Molding film

Abstract

Provided is a molding film comprising a curable coating layer. The molding film can conform to the surface shape of a molded body that has a deep-drawn shape and, after the curable coating layer has been cured, exhibits excellent surface hardness, scratch resistance, chemical resistance and high weather resistance, and in particular exhibits high weather resistance not only when laminated on transparent substrates, but also when laminated on colored substrates. Also provided are a molded body that uses this molding film as well as a method for producing a molded body that uses this molding film and an article comprising the molded body. The present invention relates to a molding film comprising an acrylic resin film (A) and a curable coating layer (B) disposed directly on at least one surface of the acrylic resin film (A). The curable coating layer (B) comprises an actinic radiation-curable resin composition comprising: a polymer (a) that contains an actinic radiation-reactive functional group and does not contain a urethane bond group in the structure; and a hindered amine light stabilizer (b) that is reactive with the actinic radiation-reactive functional group in the polymer (a).

Description

Molding film

[0001] This invention relates to a molding film containing a curable coating layer that exhibits excellent stretchability and durability, including weather resistance, surface hardness, and solvent resistance, and to a molded article using the same as its surface, and to the use of the same. Furthermore, it relates to an article containing a molded article that exhibits excellent long-term weather resistance and durability and is mainly used outdoors, such as an exterior component for automobiles.

[0002] In recent years, there has been growing momentum to review various methods of painting automobile bodies and exterior parts in automobile production, from the perspective of reducing environmental impact and CO2 emissions, given the high energy consumption, large emissions of CO2 and solvents, and high environmental burden.

[0003] As one such initiative, an attempt is being made to replace conventional paint with film-like materials to cover the body and exterior parts of automobiles.

[0004] When covering molded parts such as the exterior of an automobile with film, it is necessary to uniformly laminate the film along the three-dimensional shape of the exterior, which can have a surface area of ​​several square meters in some cases, without causing defects such as wrinkles, tears, cracks, or peeling. For this reason, the film material used may require stretchability of, for example, 100% or more, and in some cases several hundred percent. In addition, in order to protect the exterior surface of an automobile from the external environment and maintain a beautiful appearance, it is necessary to have scratch resistance against flying objects and handling during car washing, chemical resistance to chemical substances such as automobile fuel, lubricants, and cleaning agents, and durability and weather resistance against sunlight, wind and rain, and cold winter conditions.

[0005] On the other hand, wrapping films for automotive exteriors are widely known, for example, those made using polyurethane-based film substrates with good stretchability, to which adhesive layers and various printed decorative layers are formed. However, these exterior wrapping film products are primarily intended for use in modifying and decorating the appearance of manufactured vehicles by applying them to the exterior panels, and do not have the long-term durability of conventional automotive exterior paints. Furthermore, because the film substrate is relatively soft, the scratch resistance of the surface is not always sufficient.

[0006] To improve the scratch resistance, weather resistance, and durability of resin molded products such as films, a hard coat layer is often applied to the surface of the resin layer. Among these, hard coats that can achieve both high scratch resistance and weather resistance have been developed for use in transparent resin sheets to replace glass windows in automobiles and the like. For example, as shown in Patent Documents 1 and 2, a sheet made of polycarbonate resin is known to have an undercoat layer made of acrylic resin or the like, and a hard, highly weather-resistant topcoat layer made of siloxane resin laminated on its surface. However, although such a hard coat configuration is expected to have high surface hardness and scratch resistance, it has low stretchability, making it difficult to use for lamination on the surface of molded bodies such as automobile exterior panels that have a three-dimensional shape.

[0007] Furthermore, in actual applications such as automotive exteriors, it is necessary to have a variety of color tones, including black and dark colors, and to possess high scratch resistance, weather resistance, and durability. Conventional films for laminated molding using active energy ray curable hard coating agents mainly composed of urethane acrylate, which have stretchability and moldability, exhibit some degree of weather resistance when laminated onto transparent substrates. However, when laminated onto colored substrates such as black, which absorb light more easily than transparent materials, they tend to suffer from reduced transparency and gloss, as well as appearance defects such as clouding and cracking, and currently do not offer sufficiently satisfactory quality.

[0008] As mentioned above, currently, no film material has been found that possesses good stretchability while also being excellent in scratch resistance, durability, and weather resistance, making it suitable for applications such as laminated films that replace paint on the exterior parts of automobiles.

[0009] International Publication No. 2011 / 078178, International Publication No. 2017 / 171033

[0010] The present invention has been made in view of these problems, and provides a molding film including a curable coating layer that can conform to the surface shape of a molded body having a deep-drawn shape, and after the curable coating layer has hardened, it has excellent surface hardness, scratch resistance, chemical resistance, and high weather resistance, and in particular, it has high weather resistance not only on transparent substrates but also when laminated on colored substrates, a molded body using the same, a method for manufacturing a molded body, and an article including a molded body.

[0011] The gist of this invention is as follows:

[0012] (1) A moldable film (C) obtained by (directly) forming a curable coating layer (B) on the surface of an acrylic resin film (A) comprising an active energy ray curable resin composition comprising a polymer (a) containing active energy ray reactive functional groups and not containing urethane bonding groups in a functional group equivalent (average functional group equivalent) of 3000 g / mol or less in its structure, and a hindered amine-based light stabilizer (b) having reactivity with the active energy ray reactive functional groups of (a), on the surface of an acrylic resin film (A).

[0013] (2) The molding film (C) according to (1), wherein the active energy ray curable resin composition contains an active energy ray reactive functional group and does not contain a polymer (a') in which the structure contains an average functional group equivalent of 3000 g / mol or less of urethane bonding groups.

[0014] (3) The molding film according to (1) or (2), wherein the active energy ray reactive functional group is an acryloyl group and / or a methacryloyl group.

[0015] (4) A molding film (C) according to any one of (1) to (3), characterized in that polymer (a) is a vinyl polymer in which 75% by mass or more of the constituent monomer units are composed of acrylic acid esters and / or methacrylic acid esters.

[0016] (5) A molding film according to any one of (1) to (4), characterized in that the curable coating layer (B) further contains a compound (c) having hydrophobic groups and reactive functional groups.

[0017] (6) A molding film according to any one of (1) to (5), wherein the active energy ray-reactive functional group is introduced by functional group conversion of the functional group of the side chain of polymer (a).

[0018] (7) A molding film (C) according to any one of (1) to (6), characterized in that the acrylic resin film (A) is obtained by molding a thermoplastic resin composition comprising a thermoplastic polymer in which 75% or more of the constituent units are methyl methacrylate and graft copolymer particles containing a rubber component.

[0019] (8) A molding film (C) as described in any of (1) to (7), wherein the coating layer (B) of (C) is cured by irradiation with active energy rays, and the (B) layer is set to face the light source, and a xenon lamp is used as the light source with an irradiance of 180 W / m 2 A molding film (C) is characterized in that, under irradiation conditions of (300-400 nm), the following weather resistance tests are performed for a total of 2000 hours, with (1) a black panel temperature of 60°C, humidity of 65%, and no rain for 102 minutes, and (2) a chamber temperature of 38°C, humidity of 95%, and rain for 18 minutes, with a total cycle of (1) + (2) of 120 minutes, and the YI value of (C) before and after the weather resistance test is less than 5.0, the haze value is less than 5%, and the change in color difference ΔE of (A) before and after the weather resistance test is less than 2.0.

[0020] (9) A test specimen was prepared by laminating an acrylic resin film (A), which is a molding film (C) as described in any of (1) to (8) and does not form (B), onto the surface of a 3 mm thick black polycarbonate resin plate, using a xenon lamp as the light source and an irradiance of 180 W / m². 2Under irradiation conditions of (300-400 nm), a weather resistance test was conducted for a total of 2000 hours, with (1) a black panel temperature of 60°C, humidity of 65%, and no rain for 102 minutes, and (2) a chamber temperature of 38°C, humidity of 95%, and rain for 18 minutes, with a total of 120 minutes for each cycle of (1) + (2). The change in color difference ΔE of the test piece before and after the test was less than 2.0, the 60° gloss was 80 or higher, and the absolute value of the change in 60° gloss was less than 10. After curing the coating layer (B) of (C) by irradiation with active energy rays, the test piece was laminated on the surface of a 3 mm thick black polycarbonate resin plate with the (B) layer facing the surface, and the (B) layer was positioned facing the light source, using a xenon lamp as the light source with an irradiance of 180 W / m². 2 A molding film (C) characterized in that, under irradiation conditions of (300-400 nm), a weather resistance test is performed for a total of 2000 hours, with (1) a black panel temperature of 60°C, humidity of 65%, and no rain for 102 minutes, and (2) a chamber temperature of 38°C, humidity of 95%, and rain for 18 minutes, with a total of 120 minutes consisting of (1) + (2), and after the test, the change in color difference ΔE of the test piece before and after the weather resistance test is less than 2.0, the 60° gloss is 80 or higher, and the absolute value of the change in 60° gloss is less than 10.

[0021] (10) A molding film (C) according to any of (1) to (9), wherein the tensile elongation at 120°C is 200% or more.

[0022] (11) A hard coat film obtained by curing the curable coating layer (B) of a molding film (C) described in any of (1) to (10) by irradiation with active energy rays.

[0023] (12) A method for manufacturing a molded article, characterized in that a molding film (C) described in any of (1) to (10) is shaped by vacuum forming, pressure forming, or compression forming into a shape having at least a partially three-dimensional shape with an elongation rate of 0 to 300% at any part after molding, and then a coating layer (B) is cured with active energy rays.

[0024] (13) A method for manufacturing a molded body, characterized in that a molding film (C) described in any of (1) to (10) is placed on one surface of an injection molding die, either in its unmolded form or after being shaped by vacuum molding, pressure molding, or compression molding into a shape having at least a partially three-dimensional shape with an elongation rate of 0 to 300% at any part after molding, and an injection molding of thermoplastic resin is performed to obtain a laminated molded body in which the molding film (C) is laminated on the surface of a molded body having a three-dimensional shape.

[0025] (14) A method for manufacturing a molded article, characterized by laminating a molding film (C) described in any of (1) to (10) onto the surface of a molded article having a three-dimensional shape in at least a part of it.

[0026] (15) The method for manufacturing a molded article according to (14), further characterized by irradiating the coating layer (B) on the surface of the laminated molded article, in which the molding film (C) is laminated, with active energy rays to cure the coating layer (B).

[0027] (16) An article which is for use as an exterior for automobiles or motorcycles, an interior for automobiles, an interior for electrical and electronic equipment, or a building material, comprising a molded body in which a coating layer (B) of a molding film (C) described in any of (1) to (10) is laminated on at least a part of the surface in a hardened state.

[0028] The molding film of the present invention is a molding film including a curable coating layer, and exhibits excellent stretch moldability that conforms to the surface shape of a molded body having a deep-drawn shape. After the curable coating layer hardens, it exhibits excellent weather resistance, surface hardness, scratch resistance, and chemical resistance. Furthermore, the molding film of the present invention exhibits high weather resistance not only on transparent substrates but also when laminated on colored substrates. Moreover, because the molding film of the present invention has excellent long-term weather resistance, molded bodies using this film as a surface are particularly suitable for use in articles mainly used outdoors, such as exterior components for automobiles and surface protection components for building materials.

[0029] The inventors of the present invention have diligently studied to solve the above problems. As a result, they have found that in a moldable film having an active energy ray curable coating layer formed on an acrylic resin film, the main component of the active energy ray curable coating layer, which becomes a hard coat layer after curing, is a specific polymer that substantially does not contain urethane bonds and has active energy ray curable groups such as (meth)acrylate groups, and a hindered amine-based light stabilizer that is reactive with the active energy ray reactive groups of the polymer is used in combination, resulting in a moldable film containing a curable coating layer (hereinafter also referred to as moldable film (C)) that exhibits excellent stretch moldability that follows the surface shape of a molded body having a deep-drawn shape, and a hard coat film with a hard coat layer after curing the curable coating layer exhibits excellent weather resistance, surface hardness, scratch resistance, and chemical resistance, and in weather resistance tests using, for example, a xenon weather meter, it exhibits extremely excellent weather resistance equivalent to that of acrylic resin films that are normally considered to have excellent weather resistance, leading to the present invention.

[0030] Furthermore, it was revealed that by using specific compounds having hydrophobic groups and reactive functional groups, such as fluorine-containing compounds that are reactive to active energy rays, in combination with the active energy ray-curable coating layer, even higher weather resistance can be achieved.

[0031] Furthermore, by using the molding film of the present invention as a so-called after-cure type hard coat film that is cured with active energy rays after secondary molding, we have found that it is possible to achieve both high secondary moldability when laminating onto the surface of a molded body with a three-dimensional shape using vacuum / pressure molding, in-mold lamination molding, film insert molding, and 3D lamination molding methods, as well as excellent weather resistance in the resulting laminated molded body.

[0032] <Acrylic resin film (A)> The acrylic resin film (A) preferably has a tensile elongation at 120°C of 200% or more. This increases the tensile elongation at 120°C of the molded film, which is a laminate with the curable coating layer (B), and tends to improve the secondary moldability (stretch moldability) of the molded film. There is no particular upper limit to the tensile elongation at 120°C of the acrylic resin film (A).

[0033] The acrylic resin film (A) is preferably formed from an acrylic resin composition containing acrylic resin and graft copolymer particles containing a rubber component (also referred to as a crosslinked elastomer).

[0034] <Acrylic Resin> Conventional known acrylic resins can be used as appropriate. For example, from the viewpoint of hardness and moldability, when the total amount of constituent units (sum of constituent units) of the acrylic resin is set to 100% by mass, it is preferable to use an acrylic resin (also called a thermoplastic acrylic polymer) composed of 20 to 100% by mass of constituent units derived from methyl methacrylate and 0 to 80% by mass of other constituent units, and it is more preferable to use an acrylic resin composed of 75% by mass or more of constituent units derived from methyl methacrylate and 0 to 25% by mass of other constituent units. The total amount of constituent units derived from methyl methacrylate and other constituent units in the thermoplastic acrylic polymer is 100% by mass.

[0035] Other constituent units include, for example, constituent units derived from acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, aromatic vinyl derivatives, and vinyl cyanide derivatives. Other constituent units may also be glutarimide structures, lactone ring structures, N-substituted maleimide structures, and unsubstituted maleimide structures, as described later. The other constituent units contained in the acrylic resin may be one type or a combination of two or more types.

