Laminates and their uses

Abstract

The purpose of the present invention is to provide a laminate which includes an acrylic resin film and has excellent moldability and abrasion resistance. The purpose is achieved by providing a laminate comprising: a specific acrylic resin film; and a specific ultraviolet-curable hard coat layer that is laminated on at least one surface of the acrylic resin film, wherein the laminate has a specific crack elongation, and has Δ haze of at most 1.0% in a steel wool abrasion test at 50 g / cm2 and 5 reciprocations.

Description

[Technical Field]

[0001] The present invention relates to a laminate containing an acrylic resin film as a substrate. [Background technology]

[0002] Acrylic resin films, produced by processing and molding acrylic resin compositions containing elastic materials, are used and developed in a variety of applications, taking advantage of their excellent properties such as transparency, hardness, weather resistance, and secondary moldability. Examples of applications for acrylic resin films include decorative and protective uses as a substitute for paint, such as laminating the film onto automotive interior and exterior parts; decorative and protective uses for the exteriors of portable electronic devices, personal computers, and home appliances; and applications as building materials.

[0003] As an example of such an acrylic resin film, Patent Document 1 describes an acrylic resin film made by forming a film of a methacrylic resin composition (D) containing a specific methacrylic ester resin (A), a rubber-containing graft copolymer (B) of a four-stage polymer with an average particle size of rubber particles of 0.2 to 0.4 μm, and a rubber-containing graft copolymer (C) of a two-layer polymer with an average particle size of rubber particles of 0.02 to 0.15 μm, and a laminate containing the acrylic resin film.

[0004] Patent Document 2 describes an acrylic resin film containing multilayer graft copolymer particles (A) having an average particle diameter of 20 nm or more and 150 nm or less, and multilayer graft copolymer particles (B) having an average particle diameter larger than that of the graft copolymer particles (A), and a laminated film containing the acrylic resin film. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2013 / 051239 [Patent Document 2] International Publication No. 2019 / 181752 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] While the technologies described in Patent Documents 1 and 2 are excellent, there was room for further improvement in terms of moldability and wear resistance.

[0007] Therefore, the object of the present invention is to provide a laminate containing an acrylic resin film that has excellent moldability and abrasion resistance. [Means for solving the problem]

[0008] As a result of diligent research to solve the above problems, the inventors have discovered for the first time that a laminate with excellent moldability and abrasion resistance can be obtained by using an acrylic resin film having specific physical properties and a specific (e.g., UV-curable) hard coat layer in the laminate. Furthermore, they have discovered for the first time that the aforementioned laminate can be obtained by improving the manufacturing process of the laminate, thus completing the present invention.

[0009] Accordingly, one aspect of the present invention is a laminate comprising an acrylic resin film and a hard coat layer laminated 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 the breaking point at 120°C of 200% or more, and the laminate has a crack elongation at 120°C of 50% or more and a load capacity of 50 g / cm². 2 The laminate (hereinafter referred to as "this laminate") exhibits a Δ-haze of 1.0% or less in a steel wool abrasion test involving 5 back-and-forth passes.

[0010] In addition, one aspect of the present invention is a method for manufacturing a laminate including an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. The method includes a step of curing the hard coat layer by irradiating UV light on the hard coat layer applied to at least one side of the acrylic resin film on a cooling roll, where the UV integrated light quantity of the UV irradiation is 150 to 500 mJ / cm 2 and the temperature of the cooling roll is 25 to 70°C. The acrylic resin film has a glass transition temperature of 140°C or lower and a breaking elongation at 120°C of 200% or more. The laminate has a crack elongation at 120°C of 50% or more and a Δ haze in a steel wool abrasion test with 5 reciprocations of 1.0% or less. This is a method for manufacturing a laminate (hereinafter referred to as "the method for manufacturing the present laminate"). 2

[0011] In addition, one aspect of the present invention is a method for manufacturing a molded body (hereinafter referred to as "the method for manufacturing the present molded body"), which includes a step of shaping a laminate shown below at a shaping temperature of 140°C or lower during preforming: A laminate including an acrylic resin film and a hard coat 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 lower and a breaking elongation at 120°C of 200% or more. The laminate has a crack elongation at 120°C of 50% or more and a Δ haze in a steel wool abrasion test with 5 reciprocations of 1.0% or less. 2 This is the laminate.

Advantages of the Invention

[0012] According to one aspect of the present invention, a laminate including an acrylic resin film excellent in formability and wear resistance can be provided.

Modes for Carrying Out the Invention

[0013] ​One embodiment of the present invention will be described in detail below. Unless otherwise specified in this specification, "A~B" representing a numerical range means "A or more and B or less". Also, all the documents described in this specification are incorporated herein by reference as reference documents.

[0014] 〔1. Summary of the present invention〕 In recent years, in the field of in-vehicle displays, there has been a trend towards larger size and curved surfaces. As such a film for in-vehicle displays, it is required to be a film that can be formed into a curved surface and clears quality such as abrasion resistance (also referred to as scratch resistance and damage resistance), antireflection, and reliability. As a film used for such applications, a multilayer film in which a polycarbonate resin and an acrylic resin are laminated, or a functional film in which a functional layer having functions such as scratch resistance, antiglare property, antireflection property, antifouling property, etc. is formed by coating or the like on top of it is widely used. However, since such a film laminates two types of base material layers with different heat resistances, proper secondary forming processing is difficult, and whitening, delamination between layers, peeling of the functional layer, etc. are likely to occur. Also, with long-term use, peeling may occur from the display surface. Furthermore, polycarbonate resin has a large intrinsic retardation, and due to stretching during secondary forming, problems such as the occurrence of rainbow patterns or a decrease in contrast on the display surface may occur. On the other hand, as described above, acrylic resin films have excellent properties such as transparency, hardness, weather resistance, excellent optical properties with little retardation even during stretching, and excellent secondary formability. Therefore, the present inventors have studied the application of acrylic resin films to in-vehicle displays.

[0015] First, from the viewpoint of enhancing abrasion resistance in a laminate including an acrylic resin film and a hard coat layer, the present inventors attempted to increase the strength of the hard coat layer. As a result, although it was easy to increase the strength of the hard coat layer itself, a new problem was found that when the strength of the hard coat layer was increased, the hard coat layer might crack during molding and molding might become impossible.

[0016] Therefore, the inventors diligently investigated laminates that can achieve both moldability and wear resistance, and as a result succeeded in obtaining the following findings. Excellent moldability is ensured by using an acrylic resin film with a glass transition temperature (Tg) of 140°C or lower and an elongation at the breaking point of 120°C of 200% or more. • In the manufacturing process of the hard coat layer, the UV integrated light intensity is 150-500 mJ / cm². 2 By controlling the cooling roll temperature during UV irradiation to 25-70°C (preferably 40-70°C), the wear resistance of the laminate is enhanced.

[0017] This laminate was obtained based on the above findings and achieves excellent moldability and abrasion resistance simultaneously. Such a laminate containing an acrylic resin film with excellent moldability and abrasion resistance has not been reported to date, making this an extremely superior technology.

[0018] As described above, this laminate can simultaneously achieve excellent moldability and wear resistance. This can contribute to achieving Sustainable Development Goals (SDGs), such as Goal 12, "Ensure sustainable consumption and production patterns." The composition of this laminate will be described in detail below.

[0019] [2. Laminate] This laminate includes an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film.

[0020] (Acrylic resin film) The acrylic resin film is composed of an acrylic resin composition containing an acrylic resin and graft copolymer particles containing a rubber component. Preferably, the graft copolymer particles containing the rubber component include graft copolymer particles (A) having an average particle diameter of 20 nm or more and 200 nm or less, and may also include graft copolymer particles (B) with an average particle diameter larger than that of graft copolymer particles (A). Specifically, in the acrylic resin film, graft copolymer particles (A) are dispersed in an acrylic resin, or graft copolymer particles (A) and graft copolymer particles (B) are dispersed in an acrylic resin, or a matrix containing an acrylic resin and other components.

[0021] <Acrylic resin> Conventional known acrylic resins can be used for acrylic resin films. For example, from the viewpoint of hardness and moldability, it is preferable that the acrylic resin contains 20% to 100% by mass of a thermoplastic acrylic polymer, which consists of 50% to 100% by mass of methyl methacrylate units and 0% to 50% by mass of other constituent units, when the total amount of acrylic resin is 100% by mass.

[0022] Other constituent 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 other constituent units contained in the acrylic resin may be one type or a combination of two or more types.

[0023] Examples of acrylic acid derivatives include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, 2-(N,N-dimethylamino)ethyl acrylate, and glycidyl acrylate, among other acrylic acid esters.

[0024] Examples of methacrylic acid derivatives include methacrylic acid esters such as ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, glycidyl methacrylate, and adamantyl methacrylate.

[0025] Examples of aromatic vinyl derivatives include styrene, vinyltoluene, and α-methylstyrene.

[0026] Examples of vinyl cyanide derivatives include acrylonitrile and methacrylonitrile.

[0027] Examples of vinylidene halides include vinylidene chloride and vinylidene fluoride.

[0028] To improve the heat resistance, rigidity, and surface hardness of acrylic resins, specific structural units may be introduced into the acrylic resin through copolymerization, functional group modification, and modification. Examples of such specific structures include glutarimide structures as shown in Japanese Patent Publication No. 62-89705, Japanese Patent Publication No. 02-178310, and WO2005 / 54311, lactone ring structures as shown in Japanese Patent Publication No. 2004-168882 and Japanese Patent Publication No. 2006-171464, glutaric acid anhydride structures obtained by thermal condensation cyclization of (meth)acrylic acid units as shown in Japanese Patent Publication No. 2004-307834, maleic acid anhydride structures as shown in Japanese Patent Publication No. 5-119217, and N-substituted maleimide structures and unsubstituted maleimide structures as shown in WO2009 / 84541. For example, when these structures are introduced into acrylic resin, the molecular chains become rigid. As a result, improvements in heat resistance, surface hardness, thermal shrinkage, and chemical resistance can be expected.

[0029] The method for producing acrylic resin is not particularly limited, and known polymerization methods such as suspension polymerization, bulk polymerization, solution polymerization, emulsion polymerization, and dispersion polymerization can be applied. Furthermore, any of the known radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization methods can be applied.

[0030] <Graft copolymer containing rubber components> 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) if necessary.

[0031] The graft copolymer particles (A) preferably have a core-shell structure (multilayer structure) comprising a cross-linked elastomer (A1), which is a rubber component, and a graft polymer layer (A2) located on the surface side of the cross-linked elastomer (A1).

[0032] The crosslinked elastomer (A1) may be a known crosslinked elastomer. Preferably, the crosslinked elastomer (A1) is an acrylic acid ester-based crosslinked elastomer (a crosslinked elastomer consisting of a polymer mainly composed of acrylic acid ester).

[0033] The particles of the acrylic acid ester-based crosslinked elastomer (A1) may have a concentric spherical multilayer structure comprising a hard or semi-hard crosslinked resin layer within the crosslinked elastomer layer. Examples of such hard or semi-hard crosslinked resin layers include hard crosslinked methacrylic resin particles as shown in Japanese Patent Publication No. 55-27576, semi-hard crosslinked particles made of methyl methacrylate-acrylic acid ester-styrene as shown in Japanese Patent Application Publication No. 4-270751, and crosslinked rubber particles with a high degree of crosslinking. By incorporating such a hard or semi-hard crosslinked resin layer, improvements in transparency and color tone can be expected.

