Laminate, molded article comprising same, and method for manufacturing molded article

Abstract

One or more embodiments of the present invention pertain to a laminate comprising a substrate layer and a cured resin layer, the substrate layer comprising an acrylic resin film, the acrylic resin film having a tensile elongation at break of 200% or more at 120 DEG C, and the cured resin layer having a tensile elongation at break of 200% or more at 120 DEG C; the cured resin layer is formed from a cured product of an active energy ray-curable resin composition containing a urethane acrylate resin, the curing index represented by formula 1 of the cured resin layer is 0.013 or less, and the tensile crack elongation at 120 DEG C of the laminate is 80% or more. [Formula 1] Curing Index = B / D. Wherein, in formula 1, B represents the area of an infrared absorption peak of the cured resin layer in the vicinity of a wave number of 810 cm <-1 > in FT-IR measurement, and D represents the area of an infrared absorption peak of the cured resin layer in the vicinity of a wave number of 1705 cm <-1 > in FT-IR measurement.

Description

TECHNICAL FIELD

[0001] The present application relates to a laminate comprising an acrylic resin film, a molded body comprising the laminate, and a method for producing the molded body. BACKGROUND

[0002] An acrylic resin film molded from an acrylic resin composition containing an elastomer is applied to various uses because it exhibits excellent properties such as transparency, hardness, weather resistance, and secondary moldability. As the uses of the acrylic resin film, for example, there are decorative and protective uses as a coating alternative for interior and exterior parts of vehicles, decorative and protective uses for exterior parts of electronic devices such as portable electronic devices, personal computers, and home appliances, and uses as building materials, and the like.

[0003] When an acrylic resin film is used in the decoration and protection of interior and exterior parts of vehicles, and electronic devices such as portable electronic devices, personal computers, and home appliances, sufficient scratch resistance and surface hardness for protecting the surface are required, and high secondary moldability for uniform lamination on the surface of an object article including a three-dimensional shape is needed. For example, in Patent Literature 1, a technique for achieving both secondary moldability and scratch resistance by providing a hard coat layer that exhibits high surface hardness after curing and exhibits high secondary moldability on the surface of an acrylic resin film substrate is proposed.

[0004] On the other hand, in these uses, there are many opportunities for the article to come into contact with the human body, and thus in summer or hot places, when sunscreen or insect repellent is applied to the skin of the human body, there is sometimes a problem of degradation of the surface of the article caused by the attachment of the sunscreen or insect repellent to the surface of the article, and resistance against them is also required. For example, N,N-diethyl 3-ethylbenzamide (hereinafter also referred to as DEET) has a small effect on the human body and has a high insect repellent effect on pests such as mosquitoes, and thus is widely used in the form of being blended as a main component in sprays and emulsions and the like for insect repellent. However, many plastic articles containing an acrylic resin have the following problem: by coming into contact with the skin of a person who has applied insect repellent containing DEET, the DEET contained in the insect repellent is attached to the surface of the plastic article, thereby corroding the surface of the article and degrading the appearance. Therefore, in Patent Literature 2, a laminate film having a certain resistance to DEET is proposed by providing a cured resin layer composed of a resin containing a unit derived from a polyurethane resin on an acrylic resin film.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: International Publication No. 2022 / 137768

[0008] Patent Literature 2: International Publication No. 2016 / 199847 SUMMARY

[0009] However, especially in recent years, in order to improve the persistence of the repellent effect, for example, in Japan, DEET is allowed to be compounded in an insect repellent at a concentration of up to 30%, and the demand for preventing surface deterioration of an article including an acrylic resin film caused by DEET has increased. An acrylic resin film resistant to such a high concentration of a DEET-containing agent is required.

[0010] The present application was made in view of the above-described problems, and provides a laminate including an acrylic resin film, having high surface hardness and secondary moldability, and good chemical resistance to an agent such as N,N-diethyl 3-ethylbenzamide, a molded body including the laminate, and a method for manufacturing the molded body.

[0011] One or more embodiments of the present application relate to a laminate including a substrate layer and a cured resin layer, the substrate layer including an acrylic resin film, the acrylic resin film having an elongation at break at 120°C of 200% or more, the cured resin layer being formed from a cured product of a active energy ray-curable resin composition including a polyurethane acrylate resin, a curing index of the cured resin layer represented by the following Formula 1 being 0.013 or less, the laminate having an elongation at crack at 120°C of 80% or more.

[0012] [Formula 1]

[0013] Curing index = B / D

[0014] In the above Formula 1, B represents an area of an infrared absorption peak in the vicinity of a wave number of 810 cm -1 in FT-IR measurement of the cured resin layer, and D represents an area of an infrared absorption peak in the vicinity of a wave number of 1705 cm -1 in FT-IR measurement of the cured resin layer.

[0015] One or more embodiments of the present application relate to a molded body including the above-described laminate and a molded body substrate, the laminate being laminated on a surface of the molded body substrate, the cured resin layer of the laminate being disposed closer to the surface side of the molded body than the substrate layer of the laminate.

[0016] One or more embodiments of the present application relate to a method for manufacturing a molded body, which is a method for manufacturing the above-described molded body, and laminates the above-described laminate on a surface of a molded body substrate using one or more methods selected from vacuum molding, pressure air molding, thin film insert injection molding, and 3D laminate molding.

[0017] According to the present application, it is possible to provide a laminate including an acrylic resin film, having high surface hardness and secondary moldability, and good chemical resistance to a reagent such as N,N-diethyl 3-ethylbenzamide, a molded body including the laminate, and a method for producing the molded body. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a drawing for explaining a method for calculating a curing index based on the area of an infrared absorption peak in FT-IR measurement at a wave number of 810 cm -1 nearby and the area of an infrared absorption peak in FT-IR measurement at a wave number of 1705 cm -1 nearby in the cured resin layer in Comparative Example 2. DETAILED DESCRIPTION

[0019] The inventors of the present application and others have conducted intensive studies in order to solve the above problems. As a result, it has been found that by using an acrylic resin film having a tensile elongation at break at 120°C of 200% or more in a laminate including a base material layer containing an acrylic resin film and a cured resin layer, and making the tensile crack elongation at 120°C of the laminate 80% or more, and forming the cured resin layer from a cured product of a reactive energy ray-curable resin composition containing a polyurethane acrylate resin, and making the value of a curing index represented by the following Formula 1 of the cured resin layer be in a specific range, that is, making the degree of curing be in a specific range, the surface hardness and secondary moldability of the laminate are high, and the chemical resistance to high concentrations of DEET is improved.

[0020] [Formula 1]

[0021] Curing index = B / D

[0022] In the above Formula 1, B represents the area of an infrared absorption peak in FT-IR measurement at a wave number of 810 cm -1 nearby, and D represents the area of an infrared absorption peak in FT-IR measurement at a wave number of 1705 cm -1 nearby in the cured resin layer.

[0023] In the present specification, the curing index is a parameter indicating the degree of curing of the cured resin layer, and more specifically, depends on the progress of the curing reaction of the reactive energy ray-curable resin composition containing a polyurethane acrylate resin. The infrared absorption peak in FT-IR measurement at a wave number of 810 cm -1 nearby corresponds to the out-of-plane bending vibration of the C-C double bond of the acryloyl group and / or the methacryloyl group, B reflects the content of the uncured acryloyl group and methacryloyl group in the cured resin layer, and the value becomes smaller as the curing reaction proceeds. The infrared absorption peak in FT-IR measurement at a wave number of 1705 cm -1The infrared absorption peak near the peak corresponds to the stretching vibration of the C-O double bond of the ester group, and D reflects the total amount of the unhardened acryl group and methacryl group in the hardened resin layer, and the ester group after the acryl group and methacryl group have undergone a curing reaction, and the total amount of the C-O double bond functional group before and after the curing reaction does not change in principle. The curing index B / D is a value obtained by dividing the peak area value of the functional group, i.e., the acryl group and methacryl group, which decreases as a result of the curing reaction, by the peak area value which does not change in principle as a result of the curing reaction, and the value depends on the degree of progress of the curing reaction, reaches a maximum in the unreacted state of the curing reaction, and becomes 0 if the curing reaction is completely performed, and can be used as a parameter indicating the degree of curing of the hardened resin layer.

[0024] In one or more embodiments of the present application, by making the curing index B / D of the hardened resin layer formed from the cured product of the active energy ray-curable resin composition containing the polyurethane acrylate resin be 0.013 or less, the chemical resistance to a high concentration, for example, 30 w / v% of DEET is improved.

[0025] In vehicle interior materials such as automotive interior materials, the instrument panel, door trim, and the like have portions that are irradiated with sunlight through the window glass, and these interior materials are required to have weather resistance (ultraviolet light degradation resistance) at a high temperature under sunlight irradiation to prevent surface degradation due to long-term use. An acrylic resin film itself is widely used as a decorative surface material for the surface of an automotive interior material, for example, by an in-mold or insert molding method, and has excellent weather resistance in addition to high secondary moldability, but when a hard coat or chemical resistance coating is applied for surface hardness and chemical resistance, the weather resistance can be poor. In one or more preferred embodiments of the present application, by making the curing index B / D be 0.013 or less, and by further containing a hindered amine-based light stabilizer having a reactive functional group and a compound having a hydrophobic group and a reactive functional group in the active energy ray-curable resin composition in addition to the polyurethane acrylate resin, it is possible to improve the weather resistance, and in particular, the weather resistance of the properties including the chemical resistance to reagents such as DEET.

[0026] In the present specification, when a numerical range is indicated by "~", the numerical range includes both end values (upper limit and lower limit). For example, the numerical range of "X ~ Y" is a range including both end values of X and Y, and is the same range as "X or more and Y or less". In addition, any number within the range, any range included in the range is specifically disclosed. In addition, in the present specification, when a plurality of numerical ranges are described, numerical ranges obtained by appropriately combining the upper limits and lower limits of different numerical ranges are included.

[0027] (Acrylic resin film)

[0028] The acrylic resin film preferably has a tensile elongation at break at 120°C of 200% or more. Thus, the tensile crack elongation at 120°C of the laminate with the cured resin layer becomes high, and the secondary moldability of the laminate easily becomes good. The upper limit of the tensile elongation at break at 120°C of the acrylic resin film is not particularly limited. In the present specification, the tensile elongation at break at 120°C of the acrylic resin film can be measured by the method described in the examples.

[0029] The acrylic resin film is preferably formed from an acrylic resin composition containing an acrylic resin and a graft copolymer particle containing a rubber component (also referred to as a crosslinked elastomer).

[0030] <Acrylic Resin>

[0031] As the acrylic resin, an acrylic resin known heretofore can be appropriately used. For example, from the viewpoint of hardness and moldability, when the total amount of the constituent units of the acrylic resin is 100% by mass, an acrylic resin (also referred to as a thermoplastic acrylic polymer) composed of a methyl methacrylate unit of 50 to 100% by mass and other constituent units of 0 to 50% by mass is preferably used. Note that the total amount of the methyl methacrylate unit and the other constituent units in the thermoplastic acrylic polymer is 100% by mass.

[0032] As the other constituent units, for example, constituent units derived from acrylic acid, an acrylic acid derivative, methacrylic acid, a methacrylic acid derivative, an aromatic vinyl derivative, a vinyl cyanide derivative, and the like can be given. The other constituent units can be a glutarimide structure, an internal lactone ring structure, an N-substituted maleimide structure, a non-substituted maleimide structure, and the like described later. The other constituent units contained in the acrylic resin can be one or a combination of two or more.

[0033] As the acrylic acid derivative, for example, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, and glycidyl acrylate, and the like can be given, but are not limited thereto.

[0034] As the methacrylic acid derivative, methacrylic acid esters such as ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-phenoxyethyl methacrylate, and isobornyl methacrylate, and the like can be given, but are not limited thereto.

[0035] As the aromatic vinyl derivative, for example, styrene, vinyltoluene, and α-methylstyrene can be given, but are not limited thereto.

[0036] As the vinyl cyanide derivative, acrylonitrile and methacrylonitrile, etc. can be given, but are not limited to these.

[0037] In order to improve the heat resistance, rigidity, surface hardness, etc. of the acrylic resin, a constitutional unit having a specific structure can be introduced to the acrylic resin by copolymerization, functional group modification, and modification, etc. As such a specific structure, for example, a glutarimide structure as shown in Japanese Patent Application Laid-Open No. 62-89705, Japanese Patent Application Laid-Open No. 02-178310, and International Publication No. 2005 / 54311, an internal lactone ring structure as shown in Japanese Patent Application Laid-Open No. 2004-168882 and Japanese Patent Application Laid-Open No. 2006-171464, a glutaric anhydride structure obtained by thermal condensation ring closure of a (meth) acrylic acid unit as shown in Japanese Patent Application Laid-Open No. 2004-307834, etc., a maleic anhydride structure as shown in Japanese Patent Application Laid-Open No. 5-119217, and an N-substituted maleimide structure and a non-substituted maleimide structure as shown in International Publication No. 2009 / 84541, etc. can be given. For example, by introducing these structures to the acrylic resin, the molecular chain becomes rigid. As a result, an effect of improvement of heat resistance, improvement of surface hardness, reduction of heat shrinkage, and improvement of chemical resistance, etc. can be expected.

[0038] The method of producing the acrylic resin is not particularly limited, and for example, a publicly known polymerization method such as suspension polymerization, bulk polymerization, solution polymerization, and emulsion polymerization, etc. can be applied. In addition, a publicly known radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization can be applied.

[0039] The content of the acrylic resin in the acrylic resin film 100 can be 20 to 100 mass%, preferably 20 to 99 mass%, more preferably 25 to 95 mass%, and further preferably 30 to 90 mass%.

[0040] < Graft Copolymer Containing Rubber Component >

[0041] The acrylic resin film preferably contains the graft copolymer particles (A) having an average particle diameter of 20 to 200 nm as the graft copolymer particles containing a rubber component. In this case, in the acrylic resin film, the graft copolymer particles (A) are preferably dispersed in an acrylic resin or a base containing an acrylic resin and other components. In addition, in the acrylic resin film, as the graft copolymer particles containing a rubber component, in addition to the graft copolymer particles (A), graft copolymer particles (B) having a larger average particle diameter than the graft copolymer particles (A) can be contained as needed. In this case, in the acrylic resin film, the graft copolymer particles (A) and the graft copolymer particles (B) are preferably dispersed in an acrylic resin or a base containing an acrylic resin and other components.

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

[0043] The crosslinked elastomer (Al) can be a publicly known crosslinked elastomer. The crosslinked elastomer (Al) is preferably an acrylate-based crosslinked elastomer (a crosslinked elastomer composed of a polymer in which an acrylate is a main component). In the present specification, the "main component" means a component having a content of 50% by mass or more.

[0044] The particle of the acrylate-based crosslinked elastomer (Al) can have a concentric spherical multilayer structure having a hard crosslinked resin layer having a glass transition temperature of room temperature (20 ± 5°C) or more or a semi-hard crosslinked resin layer having a glass transition temperature in the range of 0°C or room temperature inside the crosslinked elastomer layer. As such a hard or semi-hard crosslinked resin layer, for example, a hard crosslinked methacrylic resin particle as shown in Japanese Patent Application Publication No. 55-27576, a semi-hard crosslinked particle composed of methyl methacrylate-acrylate-styrene as shown in Japanese Patent Application Publication No. 4-270751, and a crosslinked rubber particle having a high degree of crosslinking, and the like can be mentioned. By having such a hard or semi-hard crosslinked resin layer, improvement in transparency and color tone, and the like can sometimes be expected.

[0045] The graft copolymer particles (A) preferably have a core-shell structure formed by graft polymerization of a monomer mixture for forming the graft polymer layer (A2) in the presence of the above-described particle of the acrylate-based crosslinked elastomer (Al).

[0046] The average particle diameter of the graft copolymer particles (A) is preferably from 50 to 150 nm, and particularly preferably from 50 to 120 nm. When the average particle diameter of the graft copolymer particles (A) is too small, there is a tendency for the impact resistance and the bending breakage resistance of the acrylic resin film to decrease. When the average particle diameter of the graft copolymer particles (A) is too large, there is a tendency for the transparency of the acrylic resin film to deteriorate, or for the film to easily become whitened by bending.