[0036] 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-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-phenoxyethyl acrylate, 4-phenoxybutyl acrylate, benzyl acrylate, isobornyl acrylate, epoxycyclohexyl acrylate, and glycidyl acrylate, as well as reactive ultraviolet absorbers and acrylic acid ester derivatives having a hindered amine-based light stabilizer structure in the side chain described below.

[0037] Examples of methacrylic acid derivatives include, but are not limited to, methacrylic acid esters such as ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 2-phenoxyethyl methacrylate, glycidyl methacrylate, epoxycyclohexyl methacrylate, and isobornyl methacrylate, as well as reactive ultraviolet absorbers and methacrylic acid ester derivatives having a hindered amine-based light stabilizer structure in the side chain described below.

[0038] Examples of aromatic vinyl derivatives include, but are not limited to, styrene, vinyl toluene, and α-methylstyrene.

[0039] Examples of vinyl cyanide derivatives include, but are not limited to, acrylonitrile and methacrylonitrile.

[0040] To improve the heat resistance, rigidity, and surface hardness of acrylic resin, structural units having a specific structure may be introduced into the acrylic resin by copolymerization, functional group modification, and modification. Examples of such specific structures include glutarimide structures as shown in Japanese Patent Publication No. 62-89705, Japanese Patent Publication No. 02-178310, and International Publication No. 2005 / 54311, etc., lactone ring structures as shown in Japanese Patent Publication No. 2004-168882, and Japanese Patent Publication No. 2006-171464, etc., glutaric acid anhydride structures obtained by thermal condensation cyclization of (meth)acrylic acid units as shown in Japanese Patent Publication No. 2004-307834, etc., maleic acid anhydride structures as shown in Japanese Patent Publication No. 5-119217, and N-substituted maleimide structures and unsubstituted maleimide structures as shown in International Publication No. 2009 / 84541. For example, when these structures are introduced into an acrylic resin, the molecular chain becomes rigid. As a result, improvements in heat resistance, surface hardness, heat shrinkage, and chemical resistance can be expected. In this specification, (meth)acrylic acid means one or more substances selected from the group consisting of acrylic acid and methacrylic acid.

[0041] The method for producing acrylic resin is not particularly limited, and known polymerization methods such as suspension polymerization, bulk polymerization, solution polymerization, and emulsion polymerization can be applied. Furthermore, any of the known radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization methods can be applied.

[0042] There are no particular limitations on the stereoregularity of the acrylic resin. For example, an atactic structure obtained using conventional radical polymerization is acceptable, or a structure with increased syndiotacticity may be used by controlling the polymerization temperature and polymerization conversion rate, for example, to improve physical properties such as heat resistance. Furthermore, at least a portion of the acrylic resin may be made using coordination ion polymerization or the like to achieve highly controlled tacticity.

[0043] The copolymerization method between the constituent units derived from methyl methacrylate and the other constituent units may be either random copolymerization or block copolymerization, and can be appropriately adopted according to the requirements for hardness, flexibility, heat resistance, strength, stretchability, etc., required for acrylic resin films.

[0044] In 100% by mass of the acrylic resin film (A), the acrylic resin content may be 10 to 100% by mass, preferably 20 to 99% by mass, and more preferably 25 to 95% by mass.

[0045] <Graft copolymer containing rubber component> The acrylic resin film (A) preferably contains graft copolymer particles (A2) having an average particle diameter of 20 to 200 nm as graft copolymer particles containing a rubber component. In this case, it is preferable that the graft copolymer particles (A2) are dispersed in the matrix of the acrylic resin film (A), which contains acrylic resin or acrylic resin and other components. In addition, the acrylic resin film (A) may optionally contain graft copolymer particles (A3) with a larger average particle diameter than graft copolymer particles (A2) as graft copolymer particles containing a rubber component, in addition to graft copolymer particles (A2). In this case, it is preferable that the graft copolymer particles (A2) and graft copolymer particles (A3) are dispersed in the matrix of the acrylic resin film (A), which contains acrylic resin or acrylic resin and other components.

[0046] The graft copolymer particles (A2) preferably have a core-shell structure (multilayer structure) comprising a cross-linked elastomer (A2-1), which is a rubber component, and a graft polymer layer (A2-2) located on the surface side of the cross-linked elastomer (A2-1).

[0047] The crosslinked elastomer (A2-1) may be a known crosslinked elastomer. Preferably, the crosslinked elastomer (A2-1) is an acrylic acid ester-based crosslinked elastomer (a crosslinked elastomer consisting of a polymer mainly composed of an acrylic acid ester). In this specification, "main component" means a component whose content is 50% by mass or more.

[0048] The particles of the acrylic acid ester-based crosslinked elastomer (A2-1) may have a concentric spherical multilayer structure in which a hard crosslinked resin layer with a glass transition temperature of room temperature (20±5°C) or higher, or a semi-hard crosslinked resin layer with a glass transition temperature in the range of 0°C to room temperature, is provided inside the crosslinked elastomer layer. Examples of such hard or semi-hard crosslinked resin layers include hard crosslinked methacrylic resin particles as shown in Japanese Patent Publication No. 55-27576, semi-hard crosslinked particles made of methyl methacrylate-acrylic acid ester-styrene as shown in Japanese Patent Application Publication No. 4-270751, and crosslinked rubber particles with a high degree of crosslinking. By providing such a hard or semi-hard crosslinked resin layer, improvements in transparency and color tone can be expected.

[0049] The graft copolymer particles (A2) preferably have a core-shell structure, formed by graft polymerization of a monomer mixture that forms a graft polymer layer (A2-2) in the presence of the aforementioned acrylic acid ester-based crosslinked elastomer (A2-1) particles.

[0050] The average particle size of the graft copolymer particles (A2) should be between 20 and 200 nm, preferably between 50 and 150 nm, and particularly preferably between 50 and 120 nm. If the average particle size of the graft copolymer particles (A2) is too small, the impact resistance and bending crack resistance of the acrylic resin film (A) tend to decrease. If the average particle size of the graft copolymer particles (A2) is too large, the transparency of the acrylic resin film (A) tends to deteriorate, and whitening due to bending tends to occur more easily.

[0051] As the acrylic acid ester-based crosslinked elastomer (A2-1), crosslinked elastomer particles obtained by polymerizing a monomer mixture (m-1) comprising (1) an acrylic acid ester, (2) a polyfunctional monomer copolymerizable with the acrylic acid ester and having two or more non-conjugated double bonds per molecule, and (3) an optional other vinyl monomer copolymerizable with the acrylic acid ester are preferably used.

[0052] The acrylic acid ester, other vinyl monomers, and polyfunctional monomers may all be mixed together and polymerized in a single step. Alternatively, for the purpose of adjusting the toughness and whitening resistance of the acrylic resin film (A), the composition of the acrylic acid ester, other vinyl monomers, and polyfunctional monomers may be changed as appropriate, or the acrylic acid ester, other vinyl monomers, and polyfunctional monomers may be polymerized in two or more separate steps while maintaining the same composition.

[0053] As for the acrylic acid ester, aliphatic esters of acrylic acid are preferred, aliphatic alkyl esters of acrylic acid are more preferred, and aliphatic alkyl esters of acrylic acid with 1 to 22 carbon atoms in the alkyl group are particularly preferred, due to their excellent polymerizability, low cost, and ability to yield polymers with a low glass transition temperature (Tg). The aliphatic alkyl group may be linear, branched, or cyclic (also called alicyclic).

[0054] Specific examples of preferred aliphatic alkyl acrylates include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, phenoxybutyl acrylate, methoxyethyl acrylate, dodecyl acrylate, stearyl acrylate, heptadecyl acrylate, and octadecyl acrylate. These may be used individually or in combination of two or more.

[0055] The amount of acrylic acid ester (preferably aliphatic alkyl acrylate, more preferably aliphatic alkyl acrylate having 1 to 22 carbon atoms in the alkyl group) 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 (m-1). If the amount of acrylic acid ester is 50% by mass or more, the impact resistance and elongation at tensile break of the acrylic resin film (A) are good, and cracks are less likely to occur during secondary molding.

[0056] Other vinyl monomers include, for example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, phenoxybutyl methacrylate, isobornyl methacrylate, and dicyclopentenyl methacrylate; vinyl cyanide derivatives such as acrylonitrile and methacrylonitrile; aromatic vinyl derivatives such as styrene, vinyltoluene, and α-methylstyrene; acrylic acid; acrylic acid derivatives other than aliphatic alkyl acrylates such as phenyl acrylate and benzyl acrylate; methacrylic acid; methacrylic acid derivatives such as β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and glycidyl methacrylate; maleic anhydride; maleic acid derivatives such as N-alkylmaleimide and N-phenylmaleimide. These may be used individually or in combination of two or more. Among these, from the viewpoint of weather resistance and transparency, one or more monomers selected from the group consisting of methacrylic acid esters and aromatic vinyl derivatives are particularly preferred as other vinyl monomers.

[0057] The amount of other vinyl monomers 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 (m-1). If the amount of other vinyl monomers exceeds 49.9% by mass, the impact resistance of the acrylic resin film (A) tends to decrease, the elongation at tensile fracture decreases, and cracks may easily occur during secondary molding.

[0058] As the polyfunctional monomer, monomers commonly used as crosslinking agents and / or graft crossing agents can be suitably used. Examples of polyfunctional monomers that can be used include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, and dipropylene glycol dimethacrylate. These polyfunctional monomers may be used individually or in combination of two or more.

[0059] Among these polyfunctional monomers, those that function as graft crossing agents are more preferable because they improve the number of graft bonds of the graft polymer layer (A2-2), described later, relative to the crosslinked elastomer (A2-1), resulting in good dispersibility of graft copolymer particles (A2) in the acrylic resin, improved crack resistance to tensile and bending deformation, and reduced stress whitening. As such polyfunctional monomers having the function of graft crossing agents, those having an allyl group, such as allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and diallyl maleate, are preferred, with allyl methacrylate and allyl acrylate being particularly preferred.

[0060] The amount of polyfunctional monomer is preferably 0.1 to 10% by mass, and more preferably 1.0 to 4% by mass, based on 100% by mass of the monomer mixture (m-1). Within this range of polyfunctional monomer blending is preferable from the viewpoint of the acrylic resin film (A)'s resistance to bending cracking, resistance to bending whitening, and the fluidity of the resin during molding.

[0061] In the acrylic ester-based crosslinked elastomer (A2-1), the amount of polyfunctional monomers may be varied between the interior and near the surface of the crosslinked elastomer (A2-1) in order to improve the graft coating efficiency of the graft polymer layer (A2-2) described later. Specifically, as shown in Japanese Patent Publication No. 1460364 and Japanese Patent Publication No. 1786959, etc., by increasing the content of polyfunctional monomers that function as graft cross-intermediates near the surface of the crosslinked elastomer (A2-1) compared to the interior, the coating of graft copolymer particles (A2) by the graft polymer layer can be improved, resulting in better dispersibility in the acrylic resin and suppression of a decrease in crack resistance due to peeling at the interface between the graft copolymer particles (A2) and the acrylic resin. Furthermore, since sufficient coating can be obtained with a relatively small amount of graft polymer layer (A2-2), the amount of graft copolymer particles (A2) required to introduce a predetermined amount of crosslinked elastomer (A2-1) into the acrylic resin composition can be reduced. Therefore, the melt viscosity of the acrylic resin composition can be lowered, and improvements in the melt processability, film processing accuracy, and surface hardness of the acrylic resin film (A) can be expected.

[0062] For the purpose of controlling the molecular weight and crosslinking density of the acrylic acid ester-based crosslinked elastomer (A2-1), and for the purpose of controlling thermal stability etc. by reducing the double bond ends of the polymer due to the disproportionation termination reaction during polymerization, a chain transfer agent may be used in addition to the monomer mixture (m-1). The chain transfer agent can be selected from those normally used in radical polymerization. Preferred chain transfer agents 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, thiophenols, carbon tetrachloride, or mixtures thereof. The amount of chain transfer agent added is preferably 0 to 1.0 parts by mass, more preferably 0 to 0.3 parts by mass, per 100 parts by mass of the total amount of monomer mixture (m-1).

[0063] The particles of the crosslinked elastomer (A2-1) may be a single layer made of the acrylic acid ester-based crosslinked elastomer (A2-1) described above, or they may be a multilayer structure containing two or more layers made of the acrylic acid ester-based crosslinked elastomer (A2-1) described above.

[0064] The particles of the crosslinked elastomer (A2-1) may also be multilayer particles containing a rigid or semi-rigid crosslinked resin layer, with at least one layer being an acrylic acid ester-based crosslinked elastomer (A2-1). Examples of monomers constituting the rigid or semi-rigid crosslinked resin layer include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate; alkyl acrylate 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. As the polyfunctional monomer, the same type used for polymerization of the acrylic acid ester-based crosslinked elastomer (A2-1) layer can be used. Among these, one or more selected from the group consisting of methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, styrene, and acrylonitrile are particularly preferred. Furthermore, when polymerization of a rigid or semi-rigid crosslinked resin layer, in addition to these monomers, a chain transfer agent may be used in combination for the purpose of controlling the crosslink density and controlling thermal stability, etc., by reducing the double bond ends of the polymer. The same chain transfer agent used for polymerization of the acrylic acid ester-based crosslinked elastomer (A2-1) 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 amount of monomer mixture constituting the rigid or semi-rigid crosslinked resin layer.

[0065] When the graft copolymer particles (A2) have a two-layer structure consisting of crosslinked elastomer (A2-1) particles as core particles and a graft polymer layer (A2-2) as a shell layer, the graft copolymer particles (A2) can typically be obtained by graft copolymerizing a monomer mixture (m-2) containing 50 to 100% by mass of methacrylic acid ester and 0 to 50% by mass of other vinyl monomers copolymerizable with methacrylic acid ester (provided that the total of methacrylic acid ester and other vinyl monomers is 100% by mass) in the presence of crosslinked elastomer (A2-1) particles to form the graft polymer layer (A2-2).

[0066] The amount of methacrylic acid ester in 100% by mass of monomer mixture (m-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 viewpoint of (a) ensuring compatibility with the acrylic resin matrix and (b) preventing a decrease in the toughness of the film due to solvent impregnation during coating of the acrylic resin film (A), whitening due to stretching during molding.

