Laminate and cured product obtained by curing the same

Abstract

Provided is a laminate or the like in which cracks hardly occur even when the laminate is wiped and cleaned using an alcohol or other solvent. This laminate includes a base material layer (a) containing a polycarbonate resin, a curable resin layer (b) containing a (meth)acryloyl polymer having an acrylic equivalent of 200-600 g / mol, and an acrylic layer (c) containing a (meth)acrylic resin disposed between the base material layer (a) and the curable resin layer (b), the melt viscosity of the (meth)acrylic resin at 230°C measured at a shear rate of 122 sec−1 being 2200-10,000 Pa·s, and the thickness of the acrylic layer (c) being 10-120 μm.

Description

[Technical Field]

[0001] The present invention relates to a laminate and a cured product obtained by curing the laminate. [Background technology]

[0002] Thermoforming films (also called functional films or decorative films) are suitably used to impart desired properties (for example, scratch resistance, chemical resistance, design, etc.) to the surface of a molded product.

[0003] When applying a thermoforming film to a molded product, various molding methods are used, such as vacuum forming, pressure forming, film insert molding, in-mold molding, and three-dimensional decoration (TOM) molding.

[0004] When a molded article needs to have properties such as scratch resistance, the thermoforming film must have high hardness. Therefore, the thermoforming film is often formed into a laminate with a hard coating layer formed by curing a resin. However, the higher the hardness of the thermoforming film, the lower the moldability and the less conformability it has to the molded article. In other words, there is a trade-off between hardness and moldability in thermoforming films.

[0005] Conventionally, methods for achieving both hardness and formability in thermoforming films have been investigated. For example, Patent Document 1 describes an invention relating to a thermoforming sheet comprising at least three layers laminated in this order: Layer A containing a polycarbonate-based resin, Layer B containing an acrylic-based resin, and Layer C formed from an uncured product of an acrylate-based active energy ray-curable resin composition. The invention is characterized in that Layer A has a glass transition temperature (Tg) of 100°C or higher and 145°C or lower.

[0006] Patent Document 1 describes that, according to the invention, high moldability can be achieved by leaving the C layer, which corresponds to the hard coat layer, in an uncured state when applied to a molded article, and that a hard coat layer with high hardness can be obtained by curing the C layer by post-exposure to active energy rays after applying the thermoforming sheet to the molded article (after molding). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent Publication No. 2021-146687 Summary of the Invention [Problem to be solved by the invention]

[0008] However, it has been found that after molding the thermoforming sheet described in Patent Document 1, if adhesives and other substances that may adhere to the surface of the thermoforming sheet are wiped off and cleaned with a solvent such as alcohol, cracks may occur in the thermoforming sheet. Therefore, the present invention provides a laminate or the like that is less likely to crack even when wiped and cleaned with a solvent such as alcohol. [Means for solving the problem]

[0009] The present invention is, for example, as follows.

[0010] [1] A substrate layer (a) containing a polycarbonate resin; a curable resin layer (b) containing a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol; an acrylic layer (c) containing a (meth)acrylic resin and disposed between the substrate layer (a) and the curable resin layer (b); A laminate comprising: Shear rate of the (meth)acrylic resin: 122 sec -1 The melt viscosity at 230°C measured by is 2200 to 10000 Pa s, The laminate, wherein the acrylic layer (c) has a thickness of 10 to 120 μm. [2] The laminate according to the above [1], wherein the melt viscosity of the (meth)acrylic resin is 3000 to 6000 Pa·s. [3] The laminate according to the above [1] or [2], wherein the (meth)acrylic resin has a weight average molecular weight of 140,000 to 300,000. [4] The laminate according to any one of the above [1] to [3], wherein the intermediate glass transition temperature (Tmg) of the substrate layer (a) is 100 to 140°C. [5] The polycarbonate resin is a copolymer of bisphenol A, a carbonate binder, and a carboxylic acid represented by the following formula (1): [ka] [In the above formula (1), R 1 is an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The laminate according to any one of the above [1] to [4], which is a bisphenol A polycarbonate obtained by reacting a monohydric phenol end terminator represented by the following formula: [6] The laminate according to [5] above, wherein the monohydric phenol end-terminator represented by the formula (1) comprises at least one selected from the group consisting of 2-hexyldecyl parahydroxybenzoate, hexadecyl parahydroxybenzoate, dodecyl parahydroxybenzoate, and 2-ethylhexyl parahydroxybenzoate. [7] The (meth)acryloyl polymer is represented by the following formula (2): [ka] [In the above formula (2), m is a single bond or an alkylene group having 1 to 4 carbon atoms; n is hydrogen or an alkyl group having 1 to 4 carbon atoms; p is a single bond or an alkylene group having 1 to 2 carbon atoms; q is hydrogen or an alkyl group having 1 to 12 carbon atoms which may be substituted with at least one substituent selected from an epoxy group, a hydroxyl group, and a (meth)acryloyl group. The laminate according to any one of the above [1] to [6], which contains a repeating unit represented by the following formula: [8] The (meth)acryloyl polymer is represented by the following formulas (2-a) to (2-c): [ka] The laminate according to [7] above, comprising at least one repeating unit represented by the following formula: [9] The laminate according to any one of the above [1] to [8], which is used in TOM molding.

[10] A cured product obtained by curing the laminate according to any one of the above [1] to [9], comprising: a base layer (a); a cured film of the curable resin layer (b); and an acrylic layer (c).

[11] The cured product according to the above

[10] , wherein the pencil strength of the cured film surface of the curable resin layer (b) is H or more.

[12] A substrate layer (a) containing a polycarbonate resin; a curable resin layer (b) containing a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol; an acrylic layer (c) containing a (meth)acrylic resin and disposed between the substrate layer (a) and the curable resin layer (b); A laminate comprising: A laminate that does not show chemical cracks when wiped with alcohol. [Effects of the Invention]

[0011] According to the present invention, a laminate or the like is provided which is less likely to crack even when wiped and cleaned with a solvent such as alcohol. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described in detail.

[0013] 1.Laminate The laminate according to the present invention comprises a substrate layer (a) containing a polycarbonate resin, a curable resin layer (b) containing a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol, and an acrylic layer (c) containing a (meth)acrylic resin and disposed between the substrate layer (a) and the curable resin layer (b). That is, the laminate is formed by laminating the substrate layer (a), acrylic layer (c), and curable resin layer (b) in this order. At this time, the shear rate of the (meth)acrylic resin was 122 sec -1 The melt viscosity at 230° C. measured by is 2200 to 10000 Pa·s. The thickness of the acrylic layer (c) is 10 to 120 μm.

[0014] The laminate is less likely to crack even when wiped and cleaned with a solvent such as alcohol. Similarly, a cured product obtained by curing the laminate is less likely to crack even when wiped and cleaned with a solvent such as alcohol.

[0015] In conventional laminates, where a hard coat layer is formed by leaving the laminate uncured before molding and curing it after molding to achieve both hardness and moldability, cracks may occur when the molded laminate or its cured product is wiped and cleaned with a solvent such as alcohol. Possible reasons for this include, for example, that the laminate or cured product after molding is curved, bent, or the like, making it prone to cracking due to stress, and that the laminate or cured product has a layered structure, making it prone to chemical cracking due to solvent penetration through its cross section. In this case, for example, in the laminate, the cracks are likely to occur in the acrylic layer (c) out of the substrate layer (a), acrylic layer (c), and curable resin layer (b).

