Multilayer body, molded body including same, and method for manufacturing molded body

Abstract

One or more embodiments of the present invention relate to a multilayer body which comprises a base material layer and a cured resin layer, wherein the base material layer comprises an acrylic resin film, the acrylic resin film has a tensile elongation at break of 200% or more at 120° C, the cured resin layer is formed of a cured product of an active energy ray-curable resin composition that contains a urethane acrylate resin, the curing index represented by formula 1 of the cured resin layer is 0.013 or less, and the tensile elongation at cracking of the multilayer body is 80% or more at 120°C.　(Formula 1): Curing index = B / D In formula 1, B represents the area of an infrared absorption peak near the wave number of 810 cm-1 in an FT-IR measurement of the cured resin layer, and D represents the area of an infrared absorption peak near the wave number of 1,705 cm-1 in the FT-IR measurement of the cured resin layer.

Description

Laminate, molded body including same, and method for manufacturing molded body

[0001] The present invention relates to a laminate containing an acrylic resin film, a molded article containing the same, and a method for producing the molded article.

[0002] Acrylic resin films obtained by molding an acrylic resin composition containing an elastomer are being used in a variety of applications, taking advantage of their excellent properties such as transparency, hardness, weather resistance, and post-formability. Examples of applications of acrylic resin films include decorative and protective applications as an alternative to painting for interior and exterior members of vehicles, decorative and protective applications for exterior members of electronic devices such as portable electronic devices, personal computers, and home appliances, and applications as building materials.

[0003] When an acrylic resin film is used for decorating and protecting vehicle interior and exterior components, as well as electronic devices such as portable electronic devices, personal computers, and home appliances, sufficient scratch resistance and surface hardness for surface protection are required, as well as high post-formability for uniform lamination on the surface of the target product, including a three-dimensional shape. For example, Patent Document 1 proposes a technology for achieving both post-formability and scratch resistance by providing a hard coat layer on the surface of an acrylic resin film substrate that exhibits high surface hardness after curing and high post-formability.

[0004] On the other hand, in these applications, there are many opportunities for human bodies to come into contact with the products. When sunscreens or insect repellents are applied to human skin in summer or hot regions, adhesion of the sunscreens or insect repellents to the product surface can cause surface deterioration, which requires resistance to these factors. For example, N,N-diethyl 3-ethylbenzamide (hereinafter also referred to as DEET) has minimal effects on the human body and is highly effective against harmful insects such as mosquitoes. Therefore, it is widely used as the main ingredient in insect repellent sprays, lotions, and the like. However, many plastic products containing acrylic resins have a problem in that when a person who has applied an insect repellent containing DEET comes into contact with their skin, the DEET contained in the insect repellent adheres to the surface of the plastic product, corroding the product surface and deteriorating its appearance. Therefore, Patent Document 2 proposes a laminated film that is endowed with a certain degree of resistance to DEET by providing an acrylic resin film with a cured resin layer made of a resin containing units derived from a urethane resin.

[0005] International Publication No. 2022 / 137768 International Publication No. 2016 / 199847

[0006] However, in recent years, in order to enhance the durability of insect repellent effects, it has become permissible to incorporate DEET into insect repellents at high concentrations of up to 30%, for example in Japan, and there is an increasing demand for preventing the deterioration of the surfaces of products containing acrylic resin films caused by DEET, and there is a need for acrylic resin films that are resistant to such high concentrations of DEET-containing agents.

[0007] The present invention has been made in view of the above-mentioned problems, and provides a laminate that includes an acrylic resin film and has high surface hardness and secondary formability as well as good chemical resistance to chemicals such as N,N-diethyl-3-ethylbenzamide; a molded article that includes the laminate; and a method for producing the molded article.

[0008] One or more embodiments of the present invention relate to a laminate including a substrate layer and a cured resin layer, wherein the substrate layer includes an acrylic resin film, and the acrylic resin film has a tensile elongation at break of 200% or more at 120°C, and the cured resin layer is formed from a cured product of an active energy ray-curable resin composition containing a urethane acrylate resin, and the cured resin layer has a curing index, represented by the following formula 1, of 0.013 or less, and the laminate has a tensile crack elongation at 120°C of 80% or more. [Formula 1] Cure index = B / D where, in formula 1, B is the wavenumber of 810 cm in FT-IR measurement of the cured resin layer. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 1705 cm in the FT-IR measurement of the cured resin layer. -1 The area of ​​the infrared absorption peak in the vicinity is shown.

[0009] One or more embodiments of the present invention relate to a molded body including the laminate and a molded body substrate, wherein the laminate is laminated on the surface of the molded body substrate, and the cured resin layer of the laminate is positioned closer to the surface of the molded body than the substrate layer of the laminate.

[0010] One or more embodiments of the present invention relate to a method for manufacturing the molded body, in which the laminate is laminated onto the surface of a molded body substrate using one or more methods selected from the group consisting of vacuum forming, pressure forming, film insert injection molding, and three-dimensional laminate molding.

[0011] According to the present invention, it is possible to provide a laminate that includes an acrylic resin film and has high surface hardness and secondary formability as well as good chemical resistance to chemicals such as N,N-diethyl-3-ethylbenzamide, a molded article that includes the laminate, and a method for producing the molded article.

[0012] In Comparative Example 2, the wave number in FT-IR measurement of the cured resin layer was 810 cm -1 The area of ​​the infrared absorption peak near the wave number 1705 cm -1 1 is a diagram illustrating a method for calculating a hardening index based on the area of ​​infrared absorption peaks in the vicinity of a sample.

[0013] The inventors of the present invention conducted extensive studies to solve the above-mentioned problems, and as a result, they found that in a laminate including a substrate layer containing an acrylic resin film and a cured resin layer, by using an acrylic resin film having a tensile breaking elongation of 200% or more at 120°C, setting the tensile crack elongation of the laminate at 120°C to 80% or more, forming the cured resin layer from a cured product of an active energy ray-curable resin composition containing a urethane acrylate resin, and setting the value of the curing index represented by the following formula 1 of the cured resin layer within a specific range, i.e., the degree of curing within a specific range, the surface hardness and secondary formability of the laminate can be increased, and the chemical resistance to high concentrations of DEET can be improved.

[0014] [Formula 1] Cure index = B / D where B is the wave number of 810 cm in FT-IR measurement of the cured resin layer. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 1705 cm in the FT-IR measurement of the cured resin layer. -1 The area of ​​the infrared absorption peak in the vicinity is shown.

[0015] In this specification, the curing index is a parameter indicating the degree of curing of the cured resin layer, and more specifically, it depends on the degree of progress of the curing reaction in the active energy ray-curable resin composition containing the urethane acrylate resin. -1 The infrared absorption peak around 1705 cm corresponds to the out-of-plane bending vibration of the C-C double bond of the acryloyl group and / or methacryloyl group, and B reflects the content of uncured acryloyl and methacryloyl groups in the cured resin layer, and the value decreases as the curing reaction progresses. -1The infrared absorption peak near corresponds to the stretching vibration of the C-O double bond of the ester group, and D reflects the total amount of uncured acryloyl and methacryloyl groups in the cured resin layer, as well as the ester group after the acryloyl and methacryloyl groups have cured. The total amount of C-O double bond functional groups does not change, in principle, before and after the curing reaction. The curing index B / D is calculated by dividing the peak area value corresponding to the acryloyl and methacryloyl groups, which are functional groups that decrease with the curing reaction, by the peak area value that does not change with the curing reaction. This value depends on the degree of progress of the curing reaction, reaching a maximum value when the curing reaction is unreacted and reaching 0 when the curing reaction has completely progressed, and can be used as a parameter indicating the degree of curing of the cured resin layer. In one or more embodiments of the present invention, by setting the curing index B / D of a cured resin layer formed from a cured product of an active energy ray-curable resin composition containing a urethane acrylate resin to 0.013 or less, the chemical resistance to high concentrations of DEET, for example, 30 w / v % DEET, is improved.

[0016] In vehicle interior materials such as automobile interior materials, dashboards, door trims, etc., have portions exposed to sunlight through window glass. Therefore, these interior materials require weather resistance (resistance to ultraviolet degradation) at relatively high temperatures due to sunlight exposure so as to prevent surface deterioration over time. Acrylic resin films themselves are widely used as decorative surface materials for automobile interior materials, for example, by inside or in-mold decorative molding techniques, and have excellent weather resistance in addition to high secondary formability. However, when a hard coat or chemical-resistant coating is applied to improve surface hardness or chemical resistance, the weather resistance may be poor. In one or more preferred embodiments of the present invention, the curing index B / D is set to 0.013 or less, and the active energy ray-curable resin composition contains, in addition to the urethane 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, thereby improving weather resistance, particularly the weather resistance of physical properties including chemical resistance to chemicals such as DEET.

[0017] In this specification, when a numerical range is indicated with "to", the numerical range includes both end values ​​(upper and lower limits). For example, a numerical range of "X to Y" includes both end values ​​X and Y, and is the same range as "X or more and Y or less". Any number within that range and any range included within that range are specifically disclosed. In addition, when multiple numerical ranges are described in this specification, they are intended to include numerical ranges that combine the upper and lower limits of different numerical ranges as appropriate.

[0018] (Acrylic Resin Film) The acrylic resin film has a tensile breaking elongation of 200% or more at 120°C. This increases the tensile crack elongation at 120°C of the laminate with the cured resin layer, and tends to improve the secondary formability of the laminate. There is no particular upper limit to the tensile breaking elongation of the acrylic resin film at 120°C. In this specification, the tensile breaking elongation of the acrylic resin film at 120°C can be measured by the method described in the examples.

[0019] The acrylic resin film is preferably formed from an acrylic resin composition containing graft copolymer particles containing an acrylic resin and a rubber component (also called a crosslinked elastomer).

[0020] <Acrylic Resin> Conventionally known acrylic resins can be used as appropriate. For example, from the viewpoint of hardness and moldability, it is preferable to use an acrylic resin (also referred to as a thermoplastic acrylic polymer) composed of 50 to 100% by mass of methyl methacrylate units and 0 to 50% by mass of other structural units, where the total amount of structural units of the acrylic resin is taken as 100% by mass. The total amount of methyl methacrylate units and other structural units in the thermoplastic acrylic polymer is 100% by mass.

[0021] Examples of the other structural units include structural units derived from acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, aromatic vinyl derivatives, and vinyl cyanide derivatives. The other structural units may be glutarimide structures, lactone ring structures, N-substituted maleimide structures, and unsubstituted maleimide structures, which will be described later. The other structural units contained in the acrylic resin may be one type or a combination of two or more types.

[0022] Examples of acrylic acid derivatives include, but are not limited to, 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.

[0023] Examples of methacrylic acid derivatives include 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, as well as reactive ultraviolet absorbers described below, but are not limited to these.

[0024] Examples of aromatic vinyl derivatives include, but are not limited to, styrene, vinyltoluene, and α-methylstyrene.

[0025] Vinyl cyanide derivatives include, but are not limited to, acrylonitrile, methacrylonitrile, and the like.

[0026] In order to improve the heat resistance, rigidity, surface hardness, etc. of the acrylic resin, a structural unit having a specific structure may be introduced into the acrylic resin by copolymerization, functional group modification, denaturation, etc. Examples of such specific structures include glutarimide structures such as those disclosed in JP-A Nos. 62-89705, 02-178310, and WO 2005 / 54311, lactone ring structures such as those disclosed in JP-A Nos. 2004-168882 and 2006-171464, glutaric anhydride structures obtained by thermal cyclocondensation of (meth)acrylic acid units such as those disclosed in JP-A No. 2004-307834, maleic anhydride structures such as those disclosed in JP-A No. 5-119217, and N-substituted maleimide structures and unsubstituted maleimide structures such as those disclosed in WO 2009 / 84541. For example, the introduction of these structures into an acrylic resin rigidifies the molecular chain. As a result, effects such as improved heat resistance, improved surface hardness, reduced heat shrinkage, and improved chemical resistance can be expected.

[0027] The method for producing the acrylic resin is not particularly limited, and can be, for example, a known polymerization method such as suspension polymerization, bulk polymerization, solution polymerization, emulsion polymerization, etc. Also, any of a known radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization can be used.

[0028] In 100% by mass of the acrylic resin film, the content of the acrylic resin may be 20 to 100% by mass, preferably 20 to 99% by mass, more preferably 25 to 95% by mass, and even more preferably 30 to 90% by mass.

[0029] <Graft Copolymer Containing Rubber Component> The acrylic resin film preferably contains, as the graft copolymer particles containing a rubber component, graft copolymer particles (A) having an average particle size of 20 to 200 nm. In this case, the acrylic resin film preferably contains the graft copolymer particles (A) dispersed in a matrix containing an acrylic resin or an acrylic resin and other components. Furthermore, the acrylic resin film may contain, as the graft copolymer particles containing a rubber component, in addition to the graft copolymer particles (A), graft copolymer particles (B) having an average particle size larger than that of the graft copolymer particles (A), as necessary. In this case, the acrylic resin film preferably contains the graft copolymer particles (A) and the graft copolymer particles (B) dispersed in a matrix containing an acrylic resin or an acrylic resin and other components.

[0030] The graft copolymer particles (A) preferably have a core-shell structure (multilayer structure) including a crosslinked elastomer (A1) as a rubber component and a graft polymer layer (A2) located on the surface layer side of the crosslinked elastomer (A1).

[0031] The crosslinked elastomer (A1) may be a known crosslinked elastomer. Preferably, the crosslinked elastomer (A1) is an acrylate ester-based crosslinked elastomer (a crosslinked elastomer composed of a polymer containing an acrylate ester as a main component). In this specification, the term "main component" refers to a component whose content is 50% by mass or more.

[0032] The particles of the acrylic ester-based crosslinked elastomer (A1) may have a concentric spherical multilayer structure comprising a crosslinked elastomer layer and a hard crosslinked resin layer having a glass transition temperature of room temperature (20±5°C) or higher, or a semi-hard crosslinked resin layer having a glass transition temperature in the range of 0°C to room temperature. Examples of such hard or semi-hard crosslinked resin layers include hard crosslinked methacrylic resin particles as disclosed in JP-B No. 55-27576, semi-hard crosslinked particles consisting of methyl methacrylate-acrylic ester-styrene as disclosed in JP-A No. 4-270751, and highly crosslinked rubber particles. The provision of such a hard or semi-hard crosslinked resin layer may be expected to improve transparency, color tone, etc.

[0033] The graft copolymer particles (A) preferably have a core-shell structure formed by graft polymerizing a monomer mixture that forms the graft polymer layer (A2) in the presence of particles of the above-mentioned acrylic acid ester-based crosslinked elastomer (A1).

[0034] The average particle size of the graft copolymer particles (A) is preferably 50 to 150 nm, particularly preferably 50 to 120 nm. If the average particle size of the graft copolymer particles (A) is too small, the impact resistance and bending crack resistance of the acrylic resin film tend to decrease. If the average particle size of the graft copolymer particles (A) is too large, the transparency of the acrylic resin film tends to decrease and whitening due to bending tends to occur.

