, and the coagulated solid was washed with water and dried to obtain white powdery graft copolymer particles (B). The average particle size of the graft copolymer particles was 250 nm. It should be noted that the proportions of each component are shown in Table 2.

[0273] [Manufacturing Example 4: Grafted Copolymer Particles (B)]

[0274] Fabrication of the innermost polymer layer:

[0275] The following mixture was loaded into a glass reactor and heated to 80°C under a nitrogen gas flow while being stirred. Then, 25% of a mixture consisting of 25 parts methyl methacrylate, 1 part allyl methacrylate, and 0.1 parts tert-butyl hydroperoxide was added at once, and polymerization was carried out for 45 minutes.

[0276]

[0277]

[0278] Next, the remaining 75% of the mixture was added continuously over 1 hour. After the addition was complete, the polymerization was maintained at this temperature for 2 hours to complete. Additionally, 0.2 parts of N-lauroyl sarcosinate sodium were added during this period. The resulting innermost crosslinked methacrylate polymer latex had a polymerization conversion rate (polymer yield / monomer addition) of 98%.

[0279] Production of rubber particles:

[0280] The innermost polymer latex was maintained at 80°C under a nitrogen atmosphere. After adding 0.1 parts of potassium persulfate, a monomer mixture consisting of 41 parts of n-butyl acrylate, 9 parts of styrene, and 1 part of allyl methacrylate was continuously added over 5 hours. During this period, 0.1 parts of potassium oleate were added in three separate additions. After the monomer mixture was fully added, polymerization was completed, and then 0.05 parts of potassium persulfate were added, maintaining the polymerization for another 2 hours. The resulting rubber particles exhibited a polymerization conversion rate of 99%.

[0281] Preparation of graft copolymers:

[0282] The obtained rubber particle latex was maintained at 80°C, and 0.02 parts of potassium persulfate were added. Then, a monomer mixture of 14 parts methyl methacrylate and 1 part n-butyl acrylate was continuously added over 1 hour. After the monomer mixture was added, the mixture was maintained for 1 hour to obtain the graft copolymer latex. The polymerization conversion rate was 99%.

[0283] Preparation of graft copolymer particles:

[0284] The obtained rubber particle latex was maintained at 80°C, and a monomer mixture of 5 parts methyl methacrylate and 5 parts n-butyl acrylate was continuously added over 0.5 hours. After the monomer mixture was added, the mixture was maintained for 1 hour to obtain graft copolymer particle latex. The polymerization conversion rate was 99%.

[0285] The obtained graft copolymer particle latex was salted out and solidified with calcium chloride without heat treatment or drying, resulting in white powdery graft copolymer particles (B). It should be noted that the proportions of each component are shown in Table 2.

[0286] (Table 2)

[0287]

[0288] [Example 5: Manufacturing Example of Glutarimide]

[0289] Polymethyl methacrylate is used as a raw material, and monomethylamine is used as an imidizing agent to manufacture glutarimide acrylic resins.

[0290] In this manufacturing process, a tandem reactive extruder is used, consisting of two extrusion reactors arranged in series. For the tandem reactive extruder, both the first and second extruders are meshing co-rotating twin-screw extruders with a diameter of 75 mm and an L / D ratio (length L to diameter D) of 74. A low-weight feeder (manufactured by Kubota Corporation) is used to supply raw material to the feed port of the first extruder. The pressure reduction at each exhaust port of the first and second extruders is -0.095 MPa. Furthermore, the first and second extruders are connected by a 38 mm diameter, 2 m long pipe. A constant-flow pressure valve is used in the internal pressure control mechanism connecting the resin discharge port of the first extruder and the feed port of the second extruder. The resin discharged from the second extruder is cooled by a cooling conveyor and then granulated into cut pellets using a granulator. Here, in order to adjust the internal pressure of the component connecting the resin outlet of the first extruder and the raw material supply port of the second extruder or to determine the extrusion variation, a resin pressure gauge is installed at the outlet of the first extruder, at the center of the connecting component between the first extruder and the second extruder, and at the outlet of the second extruder.

[0291] In the first extruder, polymethyl methacrylate resin (Mw: 105,000) is used as the raw material, and monomethylamine is used as the imidizing agent to manufacture imide resin intermediate 1. At this time, the temperature of the highest temperature section of the extruder is 280°C, the screw speed is 55 rpm, the raw material resin supply rate is 150 kg / hour, and the amount of monomethylamine added is 2.0 parts per 100 parts of the raw material resin. A constant flow pressure valve is installed before the raw material supply port of the second extruder to adjust the pressure of the monomethylamine inlet of the first extruder to 8 MPa.