[0016] In contrast, in the laminate according to the present invention, the shear rate of the (meth)acrylic resin constituting the acrylic layer (c) of the laminate is 122 sec -1 By setting the melt viscosity at 230°C measured by 2200 to 10000 Pa·s and setting the thickness of the acrylic layer (c) to 10 to 120 μm, it is possible to prevent cracks that occur when wiping and cleaning with a solvent. The reasons for this are not entirely clear, but it is thought that this is due to, for example, the fact that the (meth)acrylic resin exhibits solvent resistance, the acrylic layer (c) has high mechanical strength that can withstand shapes such as curing and bending after molding, and the presence of the acrylic layer (c) allows the base layer (a) and the curable resin layer (b) to be bonded together flexibly and with high strength. This effect can also be achieved in a cured product obtained by curing the laminate.

[0017] In this specification, the solvent used for wiping and cleaning is preferably alcohol, and more preferably isopropyl alcohol from the viewpoint of facilitating cleaning of adhesives and the like that may adhere to the surface of the laminate, etc. after molding. In addition, in this specification, "crack" means the occurrence of fissures, cracks, fissures, etc. in the constituent layers of the laminate, etc., and preferably refers to chemical cracks caused by the solvent.

[0018] Therefore, according to one aspect of the present invention, there is provided a laminate that does not undergo chemical cracking in an alcohol wipe test, the laminate including: a substrate layer (a) containing a polycarbonate resin; a curable resin layer (b) containing a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol; and an acrylic layer (c) containing an acrylic resin and disposed between the substrate layer (a) and the curable resin layer (b).

[0019] Furthermore, the curable resin layer (b) of the laminate according to the present invention can be uncured before molding and cured after molding, so that both hardness and moldability can be achieved. In particular, when the curable resin layer (b) has the configuration of the present invention, it has excellent three-dimensional moldability.

[0020] In one embodiment, the laminate according to the present invention is used for vacuum forming, which is a forming method in which forming is performed under vacuum conditions, and can be in-mold forming, three-dimensional decoration (TOM) forming, etc. However, vacuum forming is usually applicable to three-dimensional shapes having irregularities, and therefore the laminate after forming tends to have a large degree of curvature, bending, etc. Therefore, the laminate after forming tends to be more susceptible to cracks when wiped and cleaned with a solvent. The laminate according to the present invention can prevent cracks from occurring due to wiping and cleaning using a solvent, even when vacuum forming is performed. Furthermore, as described above, when a laminate including the curable resin layer (b) is applied to a molded article (when being molded), it is preferable not to cause curing of the curable resin layer (b) during molding, but to cure the curable resin layer (b) after molding. However, when molding is performed under vacuum conditions, radicals are generated from oxygen atoms and the like contained in the curable resin layer (b), which may cause unintended curing of the curable resin layer (b) during vacuum molding. As a result, from this viewpoint as well, cracks may occur in the curable resin layer (b) after molding. According to the laminate of the present invention, even when molding is performed under vacuum conditions, the laminate can be formed without generating cracks, and the occurrence of cracks in the curable resin layer (b) of the laminate can be prevented.

[0021] In one embodiment, the laminate of the present invention is used in three-dimensional decoration (TOM) molding. Three-dimensional decoration (TOM) molding includes (1) a vacuum process in which a lower chamber with an open top and in which a molded product having a textured surface is placed, a lower chamber with an open bottom and in which a heater is placed, and the laminate of the present invention sandwiched between the lower chamber and the upper chamber are airtightly sealed and then placed under vacuum conditions, (2) a heating process in which the laminate is heated using the heater, (3) a contact process in which the molded product having texture is brought into contact with the heated laminate, (4) a vacuum process in which the upper chamber is placed under atmospheric pressure, and (5) a vacuum process in which the lower chamber is placed under atmospheric pressure. That is, in three-dimensional decoration (TOM) molding, a laminate is softened by heating under vacuum conditions, a molded product is pushed up from below the laminate so that they come into contact (the weight of the laminate causes them to adhere to the molded product and laminate), and then the upper chamber is set to atmospheric pressure to create a pressure difference, applying pressure from the upper chamber to the lower chamber to complete the lamination. This allows for the production of a three-dimensional decorated molded product that includes a molded product with a textured surface and a laminate placed on the textured surface. The three-dimensional decoration (TOM) molding may further include an upper chamber pressurization step of introducing compressed air into the upper chamber after the upper chamber de-vacuuming step, and may further include a trimming step of removing a portion of the laminate placed on the uneven surface and a curing step of curing the laminate after the lower chamber de-vacuuming step. When using conventional laminates for three-dimensional decoration (TOM) molding, the laminates could not be laminated with high conformality to molded articles having uneven surfaces, and even if they were able to be laminated, cracks could occur in the laminate. In particular, cracks were likely to occur when the laminate after molding was wiped clean with a solvent. However, the laminate of the present invention can be laminated with high conformality to molded articles having uneven surfaces. Furthermore, cracks are less likely to occur when the resulting laminate is wiped clean with a solvent.

[0022] <Base material layer (a)> The substrate layer (a) contains a polycarbonate resin, and may further contain other resins, plasticizers, additives, and the like.

[0023] [Polycarbonate resin] The polycarbonate resin is not particularly limited as long as it contains a carbonate bond, i.e., an -[OR-OCO]- unit (where R may contain an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and may have a linear or branched structure) in the molecular main chain.

[0024] In one embodiment, the polycarbonate resin is preferably a polycarbonate obtained by reacting a bisphenol, a carbonate binder, and a terminal capping agent.

[0025] (bisphenol) The bisphenol is not particularly limited, but examples thereof include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A: BPA), bis(4-hydroxyphenyl)methane (bisphenol F: BPF), bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E: BPE), 1,1- ... phenyl)ethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (bisphenol G: BPG), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane (bisphenol PH: BPPH), 1,1-bis(4-hydroxyphenyl)-2-methylpropane (bisphenol IBTD), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK), 1,1-bis(4-hydroxyphenyl)-2-ethylhexane (bisphenol IOTD), 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z: BPZ), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloundecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP: BPAP), bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP;Bisphenol compounds in which two phenolic groups are linked by "-C(R)2-", such as bis(4-hydroxyphenyl)sulfide; bisphenol compounds in which two phenolic groups are linked by "-O-", such as bis(4-hydroxyphenyl)ether; bisphenol compounds in which two phenolic groups are linked by "-SO-", such as bis(4-hydroxyphenyl)sulfoxide; bisphenol compounds in which two phenolic groups are linked by "-CO-", such as bis(4-hydroxyphenyl)ketone; Bisphenol compounds in which two phenolic groups are linked by "-SO2-", such as 9,9-bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, and bis(4-hydroxy-3-methylphenyl)sulfone; bisphenol compounds in which two phenolic groups are linked by a fluorene, such as 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene; bisphenol compounds in which two phenolic groups are linked by a phenylenebisalkylene, such as 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol and 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol; bisphenol compounds in which two phenolic groups are linked by an adamantyl, such as 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane;Examples of suitable bisphenol compounds include α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane and α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymerized siloxane, in which two phenol groups are linked via a polyalkylsiloxane. These bisphenols may be used alone or in combination of two or more.

[0026] Of these, the bisphenol preferably includes a bisphenol compound in which two phenol groups are linked by "-C(R)2-", and more preferably includes bisphenol A.

[0027] The content of bisphenol is preferably 1 mol % or more, more preferably 2 to 100 mol %, even more preferably 5 to 100 mol %, and particularly preferably 10 to 100 mol %, based on all structural units of the polycarbonate.

[0028] The content of bisphenol is preferably 2 to 99.8 mol %, more preferably 5 to 99 mol %, based on the total number of moles of the structural units and terminal structures of the polycarbonate.