[0035] As the acrylic acid ester-based crosslinked elastomer (A1), crosslinked elastomer particles obtained by polymerizing a monomer mixture (a-1) containing (a) an acrylic acid ester, (b) a polyfunctional monomer copolymerizable with the acrylic acid ester and having two or more non-conjugated double bonds per molecule, and (c) optionally another vinyl-based monomer copolymerizable with the acrylic acid ester can be preferably used.

[0036] The acrylic acid ester, the polyfunctional monomer, and the other vinyl-based monomer may be mixed and polymerized in one step. Alternatively, for the purpose of adjusting the toughness, whitening resistance, etc. of the acrylic resin film, the acrylic acid ester, the polyfunctional monomer, and the other vinyl-based monomer may be polymerized in two or more stages by appropriately changing the composition of the acrylic acid ester, the polyfunctional monomer, and the other vinyl-based monomer or by keeping the same composition.

[0037] As the acrylic acid ester, aliphatic esters of acrylic acid are preferred, aliphatic alkyl acrylate esters are more preferred, and aliphatic alkyl acrylate esters having an alkyl group with 1 to 22 carbon atoms are particularly preferred, from the viewpoints of excellent polymerizability, low cost, and ability to produce polymers with low glass transition temperatures (Tg). The aliphatic alkyl may be linear, branched, or cyclic (also referred to as alicyclic).

[0038] Specific examples of preferred aliphatic alkyl acrylates include 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, etc. These may be used alone or in combination of two or more.

[0039] The amount of the acrylic acid ester (preferably an aliphatic alkyl acrylate, more preferably an aliphatic alkyl acrylate having an alkyl group containing 1 to 22 carbon atoms) is preferably 50 to 99.9% by mass, more preferably 70 to 99% by mass, and most preferably 80 to 99% by mass, based on 100% by mass of the monomer mixture (a-1). When the amount of the acrylic acid ester is 50% by mass or more, the acrylic resin film has good impact resistance and elongation at tensile break, and is less likely to crack during secondary molding.

[0040] Examples of other vinyl monomers include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; vinyl cyanide derivatives such as acrylonitrile and methacrylonitrile; aromatic vinyl derivatives such as styrene, vinyl toluene, and α-methylstyrene; acrylic acid; acrylic acid derivatives other than aliphatic alkyl acrylate esters 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. These may be used alone or in combination of two or more. Among these, from the viewpoint of weather resistance and transparency, the other vinyl monomer is particularly preferably one or more monomers selected from the group consisting of methacrylic acid esters and aromatic vinyl derivatives.

[0041] The amount of the other vinyl monomer is preferably 0 to 49.9% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass, based on 100% by mass of the monomer mixture (a-1). If the amount of the other vinyl monomer exceeds 49.9% by mass, the impact resistance of the acrylic resin film is likely to decrease, the elongation at tensile break is reduced, and cracks may be more likely to occur during secondary molding.

[0042] As the polyfunctional monomer, a monomer typically used as a crosslinking agent and / or a grafting agent can be suitably used. Examples of the polyfunctional monomer include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, and dipropylene glycol dimethacrylate. These polyfunctional monomers may be used alone or in combination of two or more.

[0043] Among these polyfunctional monomers, those having the function of a graft crosslinking agent are more preferred because they increase the number of graft bonds of the graft polymer layer (A2) described below to the crosslinked elastomer (A1), resulting in good dispersibility of the graft copolymer particles (A) in the acrylic resin, improving crack resistance against tensile and bending deformation and reducing stress whitening. As such polyfunctional monomers having the function of a graft crosslinking agent, those having an allyl group such as allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and diallyl maleate are preferred, with allyl methacrylate and allyl acrylate being particularly preferred.

[0044] The amount of the polyfunctional monomer is preferably 0.1 to 10% by mass, and more preferably 1.0 to 4% by mass, based on 100% by mass of the monomer mixture (a-1). The amount of the polyfunctional monomer within this range is preferable from the viewpoints of the resistance to cracking upon bending, the resistance to whitening upon bending, and the fluidity of the resin during molding of the acrylic resin film.

[0045] In the acrylic ester-based crosslinked elastomer (A1), the amount of the polyfunctional monomer may be varied between the interior and the surface vicinity of the crosslinked elastomer (A1) for the purpose of increasing the graft coating efficiency of the graft polymer layer (A2) described below. Specifically, as shown in Japanese Patent No. 1460364 and Japanese Patent No. 1786959, by increasing the content of the polyfunctional monomer functioning as a graft crosslinking agent in the surface vicinity of the crosslinked elastomer (A1) compared to the interior, it is possible to improve the coating of the graft copolymer particles (A) with the graft polymer layer, improve dispersibility in the acrylic resin, and suppress a decrease in crack resistance due to peeling at the interface between the graft copolymer particles (A) and the acrylic resin. Furthermore, since a sufficient coating can be obtained with a relatively small amount of the graft polymer layer (A2), the amount of the graft copolymer particles (A) required to introduce a predetermined amount of the crosslinked elastomer (A1) into the acrylic resin composition can be reduced, and therefore the melt viscosity of the acrylic resin composition can be reduced, and improvements in the melt processability, film processing accuracy, and surface hardness of the acrylic resin film can be expected.

[0046] A chain transfer agent may be used in addition to the monomer mixture (a-1) for the purposes of controlling the molecular weight and crosslink density of the acrylate ester-based crosslinked elastomer (A1) and controlling thermal stability and the like by reducing the double bond terminals of the polymer due to the disproportionation termination reaction during polymerization. The chain transfer agent can be selected from those typically used in radical polymerization. Preferred examples of the chain transfer agent include monofunctional or polyfunctional mercaptan compounds having 2 to 20 carbon atoms, such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; mercapto acids; thiophenol; carbon tetrachloride; and mixtures thereof. The amount of the chain transfer agent added is preferably 0 to 1.0 part by mass, more preferably 0 to 0.2 part by mass, per 100 parts by mass of the total amount of the monomer mixture (a-1).

[0047] The particles of the crosslinked elastomer (A1) may be a single layer made of the above-mentioned acrylic ester-based crosslinked elastomer (A1), or may have a multilayer structure including two or more layers made of the above-mentioned acrylic ester-based crosslinked elastomer (A1).

[0048] The particles of the crosslinked elastomer (A1) may also be multilayer particles containing a hard or semi-hard crosslinked resin layer, and the acrylate ester crosslinked elastomer (A1) may be contained in at least one layer of the multilayer particles. Examples of monomers constituting the hard or semi-hard crosslinked resin layer include methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate; acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate; aromatic vinyl derivatives such as styrene and α-methylstyrene; vinyl cyanide derivatives such as acrylonitrile; maleic anhydride; maleic acid derivatives such as maleimides; and polyfunctional monomers having two or more non-conjugated double bonds per molecule. The polyfunctional monomer may be the same as that used in the polymerization of the acrylate ester-based crosslinked elastomer (A1) layer. Among these, one or more monomers 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 are particularly preferred. Furthermore, during polymerization of the hard or semi-hard crosslinked resin layer, a chain transfer agent may be used in addition to these monomers to control the crosslink density and to reduce the double bond terminals of the polymer to control thermal stability, etc. The same chain transfer agent as that used in the polymerization of the acrylate ester-based crosslinked elastomer (A1) layer can be used. The amount of chain transfer agent added is preferably 0 to 2 parts by mass, more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total monomer mixture constituting the hard or semi-hard crosslinked resin layer.

[0049] When the graft copolymer particle (A) has a two-layer structure consisting of a particle of crosslinked elastomer (A1) as a core particle and a graft polymer layer (A2) as a shell layer, the graft copolymer particle (A) can typically be obtained by graft copolymerizing a monomer mixture (a-2) containing 50 to 100% by mass of a methacrylic acid ester and 0 to 50% by mass of another vinyl-based monomer copolymerizable with the methacrylic acid ester (provided that the total of the methacrylic acid ester and the other vinyl-based monomer is 100% by mass) in the presence of particles of crosslinked elastomer (A1) to form the graft polymer layer (A2).

[0050] The amount of the methacrylic acid ester in 100% by mass of the monomer mixture (a-2) is preferably 60% by mass or more, more preferably 80% by mass or more, even more 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 matrix, and (b) preventing a decrease in toughness of the film due to solvent impregnation during coating on the acrylic resin film and whitening and cracking due to stretching during molding.

[0051] In the monomer mixture (a-2), examples of the methacrylic acid ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and octyl methacrylate, as well as aromatic methacrylic acid esters such as phenyl methacrylate and benzyl methacrylate. Among these, alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms are preferred.

[0052] In the monomer mixture (a-2), the other vinyl-based monomer can be an alkyl acrylate ester in which the alkyl group has 2 or more carbon atoms. As the alkyl acrylate ester in which the alkyl group has 2 or more carbon atoms, 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 are preferred, one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate are more preferred, and n-butyl acrylate is particularly preferred.

[0053] In the monomer mixture (a-2), examples of other vinyl-based monomers that can be used include aromatic vinyl derivatives such as styrene and its nucleus-substituted derivatives, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid, methacrylic acid derivatives, acrylic acid, acrylic acid derivatives, N-substituted maleimides, maleic anhydride, methacrylamide, and acrylamide.

[0054] The monomer mixture (a-2) preferably contains a reactive ultraviolet absorber as another vinyl monomer. That is, the graft polymer layer (A2) preferably contains a structural unit derived from the reactive ultraviolet absorber. When the monomer mixture (a-2) contains a reactive ultraviolet absorber, it is easy to obtain an acrylic resin film having good weather resistance and chemical resistance.

[0055] The reactive ultraviolet absorber is not particularly limited and may be any known reactive ultraviolet absorber. In terms of the moldability and weather resistance of the acrylic resin film, the reactive ultraviolet absorber is preferably a compound represented by the following general formula (1):

[0056]

[0057] In general formula (1), X is a hydrogen atom or a halogen atom, R1 is a hydrogen atom, a methyl group, or a t-alkyl group having 4 to 6 carbon atoms, R2 is a linear or branched alkylene group having 2 to 10 carbon atoms, and R3 is a hydrogen atom or a methyl group.

[0058] Specific examples of reactive ultraviolet absorbers represented by general formula (1) include 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazoles, more specific examples include 2-(2'-hydroxy-5'-acryloyloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxypropylphenyl)-2H-benzotriazole, and 2-(2'-hydroxy-5'-methacryloyloxyethyl-3'-t-butylphenyl)-2H-benzotriazole. Preferably, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole is used in terms of cost and ease of handling. In this specification, (meth)acryloyl is a general term for acryloyl and methacryloyl.

[0059] The content of the structural unit derived from the reactive ultraviolet absorber in 100% by mass of the graft polymer layer (A2) is preferably from 0.01 to 5% by mass, and more preferably from 0.1 to 3% by mass.

[0060] The graft polymer layer (A2) is preferably obtained by graft copolymerizing, in at least one stage, 10 to 95 parts by mass of a monomer mixture (a-2) containing 70 to 99.5% by mass of an alkyl methacrylate, 0.5 to 30% by mass of an alkyl acrylate having an alkyl group containing two or more carbon atoms, and 0 to 19% by mass of other vinyl monomers (provided that the total of the alkyl methacrylate, alkyl acrylate, and other vinyl monomers is 100% by mass), in the presence of 5 to 90 parts by mass of crosslinked elastomer particles (A1), provided that the total amount of the particles of the crosslinked elastomer (A1) and the monomer mixture (a-2) is 100 parts by mass.

[0061] In the production of graft copolymer particles (A), particularly during the graft copolymerization of monomer mixture (a-2) in the presence of particles of crosslinked elastomer (A1), for example, particles of acrylate ester-based crosslinked elastomer (A1), polymer components (free polymers) that are not graft-bonded to the particles of acrylate ester-based crosslinked elastomer (A1) may be generated. Such free polymers can be used to constitute part or all of the acrylic resin that constitutes the matrix phase of acrylic resin compositions and acrylic resin films.

[0062] A chain transfer agent may be added to the monomer mixture (a-2) for the purposes of controlling the molecular weight of the polymer, controlling the graft rate to the crosslinked elastomer (A1) and the amount of free polymer not bonded to the crosslinked elastomer (A1) produced, and controlling thermal stability by reducing the double bond terminals of the polymer due to the disproportionation termination reaction during polymerization. As such a chain transfer agent, the same chain transfer agents as those usable in the polymerization of the crosslinked elastomer (A1) can be used. The amount of the chain transfer agent used is preferably 0 to 2 parts by mass, more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total amount of the monomer mixture (a-2).

[0063] The graft ratio of the monomer mixture (a-2) to the particles of the crosslinked elastomer (A1), i.e., the graft ratio of the graft copolymer particles (A), is preferably 5 to 250%, more preferably 10 to 200%, and even more preferably 20 to 150%. If the graft ratio is less than 5%, the acrylic resin film tends to have reduced resistance to whitening upon bending, reduced transparency, and reduced elongation at tensile break, making it more susceptible to cracking during secondary molding. If the graft ratio exceeds 250%, the melt viscosity of the acrylic resin composition tends to increase during film molding, resulting in reduced moldability of the acrylic resin film. Herein, the graft ratio of the graft copolymer particles (A) can be calculated by dissolving the powder of the graft copolymer particles (A) in methyl ethyl ketone, separating it into an insoluble and a soluble fraction, and using the insoluble fraction as the graft fraction, according to the following formula: Graft ratio (%)=100×(mass fraction of insoluble matter−mass fraction of crosslinked elastomer (A1)) / mass fraction of crosslinked elastomer (A1)

[0064] The average particle size d (nm) of the acrylic acid ester-based crosslinked elastomer (A1) in the acrylic resin film and the amount w (mass %) of the polyfunctional monomer used in the acrylic acid ester-based crosslinked elastomer (A1) preferably satisfy the relationship: 0.015d≦w≦0.06d, more preferably 0.02d≦w≦0.05d. When the amount of the polyfunctional monomer is within the range of the above relationship, the acrylic resin film has advantages such as being less likely to reduce in elongation during secondary forming, being less likely to crack during molding or cutting, having excellent transparency, being less likely to suffer from stress whitening during bending or tensile deformation at room temperature (about 25°C), at high temperatures above the softening temperature of the acrylic resin film, or in a temperature range between room temperature and the Tg of the crosslinked elastomer (A1), and being less likely to suffer from moisture-induced clouding or whitening of the film due to moisture penetrating into the acrylic resin film upon contact with moisture.

[0065] Like the graft copolymer particles (A), the graft copolymer particles (B) comprise a crosslinked elastomer (B1) which is a rubber component. Like the graft copolymer particles (A), the graft copolymer particles (B) typically comprise a graft polymer layer (B2) located on the surface layer side of the crosslinked elastomer (B1). That is, the graft copolymer particles (B) preferably comprise a core layer of the crosslinked elastomer (B1) and a shell layer of the graft polymer layer (B2). The core layer and the shell layer may both have a multilayer structure.