[0047] As the acrylic ester-based crosslinked elastomer (A1), a crosslinked elastomer particle obtained by polymerizing a monomer mixture (a-1) containing (a) an acrylic ester, (b) a multifunctional monomer having 2 or more non-conjugated double bonds per 1 molecule and capable of copolymerizing with the acrylic ester, and (c) another vinyl-based monomer capable of copolymerizing with the acrylic ester, can be preferably used.

[0048] The acrylic ester, the multifunctional monomer, and the other vinyl-based monomer can be all mixed and polymerized in one step. Alternatively, the composition of the acrylic ester, the multifunctional monomer, and the other vinyl-based monomer can be appropriately changed, or the acrylic ester, the multifunctional monomer, and the other vinyl-based monomer can be polymerized in multiple steps of two or more steps, with the same composition, for the purpose of adjusting the toughness, the whitening resistance, and the like of the acrylic resin film.

[0049] As the acrylic ester, from the viewpoint of excellent polymerizability, low cost, and the ability to obtain a polymer having a low glass transition temperature (Tg), an aliphatic ester of acrylic acid is preferable, an aliphatic alkyl acrylate is more preferable, and an aliphatic alkyl acrylate having an alkyl group having a carbon number of from 1 to 22 is particularly preferable. The aliphatic alkyl group can be any one of a straight chain, a branched chain, and a cyclic (also referred to as alicyclic) group.

[0050] As a specific example of the preferable aliphatic alkyl acrylate, for example, mention can be made of 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. One of them can be used alone, or two or more of them can be used in combination.

[0051] In 100% by mass of the monomer mixture (a-1), the amount of the acrylic ester (preferably an aliphatic alkyl acrylate, and more preferably an aliphatic alkyl acrylate having an alkyl group having a carbon number of from 1 to 22) is preferably from 50 to 99.9% by mass, more preferably from 70 to 99% by mass, and most preferably from 80 to 99% by mass. If the amount of the acrylic ester is 50% by mass or more, the impact resistance and the elongation at the time of tensile breakage of the acrylic resin film are good, and cracks are less likely to occur at the time of secondary molding.

[0052] As the other vinyl-based monomer, for example, there can be mentioned methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, and the like; acrylonitrile and methacrylonitrile; styrene, vinyltoluene, and a-methylstyrene; acrylic acid; acrylate derivatives other than aliphatic alkyl acrylates such as phenyl acrylate and benzyl acrylate; methacrylic acid; methacrylic acid derivatives such as β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and glycidyl methacrylate; maleic anhydride; maleic acid derivatives such as N-alkylmaleimide and N-phenylmaleimide; and the like. One of them can be used alone, or two or more of them can be used in combination. Of these, from the viewpoints of weather resistance and transparency, as the other vinyl-based monomer, one or more monomers selected from the group consisting of methacrylates and aromatic vinyl derivatives are particularly preferred.

[0053] The amount of the other vinyl-based monomer in the monomer mixture (a-1) is preferably 0 to 49.9% by mass, more preferably 0 to 30% by mass, and further preferably 0 to 20% by mass, based on 100% by mass of the monomer mixture (a-1). If the amount of the other vinyl-based monomer exceeds 49.9% by mass, the impact resistance of the acrylic resin film tends to decrease, the elongation at the time of tensile fracture decreases, and cracks tend to occur at the time of secondary molding.

[0054] As the multifunctional monomer, a monomer generally used as a crosslinking agent and / or a graft crosslinking agent can be preferably used. As the multifunctional monomer, for example, there can be mentioned 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, dipropylene glycol dimethacrylate, and the like. One of these multifunctional monomers can be used alone, or two or more of them can be used in combination.

[0055] As these multifunctional monomers, multifunctional monomers having a function as a graft crosslinking agent are more preferable because they increase the number of graft bonds of the graft polymer layer (A2) to the crosslinked elastomer (Al) described later, as a result of which the graft copolymer particle (A) has good dispersibility in the acrylic resin, the resistance to cracking in tensile and bending deformation is improved, and stress whitening is reduced. As the multifunctional monomers having such a function as a graft crosslinking agent, monomers having an allyl group such as allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and diallyl maleate are preferable, and allyl methacrylate and allyl acrylate are particularly preferable.

[0056] The amount of the multifunctional monomer in the monomer mixture (a-1) 100 mass% is preferably 0.1 to 10 mass%, and more preferably 1.0 to 4 mass%. If the amount of the multifunctional monomer is within the above range, it is preferable from the viewpoint of the resistance to bending breakage, the resistance to bending whitening, and the flowability of the resin at the time of molding of the acrylic resin film.

[0057] In the acrylic ester-based crosslinked elastomer (Al), the amount of the multifunctional monomer can be increased in the interior and in the vicinity of the surface of the crosslinked elastomer (Al) for the purpose of improving the grafting efficiency of the graft polymer layer (A2) described later. Specifically, as shown in Japanese Patent No. 1460364, Japanese Patent No. 1786959, and the like, by increasing the content of the multifunctional monomer having a function as a graft crosslinking agent in the vicinity of the surface of the crosslinked elastomer (Al) more than in the interior, the graft polymer layer of the graft copolymer particle (A) can be improved in coverage, the dispersibility in the acrylic resin is good, or the decrease in the resistance to cracking due to peeling at the interface between the graft copolymer particle (A) and the acrylic resin can be suppressed. Furthermore, since sufficient coverage can be obtained with a relatively small amount of the graft polymer layer (A2), the amount of the graft copolymer particle (A) for introducing a prescribed amount of the crosslinked elastomer (Al) into the acrylic resin composition can be reduced, and thus the melt viscosity of the acrylic resin composition is reduced, and an improvement in the melt processability of the acrylic resin film, the improvement in the film processing precision, the improvement in the surface hardness, and the like can be expected.

[0058] For the purpose of controlling the molecular weight and crosslinking density of the acrylate-based crosslinked elastomer (Al), and the purpose of controlling the thermal stability and the like by the reduction of the double bond terminal of the polymer accompanying the disproportionation termination reaction at the time of polymerization, a chain transfer agent can be used in addition to the monomer mixture (a-1). The chain transfer agent can be used selected from the chain transfer agents generally used in radical polymerization. As the chain transfer agent, for example, monofunctional or polyfunctional mercaptan compounds having 2 to 20 carbon atoms such as n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, mercapto acid, thiophenol, carbon tetrachloride or a mixture thereof and the like are preferred. The addition amount of the chain transfer agent is preferably 0 to 1.0 parts by mass, more preferably 0 to 0.2 parts by mass, with respect to 100 parts by mass of the total amount of the monomer mixture (a-1).

[0059] The particles of the crosslinked elastomer (Al) can be a single layer composed of the above-described acrylate-based crosslinked elastomer (Al), or can be a multilayer structure including 2 or more layers composed of the above-described acrylate-based crosslinked elastomer (Al).

[0060] The particles of the crosslinked elastomer (Al) can also have an acrylate-based crosslinked elastomer (Al) in at least one layer of the multilayer particles including a hard or semi-hard crosslinked resin layer. As the monomers constituting the hard or semi-hard crosslinked resin layer, mention can be made of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate, and the like, methacrylate esters; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate, and the like, alkyl acrylate esters; styrene and a-methylstyrene, and the like, aromatic vinyl derivatives; acrylonitrile, and the like, vinyl cyanide derivatives; maleic anhydride; maleimide-based, and the like, maleic acid derivatives; and polyfunctional monomers having two or more non-conjugated double bonds per 1 molecule, and the like. As the polyfunctional monomers, the same polyfunctional monomers as those used in the polymerization of the acrylate-based crosslinked elastomer (Al) layer can be used. Of these, one or more selected from the group consisting of methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, styrene, and acrylonitrile, and the like, are particularly preferred. Furthermore, in the polymerization of the hard or semi-hard crosslinked resin layer, in addition to these monomers, a chain transfer agent can also be used for the purpose of controlling the crosslinking density, and the like, and for the purpose of controlling the thermal stability, and the like, by reducing the double bond terminals of the polymer. The chain transfer agent can be the same as that used in the polymerization of the acrylate-based crosslinked elastomer (Al) layer. The amount of the chain transfer agent added is preferably 0 to 2 parts by mass, and more preferably 0 to 0.5 parts by mass, relative to 100 parts by mass of the total amount of the monomer mixture constituting the hard or semi-hard crosslinked resin layer.

[0061] When the graft copolymer particles (A) are of a two-layer structure of the particles of the crosslinked elastomer (Al) as the core particles and the graft polymer layer (A2) as the shell layer, the graft copolymer particles (A) are typically obtainable by forming the graft polymer layer (A2) by graft copolymerization of a monomer mixture (a-2) containing 50 to 100 mass% of a methacrylate ester and 0 to 50 mass% of another vinyl-based monomer copolymerizable with the methacrylate ester (wherein the total of the methacrylate ester and the other vinyl-based monomer is 100 mass%) in the presence of the particles of the crosslinked elastomer (Al).

[0062] The amount of the methacrylate ester in the monomer mixture (a-2) 100% by mass is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 97% by mass or more, from the viewpoints of (a) ensuring compatibility with the acrylic resin as the base, and (b) inhibiting a decrease in the flexibility of the film caused by impregnation of a solvent or the like upon coating on an acrylic resin film, whitening and cracking caused by stretching upon molding.

[0063] In the monomer mixture (a-2), as the methacrylate ester, for example, there are mentioned methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, and the like, and aromatic methacrylate esters such as phenyl methacrylate and benzyl methacrylate. Of these, methacrylate esters having an alkyl group having 1 to 4 carbon atoms are preferred.

[0064] In the monomer mixture (a-2), as the other vinyl-based monomer, an alkyl acrylate having 2 or more carbon atoms in the alkyl group can be used. As the alkyl acrylate having 2 or more carbon atoms in the alkyl group, for example, 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 is preferred, one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate is more preferred, and n-butyl acrylate is particularly preferred.

[0065] In the monomer mixture (a-2), as the other vinyl-based monomer, aromatic vinyl derivatives such as styrene and its nucleus-substituted compounds, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid, methacrylic acid derivatives, acrylic acid, acrylic acid derivatives, N-substituted maleimides, maleic anhydride, methacrylamide, and acrylamide can also be used.

[0066] The monomer mixture (a-2) preferably contains a reactive ultraviolet absorber as the other vinyl-based monomer. That is, the graft polymer layer (A2) preferably contains a constitutional unit derived from the reactive ultraviolet absorber. When the monomer mixture (a-2) contains the reactive ultraviolet absorber, an acrylic resin film having good weather resistance and chemical resistance is easily obtained.

[0067] As the reactive ultraviolet absorber, a publicly known reactive ultraviolet absorber can be used without particular limitation. From the viewpoints of the moldability and weather resistance of the acrylic resin film, as the reactive ultraviolet absorber, a compound represented by the following general formula (1) is preferred.

[0068]

[0069] In General Formula (1), X is a hydrogen atom or a halogen atom, R1is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 6 carbon atoms, R2is a linear or branched alkylene group having 2 to 10 carbon atoms, and R3is a hydrogen atom or a methyl group.

[0070] As the reactive ultraviolet absorber represented by General Formula (1), specifically, 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, 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'-tert-butylphenyl)-2H-benzotriazole, and the like can be given. From the viewpoint of cost and workability, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole is preferably used. In the present specification, (meth)acryloyl is a general term for acryloyl and methacryloyl.

[0071] The content of the constitutional unit from the reactive ultraviolet absorber in the graft polymer layer (A2) 100 mass% is preferably 0.01 to 5 mass%, more preferably 0.1 to 3 mass%.

[0072] The graft polymer layer (A2) is preferably obtained by performing graft copolymerization of a monomer mixture (a-2) containing an alkyl methacrylate 70 to 99.5 mass%, an alkyl acrylate having 2 or more carbon atoms in the alkyl group 0.5 to 30 mass%, and other vinyl monomers 0 to 19 mass% (wherein the total of the alkyl methacrylate, the alkyl acrylate, and the other vinyl monomers is 100 mass%) in the presence of 5 to 90 parts by mass of the crosslinked elastomer particles (A1) by at least one step or more. Herein, the total amount of the crosslinked elastomer (A1) particles and the monomer mixture (a-2) satisfies 100 parts by mass.

[0073] In the production of the graft copolymer particles (A), particularly in the graft copolymerization of the monomer mixture (a-2) in the presence of the particles of the crosslinked elastomer (A1), such as the particles of the acrylate-based crosslinked elastomer (A1), a polymer component (free polymer) not grafted to the particles of the acrylate-based crosslinked elastomer (A1) is sometimes produced. Such a free polymer can be used as a part or all of the substance constituting the acrylic resin that constitutes the matrix phase of the acrylic resin composition and the acrylic resin film.

[0074] A chain transfer agent can be added to the monomer mixture (a-2) for the purpose of controlling the molecular weight of the polymer, controlling the grafting rate to the crosslinked elastomer (A1) and the amount of production of the free polymer not bonded to the crosslinked elastomer (A1), and controlling the thermal stability and the like by reduction of the double bond terminal of the polymer through disproportionation termination reaction accompanying polymerization. Such a chain transfer agent can be used as the same chain transfer agent as that usable in the polymerization of the crosslinked elastomer (A1). The amount of use of the chain transfer agent is preferably 0 to 2 parts by mass, more preferably 0 to 0.5 parts by mass, relative to 100 parts by mass of the total amount of the monomer mixture (a-2).

[0075] The grafting rate of the monomer mixture (a-2) to the particles of the crosslinked elastomer (A1), that is, the grafting rate of the graft copolymer particles (A) is preferably 5 to 250%, more preferably 10 to 200%, further preferably 20 to 150%. If the grafting rate is less than 5%, there is a tendency that the whitening resistance to bending of the acrylic resin film decreases, or the transparency decreases, or the elongation at the time of tensile fracture decreases and cracks are easily produced at the time of secondary molding. If the grafting rate exceeds 250%, there is a tendency that the melt viscosity of the acrylic resin composition easily becomes high at the time of film molding and the moldability of the acrylic resin film decreases. In the present specification, the grafting rate of the graft copolymer particles (A) can be found by the following formula, using the insoluble component as the grafted component, by dissolving the powder of the graft copolymer particles (A) in methyl ethyl ketone and separating into the insoluble component and the soluble component.

[0076] Grafting rate (%) = 100 x (mass fraction of insoluble component - mass fraction of crosslinked elastomer (A1)) / mass fraction of crosslinked elastomer (A1)

[0077] The average particle diameter d (nm) of the acrylic ester-based crosslinked elastomer (A1) in the acrylic resin film and the amount w (mass %) of the multifunctional monomer used in the acrylic ester-based crosslinked elastomer (A1) preferably satisfy the relationship: 0.015d ≤ w ≤ 0.06d, and more preferably satisfy 0.02d ≤ w ≤ 0.05d. If the amount of the multifunctional monomer is in the range of the above relationship, it has the advantage that the elongation at the secondary molding of the acrylic resin film is not easily reduced, cracks are not easily generated at the molding process or cutting, the transparency is excellent, and stress whitening is not easily generated at the bending or tensile deformation at normal temperature (about 25°C), high temperature above the softening temperature of the acrylic resin film, or the temperature region between normal temperature and the Tg of the crosslinked elastomer (A1), and further, haze or whitening of the film due to moisture caused by the moisture permeating into the acrylic resin film by the contact of the acrylic resin film with moisture is not easily generated.

[0078] The graft copolymer particle (B) has a crosslinked elastomer (B1) as a rubber component, like the graft copolymer particle (A). The graft copolymer particle (B) typically has a graft polymer layer (B2) located more on the surface layer side than the crosslinked elastomer (B1), like the graft copolymer particle (A). That is, the graft copolymer particle (B) preferably has a crosslinked elastomer (B1) of a core layer and a graft polymer layer (B2) of a shell layer. In addition, both the core layer and the shell layer can be a multilayer structure.

[0079] The graft copolymer particle (B) can be substantially the same as the graft copolymer particle (A) in terms of raw materials and manufacturing methods, etc., except that the average particle diameter is larger than that of the graft copolymer particle (A). It is preferable that the particles of the acrylic ester-based crosslinked elastomer (B1) have a concentric spherical multilayer structure having a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer. As such a hard or semi-hard crosslinked resin layer, for example, there are hard crosslinked methacrylic resin particles as shown in Japanese Patent Application Publication No. S55-27576, and crosslinked particles having a semi-hard layer composed of a methyl methacrylate-acrylate-styrene copolymer or the like as shown in Japanese Patent Application Publication No. H4-270751, International Publication No. 2014 / 41803, and the like. By introducing such a hard or semi-hard crosslinked resin layer, the transparency, the resistance to bending whitening, the resistance to bending breakage, and the like of the graft copolymer particle (B) having a larger particle diameter than the graft copolymer particle (A) can be improved.