[0029] (Compounds that derive other building blocks) The polycarbonate may be formed by further reacting with a compound that derives other structural units. By using the compound that derives other structural units, the physical properties of the polycarbonate (e.g., mid-glass transition temperature (Tmg), viscosity-average molecular weight, etc.) can be adjusted.

[0030] Compounds from which other structural units are derived include organosiloxanes.

[0031] Examples of organosiloxanes include α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymerized siloxane, etc. These organosiloxanes may be used alone or in combination of two or more.

[0032] The content of organosiloxane is preferably 50 moles or less, and more preferably 0.1 to 40 moles, per mole of bisphenol.

[0033] (carbonate binder) The carbonate binder is not particularly limited, but includes carbonyl compounds such as phosgene, triphosgene, carbon monoxide, carbon dioxide, and carbonic acid diesters.

[0034] Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate.

[0035] Among these, the carbonate binder preferably contains at least one of phosgene, triphosgene, diphenyl carbonate, and substituted diphenyl carbonate, and more preferably contains at least one of phosgene and diphenyl carbonate. The carbonate binders may be used alone or in combination of two or more.

[0036] (end terminator) The terminal terminator has functions such as adjusting the midpoint glass transition temperature (Tmg) and viscosity average molecular weight of the polycarbonate.

[0037] The terminal terminator is not particularly limited, and examples thereof include a monohydric phenol terminal terminator represented by the following formula (1) and a monohydric phenol compound having no unsaturated group.

[0038] [ka]

[0039] In the above formula (1), R 1 is an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In this specification, the "alkyl group" and "alkenyl group" may be linear or branched, but are preferably linear.

[0040] More preferably, the monohydric phenol end-terminator represented by formula (1) is represented by the following general formula (1-a): [ka]

[0041] In the above formula (1-a), R 1 is an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.

[0042] R in formula (1) or formula (1-a) 1 It is more preferable that the number of carbon atoms in R is within a specific numerical range. 1 The upper limit of the number of carbon atoms in R is preferably 36, more preferably 22, and particularly preferably 18. 1 The lower limit of the number of carbon atoms is preferably 8, and more preferably 12.

[0043] R 1When the upper limit of the carbon number of R is appropriate, the solubility of the monohydric phenol end-stopper represented by formula (1) in organic solvents tends to be high, which is preferable from the viewpoints of increasing the productivity in the production of polycarbonate resins and increasing the transparency of polycarbonate resins. 1 When the number of carbon atoms in R is 36 or less, a polycarbonate resin having high transparency can be obtained, and the productivity in producing the polycarbonate resin is high and economical. 1 When the number of carbon atoms is 22 or less, the monohydric phenol end-terminator represented by formula (1) has particularly excellent solubility in organic solvents, and can significantly increase the productivity in producing polycarbonate resins, thereby improving economic efficiency.

[0044] R 1 If the lower limit of the carbon number of R is appropriate, the glass transition temperature of the polycarbonate resin will not be too high, and the resin will have favorable thermoformability, which is preferable. 1 When a monohydric phenol end-terminator represented by formula (1), in which R is an alkyl group having 16 carbon atoms, is used, the intermediate glass transition temperature, melt fluidity, moldability, drawdown resistance, and solvent solubility of the monohydric phenol end-terminator represented by formula (1) during polycarbonate resin production are excellent, and it is particularly preferred as an end-terminator for use in polycarbonate resins.

[0045] In one embodiment, R in formula (1) or formula (1-a) 1 is preferably dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl, more preferably tetradecyl, pentadecyl, hexadecyl, heptadecyl, or 2-hexyldecyl, and even more preferably hexadecyl or 2-hexyldecyl.

[0046] In one embodiment, R in formula (1) 2are each independently preferably hydrogen, a halogen atom, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, or phenyl, more preferably hydrogen, a fluorine atom, a chlorine atom, methyl, ethyl, or phenyl, and even more preferably hydrogen, a fluorine atom, a chlorine atom, methyl, or ethyl. 2 is preferably hydrogen.

[0047] In one embodiment, the monohydric phenol end-terminator represented by formula (1) preferably includes at least one selected from the group consisting of 2-hexyldecyl parahydroxybenzoate, hexadecyl parahydroxybenzoate, dodecyl parahydroxybenzoate, and 2-ethylhexyl parahydroxybenzoate, more preferably includes at least one of 2-hexyldecyl parahydroxybenzoate and hexadecyl parahydroxybenzoate, and even more preferably includes 2-hexyldecyl parahydroxybenzoate.

[0048] The monohydric phenol end-terminator represented by the above formula (1) may be used alone or in combination of two or more kinds.

[0049] The amount of the monohydric phenol end-terminator represented by formula (1) used is preferably 0.02 to 0.07 mol, more preferably 0.025 to 0.06 mol, per 1 mol of bisphenol.

[0050] The amount of the monohydric phenol end-terminator represented by formula (1) used is preferably 0.02 to 0.07 mol, more preferably 0.025 to 0.06 mol, per 1 mol of the carbonate binder.

[0051] Examples of monohydric phenol compounds having no unsaturated group include phenol, p-cresol, o-cresol, 2,4-xylenol, p-tert-butylphenol, p-hexylphenol, p-heptylphenol, p-octylphenol, p-cumylphenol, etc. These monohydric phenol compounds may be used alone or in combination of two or more.

[0052] The amount of the monohydric phenol compound having no unsaturated group used is preferably 0.5 mol or less, more preferably 0.2 mol or less, and even more preferably 0.1 mol or less, per mol of the terminal terminator represented by formula (1).

[0053] The amount of the monohydric phenol compound having no unsaturated group used is preferably 0.02 to 0.07 mol, more preferably 0.025 to 0.06 mol, per 1 mol of bisphenol.

[0054] In one embodiment, the polycarbonate resin is preferably a bisphenol A polycarbonate obtained by reacting bisphenol A, a carbonate binder, and a monohydric phenol end-terminator represented by the following formula (1). [ka]

[0055] The bisphenol A polycarbonate can be further reacted with bisphenols other than bisphenol A, compounds that derive other structural units, monohydric phenol compounds that do not have an unsaturated group, and the like. The carbonate binder, the monohydric phenol end-terminator represented by formula (1), the bisphenol other than bisphenol A, the compound that derives other structural units, the monohydric phenol compound that does not have an unsaturated group, and the like can be those described above.

[0056] In one embodiment, the bisphenol A polycarbonate preferably contains structural units derived from bisphenol A in an amount of 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more, and particularly preferably 98 to 100% by mass, based on the mass of all structural units of the bisphenol A polycarbonate excluding the terminal structures.

[0057] The above-mentioned polycarbonate resins may be used alone or in combination of two or more kinds.

[0058] The intermediate glass transition temperature (Tmg) of the polycarbonate resin is preferably 100 to 140°C, more preferably 125 to 140°C, even more preferably 128 to 140°C, and even more preferably 128 to 135°C. When the intermediate glass transition temperature (Tmg) of the polycarbonate resin is within the above range, it is preferable because it is easy to control the intermediate glass transition temperature (Tmg) of the base layer (a). In this specification, the "intermediate glass transition temperature (Tmg)" is a value obtained by analyzing a DSC curve obtained by differential scanning calorimetry (DSC). Specifically, of the line A, which is obtained by extending the low-temperature side baseline of the DSC curve to the high-temperature side, the tangent line B at the inflection point, and the line C, which is obtained by extending the high-temperature side baseline to the low-temperature side, the intersection of line A and tangent line B is the starting glass transition temperature (Tig), and the tangent line B and line C is the ending glass transition temperature (Teg). The midpoint between the starting glass transition temperature (Tig) and the ending glass transition temperature (Teg) is the intermediate glass transition temperature (Tmg). Note that when glass transition temperature is generally used, it refers to the starting glass transition temperature (Tig), which is lower than the intermediate glass transition temperature (Tmg). The intermediate glass transition temperature (Tmg) is measured by the method described in the Examples.