[0066] The graft copolymer particles (B) may be generally similar to the graft copolymer particles (A) in terms of raw materials, production method, etc., except that the average particle size of the graft copolymer particles (B) is larger than that of the graft copolymer particles (A). Preferably, the particles of the acrylate ester-based crosslinked elastomer (B1) have a concentric spherical multilayer structure comprising a crosslinked elastomer layer and a hard or semi-hard crosslinked resin layer therein. Examples of such a hard or semi-hard crosslinked resin layer include hard crosslinked methacrylic resin particles as disclosed in JP-B-55-27576 and crosslinked particles having a semi-hard layer made of a methyl methacrylate-acrylate-styrene copolymer as disclosed in JP-A-4-270751 and WO 2014 / 41803. By introducing such a hard or semi-hard crosslinked resin layer, it is possible to improve the transparency, resistance to whitening on bending, resistance to cracking on bending, etc. of the graft copolymer particles (B) having a particle size larger than that of the graft copolymer particles (A).

[0067] The average particle size of the graft copolymer particles (B) is preferably 150 to 400 nm, more preferably 200 to 350 nm. Graft copolymer particles (B) with a large average particle size more effectively induce plastic deformation (craze) in the acrylic resin phase surrounding the graft copolymer particles in response to the action of external force on the acrylic resin material than graft copolymer particles (A) with a small average particle size. Therefore, the graft copolymer particles (B) are extremely effective in imparting 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 resistance to whitening due to bending and / or whitening due to solvents. For this reason, for example, by adding a small amount of graft copolymer particles (B) to an acrylic resin composition containing an acrylic resin and graft copolymer particles (A), (a) the total content of soft components relative to the acrylic resin film is reduced so as not to reduce the surface hardness of the acrylic resin film and laminate, (b) when external stress is applied to the acrylic resin film, when a coating liquid containing an organic solvent is applied and / or during molding processing, the whitening is less likely to deteriorate, and (c) the crack resistance, secondary formability, etc. of the acrylic resin film and laminate can be expected to be efficiently improved. Examples of acrylic resin films that use a combination of graft copolymer particles (A) and a small amount of graft copolymer particles (B) include those disclosed in WO 2013 / 051239 and WO 2019 / 181752.

[0068] In this specification, the average particle size of the graft copolymer particles (A) and the graft copolymer particles (B) refers to an average particle size on a volume basis (also referred to as a mass basis), and can be measured in a latex state by a dynamic light scattering method using a laser diffraction / scattering particle size distribution analyzer such as the Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd.

[0069] The method for producing the graft copolymer particles (A) and the graft copolymer particles (B) is not particularly limited, and known methods such as emulsion polymerization, mini-emulsion polymerization, suspension polymerization, and solution polymerization can be applied. Emulsion polymerization is particularly preferred because it allows for a wide range of adjustment of the resin structure.

[0070] The initiator used in the emulsion polymerization of the graft copolymer particles (A) and / or the graft copolymer particles (B) can be any known initiator, such as an organic peroxide, an inorganic peroxide, or an azo compound. Specific examples include organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, alkyl peroxycarbonates, and alkyl peroxy esters; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; and azo compounds such as azobisisobutyronitrile. These initiators may be used alone or in combination of two or more.

[0071] These initiators may be used (a) as thermal decomposition type radical polymerization initiators, or (b) as redox type polymerization initiator systems in which these initiators are combined with a catalyst such as ferrous sulfate and a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and hydroxyacetone acid. The catalyst may be used as a complex with 2-sodium ethylenediaminetetraacetate or the like to ensure water solubility.

[0072] 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. A wide variety of known surfactants can be used in emulsion polymerization. Preferred surfactants include, for example, (a) anionic surfactants such as sodium salts, potassium salts, and ammonium salts of alkyl sulfonic acid, alkyl benzene sulfonic acid, dialkyl sulfosuccinic acid (dioctyl sulfosuccinic acid, etc.), alkyl sulfate, fatty acid sodium salt, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether phosphate, alkyl phosphate, alkyl ether phosphate, alkyl phenyl ether phosphate, 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 may be used alone or in combination of two or more.

[0073] The graft copolymer particles (A) or (B) can be separated and recovered from the latex of the graft copolymer particles (A) or (B) obtained by emulsion polymerization by a known method. For example, after adding a water-soluble electrolyte such as calcium chloride, magnesium sulfate, magnesium chloride, calcium acetate, sodium chloride, hydrochloric acid, acetic acid, or sulfuric acid to the latex to coagulate the graft copolymer particles, or after freezing the latex to separate and coagulate the graft copolymer particles from the aqueous phase, the graft copolymer particles (A) or (B) can be separated and recovered by filtering, washing, and drying the solids. Alternatively, the graft copolymer particles (A) or (B) can be separated and recovered by treating the latex with spray drying, freeze coagulation, freeze drying, or the like.

[0074] For the purpose of reducing appearance defects and / or internal foreign matter in the acrylic resin film, preferably, prior to separation and recovery of the graft copolymer particles (A) or the graft copolymer particles (B), the latex of the graft copolymer particles (A) or the latex of the graft copolymer particles (B) may be filtered in advance with a filter and / or a mesh to remove substances that may cause foreign matter defects, such as environmental foreign matter and polymerization scale.

[0075] As the filter and mesh, known filters and meshes used for filtering liquid media can be used. The type, mesh size, filtering accuracy, and filtering capacity of the filter and mesh are appropriately selected depending on the intended use and the type, size, and amount of foreign matter to be removed. The mesh size and filtering accuracy of the filter and mesh are preferably at least twice the average particle size of the graft copolymer particles (A) or the graft copolymer particles (B), respectively.

[0076] The content of the graft copolymer particles (A) in 100% by mass of the acrylic resin film is not particularly limited, but is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass.

[0077] The content of the graft copolymer particles (B) in 100% by mass of the acrylic resin film is not particularly limited and can be appropriately adjusted within a range preferred for the intended use without impairing the quality of the laminate of the present invention, but from the viewpoint of suppressing stress whitening during stretching or bending of the acrylic resin film and clouding of the film after contact with moisture, it is desirable not to use an excessive amount, and the content is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and most preferably 0 to 5% by mass. Alternatively, the acrylic resin film may contain no graft copolymer particles (B) at all.

[0078] <Other Components> The acrylic resin film (the acrylic resin composition constituting the acrylic resin film) may contain, as necessary, a thermoplastic resin that is at least partially compatible with the acrylic resin, as long as the object of the present invention is not impaired. Examples of such thermoplastic resins include styrene-based resins, polycarbonate resins, amorphous saturated polyester resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, polyimide resins, polylactic acid resins, and PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) resins. Examples of styrene-based resins include styrene-acrylonitrile resins, styrene-(meth)acrylic acid resins, styrene-maleic anhydride resins, styrene-N-substituted or unsubstituted maleimide resins, styrene-acrylonitrile-butadiene resins, and styrene-acrylonitrile-acrylic ester resins. Among these, one or more thermoplastic resins selected from the group consisting of styrene-based resins, polycarbonate resins, and polyimide resins are preferred because they have excellent compatibility with acrylic resins and may be able to improve the acrylic resin film's resistance to cracking due to bending, solvent resistance, chemical resistance, low moisture absorption, etc. In this specification, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid.

[0079] The acrylic resin film (the acrylic resin composition constituting the acrylic resin film) may also contain, as necessary, conventionally known additives used in acrylic resin films, as long as they do not impair the objectives of one embodiment of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, light diffusing agents, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, antiblocking agents composed of organic particles and / or inorganic particles, infrared reflectors composed of metals and / or metal oxides, plasticizers, and antistatic agents. The additives are not limited to these. These additives can be used in any amount depending on the type of additive, as long as they do not impair the objectives of one embodiment of the present invention or to enhance the effects of one embodiment of the present invention.

[0080] <Physical Properties of Acrylic Resin Film> The glass transition temperature (Tg) of the acrylic resin film is preferably 145°C or lower, more preferably 140°C or lower, even more preferably 135°C or lower, and particularly preferably 130°C or lower. An acrylic resin film having a glass transition temperature of 145°C or lower has the advantage that it can be molded without increasing the molding temperature and that the occurrence of cracks during molding can be suppressed. Furthermore, the lower limit of the glass transition temperature of the acrylic resin film is not particularly limited, but is preferably 100°C or higher, for example, from the viewpoint of preventing printing misalignment during drying of the print and improving reliability. The glass transition temperature of the acrylic resin film can be determined using a known method such as differential scanning calorimetry (DSC).

[0081] The thickness of the acrylic resin film is not particularly limited, but is preferably 50 to 350 μm, more preferably 60 to 300 μm, and particularly preferably 70 to 250 μm. When the thickness of the acrylic resin film is within the above-mentioned range, the film has sufficient stretchability and excellent handleability, and has the advantage of excellent appearance after lamination onto a resin substrate (molded body substrate) during production of a molded body. In this specification, the thickness of the acrylic resin film is measured by the method described in the examples.

[0082] The pencil hardness of the acrylic resin film measured in accordance with JIS K 5600-5-4 is preferably 2B or more under a load of 500 g, more preferably B or more, and particularly preferably HB or more, from the viewpoint of excellent surface hardness and scratch resistance.

[0083] <Method for Producing Acrylic Resin Film> The acrylic resin film can be produced by a known processing method. Specific examples of known processing methods include melt processing, calendar molding, press molding, and solvent casting. Examples of melt processing methods include inflation and T-die extrusion. In the solvent casting method, for example, an acrylic resin composition is dissolved and dispersed in a solvent, and the resulting dispersion (dope) is then cast in the form of a film onto a belt-shaped substrate. Next, the solvent is volatilized from the cast film-like dope to obtain an acrylic resin film.

[0084] Among these methods, the melt processing method, which does not use a solvent, is preferred, and the T-die extrusion method and the calendar molding method are particularly preferred. The melt processing method has few limitations on the thickness of the film to be produced, can produce a film with excellent surface properties with high productivity, and can reduce the burden on the natural environment and working environment caused by solvents, as well as the production cost.

[0085] When the acrylic resin composition is formed into a film by a melt processing method or a solvent casting method, it is preferable to remove environmental foreign matter, polymerization scale, deteriorated resin, and the like from the acrylic resin composition by filtration using a filter or mesh, which may cause defects in the appearance of the acrylic resin film or internal foreign matter, from the viewpoint of improving the appearance quality of the acrylic resin film.

[0086] In producing a film by melt processing, the acrylic resin composition can be filtered at any one or more of the following times: when melt-kneading the acrylic resin composition after blending raw materials such as the acrylic resin and the graft copolymer particles, and when forming a molten film using a T-die. In addition, in the solvent casting method, the acrylic resin composition may be filtered after mixing the acrylic resin, the graft copolymer particles (A), the graft copolymer particles (B), and other components with a solvent and before casting.

[0087] As such filters and meshes, known filters and meshes can be used without any particular limitation, as long as the filters and meshes have heat resistance and durability according to the melt processing conditions, or resistance to the solvents and dopes used for casting.

[0088] When producing an acrylic resin film by melt processing, a filter with a large filtration capacity and little retention of molten resin, which can cause resin deterioration and crosslinking that impair the quality of the film, is preferred, particularly in order to obtain a high-quality acrylic resin film. For example, the use of a leaf disk-type filter or a pleated-type filter is preferred from the viewpoints of filtration efficiency and productivity.

[0089] 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 can be used that measures the film thickness distribution in the TD direction (direction perpendicular to the extrusion direction) of the extruded film online and automatically adjusts the lip clearance of the T-die during extrusion based on the measurement. By applying an automatic die using an appropriate control method, it is possible to improve the thickness accuracy of the acrylic resin film.

[0090] In the production of acrylic resin films, if necessary, both sides of a molten film can be simultaneously contacted (sandwiched) with a cooling roll or a cooling belt during film forming to obtain a film with superior surface properties. In this case, it is preferable to simultaneously contact the molten film with a cooling roll or a cooling belt maintained at a temperature equal to or higher than the glass transition temperature of the acrylic resin composition −80°C, preferably equal to or higher than the glass transition temperature −70°C. The upper limit of the temperature of the cooling roll or the cooling belt is not particularly limited, but may be, for example, the glass transition temperature of the acrylic resin composition +10°C or lower. More preferably, at least one of the rolls used for such sandwiching is a roll having an elastic metal sleeve, as disclosed in, for example, JP-A Nos. 2000-153547 and 1999-235747, and a low sandwiching pressure is used to transfer a mirror finish or a specific surface shape. This makes it possible to obtain (a) a film with little residual strain and excellent smoothness, and / or (b) a film with a moderate surface roughness, excellent surface slipperiness, suppressed film-to-film blocking, and less internal strain.

[0091] Depending on the purpose, the film may be uniaxially or biaxially stretched after molding. The uniaxial or biaxial stretching can be performed using a known stretching device. The biaxial stretching can be performed in a known manner, such as sequential biaxial stretching, simultaneous biaxial stretching, or a method in which, after longitudinal stretching, transverse stretching is performed while relaxing the longitudinal direction to suppress the bowing phenomenon of the film.

[0092] (Substrate Layer) The substrate layer includes an acrylic resin film. The substrate layer may have a smooth surface, or, as needed for the application, may have any surface shape, such as hairlines, prisms, unevenness, three-dimensional decoration, a matte surface, a rough surface with a certain surface roughness, or knurling on the film edge, on one or both sides of the substrate layer, as long as the effects of the present invention are not impaired. Such surface shapes can be imparted by known methods. For example, a method can be used in which both surfaces (also referred to as both surfaces) of a film immediately after extrusion or a formed film unwound from a feeding device are sandwiched between two rolls or belts having a surface shape on at least one surface (also referred to as one surface) to transfer the surface shape of the roll. The substrate layer may also be an acrylic resin film with a printed decorative layer laminated on one or both sides, as needed for the application, as long as the effects of the present invention are not impaired.

[0093] (Cured Resin Layer) The cured resin layer is formed from a cured product of an active energy ray curable resin composition (hereinafter also referred to simply as "curable resin composition") containing a urethane acrylate resin, or preferably a urethane acrylate resin, a hindered amine 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 coating a curable resin composition containing a urethane acrylate resin, or preferably a curable resin composition containing a urethane acrylate resin, a hindered amine light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group, onto a substrate layer containing an acrylic resin film, followed by curing. The cured resin layer may be formed on one side or both sides of the substrate layer containing an acrylic resin film. The curable resin composition for the cured resin layer preferably has active energy curability, from the viewpoints of not requiring large-scale equipment such as heating, curing quickly, and being cost-effective. It is more preferable that the urethane 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 active energy curability.