[0067] In the monomer mixture (m-2), examples of methacrylic acid esters 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 having 1 to 4 carbon atoms in the alkyl group are preferred.

[0068] In the monomer mixture (m-2), as the other vinyl monomer, an alkyl acrylate with two or more carbon atoms in the alkyl group can be used. As the alkyl acrylate with two or more carbon atoms in the alkyl group, one or more selected from the group consisting of ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, and stearyl acrylate is preferred, one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate is more preferred, and n-butyl acrylate is particularly preferred.

[0069] In the monomer mixture (m-2), other vinyl monomers that can be used include aromatic vinyl derivatives such as styrene and its nuclear-substituted derivatives, vinyl cyanide derivatives such as acrylonitrile, methacrylic acid, acrylic acid, derivatives of acrylic acid, N-substituted maleimides, maleic anhydride, methacrylamide, and acrylamide.

[0070] The monomer mixture (m-2) preferably contains a reactive ultraviolet absorber as another vinyl monomer. In other words, it is preferable that the graft polymer layer (A2-2) contains constituent units derived from the reactive ultraviolet absorber. When the monomer mixture (m-2) contains a reactive ultraviolet absorber, it is easier to obtain an acrylic resin film (A) with good weather resistance and chemical resistance.

[0071] As the reactive ultraviolet absorber, any known reactive ultraviolet absorber can be used and is not particularly limited. From the viewpoint of the moldability and weather resistance of the acrylic resin film (A), a compound represented by the following general formula (1) is preferred as the reactive ultraviolet absorber.

[0072]

[0073] In general formula (1), X is a hydrogen atom or a halogen atom, and R １ R is a hydrogen atom, a methyl group, or a t-alkyl group having 4 to 6 carbon atoms. ２R is a linear or branched alkylene group having 2 to 10 carbon atoms, ３ This is either a hydrogen atom or a methyl group.

[0074] Examples of reactive ultraviolet absorbers represented by general formula (1) include 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazoles, more specifically 2-(2'-hydroxy-5'-acryloyloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxypropylphenyl)-2H-benzotriazole, and 2-(2'-hydroxy-5'-methacryloyloxyethyl-3'-t-butylphenyl)-2H-benzotriazole. Preferably, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole is used due to cost and ease of handling. In this specification, (meth)acryloyl means one or more selected from the group consisting of acryloyl and methacryloyl.

[0075] The content of constituent units derived from the reactive ultraviolet absorber in 100% by mass of the graft polymer layer (A2-2) is preferably 0.01 to 5% by mass, and more preferably 0.1 to 3% by mass.

[0076] The graft polymer layer (A2-2) is preferably obtained by graft copolymerizing 10 to 95 parts by mass of a monomer mixture (m-2) containing 70 to 99.5% by mass of an alkyl methacrylate, 0.5 to 30% by mass of an alkyl acrylate with two or more carbon atoms in the alkyl group, and 0 to 19% by mass of other vinyl monomers (provided that the total amount 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 (A2-1) particles in at least one step. However, the total amount of the crosslinked elastomer (A2-1) particles and the monomer mixture (m-2) should satisfy 100 parts by mass.

[0077] In the production of graft copolymer particles (A2), particularly during the graft copolymerization of monomer mixtures (m-2) in the presence of crosslinked elastomer (A2-1) particles, such as acrylic ester-based crosslinked elastomer (A2-1) particles, polymer components that are not grafted to the acrylic ester-based crosslinked elastomer (A2-1) particles (free polymers) may be produced. Such free polymers can be used to constitute part or all of the acrylic resin that makes up the matrix phase of acrylic resin compositions and acrylic resin films (A).

[0078] A chain transfer agent may be added to the monomer mixture (m-2) for the purpose of controlling the molecular weight of the polymer, controlling the grafting rate to the crosslinked elastomer (A2-1) and the amount of free polymer not bonded to the crosslinked elastomer (A2-1), and controlling thermal stability, etc., by reducing the double bond ends of the polymer due to the disproportionation termination reaction during polymerization. Such a chain transfer agent can be the same as the chain transfer agent that can be used for polymerization of the crosslinked elastomer (A2-1). The amount of 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 monomer mixture (m-2).

[0079] The grafting rate of monomer mixture (m-2) relative to crosslinked elastomer (A2-1) particles, i.e., the grafting rate of graft copolymer particles (A2), is preferably 5 to 250%, more preferably 10 to 200%, and even more preferably 20 to 150%. If the grafting rate is less than 5%, the flexural resistance to whitening of the acrylic resin film (A) tends to decrease, transparency decreases, and elongation at tensile fracture decreases, making it more prone to cracking during secondary molding. If the grafting rate exceeds 250%, the melt viscosity of the acrylic resin composition tends to increase during film molding, and the moldability of the acrylic resin film (A) tends to decrease. In this specification, the grafting rate of graft copolymer particles (A2) can be determined by dissolving the powder of graft copolymer particles (A2) in methyl ethyl ketone, separating it into insoluble and soluble components, and using the following formula to determine the grafting portion from the insoluble component.

[0080] Grafting rate (%) = 100 × (mass fraction of insoluble matter - mass fraction of cross-linked elastomer (A2-1)) / mass fraction of cross-linked elastomer (A2-1)

[0081] The average particle size d (nm) of the acrylic ester-based crosslinked elastomer (A2-1) in the acrylic resin film (A) and the amount w (mass%) of the polyfunctional monomer used in the acrylic ester-based crosslinked elastomer (A2-1) preferably satisfy the relationship: 0.015d ≤ w ≤ 0.06d, and more preferably 0.02d ≤ w ≤ 0.05d. If the amount of polyfunctional monomer is within the range of the above relational expression, the acrylic resin film (A) is less likely to experience a decrease in elongation during secondary molding, less likely to crack during molding or cutting, has excellent transparency, and is less prone to stress whitening during bending or tensile deformation at room temperature (approximately 25°C), high temperatures above the softening temperature of the acrylic resin film (A), or in the temperature range between room temperature and the Tg of the crosslinked elastomer (A2-1). Furthermore, it is less prone to clouding and whitening of the film due to moisture penetration into the acrylic resin film (A) upon contact with moisture.

[0082] The graft copolymer particle (A3), like the graft copolymer particle (A2), comprises a cross-linked elastomer (A3-1), which is a rubber component. The graft copolymer particle (A3), like the graft copolymer particle (A2), also comprises a graft polymer layer (A3-2) located on the surface side of the cross-linked elastomer (A3-1). In other words, it is preferable that the graft copolymer particle (A3) comprises a cross-linked elastomer (A3-1) in the core layer and a graft polymer layer (A3-2) in the shell layer. Furthermore, both the core layer and the shell layer may have a multilayer structure.

[0083] Graft copolymer particles (A3) use the same raw materials and manufacturing methods as graft copolymer particles (A2), except that their average particle diameter is larger than that of graft copolymer particles (A2). The composition and ratio of the crosslinked elastomer layer (A3-1), graft polymer layer (A3-2), and other layers of graft copolymer particles (A3) do not necessarily have to be identical or similar to those of graft copolymer particles (A2), and may be different. Preferably, the acrylic acid ester-based crosslinked elastomer (A3-1) particles have a concentric spherical multilayer structure with a hard or semi-hard crosslinked resin layer inside the crosslinked elastomer layer. Examples of such rigid or semi-rigid crosslinked resin layers include rigid crosslinked methacrylic resin particles as shown in Japanese Patent Publication No. 55-27576, and crosslinked particles having a semi-rigid layer made of methyl methacrylate-acrylic acid ester-styrene copolymer as shown in Japanese Patent Application Publication No. 4-270751 and International Publication No. 2014 / 41803. By introducing such rigid or semi-rigid crosslinked resin layers, the transparency, resistance to bending and whitening, and resistance to bending and cracking of graft copolymer particles (A3) with a larger particle size than graft copolymer particles (A2) can be improved.

[0084] The average particle size of the graft copolymer particles (A3) is preferably 150 to 400 nm, and more preferably 200 to 350 nm. Graft copolymer particles (A3) with a larger average particle size induce plastic deformation (crazing) in the acrylic resin phase surrounding the graft copolymer particles more effectively than graft copolymer particles (A2) with a smaller average particle size in response to external forces applied to the acrylic resin material. For this reason, graft copolymer particles (A3) are very effective in imparting impact resistance and crack resistance to the acrylic resin material. On the other hand, graft copolymer particles (A3) are inferior to graft copolymer particles (A2) in terms of resistance to bending whitening and / or solvent whitening. Therefore, for example, by adding a small amount of graft copolymer particles (A3) to an acrylic resin composition containing acrylic resin and graft copolymer particles (A2), it is expected that (1) the total content of soft components in the acrylic resin film (A) will be reduced, thus not decreasing the surface hardness of the acrylic resin film (A) and the molding film (C); (2) the whitening properties will not worsen when external stress is applied to the acrylic resin film (A), when a coating solution containing an organic solvent is applied, and / or during molding; and (3) the crack resistance and secondary moldability of the acrylic resin film (A) and the molding film will be efficiently improved. Examples of acrylic resin films (A) that use graft copolymer particles (A2) and a small amount of graft copolymer particles (A3) in combination include those disclosed in International Publication No. 2013 / 051239 and International Publication No. 2019 / 181752, etc.

[0085] In this specification, the average particle diameter of graft copolymer particles (A2) and graft copolymer particles (A3) is the average particle diameter on a volume basis (also referred to as a mass basis), and can be measured in the latex state using a laser diffraction / scattering type particle size distribution analyzer such as the Microtrac particle size distribution analyzer MT3000 manufactured by Nikkiso Co., Ltd., using the dynamic light scattering method.

[0086] The method for producing graft copolymer particles (A2) and graft copolymer particles (A3) is not particularly limited, and known emulsion polymerization, miniemulsion polymerization, suspension polymerization, and solution polymerization methods can be applied. Emulsion polymerization is particularly preferred because it allows for a wide range of adjustment of the resin structure.

[0087] Known initiators such as organic peroxides, inorganic peroxides, and azo compounds can be used as initiators in the emulsion polymerization of graft copolymer particles (A2) and / or graft copolymer particles (A3). Specifically, 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 peroxyesters; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; and azo compounds such as azobisisobutyronitrile. These may be used individually or in combination of two or more.

[0088] These initiators may be used (1) as pyrolysis-type radical polymerization initiators, or (2) as redox-type polymerization initiator systems by combining these initiators with a catalyst such as ferrous sulfate and a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, or hydroxyacetone acid. The catalyst may also be used as a complex with ethylenediaminetetraacetic acid-2-sodium or the like to ensure water solubility.

[0089] There are no particular limitations on the surfactant (also called an emulsifier) ​​used in the emulsion polymerization of graft copolymer particles (A2) and / or graft copolymer particles (A3). A wide range of known surfactants can be used for emulsion polymerization. Preferred surfactants include, for example, (1) anionic surfactants such as alkyl sulfonic acid, alkylbenzene sulfonic acid, dialkyl sulfosuccinic acid (dioctyl sulfosuccinic acid, etc.), alkyl sulfuric acid, sodium fatty acid, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether phosphate, alkyl phosphate, alkyl ether phosphate, alkylphenyl ether phosphate, and surfactant, as well as their sodium salts, potassium salts, and ammonium salts; and (2) nonionic surfactants such as alkylphenols, aliphatic alcohols, and reaction products of propylene oxide and / or ethylene oxide. These surfactants may be used individually or in combination of two or more.

[0090] Graft copolymer particles (A2) or graft copolymer particles (A3) obtained by emulsion polymerization can be separated and recovered from the latex of either graft copolymer particles (A2) or graft copolymer particles (A3) by known methods. For example, graft copolymer particles (A2) or graft copolymer particles (A3) can be separated and recovered by adding a water-soluble electrolyte such as calcium chloride, magnesium sulfate, calcium acetate, sodium chloride, hydrochloric acid, acetic acid, and sulfuric acid to the latex to solidify the graft copolymer particles, or by freezing the latex to separate and solidify the graft copolymer particles from the aqueous phase, followed by filtering, washing, and drying of the solid components. Alternatively, graft copolymer particles (A2) or graft copolymer particles (A3) can also be separated and recovered by treatments such as spray drying, freeze-coagulation, and freeze-drying of the latex.

[0091] In order to reduce external defects and / or internal foreign matter of the acrylic resin film (A), preferably, prior to the separation and recovery of graft copolymer particles (A2) or graft copolymer particles (A3), the latex of the graft copolymer particles (A2) or the latex of the graft copolymer particles (A3) is filtered and / or meshed in advance to remove environmental foreign matter and substances that cause foreign matter defects such as polymerization scale.

[0092] As the filter and mesh, known filter and mesh materials used for filtering liquid media can be used. The type of filter and mesh, the mesh opening, filtration accuracy, and filtration capacity are appropriately selected according to the target application, the type, size, and amount of foreign matter to be removed. For example, the mesh opening and filtration accuracy of the filter and mesh are preferably at least twice as large as the average particle size of the graft copolymer particles (A2) or graft copolymer particles (A3), respectively, and smaller than the size of the foreign matter to be removed.

[0093] In 100% by mass of the acrylic resin film (A), the content of graft copolymer particles (A2) is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass.

[0094] The content of graft copolymer particles (A3) in 100% by mass of the acrylic resin film (A) is not particularly limited and can be appropriately adjusted within a range that is preferable for the application without impairing the quality of the laminate of the present invention. However, from the viewpoint of suppressing stress whitening during stretching or bending of the acrylic resin film (A) and clouding of the film after contact with moisture, it is desirable not to use it in excess, and is preferably 0 to 25% by mass, more preferably 0 to 15% by mass, and most preferably 0 to 10% by mass or less. Furthermore, it may be possible to have no graft copolymer particles (A3) at all.

[0095] <Other Components> The acrylic resin film (A) (the acrylic resin composition constituting the acrylic resin film (A)) may optionally contain a thermoplastic resin that is at least partially compatible with the acrylic resin, to the extent that it does not impair the objectives of the present invention. Examples of such thermoplastic resins include styrene resins, polycarbonate resins, amorphous saturated polyester resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, polyimide resins, polylactic acid resins, polymethacrylate-polyacrylate block copolymers, and PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) resins. Examples of styrene 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 acid ester resins. In particular, one or more thermoplastic resins selected from the group consisting of styrene resins, polycarbonate resins, and polyimide resins are preferred because they have excellent compatibility with acrylic resins and have the potential to improve the bending crack resistance, solvent resistance, chemical resistance, and low moisture absorption of the acrylic resin film (A).