[0059] The viscosity average molecular weight of the polycarbonate resin is preferably 14,000 or more, more preferably 16,000 or more, even more preferably 20,000 or more, particularly preferably 24,000 or more, and very preferably 26,000 or more. The viscosity average molecular weight of the polycarbonate resin is preferably 40,000 or less, more preferably 38,000 or less, even more preferably 36,000 or less, particularly preferably 34,000 or less, and very preferably 32,000 or less. In one embodiment, the viscosity average molecular weight of the polycarbonate resin is preferably 14,000 to 40,000, more preferably 16,000 to 38,000, even more preferably 18,000 to 36,000, particularly preferably 20,000 to 34,000, and very preferably 24,000 to 32,000. In this specification, the "viscosity average molecular weight" is measured by the method described in the Examples. When the polycarbonate resin is a mixture of two or more polycarbonate resins having different molecular weights, the viscosity average molecular weight after mixing is used.

[0060] The content of the polycarbonate resin is preferably 96% by mass or more, more preferably 98% by mass or more, and even more preferably 100% by mass, based on the total mass of the base layer (a).

[0061] [Plasticizer] The base layer (a) may further contain a plasticizer, which has the function of adjusting the intermediate glass transition temperature (Tmg) of the base layer (a).

[0062] The plasticizer is not particularly limited, but examples thereof include polyesters, polyethers, aromatic phosphonate compounds, and aromatic ester compounds.

[0063] Examples of the polyester include aliphatic polyesters such as polycaprolactone (PCL); and aromatic polyesters such as polyethylene terephthalate modified resins and polycaprolactone polyethylene terephthalate modified resins.

[0064] Examples of the polycaprolactone polyethylene terephthalate modified resin include glycol-modified polyethylene terephthalate (PETG) and glycol-modified polycyclohexylene dimethylene terephthalate (PCTG). PETG is a PET (dicarboxylic acid units, terephthalic acid units, and glycol units, ethylene glycol units) in which some of the ethylene glycol units are substituted with 1,4-cyclohexanedimethanol units. The content of 1,4-cyclohexanedimethanol units is preferably less than 50 mol %, more preferably 30 to 40 mol %, of the total glycol units. PCTG is a polymer in which some of the glycol units in PCT (dicarboxylic acid units, i.e., terephthalic acid units, and glycol units, i.e., 1,4-cyclohexanedimethanol units) have been substituted with glycol units. The content of the glycol units is preferably less than 50 mol %, more preferably 30 to 40 mol %, based on the total glycol units.

[0065] The number average molecular weight of the polyester is preferably 10,000 to 100,000, and more preferably 20,000 to 60,000. In this specification, the value of "number average molecular weight" is measured by gel permeation chromatography.

[0066] The polyether may be a polyether having at least one selected from the group consisting of ethylene glycol units, propylene glycol units, butylene glycol units, trimethylene glycol units, and tetramethylene glycol units. Specifically, the polyether may be a homopolymer or a copolymer, and if it is a copolymer, it may be a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or a combination thereof. Specific examples of polyethers include polyethylene glycol, polypropylene glycol, polybutylene butylene glycol, and block copolymers of polyethylene glycol and polypropylene glycol. The number average molecular weight of the polyether is preferably 500 to 4,000, more preferably 600 to 3,000, and even more preferably 800 to 2,000.

[0067] Examples of the aromatic phosphonate compound include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis-(tert-butylphenyl)phenyl phosphate, tris-(tert-butylphenyl)phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, tris-(isopropylphenyl)phosphate, resorcinol bis-diphenyl phosphate, resorcinol poly(di-2,6-xylyl)phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and biphenyl bis-diphenyl phosphate. The molecular weight of the aromatic phosphonate compound is preferably 200 to 1,000, and more preferably 400 to 800.

[0068] Examples of the aromatic ester compound include diethylene glycol dibenzoate, glyceryl tribenzoate, trimethylolpropane tribenzoate, pentaerythritol tetrabenzoate, etc. The molecular weight of the aromatic ester compound is preferably 200 to 1,000, and more preferably 400 to 800.

[0069] Of the above, the plasticizer preferably contains polyester or an aromatic phosphonate compound, more preferably contains polyester, further preferably contains at least one of polycaprolactone (PCL), glycol-modified polyethylene terephthalate (PETG), and glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), and particularly preferably contains polycaprolactone (PCL). The above plasticizers may be used alone or in combination of two or more.

[0070] The content of the plasticizer is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 0.1 to 2% by mass, based on the total mass of the base layer (a). When the content of the plasticizer is 4% by mass or less, the base layer (a) can contain 96% by mass or more of polycarbonate resin.

[0071] [Additives] The base layer (a) may further contain additives. The additives are not particularly limited, but examples thereof include antioxidants, transesterification inhibitors, release agents, heat stabilizers, flame retardants, flame retardant aids, ultraviolet absorbers, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, hue improvers, acid trapping agents, etc. These additives may be used alone or in combination of two or more.

[0072] The content of the additive is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 0.1 to 2% by mass, based on the total mass of the base layer (a). When the content of the additive is 4% by mass or less, the base layer (a) can contain 96% by mass or more of polycarbonate resin.

[0073] [Configuration of base layer (a)] The intermediate glass transition temperature (Tmg) of the substrate layer (a) is preferably 100 to 140° C., more preferably 110 to 140° C., even more preferably 120 to 140° C., particularly preferably 120 to 135° C., and most preferably 125 to 135° C. The intermediate glass transition temperature (Tmg) of the substrate layer (a) can be controlled by appropriately adjusting the structure of the polycarbonate resin (for example, the type and content of structural units of the polycarbonate resin, the type of end-terminator used, viscosity average molecular weight, etc.), the type and content of plasticizer added to the substrate layer (a), etc.

[0074] The thickness of the substrate layer (a) is preferably 10 to 800 μm, more preferably 20 to 500 μm, even more preferably 30 to 400 μm, even more preferably 50 to 300 μm, and even more preferably 60 to 200 μm.

[0075] <Curable resin layer (b)> The curable resin layer (b) contains a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol. Because the curable resin layer (b) is in an uncured state, when the laminate according to the present invention is molded, it has excellent moldability, particularly three-dimensional moldability. Therefore, for example, when three-dimensional molding is performed, the curable resin layer (b) easily conforms, and cracks are less likely to occur in the curable resin layer (b) after molding. Furthermore, the cured product obtained by curing the laminate has high hardness and may have improved scratch resistance, chemical resistance, and the like. In this specification, "(meth)acryloyl" means methacryloyl and / or acryloyl. Similarly, "(meth)acrylic" and "(meth)acrylate" mean methacrylic and / or acrylic, methacrylate and / or acrylate.

[0076] [(Meth)acryloyl polymer] The (meth)acryloyl polymer preferably contains a repeating unit represented by the following formula (2).

[0077] [ka]

[0078] In the above formula (2), m is a single bond or an alkylene group having 1 to 4 carbon atoms, preferably methylene or ethylene, and more preferably methylene.

[0079] n is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen, methyl, or ethyl, more preferably hydrogen or methyl, and even more preferably hydrogen.