[0094] In one or more embodiments of the laminate of the present invention, the cured resin layer is required to have high crack elongation as well as improved surface hardness. As a result, when the laminate is subjected to secondary molding to fit the shape of a molded body, breakage or significant whitening does not occur due to stretching, bending, etc. However, in general, in the cured resin layer, the cured product of the curable resin composition containing the curable resin is highly crosslinked and / or contains a filler with high hardness, thereby suppressing deformation of the cured product surface due to external stress and exhibiting surface hardness and scratch resistance. Surface hardness and scratch resistance are contradictory properties to deformability and extensibility, and it has not been easy to achieve both of these in the cured resin layer.

[0095] In order to impart high extensibility during secondary molding while maintaining the surface hardness of the cured resin layer, the curable resin (e.g., urethane acrylate resin) used in the cured resin layer can be designed, for example, by the following methods (1) to (3). For the cured resin layer, any of the methods (1) to (3), for example, may be used alone or in appropriate combination. For the cured resin layer, a commercially available curable resin composition containing a urethane acrylate resin that can impart high extensibility during secondary molding while maintaining the surface hardness of the cured resin layer may be used as appropriate. (1) The glass transition temperature of the curable resin composition after curing is designed to be between room temperature and the secondary molding temperature (e.g., approximately 110 to 140°C), so that the cured resin is hard at room temperature but softens and can be deformed at the secondary molding temperature. As a result, the cured product of the curable resin (cured resin layer) exhibits high surface hardness at room temperature while exhibiting high extensibility during secondary molding. (2) By using a combination of multiple curable resins with different structures, the crosslinked structure of the curable resin after curing is designed to be not uniform but to have a microstructurally heterogeneous structure with relatively hard parts having a high crosslink density and relatively soft parts having a low crosslink density and high plastic deformability. As a result, the high crosslink density parts in the cured product of the curable resin (cured resin layer) exhibit high surface hardness, and during secondary molding, the low crosslink density parts deform, exhibiting high extensibility. (3) A low-crosslinking or non-crosslinked resin component and / or a low elastic modulus resin component is blended into the curable resin. As a result, after curing of the curable resin, a structure is formed in which fine regions (domains) having a low crosslinking degree or non-crosslinked and / or a low elastic modulus are dispersed in the curable resin phase with a high crosslink density, thereby imparting deformability and extensibility to the cured product of the curable resin (cured resin layer) while maintaining a certain degree of surface hardness.Examples of such low-crosslinking, non-crosslinking, or low-elastic modulus resin components include: (a) thermoplastic resins such as thermoplastic methacrylic resins, styrene-acrylonitrile resins, aliphatic polycarbonate resins, aromatic polycarbonate resins, polyester resins, phenoxy resins, cellulose acylate resins, fluororesins, and polyurethane resins; (b) crosslinked or non-crosslinked soft resins such as acrylic rubber, silicone rubber, hydrogenated styrene butadiene rubber, acrylonitrile butadiene rubber, olefin rubber, and urethane rubber, which may have a reactive functional group as needed, as well as thermoplastic elastomer materials such as polyester-based, polyurethane-based, acrylic-based, olefin-based, styrene-based, silicone-based, and fluororesin-based materials; and (c) core-shell type rubber particles in which a thermoplastic resin is graft-polymerized onto the surface of crosslinked rubber particles.

[0096] <Urethane acrylate resin> The urethane acrylate resin can be obtained, for example, by mixing a polyhydric alcohol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate and allowing the isocyanate group and the hydroxyl group to react to form a urethane bond. In this specification, (meth)acrylate is a general term for acrylate and methacrylate.

[0097] Alternatively, the polyurethane compound can be obtained by reacting a polyhydric alcohol with a polyisocyanate to form a (meth)acryloyl group at the end or in the side chain, and then reacting the resulting isocyanate group with a hydroxyl group-containing (meth)acrylate. In this specification, the term "(meth)acryloyl group" encompasses both methacryloyl and acryloyl groups.

[0098] The various properties of the urethane acrylate resin are not particularly limited, and the molecular weight, composition, main chain structure (e.g., linear or branched), number of functional groups, etc. can be adjusted as appropriate by, for example, the structure of the polyhydric alcohol, the type of polyisocyanate, and the number of acryloyl groups or methacryloyl groups (CH2=CH-CO- or CH2=C(CH3)-CO-) derived from the hydroxyl group-containing (meth)acrylate. Further examples of the urethane acrylate resin include resin compositions containing urethane acrylate resins that are commercially available as curable coating agents.

[0099] The polyvalent isocyanate is not particularly limited as long as it is a compound containing two or more isocyanate groups. Examples of polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane triisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanatoethyl)fumarate, 6-isopropyl methyl ... propyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tolidine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene 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. Among these, polyvalent isocyanate compounds that do not contain an aromatic skeleton but have a saturated aliphatic skeleton or an alicyclic skeleton are preferred because they provide a structure that is more excellent in weather resistance.Examples of such polyisocyanate compounds include 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2,5-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, etc. These polyisocyanates can be used alone or in combination of two or more.

[0100] Specific examples of polyhydric alcohols include 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, polycaprolactone diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester diol, polycarbonate diol, polyurethane diol, bisphenol compounds, biphenol compounds, norbornanediol, dicyclopentanediol, and adamantanediol. Among these, polyhydric alcohols that do not contain an aromatic skeleton and have a saturated aliphatic skeleton or an alicyclic skeleton are preferred because they provide a structure that is more excellent in weather resistance. These polyhydric alcohols may be used alone or in combination of two or more.

[0101] The hydroxyl group-containing (meth)acrylate is not particularly limited, and examples thereof include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. If necessary, (a) compounds having an ethylenically unsaturated bond with at least one hydroxyl group, such as 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, trimethylpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, allyl alcohol, ethylene glycol allyl ether, glycerin (mono-, di-)allyl ether, and N-methylol(meth)acrylamide, (b) or mixtures thereof can be added.

[0102] To promote the reaction between the isocyanate group and the hydroxyl group of the isocyanate component, an organotin urethanization catalyst may be used. The organotin urethanization catalyst may be any catalyst commonly used in urethanization reactions, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkyl maleate, tin stearate, and tin octoate.

[0103] In one or more embodiments of the present invention, at least a portion of the curable resin composition for the cured resin layer may be a commercially available curable resin composition containing a urethane acrylate resin. Examples of such commercially available products include "Z-607-27L" manufactured by Aica Kogyo Co., Ltd., "Beamset 1200W" manufactured by Arakawa Chemical Industries, Ltd., "Acrit 8UX-116A" manufactured by Taisei Fine Chemical Co., Ltd., "NXD-004AP" manufactured by Nippon Kako Toryo Co., Ltd., "P-5820TAH-1" and "P-5820TA-20J" manufactured by Daido Chemical Industry Co., Ltd., and "Lioduras MOL7200" manufactured by Toyochem Co., Ltd. These commercially available curable resin compositions containing urethane acrylate resins have high elongation even after curing, and their use can further increase the crack elongation of the laminate at 120°C.

[0104] <Light Stabilizer> The curable resin composition for the cured resin layer preferably contains a light stabilizer. The inclusion of a light stabilizer improves the stability of the cured resin layer against ultraviolet degradation and light degradation, and suppresses weathering deterioration such as surface cracking and peeling in a portion or application exposed to sunlight outdoors or indoors of a molded article coated with a laminate including the cured resin layer.

[0105] The curable resin composition for the cured resin layer more preferably contains a hindered amine light stabilizer (hereinafter also referred to as "reactive HALS") having at least a reactive functional group as a light stabilizer. In the reactive HALS, the reactive functional group may be any group reactive with the urethane acrylate resin, such as a functional group having an ethylenic double bond. More specifically, it preferably contains 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 contains one or more selected from the group consisting of a methacryloyl group and an acryloyl group. Since the hindered amine light stabilizer has a reactive functional group, when the urethane acrylate resin is cured, the hindered amine light stabilizer molecules react with the urethane acrylate resin and are introduced in a chemically bonded state into the cured product that forms the cured resin layer. This prevents the hindered amine light stabilizer from migrating or flowing out from the surface of the cured resin layer, even under outdoor exposure conditions, thereby preventing weathering deterioration of the cured resin layer for a longer period of time.

[0106] Examples of reactive HALS include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy- Examples of reactive HALS include, but are not limited to, 2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, and 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine. These reactive HALS may be used alone or in combination of two or more.

[0107] As the reactive HALS, for example, commercially available products such as 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (also referred to as 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, manufactured by ADEKA Corporation under the trade name "ADK STAB LA-82", or manufactured by Hitachi Chemical Co., Ltd. under the trade name "FA-711MM"), 2,2,6,6-tetramethyl-piperidinyl methacrylate (also referred to as 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, manufactured by ADEKA Corporation under the trade name "ADK STAB LA-87", or manufactured by Hitachi Chemical Co., Ltd. under the trade name "FA-712HM") may be used.

[0108] The curable resin composition for the cured resin layer preferably contains 0.1 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, and even more preferably 1.0 to 4 parts by mass of a reactive HALS per 100 parts by mass of the urethane acrylate resin. By containing 0.1 parts by mass or more of the reactive HALS, long-term weather resistance is improved. Furthermore, when the reactive HALS is 10 parts by mass or less, weather resistance can be improved without impairing the quality of the cured resin layer.

[0109] In addition to the reactive HALS, the curable resin composition for the cured resin layer may optionally contain other light stabilizers such as hindered amine light stabilizers (hereinafter also referred to as HALS) that do not have a reactive functional group. Examples of HALS include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine. In this case, from the viewpoint of further improving weather resistance without causing bleed-out or curing inhibition during curing of the cured resin layer, the curable resin composition for the cured resin layer may contain a total of 0.5 to 10 parts by mass, 0.8 to 6 parts by mass, or 1.0 to 4 parts by mass of light stabilizer per 100 parts by mass of the urethane acrylate resin.

[0110] <Compound Having Hydrophobic Group and Reactive Functional Group> The curable resin composition for the cured resin layer preferably contains a compound having a hydrophobic group and a reactive group (hereinafter also referred to simply as "hydrophobic reactive compound"). Such compounds are generally referred to as leveling agents, surfactants, antifouling agents, water repellents, oil repellents, dispersants, slip agents, etc. Such compounds are appropriately adjusted and selected in terms of composition and structure according to the components such as the substrate, curable resin, and filler to be blended, and then blended into a curable resin composition and / or a coating material containing the curable resin composition. By blending such compounds into a curable resin composition and / or a coating material containing the curable resin composition, the molecules of the compound having a hydrophobic group and a reactive group distribute the hydrophobic group toward the surface side or the interface side on the surface after application of the curable resin composition and / or coating material, and / or at the interface with other materials such as the substrate or filler, thereby reducing the surface tension of the curable resin composition and / or coating material containing the curable resin composition, or improving the wettability with other materials. Furthermore, they have the effect of imparting functions such as hydrophobicity, water repellency, oil repellency, stain resistance, slipperiness, and scratch resistance to the surface of the cured resin layer after application and / or curing, smoothing the surface of the cured resin layer after application and / or curing, improving the dispersion state of components such as fillers to be blended, etc. In one or more embodiments of the present invention, by adding a compound having a hydrophobic group and a reactive group to the curable resin composition for the cured resin layer, the surface of the cured resin layer is made hydrophobic, thereby more effectively suppressing the penetration of the DEET component into the cured resin layer, and it is presumed that, in particular, when used in combination with a reactive HALS, the effect of improving the weather resistance of DEET resistance is exhibited.

[0111] <Hydrophobic Group> The hydrophobic reactive compound contains a hydrophobic group in the molecule. Specific examples of the hydrophobic group include saturated hydrocarbon groups, aromatic hydrocarbon groups, silicone groups, and fluorine-containing groups. Examples of the silicone group include alkyl-substituted polysiloxane groups such as polydimethylsiloxane groups, where a portion of the alkyl substituent may have a functional group other than a hydrocarbon group, and some or all of the hydrogen groups in the alkyl substituent may be substituted with fluorine groups. Examples of the fluorine-containing group include partially fluorinated hydrocarbon groups, perfluoroalkyl groups, partially fluorinated polyalkyleneoxy groups, polyperfluoroalkyleneoxy groups, and fluoroalkyl-substituted siloxane groups. Among these hydrophobic groups, one or more selected from the group consisting of silicone groups and fluorine-containing groups are preferred, and fluorine-containing groups are more preferred, because they are expected to have high hydrophobicity, excellent performance in imparting leveling and wettability by adding a compound, excellent water repellency and oil repellency, and excellent effect in improving DEET resistance. As the hydrophobic group containing a silicone group and a fluorine-containing group, a fluoroalkyl-substituted siloxane group can be appropriately used.

[0112] <Reactive Group> The hydrophobic reactive compound has, in addition to the hydrophobic group, a reactive group in the molecule, more preferably a functional group that can react with the urethane acrylate resin during the curing reaction. By containing such a reactive group, a chemical bond is formed between the curable resin and the hydrophobic reactive compound (a compound having a hydrophobic group and a reactive group) during the curing reaction, making it easier for the compound having the hydrophobic group and the reactive group to remain on the surface of the cured resin layer of the laminate without being washed away, and it is expected that functions such as hydrophobicity, water repellency, oil repellency, stain resistance, slipperiness, scratch resistance, and DEET resistance will be maintained for a long period of time. Specific examples of such reactive groups include carbon-carbon double bond groups such as acryloyl groups, methacryloyl groups, vinyl groups, and allyl groups, as well as thiol groups. Among these, one or more selected from the group consisting of acryloyl groups and methacryloyl groups are preferred in terms of their good reactivity with the urethane acrylate group and their excellent weather resistance and maintenance of DEET resistance after weathering tests.

[0113] The hydrophobic reactive compound may be a commercially available product such as a reactive leveling agent, antifouling agent, surfactant, etc. Specific examples include commercially available products sold as leveling agents, surfactants, surface conditioners, etc., such as the "BYK-UV" series (manufactured by BYK Chemie), the "Megafac" series (manufactured by DIC Corporation), the "Ftergent" series (manufactured by Neos Co., Ltd.), the KP series and KY-1200 series (manufactured by Shin-Etsu Chemical Co., Ltd.), the "Disparlon" series (manufactured by Kusumoto Chemical), the "Polyflow" series (manufactured by Kyoeisha Chemical Co., Ltd.), and the "Surflon" series (manufactured by AGC Seimi Chemical Co., Ltd.), but are not limited thereto. Among these, for example, "Megafac RS" (manufactured by DIC Corporation), "Ftergent 601" (manufactured by Neos Corporation), and "KY-1203" (manufactured by Shin-Etsu Chemical Co., Ltd.) are preferred because they are expected to impart a relatively high water contact angle and oleic acid contact angle to the surface of the cured resin layer and to improve DEET resistance, particularly DEET resistance after a weathering test.

[0114] The curable resin composition for the cured resin layer preferably contains 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass of a compound having a hydrophobic group and a reactive group per 100 parts by mass of urethane acrylate resin. By containing 0.01 parts by mass or more of a compound having a hydrophobic group and a reactive group, the leveling properties of the curable resin composition for the cured resin layer are improved, the wettability to the substrate and filler components is improved, and defects such as cissing are prevented. In addition, when the compound having a hydrophobic group and a reactive group is 5 parts by mass or less, adverse effects such as reduced substrate adhesion and reduced recoatability due to excessive incorporation are less likely to occur.