[0034] The graft copolymer particles (A) preferably have a core-shell structure formed by graft polymerization of a graft polymer layer (A2) in the presence of the aforementioned acrylic acid ester-based crosslinked elastomer (A1) particles.

[0035] The average particle diameter 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.

[0036] If the average particle size of the graft copolymer particles (A) is too small, the impact resistance and bending 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 deteriorate, and whitening due to bending tends to occur more easily.

[0037] As the acrylic acid ester-based crosslinked elastomer (A1), crosslinked elastomer particles obtained by polymerizing a monomer mixture (a-1) containing an acrylic acid ester, an optional other vinyl monomer copolymerizable with the acrylic acid ester, and a polyfunctional monomer copolymerizable with the acrylic acid ester and having two or more non-conjugated double bonds per molecule are preferably used.

[0038] Acrylic acid esters, other vinyl monomers, and polyfunctional monomers may all be mixed together and polymerized in a single step. Alternatively, for the purpose of adjusting the toughness, whitening resistance, etc., of the acrylic resin film, the composition of acrylic acid esters, other vinyl monomers, and polyfunctional monomers may be changed as appropriate, or the acrylic acid esters, other vinyl monomers, and polyfunctional monomers may be polymerized in two or more separate steps while maintaining the same composition.

[0039] As for acrylic acid esters, aliphatic esters of acrylic acid are preferred, alkyl acrylates are more preferred, and alkyl acrylates with 1 to 22 carbon atoms in the alkyl group are particularly preferred, due to their excellent polymerizability, low cost, and ability to yield polymers with a low Tg.

[0040] Specific examples of preferred alkyl acrylates include, for example, 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, heptadecyl acrylate, and octadecyl acrylate. These may be used individually or in combination of two or more.

[0041] The amount of acrylic acid ester is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more, based on 100% by mass of the monomer mixture (a-1). If the amount of acrylic acid ester is 50% by mass or more, the impact resistance and elongation at tensile break of the acrylic resin film are good, and cracks are less likely to occur during secondary molding.

[0042] Other vinyl monomers include, for example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; vinyl halogenates such as vinyl chloride and vinyl bromide; 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; vinylidene chloride, and vinyl fluoride. Examples include vinylidenes such as nylidene; 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-methylolacrylamide; 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; and maleic acid derivatives such as N-alkylmaleimide and N-phenylmaleimide. These may be used individually or in combination of two or more. Among these, one or more selected from the group consisting of methacrylic acid esters and aromatic vinyl derivatives are particularly preferred in terms of weather resistance and transparency.

[0043] The amount of other vinyl monomers is preferably 0% by mass or more and 49.9% by mass or less per 100% by mass of the monomer mixture (a-1), more preferably 0% by mass or more and 30% by mass or less, and most preferably 0% by mass or more and 20% by mass or less. If the amount of other vinyl monomers exceeds 49.9% by mass, the impact resistance of the acrylic resin film tends to decrease, the elongation at tensile fracture decreases, and cracks may easily occur during secondary molding.

[0044] The polyfunctional monomer can be one that is commonly used as a crosslinking agent and / or graft crossing agent. Examples of polyfunctional 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 polyfunctional monomers may be used individually or in combination of two or more.

[0045] Among these polyfunctional monomers, those that function as graft crossing agents are more preferable because they improve the number of graft bonds of the graft polymer layer (A2), described later, relative to the crosslinked elastomer (A1), resulting in good dispersibility of the graft copolymer (A) in the acrylic resin, improved crack resistance to tensile and bending deformation, and reduced stress whitening. Among such polyfunctional monomers that function as graft crossing agents, those having an allyl group, such as allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and diallyl maleate, are preferred, with allyl methacrylate and allyl acrylate being particularly preferred.

[0046] The amount of polyfunctional monomer is preferably 0.1% to 10% by mass, and more preferably 1.0% to 4% by mass, based on 100% by mass of the monomer mixture (a-1). Within this range of polyfunctional monomer blending is preferable from the viewpoint of the bending crack resistance and bending whitening resistance of the acrylic resin film, as well as the fluidity of the resin during molding.

[0047] Furthermore, in the acrylic ester-based crosslinked elastomer (A1), the amount of polyfunctional monomers may be varied between the interior and near the surface of the crosslinked elastomer (A1) in order to improve the graft coating efficiency of the graft polymer layer (A2) described later. Specifically, as shown in Japanese Patent Publication No. 1460364 and Japanese Patent Publication No. 1786959, etc., by increasing the content of polyfunctional monomers that function as graft cross-intermediates near the surface of the crosslinked elastomer (A1) compared to the interior, the coating of graft copolymer particles (A) by the graft polymer layer can be improved, resulting in better dispersibility in the acrylic resin and suppression of a decrease in crack resistance due to peeling at the interface between the graft copolymer particles (A) and the acrylic resin. Furthermore, since sufficient coating can be obtained with a relatively small amount of graft polymer layer (A2), the amount of graft copolymer particles (A) required to introduce a predetermined amount of crosslinked elastomer (A1) into the acrylic resin composition can be reduced. Therefore, the melt viscosity of the acrylic resin composition can be lowered, and improvements in melt processability, film processing accuracy, and surface hardness of the acrylic resin film can be expected.

[0048] Furthermore, a chain transfer agent may be added to the monomer mixture (a-1) for the purpose of controlling the molecular weight and crosslinking density of the acrylic acid ester-based crosslinked elastomer (A1), and controlling thermal stability, etc., by reducing the double bond ends of the polymer due to the disproportionation termination reaction during polymerization. The chain transfer agent can be selected from those commonly used in radical polymerization. Preferred chain transfer agents include, for example, monofunctional or polyfunctional mercaptan compounds with 2 to 20 carbon atoms such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan, mercapto acids, thiophenol, carbon tetrachloride, or mixtures thereof. The amount of chain transfer agent added is preferably 0 to 1.0 parts by mass, and more preferably 0 to 0.2 parts by mass, per 100 parts by mass of the total amount of monomer mixture (a-1).

[0049] The cross-linked elastomer (A1) particles may be a single layer made of the above-mentioned acrylic acid ester-based cross-linked elastomer (A1), or they may be a multilayer structure containing two or more layers made of the above-mentioned acrylic acid ester-based cross-linked elastomer (A1), or they may be multilayer particles containing a hard or semi-hard cross-linked resin layer with at least one layer made of acrylic acid ester-based cross-linked elastomer (A1).

[0050] Examples of monomers constituting a hard or semi-hard crosslinked resin layer include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate; aromatic vinyl derivatives such as styrene and α-methylstyrene; vinyl cyanide derivatives such as acrylonitrile; maleic acid derivatives such as maleic anhydride and maleimides; and polyfunctional monomers having two or more non-conjugated double bonds per molecule.

[0051] Among these, one or more selected from the group consisting of methyl methacrylate, butyl methacrylate, butyl acrylate, ethyl acrylate, styrene, acrylonitrile, etc., are particularly preferred. Furthermore, as the polyfunctional monomer, the same one used for polymerization of the acrylic acid ester-based crosslinked elastomer (A1) layer can be used. In addition, when polymerization of the rigid or semi-rigid crosslinked resin layer, in addition to these monomers, a chain transfer agent may be used in combination for the purpose of controlling the crosslink density and reducing the double bond ends of the polymer to control thermal stability, etc. The chain transfer agent can be the same as the chain transfer agent used for polymerization of the acrylic acid ester-based crosslinked elastomer (A1) layer. The amount of chain transfer agent added is preferably 0 to 2 parts by mass, and more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total amount of the rigid or semi-rigid crosslinked resin layer.

[0052] When the graft copolymer particle (A) has a two-layer structure consisting of a crosslinked elastomer particle (A1) which is a core particle and a graft polymer layer (A2), the graft copolymer particle (A) can typically be obtained by graft copolymerizing a monomer mixture (a-2) containing 50% to 100% by mass of a methacrylic acid ester and 0% to 50% by mass of another vinyl monomer copolymerizable with the methacrylic acid ester in the presence of the crosslinked elastomer particle (A1) to form the graft polymer layer (A2).

[0053] The amount of methacrylic acid ester 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, from the viewpoint of ensuring compatibility with the acrylic resin matrix and preventing a decrease in the toughness of the coating film due to solvent impregnation during coating of the acrylic resin film, as well as whitening and cracking due to stretching during molding.

[0054] The graft polymer layer (A2) is preferably obtained by graft copolymerizing 10 to 95 parts by mass of a monomer mixture (a-2) containing 70% to 99% by mass of an alkyl methacrylate, 0.5% to 30% by mass of an alkyl acrylate with 2 or more carbon atoms in the alkyl group, and 0% to 19% by mass of other vinyl monomers, in the presence of 5 to 90 parts by mass of crosslinked elastomer particles (A1), in at least one step. However, the total amount of crosslinked elastomer particles (A1) and monomer mixture (a-2) should be 100 parts by mass.

[0055] In the graft polymer layer (A2), examples of alkyl methacrylate esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Among these, alkyl methacrylate esters with 1 to 4 carbon atoms in the alkyl group are preferred.

[0056] In the graft polymer layer (A2), as other vinyl monomers, alkyl acrylates with two or more carbon atoms in the alkyl group can be used. The alkyl acrylates with two or more carbon atoms in the alkyl group are preferably one or more selected from the group consisting of ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, and stearyl acrylate; more preferably one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate; and particularly preferably n-butyl acrylate.

[0057] Other vinyl monomers that can be used in monomer mixture (a-2) include aromatic vinyl derivatives such as styrene and its nuclear-substituted derivatives, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid and its derivatives, acrylic acid and its derivatives, N-substituted maleimides, maleic anhydride, methacrylamide, acrylamide, and the like.

[0058] The monomer mixture (a-2) preferably contains a reactive ultraviolet absorber as another vinyl monomer. In other words, it is preferable that the graft polymer layer (A2) contains constituent units derived from the reactive ultraviolet absorber. When the monomer mixture (a-2) contains a reactive ultraviolet absorber, it is easier to obtain an acrylic resin film with good weather resistance and chemical resistance.

[0059] As the reactive ultraviolet absorber, any known reactive ultraviolet absorber can be used and is not particularly limited. From the viewpoint of the moldability and weather resistance of the acrylic resin film, a compound represented by the following general formula (1) is preferred as the reactive ultraviolet absorber.

[0060] [ka] (In general formula (1), X is a hydrogen atom or a halogen atom, R1 is a hydrogen atom, a methyl group, or a t-alkyl group having 4 to 6 carbon atoms, R2 is a linear or branched alkylene group having 2 to 10 carbon atoms, and R3 is a hydrogen atom or a methyl group.) Examples of reactive ultraviolet absorbers represented by general formula (1) include 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazoles, 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. Preferably, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole is used due to cost and ease of handling.

[0061] The content of constituent units derived from the reactive ultraviolet absorber in the graft polymer layer (A2) is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 3% by mass or less.