[0080] p is a single bond or an alkylene group having 1 to 2 carbon atoms, preferably a single bond or methylene, and more preferably a single bond.

[0081] q is hydrogen or an alkyl group having 1 to 12 carbon atoms which may be substituted with at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, and a (meth)acryloyl group, preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with at least one substituent selected from the group consisting of an epoxy group and a (meth)acryloyl group, and more preferably an alkyl group having 1 to 2 carbon atoms which may be substituted with at least one substituent selected from the group consisting of an epoxy group and a (meth)acryloyl group.

[0082] In one embodiment, the (meth)acryloyl polymer preferably contains at least one of the repeating units represented by the following formulas (2-a) to (2-c).

[0083] [ka]

[0084] The content of the repeating unit represented by formula (2-a) is preferably 30 to 85 mol %, more preferably 40 to 80 mol %, based on the total number of moles of the (meth)acryloyl polymer.

[0085] The content of the repeating unit represented by formula (2-b) is preferably 5 to 30 mol %, more preferably 10 to 25 mol %, based on the total number of moles of the (meth)acryloyl polymer.

[0086] The content of the repeating unit represented by formula (2-c) is preferably 10 to 40 mol %, more preferably 10 to 35 mol %, based on the total number of moles of the (meth)acryloyl polymer.

[0087] The above-mentioned (meth)acryloyl polymers may be used alone or in combination of two or more kinds.

[0088] The molar ratio of the repeating unit represented by formula (2-a) to the repeating unit represented by formula (2-b) is preferably 4.5-5.5:1.5-2.5. The molar ratio of the repeating unit represented by formula (2-a) to the repeating unit represented by formula (2-c) is preferably 4.5-5.5:2.5-3.5. The molar ratio of the repeating unit represented by formula (2-b) to the repeating unit represented by formula (2-c) is preferably 1.5 to 2.5:2.5 to 3.5.

[0089] The acrylic equivalent of the (meth)acryloyl polymer is 200 to 600 g / mol, and from the viewpoint of increasing the hardness of the cured product, it is preferably 200 to 500 g / mol, more preferably 200 to 400 g / mol, and even more preferably 200 to 300 g / mol. In this specification, the (meth)acrylic equivalent (g / mol) means the molecular weight per (meth)acryloyl group, and can be calculated by the method described in the Examples.

[0090] The weight average molecular weight of the (meth)acryloyl polymer is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, even more preferably 15,000 to 100,000, and particularly preferably 20,000 to 50,000. In this specification, the "weight average molecular weight" is calculated by the method described in the examples.

[0091] The content of the (meth)acryloyl polymer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 60 to 100% by mass, and particularly preferably 60 to 90% by mass, relative to the total mass of the curable resin layer (b).

[0092] [Multifunctional acrylate compounds] The curable resin layer (b) may further contain a polyfunctional acrylate compound. The polyfunctional acrylate compound can improve the hardness of the cured product by reacting with, for example, a (meth)acryloyl group, an epoxy group, a hydroxyl group, or the like, contained in the (meth)acryloyl polymer. In this specification, "polyfunctional" means having two or more functionalities, preferably three or more functionalities, more preferably three to eight functionalities, and even more preferably three to six functionalities.

[0093] The polyfunctional acrylate compound is not particularly limited, but examples thereof include pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0094] The content of the polyfunctional acrylate compound is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, based on the total content of the (meth)acryloyl polymer and the polyfunctional acrylate compound.

[0095] [Inorganic particles] The curable resin layer (b) may further contain inorganic particles, which can improve the hardness and scratch resistance of the cured product.

[0096] The inorganic particles are not particularly limited, but examples thereof include silica, alumina, titania, zirconia, diamond, and the like.

[0097] The inorganic particles may be surface-treated. By surface-treating the inorganic particles, they can be stably dispersed in the curable resin layer (b). The surface treatment agent used in this case is not particularly limited, but includes silane compounds, alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, etc. These surface treatment agents may be used alone or in combination of two or more. By the surface treatment, polymerizable groups (preferably vinyl groups and (meth)acrylic groups) can be introduced onto the surfaces of the inorganic particles.

[0098] The inorganic particles described above may be used alone or in combination of two or more kinds.

[0099] The average particle size of the inorganic particles is preferably 5 to 95 nm, more preferably 8 to 70 nm, and from the viewpoint of improving the scratch resistance of the resulting cured product, is further preferably 20 to 60 nm, and particularly preferably 30 to 60 nm. In this specification, "particle size" refers to the maximum distance between two points on the outer surface of a particle. The "average particle size" is measured by the method described in the Examples.

[0100] The content of the inorganic particles is preferably 5 to 60 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total mass of the curable resin layer (b).

[0101] [Leveling agent] The curable resin layer (b) may further contain a leveling agent, which has functions such as leveling properties (making the coating film flat and smooth) and improving the fingerprint wiping properties, stain resistance, and abrasion resistance of the cured product.

[0102] The leveling agent is not particularly limited, but examples thereof include fluorine-based leveling agents and silicone-based leveling agents.

[0103] As the fluorine-based leveling agent, the compound having perfluoropolyether bond can be mentioned.As the fluorine-based leveling agent, commercially available products can be used, for example, Megafac RS-56, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 (manufactured by DIC Corporation), KY-1203, X-71-1203E, KY-1207, KY-1211 (manufactured by Shin-Etsu Chemical Co., Ltd.), Optool UD120 (manufactured by Daikin Industries, Ltd.), Ftergent 710FL, 220P, 208G, 601AD, 602A, 650A, 228P, 240GFTX-218 (manufactured by Neos Corporation) etc.

[0104] Examples of silicone leveling agents include acrylic group-containing polyether-modified polydimethylsiloxane, etc. Commercially available silicone leveling agents can be used, such as BYK-UV3500 and BYK-UV3505 (manufactured by BYK Japan Co., Ltd.).

[0105] Of these, the leveling agent preferably contains a fluorine-based leveling agent from the viewpoint of improving the ease of wiping off fingerprints from the cured product, etc. The above-mentioned leveling agents may be used alone or in combination of two or more kinds.

[0106] The content of the leveling agent is preferably 0.001 to 10 mass %, more preferably 0.001 to 5 mass %, even more preferably 0.01 to 4 mass %, and particularly preferably 0.1 to 3 mass %, relative to the total mass of the curable resin layer (b).

[0107] [Photopolymerization initiator] The curable resin layer (b) may further contain a photopolymerization initiator, which has the function of accelerating the curing reaction when curing the curable resin layer (b).

[0108] The photopolymerization initiator is not particularly limited, but examples thereof include 1-hydroxycyclohexylphenyl ketone (Irgacure 184), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Irgacure 1173), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Irgacure TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure 819), 2,2'-dimethoxy-2-phenylacetophenone (Irgacure 651), oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone (EsacureONE), 1-hydroxycyclohexylphenyl ketone (Omnirad Among these, from the viewpoint of increasing heat resistance, the photopolymerization initiator preferably contains at least one of oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone (EsacureONE) and 1-hydroxycyclohexyl-phenyl ketone (Omnirad 184), and more preferably contains 1-hydroxycyclohexyl-phenyl ketone (Omnirad 184). The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.

[0109] The content of the photopolymerization initiator is preferably 1 to 10 mass %, more preferably 1 to 6 mass %, even more preferably 2 to 5 mass %, and particularly preferably 2 to 4 mass %, relative to the total mass of the curable resin layer (b).

[0110] [Light stabilizer] The curable resin layer (b) may further contain a light stabilizer, which has the function of improving the weather resistance of the cured product.