[0115] <Other Components> The curable resin composition for the cured resin layer may contain other components in addition to the components described above. Examples of other components that can be used in combination include monomers, oligomers, resins, or mixtures thereof having radical-reactive functional groups, such as (meth)acrylate compounds, epoxy acrylate monomers, polyester acrylates, and polyacrylic acrylates. Furthermore, a urethane acrylate resin may be used in combination with a composition containing, for example, (a) a hydrolysis condensate of a di- to tetrafunctional silane compound, and / or (b) a monomer, oligomer, resin, or mixtures thereof having cationically curable and / or anionically curable functional groups, such as an epoxy group and an oxetane group. These other components may be used alone or in combination.

[0116] The (meth)acrylate compound is not particularly limited as long as it has at least one (meth)acryloyl group.Specific examples thereof include monofunctional (meth)acrylates such as alkyl (meth)acrylate, aryl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc.; and polyfunctional (meth)acrylates such as 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. These may be used alone or in combination of two or more. Further examples of the (meth)acrylate compound include those commercially available as ultraviolet-curable hard coating agents.

[0117] The epoxy acrylate monomer is not particularly limited. Specific examples include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and vinylcyclohexene monoxide (i.e., 1,2-epoxy-4-vinylcyclohexane). Also usable as the epoxy acrylate monomer are so-called vinyl ester monomers obtained by reacting the epoxy group of an epoxy resin monomer having a skeleton such as a bisphenol, novolac, or biphenyl with acrylic acid.

[0118] When forming the cured resin layer, a known method can be applied to cure the resin layer (coated film of the curable resin composition). As a curing method, a method of irradiating with active energy rays, such as ultraviolet rays or electron beam rays, is preferred. When curing is performed by irradiating with ultraviolet rays, a photopolymerization initiator is used.

[0119] Specific examples of the photopolymerization initiator include acetophenone, benzophenone, benzoyl methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc. Among these, 1-hydroxycyclohexylphenyl ketone is preferred because of its excellent compatibility with urethane acrylate resins.

[0120] A curable resin composition can be applied to one or both surfaces of a substrate layer containing an acrylic resin film, and the resin layer (coating film) made of the curable resin composition can be cured to form a cured resin layer.

[0121] When a cured resin layer is formed by applying a curable resin composition for a cured resin layer to one or both surfaces of a substrate layer containing an acrylic resin film and curing the coating film, various additives such as ultraviolet absorbers, antifoaming agents, antioxidants, light diffusing agents, matting agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic particles, and antistatic agents can be added to the curable resin composition as needed. The additives are not limited to these.

[0122] Furthermore, inorganic fine particles may be added to the curable resin composition for the cured resin layer from the viewpoint of surface hardness and abrasion resistance, within a range that does not impair the object of the present invention. Examples of inorganic fine particles include, but are not limited to, silica, alumina (aluminum oxide), titanium oxide, zinc oxide, zirconia, graphene, nanocarbon, carbon black, nanodiamond, mica, barium titanate, boron nitride, metallic silver, and metallic copper. These inorganic fine particles may be used without surface treatment, or may be surface-treated in advance by a known method to control the dispersion state and maintain good stretchability, thereby appropriately controlling the affinity with the cured resin layer.

[0123] Furthermore, within a range that does not impair the object of the present invention, the curable resin composition for the cured resin layer may contain anti-glare particles from the viewpoint of enhancing the anti-glare properties of the laminate. With regard to the anti-glare particles, in order to obtain a balance of various properties such as the desired anti-glare properties, clarity of a transmitted image, glare, jet-black surface, surface hardness, slipperiness, and antistatic properties, the particle material, the number of components blended, the type of particle dispersion solvent, particle diameter, dispersed particle diameter, the thickness of the cured resin layer, the relative refractive index difference with the base layer containing an acrylic resin film, the affinity and reactivity of the particle surface with the base layer containing an acrylic resin film or the solvent, and the like can be appropriately adjusted within known technical ranges that do not impair the effects of the present invention.

[0124] The material of the anti-glare particles to be incorporated into the cured resin layer is not particularly limited as long as it enhances the anti-glare properties of the laminate within a range that does not impair the objectives of the present invention, and for example, inorganic particles and / or organic particles can be used. Examples of inorganic particles include silica, alumina, glass beads, glass flakes, mica, clay, titanium oxide, zinc oxide, zirconia, and metal particles. Examples of organic particles include crosslinked organic resin particles containing one or more main components selected from the group consisting of alkyl (meth)acrylate units, aromatic vinyl units, and siloxane units, as well as core-shell multilayered resin particles. In terms of ease of availability and ease of designing anti-glare properties according to the application, the particles are preferably one or more selected from the group consisting of inorganic oxide particles (e.g., silica, alumina, titanium oxide, zinc oxide, and zirconia) and crosslinked organic resin particles (e.g., crosslinked silicone resin, crosslinked acrylic resin, and crosslinked aromatic vinyl resin), and more preferably one or more selected from the group consisting of silica, alumina, zirconia, and crosslinked organic resin particles. From the viewpoint of the balance of physical properties such as antiglare property, dispersibility, and surface hardness, it is particularly preferable that the particles are one or more selected from the group consisting of silica, alumina, and crosslinked organic resin particles. Furthermore, from the viewpoint of controlling dispersibility, these particles may be subjected to a surface treatment using a known method such as a silane coupling agent or reactive monomer, which may have a reactive substituent, plasma treatment, or corona treatment, and / or graft polymerization treatment. It is preferable that at least some of the particles contain, on their surfaces, reactive functional groups reactive with urethane acrylate resins, since this may improve the interfacial adhesion between the particles and the cured resin layer, and may improve the dispersibility of the particles and the occurrence of cracks and / or whitening during stretching. Examples of reactive functional groups reactive with urethane acrylate resins include (a) radically reactive functional groups such as vinyl groups and (meth)acryloyl groups, (b) ionic functional groups such as epoxy groups, oxetane groups, hydroxyl groups, carboxyl groups, mercapto groups, isocyanyl groups, hydroxyl groups, and amino groups, and (c) moisture-curable functional groups such as silyl groups and alkoxysilyl groups.

[0125] In the cured resin layer, "antiglare particles" or "inorganic fine particles" may be dispersed in the form of primary particles or in the form of aggregates of multiple particles, depending on the size of the primary particles. The size of the region (dispersion domain) in which these particles or fine particles, or their aggregates, are distributed is defined as the "average dispersed particle size." When the primary particles are large, the average dispersed particle size may be the same as the primary (basic) particle size.

[0126] The average dispersed particle diameter of the anti-glare particles is not particularly limited as long as the effects of the present invention are achieved, but may be, for example, 0.1 to 50.0 μm, 0.2 to 25.0 μm, or 0.5 to 10 μm, etc. In this specification, a cross-sectional photograph of the laminate, measuring 1200 nm × 800 nm and magnifying 200,000 times, measured with an electron microscope (Hitachi High-Technologies Corporation, H7650) is observed, and the arithmetic mean value of particle diameters of 10 dispersed domains of the anti-glare particles in the cured resin layer is calculated, and the obtained value is defined as the average dispersed particle diameter of the anti-glare particles in the cured resin layer.

[0127] The average dispersed particle diameter of the inorganic fine particles is not particularly limited as long as the effects of the present invention are achieved, but may be, for example, 0.5 to 1000 nm, 1 to 500 nm, or 2 to 200 nm, etc. In this specification, a cross-sectional photograph of the laminate, 1200 nm x 800 nm, measured at 200,000 times magnification using an electron microscope (Hitachi High-Technologies Corporation, H7650) is observed, and the arithmetic mean value of particle diameters of 10 dispersed domains of the inorganic fine particles in the cured resin layer is calculated, and the obtained value is defined as the average dispersed particle diameter of the inorganic fine particles in the cured resin layer.

[0128] The content of the anti-glare particles in the curable resin composition for the cured resin layer is not particularly limited as long as it can enhance the anti-glare properties of the laminate within a range that does not impair the object of the present invention, and may be, for example, 0.1 to 30.0 mass %, 0.5 to 20.0 mass %, or 1.0 to 15.0 mass %, etc.

[0129] The content of inorganic fine particles in the curable resin composition for the cured resin layer is not particularly limited as long as it can increase the abrasion resistance of the laminate within a range that does not impair the object of the present invention, and may be, for example, 0.1 to 30.0 mass %, 0.3 to 20.0 mass %, or 0.5 to 15.0 mass %, etc.

[0130] In order to impart appropriate coatability to the curable resin composition for the cured resin layer, an organic solvent is usually blended. The organic solvent is not particularly limited as long as it can impart the desired coatability to the curable resin composition and form a cured resin layer with the desired thickness and performance. The boiling point of the organic solvent is preferably 50 to 150°C from the viewpoints of coatability and drying properties of the resin layer (coating film) formed.

[0131] Specific examples of organic solvents include saturated hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and methylene chloride, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, esters such as methyl acetate, ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran, dioxane, propylene glycol monoethyl ether, methyl cellosolve and ethyl cellosolve, and amides such as N-methylpyrrolidone and dimethylformamide. The organic solvents can be used alone or in combination of two or more.

[0132] When the curable resin composition for the cured resin layer is applied to one or both sides of a substrate layer containing an acrylic resin film, any coating method can be used without particular limitation. Examples of the coating method include reverse coating, gravure coating, bar coating, die coating, spray coating, kiss coating, wire bar coating, and curtain coating. These coating methods may be used alone or in combination.

[0133] The curable resin composition for the cured resin layer described above is applied to one or both surfaces of a substrate layer containing an acrylic resin film to form a resin layer (coating film), and then the organic solvent is removed from the coating film by drying, and the resin layer is cured by active energy rays such as ultraviolet irradiation, thereby forming a cured resin layer.

[0134] The drying temperature for removing the organic solvent from the resin layer after coating is preferably 60 to 120°C, more preferably 70 to 100°C. If the drying temperature is too low, the organic solvent may remain in the resin layer (coating film). If the drying temperature is too high, the acrylic resin film may be thermally deformed, which may impair the flatness of the laminate (cured resin layer).

[0135] The wavelength of the ultraviolet light irradiated when curing the resin layer (coating film) is preferably in the range of 200 to 400 nm. The integrated amount of ultraviolet (UV) light is 500 mJ / cm. 2 It is preferable that the concentration is equal to or higher than 550 mJ / cm 2 More preferably, 600 mJ / cm 2 The total amount of UV light is 500 mJ / cm 2 By setting the above, the degree of curing of the cured resin layer can be increased, specifically, the curing index represented by the above-mentioned formula 1 can be lowered and / or the degree of curing represented by the following formula 2 can be increased, thereby increasing the crosslink density of the cured resin layer and increasing the hardness, DEET resistance, and weather resistance of DEET resistance (DEET resistance after weathering test) of the laminate. The upper limit of the cumulative light amount may be set appropriately taking into consideration energy efficiency as well as not causing deterioration of the cured resin layer due to excessive ultraviolet irradiation and the resulting heat generation, etc. For example, 1500 mJ / cm 2 Preferably, the concentration is 1400 mJ / cm or less. 2 Below, 1300mJ / cm 2 Below, 1200mJ / cm 2 Below, 1100mJ / cm 2 Below, 1000mJ / cm 2 Below, 900mJ / cm 2 or less, or 800 mJ / cm 2 The following is also acceptable.

[0136] <"Cure Index" and "Cure Degree"> In the laminate of one or more embodiments of the present invention, the cured resin layer needs to have a cure index of 0.013 or less, as described above. More preferably, the cure degree of the cured resin layer, represented by the following formula 2, is 75% or more.

[0137] Generally, in the crosslinking reaction of a curable resin composition, the higher the degree of crosslinking, the more restricted the movement of the crosslinked polymer chains, and therefore, the curing reaction rarely proceeds to 100%, and unreacted curable functional groups often remain. Quantification of the progress of the curing reaction is generally performed by quantifying spectra corresponding to the functional groups before and after the reaction using an analytical technique such as CP / MAS (Cross Polarization Magic Angle Spinning)-1H NMR. In this specification, the progress of the curing reaction of a cured resin layer formed from a cured product of an active energy ray-curable resin composition containing a urethane acrylate resin can be expressed as a curing index calculated by the following formula 1 and / or a curing degree calculated by the following formula 2 using FT-IR analysis in reflection mode. [Formula 1] Cure index = B / D [Formula 2] Cure degree (%) = 100 × [(A / C) - (B / D)] / (A / C) In the formulas 1 and 2, A is the wave number of 810 cm in FT-IR measurement of a coating film of the active energy ray-curable resin composition before curing. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 810 cm in the FT-IR measurement of the cured resin layer. -1 C represents the area of ​​the infrared absorption peak near the wave number 1705 cm in FT-IR measurement of the coating film of the active energy ray-curable resin composition before curing. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 1705 cm in the FT-IR measurement of the cured resin layer. -1 The area of ​​the infrared absorption peak in the vicinity is shown.

[0138] Infrared spectrum wavenumber 810 cm -1The peaks around correspond to the out-of-plane bending vibration of the C-C double bonds of the acryloyl group and the methacryloyl group, and 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 cured resin layer, i.e., 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. In the FT-IR measurement, the wave number was 810 cm -1 The infrared absorption peak near 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 uncured acryloyl groups and methacryloyl groups in the coating film of the active energy ray-curable resin composition before and after the curing reaction, and the total amount of ester groups after the acryloyl groups and methacryloyl groups have been cured. The total amount of C-O double bond functional groups does not change in principle before and after the curing reaction. Therefore, the above-mentioned curing index B / D is calculated by dividing the peak area values ​​corresponding to the acryloyl and methacryloyl groups, which are functional groups that decrease upon reaction, by the peak area value that does not change in principle upon reaction. It is maximum in the unreacted state and becomes 0 when the curing reaction has completely proceeded, and can be used as an index of the progress of the curing reaction. Furthermore, the degree of curing represented by the above formula 2 indicates the ratio of the remaining amount of acryloyl groups and methacryloyl groups after curing to the content of acryloyl groups and methacryloyl groups before curing, and can be used as an index of the progress of the curing reaction.

[0139] Furthermore, for the purpose of further improving the surface hardness, DEET resistance, weather resistance, etc. of a molded article having a laminate of one or more embodiments of the present invention disposed on its surface, an operation of irradiating active energy rays such as ultraviolet rays with the laminate may be carried out after secondary molding by vacuum and / or pressure molding of the laminate, or on at least a part of the molded article having the laminate disposed on its surface.