[0062] In the production of graft copolymer particles (A), particularly during the graft copolymerization of monomer mixtures (a-2) in the presence of crosslinked elastomer particles (A1), such as acrylic ester-based crosslinked elastomer particles (A1), polymer components that are not grafted to the acrylic ester-based crosslinked elastomer particles (A1) (free polymers) may be produced. Such free polymers can be used to constitute part or all of the acrylic resin that makes up the matrix phase of acrylic resin compositions and acrylic resin films.

[0063] A chain transfer agent may be added to the monomer mixture (a-2) for the purpose of controlling the molecular weight of the polymer, the grafting rate onto the crosslinked elastomer (A1), the amount of free polymer not bonded to the crosslinked elastomer (A1) produced, and thermal stability by reducing the double bond ends of the polymer due to the disproportionation termination reaction during polymerization. Such a chain transfer agent can be the same as the chain transfer agent that can be used for polymerization of the crosslinked elastomer (A1). The amount of chain transfer agent used is 0 to 2 parts by mass, preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total amount of monomer mixture (a-2).

[0064] The grafting ratio of the monomer mixture (a-2) to 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 ratio is less than 5%, the acrylic resin film tends to have reduced resistance to bending and whitening, reduced transparency, and reduced elongation at tensile fracture, making it more prone to cracking during secondary molding. If the grafting ratio 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.

[0065] The average particle size d (nm) of the crosslinked elastomer particles (A1) in the acrylic resin film and the amount w (mass%) of the polyfunctional monomer used in the acrylic ester-based crosslinked elastomer preferably satisfy the relationship: 0.015d ≤ w ≤ 0.06d, and more preferably 0.02d ≤ w ≤ 0.05d. If the amount of polyfunctional monomer is within the range of the above relationship, the acrylic resin film has advantages such as less reduction in elongation during secondary molding, less cracking during molding and cutting, excellent transparency, and less stress whitening during bending and tensile deformation at room temperature, high temperatures above the softening temperature of the acrylic resin film, or low temperatures between room temperature and the Tg of the crosslinked elastomer particles (A1).

[0066] As mentioned above, the graft copolymer particles (B), which are used as needed, also comprise a cross-linked elastomer (B1), which is a rubber component, just like the graft copolymer particles (A). Typically, the graft copolymer particles (B), like the graft copolymer particles (A), comprise a graft polymer layer (B2) located on the surface side of the cross-linked elastomer (B1). In other words, it is preferable that the graft copolymer particles (B) comprise both a cross-linked elastomer (B1) and a graft polymer layer (B2).

[0067] Regarding graft copolymer particles (B), they may be generally the same as graft copolymer particles (A) in terms of raw materials, manufacturing method, etc., except that their average particle diameter is larger than that of graft copolymer particles (A). Preferably, the particles of the acrylic acid ester-based crosslinked elastomer (B1) have a concentric spherical multilayer structure with a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer. Examples of such hard or semi-hard crosslinked resin layers include hard crosslinked methacrylic resin particles as shown in Japanese Patent Publication No. 55-27576, etc., and crosslinked particles having a semi-hard layer made of methyl methacrylate-acrylic acid ester-styrene copolymer as shown in Japanese Patent Application Publication No. 4-270751 and WO2014 / 41803, etc. By introducing such a hard or semi-hard crosslinked resin layer, the transparency, resistance to bending whitening, and resistance to bending cracking of graft copolymer particles (B), which have a larger particle diameter than graft copolymer particles (A), can be improved.

[0068] The average particle diameter of the graft copolymer particles (B) is preferably 150 nm to 400 nm, and more preferably 200 nm to 350 nm.

[0069] The average particle size of graft copolymer particles (B) is larger than that of graft copolymer particles (A). Graft copolymer particles (B), with their larger average particle size, more effectively induce plastic deformation (crazing) in the acrylic resin phase surrounding the graft copolymer particles in response to external forces acting on the acrylic resin material. For this reason, graft copolymer particles (B) are extremely effective in imparting impact resistance and crack resistance to acrylic resin materials. On the other hand, graft copolymer particles (B) are inferior to graft copolymer particles (A) in terms of resistance to bending 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), the total content of soft components in the acrylic resin film is reduced, preventing a decrease in the surface hardness of the acrylic resin film. Furthermore, the whitening tendency when external stress is applied to the acrylic resin film, when a coating solution containing organic solvents is applied, or during molding is less likely to worsen, and the crack resistance and secondary moldability of the functional film can be expected to be efficiently improved.

[0070] In one or more embodiments of the present invention, the average particle diameter of graft copolymer particles (A) and graft copolymer particles (B) can be measured using a laser diffraction type particle size distribution analyzer such as the Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd., using the light scattering method in the latex state.

[0071] The method for producing graft copolymer particles (A) and graft copolymer particles (B) is not particularly limited, and known emulsion polymerization, miniemulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or dispersion polymerization methods can be applied. Emulsion polymerization is particularly preferred because it allows for a wide range of adjustment of the resin structure.

[0072] Known initiators such as organic peroxides, inorganic peroxides, and azo compounds can be used as initiators in the emulsion polymerization of graft copolymer particles (A) or graft copolymer particles (B). Specifically, organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinate peroxide, t-butyl peroxymaleate, cumene hydroperoxide, benzoyl peroxide, and lauroyl peroxide can be used; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate can be used; and azo compounds such as azobisisobutyronitrile can be used. These may be used individually or in combination of two or more.

[0073] These initiators may be used as pyrolysis-type radical polymerization initiators, or as redox-type polymerization initiator systems in combination with reducing agents such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, and ferrous sulfate. Ferrous sulfate may also be used in combination with complexes such as ethylenediaminetetraacetate-2-sodium.

[0074] Among these, from the viewpoint of polymerization stability and particle size control, it is more preferable to use inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate, or to use a redox initiator system that combines organic hydroxylated oxides such as t-butyl hydroperoxide and cumene hydroperoxide with an inorganic reducing agent such as a divalent iron salt and / or an organic reducing agent such as sodium formaldehyde sulfoxylate, reducing sugar, or ascorbic acid.

[0075] The inorganic or organic peroxides mentioned above can be added by known methods, such as adding them directly to the polymerization system, adding them mixed with monomers, or adding them dispersed in an aqueous emulsifier solution. From the viewpoint of transparency of the acrylic resin film, the methods of adding them mixed with monomers and adding them dispersed in an aqueous emulsifier solution are preferred.

[0076] There are no particular limitations on the surfactant (also called an emulsifier) ​​used in the emulsion polymerization of graft copolymer particles (A) or graft copolymer particles (B). A wide range of known surfactants can be used for emulsion polymerization. Preferred surfactants include, for example, anionic surfactants such as sodium, potassium, and ammonium salts of alkyl sulfonic acid, alkylbenzene sulfonic acid, dioctyl sulfosuccinate, alkyl sulfate, sodium fatty acid, polyoxyethylene alkyl ether acetate, alkyl phosphoric acid, alkyl ether phosphoric acid, alkylphenyl ether phosphoric acid, and surfactant, as well as nonionic surfactants such as alkylphenols, reaction products of aliphatic alcohols with propylene oxide and ethylene oxide. For example, polyoxyethylene lauryl ether phosphoric acid and its sodium salt can be suitably used as alkyl ether phosphoric acid and its salts. These surfactants may be used individually or in combination of two or more.

[0077] Graft copolymer particles (A) or graft copolymer particles (B) obtained by emulsion polymerization can be separated and recovered from the latex of either graft copolymer particles (A) or graft copolymer particles (B) by known methods. For example, graft copolymer particles (A) or graft copolymer particles (B) can be separated and recovered by adding a water-soluble electrolyte such as calcium chloride or magnesium sulfate to the latex and allowing it to coagulate, or by freezing and then filtering out the solids, washing, and drying. Alternatively, graft copolymer particles (A) or graft copolymer particles (B) can also be separated and recovered by spray drying, freeze-drying, or other treatments of the latex.

[0078] Preferably, in order to reduce external defects and internal foreign matter in the acrylic resin film, prior to the separation and recovery of graft copolymer particles (A) or graft copolymer particles (B), the latex of graft copolymer particles (A) or graft copolymer particles (B) is filtered using a filter or mesh to remove environmental foreign matter and substances that cause foreign matter defects, such as polymerization scale.

[0079] As filters or meshes, known filters and meshes used for filtering liquid media can be used. The type of filter or mesh, the filter opening, filtration accuracy, and filtration capacity are appropriately selected according to the target application, the type, size, and amount of foreign matter to be removed. For example, the filter or mesh opening and filtration accuracy are preferably at least twice as large as the average particle size of the graft copolymer particles (A) or graft copolymer particles (B), respectively.

[0080] In the acrylic resin film, the content of graft copolymer particles (A) is not particularly limited, but is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 65% by mass or less, and even more preferably 10% by mass or more and 60% by mass or less.

[0081] In the acrylic resin film, 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, but is, for example, 1% by mass or more.

[0082] In the acrylic resin film, 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.

[0083] <Other ingredients> The acrylic resin film (the acrylic resin composition constituting the acrylic resin film) may optionally contain a thermoplastic resin that is at least partially compatible with the acrylic resin, to the extent that it does not impair the objectives of the present invention. Examples of such thermoplastic resins include styrene 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 acylate, etc.), vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polylactic acid resins, and PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) resins). Examples of styrene resins include styrene-acrylonitrile resins, styrene Examples include styrene-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-acrylic acid ester resin. Among these, one or more thermoplastic resins selected from the group consisting of styrene-based resins, polycarbonate resins, and cellulose acylate resins are preferred because they have excellent compatibility with acrylic resins and can potentially improve the bending crack resistance, solvent resistance, low moisture absorption of acrylic resin films, as well as the glass shatter prevention performance of laminates.

[0084] The acrylic resin film (the acrylic resin composition constituting the acrylic resin film) may also contain, as necessary, conventionally known additives used in acrylic resin films, to the extent that it does not impair the objectives of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusers, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, antiblocking agents consisting of organic or inorganic particles, infrared reflectors consisting of metals or metal oxides, plasticizers, and antistatic agents. The additives are not limited to these. These additives can be used in any amount depending on the type of additive, to the extent that it does not impair the objectives of the present invention, or to enhance the effects of the present invention.

[0085] <Physical properties> 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. A glass transition temperature of 140°C or lower allows for molding without increasing the molding temperature, which has the advantage of suppressing crack formation during molding. While there is no particular lower limit, it is preferable, for example, to be 100°C or higher, from the viewpoint of preventing printing misalignment during drying and improving reliability. The glass transition temperature of the acrylic resin film is measured by the method described in the examples.

[0086] The elongation at the breaking point of the acrylic resin film at 120°C is 200% or more, preferably 210% or more, and more preferably 220% or more. An elongation at the breaking point of the acrylic resin film at 120°C of 200% or more offers the advantage of excellent shape conformability during molding. The elongation at the breaking point of the acrylic resin film at 120°C is measured by the method described in the examples.

[0087] The elongation at the breaking point of the acrylic resin film at 23°C is preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more. When the elongation at the breaking point of the acrylic resin film at 23°C is 20% or more, cracking is less likely to occur during handling such as transportation or cutting of the acrylic resin film or the laminate at room temperature, making handling easier. The elongation at the breaking point of the acrylic resin film at 23°C is measured by the method described in the examples.