[0111] The light stabilizer is not particularly limited, but examples thereof include hindered amine light stabilizers.

[0112] Hindered amine light stabilizers include bis(1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate (ADK STAB LA-81), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate (ADK STAB LA-52), tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate (ADK STAB LA-57), and 1,2,2,6,6-pentamethy-4-piperidylbutane-1,2,3,4-tetracarboxylate (ADK STAB LA-58). methyl-4-piperidyl methacrylate (ADEKASTAB LA-82), bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl) sebacate (Tinuvin 123), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770DF), bis(1,2,2,6,6-pentamethyl-4-piperidyl)-((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)butyl malonate (Tinuvin 144), and the like.

[0113] Among these, the light stabilizer preferably includes a hindered amine light stabilizer. The above light stabilizers may be used alone or in combination of two or more kinds.

[0114] The content of the light stabilizer is preferably 0.1 to 15 mass %, more preferably 0.1 to 7 mass %, even more preferably 0.3 to 5 mass %, and particularly preferably 0.3 to 3 mass %, relative to the total mass of the curable resin layer (b).

[0115] [Polymerization inhibitor] The curable resin layer (b) may further contain a polymerization inhibitor, which has the function of suppressing a polymerization reaction of the curable resin layer (b) due to light, heat, etc., and improving the storage stability of the laminate.

[0116] The polymerization inhibitor is not particularly limited, but examples thereof include phenothiazine, mequinol (4-methoxyphenol), hydroquinone, 2-hydroxynaphthoquinone, N-isopropyl-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, and 2-mercaptobenzimidazole.

[0117] Among these, the polymerization inhibitor preferably contains at least one of phenothiazine, mequinol, and hydroquinone, and more preferably contains phenothiazine. The above-mentioned polymerization inhibitors may be used alone or in combination of two or more.

[0118] The content of the polymerization inhibitor is preferably 0.001 to 5 mass %, more preferably 0.01 to 4 mass %, and even more preferably 0.01 to 3 mass %, relative to the total mass of the curable resin layer (b).

[0119] [Additives] The curable resin layer (b) may further contain an additive.

[0120] The additives are not particularly limited, but examples thereof include heat stabilizers, antioxidants, flame retardants, flame retardant assistants, ultraviolet absorbers, release agents, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc. These additives may be used alone or in combination of two or more.

[0121] [Configuration of curable resin layer (b)] The curable resin layer (b) is in an uncured state, and for example, the (meth)acryloyl polymer has a polymerizable functional group (such as a (meth)acryloyl group, an epoxy group, or a hydroxyl group). The curable resin layer (b) is easy to conform and is less likely to crack after molding, resulting in excellent moldability, particularly three-dimensional moldability. However, for example, within the scope of the present invention, the (meth)acryloyl polymer in the curable resin layer (b) may have a crosslinked structure due to a curing reaction of some of the (meth)acryloyl groups during the molding process.

[0122] The thickness of the curable resin layer (b) is preferably 1 μm or more, more preferably 3 μm or more, particularly preferably 3 to 30 μm, and most preferably 3 to 10 μm.

[0123] <Acrylic layer (c)> The acrylic layer (c) is disposed between the substrate layer (a) and the curable resin layer (b).

[0124] The acrylic layer (c) contains a (meth)acrylic resin and may further contain additives.

[0125] [(Meth)acrylic resin] The (meth)acrylic resin is not particularly limited as long as it is a polymer of a (meth)acrylic acid ester.

[0126] Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. These (meth)acrylic acid esters may be used alone or in combination of two or more.

[0127] The (meth)acrylic resin may be a copolymer of an acrylic acid ester and other polymerizable monomers.

[0128] Examples of other polymerizable monomers include (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, acrylonitrile, etc. These other polymerizable monomers may be used alone or in combination of two or more.

[0129] The (meth)acrylic resin may be a homopolymer or a copolymer, and may be crosslinked using a crosslinking agent.

[0130] Among these, the (meth)acrylic resin preferably contains polymethyl methacrylate (PMMA) resin from the viewpoints of high transparency, excellent moldability, etc. The above-mentioned (meth)acrylic resins may be used alone or in combination of two or more.

[0131] (Meth)acrylic resin shear rate 122 sec -1 The melt viscosity at 230°C measured by a shear rate of 122 sec is 2200 to 10000 Pa·s, preferably 2500 to 8000 Pa·s, more preferably 2800 to 7000 Pa·s, and even more preferably 3000 to 6000 Pa·s. When the melt viscosity of the (meth)acrylic resin is within the above range, effects such as preventing cracks that occur when wiping and cleaning with a solvent and reducing the occurrence of poor appearance can be obtained. In this specification, the term "shear rate of 122 sec" refers to a melt viscosity at 230°C measured by a shear rate of 122 sec -1 Specifically, the "melt viscosity at 230°C measured by" can be measured by the method described in the examples.

[0132] The weight-average molecular weight of the (meth)acrylic resin is preferably 140,000 to 300,000, more preferably 150,000 to 300,000, and even more preferably 170,000 to 300,000. When the weight-average molecular weight of the (meth)acrylic resin is within the above range, effects such as preventing cracks that occur during wiping and cleaning with a solvent and reducing the occurrence of poor appearance can be obtained.

[0133] The shear rate of (meth)acrylic resin is 122 sec -1 The melt viscosity and weight average molecular weight at 230°C measured in the above manner can be adjusted by appropriately changing the type of (meth)acrylic acid ester used, the type and content of other polymerizable monomers, polymerization conditions, the presence or absence of crosslinking, etc.

[0134] The content of the (meth)acrylic resin 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 90 to 100% by mass, relative to the total mass of the acrylic layer (c).

[0135] [Additives] The acrylic layer (c) may further contain an additive. Examples of the additive include, but are not limited to, an ultraviolet absorber, an antioxidant, a coloring inhibitor, inorganic particles, etc. These additives may be used alone or in combination of two or more. [Configuration of acrylic layer (c)] The thickness of the acrylic layer (c) is 10 to 120 μm, preferably 20 to 120 μm, more preferably 30 to 100 μm, still more preferably 30 to 90 μm, and particularly preferably 40 to 80 μm.

[0136] 2. Manufacturing method of laminate According to one aspect of the present invention, there is provided a method for manufacturing a laminate.

[0137] In one embodiment, the method for producing a laminate includes step (1) of co-extruding a first resin composition and a third resin composition to form a precursor including a base layer (a) and an acrylic layer (c), and step (2) of forming a curable resin layer (b) from a second resin composition on the acrylic layer (c) in the precursor.

[0138] In this case, the first resin composition contains a polycarbonate resin. The second resin composition contains a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol. The third resin composition contains a (meth)acrylic resin.

[0139] Each step will be described below.

[0140] <Process (1)> Step (1) is a step of co-extruding the first resin composition and the third resin composition to form a precursor including the substrate layer (a) and the acrylic layer (c).

[0141] [First resin composition] The first resin composition contains a polycarbonate resin, and may further contain other additives such as a plasticizer and an additive.

[0142] The polycarbonate resin, plasticizer, and additives used are the same as those described above.

[0143] The composition of the first resin composition is adjusted appropriately so that the substrate layer (a) has a desired structure.

[0144] [Third resin composition] The third resin composition contains a (meth)acrylic resin. In addition, the third resin composition may further contain additives and the like.

[0145] The composition of the third resin composition is adjusted appropriately so that the acrylic layer (c) has a desired structure.

[0146] [Method for forming precursor] The precursor is formed by co-extruding the first resin composition and the third resin composition, thereby forming a precursor including the base layer (a) and the acrylic layer (c).