[0140] (Laminate) In one or more embodiments of the present invention, the laminate may include a substrate layer containing an acrylic resin film and a cured resin layer laminated on one side of the substrate layer. Alternatively, in the laminate, the cured resin layer may be laminated on both sides of the acrylic substrate layer. Furthermore, the laminate may include other functional layers laminated between the substrate layer and the cured resin layer and / or on one or both sides of the laminate, as needed, within a range that does not impair the effects of the present invention.

[0141] The other functional layers are not particularly limited, and a wide range of conventionally known layers can be used. Examples include 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. The decorative layer may include a colored layer, a design layer, a surface irregularity layer, an embossed layer, and the like. The adhesive layer may include a primer layer, and the like. Examples of the thermoplastic resin layer include an antifouling layer, a fingerprint-resistant layer, a hard coat layer, a scratch-resistant layer, a gas barrier layer, and a gas absorption layer. Examples of the optical functional layer include a low refractive index layer, a high refractive index layer, an ultraviolet shielding layer, an infrared shielding layer (also referred to as a reflective layer), a light diffusion layer, an antiglare layer, a matte layer, a retardation adjustment layer, a viewing angle adjustment layer, and a polarizing layer. The laminate may include a combination of two or more of the other functional layers. Furthermore, one functional layer may have two or more functions.

[0142] The laminate has a crack elongation of 80% or more at 120 ° C. As a result, when the laminate is laminated on a molded body substrate such as a thermoplastic resin substrate and the molded body substrate such as a thermoplastic resin substrate is covered with the laminate, particularly when the laminate is shaped by vacuum forming or pressure forming under heating, during lamination molding onto the substrate, or when the shaped laminate is placed on the mold surface as needed and then a molded body is obtained by insert injection molding, defects such as cracks and whitening in the laminate can be suppressed, and secondary formability 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 this specification, the crack elongation of the laminate at 120 ° C. can be measured by the method described in the examples.

[0143] From the viewpoint of suppressing whitening during molding, the laminate preferably exhibits a change in haze (Δ haze) of 0.5% or less when stretched 40% at 120°C, more preferably 0.3% or less, and particularly preferably 0.2% or less. Furthermore, from the viewpoint of suppressing whitening during molding, the laminate preferably exhibits a change in haze (Δ haze) of 0.5% or less when stretched 80% at 120°C, more preferably 0.3% or less, and particularly preferably 0.2% or less. In this specification, the Δ haze of the laminate when stretched 40% at 120°C and the Δ haze of the laminate when stretched 80% at 120°C can both be measured by the method described in the Examples. In addition, in this specification, 40% stretching means that, when the size before stretching is L1 and the size after stretching is L2, [100 × (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 × (L2 - L1) / L1]% is 80%.

[0144] From the viewpoint of excellent surface hardness and enhancing the scratch resistance of molded articles using the laminate, the pencil hardness of the cured resin layer side under a load of 500 g is preferably B or higher, more preferably HB or higher, even more preferably F or higher, and particularly preferably H or higher.

[0145] From the viewpoint of excellent chemical resistance, it is preferable that the laminate shows no visual change in appearance when about 0.02 mL of isopropyl alcohol is dropped onto the surface of the cured resin layer and left at 23° C. for 6 hours. Also, from the viewpoint of excellent chemical resistance, it is preferable that the laminate shows no visual change in appearance when about 0.02 mL of acetone is dropped onto the surface of the cured resin layer and left at 23° C. for 6 hours.

[0146] From the viewpoint of excellent abrasion resistance, the laminate is applied with a pressure of 500 g / cm to the surface of the cured resin layer. 2 The change in haze (Δ haze) of the laminate before and after an abrasion resistance test in which a gauze is reciprocated 20 times under a load of 0.5% or less is preferably 0.5% or less, more preferably 0.4% or less, and even more preferably 0.3% or less.

[0147] From the viewpoint of excellent abrasion resistance, the laminate is applied with a pressure of 100 g / cm to the surface of the cured resin layer. 2 The change in haze (Δ haze) of the laminate before and after an abrasion resistance test in which steel wool (#0000) is reciprocated 10 times under a load of 1.0 g / cm<2> is preferably 2% or less, more preferably 1.8% or less, and even more preferably 1.6% or less.

[0148] It is desirable that the laminate show no change in appearance when its DEET resistance is evaluated under the following conditions: that is, gauze coated with 0.05 g 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, and the laminate is left standing for 30 seconds under conditions of 23°C and a relative humidity of 65%, and then further left to stand in a thermostatic chamber at 74°C for 1 hour, after which it is desirable that no visual change in appearance occurs.

[0149] It is desirable that the laminate maintains its DEET resistance after a weathering test according to the weathering resistance level required for some automotive interior applications, i.e., that it has weathering resistance to DEET. That is, the laminate is placed so that the cured resin layer side faces the light source, and a xenon lamp is used as the light source, and the irradiance is 180 W / m 2 (300 to 400 nm), a black panel temperature of 89°C, and no rainfall, for 300 hours. Then, gauze coated with 0.05 g 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, and the laminate is left standing for 30 seconds under conditions of 23°C and a relative humidity of 65%, and further left standing for 1 hour in a thermostatic chamber at 74°C. More preferably, there is no visible change in appearance when the laminate is placed so that the cured resin layer side faces the light source, and a xenon lamp is used as the light source, and the irradiance is 180 W / m 2It is more preferable that a weather resistance test be conducted for 500 hours under conditions of a black panel temperature of 89°C (300 to 400 nm), a black panel temperature of 89°C, and no rainfall, and then gauze coated with 0.05 g 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, and the laminate is left to stand for 30 seconds under conditions of 23°C and a relative humidity of 65%, and then further left to stand for 1 hour in a thermostatic chamber at 74°C, after which no visual change in appearance occurs.

[0150] From the viewpoint of weather resistance, the laminate preferably has a color difference ΔE of 0.5 or less, more preferably 0.3 or less, between the laminate after the above-mentioned 300-hour or 500-hour weather resistance test and the laminate before the weather resistance test.

[0151] From the viewpoint of weather resistance, the laminate preferably has a ΔYI of 0.5 or less, more preferably 0.3 or less, after the 300-hour or 500-hour weather resistance test, relative to the laminate before the weather resistance test. In this specification, ΔYI can be measured and calculated by the method described in the examples.

[0152] From the viewpoint of DEET resistance, the laminate preferably has a water contact angle of 105° or more on the surface of the cured resin layer. Furthermore, from the viewpoint of weather resistance of DEET resistance, the laminate preferably has a water contact angle of 95° or more on the surface of the cured resin layer after the above-mentioned 300-hour weather resistance test. Furthermore, from the viewpoint of weather resistance of DEET resistance, the laminate preferably has a water contact angle of 92° or more on the surface of the cured resin layer after the above-mentioned 500-hour weather resistance test. In this specification, the water contact angle can be measured by the method described in the Examples.

[0153] From the viewpoint of DEET resistance, the laminate preferably has an oleic acid contact angle of 65° or more on the surface of the cured resin layer. The oleic acid contact angle on the surface of the laminate on the cured resin layer side can be measured by the method described in the Examples.

[0154] From the viewpoint of transparency, the laminate preferably has a haze of 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, even more preferably 0.8% or less, even more preferably 0.6% or less, and particularly preferably 0.4% or less. Furthermore, from the viewpoint of transparency and weather resistance, the laminate preferably has a haze of 2.0% or less after the above-mentioned 300-hour weather resistance test, more preferably 1.5% or less, even more preferably 1.0% or less, even more preferably 0.8% or less, and even more preferably 0.6% or less. Furthermore, from the viewpoint of transparency and weather resistance, the laminate preferably has a haze of 2.0% or less after the above-mentioned 500-hour weather resistance test, more preferably 1.5% or less, even more preferably 1.0% or less, even more preferably 0.8% or less, and even more preferably 0.6% or less. However, this does not necessarily apply when components such as a matting agent or an antiglare agent are introduced into the acrylic resin film substrate and / or the cured resin layer based on requirements for quality such as appearance. In this specification, the haze can be measured by the method described in the examples.

[0155] From the viewpoint of transparency, the laminate preferably has a total light transmittance of 90% or more, more preferably 91% or more. Furthermore, from the viewpoint of weather resistance of transparency, the laminate preferably has a total light transmittance of 90% or more, more preferably 91% or more, after the above-mentioned 300-hour weather resistance test. Furthermore, from the viewpoint of weather resistance of transparency, the laminate preferably has a total light transmittance of 90% or more, more preferably 91% or more, after the above-mentioned 500-hour weather resistance test. In this specification, the total light transmittance can be measured by the method described in the examples.

[0156] The laminate can be used as a decorative protective sheet that decorates and / or protects a molded article. When used as a decorative protective sheet, the laminate can further include, in addition to the substrate layer and the cured resin layer, one or more layers selected from the group consisting of the above-mentioned printed layer, decorative layer, adhesive layer, antistatic layer, thermoplastic resin layer, and optical functional layer. By using the laminate as a decorative protective sheet, it is possible to impart various functionalities to the molded article, such as DEET resistance, weather resistance, scratch resistance, and DEET resistance after weathering tests.

[0157] (Molded Product) In one or more embodiments of the present invention, the molded product includes the above-described laminate, wherein the laminate is laminated on the surface of the molded product substrate, and the cured resin layer of the laminate is disposed closer to the surface of the molded product than the substrate layer of the laminate. The laminate may be laminated on part or all of the surface of the molded product substrate. Due to the high crack elongation at 120 ° C of the laminate, a molded product substrate having at least a non-planar three-dimensional shape in a portion thereof can be coated with the laminate to preferably obtain a molded product having a three-dimensional shape, more specifically a resin molded product. In molded products having various shapes, the laminate can be coated on the molded product substrate to impart various functionalities to the molded product, such as DEET resistance, weather resistance, scratch resistance, and DEET resistance after weathering tests.

[0158] The molded body substrate is not particularly limited, but a thermoplastic resin substrate can be suitably used. The thermoplastic resin substrate may be, for example, a polycarbonate resin having a bisphenol-based skeleton, a fluorene-based skeleton, or an isosorbide-based skeleton, an acrylic resin, a styrene-based resin (AS resin, ABS resin, MAS resin, styrene-maleimide-based resin, styrene-maleic anhydride resin, etc.), a saturated polyester resin, a polyvinyl chloride resin, a polyarylate resin, a PPS-based resin, a POM-based resin, a polyamide resin, a polylactic acid resin, a cellulose acylate-based resin, and a polyolefin-based resin. Among them, one or more selected from the group consisting of polycarbonate resin, acrylic resin, styrene-based resin, and amorphous polyolefin-based resin are preferred because of their excellent transparency, and polycarbonate resin and / or acrylic resin are more preferred because of their good adhesion to the laminate, and polycarbonate resin is even more preferred from the viewpoints of high rigidity, high heat resistance, and high impact resistance.

[0159] The molded article has excellent weather resistance, abrasion resistance, and DEET resistance, as well as excellent DEET resistance before and after weathering tests, and can therefore be used, for example, as vehicle interior materials such as automobile interior materials, vehicle exterior materials such as automobile exterior materials, housings and exterior components for portable electronic devices and personal computers, and exterior materials for home appliances. It is particularly suitable for use as an automobile interior material. Specific examples of automobile interior materials include console boxes, meter covers, door panels, armrests, door lock bezels, steering wheels, various switch buttons and switch bases, shift levers, center clusters, dashboards, instrument panels, in-vehicle display front panels, sensor covers, plated parts such as emblems, and garnishes.

[0160] The method for producing a molded article is not particularly limited as long as it is a molding method that can cover at least a portion of a molded article substrate, preferably a thermoplastic resin substrate, with a laminate. Using a laminate, a molded article having a laminate disposed on its surface can be produced, for example, by in-mold molding, film insert injection molding, or the like. Furthermore, prior to in-mold molding or film insert injection molding, the laminate may be pre-shaped, as necessary, by methods such as vacuum molding, pressure molding, or compression molding. Alternatively, the laminate may be heated under reduced pressure and / or pressure conditions, and the laminate may be disposed on the surface of a thermoplastic resin substrate having at least a non-planar three-dimensional shape to produce a resin molded article, a so-called three-dimensional laminate molding. Furthermore, the laminate may be heated and stretched appropriately, and then manually laminated onto the surface of a thermoplastic resin substrate to produce a resin molded article.

[0161] The present invention will be described in more detail below based on examples. The present invention is not limited to these examples. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0162] The measurement and evaluation methods used in the examples and comparative examples will be explained below.

[0163] (Cure Index and Cure Degree) The cure index and cure degree of the cured resin layer were measured by measuring the infrared absorption spectra of the surface of the coating film (in a dry state) of the active energy ray-curable resin composition before curing and the surface of the cured resin layer by an ATR method (attenuated total reflection measurement method) using a diamond prism using an FT / IR-4700 (manufactured by JASCO Corporation), and after correcting for components derived from the infrared absorption spectrum of the prism material, the horizontal axis was used to calculate the curing index and cure degree. -1 ) and the vertical axis is the transmittance (%). In the infrared absorption spectrum, the wave number 810 cm was calculated using the "spectrum analysis" function of the instrument. -1 Infrared absorption peaks around 1705 cm -1 A baseline, which is a straight line connecting two points at the base of each infrared absorption peak in the vicinity, was set by the method described below, and a value corresponding to the peak area was calculated. -1), and in the infrared absorption spectrum where the vertical axis is transmittance (%), the infrared absorption peak is observed pointing downward. These values ​​were regarded as the areas of the respective peaks, and the curing index and degree of curing were calculated using the following formulas 1 and 2. [Formula 1] Curing index = B / D [Formula 2] Degree of curing (%) = 100 × [(A / C) - (B / D)] / (A / C) In formulas 1 and 2, A is the wave number of 810 cm in FT-IR measurement of a coating film of the active energy ray-curable resin composition before curing. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 810 cm in the FT-IR measurement of the cured resin layer. -1 C represents the area of ​​the infrared absorption peak near the wave number 1705 cm in FT-IR measurement of the coating film of the active energy ray-curable resin composition before curing. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 1705 cm in the FT-IR measurement of the cured resin layer. -1 The peak areas of A and C were calculated from the same infrared absorption spectrum chart by using a line connecting two points at the base of the corresponding peak as the baseline, and the area enclosed by the curve of the peak was calculated as the peak area. The peak areas of B and D were calculated from the same infrared absorption spectrum chart by using a line connecting two points at the base of the corresponding peak as the baseline, and the area enclosed by the curve of the peak was calculated as the peak area. -1 The peak around 1705 cm corresponds to the out-of-plane bending vibration of the carbon-carbon (C-C) double bond of the acrylate group. -1 The peaks around 800 cm correspond to the stretching vibration of the carbon-oxygen (C-O) double bond of the ester group. In an infrared absorption spectrum (IR spectrum) chart, the two points at the base of a given peak refer to the points where the IR spectrum lines on both sides of the peak start to bend downward toward the center of the peak. Figure 1 shows an example of determining the curing index B / D from the IR spectrum chart for Comparative Example 2. In Figure 1, Peak 1 is at a wavenumber of 810 cm -1 Peak 2 is an infrared absorption peak at a wave number of 1705 cm -1It is an infrared absorption peak near. In Peak 1, the numerical value corresponding to the peak area, which is the area surrounded by the baseline Lb1, which is a straight line connecting the two base points a and b, and the curve of Peak 1, i.e., B, is 23.5038, and in Peak 2, the numerical value corresponding to the peak area, which is the area surrounded by the baseline Lb2, which is a straight line connecting the two base points c and d, and the curve of Peak 2, i.e., D, is 1276.81. As a result, the curing index B / D is calculated to be 0.0184. In the IR spectrum chart, points a and b where the IR spectrum lines on both sides adjacent to Peak 1 begin to bend downward toward the center of Peak 1, respectively, are two points at the base of Peak 1. Furthermore, in the IR spectrum chart, points c and d where the IR spectrum lines on both sides adjacent to Peak 2 begin to bend downward toward the center of Peak 2, respectively, are two points at the base of Peak 2, respectively.