[0096] The acrylic resin film (A) (the acrylic resin composition constituting the acrylic resin film (A)) may also contain, as necessary, conventionally known additives used in the acrylic resin film (A), to the extent that it does not impair the purpose of one embodiment of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers (hereinafter also referred to as UVA), light stabilizers, light diffusers, matting agents, lubricants, colorants such as pigments and dyes, fibrous fillers, antiblocking agents consisting of organic and / or inorganic particles, infrared reflectors consisting of metals and / or metal oxides, plasticizers, and antistatic agents. The additives are not limited to these. These additives may be used in any amount depending on the type of additive, to the extent that it does not impair the purpose of one embodiment of the present invention, or to enhance the effect of one embodiment of the present invention.

[0097] <Physical Properties of Acrylic Resin Film (A)> The glass transition temperature (Tg) of the acrylic resin film (A) 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. When the glass transition temperature of the acrylic resin film (A) is 145°C or lower, it has the advantage that molding can be performed without raising the molding temperature and crack generation during molding can be suppressed. Furthermore, there is no particular lower limit to the glass transition temperature of the acrylic resin film (A). For example, if flexibility is required for the acrylic resin film (A) depending on the application or the lamination method on the surface of the molded body, the softening temperature may be set to any temperature above room temperature by using a soft resin component as appropriate. The glass transition temperature of the acrylic resin film (A) can be determined using known methods such as differential scanning calorimeter (DSC).

[0098] The thickness of the acrylic resin film (A) is not particularly limited, but is preferably 40 to 400 μm, more preferably 50 to 350 μm, and particularly preferably 60 to 300 μm. When the thickness of the acrylic resin film (A) is within the above range, the film has sufficient stretchability and excellent handling properties, as well as the advantage of having an excellent appearance after lamination on the resin substrate during the production of a molded article. In this specification, the thickness of the acrylic resin film (A) is measured by the method described in the examples.

[0099] The pencil hardness of the acrylic resin film (A), measured in accordance with JIS K 5600-5-4, is not particularly limited, but from the viewpoint of excellent surface hardness and scratch resistance, a hardness of 4B or higher under a 500g load is preferred, a hardness of 2B or higher is more preferred, a hardness of B or higher is particularly preferred, and a hardness of HB or higher is most preferred.

[0100] <Method for Manufacturing Acrylic Resin Film (A)> Acrylic resin film (A) can be manufactured by known processing methods. Specific examples of known processing methods include melt processing, calendering, 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 flowed onto a belt-shaped substrate in a film-like manner. Subsequently, the solvent is evaporated from the flowed film-like dope to obtain acrylic resin film (A).

[0101] Among these methods, solvent-free melt processing methods are preferred, and T-die extrusion and calendering methods are particularly preferred. Melt processing methods have fewer limitations on the thickness of the film to be manufactured, allow for the production of films with excellent surface properties with high productivity, and reduce the burden on the natural and working environment caused by solvents, as well as manufacturing costs.

[0102] When forming an acrylic resin composition into a film by melt processing or solvent casting, it is preferable to use filtration with a filter or mesh to remove environmental contaminants, polymerization scale, degraded resin, etc., from the acrylic resin composition that cause surface defects or internal contaminants in the acrylic resin film (A), in order to improve the appearance quality of the acrylic resin film (A).

[0103] During film manufacturing by melt processing, the acrylic resin composition can be filtered at one or more arbitrary timings during the melt mixing of the acrylic resin composition after the blending of raw materials such as acrylic resin and graft copolymer particles, and during the melt film formation process using a T-die. In the solvent casting method, the acrylic resin composition can be filtered after mixing the acrylic resin, graft copolymer particles (A2), graft copolymer particles (A3), and other components with a solvent, and before casting.

[0104] Such filters and meshes can be used without particular limitation, as long as they have heat resistance and durability according to the melting process conditions, as well as resistance to casting solvents and dopes.

[0105] When manufacturing an acrylic resin film (A) by melt processing, in particular, to obtain a high-quality acrylic resin film (A), a filter with a large filtration capacity and minimal retention of molten resin, which can cause the generation of resin degradation products and crosslinked materials that impair the quality of the film, is preferred. For example, using a leaf-disc type filter or a pleated type filter is preferred from the viewpoint of filtration efficiency and productivity.

[0106] When manufacturing an acrylic resin film (A) by T-die extrusion, an automated die system can be used to improve the thickness accuracy of the film. For example, an automated die system 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 film extrusion based on this measurement. By applying an automated die system with an appropriate control method, it may be possible to improve the thickness accuracy of the acrylic resin film (A).

[0107] In the manufacture of an acrylic resin film (A), if necessary, when forming the film, both sides of the molten film can be simultaneously brought into contact with (sandwiched) a cooling roll or cooling belt to obtain a film with superior surface properties. In this case, it is preferable to simultaneously bring the molten film into contact with a roll or cooling belt maintained at a temperature of -80°C or higher, preferably -70°C or higher, which is the glass transition temperature of the acrylic resin composition. More preferably, at least one of the rolls used for such sandwiching is a roll having an elastic metal sleeve, such as those disclosed in Japanese Patent Application Publication No. 2000-153547 and Japanese Patent Application Publication No. 11-235747, and a low sandwiching pressure is used to transfer the roll's mirror surface or a specific surface shape. This makes it possible to obtain an acrylic resin film (A) that has (1) low residual strain and excellent smoothness, and / or (2) moderate surface roughness, excellent slipperiness of the film surface, suppression of blocking between films, and less internal strain.

[0108] Furthermore, depending on the purpose, uniaxial stretching or biaxial stretching can be performed following the film formation. Uniaxial or biaxial stretching can be carried out using known stretching equipment. Biaxial stretching can be carried out in known forms, such as sequential biaxial stretching, simultaneous biaxial stretching, or a method in which longitudinal stretching is followed by transverse stretching while relaxing the longitudinal direction to suppress the bowing phenomenon of the film.

[0109] The acrylic resin film (A) may have a smooth surface, and, within the limits that do not impede the effects of the present invention, depending on the application, any surface shape such as hairline, prism, uneven shape, three-dimensional decoration, matte surface, rough surface with a certain surface roughness, or knurling at the film edge may be applied to one or both sides of the acrylic resin film (A). Such surface shapes can be applied by known methods. For example, one method is to transfer the surface shape of the rolls by sandwiching both sides of the film immediately after extrusion using a melt extrusion method with a T-die, or a molded film fed from a feeding device, between two rolls or belts having a surface shape on at least one of their surfaces. Furthermore, within the limits that do not impede the effects of the present invention, depending on the application, a printed decorative layer may be laminated on the side of the acrylic resin film (A) opposite to the side forming the curable coating layer (B) after or prior to the application of the curable coating layer (B). In addition, a layer made of other thermoplastic resin may be laminated on the side of the acrylic resin film (A) opposite to the curable coating layer (B), as needed. Examples of such thermoplastic resins include styrene resins, polycarbonate resins containing aromatic diols or heteroalicyclic diols as constituent components, amorphous saturated polyester resins, polyvinyl chloride resins, olefin-methacrylic acid derivative resins, olefin-acrylic acid derivative resins, polyimide resins, polylactic acid resins, polymethacrylate-polyacrylate block copolymers, and PHBH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)) resins. Examples of styrene 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 acid ester resins.Among these, one or more thermoplastic resins selected from the group consisting of styrene resins, polycarbonate resins, amorphous polyester resins, polypropylene, amorphous olefin resins having an alicyclic structure, and polyimide resins are preferred because they offer excellent transparency, toughness, and moisture resistance. Known methods can be used to laminate a layer made of these thermoplastic resins onto an acrylic resin film (A). Specifically, examples include a method of forming an acrylic resin composition that forms the acrylic resin film (A) and another thermoplastic resin by co-extrusion while laminating them into a film or sheet, or a method of laminating a layer made of another thermoplastic resin onto the side of the acrylic resin film (A) opposite to the side where the curable coating layer is formed, using a heat lamination method or a lamination method using an adhesive.

[0110] <Curable Coating Layer (B)> The curable coating layer (B) is obtained by directly coating an active energy ray-curable resin composition containing an active energy ray-curable resin composition (a) which contains active energy ray-reactive functional groups and substantially does not contain urethane bonding groups (also referred to as urethane bonds, -NH-CO-O-, or urethane functional groups) (i.e., has a low or no urethane bond content) and a hindered amine-based light stabilizer (b) having reactive functional groups onto at least one surface (main surface) of an acrylic resin film (A) on the market, forming a curable coating layer that can be cured by active energy rays. Furthermore, by curing the curable coating layer (B) by irradiation with active energy rays, a hard coat layer is formed that has excellent weather resistance in addition to surface hardness, chemical resistance, and scratch resistance (also referred to as abrasion resistance). In this specification, "substantially free of urethane functional groups" means that the polymer structure does not contain urethane bonds with a functional group equivalent (average functional group equivalent) of 3000 g / eq. or less.

[0111] <Polymer (a), Polymer (a')> Polymer (a) is a polymer that contains active energy ray-reactive functional groups and substantially does not contain urethane bonding groups in its structure, preferably a polymer that does not contain urethane bonding groups. That is, it is preferable that the curable coating layer (B) (the active energy ray-curable resin composition constituting the curable coating layer (B)) does not contain urethane bonding groups. To distinguish it from polymer (a), a polymer that contains active energy ray-reactive functional groups and contains an average functional group equivalent of 3000 g / eq. or less of urethane bonding groups in its structure is referred to as polymer (a') in this specification. From the viewpoint of further improving durability against surface degradation due to exposure to sunlight and ultraviolet rays, it is preferable that the curable coating layer (B) (the active energy ray-curable resin composition constituting the curable coating layer (B)) does not contain polymer (a'). It is particularly preferable that the curable coating layer (B) (the active energy ray-curable resin composition constituting the curable coating layer (B)) does not contain a polymer having urethane bonding groups. In other words, it is particularly preferable that the curable coating layer (B) (the active energy ray curable resin composition constituting the curable coating layer (B)) does not contain urethane bonding groups. In this specification, the presence or content of urethane bonding groups in the polymer, the active energy ray curable resin composition, or the curable coating layer (B) can be confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy, etc., including 13C-NMR.

[0112] Urethane bonds have relatively low stability against long-term exposure to sunlight and ultraviolet rays, making them prone to yellowing and degradation of appearance. Therefore, polymer (a) can be made to have a low content of urethane bonding groups or to be made

[0113] The polymer (a) and the curable coating layer (B) (the active energy ray curable resin composition constituting the curable coating layer (B)) preferably do not contain aromatic ring structures in their structure. This makes it possible to further improve durability against surface degradation due to exposure to, for example, sunlight or ultraviolet rays. In this specification, whether or not the polymer, the active energy ray curable resin composition, or the curable coating layer (B) contains aromatic ring structures can be confirmed by known methods such as nuclear magnetic resonance spectroscopy (NMR) and infrared spectroscopy.

[0114] Polymer (a) includes polymers whose main chain portion is obtained by polymerizing vinyl polymerizable monomers by known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Furthermore, it also includes polymers in which the side chains or terminal portions have been modified by chemical reactions.

[0115] Polymer (a) is a polymer in which the main chain portion preferably contains 50% by mass or more of constituent units derived from (meth)acrylate monomers as vinyl polymerizable monomers. Preferably, it is a polymer containing 75% by mass or more of constituent units derived from (meth)acrylate monomers, and more preferably a polymer consisting of 100% by mass of constituent units derived from (meth)acrylate monomers. Generally, constituent units derived from (meth)acrylate monomers have excellent weather resistance, and the weather resistance of polymer (a) is improved by including 50% by mass or more of them. In this specification, (meth)acrylate means one or more selected from the group consisting of methacrylate and acrylate.

[0116] Furthermore, polymer (a) contains an active energy ray-reactive functional group. The active energy ray-reactive functional group preferably contains any active energy ray-reactive functional group selected from the group consisting of (meth)acryloyl group, epoxy group, allyl group, vinyl group, vinylidene group, isoprenyl group, oxetane group, acid anhydride group, amino group, and hydroxyl group, and more preferably one or more selected from the group consisting of (meth)acryloyl group, allyl group, isoprenyl group, epoxy group, and oxetane group are preferred due to their high reactivity with active energy rays. The active energy ray-reactive functional group more preferably contains one or more selected from the group consisting of (meth)acryloyl group, epoxy group, and oxetane group, and most preferably contains a (meth)acryloyl group.

[0117] Methods for forming active energy ray-reactive functional groups in polymer (a) can be broadly applied using conventionally known methods. For example, one method involves directly introducing active energy ray-reactive functional groups into polymer (a) by using at least a portion of a vinyl monomer having active energy ray-reactive functional groups in its side chains during polymerization of polymer (a). Another method involves introducing precursor functional groups into the polymer by using at least a portion of a monomer having precursor functional groups in its side chains during polymerization, and then converting the precursor functional groups into predetermined active energy-reactive functional groups to obtain polymer (a) with predetermined active energy-reactive functional groups.

[0118] Among these methods, a method for introducing a (meth)acryloyl group, which is preferred as an active energy ray curable functional group, to the side chain of the aforementioned precursor vinyl polymer is to use a yl polymerizable monomer having functional groups such as epoxy or oxetane groups in its side chains, which have low reactivity during polymerization of the precursor monomer, to obtain a polymer in which the precursor functional group has been introduced to the side chain. Then, an addition reaction between a carboxylic acid compound derivative having a (meth)acryloyl group and the epoxy or oxetane group is used to convert the epoxy or oxetane groups in the side chain of the polymer to (meth)acryloyl groups.

[0119] Based on this method of introducing (meth)acryloyl groups, preferred monomer units that constitute the polymer that serves as a precursor to polymer (a) include monomer units containing epoxy groups or oxetane groups in their side chains, which serve as precursors for introducing (meth)acryloyl functional groups in the side chains. Specifically, examples include, but are not limited to, one or more selected from the group consisting of glycidyl (meth)acrylate, epoxycyclohexyl (meth)acrylate, and oxetanyl (meth)acrylate.