[0147] The melting temperature of the first resin composition is not particularly limited, but is preferably 230 to 320°C, and more preferably 260 to 300°C.

[0148] The cooling temperature of the first resin composition is not particularly limited, but is preferably 50 to 200°C, and more preferably 70 to 150°C.

[0149] The melting temperature of the third resin composition is not particularly limited, but is preferably 200 to 300°C, and more preferably 210 to 280°C.

[0150] The cooling temperature of the third resin composition is not particularly limited, but is preferably 50 to 200°C, and more preferably 70 to 150°C.

[0151] <Process (2)> Step (2) is a step of forming a curable resin layer (b) from a second resin composition on the acrylic layer (c) in the precursor formed in step (1).

[0152] [Second resin composition] The second resin composition contains a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol, and may further contain other ingredients such as a polyfunctional acrylate compound, inorganic particles, a leveling agent, a photopolymerization initiator, a light stabilizer, a polymerization inhibitor, an additive, and a dilution solvent.

[0153] The dilution solvent is not particularly limited, but examples thereof include acetone, methyl ethyl ketone, cyclohexanone, etc. These dilution solvents may be used alone or in combination of two or more.

[0154] The composition of the second resin composition is adjusted appropriately so that the curable resin layer (b) has a desired structure.

[0155] [Method for forming curable resin layer (b)] The method for forming the curable resin layer (b) is not particularly limited, but is preferably a method in which the second resin composition is applied onto the acrylic layer (c) in the precursor.

[0156] Examples of the method for applying the second resin composition include spray coating, spin coating, bar coating, gravure coating, and die coating.

[0157] The coating film formed by application is preferably dried. For example, drying volatilizes the dilution solvent that may be contained in the second resin composition, thereby obtaining the curable resin layer (b).

[0158] The temperature for drying the coating film is preferably 50 to 200°C, and more preferably 70 to 150°C.

[0159] 3.Cured product According to one embodiment of the present invention, a cured product is provided. The cured product is obtained by curing the above-described laminate, and includes a substrate layer (a), a cured film of the curable resin layer (b), and an acrylic layer (c). In this specification, "curing of the laminate" means curing the curable resin layer (b) of the laminate to obtain a cured film. Furthermore, "cured film" means a cured film (single-layer film) obtained by curing the curable resin layer (b). Furthermore, "cured product" means a laminate of two or more layers including the cured film and each layer derived from the laminate (such as the substrate layer (a)).

[0160] In one embodiment, the cured product preferably has a cured film of a substrate layer (a), an acrylic layer (c), and a curable resin layer (b) laminated in this order. In this case, the configuration of the base layer (a) and the acrylic layer (c) is usually the same as that in the laminate.

[0161] The cured film of the curable resin layer (b) has high hardness, which can result in the cured product having high scratch resistance, chemical resistance, and the like. In one embodiment, the pencil hardness of the cured film surface of the curable resin layer (b) is preferably H or higher, more preferably 2H or higher, even more preferably 3H or higher, and particularly preferably 3H to 5H. Note that the "pencil hardness of the cured film surface of the curable resin layer (b)" may be affected not only by the cured film of the curable resin layer (b) but also by other layers of the cured product (e.g., the configuration of the base layer (a) and the configuration of the acrylic layer (c)). In addition, in this specification, the "pencil hardness" is measured by the method described in the Examples.

[0162] In one embodiment, the cured product may have improved fingerprint wiping properties, weather-resistant adhesion, etc. Furthermore, cracks are less likely to occur when the cured product is wiped and cleaned using a solvent.

[0163] Since the cured product can be used as a thermoforming film (functional film, decorative film), it is preferably formed so as to cover the surface of a molded article. That is, in one embodiment, there is provided a thermoforming film-containing molded article comprising a molded article and the cured product according to the present invention arranged on the surface of the molded article.

[0164] The molded article is not particularly limited, but is preferably a molded article having an uneven surface, and examples of the molded article include goggles, sinks, organs, beds, and vehicle housings.

[0165] In a preferred embodiment, the molded article is a molded article having a textured surface, and the laminate is three-dimensionally decorated and molded (TOM molding) onto the molded article, thereby providing a three-dimensionally decorated molded article comprising a molded article having a textured surface and a laminate arranged on the textured surface.

[0166] 4. Manufacturing method of the cured product According to one aspect of the present invention, there is provided a method for producing a cured product. The method for producing a cured product includes a curing step of curing the above-described laminate. The method for producing a cured product may further include a molding step of molding the laminate onto a surface of a molded article.

[0167] [Molding process] The molding step is a step of molding a laminate on the surface of a molded article. The molding is preferably three-dimensional molding. Since the curable resin layer (b) of the laminate is in an uncured state, the moldability of the laminate, particularly the three-dimensional moldability, is high. As a result, even when three-dimensional molding is performed, the conformability of the laminate is high, and cracks are unlikely to occur even when the laminate after molding is wiped and cleaned with a solvent.

[0168] (molded product) The molded article is not particularly limited, but for example, the above-mentioned molded articles can be used.

[0169] (Laminate) The laminate used is the one described above.

[0170] (molding) The molding is not particularly limited, but three-dimensional molding is preferred, and three-dimensional decoration (TOM) molding is more preferred. As described above, the three-dimensional decoration (TOM) molding process includes: (1) a vacuum process in which a lower chamber that opens at the top and in which a molded product having a textured surface is placed, an upper chamber that opens at the bottom and in which a heater is placed, and the laminate of the present invention sandwiched between the lower chamber and the upper chamber are made airtight, and then placed under vacuum conditions; (2) a heating process in which the laminate is heated using the heater; (3) a contact process in which the molded product having textured surfaces is brought into contact with the heated laminate; (4) an upper chamber de-vacuum process in which the upper chamber is placed under atmospheric pressure; and (5) a lower chamber de-vacuum process in which the lower chamber is placed under atmospheric pressure. The method may further include an upper chamber pressurization step of introducing compressed air into the upper chamber after the upper chamber de-vacuuming step, and a trimming step of removing a portion of the laminate disposed on the uneven surface after the lower chamber de-vacuuming step.

[0171] [Curing process] The curing step is a step of curing the laminate. More specifically, it is a step of curing the curable resin layer (b) in the laminate by a curing reaction to obtain a cured film of the curable resin layer (b).

[0172] The curing reaction is not particularly limited, but is preferably carried out by irradiation with active energy rays.

[0173] Examples of the active energy rays include ultraviolet rays, electron beams, and radioactive rays, and ultraviolet rays are preferred.

[0174] The irradiation dose of the active energy ray is not particularly limited, but is preferably 100 to 5000 mJ / cm as the cumulative exposure dose at an ultraviolet wavelength of 365 nm. 2 is preferably 300 to 3000 mJ / cm 2 It is more preferable that: [Example]

[0175] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0176] 1.Measurement method (1) Glass transition temperature The glass transition temperature (Tg) of each resin and resin composition was measured by performing two cycles of temperature increase and decrease according to the differential scanning calorimetry (DSC) measurement conditions below, and measuring the glass transition temperature during the second temperature increase cycle. The intersection of a line (line A) extending the low-temperature baseline toward the high temperature side and a tangent to the inflection point (tangent B) was defined as the onset glass transition temperature (Tig). The intersection of a line (line C) extending the high-temperature baseline toward the low temperature side and a tangent to the inflection point (tangent B) was defined as the end glass transition temperature (Teg). The midpoint between the onset glass transition temperature (Tig) and the end glass transition temperature (Teg) was defined as the intermediate glass transition temperature (Tmg).