[0292] In the second extruder, after degassing the residual imidizing agent and byproducts from the rear exhaust vent and vacuum exhaust vent, dimethyl carbonate is added as an esterifying agent to produce imide resin intermediate 2. At this time, the temperature of each barrel in the extruder is 260°C, the screw speed is 55 rpm, and the amount of dimethyl carbonate added is 3.2 parts per 100 parts of the raw material resin. Furthermore, after removing the esterifying agent at the exhaust vent, the resin is extruded through a spool die, cooled in a water bath, and then granulated using a granulator to obtain glutarimide acrylic resin.

[0293] The obtained glutarimide acrylic resin was subjected to the above-described method to determine its imidization rate, glutarimide unit content, acid value, and glass transition temperature. The results showed an imidization rate of 13%, a glutarimide unit content of 7 wt%, an acid value of 0.4 mmol / g, and a glass transition temperature of 124 °C.

[0294] [Manufacturing Example 6]

[0295] The obtained powdered graft copolymer particles (A) and (B), along with Parapet HM (manufactured by Kuraray Co., Ltd., methyl methacrylate 100% by weight) and AO60 (manufactured by ADEKA Co., Ltd.), were compounded according to the proportions (parts) shown in Table 3. The resulting mixture was mixed using a Henschel mixer. Next, the mixture was melt-blended using a 58mm Φ vented co-rotating twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM58 L / D = 41.7) with the barrel temperature adjusted to 190℃~250℃, at a screw speed of 150rpm and a discharge rate of 180kg / h. The resulting material was drawn into a wire bundle, cooled in a water bath, and then cut into granules using a granulator. A Φ4.5×15 hole die was used, and a vane filter (manufactured by Nagase Kogyo, filtration regime 10μ, size 7 inches, number of sheets 33) was installed between the die and the extruder head as a polymer filter. The obtained granules were melt-mixed using a 90mmΦ single-shaft extruder with a T-die at a barrel temperature of 180℃~240℃ and a discharge rate of 150kg / hr. The granules were discharged from the T-die at a die temperature of 240℃. The granules were cooled and solidified by contacting a metallic casting roller with a temperature of 90℃ and a touch roller with a flexible metal sleeve with a temperature of 60℃ on both sides, and then wound into a film to obtain a film with a thickness of 175μm.

[0296] [Manufacturing Example 7]

[0297] Parapet HM (manufactured by Kuraray Co., Ltd., 100% by weight of methyl methacrylate) was replaced with Sumipex EX (manufactured by Sumitomo Chemical, 95% by weight of methyl methacrylate / 5% by weight of methyl acrylate methacrylate resin), and the film was otherwise manufactured in the same manner as in Manufacturing Example 5.

[0298] [Manufacturing Example 8]

[0299] Parapet HM (manufactured by Kuraray Co., Ltd., methyl methacrylate 100% by weight) was replaced with glutarimide acrylic resin, and the film was otherwise manufactured in the same manner as in Manufacturing Example 5.

[0300] [Manufacturing Examples 9-11]

[0301] As shown in Table 3, the type of rubber and the proportions of each component were changed, and no additives were added. Otherwise, the film was manufactured in the same way as in Manufacturing Example 6.

[0302]

[0303] [Preparation of Coatings]

[0304] (Paint 1)

[0305] In Z607-5AFH (30% solids concentration, manufactured by Agk Industries, Ltd.), propylene glycol monomethyl ether (PGM) is incorporated at a solids concentration of 20%.

[0306] (Paint 2)

[0307] Alumina particles (Z-607-ALU, manufactured by Agk Industries, Ltd., 30% solids concentration) are added in a 9:1 ratio to Z607-5AFH (30% solids concentration). Propylene glycol monomethyl ether (PGM) is added at a solids concentration of 20%.

[0308] (Paint 3-7)

[0309] Prepare the mixture according to the proportions in Table 4, in the same manner as coatings 1 and 2. It should be noted that the main components in Table 4 are all polyurethane acrylate resins.

[0310]

[0311] [Examples 1-12, Comparative Examples 1-12]

[0312] Coatings 1 to 7 were applied to the films obtained in Manufacturing Examples 6 to 11 or AW10U (PCPMMA multilayer films) according to the combinations described in Tables 5 and 6. A 200-line gravure roller was used for 1 μm, a 150-line gravure roller for 2 μm, and a 120-line gravure roller for 3.5 μm. The linear speed was 20 m / min, and the rotational speed of the gravure roller was 20 rpm. After coating, the solvent was evaporated by drying at 80°C for 1 min. Ultraviolet light was then applied using the cumulative UV light intensity described in Tables 5 and 6 to form a hard coating with the film thicknesses described in Tables 5 and 6. Various properties of the obtained films and laminates were evaluated. The results are shown in Tables 5 and 6.