[0088] The film thickness of the acrylic resin film is not particularly limited, but is preferably 75 to 500 μm, more preferably 75 to 300 μm, and more preferably 100 to 250 μm. A film thickness of 75 to 500 μm for the acrylic resin film has the advantage of being stiff and easy to handle. The film thickness of the acrylic resin film is measured by the method described in the examples.

[0089] The pencil hardness of the surface of an acrylic resin film without a hard coat layer is preferably B or higher, and more preferably HB or higher, from the viewpoint of scratch resistance. The pencil hardness of the surface of an acrylic resin film without a hard coat layer is measured in accordance with JIS K5600-5-4, as described in the examples.

[0090] <Method for manufacturing acrylic resin film> Acrylic resin films can be manufactured by known processing methods. Specific examples of known processing methods include melt processing, calendering, press molding, and solvent casting. Melt processing methods include inflation and T-die extrusion. In the solvent casting method, an acrylic resin composition is dissolved and dispersed in a solvent, and the resulting dispersion (dope) is then flowed onto a belt-shaped substrate in a film-like manner. Subsequently, the solvent is evaporated from the flowed film-like dope to obtain an acrylic resin film.

[0091] Among these methods, a solvent-free melt processing method, particularly the T-die extrusion method, is preferred. The melt processing method has fewer limitations on the thickness of the film to be manufactured, allows for the production of films with excellent surface properties with high productivity, and reduces the burden on the natural and working environment caused by solvents, as well as manufacturing costs.

[0092] When forming an acrylic resin composition into a film by melt processing or solvent casting, it is preferable to use filtration with a filter or mesh to remove environmental contaminants, polymerization scale, degraded resin, etc., from the acrylic resin composition that cause surface defects or internal contaminants in the acrylic resin film, in order to improve the appearance quality of the acrylic resin film.

[0093] During film manufacturing by melt processing, filtration can be performed at one or more arbitrary timings among the following: preparation of the acrylic resin composition by melt mixing, pelletization of the molten acrylic resin composition, and film formation using a T-die. In the solvent casting method, after mixing the acrylic resin, graft copolymer particles (A), (B), and other components with the solvent, filtration can be performed before casting.

[0094] Such filters and meshes can be used without particular restriction, as long as they have heat resistance, durability, and resistance to casting solvents, dopes, etc., according to the melting process conditions.

[0095] When manufacturing acrylic resin films by melt processing, a filter with a large filtration capacity and minimal retention of molten resin, which can cause the formation of resin degradation products and crosslinking products that impair film quality, is preferable, especially in order to obtain high-quality acrylic resin films. For example, using leaf-disc type filters or pleated type filters is preferable in terms of filtration efficiency and productivity.

[0096] When manufacturing acrylic resin films by T-die extrusion, an automated die system can be used to improve the film thickness accuracy. This system can, for example, measure the film thickness distribution in the TD direction (perpendicular to the extrusion direction) of the extruded film online and automatically adjust the lip clearance of the T-die during film extrusion based on this measurement. By applying an automated die system with an appropriate control method, it may be possible to improve the thickness accuracy of acrylic resin films.

[0097] In the manufacture of acrylic resin films, if necessary, a film with superior surface properties can be obtained by simultaneously contacting (sandwiching) both sides of the molten film with a cooling roll or cooling belt during the molding process. In this case, it is preferable to simultaneously contact the molten film with a roll or cooling belt maintained at a temperature of -80°C or higher, preferably -70°C or higher, which is the glass transition temperature of the acrylic resin composition.

[0098] More preferably, at least one of the rolls used for such clamping is a roll having an elastic metal sleeve, such as those disclosed in Japanese Patent Application Publication No. 2000-153547 or Japanese Patent Application Publication No. 11-235747, and by transferring the roll's mirror surface or a specific surface shape using a low clamping pressure, it is possible to obtain a film with excellent smoothness or moderate surface roughness, excellent slipperiness on the film surface, suppressed blocking between films, and less internal strain.

[0099] Furthermore, depending on the purpose, uniaxial stretching or biaxial stretching can be performed following film formation. Uniaxial or biaxial stretching can be carried out using known stretching equipment. Biaxial stretching can be carried out in known forms, such as sequential biaxial stretching, simultaneous biaxial stretching, or a method in which longitudinal stretching is followed by transverse stretching while relaxing the longitudinal direction to reduce film bowing.

[0100] Furthermore, depending on the application, any surface shape such as hairline, prism, uneven shape, three-dimensional decoration, matte surface, rough surface with a certain surface roughness, or knurling at the film edge may be applied to one or both sides of the acrylic resin film. Such surface shapes can be applied by known methods. For example, one method involves sandwiching both sides of the molten film immediately after extrusion, or the molded film fed from a feeding device, between two rolls or belts, each having a surface shape on at least one of its surfaces, thereby transferring the surface shape of the rolls.

[0101] (Hard coat layer) The hard coat layer in this laminate is a functional layer laminated on at least one side of the acrylic resin film. The hard coat layer may be laminated on one side of the acrylic resin film or on both sides.

[0102] The hard coat layer in this laminate is preferably a cured product of a resin composition containing a polyfunctional (meth)acrylate and a photopolymerization initiator. The hard coat layer is preferably obtained by curing using known curing methods such as thermosetting or active energy ray curing. More preferably, it is obtained by curing by irradiation with active energy rays such as ultraviolet light.

[0103] As the hard coat layer, various UV-curable hard coat layers that have been conventionally provided in various functional films and resin molded products can be used without particular limitation. The hard coat layer can be formed by curing a composition containing monomers, oligomers, resins, or mixtures thereof that have radical-reactive functional groups such as polyfunctional (meth)acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, silicone acrylate, polycarbonate acrylate, and polyacrylic acrylate. Alternatively, a hard coat layer can be formed by curing a composition containing monomers, oligomers, resins, or mixtures thereof that have cationic or anionic curable functional groups such as epoxy groups and oxetane groups. Furthermore, a hard coat layer can be formed by thermally curing a polysiloxane-based resin obtained by hydrolysis and partial condensation of an alkoxy-substituted silyl compound. Or, a hard coat layer can be formed by introducing reactive functional groups into a silyl compound and curing the reaction. The above-mentioned components used to form the hard coat layer may be used individually or mixed together as appropriate.

[0104] In the above examples of hard coat layers, for the sake of convenience in the explanation that follows, "polyfunctional (meth)acrylate" is described separately from epoxy acrylate, urethane acrylate, etc. However, "polyfunctional (meth)acrylate" is a general term for monomers, oligomers, polymers, etc. that contain two or more (meth)acryloyl functional groups in their structure, and is a concept that includes epoxy acrylate, urethane acrylate, and further, compounds that have any main chain or skeletal structure such as alkyl, alkenyl, aryl, ester, amide, ether, fluoroalkyl, silyloxy, etc., and two or more (meth)acryloyl functional groups. In other words, when "polyfunctional (meth)acrylate" is written, it is intended to include epoxy acrylate, urethane acrylate, and further, polyvalent (meth)acrylate compounds having any of the above-mentioned structures, as would be normally understood by those skilled in the art.

[0105] Polyfunctional (meth)acrylates are not particularly limited as long as they have at least two (meth)acryloyl groups. Specifically, examples include polyfunctional (meth)acrylates such as 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. These may be used individually or in combination of two or more. Furthermore, commercially available UV-curable hard coat agents are also mentioned. In this specification, (meth)acrylate encompasses both methacrylate and acrylate. In this specification, the term (meth)acryloyl group encompasses both methacryloyl and acryloyl groups.

[0106] There are no particular restrictions on the epoxy acrylate monomers used. Specifically, examples include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and vinylcyclohexene monooxide (i.e., 1,2-epoxy-4-vinylcyclohexane).

[0107] Urethane acrylate resins can be obtained, for example, by mixing a polyhydric alcohol, a polyhydric isocyanate, and a hydroxyl group-containing (meth)acrylate, and generating urethane bonds through the reaction of isocyanate groups with hydroxyl groups.

[0108] The various properties of urethane acrylate resins can be appropriately adjusted by the structure of the polyhydric alcohol, the type of polyhydric isocyanate, and the number of acryloyl groups or methacryloyl groups (CH2=CH-CO- or CH2=C(CH3)-CO-) derived from the hydroxyl group-containing (meth)acrylate, and are not particularly limited. Furthermore, commercially available urethane acrylate resins that are UV-curable hard coat agents can also be mentioned.

[0109] The hydroxyl group-containing (meth)acrylate is not particularly limited, and in addition to hydroxyl group-containing (meth)acrylates, such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, compounds having an ethylenically unsaturated bond with at least one hydroxyl group may be added as needed, such as 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, trimethylpropane mono(meth)acrylate, trimethylolpropanedi(meth)acrylate, allyl alcohol, ethylene glycol allyl ether, glycerin (mono, di)allyl ether, N-methylol (meth)acrylamide, etc., or mixtures thereof.

[0110] There are no particular restrictions on the polyvalent isocyanate. Examples of polyvalent isocyanate compounds containing two or more isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane triisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, and bis(2-isocyanate). Examples include chloro(Tyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, toridine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5-bis(isocyanate methyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanate methyl)-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, uretdione of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, and the like. Furthermore, these polyisocyanates can be used individually or in combination of two or more types.

[0111] Specific examples of the polyhydric alcohol 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, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, and polytetramethylene glycol. These polyhydric alcohols may be used alone or in combination of two or more.

[0112] In order to accelerate the reaction with the isocyanate group of the isocyanate component, an organotin-based urethanization catalyst is used. The organotin-based urethanization catalyst may be any one generally used in the urethanization reaction. Examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkyl maleate, tin stearate, and tin octylate. The amount of use of these organotin-based urethanization catalysts is not particularly limited, but it is appropriate to use them within the range of 0.005% by mass or more and 3% by mass or less. If it is less than the lower limit, the urethane reaction does not proceed sufficiently, and if it exceeds the upper limit, it becomes difficult to control the reaction due to the heat generation during the urethane reaction.

[0113] The composition for forming a hard coat comprising a polysiloxane-based resin composition preferably has the following general formula (2): R 4 -(SiR 5 a (OR 6 ) 3-a )···(2) (In the general formula (2), R 4 is a monovalent hydrocarbon group selected from the group consisting 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, at least a part of the terminals of which is substituted with a reactive substituent selected from the group consisting of an epoxy group, an oxetane group, a (meth)acryloyl group, a vinyl group, a hydroxyl group, a carboxyl group, an amino group, and a protected amino group. R 5Each of these is independently a monovalent hydrocarbon group selected from the group consisting of a hydrogen atom, 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. 6 Each of the elements is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a is an integer between 0 and 2. The curable composition contains a condensate (A) obtained by hydrolyzing and condensing a silane compound (Z) having a hydrolyzable silyl group, represented by ( ), and a catalyst or curing agent (B) for reacting the reactive substituent.

[0114] Preferably, the weight-average molecular weight of the condensate (A) is 30,000 or less. Furthermore, it is preferable that the proportion of silane compounds having reactive substituents is 10% by mass or more of the total. In this case, the cured product as a hard coat layer exhibits excellent hardness, chemical resistance, and durability.

[0115] The catalyst or curing agent (B) is preferably one or more catalysts or curing agents selected from photoradical generators, photocation generators, and photoanion generators, from the viewpoint of the photocurability of the composition.