[0164] (Tensile elongation at break at 120°C) An acrylic resin film was cut into a size of 10 mm (width) x 100 mm (length) to prepare a test specimen. The test specimen 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 chuck distance of 40 mm, and a tensile speed of 200 mm / min. The elongation at break of the acrylic resin film was taken as the tensile elongation at break. The value of the tensile elongation at break was the arithmetic mean of the three values ​​excluding the highest and lowest values ​​among the measurement results obtained using five test specimens.

[0165] (Crack elongation at 120°C) The laminate was cut into a sample measuring 10 mm (width) x 100 mm (length). The sample was measured using a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a high-temperature bath set to 120°C, under conditions of a preheating time of 2 minutes, a chuck distance of 40 mm, and a tensile speed of 200 mm / min. The elongation at which cracks occurred in the cured resin layer was taken as the crack elongation at 120°C. The crack elongation value was the arithmetic mean of the test results (three) obtained by measuring three samples.

[0166] (Thickness) The thickness (film thickness) of the acrylic resin film was measured using a PEACOCK Dial Gauge No. 25 (manufactured by Ozaki Manufacturing Co., Ltd.). The thickness (film thickness) of the cured resin layer was measured using an F20 Film Thickness Measurement System (manufactured by Filmetrics Inc.). The surface opposite the cured resin layer was painted black with a felt-tip pen, and measurements were performed with the refractive index of the acrylic resin film set to 1.49 and the refractive index of the cured resin layer set to 1.50.

[0167] (Total Light Transmittance and Haze) The total light transmittance and haze of the laminate were measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7375:2008 and JIS K 7136:2000, respectively.

[0168] (Δ haze after stretching at 120°C) The laminate was cut into a 10 mm (width) x 100 mm (length) sample. The sample was stretched by 40% or 80% using a Tensilon tensile tester (Shimadzu Corporation, AG-2000D) equipped with a thermostatic chamber set at 120°C under conditions of a preheating time of 2 minutes, a chuck distance of 40 mm, and a tensile speed of 200 mm / min, and the haze of the stretched portion of the laminate after stretching was measured in accordance with JIS K 7136:2000 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The chuck distance was 56 mm at 40% stretching and 72 mm at 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 defined as "Δ haze after 40% stretching at 120°C" or "Δ haze after 80% stretching at 120°C."

[0169] (Pencil Hardness) The pencil hardness of the surface of the laminate on the cured resin layer side was measured under a load of 500 g in accordance with JIS K 5600-5-4:1999.

[0170] (Weather resistance test) A super xenon weather meter (SX2D-75, manufactured by Suga Test Instruments Co., Ltd.) was used. The filter configuration used quartz glass on the inside and polysilicate #275 on the outside to simulate direct sunlight. A laminate sample (40 mm x 50 mm) was placed with the cured resin layer side facing the light source, and a weather resistance test was performed for 300 hours or 500 hours under the following conditions: Condition: Irradiance 180 W / m 2 (300-400 nm), black panel temperature 89±3°C, relative humidity 50±5%, no rain

[0171] (DEET Resistance Test) A sample of the laminate cut into a 5 cm x 5 cm square was placed on a horizontal surface with the cured resin layer facing up, and a piece of gauze (FC gauze, manufactured by Hakujuji Co., Ltd.) cut into a 5 cm x 5 cm size was placed on top of it. 0.05 g of insect repellent (Mukhi's insect repellent Mushipairu α30, manufactured by Ikeda Mohando, an alcohol solution of DEET (N,N-diethyl 3-methylbenzamide), containing 30 g of DEET per 100 mL) was dropped into the center of the gauze and left for 30 seconds. The insect repellent penetrated the gauze and came into contact with the surface of the cured resin layer of the laminate. After that, the sample was left in an oven at 74 ° C. for 1 hour, after which the gauze was removed, the remaining chemical (insect repellent) was wiped off with a wet cloth, and the surface of the cured resin layer was visually observed. The DEET resistance was evaluated according to the following criteria. Good: No change in appearance. Bad: A mark remains along the outline of the dripped area and / or the dripped area turns white.

[0172] (Isopropyl alcohol resistance test, acetone resistance test) A laminate sample cut into a 5 cm x 5 cm square was placed on a horizontal surface with the cured resin layer side facing up, and one drop (approximately 0.02 mL) of isopropyl alcohol (hereinafter also referred to as IPA) or acetone taken with a dropper was dropped onto it. The sample was then left as is at room temperature (23°C) for 6 hours, and the surface of the cured resin layer was visually observed, and the chemical resistance was evaluated according to the following criteria: Good: No change in appearance; Poor: A mark remains along the outline of the dropped area and / or the surface of the dropped area is dissolved.

[0173] (Steel wool abrasion test) A surface property tester (HEIDON Type 14DR, manufactured by Shinto Scientific Co., Ltd.) was used. Steel wool #0000 was attached to a probe with a diameter of 1 mm, and a 100 g weight was placed on it. The steel wool was placed on the surface of the cured resin layer of the laminate, and a test was performed 10 times with a stroke of 70 mm and a speed of 6000 mm / min. After the steel wool (SW) abrasion test, the presence and degree of scratches on the surface of the cured resin layer of the laminate were visually observed. Furthermore, the haze value after the test was measured, and the absolute value of the difference between the haze value after the test and the haze value before the test was taken as Δ haze.

[0174] (Gauze Abrasion Test) A reciprocating abrasion tester, HEIDON Type 30S (manufactured by Shinto Scientific Co., Ltd.), was used. Gauze was attached to a 1 mm diameter probe, and a 500 g weight was placed on it. The gauze was placed on the surface of the cured resin layer of the laminate, and the test was carried out 200 times with a stroke of 100 mm and a speed of 6000 mm / min. After the test, the presence and extent of scratches on the laminate surface were visually observed. Furthermore, the haze value after the test was measured, and the absolute value of the difference between the haze value after the test and the haze value before the test was taken as Δ haze.

[0175] (Adhesion test) On the surface of the cured resin layer of the laminate, 100 squares were cut in a grid pattern at 1 mm intervals using a cutter knife, penetrating the cured resin layer until they reached the surface of the acrylic resin film. Cellophane tape was firmly pressed from above, and then the end of the tape was quickly peeled off. The adhesion between the cured resin layer and the substrate was evaluated according to the degree of peeling of the cured resin layer using the following criteria: Good: No peeling in all 100 squares Fair: Peeling in some squares Poor: Peeling in all 100 squares

[0176] (Color Tone) In accordance with JIS Z 8781-4:2013, the color tone of the laminate was measured under the following conditions using a spectrophotometer SE7700 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). 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 defined as ΔYI. Mode: Transmission, Light Source: D65, Field of View: 2°, Measurement Diameter: 28 mm

[0177] (Water Contact Angle, Oleic Acid Contact Angle) Using a contact angle measuring device (DMo-501 model) manufactured by Kyowa Interface Science Co., Ltd., water or oleic acid was dropped onto the surface of the cured resin layer side of the laminate, and the contact angle was measured.

[0178] [Production Example 1: Graft Copolymer Particles (A)] The following substances were charged into an 8-L polymerization reactor equipped with a stirrer: 200 parts deionized water, 0.24 parts dioctyl sodium sulfosuccinate, 0.15 parts sodium formaldehyde sulfoxylate (also known as Rongalite), 0.001 parts 2-sodium ethylenediaminetetraacetate, and 0.00025 parts ferrous sulfate. The gas inside the polymerization reactor was thoroughly purged with nitrogen gas to create a substantially oxygen-free environment. The internal temperature of the polymerization reactor was then raised to 60°C. Next, the following monomer mixture was continuously added to the polymerization reactor at a rate of 10 parts by mass / hour. After the addition of the following monomer mixture was completed, polymerization was continued for an additional 0.5 hours to obtain particles of crosslinked elastomer (A1) (average particle size 90 nm). The polymerization conversion rate was 99.5%. In the following, RUVA is a reactive ultraviolet absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2-H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd., RUVA-93).

[0179] Monomer mixture: 30 parts of vinyl monomer mixture (90% n-butyl acrylate (BA) and 10% methyl methacrylate (MMA)); 0.3 parts of RUVA; 0.63 parts of allyl methacrylate (ALMA); 0.2 parts of cumene hydroperoxide (CHP).

[0180] Then, 0.05 parts of dioctyl sodium sulfosuccinate was charged into the polymerization reactor containing the crosslinked elastomer (A1) particles. The internal temperature of the polymerization reactor was then raised to 60°C, and a monomer mixture consisting of 70 parts of a vinyl monomer mixture (98% MMA, 1% BA, and 1% RUVA) for forming the graft polymer layer (A2), 0.5 parts of t-dodecyl mercaptan, and 0.5 parts of CHP was continuously added to the polymerization reactor at a rate of 10 parts / hour. Polymerization was continued for another hour to obtain a latex of graft copolymer particles (A) (average particle size 90 nm). The polymerization conversion was 98.2%. The obtained latex was salted out and coagulated with calcium chloride, and the coagulated solid was washed with water and dried to obtain powdery graft copolymer particles (A).

[0181] [Production Example 2: Graft Copolymer Particles (B)] The following materials were charged into an 8-L polymerization reactor equipped with a stirrer, and stirring was initiated: 175 parts deionized water, 0.01 parts polyoxyethylene lauryl ether phosphate, 0.4725 parts boric acid, and 0.04725 parts sodium carbonate. The internal temperature of the polymerization reactor was set to 80°C, and the gas inside the polymerization reactor was thoroughly purged with nitrogen gas to create a substantially oxygen-free environment. After the internal temperature of the polymerization reactor reached 80°C, a mixed solution consisting of 7 parts of a vinyl monomer mixture (97% MMA and 3% BA), 0.035 parts allyl methacrylate, and 0.02 parts t-dodecyl mercaptan was added to the polymerization reactor. Subsequently, 0.03 parts t-butyl hydroperoxide was added to the polymerization reactor. Five minutes later, 0.065 parts of sodium formaldehyde sulfoxylate was added as a 5% aqueous solution. After 10 minutes, 0.05 parts of t-butyl hydroperoxide was added, and after a further 15 minutes, 0.01 parts of sodium hydroxide was added as a 2% aqueous solution.

[0182] Next, a mixture consisting of 20 parts of a vinyl monomer mixture (97% MMA and 3% BA), 0.1 parts of allyl methacrylate, 0.07 parts of t-dodecyl mercaptan, and 0.085 parts of polyoxyethylene lauryl ether phosphate was continuously added to the polymerization reactor over 60 minutes. Five minutes after the completion of the continuous addition, 0.003 parts of t-butyl hydroperoxide was added. Polymerization was continued for an additional 30 minutes to obtain hard crosslinked polymer particles that would become the first layer of the core (crosslinked elastomer (B1)). The polymerization conversion was 99.0%.

[0183] Next, 0.027 parts of sodium hydroxide was added to the polymerization reactor as a 2% aqueous solution. Next, 0.08 parts of potassium persulfate was added to the polymerization reactor as a 2% aqueous solution. Then, a mixture consisting of 50 parts of a vinyl monomer mixture (82% BA and 18% styrene (St)) and 0.375 parts of allyl methacrylate was continuously added to the polymerization reactor over 150 minutes. After the addition was completed, 0.015 parts of potassium persulfate was added to the polymerization reactor as a 2% aqueous solution. Polymerization was then continued for 120 minutes to obtain a core layer polymer consisting of a two-layer structure of a hard crosslinked resin layer and a crosslinked elastomer layer. The polymerization conversion was 99.0%, and the average particle size was 225 nm.

[0184] Subsequently, 0.03 parts of potassium persulfate was added to the polymerization reactor as a 2% aqueous solution. Next, 15 parts of a vinyl monomer mixture (97% MMA and 3% BA) for the first shell layer were continuously added to the polymerization reactor over 45 minutes. After another 30 minutes of polymerization, 8 parts of a vinyl monomer mixture (55% MMA and 45% BA) for the second shell layer were continuously added to the polymerization reactor over 20 minutes. Polymerization was continued for another 60 minutes to obtain a latex of graft copolymer particles (B) consisting of a two-layer core layer and two shell layers. The polymerization conversion rate was 100.0%. The obtained latex was salted out and coagulated with magnesium chloride, and the coagulated solids were then washed with water and dried to obtain powdery graft copolymer particles (B). The average particle size of the graft copolymer particles (B) was 240 nm.

[0185] [Production Example 3: Acrylic Resin Film] 30 parts of the powdered graft copolymer particles (A) obtained in Production Example 1, 4 parts of the powdered graft copolymer particles (B) obtained in Production Example 2, 66 parts of Parapet HM (polymethyl methacrylate; manufactured by Kuraray Co., Ltd., 100% methyl methacrylate), and 0.6 parts of a hindered phenol-based antioxidant ("AO60" manufactured by ADEKA Corporation) were mixed using a Henschel mixer. Next, a 58 mm diameter vented co-rotating twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM58, L / D = 41.7) equipped with a leaf disk-type polymer filter (manufactured by Nagase & Co., Ltd., filtration accuracy 10 μm, size 7 inches, number of sheets: 33) was used between the die and the extruder head. The cylinder temperature was adjusted to 190°C to 250°C, and the mixture was melt-kneaded at a screw rotation speed of 150 rpm and a discharge rate of 180 kg / hour. The mixture was taken up in the form of a strand from the extruder, cooled, and cut to obtain pellets. The obtained pellets were melt-kneaded using a 90 mmΦ single-screw extruder with a T-die at a cylinder setting temperature of 180°C to 240°C and a discharge rate of 150 kg / hr, and extruded from the T-die at a die temperature of 240°C. Both sides were brought into contact with a metal casting roll temperature-controlled at 90°C and a touch roll equipped with an elastic metal sleeve temperature-controlled at 60°C, and the pellets were cooled and solidified while forming a film, which was then wound up to obtain an acrylic resin film with a thickness of 75 μm. The tensile elongation at break of the acrylic resin film at 120°C, measured as described above, was 220%.