[0080] The average particle diameter of the graft copolymer particles (B) is preferably 150 to 400 nm, and more preferably 200 to 350 nm. The graft copolymer particles (B) having a large average particle diameter are more effective than the graft copolymer particles (A) having a small average particle diameter in causing plastic deformation (cracking) in the acrylic resin phase around the graft copolymer particles in response to an external force on the acrylic resin material. Thus, the graft copolymer particles (B) are very excellent in imparting the effects of impact resistance and crack resistance to the acrylic resin material. On the other hand, the graft copolymer particles (B) are inferior to the graft copolymer particles (A) in terms of, for example, resistance to whitening upon bending and / or resistance to solvent whitening. Thus, for example, by adding a small amount of the graft copolymer particles (B) to an acrylic resin composition containing an acrylic resin and the graft copolymer particles (A), it is possible to expect the following effects: (a) to reduce the total content of soft components in the acrylic resin film without reducing the surface hardness of the acrylic resin film and the laminate, (b) to prevent whitening upon application of an external stress to the acrylic resin film, upon coating of a coating liquid containing an organic solvent, and / or upon molding processing, and (c) to effectively improve the crack resistance and secondary molding properties of the acrylic resin film and the laminate. As an acrylic resin film using the graft copolymer particles (A) in combination with a small amount of the graft copolymer particles (B), for example, there are the acrylic resin films disclosed in International Publication No. 2013 / 051239 and International Publication No. 2019 / 181752.

[0081] In the present specification, the average particle diameter of the graft copolymer particles (A) and the graft copolymer particles (B) is the average particle diameter on a volume basis (also referred to as a mass basis), and can be measured using a particle size distribution measuring device of the laser diffraction / scattering type, such as a Microtrac particle size distribution measuring device MT3000 manufactured by NIKKISO CO., LTD., in a latex state, by a dynamic light scattering method.

[0082] The method for producing the graft copolymer particles (A) and the graft copolymer particles (B) is not particularly limited, and known emulsion polymerization, miniemulsion polymerization, suspension polymerization, and solution polymerization, and the like can be applied. From the viewpoint of a large adjustment range of the resin structure, emulsion polymerization is particularly preferable.

[0083] As the initiator used in the emulsion polymerization of the graft copolymer particles (A) and / or the graft copolymer particles (B), known initiators such as organic peroxides, inorganic peroxides, and azo compounds can be used. Specifically, mention can be made of organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauryl peroxide, alkyl percarbonates, and alkyl peroxides; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; and azo compounds such as azobisisobutyronitrile. These can be used singly or in combination of two or more.

[0084] These initiators can be used as (a) a radical polymerization initiator of the thermal decomposition type, or (b) a redox-type polymerization initiator system in which these initiators, a catalyst such as ferrous sulfate, and a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and hydroxypyruvic acid are combined. Note that the catalyst can be used as a complex with ethylenediaminetetraacetic acid-2-sodium salt or the like to ensure water solubility.

[0085] The surfactant (also referred to as an emulsifier) used in the emulsion polymerization of the graft copolymer particles (A) and / or the graft copolymer particles (B) is not particularly limited. Known surfactants can be widely used in the emulsion polymerization. As the preferred surfactant, mention can be made of, for example, (a) anionic surfactants such as sodium, potassium, and ammonium salts of alkyl sulfonic acids, alkylbenzenesulfonic acids, dialkylsulfosuccinic acids (dioctylsulfosuccinic acid and the like), alkyl sulfates, fatty acid sodium salts, polyoxyethylene alkyl ether acetic acids, polyoxyethylene alkyl ether phosphoric acids, alkyl phosphoric acids, alkyl ether phosphoric acids, alkylphenyl ether phosphoric acids, and surfactin; and (b) nonionic surfactants such as reaction products of alkylphenols with propylene oxide and / or ethylene oxide, and reaction products of aliphatic alcohols with propylene oxide and / or ethylene oxide. These surfactants can be used singly or in combination of two or more.

[0086] The graft copolymer particles (A) or the graft copolymer particles (B) can be separated and recovered from the latex of the graft copolymer particles (A) or the latex of the graft copolymer particles (B) obtained by the emulsion polymerization by known methods. For example, after the graft copolymer particles are coagulated by adding a water-soluble electrolyte such as calcium chloride, magnesium sulfate, magnesium chloride, calcium acetate, sodium chloride, hydrochloric acid, acetic acid, and sulfuric acid to the latex, or after the graft copolymer particles are coagulated by separating and freezing the latex, the graft copolymer particles (A) or the graft copolymer particles (B) can be separated and recovered by filtration, washing, and drying of the solid components. Alternatively, the graft copolymer particles (A) or the graft copolymer particles (B) can be separated and recovered by spray drying, freeze coagulation, freeze drying, or the like of the latex.

[0087] For the purpose of reducing appearance defects and / or internal foreign matters of the acrylic resin film, it is preferable to filter the latex of the graft copolymer particles (A) or the latex of the graft copolymer particles (B) in advance with a filter and / or a screen mesh, thereby removing environmental foreign matters and substances that are causes of foreign matter defects such as polymer dirt, before the separation and recovery of the graft copolymer particles (A) or the graft copolymer particles (B).

[0088] As the filter and the screen mesh, publicly known filters and screen meshes used in the filtration of liquid media can be used. The form of the filter and the screen mesh, the pore diameter of the filter and the screen mesh, the filtration precision, and the filtration capacity, etc. can be appropriately selected according to the purpose of the object, the kind, the size, and the amount of the foreign matters to be removed. The pore diameter and the filtration precision of the filter and the screen mesh are, for example, preferably 2 times or more larger than the average particle diameter of the graft copolymer particles (A) or the graft copolymer particles (B), respectively.

[0089] The content of the graft copolymer particles (A) in the acrylic resin film 100 mass% is not particularly limited, and is preferably 10 to 70 mass%, more preferably 15 to 50 mass%, and further preferably 20 to 45 mass%.

[0090] The content of the graft copolymer particles (B) in the acrylic resin film 100 mass% is not particularly limited, and can be appropriately adjusted within a range that is preferable for the application of use without impairing the quality of the laminate of the present application, but from the viewpoint of suppressing stress whitening at the time of stretching or bending processing of the acrylic resin film and haze of the film after contact with moisture, it is preferable not to be excessively used, and is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and most preferably 0 to 5 mass%. In addition, the graft copolymer particles (B) can not be contained at all.

[0091] <Other Components>

[0092] The acrylic resin film (acrylic resin composition constituting the acrylic resin film) can contain, as necessary, a thermoplastic resin which is at least partially compatible with the acrylic resin, within a range not impairing the object of the present application. As such a thermoplastic resin, for example, a styrene resin, a polycarbonate resin, an amorphous saturated polyester resin, an olefin-methacrylic acid derivative resin, an olefin-acrylic acid derivative resin, a polyimide resin, a polylactic acid resin, and a PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) resin, and the like can be exemplified. As the styrene resin, for example, a styrene-acrylonitrile resin, a styrene-(meth)acrylic acid resin, a styrene-maleic anhydride resin, a styrene-N-substituted or unsubstituted maleimide resin, a styrene-acrylonitrile-butadiene resin, and a styrene-acrylonitrile-acrylate resin, and the like can be exemplified. Among them, from the viewpoint that the compatibility with the acrylic resin is excellent and that the bending crack resistance, the solvent resistance, the chemical resistance, and the low moisture absorption of the acrylic resin film can be improved, it is preferable that the thermoplastic resin be selected from one or more of a styrene resin, a polycarbonate resin, and a polyimide resin. In the present specification, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid.

[0093] In addition, the acrylic resin film (acrylic resin composition constituting the acrylic resin film) can contain, as necessary, a hitherto known additive used in the acrylic resin film, within a range not impairing the object of one embodiment of the present application. As such an additive, an antioxidant, an ultraviolet absorber, a light stabilizer, a light diffusing agent, a matting agent, a lubricant, a coloring agent such as a pigment and a dye, a fibrous filler, an antiblocking agent composed of organic particles and / or inorganic particles, an infrared reflector composed of a metal and / or a metal oxide, a plasticizer, an antistatic agent, and the like can be exemplified. The additive is not limited to these. These additives can be used in an arbitrary amount according to the kind of the additive, within a range not impairing the object of one embodiment of the present application, or for the purpose of enhancing the effect of one embodiment of the present application.

[0094] <Physical properties of the acrylic resin film>

[0095] The glass transition temperature (Tg) of the acrylic resin film is preferably 145°C or lower, more preferably 140°C or lower, further preferably 135°C or lower, and particularly preferably 130°C or lower. If the glass transition temperature of the acrylic resin film is 145°C or lower, it has the advantage that the film can be molded without increasing the molding temperature, and the generation of cracks at the time of molding can be suppressed. In addition, the lower limit of the glass transition temperature of the acrylic resin film is not particularly limited, and from the viewpoint of preventing the print from shifting at the time of drying and improving the reliability, it is preferably 100°C or higher, for example. The glass transition temperature of the acrylic resin film can be found by a known method such as differential scanning calorimetry (DSC).

[0096] The thickness of the acrylic resin film is not particularly limited, and for example, is preferably 50 to 350 μm, more preferably 60 to 300 μm, and particularly preferably 70 to 250 μm. If the thickness of the acrylic resin film is within the above range, the film has sufficient stretchability, excellent workability, and excellent appearance after being laminated to a resin substrate (molded body substrate) when a molded body is produced. In the present specification, the thickness of the acrylic resin film is measured by the method described in the Examples.

[0097] From the viewpoint of excellent surface hardness and scratch resistance, the pencil hardness of the acrylic resin film, measured based on JIS K 5600-5-4, is preferably a hardness of 2B or more, more preferably a hardness of B or more, and particularly preferably a hardness of HB or more under a load of 500 g.

[0098] <Method for producing acrylic resin film>

[0099] The acrylic resin film can be produced by a publicly known processing method. As specific examples of the publicly known processing method, there are, for example, melt processing, calender molding, press molding, and solvent casting, and the like. As the melt processing, for example, there are, for example, a blow molding method and a T-die extrusion method, and the like. In the solvent casting, for example, the acrylic resin composition is dissolved and dispersed in a solvent, and then the obtained dispersion liquid (slurry) is cast in a film shape on a belt-like substrate. Subsequently, the solvent is volatilized from the cast slurry in a film shape, and thereby the acrylic resin film is obtained.

[0100] Among these methods, the melt processing method, particularly the T-die extrusion method and the calender molding method, are preferred, since no solvent is used. According to the melt processing method, the thickness of the produced film is less limited, and a film having excellent surface properties can be produced at a high productivity, and the load of the solvent on the natural environment and the working environment can be reduced, and the production cost can be reduced.

[0101] When the acrylic resin composition is molded into a film by the melt processing method or the solvent casting method, from the viewpoint of improving the appearance quality of the acrylic resin film, it is preferred to remove environmental foreign matter, polymerization dirt, deteriorated resin, and the like in the acrylic resin composition, which are causes of appearance defects, internal foreign matter, and the like of the acrylic resin film, by filtration using a filter or a screen.

[0102] In the case of producing a film by melt processing, the filtration of the acrylic resin composition can be performed at one or more of any of the following timings: during the melt kneading of the acrylic resin and the raw material mixture including the graft copolymer particles; and during the melt film production process using a T-die. In the case of the solvent casting method, the filtration of the acrylic resin composition can be performed before the acrylic resin, the graft copolymer particles (A), the graft copolymer particles (B), and other components are mixed with a solvent and before the casting film production.

[0103] As such a filter and a screen, the filter and the screen can be used without particular limitation as long as they have heat resistance and durability corresponding to the melt processing conditions, or resistance to solvents and pastes for casting and the like.

[0104] When an acrylic resin film is produced by melt processing, particularly in order to obtain a high-quality acrylic resin film, a filter having a large filtration capacity and in which the residence of molten resin, which is a cause of the generation of resin degradation products and crosslinked products that impair the quality of the film, is less is preferred. For example, from the viewpoints of filtration efficiency and productivity, a leaf disc filter and a folding filter are preferably used.

[0105] When an acrylic resin film is produced by a T-die extrusion method, in order to improve the thickness accuracy of the film, for example, an automatic die device that measures the film thickness distribution of the film extrusion-molded in the TD direction (a direction perpendicular to the extrusion direction) on line and automatically adjusts the die lip gap of the T-die in the extrusion based on the measurement result can be used. By using an appropriate control method and applying the automatic die, the thickness accuracy of the acrylic resin film can be improved.

[0106] In the production of an acrylic resin film, as needed, when the film is subjected to a molding process, the film in a molten state is simultaneously contacted (sandwiched) with a cooling roll or a cooling belt on both sides, and thus a film having more excellent surface properties can be obtained. In this case, it is preferred that the film in a molten state be simultaneously contacted with a cooling roll or a cooling belt maintained at a temperature of -80°C or higher than the glass transition temperature of the acrylic resin composition, preferably -70°C or higher than the glass transition temperature. The upper limit of the temperature of the cooling roll or the cooling belt is not particularly limited, and for example, can be +10°C or lower than the glass transition temperature of the acrylic resin composition. As at least one of the rolls used for such sandwiching, for example, a roll having an elastic metal sleeve as disclosed in Japanese Patent Application Publication No. 2000-153547 and Japanese Patent Application Publication No. H11-235747, and the like is more preferably used, and the roll mirror surface or a specific surface shape is transferred using a low sandwiching pressure. Thereby, a film (a) having less residual strain and excellent smoothness, and / or (b) having a moderate surface roughness, excellent lubricity of the film surface, and less internal strain in which the adhesion of the films to each other is suppressed can be obtained.

[0107] In addition, depending on the purpose, uniaxial stretching or biaxial stretching can be performed after the film is formed. The uniaxial stretching or biaxial stretching can be performed using a publicly known stretching device. The biaxial stretching can be performed by a publicly known method such as sequential biaxial stretching, simultaneous biaxial stretching, and longitudinal stretching followed by stretching in the transverse direction while relaxing the longitudinal direction to suppress the bowing phenomenon of the film.

[0108] (Base material layer)

[0109] The base material layer contains an acrylic resin film. The base material layer can have a smooth surface, and in a range not impairing the effects of the present application, a fine line, a prism, a concave-convex shape, a three-dimensional decoration, a matte surface, a rough surface having a certain surface roughness, knurling to the film end, or the like can be imparted to one side or both sides of the base material layer as needed depending on the use. The imparting of such a surface shape can be performed by a publicly known method. For example, a method in which both surfaces (also referred to as both sides) of a film immediately after extrusion or a formed film being fed out from a feeding device are sandwiched by two rollers or belts having a surface shape on at least one surface (also referred to as one side), and thus the surface shape of the rollers is transferred. In addition, in a range not impairing the effects of the present application, a print decoration layer can be laminated on one side or both sides of the acrylic resin film of the base material layer as needed depending on the use.

[0110] (Cured resin layer)

[0111] The cured resin layer is formed from a cured product of a curable energy ray resin composition (hereinafter also simply referred to as "curable resin composition") containing a polyurethane acrylate resin, or preferably containing a polyurethane acrylate resin, a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group. Specifically, the cured resin layer can be formed by laminating a curable resin composition containing a polyurethane acrylate resin, or preferably a curable resin composition containing a polyurethane acrylate resin, a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group on the base material layer containing an acrylic resin film by coating, and then curing it. The cured resin layer can be formed on one side of the base material layer containing an acrylic resin film, or on both sides. From the viewpoint of not requiring a large-scale heating device or the like, fast curing, and excellent cost, it is preferable that the curable resin composition for the cured resin layer have energy ray curability, and more preferably that the polyurethane acrylate resin, the hindered amine-based light stabilizer having a reactive functional group, and the compound having a hydrophobic group and a reactive functional group have energy ray curability.

[0112] In the laminate of one or more embodiments of the present application, it is required that the cured resin layer has a high crack elongation while improving the surface hardness. Thus, when the laminate is subjected to secondary molding according to the shape of the molded body, no cracking or significant whitening occurs with stretching or bending processing or the like.