[0116] In general formula (2), the reactive substituent is preferably an epoxy group or an oxetane group, due to the low curing shrinkage during hard coat layer formation and the ease with which a functional film with excellent durability and suppressed curling can be obtained.

[0117] When performing the hydrolysis condensation reaction of silane compounds (Z), it is more preferable to use a neutral salt catalyst. This is because it is easier to suppress the decomposition of the reactive substituents during hydrolysis condensation when the reactive substituents are epoxy groups or oxetane groups.

[0118] OR, which is directly bonded to the silicon atom of the silane compound (Z), which is the raw material for the condensate (A). It is more preferable that the ratio Q / P of the number of moles Q of the 6 OR groups directly bonded to silicon atoms in the condensate (A) to the number of moles P of the 6 OR groups is 0.2 or less. This is because the hardness, chemical resistance, and durability of the cured product are excellent.

[0119] When forming a hard coat layer, known methods can be applied to cure the resin composition. A preferred curing method is irradiation with active energy rays, such as ultraviolet light. When curing is performed by irradiation with active energy rays, a photopolymerization initiator, a photoanion generator, and a photocation generator are usually added to the hard coat layer formation composition.

[0120] Specific examples of photopolymerization initiators include, for example, acetophenone, benzophenone, benzoyl methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-2-phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one compounds. Among these, 1-hydroxy-cyclohexyl-phenyl-ketone is preferred due to its excellent compatibility with resins.

[0121] Specific examples of photocation generators include, for example, CPI-100P, CPI-101A, CPI-200K, and CPI-200S from Sunapro Corporation; WPI-124, WPI-113, WPI-116, WPI-169, WPI-170, and WPI-124 from Wako Pure Chemical Industries, Ltd.; and Rhodia Corporation's Roadsil 2074, among others. Specific examples of photoanion generators include, for example, acetophenone o-benzoyloxium, nifedipine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene 2-(9-oxoxanthene2-yl)propionic acid, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3-[bis(dimelamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylpyguanidium, and n-butyltriphenylbalate.

[0122] When curing a coating film made of a curable composition to form a hard coat layer, the curable composition may contain various known leveling agents for purposes such as improving coatability, scratch resistance after curing, and stain resistance. Fluorine-based leveling agents, acrylic-based leveling agents, silicone-based leveling agents, and adducts or mixtures thereof can be used as leveling agents. The amount of leveling agent is not particularly limited, but for example, it is in the range of 0.03 parts by mass to 3.0 parts by mass per 100 parts by mass of the curable composition.

[0123] When forming a hard coat layer by applying a curable composition, various additives such as UV absorbers, light stabilizers, defoamers, antioxidants, light diffusers, matting agents, antifouling agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic fine particles, and antistatic agents may be added to the curable composition as needed. The additives are not limited to these.

[0124] To impart appropriate coatability to a curable composition, an organic solvent is usually added. The organic solvent is not particularly limited as long as it can impart the desired coatability to the curable composition and form a hard coat layer with the desired film thickness and performance. A boiling point of 50°C to 150°C is preferable for the organic solvent from the viewpoint of coatability and the drying properties of the formed coating film.

[0125] Specific examples of organic solvents include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, dioxane, propylene glycol monoethyl ether, methyl cellosolve, and ethyl cellosolve; and amides such as N-methylpyrrolidone and dimethylformamide. Organic solvents can be used individually or in combination of two or more.

[0126] When applying a curable composition onto the main surface of the aforementioned acrylic resin film, which is the base film, any application method can be used without particular limitations. Examples of application methods include the reverse coating method, gravure coating method, bar coating method, die coating method, spray coating method, kiss coating method, wire bar coating method, and curtain coating method. These application methods may be carried out individually or in combination.

[0127] After applying the curable composition for forming the hard coat layer described above to the surface of the aforementioned acrylic resin film, which is the base film, the hard coat layer is formed by removing the organic solvent from the coating film by drying and curing by ultraviolet irradiation.

[0128] When removing organic solvents by drying, the drying temperature of the coating film is preferably 60°C to 120°C, and more preferably 70°C to 100°C. If the drying temperature is too low, organic solvents may remain in the coating film. If the drying temperature is too high, the flatness of the functional film (hard coat layer) may be impaired due to thermal deformation of the base film.

[0129] The wavelength of ultraviolet light irradiated when curing the coated film is preferably in the range of 200 nm to 400 nm. The integrated ultraviolet (UV) light amount is preferably the condition described in [4. Method for Manufacturing Laminates] below. As the irradiation device for ultraviolet exposure light, for example, an irradiation device equipped with a lamp 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 light source such as an argon ion laser and a helium-neon laser can be used.

[0130] During ultraviolet irradiation, heat is generated and the temperature rises, so it is preferable to cool the roll by lowering its temperature while irradiating it with ultraviolet light. The cooling roll temperature at this time is preferably the condition described in [4. Method for Manufacturing Laminates] below.

[0131] As the hard coat layer forming composition, commercially available products such as "Z-879" from Aica Kogyo Co., Ltd., "Unidic ESS108" from DIC Corporation, "NSC-7312" from Dainichi Seika Kogyo Co., Ltd., "Beamset 575" from Arakawa Chemical Industries, Ltd., "UV-1700B" from Nippon Synthetic Chemical Industry Co., Ltd., "8BR-600" from Taisei Fine Chemical Co., Ltd., and "FA-3280H" from Nippon Chemical Paint Co., Ltd. may be used. Since it retains elongation even after curing, the 120°C crack elongation of this laminate can be further increased.

[0132] The thickness of the hard coat layer 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. A hard coat layer thickness of 0.6 to 10.0 μm has the advantage of achieving both wear resistance and moldability. The thickness of the hard coat layer is measured by the method described in the examples.

[0133] Furthermore, in one embodiment of the present invention, inorganic particles or metal particles may be added to improve the wear resistance of the hard coat layer. The inorganic particles and metal particles are not particularly limited, but examples include silica, alumina, titanium oxide, zinc oxide, zirconia, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, metallic copper, and the like. These particles may be used without surface treatment, or surface treatment may be performed using a known method to control the dispersion state and appropriately control the affinity with the hard coat layer.

[0134] <Other Functional Layers> The laminate may have other functional layers in addition to the hard coat layer. Such other functional layers are not particularly limited, and 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, anti-static layers, ultraviolet shielding layers, infrared shielding layers, surface texture layers, light diffusion layers, matte layers, polarizing layers, colored layers, design layers, embossed layers, conductive layers, gas barrier layers, and gas absorption layers. Two or more of these functional layers may be combined. Furthermore, one functional layer may possess two or more functions. The anti-reflective layer may be composed of a low refractive index layer, a combination of a high refractive index layer and a low refractive index layer, or it may be formed by creating a surface texture on the surface of the functional layer that is finer than the wavelength of visible light.

[0135] (Laminated structure) As described above, this laminate is composed of a specific acrylic resin film and a hard coat layer, and exhibits excellent moldability and abrasion resistance.

[0136] The crack elongation of this laminate at 120°C is 50% or more, preferably 52% or more, and more preferably 54% or more. A crack elongation of 50% or more at 120°C has the advantage of preventing crack formation during molding. The crack elongation of this laminate at 120°C is measured by the method described in the examples.

[0137] This laminate contains 50 g / cm³ 2 The Δ-haze of the steel wool abrasion test over 5 cycles is 1.0% or less, preferably 0.8% or less, and more preferably 0.6% or less. 50 g / cm 2 Furthermore, if the Δ-haze in the steel wool abrasion test over 5 back-and-forth strokes is 1.0% or less, it has the advantage of not scratching when wiped. 2 The Δ-haze of the steel wool abrasion test over 5 cycles is measured by the method described in the examples.

[0138] This laminate contains 50 g / cm³ 2 The Δ-haze of the steel wool abrasion test over 10 cycles is, for example, 1.0% or less, preferably 0.9% or less, and more preferably 0.8% or less. 50 g / cm³ 2 Furthermore, if the Δ-haze in the steel wool abrasion test over 10 back-and-forth strokes is 1.0% or less, it has the advantage of not scratching when wiped. 2 The Δ-haze of the steel wool abrasion test over 10 cycles is measured by the method described in the examples.

[0139] The pencil hardness of this laminate is preferably H or higher, and more preferably 2H or higher, from the viewpoint of scratch resistance. The pencil hardness of this laminate is measured by the method described in the examples.

[0140] The above-mentioned "steel wool abrasion test" and "pencil hardness" are both indicators of abrasion resistance. The "steel wool abrasion test" evaluates abrasion resistance based on the scratches made when wiping, while "pencil hardness" evaluates abrasion resistance based on the scratches made when scratching. It is preferable that this laminate exhibits effectiveness in both indicators.

[0141] 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. When the phase difference (Re) is 38 nm or less, a decrease in contrast can be suppressed in the liquid crystal display device. The phase difference (Re) is measured by the method described in the examples.

[0142] 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. When the phase difference (Rth) is 30 nm or less, a decrease in contrast can be suppressed in the liquid crystal display device. The phase difference (Rth) is measured by the method described in the examples.

[0143] The ΔE (color difference) of this laminate after the weathering test is, for example, 5.2% or less, preferably 4.0% or less, and more preferably 3.0% or less. A ΔE of 5.2% or less after the weathering test has the advantage of excellent long-term durability. The ΔE after the weathering test is measured by the method described in the examples.

[0144] The moldable 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. A moldable radius of curvature of 1 mm or less has the advantage of allowing for the molding of complex shapes. Furthermore, the moldable radius of curvature is measured by the method described in the examples.

[0145] The laminate may have a primer layer on the side opposite to the side with the hard coat layer. The primer layer can be composed of a resin that provides good adhesion to inks used in printing and metals used in metal vapor deposition during post-processing. Examples include urethane resins, acrylic resins, polyester resins, polycarbonates, 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.

[0146] The primer layer thickness is preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm, and most preferably 0.5 to 3 μm. A thickness of 0.5 μm or more ensures adhesion, while a thickness of 10 μm or less improves productivity.

[0147] [3. Molded body] In one embodiment of the present invention, a molded article (hereinafter referred to as "the molded article") comprising the laminate is provided.

[0148] Specific examples of applications for this molded product include: automotive interior applications such as instrument panels, in-car display front panels, console boxes, meter covers, door lock bezels, steering wheels, power window switch bases, center clusters, and dashboards; automotive exterior applications such as weatherstrips, bumpers, bumper guards, side mudguards, body panels, spoilers, front grilles, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, window moldings, windows, headlamp covers, taillamp covers, and windshield components; and mobile phone applications such as smartphones, mobile phones, and tablets. Examples of applications include housings, display windows, buttons, etc., for mobile phones and other electronic devices; televisions, DVD players, stereo systems, rice cookers, washing machines, refrigerators, air conditioners, humidifiers, dehumidifiers, electric fans, and other household electronic and electrical equipment; casings, front panels, buttons, emblems, surface decorative materials for furniture products, and exterior furniture materials; interior building materials for walls, ceilings, floors, bathtubs, toilet seats, etc.; exterior building materials such as siding for walls, fences, roofs, gates, and gable boards; surface decorative materials for furniture such as window frames, doors, railings, sills, 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, such as trains, aircraft, and ships.