[0120] Furthermore, as monomers copolymerized with these monomers to constitute the main chain of polymer (a), preferred examples include (meth)acrylic acid esters having aliphatic, aromatic ring-containing, or alicyclic side chains, such as alkyl (meth)acrylates, aryl (meth)acrylates, and cycloalkyl (meth)acrylates, which have 1 to 20 carbon atoms in their side chains. From the viewpoint of improving the weather resistance of the curable coating layer (B), (meth)acrylate monomers having aliphatic or alicyclic alkyl side chains that do not contain aromatic rings or carbon-carbon double bonds are more preferred. Specifically, examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, and 2-methoxyethyl (meth)acrylate.

[0121] Furthermore, in order to avoid inhibiting or enhance the function of polymer (a) and the curable coating layer (B), small amounts of polyfunctional (meth)acrylate monomers may be used in combination with these monofunctional (meth)acrylate monomers. Specifically, examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, pentaerythritol di, tri, or tetraacrylate, dipentaerythritol hexaacrylate, glycerin di or tri(meth)acrylate, polyoxyalkylene-modified bisphenol A di(meth)acrylate, and the like.

[0122] Furthermore, within the limits that do not inhibit the effects of the present invention or the reaction of introducing (meth)acryloyl functional groups into the side chains, one or more functional groups selected from the group consisting of hydroxyl groups, allyl groups, amide groups, halogen groups such as fluorine groups and chlorine groups, polyalkylene oxy groups, and alkylsiloxane groups may be introduced into the structure of the monomer used in the present invention. Furthermore, depending on the application, components such as aromatic vinyl monomers such as styrene, vinyl cyanide monomers such as acrylonitrile, vinyl halides such as vinylidene fluoride, or vinylidene compounds may be used in combination.

[0123] The method for producing polymer (a) by converting the epoxy or oxetane functional groups in the side chains of the precursor polymer to (meth)acryloyl groups can be broadly utilized using known methods. For example, one method involves reacting a polymer having epoxy functional groups as a precursor in its side chains with a substance having carboxylic acid groups and (meth)acryloyl groups, such as (meth)acrylic acid, in the presence of a catalyst such as triphenylphosphine.

[0124] Polymer (a) is the main component of the curable coating layer (B) formed on at least one surface of the acrylic resin film (A). Here, if the molding film (C) is used as a so-called after-cure type coating film, in which the curable coating layer (B) is handled in an uncured state for the purpose of ensuring good moldability during the stages of shaping into a molded body and lamination onto the molded body, and the coating layer (B) is cured after shaping into a specific shape or after lamination onto the molded body, then it is desirable that polymer (a) be designed to have a hardness such that the curable coating layer (B) does not deform, become sticky, or develop surface tackiness in its uncured state.

[0125] For such applications, for example, the glass transition temperature of polymer (a) is required to be above room temperature, preferably 30°C or higher, and more preferably 40°C or higher. Therefore, the composition of the preferred monomer units described above, the hindered amine-based light stabilizer (b) described below, and the other components of polymer (a) can be appropriately adjusted so that the glass transition temperature after polymerization falls within the aforementioned range.

[0126] In the curable coating layer (B) constituting the molding film (C) of the present invention, a commercially available product containing a polymer having an active energy ray-reactive functional group may be used as a component containing at least a portion of the polymer (a). Examples of such commercially available products include Luxidia® V-6850, V-6840, and V-6841 from DIC Corporation, EBECYL® KRM8912 from Daicel Corporation, the ARUFON® series from Toagosei Co., Ltd., and the ART CURE® series from Negami Kogyo Co., Ltd. These commercially available products contain a polymer having an active energy ray-reactive functional group corresponding to polymer (a), and provide excellent moldability to the molding film (C) after coating onto the acrylic resin film (A). Furthermore, by curing by irradiation with active energy rays, excellent surface hardness, scratch resistance, and weather resistance can be obtained.

[0127] <Hindered amine light stabilizer having a reactive functional group (b)> The curable coating layer (B) contains a hindered amine light stabilizer (b) having a reactive functional group (hereinafter also referred to as "reactive HALS (b)") as a light stabilizer, which has reactivity with at least an active energy ray reactive functional group. In reactive HALS (b), the reactive functional group can be any functional group that has reactivity with the active energy ray reactive functional group of polymer (a), for example, a functional group having an ethylenic double bond. More specifically, it is preferable to include one or more selected from the group consisting of methacryloyl group, acryloyl group, vinyl group, and allyl group, and more preferably one or more selected from the group consisting of methacryloyl group and acryloyl group. Because the hindered amine light stabilizer has reactive functional groups, when the polymer (a) is cured with active energy rays, the hindered amine light stabilizer molecules react with the reactive functional groups derived from the monomers constituting the polymer (a) to form chemical bonds and are introduced into the cured curable coating layer (B). As a result, even in environments such as outdoor exposure, the migration and leaching of the hindered amine light stabilizer from the surface of the cured curable coating layer (B) is suppressed, thereby suppressing weather degradation of the cured curable coating layer (B) for a longer period of time. Furthermore, even when the molding film (C) is laminated on a molded body of any color, including black and dark colors, which are thought to absorb more solar energy and are more susceptible to thermal and light degradation, degradation such as loss of transparency and gloss, clouding, cracking, and fissures can be suppressed for a longer period of time.

[0128] Examples of such reactive HALS(b) 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, and 4-crotonoylo Examples include, but are not limited to, xy-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(b) may be used individually or in combination of two or more.

[0129] As the reactive HALS(b), commercially available products such as 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (manufactured by ADEKA Corporation, trade name "ADEKA Stab LA-82", or manufactured by Hitachi Chemical Co., Ltd., trade name "FA-711MM") and 2,2,6,6-tetramethyl-piperidinyl methacrylate (manufactured by ADEKA Corporation, trade name "ADEKA Stab LA-87", or manufactured by Hitachi Chemical Co., Ltd., trade name "FA-712HM") may be used.

[0130] The curable coating layer (B) preferably contains 1 to 10 parts by mass of reactive HALS (b) per 100 parts by mass of polymer (a) and reactive HALS (b), more preferably 1.5 to 6 parts by mass, and even more preferably 2 to 4 parts by mass. Including 1 part by mass or more of reactive HALS (b) improves the long-term weather resistance of the curable coating layer (B) after curing. Furthermore, if the amount of reactive HALS (b) is 10 parts by mass or less, the weather resistance of the molding film (C) and the transparent or colored (black or dark colored, etc.) laminates obtained by laminating them can be improved without impairing the quality of the curable coating layer (B) after curing.

[0131] The curable coating layer (B) may, in addition to the reactive HALS (b), optionally contain other light stabilizers such as hindered amine light stabilizers (hereinafter also referred to as HALS) that do not have reactive functional groups. 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-tetramethylpiperidine-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 the curing of the curable coating layer (B), the curable coating layer (B) may contain a total of 1 to 10 parts by mass, 1.5 to 6 parts by mass, or 2 to 4 parts by mass of light stabilizer per 100 parts by mass of polymer (a).

[0132] <Compounds having hydrophobic and reactive functional groups (c)> The curable coating layer (B) preferably contains compounds (c) having hydrophobic and reactive groups (hereinafter also simply referred to as "hydrophobic reactive compounds"). Such compounds are generally referred to as leveling agents, surfactants, antifouling agents, water repellents, oil repellents, dispersants, and lubricants. Such compounds are appropriately adjusted and selected in terms of composition and structure according to the components of the acrylic resin film (A), polymer (a), and fillers to be added, and then incorporated into the curable coating layer (B). As a result, the molecules of the compounds having hydrophobic and reactive groups distribute their hydrophobic groups toward the surface side or interface side on the surface of the curable coating layer (B) after its formation, and / or at the interface with other materials such as the acrylic resin film (A) and fillers, thereby reducing the surface tension of the curable coating layer (B) and improving wettability with other materials. Furthermore, it has the effect of imparting functions such as hydrophobicity, water repellency, oil repellency, stain resistance, slipperiness, scratch resistance, chemical resistance, and weather resistance to the surface of the curable coating layer (B) after application and / or curing, as well as smoothing the surface of the curable coating layer (B) and improving the dispersion state of components such as fillers that are added. In one or more embodiments of the present invention, it is presumed that by adding a compound (c) having hydrophobic groups and reactive groups to the curable coating layer (B), the surface of the curable coating layer (B) becomes hydrophobic, which may reduce stickiness and tackiness of the coating layer surface and improve weather resistance, stain resistance, chemical resistance, and scratch resistance after curing.

[0133] <Hydrophobic Groups> Hydrophobic reactive compounds (c) contain hydrophobic groups within their molecules. Specific examples of hydrophobic groups include saturated hydrocarbon groups, aromatic hydrocarbon groups, silicone groups, and fluorine-containing groups. Examples of silicone groups include alkyl-substituted polysiloxane groups such as polydimethylsiloxane groups, which may have functional groups other than hydrocarbon groups on some of their alkyl substituents, and some or all of the hydrogen groups of their alkyl substituents may be substituted with fluorine groups. Examples of fluorine-containing groups include partially fluorinated hydrocarbon groups, perfluoroalkyl groups, partially fluorinated polyalkylene oxy groups, polyperfluoroalkylene oxy groups, and fluoroalkyl-substituted siloxane groups. Among such hydrophobic groups, one or more selected from the group consisting of silicone groups and fluorine-containing groups are preferred, with fluorine-containing groups being more preferred, as they possess high hydrophobicity, excellent performance in imparting leveling and wettability through the addition of compounds, and excellent water and oil repellency, thus reducing surface stickiness and tackiness, and improving chemical resistance and scratch resistance. As hydrophobic groups including silicone groups and fluorine-containing groups, fluoroalkyl-substituted siloxane groups can be used as appropriate.

[0134] <Reactive Groups> The hydrophobic reactive compound (c) has a reactive group, more preferably a functional group that can react together with the polymer (a) during the curing reaction, in addition to the hydrophobic group described above. By containing such reactive groups, chemical bonds are formed between the polymer (a), reactive HALS (b), other components and the hydrophobic reactive compound (compound having hydrophobic and reactive groups) (c) during the curing reaction. As a result, the compound having hydrophobic and reactive groups does not easily leach out from the surface of the cured coating layer (B) but remains on the surface of the cured resin layer, and it is expected that functions such as hydrophobicity, water repellency, oil repellency, stain resistance, slipperiness, scratch resistance, and chemical resistance can 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 because they have good reactivity with (meth)acrylate groups and are excellent in maintaining long-term scratch resistance, chemical resistance, and weather resistance.

[0135] As the hydrophobic reactive compound (c), commercially available products having reactive functional groups, such as leveling agents, surfactants, water repellents, oil repellents, antifouling agents, and surface modifiers, may be used. Specifically, examples include, but are not limited to, commercially available products sold as leveling agents, surfactants, water repellents, oil repellents, antifouling agents, and surface modifiers, such as the "BYK-UV" series (manufactured by BYK Chemie), the "Megafac" series (manufactured by DIC Corporation), the "Futergent" series (manufactured by Neos Corporation), the KP series and KY-1200 series (manufactured by Shin-Etsu Chemical), the "Disparon" series (manufactured by Kusumoto Chemical), the "Polyflow" series (manufactured by Kyoeisha Chemical), the "Surflon" series (manufactured by AGC Seimi Chemical), and the "DURASURF" DH series and DS series (manufactured by Harves Co., Ltd.). Among these, for example, Megafac RS (manufactured by DIC Corporation), Futergent 601 (manufactured by Neos Corporation), KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.), and DURASURF DS-7032E (manufactured by Harves Co., Ltd.) are more preferable because they provide the surface with relatively high water contact angles and oleic acid contact angles before and after the curable coating layer (B) takes effect, and are expected to reduce stickiness and tackiness before curing, as well as maintain long-term weather resistance, scratch resistance, and chemical resistance.

[0136] The curable coating layer (B) may contain, as necessary, various additives such as UV absorbers, reactive UV absorbers, defoamers, antioxidants, light diffusers, matting agents, lubricants, colorants such as pigments and dyes, organic particles, inorganic particles, and antistatic agents, within limits that do not hinder the objectives of the present invention. The additives are not limited to these.

[0137] Furthermore, within the limits that do not hinder the objectives of the present invention, hard inorganic fine particles may be added to the curable coating layer (B) from the viewpoint of surface hardness and wear resistance. The inorganic fine particles are not particularly limited, but examples include 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 surface treatment may be performed by known methods to control the dispersion state and maintain good stretchability, thereby appropriately controlling the affinity with the curable coating layer (B).

[0138] 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. In this specification, a cross-sectional photograph of a laminate with a magnification of 200,000x and a size of 1200 nm × 800 nm is observed using an electron microscope (Hitachi High-Technologies Corporation, H7650), and the arithmetic mean value of the particle diameters of 10 dispersed domains of inorganic fine particles in the curable coating layer (B) is calculated, and the obtained value is defined as the average dispersed particle diameter of the inorganic particles in the curable coating layer (B).

[0139] The amount of inorganic fine particles in the curable resin composition for the curable coating layer (B) is not particularly limited, as long as it does not hinder the objectives of the present invention and can improve the wear resistance of the laminate. For example, it may be 0.1 to 30.0% by mass, 0.3 to 20.0% by mass, or 0.5 to 15.0% by mass.

[0140] When curing the curable coating layer (B) by irradiation with ultraviolet light, a photopolymerization initiator is preferably used. Conventionally known photopolymerization initiators can be used.

[0141] Specific examples of photopolymerization initiators include, for example, acetophenone, benzophenone, benzoyl methyl ether, benzoyl ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 1-hydroxycyclohexyl-phenyl-ketone, 2,2-dimethoxy-2-phenylacetophenone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one compounds. Among these, 1-hydroxycyclohexyl-phenyl-ketone is preferred due to its excellent compatibility.

[0142] To impart appropriate coatability to the curable coating layer (B), an organic solvent is usually incorporated. The organic solvent is not particularly limited, as long as it has sufficient solubility or dispersibility for the polymer (a), reactive HALS (b), and other components that make up the curable coating layer (B), allows for sufficient volatilization and drying under appropriate drying conditions after application of the curable coating layer (B), and forms a curable coating layer (B) of the desired thickness and performance. A boiling point of 50 to 150°C for the organic solvent is preferable from the viewpoint of coatability and the drying properties of the formed resin layer (coated film).

[0143] Specific examples of organic solvents include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, dioxane, propylene glycol monoethyl ether, methyl cellosolve, and ethyl cellosolve; and amides such as N-methylpyrrolidone and dimethylformamide. Organic solvents can be used individually or in combination of two or more.