[0113] However, in general, in the cured resin layer, the cured product of the curable resin composition containing the curable resin is inhibited from deforming the surface of the cured product with respect to external stress by highly cross-linking and / or containing a filler having high hardness, thereby exhibiting surface hardness and scratch resistance. Surface hardness and scratch resistance are properties opposite to deformability and stretchability, and in the cured resin layer, it is difficult to balance them.

[0114] In order to impart high stretchability at the time of secondary molding while maintaining the surface hardness of the cured resin layer, the curable resin (e.g., polyurethane acrylate resin) used in the cured resin layer can be designed by, for example, the methods of (1) to (3) below. In the cured resin layer, any of the methods of (1) to (3) or the like can be used alone or in appropriate combination. Note that the cured resin layer can appropriately use a commercially available curable resin composition containing a polyurethane acrylate resin capable of imparting high stretchability at the time of secondary molding while maintaining the surface hardness of the cured resin layer.

[0115] (1) The cured resin composition is designed to have a glass transition temperature after curing between room temperature and the secondary molding temperature (e.g., about 110 to 140°C), which enables design to be hard at room temperature and to soften and deform at the secondary molding temperature. Thus, the cured product of the curable resin (cured resin layer) exhibits high surface hardness at room temperature and high stretchability at the time of secondary molding.

[0116] (2) It is designed to make the cross-linking structure of the curable resin after curing non-uniform by using a plurality of different structures of curable resin in combination, so as to have a relatively hard portion having a high cross-linking density and a relatively soft portion having a low cross-linking density and a large plastic deformation, and to be non-uniform in the microstructure. Thus, high surface hardness is exhibited by the portion having a high cross-linking density in the cured product of the curable resin (cured resin layer), and at the time of secondary molding, the portion having a low cross-linking density deforms to exhibit high stretchability.

[0117] (3) A resin component with low cross-linking density or non-cross-linking and / or a resin component with low elastic modulus is compounded in the curable resin. Thus, after curing of the curable resin, a structure in which fine regions (domains) with low cross-linking density or non-cross-linking and / or low elastic modulus are dispersed in the curable resin phase with high cross-linking density is formed, whereby the surface hardness is maintained to some extent in the cured product (cured resin layer) of the curable resin, and deformability and stretchability are imparted. As such a resin component with low cross-linking density or non-cross-linking or low elastic modulus, for example, there are mentioned (a) thermoplastic resins such as a methyl methacrylate resin, a styrene acrylonitrile resin, an aliphatic polycarbonate resin, an aromatic polycarbonate resin, a polyester resin, a phenoxy resin, a cellulose acylate resin, a fluorine resin, a polyurethane resin, and the like, (b) cross-linked or non-cross-linked soft resins such as an acrylic rubber, a silicone rubber, a hydrogenated styrene butadiene rubber, an acrylonitrile butadiene rubber, an olefin-based rubber, a polyurethane rubber, and the like, which can have a reactive functional group as needed, and thermoplastic elastomer materials such as a polyester-based, a polyurethane-based, an acrylic-based, an olefin-based, a styrene-based, a silicone-based, a fluorine resin-based, and the like, (c) core-shell type rubber particles in which a thermoplastic resin is grafted and polymerized on the surface of a cross-linked rubber particle, and the like.

[0118] <Polyurethane Acrylate Resin>

[0119] A polyurethane acrylate resin can be obtained, for example, by mixing a polyol, a polyisocyanate, and a (meth)acrylate containing a hydroxyl group, and generating a urethane bond by reaction of an isocyanate group with a hydroxyl group. In the present specification, a (meth)acrylate is a general term for an acrylate and a methacrylate.

[0120] Alternatively, a polyurethane acrylate resin can be obtained by reacting an isocyanate group at the terminal or side chain of a polyurethane compound obtained by reacting a polyol with a polyisocyanate, with a (meth)acrylate containing a hydroxyl group, to form a (meth)acryloyl group at the terminal or side chain. In the present specification, a (meth)acryloyl group means a methacryloyl group and an acryloyl group.

[0121] The various properties of the polyurethane acrylate resin are not particularly limited, and for example, the molecular weight, the composition, the main chain structure such as linear or branched, the number of functional groups, and the like can be appropriately adjusted depending on the structure of the polyol, the kind of the polyisocyanate, and the number of acryloyl groups or methacryloyl groups (CH2=CH-CO- or CH2=C(CH3)-CO-) from the (meth)acrylate containing a hydroxyl group. As the polyurethane acrylate resin, further mentioned are resin compositions containing a polyurethane acrylate resin, which are commercially available as curable coating agents, and the like.

[0122] As the polyvalent isocyanate, any compound having 2 or more isocyanate groups can be used without particular limitation. As the polyvalent isocyanate compound, for example, 2,4-toluene diisocyanate, 2,6-toluene 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, methylene bis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, toluidine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-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, and isocyanurate of isophorone diisocyanate, and the like can be given. Among them, polyvalent isocyanate compounds having no aromatic skeleton and having a saturated aliphatic skeleton or a alicyclic skeleton are preferred because they provide a structure more excellent in weather resistance. As such polyvalent isocyanate compounds, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, and the like can be given. These polyisocyanates can be used alone or in combination of two or more.

[0123] As specific examples of the polyhydric alcohol, ethylene glycol, 1,3-propanediol, 1,3-butanediol, 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, cyclohexanediol, 1,4-cyclohexanedimethanol, glycerol, pentaerythritol, dipentaerythritol, polyhexamethylene adipamide glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyester glycol, polycarbonate glycol, polyurethane glycol, bisphenol compound, diphenol compound, norbornane diol, dicyclopentanediol, and adamantane diol, and the like can be given. Among these, polyhydric alcohols having a saturated aliphatic skeleton and an alicyclic skeleton without an aromatic skeleton are preferred because they provide a structure more excellent in weather resistance. These polyhydric alcohols can be used singly or in combination of two or more.

[0124] As the hydroxyl group-containing (meth)acrylate, there is no particular limitation, and, for example, in addition to 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, (a) a compound having at least one hydroxyl group and having an ethylenic unsaturated bond, such as 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, allyl alcohol, ethylene glycol allyl ether, glycerol (mono, di)allyl ether, and N-hydroxymethyl (meth)acrylamide, and the like, (b) or a mixture thereof can be added as needed.

[0125] In order to promote the reaction of the isocyanate group of the isocyanate component with the hydroxyl group, an organotin-based urethanization catalyst can be used. As the organotin-based urethanization catalyst, any catalyst generally used in urethanization reactions can be used, and, for example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkylmaleate, tin stearate, tin octoate, and the like can be given.

[0126] In one or more embodiments of the present application, as at least a part of the curable resin composition for the cured resin layer, a commercially available curable resin composition containing a urethane acrylate resin can be used. As such commercially available products, for example, "Z-607-27L" manufactured by Aica Kogyo Co., Ltd., "Beamset 1200W" manufactured by Arakawa Chemical Industries, Ltd., "Acryt 8UX-116A" manufactured by DKS Co., Ltd., "NXD-004AP" manufactured by Nippon Kayaku Co., Ltd., "P-5820TAH-1" and "P-5820TA-20J" manufactured by Daito Kasei Kogyo Co., Ltd., and "Lioduras MOL7200" manufactured by TOYO CHEMICAL INDUSTRY CO., LTD., and the like can be mentioned. These commercially available curable resin compositions containing a urethane acrylate resin also have a high elongation after curing, and by using them, the crack elongation of the laminate at 120°C can be further improved.

[0127] <Light stabilizer>

[0128] The curable resin composition for the cured resin layer preferably contains a light stabilizer. By containing a light stabilizer, the stability of the cured resin layer against ultraviolet light degradation or light degradation is improved, and surface cracking and peeling and the like in the outdoor or indoor use of the molded body coated with the laminate containing the cured resin layer can be suppressed.

[0129] The curable resin composition for the cured resin layer more preferably contains a hindered amine light stabilizer having at least a reactive functional group (hereinafter also referred to as "reactive HALS") as a light stabilizer. In the reactive HALS, the reactive functional group only needs to have reactivity with the urethane acrylate resin, and for example, a functional group having an ethylenic double bond can be mentioned, and more specifically, it is preferable to contain one or more selected from the group consisting of a methacryloyl group, an acryloyl group, a vinyl group, and an allyl group, and more preferably one or more selected from the group consisting of a methacryloyl group and an acryloyl group. By having a reactive functional group, the hindered amine light stabilizer reacts with the urethane acrylate resin when the urethane acrylate resin is cured, and is introduced into the cured product forming the cured resin layer in a chemically bonded state. Thereby, even in an environment such as outdoor exposure, the transfer and loss of the hindered amine light stabilizer from the surface of the cured resin layer can be suppressed, and thus the weather resistance degradation of the cured resin layer can be suppressed for a longer period of time.

[0130] As the reactive HALS, for example, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acrylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acrylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acrylamino-2,2,6,6-tetramethylpiperidine, 4-crotonyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acrylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acrylamino-2,2,6,6-tetramethylpiperidine, and 1-crotonoyl-4-crotonyloxy-2,2,6,6-tetramethylpiperidine, and the like can be given, but are not limited to these. These reactive HALS can be used alone in one kind or in combination of two or more kinds.

[0131] As the reactive HALS, for example, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (also called 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, trade name "Adekastab LA-82" manufactured by ADEKA CORPORATION or trade name "FA-711MM" manufactured by Hitachi Chemical Co., Ltd.), 2,2,6,6-tetramethyl-piperidyl methacrylate (also called 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, trade name "Adekastab LA-87" manufactured by ADEKA CORPORATION or trade name "FA-712HM" manufactured by Hitachi Chemical Co., Ltd.), and the like commercially available products can be used.

[0132] The curable resin composition for the cured resin layer preferably contains 0.1 to 10 parts by mass of the reactive HALS, more preferably 0.5 to 6 parts by mass, and further preferably 1.0 to 4 parts by mass, with respect to 100 parts by mass of the polyurethane acrylate resin. By containing 0.1 parts by mass or more of the reactive HALS, the long-term weather resistance is improved. In addition, if the reactive HALS is 10 parts by mass or less, the weather resistance can be improved without impairing the quality of the cured resin layer.

[0133] The curable resin composition for a cured resin layer can contain, in addition to the reactive HALS, other light stabilizers such as a hindered amine light stabilizer (hereinafter also referred to as HALS) having no reactive functional group, as necessary. As the HALS, for example, bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and 2,4-bis[n-butyl-N-(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamino)-l,3,5-triazine, and the like can be given. At this time, from the viewpoint of further improving weather resistance in the case where bleeding and curing hindrance of the cured resin layer do not occur, the curable resin composition for a cured resin layer can contain a total of 0.5 to 10 parts by mass of a light stabilizer with respect to 100 parts by mass of the urethane acrylate resin, can contain 0.8 to 6 parts by mass, or can contain 1.0 to 4 parts by mass.

[0134] <Compound having a hydrophobic group and a reactive functional group>

[0135] The curable resin composition for a cured resin layer preferably contains a compound having a hydrophobic group and a reactive group (hereinafter also simply referred to as "hydrophobic reactive compound"). Such a compound is also generally referred to as a leveling agent, a surfactant, an antifouling agent, a water repellent, an oil repellent, a dispersant, a lubricant, and the like. Such a compound can be selected by appropriately adjusting the composition, structure, and the like according to the base material, the curable resin, the filler, and the like, and then compounded into the curable resin composition and / or the paint containing the curable resin composition, so that the molecules of the compound having a hydrophobic group and a reactive group are distributed toward the surface side or the interface side of the curable resin composition and / or the paint after application, and / or the interface with the base material, the filler, and the like, thereby having an effect of reducing the surface tension of the curable resin composition and / or the paint containing the curable resin composition, or improving the wettability with other materials. It also has an effect of imparting hydrophobicity, water repellency, oil repellency, antifouling properties, smoothness, scratch resistance, and the like to the surface of the cured resin layer after application and / or curing, or smoothing the surface of the cured resin layer after application and / or curing, or improving the dispersion state of the compounded filler and the like. In one or more embodiments of the present application, by adding the compound having a hydrophobic group and a reactive group to the curable resin composition for a cured resin layer, it is inferred that the surface of the cured resin layer can be made hydrophobic, thereby more effectively suppressing the penetration of the DEET component into the cured resin layer, and particularly by being used in combination with the reactive HALS, exhibiting an effect of improving the weather resistance against DEET.

[0136] <Hydrophobic group>

[0137] The hydrophobic reactive compound contains a hydrophobic group in the molecule. As the hydrophobic group, specifically, a saturated hydrocarbon group, an aromatic hydrocarbon group, a silicone group, and a fluorine-containing group, etc. can be given. As the silicone group, for example, an alkyl-substituted polysiloxane group such as a polydimethylsiloxane group, a part of the alkyl substituent group can have a functional group other than a hydrocarbon group, a part or all of the hydrogen group of the alkyl substituent group can be substituted with a fluorine group. As the fluorine-containing group, for example, a partially fluorinated hydrocarbon group, a perfluoroalkyl group, a partially fluorinated polyalkylene oxide group, a polyperfluoroalkylene oxide group, and a fluoroalkyl-substituted siloxane group, etc. can be given. Among such hydrophobic groups, from the viewpoint of deducing high hydrophobicity, the performance of imparting leveling property or wettability by the addition of the compound being excellent, and water repellency, oil repellency, etc. being excellent, the effect of improving DEET resistance being excellent, it is preferable to select one or more selected from a silicone group and a fluorine-containing group, and more preferable to a fluorine-containing group. As the hydrophobic group containing a silicone group and a fluorine-containing group, a fluoroalkyl-substituted siloxane group can be appropriately used.

[0138] <Reactive Group>

[0139] The hydrophobic reactive compound has a reactive group in the molecule in addition to the above-mentioned hydrophobic group, and more preferably has a functional group that can react together at the time of curing reaction of the polyurethane acrylate resin. By containing such a reactive group, a chemical bond can be formed between the curable resin and the hydrophobic reactive compound (compound having a hydrophobic group and a reactive group) at the time of curing reaction, and therefore the compound having a hydrophobic group and a reactive group does not flow out from the surface of the cured resin layer of the laminate, is easily left on the surface of the cured resin layer, and long-term maintenance of the functions of hydrophobicity, water repellency, oil repellency, stain repellency, smoothness, scratch resistance, and DEET resistance, etc. can be expected. As such a reactive group, specifically, a carbon-carbon double bond group such as an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group, and a thiol group, etc. can be given. Among them, one or more selected from an acryloyl group and a methacryloyl group is preferable in terms of good reactivity with a polyurethane acrylate group, excellent maintenance of weather resistance and DEET resistance after weather resistance tests, etc.

[0140] As the hydrophobic reactive compound, commercially available products can be used as reactive leveling agents, stain preventing agents, and surfactants, etc. Specifically, as commercially available products sold as leveling agents, surfactants, and surface adjusting agents, etc., "BYK-UV" series (manufactured by BYK Chemie), "MEGAFAC" series (manufactured by DIC Corporation), "FTERGENT" series (manufactured by Neos Corporation), KP series and KY-1200 series (manufactured by Shin-Etsu Chemical), "DISPARLON" series (manufactured by Nippon Shokubai), "Polyflow" series (manufactured by Kyoeisha Chemical), "Surflon" series (manufactured by AGC SEIMI CHEMICAL), etc. can be mentioned, but are not limited to these. Among these, for example, "MEGAFAC RS" (manufactured by DIC Corporation), "FTERGENT 601" (manufactured by Neos Corporation), "KY-1203" (manufactured by Shin-Etsu Chemical), etc. can be expected to be able to impart a higher water contact angle and oleic acid contact angle to the surface of the cured resin layer, and improve the DEET resistance, in particular, the DEET resistance after the weather resistance test, etc., and thus are preferred.

[0141] The curable resin composition for a cured resin layer preferably contains 0.01 to 5 parts by mass of the compound having a hydrophobic group and a reactive group, more preferably 0.05 to 4 parts by mass, and further preferably 0.1 to 3 parts by mass, with respect to 100 parts by mass of the polyurethane acrylate resin. By containing 0.01 parts by mass or more of the compound having a hydrophobic group and a reactive group, in addition to the effects of improvement of the leveling property of the curable resin composition for a cured resin layer, improvement of the wettability to the base material or the filler component, prevention of defects such as shrinkage, and the like, the weather resistance of the DEET resistance can also be improved by the combination with the reactive HALS. If the compound having a hydrophobic group and a reactive group is 5 parts by mass or less, adverse effects such as a decrease in the adhesion to the base material and a decrease in the re-coatability due to excessive addition are less likely to occur.