[0149] Using this laminate, it is possible to easily manufacture molded articles with complex three-dimensional shapes and excellent appearance, where surface hardness, scratch resistance, chemical resistance, stain resistance, reflective properties, and anti-glare properties are controlled. For this reason, this molded article is preferably used in applications such as front panels for automotive displays having planar, curved, or three-dimensional shapes. Accordingly, in one embodiment of the present invention, an automotive display front panel comprising this molded article is provided.

[0150] [4. Method for manufacturing laminates] One embodiment of the present invention provides a method for manufacturing a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film. The method for manufacturing the laminate includes a step of curing the hard coat layer by irradiating the hard coat layer applied to at least one side of the acrylic resin film with UV light on a cooling roll, wherein the integrated UV light amount of the UV irradiation is 150 to 500 mJ / cm². 2 The cooling roll temperature is 25-70°C, the acrylic resin film has a glass transition temperature of 140°C or less and an elongation at the breaking point at 120°C of 200% or more, the laminate has a crack elongation at 120°C of 50% or more, and the weight is 50 g / cm². 2 Furthermore, the Δ-haze in the steel wool abrasion test over 5 cycles is 1.0% or less.

[0151] In the manufacturing method of this laminate, the integrated ultraviolet (UV) light intensity is, for example, 150 to 500 mJ / cm². 2 Therefore, the concentration is 160-480 mJ / cm². 2 Preferably, the concentration is 170-460 mJ / cm². 2 It is more preferable that the UV integrated light intensity is 150-500 mJ / cm². 2 This allows for obtaining an appropriate hardness in the hard coat layer while ensuring moldability.

[0152] In the method for manufacturing this laminate, the cooling roll temperature is, for example, 25 to 70°C, preferably 30 to 70°C, more preferably 35 to 70°C, even more preferably 40 to 70°C, particularly preferably 42 to 68°C, and especially preferably 45 to 65°C. When the cooling roll temperature is 25 to 70°C, the hard coat layer can be cured while suppressing the temperature rise during ultraviolet irradiation, and a laminate with the desired physical properties can be manufactured.

[0153] The method for manufacturing the laminate may include steps such as applying a curable composition for forming the hard coat layer to the surface of an acrylic resin film, which is a base film, before the step of curing the hard coat layer, and removing the organic solvent from the coating film formed therein by drying.

[0154] Furthermore, for matters other than the above conditions in the manufacturing method of this laminate, the provisions described in [2. Laminate] above shall apply.

[0155] [5. Method for manufacturing molded articles] One embodiment of the present invention provides a method for manufacturing a molded article, which includes a step of shaping the laminate shown below at a molding temperature of 140°C or less during preforming: A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, The aforementioned acrylic resin film has a glass transition temperature of 140°C or lower, and an elongation at the breaking point at 120°C of 200% or more. The laminate has a crack elongation of 50% or more at 120°C, and a density of 50 g / cm². 2 A laminate in which the Δ-haze in a steel wool abrasion test over 5 cycles is 1.0% or less.

[0156] In this method of manufacturing the molded product, the film is formed by preforming at a temperature of 140°C or lower. Because this laminate contains the specific acrylic resin film described above, low-temperature molding is possible when laminating resin onto this laminate.

[0157] In the method for manufacturing this molded article, the preforming temperature is, for example, 140°C or lower, preferably 130°C or lower, and more preferably 120°C or lower. A preforming temperature of 140°C or lower has the advantage of making it less likely for cracks to occur in the hard coat layer. Furthermore, there is no particular lower limit, but from the viewpoint of shape imparting, for example, it is preferably 100°C or higher, and preferably 105°C or higher.

[0158] The resin used in injection molding is not particularly limited, but examples include thermoplastic resins and curable resins. Examples of thermoplastic resins include polycarbonate resins having a bisphenol-based backbone, fluorene-based backbone, or isosorbide-based backbone, acrylic resins, styrene-based resins (AS resins, ABS resins, and MAS resins, styrene-maleimide resins, styrene-maleic anhydride resins, etc.), saturated polyester resins, polyvinyl chloride resins, polyarylate resins, PPS-based resins, POM-based resins, polyamide resins, polylactic acid resins, cellulose acylate resins, and polyolefin resins. Examples of curable resins include epoxy resins, vinyl ester resins, unsaturated polyester resins, phenol-based resins, melamine-based resins, and benzoxazine resins. Among these, transparent resins such as polycarbonate resins, acrylic resins, styrene-based resins, polyarylate resins, and polyolefin resins are preferably used.

[0159] In one embodiment of the present invention, the molded article can be manufactured by preforming (shaping a curved surface) the printed laminate at a temperature of 140°C or lower, trimming it, placing it in a mold, and then integrating it by injection molding with resin.

[0160] Furthermore, for matters other than the above conditions in the manufacturing method of this molded product, the provisions described in [2. Laminate] above shall apply.

[0161] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0162] In other words, one embodiment of the present invention is as follows: <1> A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, The aforementioned acrylic resin film has a glass transition temperature of 140°C or lower, and an elongation at the breaking point at 120°C of 200% or more. The laminate has a crack elongation of 50% or more at 120°C, and a density of 50 g / cm². 2 A laminate in which the Δ-haze in a steel wool abrasion test over 5 cycles is 1.0% or less. <2> Having at least one of the following physical properties: <1> The laminate described above: The phase difference (Re) is 38 nm or less. The ΔE after the weathering test is 5.2% or less. <3> The hard coat layer is a cured product of a resin composition containing a polyfunctional (meth)acrylate and a photopolymerization initiator. <1> or <2> The laminate described above. <4> The acrylic resin film contains 1 to 70% by mass of graft copolymer particles (A) having an average particle diameter of 20 nm to 200 nm, and 20% by mass or less of graft copolymer particles (B) having an average particle diameter larger than that of the graft copolymer particles (A), wherein the total content of crosslinked elastomer (A1) and crosslinked elastomer (B1) in the acrylic resin film is 15% by mass or less. <1> ~ <3> A laminate as described in any of the following. <5> The average particle diameter of the graft copolymer particles (B) is 150 nm or more, and the graft copolymer particles (B) are present in an amount of 1 to 10% by mass. <4> The laminate described above. <6> The surface of the acrylic resin film without a hard coat layer has a pencil hardness of B or higher, and the elongation at the breaking point at 23°C is 20% or higher. <1> ~ <5> A laminate as described in any of the following. <7> The graft copolymer particles (A) contain 0.01 to 5% by mass of a reactive ultraviolet absorber. <4> ~ <6> A laminate as described in any of the following. <8> <1> ~ <7> A molded body comprising a laminate as described in any of the following. <9> <8> A front panel for an in-vehicle display, comprising the molded body described above. <10> A method for manufacturing a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, The process includes a step of curing the hard coat layer applied to at least one side of the acrylic resin film by irradiating it with UV light on a cooling roll, The integrated UV light intensity of the aforementioned UV irradiation is 150-500 mJ / cm². 2 And, The temperature of the cooling roll is 25 to 70°C. The aforementioned acrylic resin film has a glass transition temperature of 140°C or lower, and an elongation at the breaking point at 120°C of 200% or more. The laminate has a crack elongation of 50% or more at 120°C, and a density of 50 g / cm². 2 A method for manufacturing a laminate in which the Δ-haze of a steel wool abrasion test over 5 cycles is 1.0% or less. <11> A method for manufacturing a molded article, comprising the step of shaping the laminate shown below at a molding temperature of 140°C or lower during preforming: A laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, The aforementioned acrylic resin film has a glass transition temperature of 140°C or lower, and an elongation at the breaking point at 120°C of 200% or more. The laminate has a crack elongation of 50% or more at 120°C, and a density of 50 g / cm². 2 A laminate in which the Δ-haze in a steel wool abrasion test over 5 cycles is 1.0% or less. [Examples]

[0163] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0164] [Measurement and evaluation methods] Measurements and evaluations in the examples and comparative examples were performed using the following methods.

[0165] (Glass transition temperature (Tg)) A differential scanning calorimetry (DSC) SSC-5200 manufactured by Seiko Instruments was used. The sample was first heated to 200°C at a rate of 25°C / min, held for 10 minutes, and then pre-adjusted by lowering the temperature to 50°C at a rate of 25°C / min. Measurements were then taken while the sample was heated to 200°C at a rate of 10°C / min. The differential values ​​were determined from the obtained DSC curve (SSDC), and the glass transition temperature was determined from its maximum point.

[0166] (Tensile elongation at the breaking point) Laminated film was cut into 10 mm (width) x 100 mm (length) pieces and measured using a Tensilon tensile testing machine (Shimadzu Corporation, AG-2000D) equipped with a high-temperature chamber set to 120°C, under the following conditions: preheating time of 2 minutes, chuck distance of 50 mm, and tensile speed of 200 mm / min. The elongation at which the laminated film broke was defined as the tensile break elongation.

[0167] The tensile elongation at fracture value is the average value obtained by excluding the highest and lowest values ​​from the measurements taken using five test specimens.

[0168] (Crack elongation) Crack elongation was measured on laminated films with a hard coat layer formed on one side (HC layer formation). Specifically, the laminated film was cut into 10 mm (width) x 100 mm (length) sections, and measured using a Tensilon tensile testing machine (Shimadzu Corporation, AG-2000D) equipped with a high-temperature chamber set to 120°C, under the conditions of a preheating time of 2 minutes, a chuck distance of 50 mm, and a tensile speed of 200 mm / min. The elongation when a crack occurred in the hard coat layer was measured as the 120°C crack elongation. The average values ​​of the test results obtained from measurements of three samples are shown in Tables 5 and 6.

[0169] (Moldable radius of curvature) A vacuum pressure forming machine (manufactured by Fuse Vacuum Co., Ltd., NGF-0406-S) was used. The forming machine consisted of an upper and lower section. A mold with multiple protrusions of 3 mm in height and R (radius of curvature) of 0.3, 0.5, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0 was installed in the lower section, and a laminated film was placed in the upper section. Subsequently, the pressure in both the upper and lower sections was reduced to -100 kPa, and the laminated film was heated using an infrared heater installed in the upper section. In Examples 1-12, Comparative Examples 1-4, and Comparative Examples 8-12, the laminated film was heated to 120°C, and in Comparative Examples 5-7, it was heated to 160°C. At this stage, the laminated film was pressed against the mold, and then compressed air was introduced into the upper section to 300 kPa to perform the molding. ○: No cracks in the protrusions, △: Cracks in part of the circumference of the protrusions, ×: Cracks around the entire circumference of the protrusions.

[0170] (Abrasion test) A HEIDON Type 14DR surface texture measuring instrument (manufactured by Shinto Kagaku Co., Ltd.) was used. Steel wool #0000 was attached to a 1 mm diameter probe, and a 50 g weight was placed on top. Steel wool was placed on the hard coat surface of a laminated film, and tests of 5 and 10 reciprocations were performed with a stroke of 50 mm and a speed of 6000 mm / min. Haze was measured before and after the test. Haze was measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with ISO 14782.

[0171] (phase difference) A 40mm x 40mm test specimen was cut from the film. Using an automatic birefringent (KOBRA-WR, manufactured by Oji Instruments Co., Ltd.), the in-plane phase difference Re and the thickness-direction phase difference Rth were measured on this specimen at a temperature of 23±2℃, humidity of 50±5%, wavelength of 590nm, and incident angle of 0°.