[0144] When applying a curable coating layer (B) to the surface of an acrylic resin film (A), any application method can be used without particular restriction. Examples of application methods include the reverse coating method, gravure coating method, bar coating method, die coating method, spray coating method, kiss coating method, wire bar coating method, and curtain coating method.

[0145] The curable coating layer (B) is formed by applying the curable coating layer (B) to at least one surface of the acrylic resin film (A), and then removing the organic solvent from the coating film by drying. The drying temperature when removing the organic solvent from the resin layer after application is preferably 60 to 120°C, and more preferably 70 to 100°C. If the drying temperature is too low, organic solvent may remain in the resin layer (coating film). If the drying temperature is too high, the flatness of the curable coating layer (B) and the molding film may be impaired due to thermal deformation of the acrylic resin film (A).

[0146] After applying a curable coating layer (B) to an acrylic resin film (A) and drying it, a protective film may be further applied to the surface of the curable coating layer (B) at any stage after application and drying, before winding into a film roll, before transport, trimming, secondary molding, or lamination into a molded body, in order to protect the curable coating layer (B) from defects such as the adhesion of foreign matter such as dust or scratches caused by contact with other objects. As such a protective film, known substrates such as polyethylene, polypropylene, modified polyolefin, and polyester can be used. The surface of the protective film may be given self-adhesiveness or an adhesive layer may be formed on it by known methods as appropriate. Furthermore, if it is possible to avoid interfering with the lamination of the molding film (C) onto the molded body and the curing of the curable coating layer (B), and / or to protect the quality of the curable coating layer (B), the protective film may be left laminated on the surface of the curable coating layer (B) during any of the following stages: the shaping stage of the molding film (C) into a three-dimensional form, the lamination stage onto the molded body, or the curing stage of the curable coating layer (B) by irradiation with active energy rays.

[0147] The film (C) for molding is obtained by forming a curable coating layer (B) on at least one surface of an acrylic resin film and then curing the curable coating layer (B) by irradiation with active energy rays, thereby forming a hard coat layer and using it as a hard coat film. As the active energy rays, preferably electron beams or ultraviolet rays are used. More preferably, ultraviolet rays are used.

[0148] In the production of a molded body laminated with the film (C) for molding, as the step of curing the curable coating layer (B) by irradiation with active energy rays, depending on its usage method, immediately after the preparation of the film (C) for molding, the step of shaping or molding the film for molding into an arbitrary shape, the step of laminating the film (C) for molding on the surface of a molded body of an arbitrary shape, etc. may be used. Also, during the production stage of a laminated molded body using the film (C) for molding or laminated with the film (C) for molding, irradiation with active energy rays may be performed in multiple timings.

[0149] The wavelength of the ultraviolet rays irradiated when curing the curable coating layer (B) is preferably in the range of 200 to 400 nm. The integrated light amount of ultraviolet rays (UV) is, for example, 150 to 700 mJ / cm ２ is preferable, 200 to 2000 mJ / cm ２ is more preferable, 250 to 1500 mJ / cm ２ is even more preferable, 300 to 1000 mJ / cm ２ is even more preferable. When the integrated light amount of the UV irradiation is 200 to 2000 mJ / cm ２ it is possible to obtain a hard coat layer with appropriate hardness while ensuring moldability. As the irradiation device for the exposure light of ultraviolet rays, for example, (a) lamp light sources such as high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, electrodeless lamps, and excimer lamps, and / or (b) pulsed or continuous laser light sources such as argon ion lasers and helium neon lasers, etc. can be used.

[0150] Furthermore, the temperature at which the curable coating layer (B) is cured by irradiation with active energy rays is not particularly limited, but can be appropriately selected according to the required quality of the resulting molded body, such as surface hardness, scratch resistance, weather resistance, and chemical resistance. Generally, the higher the curing temperature, the higher the degree of curing that can be achieved, but at the same time, the amount of shrinkage during curing tends to increase, and consequently, the possibility of defects such as warping, cracking, shrinkage wrinkles, and peeling of the molded body, molding film (C), and curable coating layer (B) also increases. Therefore, it is desirable to adjust the curing temperature to an appropriate range, taking into consideration the quality of the molded body or the product to which it is applied, as well as the size and cost of the curing equipment.

[0151] From the viewpoint of excellent weather resistance, when a weather resistance test is performed using a test piece I (a hard coat film test piece) in which the coating layer (B) of the molding film (C) has been cured by irradiation with active energy rays, as described below, it is preferable that the YI value of test piece I in terms of transmission mode is less than 5.0, the haze value is less than 5%, and the change in color difference ΔE of test piece I before and after the weather resistance test is less than 2.0. (Weather Resistance Test) Test piece I is set up so that the cured coating (B) layer (i.e., the hard coat layer) is on the light source side, and a xenon lamp is used as the light source with an irradiance of 180 W / m 2 Under irradiation conditions of (300-400 nm), the following (1) + (2) will be performed for a total of 120 minutes as one cycle, for a total of 2000 hours. (1) Black panel temperature 60°C, humidity 65%, no rainfall, 102 minutes (2) Chamber temperature 38°C, humidity 95%, rainfall present, 18 minutes

[0152] When the molding film (C) is laminated on a colored substrate or molded body, and with respect to its excellent weather resistance, a weather resistance test was conducted using test piece II, which was prepared by laminating the acrylic resin film (A) that constitutes the molding film (C) onto the surface of a 3 mm thick black polycarbonate resin plate. The results showed that the change in color difference ΔE before and after the weather resistance test of test piece II was less than 2.0, the 60° gloss after the weather resistance test was 80 or higher, the absolute value of the change in 60° gloss before and after the weather resistance test was less than 10, and the curing properties of the molding film (C) were excellent. When a weather resistance test is performed using test piece IV, which is prepared by laminating test piece III (hard coat film test piece), in which the coating layer (B) has been cured by irradiation with active energy rays, onto the surface of a 3 mm thick black polycarbonate resin plate so that the acrylic resin film (A) side faces the black polycarbonate resin plate side, as described below, it is preferable that the change in color difference ΔE of test piece IV before and after the weather resistance test is less than 2.0, the 60° gloss after the weather resistance test is 80 or higher, and the absolute value of the change in 60° gloss before and after the weather resistance test is less than 10. <Weather Resistance Test> Test piece II is prepared so that the acrylic resin film (A) side faces the light source, and test piece IV is prepared so that the cured coating layer (B) (hard coat layer) side faces the light source, and a xenon lamp is used as the light source with an irradiance of 180 W / m ２ Under irradiation conditions of (300-400 nm), the following (1) + (2) will be performed for a total of 120 minutes as one cycle, for a total of 1000 cycles (2000 hours). (1) Black panel temperature 60°C, humidity 65%, no rain, 102 minutes (2) Chamber temperature 38°C, humidity 95%, with rain, 18 minutes

[0153] <Method for manufacturing molded articles> The molding film (C) can be laminated onto at least one surface of a molded article having any shape for the purpose of protecting the surface of the molded article from scratches, weathering, and chemicals, as well as for decoration and coloring.

[0154] Methods for molding a molding film (C) into any shape having at least a partially three-dimensional shape, and methods for laminating it onto the surface of a molded body having any shape, can be broadly applied using conventionally known techniques.

[0155] A method for molding a molding film (C) into any shape having at least a partially three-dimensional shape includes, for example, heating the molding film (C) in a molding apparatus to a temperature at which the acrylic resin film (A) that serves as the base material softens, using so-called vacuum molding, pressure molding, or compression molding, and then shaping it according to a mold of any shape by reducing or increasing pressure, or by pressing with a mold. More specifically, the molding film can be shaped into a pre-molded body having at least a partially three-dimensional shape, with an elongation rate of 0 to 300% in any part after molding, by vacuum molding, pressure molding, or compression molding, and then the resulting pre-molded body can be irradiated with active energy rays to cure the coating layer (B) and obtain a molded body.

[0156] Methods for laminating the molding film (C) onto the surface of a molded body include so-called in-mold injection molding, film insert injection molding, 3D lamination molding, and methods for lamination by hand application.

[0157] In-mold injection molding, or film insert injection molding, is a method of laminating a molding film (C) onto the surface of an injection-molded body, for example, by optionally providing an adhesive layer, decorative layer, backer sheet layer, or other functional layer on the surface opposite to the curable coating layer (B) of an acrylic resin film (A), as needed for the application. Specifically, examples include a method in which the molding film (C) is pre-shaped by the vacuum / pressure molding method described above, or without pre-shaping, and placed on the surface of the mold of an injection molding machine, and molten thermoplastic resin is injected into the mold to obtain a laminated molded body in which the molding film (C) is laminated on the surface of a molded body of any shape; or a method in which the molding film (C) is placed in an injection molding mold, the molding film (C) is shaped to the surface shape of the mold, and then molten thermoplastic resin is injected into the mold to obtain a laminated molded body in which the molding film (C) is laminated on the surface of a molded body of any shape.

[0158] The three-dimensional lamination molding method is a method in which, for example, a molding film (C) is given an adhesive layer, decorative layer, or other functional layer on the surface opposite to the curable coating layer (B) of an acrylic resin film (A), as needed for the application, and then laminated while shaping along the surface of a molded body of any shape, in accordance with the procedure of the vacuum / pressure molding method described above.

[0159] Examples of thermoplastic resins used in the manufacture of laminated molded articles in which a molding film (C) is laminated on the surface include, for example, polycarbonate resins having a bisphenol-based skeleton, a fluorene-based skeleton, or an isosorbide-based skeleton, acrylic resins, styrene-based resins (AS resin, ABS resin, and MAS resin, styrene-maleimide resin, styrene-maleic anhydride resin, etc.), saturated polyester resins, polyvinyl chloride resins, polyarylate resins, PPS-based resins, POM-based resins, polyamide resins, polylactic acid resins, cellulose acylate resins, and thermoplastic resins such as polypropylene resins and amorphous polyolefin resins, which are used in in-mold injection molding and film insert injection molding. In particular, one or more resins selected from the group consisting of polycarbonate resin, amorphous unsaturated polyester resin, acrylic resin, styrene resin, polypropylene resin, and amorphous polyolefin resin are preferred due to their excellent transparency, and polycarbonate resin and / or acrylic resin are more preferred due to their good adhesion to the molding film (C), with polycarbonate resin being even more preferred from the viewpoint of high rigidity, high heat resistance, and high impact resistance.

[0160] Furthermore, examples of materials that constitute the molded body to be laminated by three-dimensional lamination molding or manual lamination include the thermoplastic resins mentioned above, curable resins such as epoxy resins, unsaturated polyester resins, vinyl ester resins, phenolic resins, and melamine resins, composite materials using these as binder resins with carbon fibers, glass fibers, inorganic fillers, etc., metallic materials such as steel and aluminum, ceramic materials, painted surfaces of painted articles such as automobile bodies, paper materials, and wood materials such as plywood and solid wood.

[0161] The molding film (C) may optionally include other functional layers laminated on the surface of the curable coating layer (B) and / or on the side of the acrylic resin film (A) opposite to the curable coating layer (B), provided that these layers do not impede the effects of the present invention.

[0162] Other functional layers are not particularly limited and conventionally known ones can be widely applied. Examples include primer layers, adhesive layers, matte layers, antistatic layers, ultraviolet shielding layers, infrared shielding layers, reflective layers, diffusion layers, coloring layers, design layers, printing layers, textured layer, vapor deposition layer, metal layer, conductive layer, gas barrier layer, antifouling layer, anti-fingerprint layer, slip layer, and gas absorption layer. The molding film (C) may be equipped with two or more of the other functional layers in combination. Alternatively, one functional layer may possess two or more functions.

[0163] The present invention will be described in more detail below based on the examples. The present invention is not limited to these examples. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0164] The measurement and evaluation methods used in the examples and comparative examples will be explained.

[0165] <Tensile Elongation at 120°C> An acrylic resin film (A) or a cured molding film (C) was cut into 10 mm (width) x 100 mm (length) pieces to serve as test specimens. These test specimens were measured using a Tensilon tensile testing machine (Shimadzu Corporation, AG-2000D) equipped with a high-temperature chamber set to 120°C, under the conditions of a preheating time of 2 minutes, a chuck distance of 40 mm, and a tensile speed of 200 mm / min. The elongation at which the acrylic resin film (A) or the cured molding film (C) broke was defined as the tensile elongation at break. The value of the tensile elongation at break is the arithmetic mean of the three values ​​obtained from the measurement results using five test specimens, excluding the highest and lowest values.

[0166] <Thickness> The thickness (film thickness) of the acrylic resin film (A) was measured using a PEACOCK dial gauge No. 25 (manufactured by Ozaki Seisakusho Co., Ltd.).

[0167] The thickness (film thickness) of the curable coating layer (B) was measured using the F20 film thickness measurement system (manufactured by Filmetrics Co., Ltd.). The opposite side of the curable coating layer (B) was colored black with a marker pen, and the refractive index of the acrylic resin film (A) was set to 1.49 and the refractive index of the curable coating layer (B) to 1.50 for measurement.

[0168] <Total Light Transmittance and Haze> The total light transmittance and haze of the acrylic resin film (A) or the cured molding film (C) (hard coat film) 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.

[0169] <Pencil Hardness> In accordance with JIS K5600-5-4:1999, the pencil hardness of the surface of the curable coating layer (B) (hard coat layer) of the acrylic resin film (A) or the cured molding film (C) (hard coat film) was measured with a load of 750g.

[0170] <Weather Resistance Test> A super xenon weather meter (SX2D-75, manufactured by Suga Test Instruments Co., Ltd.) was used. The filter configuration consisted of quartz glass on the inside and polysilicate #275 on the outside. Test specimens (40 mm x 50 mm) of laminated molded bodies in which acrylic resin film (A) or the acrylic resin film (A) described later was laminated on the surface of a black resin plate were set up so that the acrylic resin film (A) side faced the light source, or test specimens (40 mm x 50 mm) of plate-shaped laminated molded bodies in which cured molding film (C) (hard coat film) or the cured molding film (C) described later was laminated on the surface of a black resin plate were set up so that the curable coating layer (B) (hard coat layer) side faced the light source. Weather resistance tests were then conducted under the following conditions.