[0186] [Production Example 4: Paint] A curable resin composition containing a urethane acrylate resin (manufactured by Daido Chemical Industry Co., Ltd., product name "P-5820TAH-1", containing a urethane acrylate resin as the main component, a small amount of an acrylic acid ester, a trace amount of aluminum oxide nanoparticles (inorganic fine particles), and a photopolymerization initiator, solid content concentration of 30 mass%, solvent: a mixed solvent of methyl ethyl ketone, propylene glycol, and methyl isobutyl ketone, hereinafter simply referred to as "P-5820TAH-1") was diluted with methyl ethyl ketone to a solid content concentration of 24 mass%, and then, based on 100 parts of the solid content of the resulting resin composition, reactive HALS (manufactured by ADEKA, product name "ADEKA STAB To the mixture was added 0.5 parts of LA-82 (hereinafter also referred to as "LA-82") and 0.3 parts as solids of a fluorine-containing acrylic compound (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KY-1203", solids concentration 20%, solvent: mixed solvent of methyl ethyl ketone and methyl isobutyl ketone; hereinafter also referred to as "KY-1203"), and the mixture was stirred to obtain paint 1. Paints 2, 3 and 7 were prepared in the same manner as paint 1, except that the blending amounts of LA-82 and KY-1203 were as shown in Table 1 below. A curable resin composition containing a urethane acrylate resin (manufactured by Daido Chemical Industry Co., Ltd., product name "P-5820TA-20J", consisting mainly of urethane acrylate resin with small amounts of acrylic ester and photopolymerization initiator, solids concentration 24%, solvent: mixed solvent of methyl ethyl ketone, propylene glycol and methyl isobutyl ketone; hereinafter also referred to simply as "P-5820TA-20J") was used, and paints 4 to 6, 8 and 9 were prepared in the same manner as paint 1, except that the amounts of LA-82 and KY-1203 blended per 100 parts solids of the resin composition were as shown in Table 1 below. P-5820TA-20J was used as is for paint 10.

[0187]

[0188] Example 1 Coating material 1 was applied to the acrylic resin film obtained in Production Example 3 using a bar coater, forming 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 light at the UV integrated light amount shown in Table 2 to cure the curable resin layer, forming a cured resin layer (cured product of the active energy ray-curable resin composition) having the thickness shown in Table 2 below, and obtaining a laminate. The temperature of the cooling roll when forming the cured resin layer was 50°C.

[0189] Examples 2 to 9 Laminates were prepared in the same manner as in Example 1, except that the coating materials shown in Table 2 below were used.

[0190] Examples 10 and 11 Laminates were prepared in the same manner as in Example 1, except that the coating materials shown in Table 2 below were used and the thicknesses of the cured resin layers were set as shown in Table 2 below.

[0191] Comparative Example 1 A laminate was produced in the same manner as in Example 6, except that the UV integrated light amount was set as shown in Table 2 below.

[0192] Comparative Example 2 A laminate was produced in the same manner as in Example 1, except that the coating material shown in Table 2 below was used and the thickness of the cured resin layer and the integrated UV light amount were set as shown in Table 2 below.

[0193] The laminates obtained in the Examples and Comparative Examples were measured and evaluated for various physical properties (initial) as described above, and the results are shown in Table 2 below. Furthermore, weather resistance tests were conducted using the laminates obtained in the Examples and Comparative Examples, and then various physical 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 physical properties of the laminate after 300 hours of weather resistance testing, and "500 hours" refers to the physical properties of the laminate after 500 hours of weather resistance testing. Furthermore, in Table 3 below, the amounts of reactive HALS and fluorine-containing acrylic compound in the coating material are expressed in parts by mass per 100 parts by mass of the solids (urethane acrylate resin) in the coating material.

[0194]

[0195]

[0196] As can be seen from Table 2 above, the laminates of the examples have excellent transparency, good surface hardness and scratch resistance, excellent secondary formability, and good DEET resistance. Furthermore, the laminates of Examples 1-3, 8, 10, and 11, in which the cured resin layer contains inorganic fine particles, have excellent steel wool abrasion resistance and gauze abrasion resistance. On the other hand, the laminates of the comparative examples, in which the cured resin layer had a curing index of more than 0.013, had poor DEET resistance. In the laminates of the comparative examples, the cured resin layer had a degree of curing of less than 75.

[0197] Furthermore, as can be seen from Table 3 above, the laminates of Examples 1 to 6, in which the curable resin layer contained a hindered amine light stabilizer having a reactive functional group and a compound having a hydrophobic group and a reactive functional group, i.e., the curable resin layer was formed from a cured product of an active energy ray-curable resin composition containing a urethane acrylate resin, a hindered amine light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group, also exhibited good DEET resistance after a 300-hour weather resistance test. In particular, the laminates of Examples 2, 3, 5, and 6, in which the reactive HALS was contained in an amount of more than 0.5 parts by mass per 100 parts by mass of the urethane acrylate resin, also exhibited good DEET resistance after a 500-hour weather resistance test. On the other hand, the laminates of Examples 7 to 11, in which the curable resin layer contained only a hindered amine light stabilizer having a reactive functional group and a compound having only a hydrophobic group and a reactive functional group, exhibited good initial DEET resistance but poor DEET resistance after the weather resistance test.

[0198] The present invention is not particularly limited, but may include, for example, the following embodiments.

[0199] [1] A laminate comprising a substrate layer and a cured resin layer, wherein the substrate layer comprises an acrylic resin film, the acrylic resin film has a tensile elongation at break of 200% or more at 120°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 cured resin layer has a curing index represented by the following formula 1 of 0.013 or less, and the laminate has a tensile crack elongation at 120°C of 80% or more. [Formula 1] Cure index = B / D where, in formula 1, B is the wave number of 810 cm in FT-IR measurement of the cured resin layer. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 1705 cm in the FT-IR measurement of the cured resin layer. -1 The area of ​​an infrared absorption peak near the active energy ray curable resin composition is shown. [2] The laminate according to [1], wherein the active energy ray curable resin composition further contains a hindered amine light stabilizer having a reactive functional group, and a compound having a hydrophobic group and a reactive functional group. [3] The laminate according to [2], wherein the reactive functional group includes at least one selected from the group consisting of a methacryloyl group and an acryloyl group. [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. [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. [6] The laminate according to any one of [2] to [5], wherein the ratio of the hindered amine light stabilizer having a reactive functional group to 100 parts by mass of the urethane acrylate resin is 1 to 10 parts by mass. [7] The laminate according to any one of [2] to [6], wherein the ratio of the compound having a hydrophobic group and a reactive functional group to 100 parts by mass of the urethane acrylate resin is 0.1 to 5 parts by mass. [8] The laminate according to any one of [1] to [7], wherein the cured resin layer has a degree of cure represented by the following formula 2 of 75% or more. [Formula 2] Degree of cure (%) = 100 × [(A / C) - (B / D)] / (A / C), where A is the wavenumber of 810 cm in FT-IR measurement of a coating film of the active energy ray-curable resin composition before curing.-1 indicates the area of ​​the infrared absorption peak in the vicinity of 810 cm in the FT-IR measurement of the cured resin layer. -1 C represents the area of ​​the infrared absorption peak near the wave number 1705 cm in FT-IR measurement of the coating film of the active energy ray-curable resin composition before curing. -1 indicates the area of ​​the infrared absorption peak in the vicinity of 1705 cm in the FT-IR measurement of the cured resin layer. -1 The area of ​​the infrared absorption peak near the cured resin layer of the laminate is shown. [9] The laminate according to any one of [1] to [8], wherein the surface of the cured resin layer of the laminate has a water contact angle of 105° or more.

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

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

[10] , wherein gauze to which 0.05 g of an insect repellent consisting of a 30 w / v % ethanol solution of N,N-diethyl-3-methylbenzamide is applied is placed on the surface of the cured resin layer of the laminate, and the laminate is left for 30 seconds under conditions of 23°C and a relative humidity of 65%, and then further left to stand in a thermostatic chamber at 74°C for 1 hour, and there is no visible change in appearance.

[12] The laminate is placed so that the cured resin layer side faces the light source, and a xenon lamp is used as the light source, and an irradiance of 180 W / m 2 The laminate according to any one of [1] to

[11] , wherein the laminate is subjected to a weathering test for 500 hours under conditions of a black panel temperature of 89°C (300 to 400 nm), a black panel temperature of 89°C, and no rainfall, and then a gauze coated with 0.05 g 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, and the laminate is left for 30 seconds under conditions of 23°C and a relative humidity of 65%, and then further left for 1 hour in a thermostatic oven at 74°C, and there is no visible change in appearance.

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

[12] , wherein the change in haze value before and after 80% stretching at 120°C is 0.5% or less.

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

[13] , wherein the laminate is subjected to a weathering test for 500 hours under conditions of a black panel temperature of 89°C (300 to 400 nm), a black panel temperature of 89°C, and no rainfall, and there is no visible change in appearance after the laminate is left for 6 hours at 23°C after about 0.02 mL of isopropyl alcohol or acetone is dropped on the surface of the cured resin layer.

[15] 500 g / cm on the surface of the cured resin layer of the laminate 2

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

[14] , wherein the change in haze of the laminate before and after an abrasion resistance test in which a gauze is reciprocated 20 times under a load of 100 g / cm 2

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

[15] , wherein the change in haze of the laminate before and after an abrasion resistance test in which steel wool (#0000) is reciprocated 10 times under a load of 1000 W / m is 2% or less. 2 The laminate according to any one of [1] to

[16] , wherein the change in color difference ΔE of the laminate after a 500-hour weathering test under conditions of a black panel temperature of 89°C (300 to 400 nm), a black panel temperature of 89°C, and no rainfall is less than 0.5.

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

[17] , wherein the laminate is used to decorate and / or protect a molded article.

[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 optically functional layer.

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

[19] and a molded article substrate, wherein the laminate is laminated on the surface of the molded article substrate, and the cured resin layer of the laminate is positioned closer to the surface of the molded article than the substrate layer of the laminate.

[21] The molded article according to

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

[22] A method for producing the molded article according to

[20] , comprising laminating the laminate according to any one of [1] to

[19] onto the surface of a molded article substrate using one or more methods selected from the group consisting of vacuum forming, pressure forming, film insert injection molding, and three-dimensional lamination molding.

[0200] The embodiments described above are not independent of each other, and those skilled in the art can combine them as appropriate without needing to go into excessive detail. Furthermore, components from different embodiments may be combined as appropriate.

Claims

1. A laminate comprising a base layer and a cured resin layer, wherein the base layer comprises an acrylic resin film, the acrylic resin film has a tensile breaking elongation of 200% or more at 120°C, the cured resin layer is formed of a cured product of an active energy ray curable resin composition containing a urethane acrylate resin, the cured resin layer has a curing index represented by the following formula 1 of 0.013 or less, and the laminate has a tensile crack elongation of 80% or more at 120°C. [Formula 1] Curing index = B / D where, in formula 1, B is the wave number of 810 cm in FT-IR measurement of the cured resin layer. -1 The area of ​​the infrared absorption peak in the vicinity of 1705 cm is shown, and D is the wave number in the FT-IR measurement of the cured resin layer. -1 The areas of the infrared absorption peaks in the vicinity are shown.

2. The laminate according to claim 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.

3. The laminate according to claim 2, wherein the reactive functional group includes at least one selected from the group consisting of 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 ratio of the hindered amine-based light stabilizer having a reactive functional group is 1 to 10 parts by mass per 100 parts by mass of the urethane acrylate resin.

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

8. The laminate according to claim 1, wherein the degree of cure of the cured resin layer is 75% or more, as represented by the following formula 2: [Formula 2] Degree of cure (%) = 100 x [(A / C) - (B / D)] / (A / C), where A is the wave number of 810 cm in FT-IR measurement of a coating film of the active energy ray-curable resin composition before curing. -1 The area of ​​the infrared absorption peak in the vicinity of 810 cm is shown, and B is the wave number in the FT-IR measurement of the cured resin layer. -1 C is the area of ​​the infrared absorption peak near the wave number 1705 cm in FT-IR measurement of the coating film of the active energy ray-curable resin composition before curing. -1 The area of ​​the infrared absorption peak in the vicinity of 1705 cm is shown, and D is the wave number in the FT-IR measurement of the cured resin layer. -1 The areas of the infrared absorption peaks in the vicinity are shown.

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

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

11. The laminate according to claim 1, in which no visible change in appearance occurs when 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 placed on the surface of the cured resin layer of the laminate, the gauze is left for 30 seconds under conditions of 23°C and a relative humidity of 65%, and then the gauze is allowed to stand in a thermostatic chamber at 74°C for 1 hour.

12. The laminate was placed so that the cured resin layer side was facing the light source, and a xenon lamp was used as the light source, with an irradiance of 180 W / m 2 The laminate according to claim 1, wherein after a weather resistance test is carried out for 500 hours under the conditions of a black panel temperature of 89° C. and no rainfall, a gauze coated with 0.05 g 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, and the laminate is allowed to stand for 30 seconds under conditions of 23° C. and a relative humidity of 65%, and then the laminate is allowed to stand for 1 hour in a thermostatic chamber at 74° C., and there is no visible change in appearance.

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

14. The laminate according to claim 1, which shows no visible change in appearance when approximately 0.02 mL of isopropyl alcohol or acetone is dropped onto the surface of the cured resin layer and allowed to stand at 23°C for 6 hours.

15. 500 g / cm2 on the surface of the cured resin layer of the laminate 2 2. The laminate according to claim 1, wherein the change in haze of the laminate before and after an abrasion resistance test in which a gauze is reciprocated 20 times under a load of 1000 mm is 0.5% or less.

16. 100 g / cm2 on the surface of the cured resin layer of the laminate 2 2. The laminate according to claim 1, wherein the change in haze of the laminate before and after an abrasion resistance test in which steel wool (#0000) is reciprocated 10 times under a load of 1000 g / m is 2% or less.

17. The laminate was placed so that the cured resin layer side was facing the light source, and a xenon lamp was used as the light source, with an irradiance of 180 W / m 2 The laminate according to claim 1, wherein the change in color difference ΔE of the laminate after a weathering test is carried out for 500 hours under the conditions of a black panel temperature of 89° C. (300 to 400 nm), a black panel temperature of 89° C., and no rainfall is less than 0.

5.

18. The laminate according to claim 1, which is used to decorate and / or protect a molded body.

19. The laminate according to claim 18, further comprising 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 optically functional layer.

20. A molded body comprising the laminate according to any one of claims 1 to 19 and a molded body substrate, wherein 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 of the molded body than the substrate layer of the laminate.

21. The molded article according to claim 20, wherein the surface of the molded article substrate on which the laminate is laminated has a three-dimensional shape.

22. A method for producing a molded body according to claim 20, comprising laminating the laminate according to any one of claims 1 to 19 onto a surface of a substrate of the molded body by using one or more methods selected from the group consisting of vacuum forming, compressed air forming, film insert injection molding, and three-dimensional laminate molding.

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