[0172] (Weather resistance test) A Suga SX2D-75 (manufactured by Suga Test Instruments Co., Ltd.) was used. The irradiation intensity was 180 (W / m2, 300-400nm), the black panel temperature was 83±3℃, and the relative humidity was 50±5%. The glass filter configuration consisted of quartz on the inside and polysilicate #275 on the outside, and the test was conducted for 500 hours. The color difference (ΔE) was measured before and after the test. ΔE was measured using a spectrophotometer SE7700 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). Mode: Transmittance, Light source: D65, Field of view: 2°, Measurement diameter: 28mm.

[0173] (film thickness) The film thickness of the acrylic resin film was measured using a PEACOCK dial gauge No. 25 (manufactured by Ozaki Seisakusho Co., Ltd.).

[0174] The thickness of the hard coat layer was measured using the F20 film thickness measurement system (manufactured by Filmetrics Co., Ltd.). The opposite side of the hard coat layer was colored black with a marker pen, and the refractive index of the acrylic resin film was set to 1.49 and the refractive index of the hard coat layer to 1.50 for measurement.

[0175] (Pencil hardness) Pencil hardness was measured in accordance with JIS K5600-5-4. An electric pencil hardness tester (manufactured by MIZ Testing Machine Co., Ltd.) was used, and five pencils were tested at a load of 750g and a speed of 60mm / min. A pencil was judged to pass if it had one or fewer scratches.

[0176] Pencil hardness was measured on the hard coat layer of the functional film.

[0177] [Manufacturing Example 1: Graft Copolymer Particles (A)] The following substances were charged into an 8L polymerization apparatus equipped with a stirrer. • Deionized water (200 copies) • Sodium dioctyl sulfosuccinate 0.24 parts Sodium formaldehyde sulfoxylate 0.15 parts • 0.001 parts of ethylenediaminetetraacetic acid-2-sodium • Ferrous sulfate 0.00025 parts The polymerization apparatus was thoroughly purged with nitrogen gas to create a substantially oxygen-free environment. The internal temperature of the polymerization apparatus was then raised to 60°C. Next, 30 parts of the monomer mixture described below were continuously added to the polymerization apparatus at a rate of 10 parts by mass / hour. After the addition was complete, polymerization was continued for another 0.5 hours to obtain crosslinked elastomer (A1) particles (average particle size 90 nm). The polymerization conversion rate was 99.5%.

[0178] Monomer mixture: • Vinyl monomer mixture (90% n-butyl acrylate (BA) and 10% methyl methacrylate (MMA)) 30 parts • Allyl methacrylate (AlMA) 1 part • Cumene hydroperoxide (CHP) 0.2 parts Subsequently, 0.05 parts by mass of sodium dioctyl sulfosuccinate was 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 70 parts of vinyl monomer mixture (98% MMA, 1% BA, and 1% RUVA), 0.5 parts of tert-decyl mercaptan (t-DM), and 0.5 parts of CHP for graft polymer layer (A2) formation was continuously added to the polymerization apparatus at a rate 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, and the solidified solid was washed with water and dried to obtain graft copolymer particle (A) powder. The amounts of each component are shown in Table 1.

[0179] Furthermore, RUVA is a reactive ultraviolet absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2-H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., RUVA-93)).

[0180] [Manufacturing Example 2: Graft Copolymer Particles (A)] The following substances were charged into an 8L polymerization apparatus equipped with a stirrer. Deionized water, 200 copies Sodium dioctyl sulfosuccinate 0.25 parts Sodium formaldehyde sulfoxylate 0.15 parts 0.001 parts of ethylenediaminetetraacetic acid-2-sodium Ferrous sulfate 0.00025 parts After thoroughly replacing the inside of the polymerization reactor with nitrogen gas to create a substantially oxygen-free environment, the internal temperature was set 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 was continued for another 0.5 hours to obtain rubber particles. The polymerization conversion rate was 99.5%.

[0181] Subsequently, 0.05 parts of sodium dioctyl sulfosuccinate were added, the internal temperature was raised to 60°C, and a mixture of monomers consisting of 7 parts n-butyl acrylate and 63 parts methyl methacrylate, along with 0.2 parts cumene hydroperoxide, was continuously added over 5 hours. Polymerization was then continued for another hour to obtain graft copolymer particle latex. The polymerization conversion rate was 98.5%. The obtained latex was salted out with calcium chloride, coagulated, washed with water, and dried to obtain white powdery graft copolymer particles (A). The amounts of each component are shown in Table 1.

[0182] The average particle size of the rubber particles in the graft copolymer particles (A) was 80 nm.

[0183] [Table 1] [Manufacturing Example 3: Graft Copolymer Particles (B)] The following substances were charged into an 8L polymerization apparatus equipped with a stirrer. • Deionized water (180 units) • Polyoxyethylene lauryl ether phosphate 0.002 parts • Boric acid 0.4725 parts Sodium carbonate 0.04725 parts • Sodium hydroxide 0.0098 parts The polymerization apparatus was thoroughly purged with nitrogen gas to create a virtually oxygen-free environment. The internal temperature of the polymerization apparatus was then raised to 80°C. 0.027 parts of potassium persulfate as a 2% aqueous solution was added to the polymerization apparatus, and then a mixture consisting of 27 parts of a vinyl monomer mixture (97% MMA and 3% BA) and 0.036 parts of allyl methacrylate was continuously added to the polymerization apparatus over 81 minutes.

[0184] By continuing polymerization for another 60 minutes, polymer particles forming the first layer of the core (cross-linked elastomer (B1)) were obtained. The polymerization conversion rate was 99.0%.

[0185] Subsequently, 0.0267 parts of sodium hydroxide were added to the polymerization apparatus as a 2% aqueous solution. Next, 0.08 parts of potassium persulfate were added to the polymerization apparatus as a 2% aqueous solution. Then, a mixture consisting of 50 parts of 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 as a 2% aqueous solution. Polymerization was then continued for 120 minutes to obtain a core (crosslinked elastomer (B1)) consisting of the first and second layers. The polymerization conversion rate was 99.0%, and the average particle size was 230 nm.

[0186] Subsequently, 0.023 parts of potassium persulfate were added to the polymerization apparatus as 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 was continued for another 30 minutes to obtain 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 and solidified, and the solidified 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. The amounts of each component are shown in Table 2.

[0187] [Manufacturing Example 4: Graft Copolymer Particles (B)] Preparation of the innermost polymer: A mixture of the following composition was placed in a glass reactor and heated to 80°C while stirring under a nitrogen atmosphere. Then, 25% of the mixture of monomers consisting of 25 parts methyl methacrylate and 1 part allyl methacrylate, and 0.1 parts t-butyl hydroperoxide was added all at once, and polymerization was carried out for 45 minutes. Deionized water, 220 units Boric acid 0.3 parts Sodium carbonate 0.03 parts Sodium N-lauroyl sarcosinate 0.09 parts Sodium formaldehyde sulfoxylate 0.0 9 parts 0.006 parts of ethylenediaminetetraacetic acid-2-sodium Ferrous sulfate 0.002 parts Next, the remaining 75% of this mixture was continuously added over a period of 1 hour. After the addition was complete, the mixture was maintained at the same temperature for 2 hours to complete the polymerization. During this time, 0.2 parts of sodium N-lauroyl sarcosinate were also added. The polymerization conversion rate (amount of polymerization produced / amount of monomer added) of the resulting innermost cross-linked methacrylic polymer latex was 98%.

[0188] Manufacturing of rubber particles: The obtained innermost polymer latex was maintained at 80°C in a nitrogen atmosphere, and 0.1 parts of potassium persulfate were added, followed by continuous addition of a monomer mixture consisting of 41 parts n-butyl acrylate, 9 parts styrene, and 1 part allyl methacrylate over a period of 5 hours. During this time, 0.1 parts of potassium oleate were added in three separate additions. After the addition of the monomer mixture was complete, an additional 0.05 parts of potassium persulfate was added to complete the polymerization, and the mixture was held for 2 hours. The polymerization conversion rate of the obtained rubber particles was 99%.

[0189] Fabrication of graft copolymers: The obtained rubber particle latex was kept at 80°C, and 0.02 parts of potassium persulfate were added, followed by continuous addition of a monomer mixture of 14 parts of methyl methacrylate and 1 part of n-butyl acrylate over 1 hour. After the addition of the monomer mixture was completed, the mixture was held for 1 hour to obtain graft copolymer latex. The polymerization conversion rate was 99%.

[0190] Fabrication of graft copolymer particles: 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 addition of the monomer mixture was completed, the mixture was held for 1 hour to obtain graft copolymer particle latex. The polymerization conversion rate was 99%.

[0191] The obtained graft copolymer particle latex was subjected to salting-out coagulation with calcium chloride, heat treatment, and drying to obtain white powdery graft copolymer particles (B). The amounts of each component are shown in Table 2.

[0192] [Table 2] [Manufacturing Example 5: Manufacturing Example of Glutalimide] A glutarimide acrylic resin was manufactured using polymethyl methacrylate as a raw material and monomethylamine as an imidizing agent.

[0193] In this manufacturing process, a tandem-type reaction extruder was used, consisting of two extrusion reactors arranged in series. Both the first and second extruders were 75mm in diameter and had an L / D ratio (extruder length L to diameter D) of 74. These were coaxial twin-screw extruders, and a low-weight feeder (manufactured by Kubota Corporation) was used to supply the raw material to the first extruder's raw material supply port. The pressure reduction at each vent in both the first and second extruders was set to -0.095 MPa. Furthermore, a 38mm diameter, 2m long pipe connected the first and second extruders, and a constant-flow pressure valve was used in the internal pressure control mechanism connecting the resin discharge port of the first extruder to the raw material supply port of the second extruder. The resin discharged from the second extruder was cooled on a cooling conveyor and then cut into pellets using a pelletizer. To adjust the internal pressure of the component connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, or to determine extrusion fluctuations, resin pressure gauges were installed at the discharge port of the first extruder, the central part of the connecting component between the first and second extruders, and the discharge port of the second extruder.

[0194] In the first extruder, polymethyl methacrylate resin (Mw: 105,000) was used as the raw material resin, and monomethylamine was used as the imidizing agent to produce imide resin intermediate 1. At this time, the temperature of the extruder's highest heating section was 280°C, the screw rotation speed was 55 rpm, the raw material resin supply rate was 150 kg / hour, and the amount of monomethylamine added was 2.0 parts per 100 parts of raw material resin. A constant flow pressure valve was installed immediately before the raw material supply port of the second extruder, and the pressure of the monomethylamine injection section of the first extruder was adjusted to 8 MPa.

[0195] In the second extruder, after degassing the remaining imidizing agent and by-products through the rear vent and vacuum vent, dimethyl carbonate was added as an esterifying agent to produce imide resin intermediate 2. At this time, the temperature of each barrel of the extruder was 260°C, the screw rotation speed was 55 rpm, and the amount of dimethyl carbonate added was 3.2 parts per 100 parts of raw resin. Furthermore, after removing the esterifying agent with a vent, the mixture was extruded from the strand die, cooled in a water bath, and then pelletized in a pelletizer to obtain a glutarimide acrylic resin.