[0142] <Other Components>

[0143] The curable resin composition for a cured resin layer can contain other components in addition to the above-described components. As the other components, for example, a (meth)acrylate-based compound, an epoxy acrylate-based monomer, a polyester acrylate, a polyacrylic acid acrylate, and the like having a radical-reactive functional group, a monomer, an oligomer, a resin, or a mixture thereof can be used in combination. In addition, the polyurethane acrylate resin can be used in combination with, for example, a composition containing (a) a di- to tetra-functional silane compound, and / or (b) a monomer, an oligomer, a resin, or a mixture thereof having a cationically and / or anionically curable functional group such as an epoxy group and an oxetane group. These other components can be used alone or in combination with two or more.

[0144] The (meth)acrylate compound is not particularly limited as long as it has at least one or more (meth)acryloyl groups. Specifically, mention can be made of monofunctional (meth)acrylates such as alkyl (meth)acrylate, aryl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and the like; polyalkylene glycol di(meth)acrylate, 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, and the like. One of them can be used alone, or two or more of them can be used in combination. As the (meth)acrylate compound, mention can further be made of commercially available products for ultraviolet-curable hard coating agents, and the like.

[0145] The epoxy acrylate monomer is not particularly limited. Specifically, mention can be made of glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and ethylene vinyl cyclohexene monoxide (i.e., 1,2-epoxy-4-ethenylcyclohexane), and the like. In addition, so-called vinyl ester monomers obtained by reacting an epoxy group of an epoxy resin monomer having a bisphenol-based, novolak-based, and biphenyl-based skeleton, and the like, with acrylic acid can also be used as the epoxy acrylate monomer.

[0146] As the method for curing the resin layer (coated film of the curable resin composition) when forming the cured resin layer, a publicly known method can be applied. As the curing method, a method of irradiating a living energy ray typified by ultraviolet rays or electron beams is preferred. When curing is performed by irradiation of ultraviolet rays, a photopolymerization initiator can be used.

[0147] As a specific example of the photopolymerization initiator, mention can be made of, for example, acetophenone, benzophenone, benzoyl methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzpinacol, 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-morpholinopropane-1- one, and the like. Among them, 1-hydroxy-cyclohexyl-phenyl-ketone, which is excellent in compatibility with the urethane acrylate resin, is preferred.

[0148] The curable resin composition can be applied to one side or both sides of the substrate layer including the acrylic resin film, and the resin layer (coated film) composed of the curable resin composition is cured to form the cured resin layer.

[0149] When the cured resin layer is formed by coating the cured resin composition on one side or both sides of the substrate layer including the acrylic resin film and curing the coated film, various additives such as ultraviolet absorbers, defoaming agents, antioxidants, light diffusers, flatting agents, lubricants, pigments and dyes, coloring materials, organic particles, inorganic particles, and antistatic agents can be added to the cured resin composition as needed. The additives are not limited to these.

[0150] In addition, inorganic microparticles can be added to the cured resin composition for the cured resin layer, within a range not impeding the object of the present application, from the viewpoint of surface hardness and abrasion resistance. The inorganic microparticles are not particularly limited, and examples include silica, aluminium oxide, titanium oxide, zinc oxide, zirconium oxide, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, and metallic copper. These inorganic microparticles can be used without surface treatment, or surface treatment can be performed in advance by a known method in order to control the dispersion state, maintain good stretchability, and appropriately control the affinity with the cured resin layer.

[0151] In addition, within a range not impeding the object of the present application, the cured resin composition for the cured resin layer can include anti-glare particles from the viewpoint of improving the anti-glare property of the laminate. With respect to the anti-glare particles, the material of the particles, the blending amount, the kind of the dispersion solvent of the particles, the particle diameter, the dispersed particle diameter, the thickness of the cured resin layer, the difference in the relative refractive index with the substrate layer including the acrylic resin film, the affinity of the surface of the particles with the substrate layer including the acrylic resin film or the solvent, the reactivity, and the like can be appropriately adjusted within a known technical range not impairing the effect of the present application, for example, in order to obtain a balance of various properties such as the desired anti-glare property, the sharpness of the transmitted image, the glare, the blackness of the surface, the surface hardness, the lubricity, and the antistatic property.

[0152] As the material of the anti-glare particles incorporated into the cured resin layer, any material can be used as long as it improves the anti-glare property of the laminate without impairing the object of the present application, and for example, inorganic particles and / or organic particles can be used. As the inorganic particles, for example, silica, alumina, glass beads, glass flakes, mica, clay, titanium oxide, zinc oxide, zirconium oxide, and metal particles can be given. As the organic particles, for example, crosslinked organic resin particles in which one or more selected from the group consisting of (meth)acrylic alkyl ester units, aromatic vinyl units, and siloxane units are the main component, and core-shell type multi-layer structure resin particles can be given. From the viewpoint of easy availability and easy design of the anti-glare property according to the use, the particles are preferably one or more selected from the group consisting of inorganic oxide particles (for example, silica, alumina, titanium oxide, zinc oxide, zirconium oxide, and the like) and crosslinked organic resin particles (for example, crosslinked organic silicone resin, crosslinked acrylic resin, crosslinked aromatic vinyl resin, and the like), and more preferably one or more selected from the group consisting of silica, alumina, zirconium oxide, and crosslinked organic resin particles. Further, from the viewpoint of the balance of the anti-glare property, dispersibility, and surface hardness and the like, one or more selected from the group consisting of silica, alumina, and crosslinked organic resin particles is particularly preferable. Further, from the viewpoint of controlling the dispersibility, a silane coupling agent, a reactive monomer, or the like having a reactive substituent can be used, and these particles can be subjected to surface treatment and / or graft polymerization treatment and the like by a publicly known method such as plasma treatment or corona treatment. From the viewpoint of improving the interfacial adhesion of the particles to the cured resin layer, and improving the dispersibility of the particles, cracking and / or whitening during stretching, it is preferable that at least a part of the particles contain a reactive functional group having reactivity with the polyurethane acrylate resin on the surface of the particles. As the reactive functional group having reactivity with the polyurethane acrylate resin, for example, a radical reactive functional group such as a vinyl group and a (meth)acryl group, an ionic functional group such as an epoxy group, an oxetanyl group, a hydroxyl group, a carboxyl group, a mercapto group, an isocyanate group, a hydroxyl group, and an amino group, and a moisture-curable functional group such as a silyl group and an alkoxysilyl group can be given.

[0153] In the cured resin layer, the "anti-glare particles" or the "inorganic fine particles" are dispersed in the state of primary particles, or are dispersed in the state of a plurality of particles agglomerated, depending on the size of the primary particles. The size of the region (dispersion domain) in which these particles or fine particles or agglomerates thereof are distributed is defined as the "average dispersion particle diameter". There are cases where the average dispersion particle diameter is the same as the primary (basic) particle diameter for particles having a large primary particle size.

[0154] The average dispersion particle diameter of the antiglare particles is not particularly limited as long as the effect of the present application is exerted, and can be, for example, 0.1 to 50.0 μm, 0.2 to 25.0 μm, or 0.5 to 10 μm, or the like. In the present specification, the cross-sectional photograph of the laminate at a magnification of 200,000 times, 1200 nm x 800 nm, measured using an electron microscope (Hitachi High-Technologies Corporation, H7650) is observed, the arithmetic mean of the particle diameters of 10 dispersion domains of the antiglare particles in the cured resin layer is calculated, and the obtained value is taken as the average dispersion particle diameter of the antiglare particles in the cured resin layer.

[0155] The average dispersion particle diameter of the inorganic fine particles is not particularly limited as long as the effect of the present application is exerted, and can be, for example, 0.5 to 1000 nm, 1 to 500 nm, or 2 to 200 nm, or the like. In the present specification, the cross-sectional photograph of the laminate at a magnification of 200,000 times, 1200 nm x 800 nm, measured using an electron microscope (Hitachi High-Technologies Corporation, H7650) is observed, the arithmetic mean of the particle diameters of 10 dispersion domains of the inorganic fine particles in the cured resin layer is calculated, and the obtained value is taken as the average dispersion particle diameter of the inorganic fine particles in the cured resin layer.

[0156] The content of the antiglare particles in the curable resin composition for the cured resin layer is not particularly limited as long as the antiglare property of the laminate can be improved, and can be, for example, 0.1 to 30.0 mass%, 0.5 to 20.0 mass%, or 1.0 to 15.0 mass%, or the like, within a range not impairing the object of the present application.

[0157] The content of the inorganic fine particles in the curable resin composition for the cured resin layer is not particularly limited as long as the wear resistance of the laminate can be improved, and can be, for example, 0.1 to 30.0 mass%, 0.3 to 20.0 mass%, or 0.5 to 15.0 mass%, or the like, within a range not impairing the object of the present application.

[0158] In order to impart appropriate coatability to the curable resin composition for the cured resin layer, an organic solvent is generally incorporated. As the organic solvent, there is no particular limitation as long as the desired coatability can be imparted to the curable resin composition, and a cured resin layer of the desired thickness and properties can be formed. From the viewpoint of coatability and dryability of the formed resin layer (coated film), the boiling point of the organic solvent is preferably 50 to 150°C.

[0159] Specific examples of organic solvents include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; alcohols such as methanol, ethanol, isopropanol, and butanol; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and tetrahydrofuran, dichloromethane ... Ethers such as alkanes, propylene glycol monoethyl ether, methyl cellosolve, and ethyl cellosolve; amides such as N-methylpyrrolidone and dimethylformamide, etc. Organic solvents can be used alone or in combination of two or more.

[0160] When a curable resin layer is applied to one or both sides of a substrate layer comprising an acrylic resin film using a curable resin composition, any method can be used without limitation. Examples of coating methods include reverse coating, gravure coating, bar coating, mold coating, spray coating, kiss coating, wire bar coating, and curtain coating. These coating methods can be implemented individually or in combination.

[0161] After the above-mentioned curable resin layer is coated with a curable resin composition on one or both sides of a substrate layer containing an acrylic resin film to form a resin layer (coated film), the resin layer is cured by removing organic solvents from the coating film by drying and by curing the resin layer with active energy rays such as ultraviolet irradiation.

[0162] The drying temperature for removing organic solvents from the coated resin layer is preferably 60–120°C, more preferably 70–100°C. If the drying temperature is too low, organic solvents may remain in the resin layer (coated film). In addition, if the drying temperature is too high, the flatness of the laminate (cured resin layer) may be damaged due to thermal deformation of the acrylic resin film.

[0163] The wavelength of the ultraviolet light irradiated during the curing of the resin layer (coating film) is preferably in the range of 200–400 nm. The cumulative ultraviolet (UV) light intensity is preferably 500 mJ / cm². 2 The above, more preferably 550 mJ / cm 2 The above is further optimized to 600 mJ / cm. 2 The above. By making the cumulative UV light intensity 500 mJ / cm 2 The above can improve the curing degree of the cured resin layer. Specifically, it can reduce the curing index represented by Formula 1 and / or increase the curing degree represented by Formula 2. The crosslinking density of the cured resin layer increases, which can improve the hardness, DEET resistance, and DEET resistance weather resistance (DEET resistance after weathering test) of the laminate. The upper limit of the cumulative light intensity can be appropriately set from the perspective of not causing the cured resin layer to deteriorate due to excessive ultraviolet radiation or the heat generated therefrom, and energy efficiency. For example, 1500 mJ / cm is preferred.2 The following, 1400 mJ / cm 2 The following, 1300 mJ / cm 2 The following, 1200 mJ / cm 2 The following, 1100 mJ / cm 2 The following, 1000 mJ / cm 2 The following, 900 mJ / cm 2 The following, or 800 mJ / cm 2 The following.

[0164] <“Curing index” and “curing degree”>

[0165] In the laminate of one or more embodiments of the present application, as described above, the curing index of the cured resin layer needs to be 0.013 or less. Further, it is preferable that the curing degree of the cured resin layer, which is represented by the following Formula 2, be 75% or more.

[0166] Generally, the higher the crosslinking degree of the crosslinking reaction of the curable resin composition, the more the movement of the crosslinked polymer chain is restricted, and thus, generally, the curing reaction is rarely progressed to 100%, and a large amount of unreacted curable functional groups remain. The degree of progress of the curing reaction is generally quantified by, for example, an analysis method such as CP / MAS (Cross Polarization Magic Angle Spinning)-1H NMR, and the progress of the curing reaction of the cured resin layer formed from the cured product of the active energy ray-curable resin composition containing the urethane acrylate resin can be represented by the curing index calculated from the following Formula 1 and / or the curing degree calculated from the following Formula 2 using FT-IR analysis in a reflection mode.

[0167] [Formula 1]

[0168] Curing index = B / D

[0169] [Formula 2]

[0170] Curing degree (%) = 100 x [(A / C) - (B / D)] / (A / C)

[0171] In the above Formula 1 and Formula 2, A represents the area of the infrared absorption peak in the vicinity of a wave number of 810 cm -1 in FT-IR measurement of the coated film of the active energy ray-curable resin composition before curing, B represents the area of the infrared absorption peak in the vicinity of a wave number of 810 cm -1 in FT-IR measurement of the cured resin layer, and C represents the area of the infrared absorption peak in the vicinity of a wave number of 1705 cm -1The area of the infrared absorption peak near 1705 cm"1" in FT-IR measurement, D indicates the cured resin layer -1 The area of the infrared absorption peak near 1705 cm"1" in FT-IR measurement, D indicates the cured resin layer

[0172] The wave number of the infrared spectrum 810 cm"1" -1 The peak near 810 cm"1" corresponds to the out-of-plane bending vibration of the C-C double bond of the acryloyl group and the methacryloyl group, A reflects the content of the acryloyl group and the methacryloyl group in the coating film of the active energy ray-curable resin composition before curing, and B reflects the content of the acryloyl group and the methacryloyl group in the coating film of the active energy ray-curable resin composition after curing. The values of A and B decrease as the curing reaction progresses. The wave number of the FT-IR measurement 810 cm"1" -1 The infrared absorption peak near 1705 cm"1" in FT-IR measurement corresponds to the stretching vibration of the C-O double bond of the ester group, and C and D respectively reflect the total amount of the unreacted acryloyl group and the methacryloyl group, and the ester group after the curing reaction of the acryloyl group and the methacryloyl group in the coating film of the active energy ray-curable resin composition before and after the curing reaction. The total amount of the C-O double bond functional group before and after the curing reaction does not change in principle. Therefore, the above curing index B / D is a value obtained by dividing the peak area value of the functional group, i.e., the acryloyl group and the methacryloyl group, which decreases by the reaction, by the peak area value which does not change in principle by the reaction, and is largest in the unreacted state, and becomes 0 if the curing reaction is completely performed, and can be used as an index of the progress of the curing reaction. In addition, the degree of curing represented by the above formula 2 represents the proportion of the residual amount of the acryloyl group and the methacryloyl group after curing with respect to the content of the acryloyl group and the methacryloyl group before curing, and can be used as an index of the progress of the curing reaction.

[0173] Further, for the purpose of further improving the surface hardness, DEET resistance, weather resistance, and the like of the molded body on which the laminate of one or more embodiments of the present application is disposed on the surface, the operation of irradiating active energy rays such as ultraviolet rays can be further performed on at least a part of the molded body on which the laminate is disposed on the surface after the secondary molding of the laminate using vacuum and / or pressure air molding.

[0174] (Laminate)

[0175] In one or more embodiments of the present application, the laminate can include a substrate layer including an acrylic resin film and a cured resin layer laminated on one face of the substrate layer. In addition, in the laminate, the cured resin layer can be laminated on both faces of the acrylic substrate layer. In addition, within a range that does not hinder the effects of the present application, the laminate can include other functional layers laminated between the substrate layer and the cured resin layer and / or on one or both faces of the laminate as needed.