[0313] It should be noted that in Comparative Examples 5 to 7, which used PCPMMA multilayer films, the Tg of PMMA (115°C) and the Tg of PC (144°C) were obtained. However, in the case of multilayer films, the higher Tg is considered to be the Tg of acrylic resin films.

[0314]

[0315] 〔result〕

[0316] Tables 5 and 6 show that specific acrylic resin films and specific hard coatings possess a glass transition temperature below 140°C and a crack elongation at 120°C of 200% or more, and a crack elongation at 120°C of 50% or more, and a strength of 50 g / cm³. 2The laminate of the embodiment with a Δhaze of less than 1.0% after 5 rounds of steel wool abrasion test exhibits excellent formability and abrasion resistance. On the other hand, it is known that the laminate of the comparative example that does not meet at least one of the above parameters cannot simultaneously achieve both formability and abrasion resistance.

[0317] Industrial availability

[0318] This laminate has excellent formability and wear resistance, making it suitable for various applications, including automotive interiors such as in-vehicle displays.

Claims

1. A laminate comprising an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film, The acrylic resin film is composed of an acrylic resin composition, wherein, when the total amount of the acrylic resin composition is set to 100% by mass, it contains 20% to 100% by mass of a thermoplastic acrylic polymer consisting of 50% to 100% by mass of methyl methacrylate units and 0% to 50% by mass of other structural units, and has a glass transition temperature of 140°C or lower, and an elongation at break of 200% or higher at 120°C. The hard coating is a 0.6–10.0 μm thick hard coating formed by coating a resin composition containing polyfunctional (meth)acrylate and a photopolymerization initiator onto the acrylic resin film and curing it by UV irradiation on a cooling roller at 25–70°C. The crack elongation of the laminate at 120°C is greater than 50%, and at 50 g / cm³. 2 The Δ haze in the 5-round steel wool abrasion test was below 1.0%.

2. The laminate according to claim 1, having at least one of the following physical properties: The phase difference (Re) is below 38 nm. The ΔE after the weathering test is less than 5.2%.

3. The laminate according to claim 1 or 2, wherein, The hard coating is a cured product of a resin composition comprising a polyfunctional (meth)acrylate and a photopolymerization initiator.

4. The laminate according to claim 1 or 2, wherein, The acrylic resin film contains 1 to 70% by mass of graft copolymer particles (A) with an average particle size of 20 nm to 200 nm and less than 20% by mass of graft copolymer particles (B) with an average particle size larger than the graft copolymer particles (A). The total content of crosslinked elastomer (A1) and crosslinked elastomer (B1) in the acrylic resin film is less than 15% by mass.

5. The laminated body according to claim 4, wherein, The graft copolymer particles (B) have an average particle size of 150 nm or more, and contain 1 to 10% by mass of the graft copolymer particles (B).

6. The laminate according to claim 1 or 2, wherein, The surface of the acrylic resin film without the laminated hard coating has a pencil hardness of B or higher, and the elongation at break at 23°C is 20% or higher.

7. The laminate according to claim 4, wherein, The graft copolymer particles (A) contain 0.01 to 5% by mass of a reactive ultraviolet absorber.

8. A molded body comprising the laminated body as described in claim 1 or 2.

9. A vehicle display front panel comprising the molded body as described in claim 8.

10. A method for manufacturing a laminate, the laminate comprising an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film. The method for manufacturing the laminate includes a step of UV irradiating at least one side of the hard coating applied to the acrylic resin film on a cooling roller, and then curing the hard coating. The cumulative UV light intensity of the UV irradiation is 150–500 mJ / cm². 2 , The temperature of the cooling roller is 25–70°C. The acrylic resin film has a glass transition temperature below 140°C and an elongation at break of more than 200% at 120°C. The crack elongation of the laminate at 120°C is greater than 50%, and at 50 g / cm³. 2 The Δ haze in the 5-round steel wool abrasion test was below 1.0%.

11. A method for manufacturing a molded body, comprising a step of shaping the laminate shown below at a molding temperature of 140°C or below during preforming; The laminate comprises an acrylic resin film and a hard coating layer laminated on at least one side of the acrylic resin film. The acrylic resin film has a glass transition temperature below 140°C and an elongation at break of more than 200% at 120°C. The hard coating is a 0.6–10.0 μm thick hard coating formed by coating a resin composition containing polyfunctional (meth)acrylate and a photopolymerization initiator onto the acrylic resin film and curing it by UV irradiation on a cooling roller at 25–70°C. The crack elongation of the laminate at 120°C is greater than 50%, and at 50 g / cm³. 2 The Δ haze in the 5-round steel wool abrasion test was below 1.0%.

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