[0196] The obtained glutarimide acrylic resin was measured according to the method described above for imidation rate, glutarimide unit content, acid value, and glass transition temperature. The results showed an imidation rate of 13%, a glutarimide unit content of 7% by weight, an acid value of 0.4 mmol / g, and a glass transition temperature of 124°C.

[0197] [Manufacturing Example 6] The obtained powdered graft copolymer particles (A) and (B), along with Parapet HM (manufactured by Kuraray Co., Ltd., 100% by weight of methyl methacrylate) and AO60 (manufactured by ADEKA Corporation), were blended in the amounts (parts) shown in Table 3. The resulting mixture was mixed using a Henschel mixer. Next, a 58 mmΦ vented co-directional twin-screw extruder (Toshiba Machine Co., Ltd., TEM58 L / D=41.7) with the cylinder temperature adjusted to 190°C to 250°C was used to perform melt kneading at a screw rotation speed of 150 rpm and a discharge rate of 180 kg / hour. The mixture was drawn into strands, cooled in a water bath, and then cut using a pelletizer to obtain pellets. A die with Φ4.5 × 15 holes was used, and a leaf disc filter (manufactured by Nagase & Co., Ltd., filtration efficiency 10 μm, size 7 inches, 33 discs) was installed as a polymer filter between the die and the extruder head. The obtained pellets were melted and kneaded using a 90mmΦ single-screw extruder with a T-die at a cylinder temperature of 180°C to 240°C and a discharge rate of 150 kg / hr. The mixture was then extruded from the T-die at a die temperature of 240°C, and both sides were brought into contact with a touch roll equipped with a metallic cast roll heated to 90°C and an elastic metal sleeve heated to 60°C. The mixture was cooled and solidified while forming a film, and then wound up to obtain a film with a thickness of 175 μm.

[0198] [Manufacturing Example 7] The film was manufactured using the same method as in Manufacturing Example 5, except that Parapet HM (manufactured by Kuraray Co., Ltd., 100% by weight of methyl methacrylate) was replaced with Sumipex EX (manufactured by Sumitomo Chemical, methacrylic ester resin containing 95% by weight of methyl methacrylate and 5% by weight of methyl acrylate).

[0199] [Manufacturing Example 8] The film was manufactured using the same method as in Manufacturing Example 5, except that Parapet HM (manufactured by Kuraray Co., Ltd., 100% by weight of methyl methacrylate) was replaced with a glutarimide acrylic resin.

[0200] [Manufacturing Examples 9-11] The film was manufactured using the same method as in Manufacturing Example 6, except that the type of rubber and the proportions of each component were changed as shown in Table 3, and no additives were added.

[0201] [Table 3] [Preparation of paint] (Paint 1) Propylene glycol monomethyl ether (PGM) was added to Z607-5AFH (solids content 30%, manufactured by Aica Kogyo Co., Ltd.) to bring the solids content to 20%.

[0202] (Paint 2) Z607-5AFH (solids content 30%, manufactured by Aica Kogyo Co., Ltd.) was blended with alumina particles (Z-607-ALU, manufactured by Aica Kogyo Co., Ltd., solids content 30%) in a 9:1 ratio. Propylene glycol monomethyl ether (PGM) was added to bring the solids content to 20%.

[0203] (Paint 3~7) The paints were formulated in the same way as paints 1 and 2, according to the formulations shown in Table 4. Note that the main component in all of the formulations in Table 4 is urethane acrylate resin.

[0204] [Table 4] [Examples 1-12, Comparative Examples 1-12] Paints 1 to 7 were applied to the films obtained in Production Examples 6 to 11, or to AW10U (PCPMMA multilayer film), in the combinations shown in Tables 5 and 6. A gravure roll with 200 lines for 1 μm, 150 lines for 2 μm, and 120 lines for 3.5 μm was used, with a line speed of 20 m / min and a gravure roll rotation speed of 20 rpm. After coating, the film was dried at 80°C for 1 minute to evaporate the solvent, and ultraviolet light was irradiated at the UV integrated light intensity shown in Tables 5 and 6 to form a hard coat layer with the film thickness shown in Tables 5 and 6. Various properties of the obtained films and laminates were evaluated. The results are shown in Tables 5 and 6.

[0205] In Comparative Examples 5-7, which used PCPMMA multilayer films, the Tg (115°C) of PMMA and the Tg (144°C) of PC were obtained. However, in the case of multilayer films, the higher Tg was considered to be the Tg of the acrylic resin film. [Table 5]

[0206] [Table 6] 〔result〕 Tables 5 and 6 show that a specific acrylic resin film has a glass transition temperature of 140°C or less and an elongation at the breaking point of 200% or more at 120°C, and a specific hard coat layer, and the crack elongation at 120°C is 50% or more, and the weight is 50 g / cm 2 The laminate of the example, which showed a Δ-haze of 1.0% or less in a steel wool abrasion test over 5 cycles, was found to have excellent formability and abrasion resistance. On the other hand, the laminate of the comparative example, which did not satisfy at least one of the above parameters, was found to be unable to simultaneously achieve formability and abrasion resistance. [Industrial applicability]

[0207] Because this laminate exhibits excellent moldability and wear resistance, it can be suitably used in various fields, including automotive interior applications such as in-vehicle displays.

Claims

1. A laminate comprising an acrylic resin film and a hard coat 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 lower, and an elongation at the breaking point at 120°C of 200% or more. The laminate has a crack elongation of 50% or more at 120°C and a density of 50 g / cm². ２ The Δ-haze in the steel wool abrasion test over 5 cycles was 1.0% or less. The acrylic resin film comprises 1 to 70% by mass of graft copolymer particles (A) having an average particle diameter of 20 nm to 200 nm, and 20% by mass or less of graft copolymer particles (B) having an average particle diameter larger than that of the graft copolymer particles (A). The graft copolymer particle (A) comprises a crosslinked elastomer (A1) and a graft polymer layer (A2) located on the surface side of the crosslinked elastomer (A1). The graft copolymer particle (B) comprises a crosslinked elastomer (B1) and a graft polymer layer (B2) located on the surface side of the crosslinked elastomer (B1). The hard coat layer is a cured product of a resin composition containing a polyfunctional (meth)acrylate and a photopolymerization initiator. The hard coat layer is obtained by curing the resin composition on a cooling roll at a temperature of 40 to 70°C by UV irradiation with an integrated UV light amount of 150 to 500 mJ / cm². The pencil hardness of the laminate is H or higher. A laminate in which the thickness of the hard coat layer is 0.6 μm to 10.0 μm.

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

3. The laminate according to claim 1 or 2, wherein the total content of crosslinked elastomer (A1) and crosslinked elastomer (B1) in the acrylic resin film is 15% by mass or less.

4. The laminate according to claim 3, wherein the average particle diameter of the graft copolymer particles (B) is 150 nm or more, and the laminate contains 1 to 10% by mass of the graft copolymer particles (B).

5. The laminate according to any one of claims 1 to 4, wherein the pencil hardness of the surface of the acrylic resin film without a hard coat layer is B or higher, and the elongation at the breaking point at 23°C is 20% or higher.

6. The laminate according to any one of claims 3 to 5, wherein the graft copolymer particles (A) contain 0.01 to 5% by mass of a reactive ultraviolet absorber.

7. The laminate according to Claim 1, wherein the curable composition for forming the hard coat layer is one or more selected from the group consisting of (i) "Z-879", "Z607-5AFH", and "Z607-26AFH" manufactured by Aica Kogyo Co., Ltd., (ii) "Unidic ESS108" manufactured by DIC Corporation, (iii) "NSC-7312" manufactured by Dainichi Seika Kogyo Co., Ltd., (iv) "Beamset 575" manufactured by Arakawa Chemical Industries, Ltd., (v) "UV-1700B" manufactured by Nippon Synthetic Chemical Industries, Ltd., (vi) "8BR-600" manufactured by Taisei Fine Chemical Co., Ltd., and (vii) "FA-3280H" manufactured by Nippon Chemical Paint Co., Ltd.

8. The laminate according to claim 1, wherein the content of the graft copolymer particles (A) in the acrylic resin film is 10% to 65%.

9. The laminate according to claim 8, wherein the content of the graft copolymer particles (B) in the acrylic resin film is 1% to 20%.

10. A molded article comprising a laminate according to any one of claims 1 to 9.

11. Front panel for an in-vehicle display, comprising the molded body described in claim 10.

12. A method for manufacturing a laminate comprising an acrylic resin film and a hard coat layer laminated on at least one side of the acrylic resin film, The process includes a step of curing the hard coat layer, which is applied to at least one side of the acrylic resin film, by UV irradiation on a cooling roll, The UV integrated light dose of the aforementioned UV irradiation is 150 to 500 mJ / cm². ２ And, The temperature of the cooling roll is 40 to 70°C. The acrylic resin film has a glass transition temperature of 140°C or lower, and an elongation at the breaking point at 120°C of 200% or more. The laminate has a crack elongation of 50% or more at 120°C, and a density of 50 g / cm². ２ The Δ-haze in the steel wool abrasion test over 5 cycles was 1.0% or less. The acrylic resin film comprises 1 to 70% by mass of graft copolymer particles (A) having an average particle diameter of 20 nm to 200 nm, and 20% by mass or less of graft copolymer particles (B) having an average particle diameter larger than that of the graft copolymer particles (A). The graft copolymer particle (A) comprises a crosslinked elastomer (A1) and a graft polymer layer (A2) located on the surface side of the crosslinked elastomer (A1). The graft copolymer particle (B) comprises a crosslinked elastomer (B1) and a graft polymer layer (B2) located on the surface side of the crosslinked elastomer (B1). The hard coat layer is a cured product of a resin composition containing a polyfunctional (meth)acrylate and a photopolymerization initiator. The pencil hardness of the laminate is H or higher. A method for manufacturing a laminate, wherein the thickness of the hard coat layer is 0.6 μm to 10.0 μm.

13. A method for manufacturing a molded article, comprising the step of shaping the laminate shown below at a molding temperature of 140°C or lower during preforming: A laminate comprising an acrylic resin film and a hard coat 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 lower, and an elongation at the breaking point at 120°C of 200% or more. The laminate has a crack elongation of 50% or more at 120°C, and a density of 50 g / cm². ２ The Δ-haze in the steel wool abrasion test over 5 cycles was 1.0% or less. The acrylic resin film comprises 1 to 70% by mass of graft copolymer particles (A) having an average particle diameter of 20 nm to 200 nm, and 20% by mass or less of graft copolymer particles (B) having an average particle diameter larger than that of the graft copolymer particles (A). The graft copolymer particle (A) comprises a crosslinked elastomer (A1) and a graft polymer layer (A2) located on the surface side of the crosslinked elastomer (A1). The graft copolymer particle (B) comprises a crosslinked elastomer (B1) and a graft polymer layer (B2) located on the surface side of the crosslinked elastomer (B1). The hard coat layer is a cured product of a resin composition containing a polyfunctional (meth)acrylate and a photopolymerization initiator. The hard coat layer is obtained by curing the resin composition on a cooling roll at a temperature of 40 to 70°C by UV irradiation with an integrated UV light amount of 150 to 500 mJ / cm². The pencil hardness of the laminate is H or higher. A laminate in which the thickness of the hard coat layer is 0.6 μm to 10.0 μm.

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