[0171] Irradiation conditions: Xenon lamp, irradiance 180 W / m² 2(300-400 nm) Operating conditions: (1) Black panel temperature 60°C, humidity 65%, no rainfall, 102 minutes (2) Chamber temperature 38°C, humidity 95%, with rainfall, 18 minutes A total of 120 minutes (1) + (2) was used as one cycle, and tests were conducted for a total of 500 cycles (1000 hours) or 1000 cycles (2000 hours).

[0172] <DEET Resistance Test> 1) Test conditions using aluminum plate: A sample of acrylic resin film (A) or moldable film (C) after curing, cut into a 5cm x 5cm square, was placed on a horizontal surface with the curable coating layer (B) (hard coat layer) side facing upwards. A 5cm x 5cm piece of gauze was placed on top, and 0.05g of insect repellent (Muhi's insect repellent Mushipel α30, manufactured by Ikeda Mohando, an alcohol solution of DEET (N,N-diethyl3-methylbenzamide), containing 30g of DEET in 100mL) was dropped into the center of the gauze and left for 30 seconds. Subsequently, an aluminum plate (5 cm x 5 cm x 0.5 cm thick, weighing 33.6 g) was placed on gauze and left in a 74°C oven for 1 hour. After removing the sample, the aluminum plate and gauze were removed, and the chemicals were wiped off the sample surface with a damp cloth. The surface was then observed, and the DEET resistance was evaluated according to the following criteria.

[0173] ○: No change in appearance ×: A trace remains in the shape of the outline of the drop, and / or the drop turns white

[0174] 2) Test conditions without using aluminum plate: The test was carried out under the same conditions as in 1) above, except that after dropping the alcohol solution of insect repellent onto the gauze and letting it stand for 30 seconds, the aluminum plate was not placed on the gauze.

[0175] <Metal Width Abrasion Test> A reciprocating abrasion testing machine HEIDON Type 30S (manufactured by Shinto Kagaku Co., Ltd.) was used. Cotton (Kanakin No. 3) was attached to a measuring probe with a diameter of 1 mm, and a 500 g weight was placed on it. Steel wool was placed on the surface of the curable coating layer (B) (hard coat layer) of the cured molding film (C) (hard coat film), and a 200 reciprocating test was performed with a stroke of 70 mm and a speed of 6000 mm / min. The haze value of the cured molding film (C) before and after the test was measured, and the absolute value of the difference between the haze value of the hard coat film after the test and the haze value of the hard coat film before the test was defined as Δhaze. A Δhaze of 2 or less indicates good scratch resistance.

[0176] <Abrasion Paper Test> A reciprocating abrasion testing machine HEIDON Type 30S (manufactured by Shinto Kagaku Co., Ltd.) was used. Abrasion paper was attached to a measuring probe with a diameter of 1 mm, and a 200 g weight was placed on top. Gauze was placed on the surface of the curable coating layer (B) (hard coat layer) of the cured molding film (C) (hard coat film), and a 10-reciprocating test was performed with a stroke of 100 mm and a speed of 6000 mm / min. The haze value of the hard coat film was measured before and after the test, and the absolute value of the difference between the haze value of the hard coat film after the test and the haze value of the hard coat film before the test was defined as Δhaze. A Δhaze of 2 or less indicates good scratch resistance.

[0177] <Cleanser Abrasion Test> A reciprocating abrasion tester HEIDON Type 30S (manufactured by Shinto Kagaku Co., Ltd.) was used. Gauze was attached to a measuring probe with a diameter of 1 mm, and a 500 g weight was placed on it. Jif Cream Cleanser (Unilever Japan Co., Ltd.) was dropped onto the surface of the curable coating layer (B) (hard coat layer) of the cured molding film (C) (hard coat film) where the gauze would come into contact, and the gauze was placed on top. A 40-reciprocating test was performed with a stroke of 100 mm and a speed of 6000 mm / min. The haze value of the hard coat film was measured before and after the test, and the absolute value of the difference between the haze value of the hard coat film after the test and the haze value of the hard coat film before the test was defined as Δhaze. A Δhaze of 2 or less indicates good scratch resistance.

[0178] (Water Contact Angle) The contact angle was measured by dropping water onto the surface of the cured resin layer of the laminate using a contact angle measuring device (DMo-501 model) manufactured by Kyowa Interface Science Co., Ltd.

[0179] <Adhesion Test> Using a utility knife, 100 grid-like cuts were made at 1 mm intervals on the surface of the curable coating layer (B) (hard coat layer) of the cured molding film (C) (hard coat film), penetrating the hard coat layer to reach the surface of the acrylic resin film (A). Cellophane tape was then firmly pressed onto the surface, and the end of the tape was quickly peeled off. The degree of peeling of the hard coat layer was used to evaluate the adhesion between the hard coat layer and the substrate according to the following criteria.

[0180] Good: No peeling in any of the 100 squares. Average: Some peeling in some squares. Poor: Peeling in all 100 squares. <Color Tone> In accordance with JIS Z 8781-4:2013, a spectrophotometer SE7700 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure the color tones of the following: the molded film (C) (hard coat film) after curing before and after the weathering test, the hard coat film after the weathering test, the laminated molded body in which acrylic resin film (A) was laminated on the surface of a black resin board, the laminated molded body in which acrylic resin film (A) was laminated on the surface of a black resin board, and the laminated molded body in which the molded film (C) after curing was laminated on the surface of a black resin board. The color difference ΔE and YI values ​​were determined from the XYZ and L*a*b* values ​​obtained from measurements of the hard coat film and laminated molded body before and after the weathering test. Measurements of the hard coat film before and after the weathering test were performed in reflection mode using a standard white board, while measurements of the laminated molded body before and after the weathering test were performed in transmission mode. Mode: Transmission or reflection, Light source: D65, Field of view: 2°, Measurement diameter: 28 mm

[0181] <Gloss> In accordance with JIS Z 8741, the 60° gloss on the hard coat surface of a plate-shaped laminated molded body, in which the cured molding film (C) was laminated on the surface of a black resin plate, was measured using a gloss meter VG7000 (manufactured by Nippon Denshoku Industries Co., Ltd.) before and after the weathering test. The absolute value of the difference between the gloss value of the plate-shaped laminated molded body after the test and the gloss value of the plate-shaped laminated molded body before the test was defined as Δ gloss. If the gloss value of the plate-shaped laminated molded body before the test is 80 or higher, and the absolute value of Δ gloss is less than 10, it means that the decrease in gloss after the weathering test is small and the weather resistance is good.

[0182] <Lamination of molding film (C) and black resin plate by in-mold injection molding> The cured molding film (C) (hard coat film) was placed on the movable side surface (main surface) of a 150 x 150 x 3 mm flat plate injection molding die attached to an injection molding machine, with the cured hard coating layer (B) (hard coat layer) in contact with the die surface, and the die was clamped. Using a black polycarbonate resin compound (Sumika Polycarbonate's "SD POLYCA 301-22") as the injection molding resin, insert injection molding was performed under the following conditions to obtain a 3 mm thick black plate-shaped laminated molded body in which the cured molding film (C) (hard coat film) was laminated on the surface of a black polycarbonate resin plate. Molding conditions: Injection nozzle temperature 300°C, injection pressure 1500 kg / cm² ２ Injection speed 20 mm / sec, injection time 4 seconds, mold temperature 80°C, cooling 20 seconds

[0183] <Lamination of acrylic resin film (A) and black resin plate by in-mold injection molding> Except for using acrylic resin film (A) instead of the cured molding film (C), a 3 mm thick black plate-shaped laminated molded body was obtained in the same manner as in the case of lamination of the molding film (C) and black resin plate by in-mold injection molding described above, in which the acrylic resin film (A) was laminated on the surface of a black polycarbonate resin plate.

[0184] <Insert injection moldability using uncured film> Using an uncured molding film (C), the surface condition of the plate-shaped laminated molded body after in-mold injection molding under the above conditions, and the adhesion state of the curable coating layer (B) component to the mold surface were observed, and the insert injection moldability was evaluated based on the following criteria. OK: There is no adhesion of the curable coating layer (B) component to the mold, and the surface of the plate-shaped laminated molded body is smooth. NG: The molded body is stuck to the mold, or some adhesion of the curable coating layer (B) component is observed. Alternatively, the surface of the plate-shaped laminated molded body is rough and not smooth.

[0185] [Production Example 1: Graft Copolymer Particles (A2)] Multilayer polymer particles (C4) with an average particle diameter of 85 nm, prepared by the same method as in Production Example 4 of Japanese Patent Publication No. 2020-147653, were used as graft copolymer particles (A2).

[0186] [Manufacturing Example 2: Acrylic Resin Film] 38 parts of graft copolymer particles (A2) manufactured in Manufacturing Example 1, 62 parts of thermoplastic methacrylic resin (Sumitomo Chemical's "Sumipex MG5"), 0.3 parts of hindered phenol type stabilizer (BASF's "Irganox 1010"), 0.3 parts of hindered phenol type stabilizer (Sumitomo Chemical's "Sumilyzer GS"), and 0.6 parts of ultraviolet absorber (ADEKA's "ADEKA Stab LA-31") were mixed using a Henschel mixer. Next, a 58 mmΦ vented co-directional twin-screw extruder (TEM58 L / D = 41.7, manufactured by Toshiba Machine Co., Ltd.) equipped with a leaf-disc type polymer filter (manufactured by Nagase & Co., Ltd., filtration accuracy 10 μm, size 7 inches, number of discs) between the die and the extruder head was used. 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 then taken out of the extruder in strand form, 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. The mixture was discharged from the T-die at a die temperature of 240°C, and both sides were brought into contact with a touch roll equipped with a metallic cast roll heated to 90°C and an elastic metal sleeve heated to 60°C. The film was formed while cooling and solidifying, and then wound up to obtain an acrylic resin film (A) with a thickness of 75 μm. As described above, the tensile elongation at 120°C of the acrylic resin film (A) was over 200%.

[0187] [Manufacturing Example 3: Paint for Curable Coating Layer (B)] Paint 1 was prepared by adding 2.0 parts of reactive HALS (b) (ADEKA "ADEKA Stab LA-82", hereinafter also referred to as "LA-82") to 100 parts of the solid content of an active energy ray curable resin composition (DIC Corporation "V-6850") containing an acrylic polymer (a) that does not contain urethane bonds and contains acryloyl functional groups at a concentration of 50% by mass in a mixed solvent of butyl acetate and ethyl acetate. The mixture was then diluted with methyl ethyl ketone so that the total solid content of components (a) + (b) was 20% by mass of the total paint. Paints 2 to 14 were prepared in the same manner as above, except that the composition was changed as shown in Table 1 below. Paints 2, 6 and 7 were prepared by diluting with methyl ethyl ketone so that the total solid content of components (a) + (b) + (c) was 20% by mass of the total paint.

[0188]

[0189] Details of the polymer (a), reactive HALS (A), and hydrophobic reactive compound (c) used in the coatings listed in Table 1 above are shown below. V6850: Manufactured by DIC Corporation, product name "Luxidia (registered trademark) V-6850", a 50% solution of an after-curable hard coat agent mainly composed of an acrylic acrylate type UV-curable resin that does not contain urethane bonds and does not contain aromatic rings in its structure. Z607-5HL: Manufactured by Aica Kogyo Co., Ltd., Aica Aitron (registered trademark) Z607-HL, a 40% solution of a urethane acrylate-based UV-curable hard coat agent containing urethane bonds with an average functional group equivalent of 3000 g / eq. or less. SPC-23054: Manufactured by Fujikura Kasei Co., Ltd., with an average functional group equivalent of 3000 g / eq. A 32% solution of a urethane acrylate-based UV-curable hard coat agent containing the following urethane bonds: HO3409U-AC: FUJIHARD HO3409-AC, manufactured by Fujikura Chemicals Co., Ltd., with an average functional group equivalent of 3000 g / eq. A 31% solution of a urethane acrylate-based UV-curable after-cure hard coat agent containing the following urethane bonds: DioleD 5821: manufactured by Daido Chemical Industries, Ltd., formerly known as "P-5820TAH-1" (DioRED® registered trademark 5820TAH-1), with an average functional group equivalent of 3000 g / eq. A 30% solution of an ultraviolet-curable hard coat agent (DioRed® 5820TA-20J) consisting mainly of a urethane acrylate resin containing the following urethane bonds and no aromatic rings in its structure, with a small amount of acrylic acid ester and photopolymerization initiator added, to which a trace amount of aluminum oxide nanoparticles are added: LA-82: Manufactured by ADEKA Corporation, ADEKA Stab® LA-82, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate LA-87: Manufactured by ADEKA Corporation, ADEKA Stab® LA-87, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate LA-81: Manufactured by ADEKA Corporation, ADEKA Stab® LA-81, bis(1-undecanooxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate Tinuvin® 249: Manufactured by BASF Japan, structurally undisclosed, without reactive functional groups, N-R type hindered amine type light stabilizer KY-1203: Manufactured by Shin-Etsu Chemical Co., Ltd., SHIN-ETSU SUBERYN® KY-1203, UV-curable fluorine-based antifouling additive DS-7032E: Manufactured by Harves Co., Ltd., DURASURF® DS-7032E, fluorine-based coating agent,

[0190] (Example 1) Paint 1 was applied to one surface of the acrylic resin film (A) obtained in Manufacturing Example 3 using a bar coater to form a coating film of paint (1) on one surface of the acrylic resin film (A). Subsequently, the coating film of paint (1) was dried at 80°C for 2 minutes to evaporate the solvent from the coating film and form a curable coating layer (B), thereby obtaining a moldable film (C). The thickness of the curable coating layer (B) was 3 μm.

[0191] <Curing Conditions> The curable coating layer (B) of the uncured molding film (C) was irradiated with ultraviolet light at the UV integrated light intensity described in Tables 2 and 3 below to cure the curable coating layer (B), form a hard coat layer, and obtain a hard coat film.

[0192] (Examples 2-3, Comparative Examples 1-11) Molding films (C) were manufactured using the same procedure as in Example 1, except that the paint for the curable coating layer (B) was changed as shown in Tables 2 and 3 below.

[0193] For the molding film (C) obtained in the examples and comparative examples, various physical properties (initial) of the uncured molding film (C) or the cured molding film (C) (hard coat film) were measured and evaluated as described above, and the results are shown in Tables 2 and 3 below. The acrylic resin film (A) obtained in Production Example 1 was used as Reference Example 1. In Tables 2 and 3 below, the tensile elongation at 120°C (before curing) is a physical property of the molding film (C), and all other properties are physical properties of the hard coat film. In Tables 2 and 3 below, the color tone results were measured in reflection mode using a standard white board.