[0176] As the other functional layer, there is no particular limitation, and a widely known functional layer can be used. For example, a printing layer, a decorative layer, an adhesive layer, an antistatic layer, a conductive layer, a dielectric layer, a thermoplastic resin layer, and an optical functional layer can be mentioned. The decorative layer can include a colored layer, a design layer, a surface concave-convex layer, and a knurl layer. The adhesive layer can include a primer layer. As the thermoplastic resin layer, an antifouling layer, a fingerprint-resistant layer, a hard coat layer, a scratch-resistant layer, a gas barrier layer, and a gas absorbing layer can be mentioned. As the optical functional layer, a low-refractive layer, a high-refractive layer, an ultraviolet ray shielding layer, an infrared ray shielding layer (also referred to as a reflective layer), a light diffusing layer, an anti-glare layer, a matting layer, a phase difference adjusting layer, a viewing angle adjusting layer, and a polarizing layer can be mentioned. The laminate can have two or more other functional layers combined. In addition, one functional layer can have two or more functions.

[0177] The crack elongation of the laminate at 120°C is 80% or more. Thus, when the laminate is laminated on a molded body substrate such as a thermoplastic resin substrate, and the molded body substrate is coated with the laminate, particularly when the laminate is shaped by vacuum forming or pressure air forming under heating, when the laminate is molded on the substrate, or when the shaped laminate is placed on the surface of a mold and then insert-molded as needed, the occurrence of cracks, whitening, and the like in the laminate can be suppressed, and the secondary moldability is good. The crack elongation of the laminate at 120°C is preferably 90% or more. The upper limit of the crack elongation of the laminate at 120°C is not particularly limited. In the present specification, the crack elongation of the laminate at 120°C can be measured by the method described in the examples.

[0178] From the viewpoint of suppressing whitening during molding, the change in haze (Δhaze) of the laminate at 40% stretching at 120°C is preferably 0.5% or less, more preferably 0.3% or less, and particularly preferably 0.2% or less. In addition, from the viewpoint of suppressing whitening during molding, the change in haze (Δhaze) of the laminate at 80% stretching at 120°C is preferably 0.5% or less, more preferably 0.3% or less, and particularly preferably 0.2% or less. In the present specification, the Δhaze at 40% stretching at 120°C and the Δhaze at 80% stretching at 120°C of the laminate can be measured by the method described in the examples. In addition, in the present specification, 40% stretching means that when the size before stretching is L1 and the size after stretching is L2, [100 x (L2 - L1) / L1]% is 40%, and 80% stretching means that when the size before stretching is L1 and the size after stretching is L2, [100 x (L2 - L1) / L1]% is 80%.

[0179] From the viewpoint of achieving excellent surface hardness and improving the scratch resistance of the molded article using the laminate, the pencil hardness of the cured resin layer side of the laminate is preferably B or higher under a 500g load, more preferably HB or higher, even more preferably F or higher, and particularly preferably H or higher.

[0180] From the viewpoint of excellent chemical resistance, it is preferable that when approximately 0.02 mL of isopropanol is dropped onto the surface of the cured resin layer of the laminate and left at 23°C for 6 hours, no visual change is observed. Furthermore, from the viewpoint of excellent chemical resistance, it is preferable that when approximately 0.02 mL of acetone is dropped onto the surface of the cured resin layer of the laminate and left at 23°C for 6 hours, no visual change is observed.

[0181] From the perspective of excellent wear resistance, at 500g / cm 2 The change in haze (Δhaze) of the laminate before and after the abrasion resistance test in which the gauze is subjected to 20 round trips on the surface of the cured resin layer of the laminate under load is preferably 0.5% or less, more preferably 0.4% or less, and even more preferably 0.3% or less.

[0182] From the perspective of excellent wear resistance, at 100g / cm 2 The change in haze (Δhaze) of the laminate before and after the wear resistance test in which steel wool (#0000) is 10 times back and forth on the surface of the cured resin layer of the laminate under load is preferably 2% or less, more preferably 1.8% or less, and even more preferably 1.6% or less.

[0183] In the DEET resistance evaluation of the laminate, it is preferable that there is no change in appearance. That is, when a gauze coated with an insect repellent consisting of 0.05 g of a 30% ethanol solution of N,N-diethyl-3-methylbenzamide is placed on the surface of the cured resin layer of the laminate, and placed at 23°C and 65% relative humidity for 30 seconds, and further placed in a constant temperature bath at 74°C for 1 hour, it is preferable that there is no change in appearance by visual observation.

[0184] After weathering tests to the required weathering resistance level for applications such as automotive interiors, the laminate preferably retains DEET resistance, i.e., it exhibits DEET-resistant weathering. More preferably, after conducting the following weathering test, gauze coated with 0.05g of an insect repellent consisting of a 30% ethanol solution of N,N-diethyl-3-methylbenzamide is placed on the surface of the cured resin layer of the laminate. This gauze is then placed at 23°C and 65% relative humidity for 30 seconds, and further placed in a constant temperature bath at 74°C for 1 hour. Visual observation reveals no changes in appearance. In this weathering test, the laminate is positioned with the cured resin layer side as the light source side, and a xenon lamp is used as the light source at an irradiance of 180W / m².2 (300 to 400 nm), a black panel temperature of 89°C, and no rainfall for 300 hours, and further preferably, after the weather resistance test described below, a gauze coated with 0.05 g of an insect repellent composed of a 30% ethanol solution of N,N-diethyl-3-methylbenzamide is arranged on the surface of the cured resin layer of the laminate, and left for 30 seconds under conditions of 23°C and a relative humidity of 65%, and further left for 1 hour in a constant-temperature bath at 74°C, no change in appearance is observed by visual observation, wherein the weather resistance test is performed by arranging the laminate with the cured resin layer side as the light source side, using a xenon lamp as the light source, at a radiation illuminance of 180 W / m2 2 (300 to 400 nm), a black panel temperature of 89°C, and no rainfall for 500 hours.

[0185] For the laminate, from the viewpoint of weather resistance, the color difference ΔE of the laminate after the weather resistance test of 300 hours or 500 hours described above with respect to the laminate before the weather resistance test is preferably 0.5 or less, and more preferably 0.3 or less.

[0186] For the laminate, from the viewpoint of weather resistance, the ΔYI of the laminate after the weather resistance test of 300 hours or 500 hours described above with respect to the laminate before the weather resistance test is preferably 0.5 or less, and more preferably 0.3 or less. In the present specification, ΔYI can be measured and calculated by the method described in the examples.

[0187] From the viewpoint of DEET resistance, the water contact angle of the surface of the cured resin layer of the laminate is preferably 105° or more. In addition, from the viewpoint of weather resistance of DEET resistance, the water contact angle of the surface of the cured resin layer of the laminate after the weather resistance test of 300 hours described above is preferably 95° or more. In addition, from the viewpoint of weather resistance of DEET resistance, the water contact angle of the surface of the cured resin layer of the laminate after the weather resistance test of 500 hours described above is preferably 92° or more. In the present specification, the water contact angle can be measured by the method described in the examples.

[0188] From the viewpoint of DEET resistance, the oleic acid contact angle of the surface of the cured resin layer of the laminate is preferably 65° or more. The oleic acid contact angle of the surface of the cured resin layer side of the laminate can be measured by the method described in the examples.

[0189] From the viewpoint of transparency, the haze of the laminate is preferably 2.0% or less, more preferably 1.5% or less, further preferably 1.0% or less, further more preferably 0.8% or less, further more preferably 0.6% or less, particularly preferably 0.4% or less. In addition, from the viewpoint of weather resistance of transparency, the haze of the laminate after the weather resistance test for 300 hours described above is preferably 2.0% or less, more preferably 1.5% or less, further preferably 1.0% or less, further more preferably 0.8% or less, further more preferably 0.6% or less. In addition, from the viewpoint of weather resistance of transparency, the haze of the laminate after the weather resistance test for 500 hours described above is preferably 2.0% or less, more preferably 1.5% or less, further preferably 1.0% or less, further more preferably 0.8% or less, further more preferably 0.6% or less. However, there is no such limitation when a component such as a matting agent, an anti-glare agent, or the like is introduced into the acrylic resin film substrate and / or the cured resin layer depending on the quality requirements of appearance and the like. In the present specification, the haze can be measured by the method described in the Examples.

[0190] From the viewpoint of transparency, the total light transmittance of the laminate is preferably 90% or more, more preferably 91% or more. In addition, from the viewpoint of weather resistance of transparency, the total light transmittance of the laminate after the weather resistance test for 300 hours described above is preferably 90% or more, more preferably 91% or more. In addition, from the viewpoint of weather resistance of transparency, the total light transmittance of the laminate after the weather resistance test for 500 hours described above is preferably 90% or more, more preferably 91% or more. In the present specification, the total light transmittance can be measured by the method described in the Examples.

[0191] The laminate can be used as a decorative and / or protective sheet for a molded body. When used as a decorative and / or protective sheet, the laminate can further include one or more layers selected from the above-described printing layer, decorative layer, adhesive layer, antistatic layer, thermoplastic resin layer, and optical functional layer, in addition to the substrate layer and the cured resin layer. By using the laminate as a decorative and / or protective sheet, various functionalities such as DEET resistance, weather resistance, scratch resistance, and DEET resistance after weather resistance test can be imparted to the molded body.

[0192] (Molded Body)

[0193] In one or more embodiments of the present application, the molded body includes the above-described laminate, the laminate is laminated on the surface of the molded body substrate, and the cured resin layer of the laminate is disposed closer to the surface side of the molded body than the substrate layer of the laminate. The laminate can be laminated on a part or all of the surface of the molded body substrate. By making the laminate have a high crack elongation at 120°C, a molded body, more specifically a resin molded body, having a three-dimensional shape can be appropriately obtained by coating at least a part of the molded body substrate having a non-planar three-dimensional shape with the laminate. The laminate can impart various functional properties such as DEET resistance, weather resistance, scratch resistance, and DEET resistance after a weather test to the molded body by coating the molded body substrate in a molded body having various shapes.

[0194] The molded body substrate is not particularly limited, and a thermoplastic resin substrate can be preferably used. The thermoplastic resin substrate can be composed of, for example, a polycarbonate resin having a bisphenol skeleton, a fluorene skeleton, or an isosorbide skeleton, an acrylic resin, a styrene resin (an AS resin, an ABS resin, an MAS resin, a styrene maleimide resin, a styrene maleic anhydride resin, and the like), a saturated polyester resin, a polyvinyl chloride resin, a polyarylate resin, a PPS resin, a POM resin, a polyamide resin, a polylactic acid resin, a cellulose acylate resin, and a polyolefin resin, or the like. Among them, from the viewpoint of having excellent transparency, one or more selected from the group consisting of a polycarbonate resin, an acrylic resin, a styrene resin, and an amorphous polyolefin resin, or the like is preferable, a polycarbonate resin and / or an acrylic resin is more preferable from the viewpoint of having good adhesion to the laminate, and a polycarbonate resin is further preferable from the viewpoint of having high rigidity, high heat resistance, and high impact resistance.

[0195] The molded body is excellent in weather resistance, scratch resistance, DEET resistance, and DEET resistance before and after a weather test, and thus can be used as, for example, a vehicle interior material such as an automotive interior material, a vehicle exterior material such as an automotive exterior material, a housing or an exterior member of a portable electronic device or a personal computer, and a home appliance exterior material, or the like. It is particularly suitable for use as an automotive interior material. As the automotive interior material, specifically, a console, an instrument cover, a door panel, an armrest, a door lock shield, a steering wheel, various switch buttons and switch bases, a shift lever, a center instrument cluster, an instrument panel, a dashboard, a vehicle display screen front panel, a sensor cover, a plated member such as a vehicle emblem, and a decoration, or the like can be mentioned.

[0196] The method for manufacturing the molded body is not particularly limited as long as it is a molding method that can cover at least a portion of the molded body substrate, preferably a thermoplastic resin substrate, with a laminate. A molded body with a laminate disposed on its surface can be manufactured using, for example, in-mold molding or film-embedded injection molding. Furthermore, the laminate can be pre-shaped as needed before in-mold molding or film-embedded injection molding using methods such as vacuum forming, air-forming, or compression molding. Alternatively, so-called 3D lamination molding can be performed, in which a resin molded body is manufactured by disposing the laminate on the surface of at least a portion of a thermoplastic resin substrate having a non-planar three-dimensional shape under heating and applying depressurization and / or pressurization conditions. Furthermore, a resin molded body can be manufactured by appropriately stretching the laminate while heating and manually attaching it to the surface of a thermoplastic resin substrate.

[0197] Example

[0198] The present invention will be described in more detail below based on embodiments. The present invention is not limited to these embodiments. In the following text, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0199] The measurement and evaluation methods used in the examples and comparative examples are described.

[0200] (Cure index and degree of cure)

[0201] The curing index and degree of curing of the cured resin layer were determined as follows: Using an FT / IR-4700 (manufactured by Nippon Spectrophotometer Co., Ltd.), the infrared absorption spectra of the surface of the coating film (dry state) of the active energy X-ray curable resin composition before curing and the surface of the cured resin layer were measured using the ATR method (total internal reflection measurement) with a diamond prism. After correcting for the composition of the infrared absorption spectrum from the prism material, the values ​​were plotted on the horizontal axis as wavenumber (cm²). -1 In the infrared absorption spectrum with transmittance (%) as the vertical axis, the connection wavenumber of 810 cm⁻¹ was set using the machine's "spectral analysis" function via the method described below. -1 Nearby infrared absorption peaks and 1705 cm⁻¹ -1 The baseline is the straight line drawn between the two points at the base of each of the nearby infrared absorption peaks. The corresponding peak area can then be calculated. It should be noted that the horizontal axis represents the wavenumber (cm²). -1 In an infrared absorption spectrum with transmittance (%) as the vertical axis, observe the infrared absorption peaks downwards. Treat this value as the area of ​​each peak, and calculate the curing index and degree of curing using Equations 1 and 2 below.

[0202] [Equation 1]

[0203] Curing index = B / D

[0204] [Equation 2]

[0205] Curing degree (%) = 100 x [(A / C) - (B / D)] / (A / C)

[0206] In Formula 1 and Formula 2, A represents an area of an infrared absorption peak near wave number 810 cm"1of a coated film of the active energy ray-curable resin composition before curing in FT-IR measurement, B represents an area of an infrared absorption peak near wave number 810 cm"1of the cured resin layer in FT-IR measurement, C represents an area of an infrared absorption peak near wave number 1705 cm"1of the coated film of the active energy ray-curable resin composition before curing in FT-IR measurement, and D represents an area of an infrared absorption peak near wave number 1705 cm"1of the cured resin layer in FT-IR measurement. -1 -1 -1 -1 -1 -1

[0207] Figure 1 This shows an example of calculating the curing index B / D from the spectrum of the IR spectrum for Comparative Example 2. Figure 1 In Formula 1 and Formula 2, A represents an area of an infrared absorption peak near wave number 810 cm"1of a coated film of the active energy ray-curable resin composition before curing in FT-IR measurement, B represents an area of an infrared absorption peak near wave number 810 cm"1of the cured resin layer in FT-IR measurement, C represents an area of an infrared absorption peak near wave number 1705 cm"1of the coated film of the active energy ray-curable resin composition before curing in FT-IR measurement, and D represents an area of an infrared absorption peak near wave number 1705 cm"1of the cured resin layer in FT-IR measurement. -1 -1

[0208] ​​​​​​​​In the spectrum of the IR spectrum, points a and b at which the lines of the IR spectrum on both sides adjacent to peak 1 start to bend downward toward the center of peak 1 are the two points of the peak bottom of peak 1, respectively. In addition, in the spectrum of the IR spectrum, points c and d at which the lines of the IR spectrum on both sides adjacent to peak 2 start to bend downward toward the center of peak 2 are the two points of the peak bottom of peak 2, respectively.

[0209] (Stretching elongation at 120°C)

[0210] A 10 mm (width) x 100 mm (length) piece was cut from the acrylic resin film as a test piece. The test piece was measured using a TENSILON tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high-temperature bath set at 120°C under conditions of a preheating time of 2 minutes, a jaw spacing of 40 mm, and a stretching speed of 200 mm / minute. The elongation at the time of breaking of the acrylic resin film was taken as the stretching elongation at break. The value of the stretching elongation at break was the arithmetic mean of the three values remaining after the highest value and the lowest value were removed from the measured results of five test pieces.

[0211] (Cracking elongation at 120°C)

[0212] A 10 mm (width) x 100 mm (length) piece was cut from the acrylic resin film as a test piece. The test piece was measured using a TENSILON tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high-temperature bath set at 120°C under conditions of a preheating time of 2 minutes, a jaw spacing of 40 mm, and a stretching speed of 200 mm / minute. The elongation at the time of breaking of the acrylic resin film was taken as the stretching elongation at break. The value of the stretching elongation at break was the arithmetic mean of the three values remaining after the highest value and the lowest value were removed from the measured results of five test pieces.

[0213] (Thickness)

[0214] The thickness (film thickness) of the acrylic resin film was measured using a PEACOCK micrometer No. 25 (Ozaki Seisakusho Co., Ltd.).

[0215] The thickness (film thickness) of the cured resin layer was measured using an F20 film thickness measurement system (Filmetrics, Inc.). The back surface of the cured resin layer was blackened with a marker pen, and the measurement was performed so that the refractive index of the acrylic resin film was 1.49 and the refractive index of the cured resin layer was 1.50.

[0216] (Visible light transmittance and haze)

[0217] The total light transmittance and haze of the laminate were measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7375:2008 and JIS K 7136:2000, respectively.

[0218] (Δ haze after stretching at 120°C)

[0219] A 10 mm (width) x 100 mm (length) was cut out from the laminate as a test sample. The test sample was stretched by 40% or 80% using a TENSILON tensile tester (Shimadzu Corporation, AG-2000D) equipped with a constant temperature chamber set at 120°C under conditions of a preheating time of 2 minutes, a jaw gap of 40 mm, and a stretching speed of 200 mm / minute, and the haze of the stretched part of the stretched laminate was measured according to JIS K 7136:2000 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.). Note that the jaw gap was 56 mm at the time of 40% stretching and the jaw gap was 72 mm at the time of 80% stretching. The absolute value of the difference between the haze of the laminate before stretching and the haze of the laminate after 40% or 80% stretching was taken as "Δ haze after 40% stretching at 120°C" or "Δ haze after 80% stretching at 120°C".

[0220] (Pencil hardness)

[0221] The pencil hardness of the surface of the cured resin layer side of the laminate was measured according to JIS K 5600-5-4:1999 under a load of 500 g.

[0222] (Weather resistance test)

[0223] A super xenon weather resistance tester (Suga Tester Machine Co., Ltd., SX2D-75) was used. A filter was constituted with quartz glass on the inside and polysilicate #275 on the outside, and direct sunlight was simulated. A test sample (40 mm x 50 mm) of the laminate was set with the cured resin layer side as the light source side, and a weather resistance test was performed for 300 hours or 500 hours under the following conditions.

[0224] Conditions: irradiation illuminance 180 W / m 2 (300 to 400 nm), black panel temperature 89 ± 3°C, relative humidity 50 ± 5%, no rainfall

[0225] (DEET resistance test)

[0226] A sample of the laminate cut into a square of 5 cm x 5 cm was placed on a horizontal place with the cured resin layer side as the upper side, and 1 piece of gauze (FC gauze, manufactured by Hakuzan Co., Ltd.) cut into 5 cm x 5 cm was placed thereon, 0.05 g of insect repellent (Mushi no Mushi Mushi-Pel alpha 30, manufactured by Ikeda Mofun Corporation, an alcohol solution of DEET (N,N-diethyl 3-methylbenzamide) containing 30 g of DEET in 100 mL) was added to the center of the gauze and left for 30 seconds. Note that the insect repellent permeated the gauze and contacted the surface of the cured resin layer of the laminate. Thereafter, after being left in an oven at 74°C for 1 hour, the gauze was removed, the remaining reagent (insect repellent) was wiped with a moistened cloth, the surface of the cured resin layer was visually observed, and the DEET resistance was evaluated in accordance with the following criteria.

[0227] Good: no change in appearance

[0228] Poor: leaving a contour-like mark at the added portion and / or whitening of the added portion

[0229] (Isopropyl alcohol resistance test, acetone resistance test)

[0230] A sample of the laminate cut into a square of 5 cm x 5 cm was placed on a horizontal place with the cured resin layer side as the upper side, and 1 drop of isopropyl alcohol (hereinafter also referred to as IPA.) or acetone (about 0.02 mL) taken up with a dropper was added thereon, and after being left directly at room temperature (23°C) for 6 hours, the surface of the cured resin layer was visually observed, and the chemical resistance was evaluated in accordance with the following criteria.

[0231] Good: no change in appearance

[0232] Poor: leaving a contour-like mark at the added portion and / or surface dissolution of the added portion

[0233] (Steel wool abrasion test)

[0234] A surface property measuring machine (HEIDON Type 14DR, manufactured by Shinto Scientific Co., Ltd.) was used. Steel wool #0000 was installed on a 1 mm diameter probe, and a 100 g weight was placed. The steel wool was placed on the surface of the cured resin layer of the laminate, and a test was performed with a stroke of 70 mm and a speed of 6000 mm / minute for 10 reciprocations. The presence or absence and degree of scratches on the surface of the cured resin layer of the laminate after the steel wool (SW) abrasion test were visually observed. Further, the haze value after the test was measured, and the absolute value of the difference between the haze value before the test and the haze value after the test was taken as Δhaze.

[0235] (Gauze abrasion test)

[0236] A reciprocating abrasion tester, HEIDON Type 30S (manufactured by Shinto Scientific Co., Ltd.), was used. Gauze was installed on a 1-mm-diameter probe, and a 500-g weight was placed thereon. The gauze was placed on the surface of the cured resin layer of the laminate, and a test was performed 200 times at a stroke of 100 mm and a speed of 6000 mm / min. The surface of the laminate after the test was visually observed for the presence or absence of scratches and the degree thereof. The haze value after the test was measured, and the absolute value of the difference between the haze value before the test and the haze value after the test was taken as Δhaze.

[0237] (Adhesion Test)

[0238] A 100-grid checkerboard pattern of cuts through the cured resin layer to the surface of the acrylic resin film was made at 1-mm intervals on the surface of the cured resin layer of the laminate with a utility knife. The end portion of the transparent tape was peeled off at once after pressing the tape firmly from above. The adhesion between the cured resin layer and the substrate was evaluated according to the following criteria based on the degree of peeling of the cured resin layer.

[0239] Good: no peeling of all 100 grids

[0240] Fair: peeling of some grids

[0241] Poor: peeling of all 100 grids

[0242] (Tone)

[0243] The tone of the laminate was measured according to JIS Z 8781-4:2013 using a spectrocolorimeter SE7700 (manufactured by Nippon Denshoku Industries Co., Ltd.) under the following conditions. The color difference (ΔE) and YI value before and after the weather resistance test were calculated from the XYZ values and L*a*b* values obtained by measuring the laminate before and after the weather resistance test. Furthermore, the absolute value of the difference between the YI value after the weather resistance test and the YI value before the weather resistance test was taken as ΔYI.

[0244] Mode: projection, light source: D65, field of view: 2°, measurement diameter: 28 mm

[0245] (Water contact angle, oleic acid contact angle)

[0246] A contact angle measuring device (DMo-501 type) manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle by dropping water or oleic acid on the surface of the cured resin layer side of the laminate.

[0247] [Production Example 1: Graft Copolymer Particle (A)]

[0248] The following substances were charged into an 8-L polymerization device with a stirrer.

[0249] • Deionized water 200 parts

[0250] • Sodium dioctyl sulfosuccinate 0.24 parts

[0251] • Sodium formaldehyde sulfoxylate (alias: Rongalit) 0.15 parts

[0252] • Ethylenediaminetetraacetic acid-2-sodium 0.001 part

[0253] • Ferrous sulfate 0.00025 part

[0254] The gas in the polymerization apparatus was replaced with nitrogen gas to become a substantially oxygen-free state. Thereafter, the internal temperature of the polymerization apparatus was made 60°C. Next, the monomer mixture described below was continuously added to the polymerization apparatus at a rate (speed) of 10 parts by mass / hour. After the addition of the monomer mixture described below was completed, the polymerization was further continued for 0.5 hours, and particles of crosslinked elastomer (Al) (average particle diameter 90 nm) were obtained. The polymerization conversion rate was 99.5%. In the following, RUVA is a reactive ultraviolet absorber (2-(2'-hydroxy-5'-methylacryloyloxyethylphenyl)-2-H-benzotriazole, manufactured by Takatsuka Chemical Industries, Ltd., RUVA-93).

[0255] Monomer mixture:

[0256] • Vinyl monomer mixture (n-butyl acrylate (BA) 90% and methyl methacrylate (MMA) 10%) 30 parts

[0257] • RUVA 0.3 part

[0258] • Allyl methacrylate (ALMA) 0.63 part

[0259] • Cumene hydroperoxide (CHP) 0.2 part.

[0260] Thereafter, 0.05 parts of sodium dioctyl sulfosuccinate was put into the above polymerization apparatus containing the particles of crosslinked elastomer (Al). Next, the internal temperature of the polymerization apparatus was made 60°C, and a monomer mixture composed of 70 parts of the vinyl monomer mixture (MMA 98%, BA 1%, and RUVA 1%) for forming the graft polymer layer (A2), 0.5 parts of tertiary dodecyl mercaptan, and 0.5 parts of CHP was continuously added to the polymerization apparatus at a rate of 10 parts / hour. The polymerization was further continued for 1 hour, and a latex of graft copolymer particles (A) (average particle diameter 90 nm) was obtained. The polymerization conversion rate was 98.2%. After the obtained latex was salted out and coagulated with calcium chloride, the coagulated solid component was washed with water and dried, and a powder-like graft copolymer particle (A) was obtained.

[0261] [Manufacture Example 2: Graft Copolymer Particle (B)]

[0262] Into an 8L polymerizer equipped with a stirrer, the following materials were charged, and stirring was started.

[0263] • Deionized water 175 parts

[0264] • Dodecyl polyoxyethylene ether phosphate 0.01 part

[0265] • Boric acid 0.4725 parts

[0266] • Sodium carbonate 0.04725 parts

[0267] The internal temperature of the polymerizer was set to 80°C, and the gas in the polymerizer was sufficiently replaced with nitrogen to make it substantially oxygen-free. After the internal temperature of the polymerizer reached 80°C, a mixture of 7 parts of a vinyl monomer mixture (MMA 97% and BA 3%), 0.035 parts of allyl methacrylate, and 0.02 parts of t-dodecyl mercaptan was charged into the polymerizer. Next, 0.03 parts of t-butyl hydroperoxide was charged into the polymerizer. After 5 minutes, 0.065 parts of sodium formaldehyde sulfoxylate was charged as a 5% aqueous solution. After 10 minutes, 0.05 parts of t-butyl hydroperoxide was charged. Further, after 15 minutes, 0.01 parts of sodium hydroxide was charged as a 2% aqueous solution.

[0268] Next, a mixture of 20 parts of a vinyl monomer mixture (MMA 97% and BA 3%), 0.1 parts of allyl methacrylate, 0.07 parts of t-dodecyl mercaptan, and 0.085 parts of dodecyl polyoxyethylene ether phosphate was continuously added to the polymerizer over a period of 60 minutes. After 5 minutes from the completion of the continuous addition, 0.003 parts of t-butyl hydroperoxide was charged. Further, the polymerization was continued for 30 minutes, and particles of a hard crosslinked polymer which became the first layer of the core (crosslinked elastomer (Bl) ) were obtained. The polymerization conversion rate was 99.0%.

[0269] Next, 0.027 parts of sodium hydroxide was added to the polymerizer as a 2% aqueous solution. Next, 0.08 parts of potassium persulfate was added to the polymerizer as a 2% aqueous solution. Thereafter, a mixture of 50 parts of a vinyl monomer mixture (BA 82% and styrene (St) 18%) and 0.375 parts of allyl methacrylate was continuously added to the polymerizer over a period of 150 minutes. After the addition was completed, 0.015 parts of potassium persulfate was added to the polymerizer as a 2% aqueous solution. Next, the polymerization was continued for 120 minutes, and a core layer polymer composed of a two-layer structure of a hard crosslinked resin layer and a crosslinked elastomer layer was obtained. The polymerization conversion rate was 99.0%, and the average particle diameter was 225 nm.

[0270] After that, potassium persulfate 0.03 parts was added to the polymerization apparatus in the form of a 2% aqueous solution. Next, the vinyl monomer mixture (MMA 97% and BA 3%) for the first layer of the shell layer was continuously added to the polymerization apparatus at 15 parts over 45 minutes. After further polymerization for 30 minutes, the vinyl monomer mixture (MMA 55% and BA 45%) for the second layer of the shell layer was continuously added to the polymerization apparatus at 8 parts over 20 minutes. After further polymerization for 60 minutes, a latex of the graft copolymer particles (B) composed of a core layer of two layers and a shell layer of two layers was obtained. The polymerization conversion rate was 100.0%. After the obtained latex was salted out and coagulated with magnesium chloride, the coagulated solid components were washed with water and dried to obtain the graft copolymer particles (B) in powder form. The average particle diameter of the graft copolymer particles (B) was 240 nm.

[0271] [Manufacturing Example 3: Acrylic Resin Film]

[0272] The graft copolymer particles (A) in powder form obtained in Manufacturing Example 1, 30 parts, the graft copolymer particles (B) in powder form obtained in Manufacturing Example 2, 4 parts, Parapet HM (polymethyl methacrylate; manufactured by KURARAY Co., Ltd., methyl methacrylate 100%), 66 parts, and a hindered phenol-based antioxidant ("AO60" manufactured by ADEKA Co., Ltd.), 0.6 parts were mixed using a Henschel mixer. Next, the mixture was melt-kneaded at a screw rotation speed of 150 rpm and a discharge amount of 180 kg / hour using a 58 mm Φ vented co-rotating twin-screw extruder (TEM58 L / D = 41.7 manufactured by Toshiba Machine Co., Ltd.) having a leaf disc type polymer filter (manufactured by Nagase Industry, filter precision 10 μm, size 7 inches, number of pieces 33) between the die and the head of the extruder, with the cylinder temperature adjusted to 190°C to 250°C, and the obtained pellets were drawn out in a filament shape from the extruder and cut after cooling to obtain granules. The obtained granules were melt-kneaded at a discharge amount of 150 kg / hour at a cylinder setting temperature of 180°C to 240°C using a 90 mm Φ single-screw extruder with a T die, and discharged from the T die at a die temperature of 240°C, and cooled and solidified by making both sides contact a metallic casting roll adjusted to 90°C and a touch roll having an elastic metal sleeve adjusted to 60°C, and wound after film formation to obtain an acrylic resin film having a thickness of 75 μm. The tensile elongation at break of the acrylic resin film at 120°C, measured as described above, was 220%.

[0273] [Manufacturing Example 4: Coating]

[0274] A curable resin composition (Daito Kasei Kogyo Co., Ltd., trade name "P-5820TAH-1", containing a polyurethane acrylate resin as a main component, a small amount of an acrylate, a trace amount of an alumina nanoparticle (inorganic fine particle), and a photopolymerization initiator, solid content concentration 30 mass%, mixed solvent of methyl ethyl ketone, propylene glycol, and methyl isobutyl ketone as a solvent, hereinafter simply referred to as "P-5820TAH-1") was diluted with methyl ethyl ketone so as to have a solid content concentration of 24 mass%, and then, 0.5 parts by solid content of a reactive HALS (ADEKA Co., Ltd., trade name "Adekastab LA-82", hereinafter also referred to as "LA-82") and 0.3 parts by solid content of a fluorine-containing acrylic compound (Shin-Etsu Chemical Co., Ltd., trade name "KY-1203", solid content concentration 20%, mixed solvent of methyl ethyl ketone and methyl isobutyl ketone as a solvent, hereinafter also simply referred to as "KY-1203") were added with respect to 100 parts by mass of the solid content of the obtained resin composition, and the mixture was stirred to obtain a coating material 1.

[0275] Coating materials 2, 3, and 7 were produced in the same manner as in the case of the coating material 1, except that the amounts of LA-82 and KY-1203 were as shown in Table 1 below.

[0276] A curable resin composition (Daito Kasei Kogyo Co., Ltd., trade name "P-5820TA-20J", containing a polyurethane acrylate resin as a main component, a small amount of an acrylate, and a photopolymerization initiator, solid content concentration 24%, mixed solvent of methyl ethyl ketone, propylene glycol, and methyl isobutyl ketone as a solvent, hereinafter also simply referred to as "P-5820TA-20J") was used, and the amounts of LA-82 and KY-1203 were as shown in Table 1 below with respect to 100 parts by mass of the solid content of the resin composition, and coating materials 4 to 6, 8, and 9 were produced in the same manner as in the case of the coating material 1.