[0194] Furthermore, the insert injection moldability when laminating the molding film (C) onto a black polycarbonate resin plate was evaluated as described above. In addition, a weather resistance test was performed using a plate-shaped laminated molded body obtained by laminating the molding film (C) onto a black polycarbonate resin plate, and thereafter, various physical properties of the plate-shaped laminated molded body were measured and evaluated as described above, and the results are shown in Tables 4 and 5 below. The acrylic resin film (A) obtained in Manufacturing Example 1 was used as Reference Example 1. In Tables 4 and 5 below, the times indicated mean the physical properties of the plate-shaped laminated molded body after the weather resistance test for that time. In Tables 4 and 5 below, the color tone results were measured in transmission mode.

[0195]

[0196]

[0197]

[0198]

[0199] As shown in Tables 2 and 4 above, the molding films of Examples 1 to 3 exhibited excellent weather resistance, with small color difference ΔE and Δgloss (degree of decrease in 60° gloss) after predetermined weather resistance tests, demonstrating a level equivalent to Reference Example 1, which is an acrylic resin film substrate. Furthermore, a comparison of Examples 1 and 2 shows that by adding a compound (c) having hydrophobic groups and reactive functional groups to the curable coating layer (B), the chemical resistance to DEET, ΔE, and Δgloss after curing were further improved.

[0200] On the other hand, as shown in Tables 2 to 5, in Comparative Examples 1 to 11, which used urethane acrylate resin instead of polymer (a), and Comparative Examples 12 and 13, which did not use reactive HALS, ΔE and Δgloss rapidly deteriorated in the predetermined weather resistance test, indicating that they did not have sufficient weather resistance.

[0201] The present invention is not particularly limited, but preferably includes, for example, the following embodiments: [1] A moldable film comprising an acrylic resin film (A) and a curable coating layer (B) directly disposed on at least one surface of the acrylic resin film (A), wherein the curable coating layer (B) comprises a polymer (a) containing active energy ray reactive functional groups and not containing urethane bonding groups in its structure, and a hindered amine-based light stabilizer (b) having reactivity with the active energy ray reactive functional groups of polymer (a), comprising an active energy ray curable resin composition. [2] The moldable film according to [1], wherein polymer (a) does not contain an aromatic ring structure in its structure. [3] The moldable film according to [1] or [2], wherein the active energy ray curable resin composition does not contain urethane bonding groups. [4] The moldable film according to any one of [1] to [3], wherein the active energy ray reactive functional group is one or more selected from the group consisting of acryloyl groups and / or methacryloyl groups. [5] A molding film according to any one of [1] to [4], wherein the polymer (a) is a vinyl polymer containing 75% by mass or more of constituent units derived from one or more monomers selected from the group consisting of acrylic acid esters and methacrylic acid esters, based on 100% by mass of all constituent units. [6] A molding film according to any one of [1] to [5], wherein the active energy ray curable resin composition further contains a compound (c) having hydrophobic groups and reactive functional groups. [7] A molding film according to any one of [1] to [6], wherein the polymer (a) contains an active energy ray reactive functional group in its side chain. [8] A molding film according to any one of [1] to [7], wherein the acrylic resin film (A) is formed from an acrylic resin composition containing an acrylic resin in which 75% by mass or more of the constituent units out of 100% by mass of all constituent units are derived from methyl methacrylate, and graft copolymer particles containing a rubber component.[9] A molding film according to any one of [1] to [8], wherein when a weather resistance test is performed using a test piece I in which the coating layer (B) of the molding film has been cured by irradiation with active energy rays, the YI value of the test piece I in transmission mode is less than 5.0, the haze value is less than 5%, and the change in color difference ΔE of the test piece I before and after the weather resistance test is less than 2.0. (Weather resistance test) The test piece I is set up so that the cured coating (B) layer faces the light source, and a xenon lamp is used as the light source with an irradiance of 180 W / m. 2 Under irradiation conditions of (300-400 nm), the following (1) + (2) shall be performed for a total of 120 minutes as one cycle, for a total of 2000 hours. (1) Black panel temperature 60°C, humidity 65%, no rain, 102 minutes (2) Chamber temperature 38°C, humidity 95%, with rain, 18 minutes

[10] When a weather resistance test was performed using test piece II, which was made by laminating an acrylic resin film (A) before it was formed into a molding film onto the surface of a 3 mm thick black polycarbonate resin plate, as described below, the change in color difference ΔE before and after the weather resistance test of test piece II was less than 2.0, the 60° gloss after the weather resistance test was 80 or higher, and the absolute value of the change in 60° gloss before and after the weather resistance test was less than 10, A molded film as described in any of [1] to [9], wherein a test specimen III, in which the coating layer (B) of the molding film has been cured by irradiation with active energy rays, is laminated onto the surface of a 3 mm thick black polycarbonate resin plate so that the acrylic resin film (A) is on the black polycarbonate resin plate side, and a weather resistance test is performed as described below, wherein the change in color difference ΔE of test specimen IV before and after the weather resistance test is less than 2.0, the 60° gloss after the weather resistance test is 80 or higher, and the absolute value of the change in 60° gloss before and after the weather resistance test is less than 10. (Weather resistance test) Test specimen II is set up so that the acrylic resin film (A) is on the light source side, and test specimen IV is set up so that the cured coating layer (B) is on the light source side, and a xenon lamp is used as the light source with an irradiance of 180 W / m ２Under irradiation conditions of (300-400 nm), the following (1) + (2) are performed for a total of 120 minutes as one cycle, for a total of 2000 hours. (1) Black panel temperature 60°C, humidity 65%, no rain, 102 minutes (2) Chamber temperature 38°C, humidity 95%, with rain, 18 minutes

[11] A molding film according to any one of [1] to

[10] , wherein the tensile elongation at 120°C is 200% or more.

[12] A hard coat film in which the curable coating layer (B) of the molding film according to any one of [1] to

[11] has been cured.

[13] A method for manufacturing a molded body, wherein the molding film according to any one of [1] to

[11] is laminated on the surface of a laminated substrate using an adhesive or a heat fusion method to obtain a laminated molded body.

[14] A method for manufacturing a molded body according to

[13] , wherein the laminated substrate has a three-dimensional shape on at least a part of the surface to which it is laminated.

[15] A method for manufacturing a molded article according to

[13] or

[14] , wherein the coating layer (B) on the surface of the obtained laminated molded article is irradiated with active energy rays to harden the coating layer (B).

[16] A method for manufacturing a molded article, comprising shaping a molding film according to any one of [1] to

[11] into a pre-molded article having at least a partially three-dimensional shape, wherein the elongation rate of any part after molding is 0 to 300%, by vacuum molding, pressure molding, or compression molding, and irradiating the pre-molded article with active energy rays to harden the coating layer (B).

[17] A method for manufacturing a laminated molded body, characterized in that a molding film according to any one of [1] to

[11] , or a pre-molded body formed by vacuum molding, pressure molding, or compression molding of a molding film according to any one of [1] to

[11] , to have at least a partially three-dimensional shape with an elongation rate of 0 to 300% at any part after molding, is placed on one surface of an injection molding die, and injection molding of a thermoplastic resin is performed to obtain a laminated molded body in which a molding film (C) or a pre-molded body is laminated on the surface of a molded body having a three-dimensional shape.

[18] An article comprising a molded body, wherein the molded body comprises a hard coat film according to

[12] laminated on at least a part of its surface, and the article is used for one or more applications selected from the group consisting of automobile exteriors, motorcycle exteriors, automobile interiors, electrical and electronic equipment covering materials, and building materials.

[0202] Laminated molded bodies, in which a molding film (C) is laminated on the surface, can be used, for example, as interior materials for automobiles, exterior materials for automobiles, optical components, covering materials for electrical and electronic equipment, and exterior materials for buildings. Laminated molded bodies have excellent conformability and coverage of the molding film (C) to the three-dimensional shape during manufacturing, and also have excellent long-term weather resistance, scratch resistance, and chemical resistance. Therefore, articles using these laminated molded bodies can be suitably used as exterior materials for automobiles, exterior materials for buildings, and so on. Examples of exterior materials for automobiles are not particularly limited, but include door mirrors, windows, headlamp covers, taillamp covers, windshield components, weatherstrips, bumpers, bumper guards, side mudguards, body panels, spoilers, front grilles, strut mounts, wheel caps, center pillars, center ornaments, side moldings, door moldings, window moldings, and other decorative parts. Examples of electrical and electronic equipment covering materials include casings for personal computers, portable electronic devices, and home appliances, as well as casings and covering materials for solar cells, and examples of building exterior materials include siding and other exterior wall materials, fences, roofs, gates, gable boards, and ornaments.

Claims

1. A moldable film comprising an acrylic resin film (A) and a curable coating layer (B) directly disposed on at least one surface of the acrylic resin film (A), wherein the curable coating layer (B) comprises a polymer (a) containing active energy ray-reactive functional groups and not containing urethane bonding groups in its structure, and a hindered amine-based light stabilizer (b) having reactivity with the active energy ray-reactive functional groups of the polymer (a), the composition of an active energy ray-curable resin.

2. The molding film according to claim 1, wherein polymer (a) does not contain an aromatic ring structure in its structure.

3. The molding film according to claim 1, wherein the active energy ray curable resin composition does not contain urethane bonding groups.

4. The molding film according to claim 1, wherein the active energy ray-reactive functional group is one or more selected from the group consisting of acryloyl groups and methacryloyl groups.

5. The molding film according to claim 1, wherein the polymer (a) is a vinyl polymer containing 75% by mass or more of constituent units derived from one or more monomers selected from the group consisting of acrylic acid esters and methacrylic acid esters, based on 100% by mass of all constituent units.

6. The molding film according to claim 1, wherein the active energy ray curable resin composition further contains a compound (c) having a hydrophobic group and a reactive functional group.

7. The molding film according to claim 1, wherein the polymer (a) contains an active energy ray-reactive functional group in its side chain.

8. The molding film according to claim 1, wherein the acrylic resin film (A) is formed from an acrylic resin composition comprising an acrylic resin in which 75% or more of the constituent units out of 100% by mass of the total constituent units are derived from methyl methacrylate, and graft copolymer particles containing a rubber component.

9. The molding film according to claim 1, wherein when a weather resistance test is performed using a test piece I in which the coating layer (B) of the molding film has been cured by irradiation with active energy rays, the YI value of the test piece I in terms of transmission mode is less than 5.0, the haze value is less than 5%, and the change in color difference ΔE of the test piece I before and after the weather resistance test is less than 2.

0. (Weather resistance test) The test piece I is set up so that the cured coating (B) layer faces the light source, and a xenon lamp is used as the light source with an irradiance of 180 W / m². 2 Under irradiation conditions of (300-400 nm), the following (1) + (2) will be performed for a total of 120 minutes as one cycle, for a total of 2000 hours. (1) Black panel temperature 60°C, humidity 65%, no rainfall, 102 minutes (2) Chamber temperature 38°C, humidity 95%, rainfall present, 18 minutes 10. When a weather resistance test is performed using test piece II, which is prepared by laminating an acrylic resin film (A) before it is formed into a molding film onto the surface of a 3 mm thick black polycarbonate resin board, as described below, the change in color difference ΔE of test piece II before and after the weather resistance test is less than 2.0, the 60° gloss after the weather resistance test is 80 or higher, and the absolute value of the change in 60° gloss before and after the weather resistance test is less than 10. The molding film according to claim 1. When a weather resistance test is performed using test piece IV, which is prepared by laminating a coating layer (B) of the molding film, which is prepared by curing a coating layer (B) of the molding film by irradiation with active energy rays, onto the surface of a 3 mm thick black polycarbonate resin board so that the acrylic resin film (A) is on the black polycarbonate resin board side, as described below, the change in color difference ΔE of test piece IV before and after the weather resistance test is less than 2.0, the 60° gloss after the weather resistance test is 80 or higher, and the absolute value of the change in 60° gloss before and after the weather resistance test is less than 10. (Weathering resistance test) Test specimen II was set up so that the acrylic resin film (A) faced the light source, and test specimen IV was set up so that the cured coating layer (B) faced the light source. A xenon lamp was used as the light source, with an irradiance of 180 W / m². ２ Under irradiation conditions of (300-400 nm), the following (1) + (2) will be performed for a total of 120 minutes as one cycle, for a total of 2000 hours. (1) Black panel temperature 60°C, humidity 65%, no rainfall, 102 minutes (2) Chamber temperature 38°C, humidity 95%, rainfall present, 18 minutes 11. The molding film according to claim 1, wherein the tensile elongation at 120°C is 200% or more.

12. A hard coat film having a curable coating layer (B) of a molding film according to any one of claims 1 to 11 cured.

13. A method for manufacturing a molded body, comprising laminating a molding film according to any one of claims 1 to 11 onto the surface of a laminated substrate using an adhesive or a heat-sealing method to obtain a laminated molded body.

14. The method for manufacturing a molded article according to claim 13, wherein the laminated substrate has a three-dimensional shape on at least a portion of the surface on which it is laminated.

15. The method for manufacturing a molded article according to claim 13, comprising irradiating the coating layer (B) on the surface of the obtained laminated molded article with active energy rays to cure the coating layer (B).

16. A method for manufacturing a molded body, comprising: forming a pre-molded body having at least a partially three-dimensional shape, with an elongation rate of 0 to 300% at any part after molding, by vacuum molding, pressure molding, or compression molding, using a molding film according to any one of claims 1 to 11; and curing a coating layer (B) by irradiating the pre-molded body with active energy rays.

17. A method for manufacturing a laminated molded body, characterized in that a molding film according to any one of claims 1 to 11, or a pre-molded body formed by vacuum molding, pressure molding, or compression molding of the molding film according to any one of claims 1 to 11, to have at least a partially three-dimensional shape with an elongation rate of 0 to 300% at any part after molding, is placed on one surface of an injection molding die, and injection molding of a thermoplastic resin is performed to obtain a laminated molded body in which a molding film (C) or a pre-molded body is laminated on the surface of a molded body having a three-dimensional shape.

18. An article comprising a molded body, wherein the molded body comprises a hard coat film according to claim 12 laminated on at least a portion of its surface, and the article is used for one or more applications selected from the group consisting of automobile exteriors, motorcycle exteriors, automobile interiors, electrical and electronic equipment covering materials, and building materials.

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