[0277] The P-5820TA-20J was used as a coating material 10 as it was.

[0278]

[0279] (Example 1)

[0280] A coating material 1 was applied to the acrylic resin film obtained in Production Example 3 using a bar coater to form a curable resin layer on the acrylic resin film. Subsequently, the curable resin layer was dried at 80°C for 1 minute to volatilize the solvent from the curable resin layer. Next, the dried curable resin layer (coated film of the active energy ray-curable resin composition before curing) was irradiated with ultraviolet rays at the UV cumulative light amount described in Table 2 to cure the curable resin layer to form a cured resin layer (cured product of the active energy ray-curable resin composition) having the thickness described in Table 2 below, thereby obtaining a laminate. The temperature of the chill roll at the time of forming the cured resin layer was 50°C.

[0281] (Examples 2 to 9)

[0282] A laminate was produced in the same manner as in Example 1, except that the coating material described in Table 2 below was used.

[0283] (Examples 10 to 11)

[0284] A laminate was produced in the same manner as in Example 1, except that the coating material described in Table 2 below was used to make the thickness of the cured resin layer as described in Table 2 below.

[0285] (Comparative Example 1)

[0286] A laminate was produced in the same manner as in Example 6, except that the UV cumulative light amount was as described in Table 2 below.

[0287] (Comparative Example 2)

[0288] A laminate was produced in the same manner as in Example 1, except that the coating material described in Table 2 below was used to make the thickness of the cured resin layer and the UV cumulative light amount as described in Table 2 below.

[0289] The various properties (initial) of the laminates obtained in the examples and comparative examples were measured and evaluated as described above, and the results are shown in Table 2 below. In addition, weather resistance tests were performed using the laminates obtained in the examples and comparative examples, and thereafter the various properties of the laminates were measured and evaluated as described above, and the results are shown in Table 3 below. In Table 3 below, 300 hours refers to the properties of the laminate after the weather resistance test was performed for 300 hours, and 500 hours refers to the properties of the laminate after the weather resistance test was performed for 500 hours. In addition, in Table 3 below, the combined amount of the reactive HALS and the fluorine-containing acrylic compound in the coating material is the amount in mass parts with respect to 100 mass parts of the solid component (polyurethane acrylate resin) in the coating material.

[0290]

[0291]

[0292] As is apparent from Table 2 above, the laminates of the examples have excellent transparency, good surface hardness and scratch resistance, excellent overmolding properties, and good DEET resistance. In addition, the laminates of Examples 1-3, 8, 10, and 11, in which the cured resin layer contains inorganic microparticles, have excellent steel wool and gauze abrasion resistance.

[0293] On the other hand, the laminates of the comparative examples in which the cured resin layer has a curing index greater than 0.013 have poor DEET resistance. In the laminates of the comparative examples, the degree of curing of the cured resin layer is less than 75.

[0294] In addition, as is apparent from Table 3 above, the laminates of Examples 1 to 6, in which the curable resin layer contains a hindered amine-based light stabilizer having a reactive functional group and a compound having a hydrophobic group and a reactive functional group, i.e., the cured product of the active energy ray-curable resin composition in which the curable resin layer contains a polyurethane acrylate resin, a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group, also have good DEET resistance after the weather resistance test of 300 hours. In particular, the laminates of Examples 2, 3, 5, and 6, in which 0.5 parts by mass or more of the reactive HALS are contained relative to 100 parts by mass of the polyurethane acrylate resin, also have good DEET resistance after the weather resistance test of 500 hours.

[0295] On the other hand, the laminates of Examples 7 to 11, in which the curable resin layer contains only one of a hindered amine-based light stabilizer having a reactive functional group and a compound having a hydrophobic group and a reactive functional group, have good initial DEET resistance, but the DEET resistance after the weather resistance test deteriorates.

[0296] The present application is not particularly limited, and may, for example, include the following embodiments.

[0297] [1] A laminate comprising a substrate layer and a cured resin layer,

[0298] The substrate layer described above contains an acrylic resin film,

[0299] The acrylic resin film described above has a tensile elongation at break at 120°C of 200% or more,

[0300] The cured resin layer described above is formed from a cured product of an active energy ray-curable resin composition containing a polyurethane acrylate resin,

[0301] The cured resin layer described above has a curing index represented by Formula 1 below of 0.013 or less,

[0302] The laminate described above has a tensile crack elongation at 120°C of 80% or more.

[0303] [Formula 1]

[0304] Curing index = B / D

[0305] wherein, in the above formula 1, B represents an area of an infrared absorption peak in the vicinity of a wave number of 810 cm -1 of the cured resin layer in FT-IR measurement, and D represents an area of an infrared absorption peak in the vicinity of a wave number of 1705 cm -1 of the cured resin layer in FT-IR measurement.

[0306] [2] The laminate according to [1], wherein the active energy ray-curable resin composition further contains a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group.

[0307] [3] The laminate according to [2], wherein the reactive functional group contains one or more selected from the group consisting of a methacryl group and an acryl group.

[0308] [4] The laminate according to [2] or [3], wherein the compound having a hydrophobic group and a reactive functional group is a fluorine compound having a reactive functional group or a silicone compound having a reactive functional group.

[0309] [5] The laminate according to any one of [2] to [4], wherein the compound having a hydrophobic group and a reactive functional group is a fluorine compound having a reactive functional group.

[0310] [6] The laminate according to any one of [2] to [5], wherein the proportion of the hindered amine-based light stabilizer having a reactive functional group is 1 to 10 parts by mass with respect to 100 parts by mass of the polyurethane acrylate resin.

[0311] [7] The laminate according to any one of [2] to [6], wherein the proportion of the compound having a hydrophobic group and a reactive functional group is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane acrylate resin.

[0312] [8] The laminate according to any one of [1] to [7], wherein the degree of cure of the cured resin layer, which is represented by the following formula 2, is 75% or greater.

[0313] [Formula 2]

[0314] Degree of cure (%) = 100 x [(A / C) - (B / D)] / (A / C)

[0315] wherein, in the above formula 2, A represents an area of an infrared absorption peak in the vicinity of a wave number of 810 cm -1Area of infrared absorption peak in the vicinity, B indicates wave number 810 cm -1 Area of infrared absorption peak in the vicinity, C indicates wave number 1705 cm -1 Area of infrared absorption peak in the vicinity, D indicates wave number 1705 cm -1 Area of infrared absorption peak in the vicinity.

[0316] [9] The laminate according to any one of [1] to [8], wherein a water contact angle of the surface of the cured resin layer of the laminate is 105° or more.

[0317]

[10] The laminate according to any one of [1] to [9], wherein an oleic acid contact angle of the surface of the cured resin layer of the laminate is 65° or more.

[0318]

[11] The laminate according to any one of [1] to

[10] , wherein a gauze coated with 0.05 g of an insect repellent composed of a 30 w / v% ethanol solution of N,N-diethyl-3-methylbenzamide is disposed on the surface of the cured resin layer of the laminate, and when left to stand for 30 seconds under conditions of 23°C and a relative humidity of 65% and further left to stand for 1 hour in a constant-temperature bath at 74°C, no change in appearance is observed by visual observation.

[0319]

[12] The laminate according to any one of [1] to

[11] , wherein after a weather resistance test, a gauze coated with 0.05 g of an insect repellent composed of a 30% ethanol solution of N,N-diethyl-3-methylbenzamide is disposed on the surface of the cured resin layer of the laminate, and when left to stand for 30 seconds under conditions of 23°C and a relative humidity of 65% and further left to stand for 1 hour in a constant-temperature bath at 74°C, no change in appearance is observed by visual observation, the weather resistance test being performed by disposing the laminate with the cured resin layer side as the light source side, using a xenon lamp as the light source, under conditions of irradiation luminance of 180 W / m 2 (300 to 400 nm), black panel temperature of 89°C, and no rainfall for 500 hours.

[0320]

[13] The laminate according to any one of [1] to

[12] , wherein the laminate has a change value of the haze value before and after 80% stretching at 120°C of 0.5% or less.

[0321]

[14] The laminate according to any one of [1] to

[13] , wherein, when about 0.02 mL of isopropyl alcohol or acetone is dropped on the surface of the cured resin layer and left for 6 hours at 23°C, no change in appearance is observed by visual observation.

[0322]

[15] The laminate according to any one of [1] to

[14] , wherein the change in haze of the laminate before and after a wear resistance test is 0.5% or less, the wear resistance test being such that gauze is passed over the surface of the cured resin layer of the laminate 20 times back and forth under a load of 500 g / cm 2 .

[0323]

[16] The laminate according to any one of [1] to

[15] , wherein the change in haze of the laminate before and after a wear resistance test is 2% or less, the wear resistance test being such that steel wool (#0000) is passed over the surface of the cured resin layer of the laminate 10 times back and forth under a load of 100 g / cm 2 .

[0324]

[17] The laminate according to any one of [1] to

[16] , wherein the change in color difference ΔE of the laminate after a weather resistance test is less than 0.5, the weather resistance test being such that the laminate is arranged with the cured resin layer side as the light source side, a xenon lamp is used as the light source, and the test is performed for 500 hours under conditions of irradiance of 180 W / m 2 (300 to 400 nm), black panel temperature of 89°C, and no rainfall.

[0325]

[18] The laminate according to any one of [1] to

[17] , wherein the laminate is used for decoration and / or protection of a molded body.

[0326]

[19] The laminate according to

[18] , wherein the laminate further comprises one or more layers selected from the group consisting of a printing layer, a decorative layer, an adhesive layer, an antistatic layer, a thermoplastic resin layer, and an optical functional layer.

[0327]

[20] A molded body comprising the laminate according to any one of [1] to

[19] and a molded body substrate,

[0328] the laminate being laminated to the surface of the molded body substrate, the cured resin layer of the laminate being disposed closer to the surface side of the molded body than the base layer of the laminate.

[0329]

[21] The molded body according to

[20] , wherein the surface of the molded body substrate to which the laminate is laminated has a three-dimensional shape.

[0330]

[22] A method for producing a molded body, which is the method for producing a molded body described in

[20] , wherein the laminate described in any one of [1] to

[19] is laminated on a surface of a molded body substrate using one or more methods selected from vacuum molding, pressure air molding, thin film insert injection molding, and 3D laminated molding.

[0331] The embodiments described above are not independent of each other, and no undue elaboration is required, and those skilled in the art can appropriately combine them. Furthermore, the constituent elements of different embodiments can be appropriately combined.

Claims

1. A laminate comprising a substrate layer and a cured resin layer, the substrate layer comprises an acrylic resin film, the acrylic resin film has a tensile elongation at break at 120°C of 200% or more, the cured resin layer is formed from a cured product of an active energy ray-curable resin composition comprising a polyurethane acrylate resin, a curing index represented by the following Formula 1 of the cured resin layer is 0.013 or less, the laminate has a tensile crack elongation at 120°C of 80% or more, Formula 1 Curing index = B / D wherein In the formula 1, B represents an area of an infrared absorption peak in the vicinity of 810 cm -1 of the cured resin layer in FT-IR measurement, D represents an area of an infrared absorption peak in the vicinity of 1705 cm -1 of the cured resin layer in FT-IR measurement.

2. The laminate according to claim 1, wherein the active energy ray-curable resin composition further comprises a hindered amine-based light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group.

3. The laminate according to claim 2, wherein the reactive functional group comprises one or more selected from a methacryloyl group and an acryloyl group.

4. The laminate according to claim 2, wherein the compound having a hydrophobic group and a reactive functional group is a fluorine compound having a reactive functional group or a silicone compound having a reactive functional group.

5. The laminate according to claim 2, wherein the compound having a hydrophobic group and a reactive functional group is a fluorine compound having a reactive functional group.

6. The laminate according to claim 2, wherein the proportion of the hindered amine-based light stabilizer having a reactive functional group is 1 to 10 parts by mass relative to 100 parts by mass of the polyurethane acrylate resin.

7. The laminate according to claim 2, wherein the proportion of the compound having a hydrophobic group and a reactive functional group is 0.1 to 5 parts by mass relative to 100 parts by mass of the polyurethane acrylate resin.

8. The laminate according to claim 1, wherein a degree of curing represented by the following Formula 2 of the cured resin layer is 75% or more, Formula 2 Degree of curing (%) = 100 x [(A / C) - (B / D)] / (A / C) In the formula 2, A represents an area of an infrared absorption peak in the vicinity of 810 cm -1 in FT-IR measurement of a coated film of the active energy ray-curable resin composition before curing, B represents an area of an infrared absorption peak in the vicinity of 810 cm -1 in FT-IR measurement of the cured resin layer, C represents an area of an infrared absorption peak in the vicinity of 1705 cm -1 in FT-IR measurement of the cured resin layer, D represents an area of an infrared absorption peak in the vicinity of 1705 cm -1 in FT-IR measurement of the cured resin layer.

9. The laminate according to claim 1, wherein the water contact angle of the surface of the cured resin layer of the laminate is 105° or more.

10. The laminate according to claim 1, wherein the oleic acid contact angle of the surface of the cured resin layer of the laminate is 65° or more.

11. The laminate according to claim 1, wherein a gauze coated with 0.05 g of an insect repellent consisting of a 30 w / v% ethanol solution of N,N-diethyl-3-methylbenzamide is disposed on the surface of the cured resin layer of the laminate, and when left to stand for 30 seconds under conditions of 23°C and a relative humidity of 65% and further left to stand for 1 hour in a constant-temperature bath at 74°C, no change in appearance is observed by visual observation.

12. The laminate according to claim 1, wherein After the weather resistance test, a gauze coated with 0.05 g of an insect repellent consisting of a 30% ethanol solution of N,N-diethyl-3-methylbenzamide was arranged on the surface of the cured resin layer of the laminate, and left for 30 seconds under conditions of 23°C and a relative humidity of 65%, and further left for 1 hour in a constant-temperature bath at 74°C, and no change in appearance was observed by visual observation, the weather resistance test being performed for 500 hours under conditions of a black panel temperature of 89°C and no rainfall, with the cured resin layer side being the light source side, using a xenon lamp as the light source, at a radiation intensity of 180 W / m2 2 in the range of 300 to 400 nm.

13. The laminate according to claim 1, wherein the change in the haze value before and after 80% stretching of the laminate at 120°C is 0.5% or less.

14. The laminate according to claim 1, wherein when about 0.02 mL of isopropyl alcohol or acetone is added dropwise to the surface of the cured resin layer and left to stand for 6 hours at 23°C, no change in appearance is observed by visual observation.

15. The laminate according to claim 1, wherein The change in haze of the laminate before and after the abrasion resistance test is 0.5% or less, the abrasion resistance test being 20 passes of a gauze over the surface of the cured resin layer of the laminate under a load of 500 g / cm 2 2.

16. The laminate of claim 1, wherein, The change in haze of the laminate before and after the abrasion resistance test was 2% or less, the abrasion resistance test being 10 passes of steel wool (#0000) over the surface of the cured resin layer of the laminate under a load of 100 g / cm 2 2.

17. The laminate of claim 1, wherein, The change in color difference ΔE of the laminate after a weather resistance test is less than 0.5, the weather resistance test is performed by disposing the laminate with the cured resin layer side as the light source side, using a xenon lamp as a light source, under the conditions of irradiance of 180 W / m2 of 300 to 400 nm, black panel temperature of 89°C, and no rainfall for 500 hours. 2 , black panel temperature of 89°C, and no rainfall for 500 hours.

18. The laminate of claim 1, wherein, the laminate is used for decorating and / or protecting a molded body.

19. The laminate of claim 18, wherein, the laminate further comprises one or more layers selected from a printing layer, a decorative layer, an adhesive layer, an antistatic layer, a thermoplastic resin layer, and an optical functional layer.

20. A molded body comprising the laminate of any one of claims 1 to 19 and a molded body substrate, the laminate is laminated to the surface of the molded body substrate, and the cured resin layer of the laminate is disposed closer to the surface side of the molded body than the substrate layer of the laminate.

21. The shaped body of claim 20, wherein, in the molded body substrate, the surface on which the laminate is laminated has a three-dimensional shape.

22. A method for manufacturing a molded body, the method for manufacturing a molded body according to claim 20, The laminate described in any one of claims 1 to 19 is laminated to the surface of a molded body substrate using one or more methods selected from vacuum forming, pressure air forming, thin film insert injection molding, and 3D laminated molding.

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