[0177] Measurement start temperature: 30℃ Heating rate: 10°C / min Achieved temperature: 250℃ The temperature drop rate was 20°C / min. Measurement equipment: Differential scanning calorimeter "DSC7020" (Hitachi High-Tech Science Corporation)

[0178] (2) Viscosity average molecular weight The viscosity average molecular weight was calculated from Schnell's viscosity equation. Specifically, first, the intrinsic viscosity [η] (unit: dL / g) of the resin was measured using methylene chloride as a solvent. The temperature was set at 25°C. The specific viscosity [η] at each solution concentration [C] (g / dL) was measured using an Ubbelohde viscometer. sp The intrinsic viscosity was calculated from the obtained specific viscosity value and concentration using the following formula.

number

[0179] Next, the viscosity average molecular weight [Mv] is calculated using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 was calculated from

[0180] (3) Weight average molecular weight The weight average molecular weight (Mw) was measured by gel permeation chromatography. Specifically, the gel permeation chromatography apparatus used was an LC-20AD system (Shimadzu Corporation), and the column was an LF-804 (Shodex). The column temperature was set to 40°C. The RI detector used was an RID-10A (Shimadzu Corporation). Chloroform was used as the eluent, and a calibration curve was created using standard polystyrene (Tosoh Corporation).

[0181] (4) Acrylic equivalent The acrylic equivalent was calculated using the formula "molecular weight / number of (meth)acryloyl groups".

[0182] (5) Average particle size The average particle diameter was determined by randomly selecting 30 inorganic particles observed under a transmission electron microscope (TEM), determining the maximum distance between two points on the outer surface of each particle as the particle diameter, and then calculating the average value of these.

[0183] (6) Melt viscosity The melt viscosity was measured using a capillograph. Specifically, the (meth)acrylic resin was pre-dried at 90°C for 4 hours, and then the melt viscosity was measured using a capillograph. The measurement was performed at a temperature of 230°C, a capillary length of 10 mm, a capillary diameter of 1 mm, a furnace diameter of 9.55 mm, and a shear rate of 122 sec. -1 The experiment was carried out under the following conditions. The capillograph used was a Capillograph 1D PMD-C (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

[0184] 2. Manufacturing of laminates [Example 1] A laminate was produced in which a substrate layer (a), an acrylic layer (c), and a curable resin layer (b) were laminated in this order. (1) Preparation of a laminate (precursor) of a substrate layer (a) and an acrylic layer (c) Polycarbonate resin T-1380 (bisphenol A (BPA)-type polycarbonate resin using parahydroxybenzoic acid hexadecyl ester (p-HBAHE) as an end-capping agent, viscosity average molecular weight: 25,500, Tig: 126°C, Tmg: 131°C, manufactured by Mitsubishi Gas Chemical Company, Inc.) was melt-kneaded at a cylinder temperature of 280°C using a vented twin-screw extruder TEX30α (manufactured by The Japan Steel Works, Ltd.) with a screw diameter of 32 mm and a screw L / D = 31.5, and pellets were obtained by strand cutting.

[0185] A laminate (precursor) of a substrate layer (a) and an acrylic layer (c) was prepared using the pellets and PMMA (polymethyl methacrylate) resin Delpet 80NB (melt viscosity: 3350 Pa·s, weight average molecular weight: 175000, manufactured by Asahi Kasei Corporation). Specifically, a multilayer extrusion device was used, which had a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block. PMMA resin (Delpet 80NB) was continuously introduced into the single-screw extruder with a shaft diameter of 32 mm at a cylinder temperature of 280°C, and the pellets were continuously introduced into the single-screw extruder with a shaft diameter of 65 mm at a cylinder temperature of 280°C and extruded. The discharge rates of the PMMA resin and the pellets were controlled so that the thickness of the acrylic layer (c) was 60 μm and the thickness of the pellets was 140 μm, respectively. The feed block connected to all extruders was equipped with two-type, two-layer distribution pins, and the laminar flow was laminated and extruded into a sheet using a T-die.Then, three mirror-finished rolls, each heated to 100°C, 100°C, and 115°C from the upstream side, were used to transfer the mirror surface while cooling the material, producing a laminate (precursor) consisting of a substrate layer (a) containing T-1380, a polycarbonate resin, and an acrylic layer (c) containing Delpet 80NB, a PMMA resin.

[0186] (2) Manufacturing of laminates Of the laminate (precursor) of the base material layer (a) and the acrylic layer (c), the curable resin layer (b) was formed on the acrylic layer (c) to produce a laminate.

[0187] A curable resin composition was obtained by mixing 70 parts by weight of an acryloyl group-containing polymer, SMP-360A (acrylic equivalent: 360 g / mol, manufactured by Kyoeisha Chemical Co., Ltd.), 30 parts by weight of nanosilica, PGM-AC4130Y (average particle size 45 nm, surface acrylic treatment, PGM dispersion, manufactured by Nissan Chemical Co., Ltd.), 3 parts by weight of a photopolymerization initiator, Omnirad 184 (manufactured by IGM Resins BV), 1 part by weight of a fluorine-based leveling agent, RS-90 (manufactured by DIC Corporation), and cyclohexanone as a diluent. Cyclohexanone was added in an amount such that the solids concentration of the curable resin composition was 25% by weight.

[0188] Of the laminate of the base material layer (a) and the acrylic layer (c), the curable resin composition was applied to the acrylic layer (c) using a bar coater so that the film thickness after drying would be 4 μm, and the resulting coating film was dried for 3 minutes at 130° C. to form the curable resin layer (b). In this way, a laminate in which the base material layer (a), the acrylic layer (c), and the curable resin layer (b) were laminated in this order was produced.

[0189] [Example 2] A laminate was produced in the same manner as in Example 1, except that the acrylic layer (c) was made of a PMMA resin, ACRYPET VH4-001 (melt viscosity: 2650 Pa·s, weight average molecular weight: 160,000, manufactured by Mitsubishi Chemical Corporation), instead of Delpet 80NB.

[0190] [Comparative Example 1] A laminate was produced in the same manner as in Example 1, except that Delpet 80HD, a PMMA resin (methyl methacrylate (MMA):methyl acrylate = 99% by mass: 1% by mass, melt viscosity: 2040 Pa s, weight average molecular weight: 114000, manufactured by Asahi Kasei Corporation), was used in place of Delpet 80NB for the acrylic layer (c).

[0191] Comparative Example 2 A laminate was produced in the same manner as in Example 1, except that the acrylic layer (c) was made of a PMMA resin, ACRYPET VH-001 (melt viscosity: 2060 Pa·s, weight average molecular weight: 114000, manufactured by Mitsubishi Chemical Corporation), instead of Delpet 80NB.

[0192] Comparative Example 3 A laminate of an acrylic layer (c) and a curable resin layer (b) was produced. (1) Preparation of a single layer film consisting of an acrylic layer (c) Using Delpet 80NB, a single layer film (thickness: 200 μm) consisting of an acrylic layer (c) was prepared. Specifically, a T-die melt extruder consisting of a vented twin-screw extruder TEX30α (manufactured by The Japan Steel Works, Ltd.) with a barrel diameter of 32 mm and a screw length / distance ratio of 31.5 was used to continuously extrude the PMMA resin Delpet 80NB at a cylinder temperature of 280°C. The PMMA resin extrusion rate was controlled so that the thickness of the acrylic layer (c) was 200 μm. The PMMA resin was extruded into a sheet through a T-die connected to the extruder, and cooled while transferring a mirror finish using three mirror-finishing rolls heated to 90°C, 90°C, and 100°C from the upstream side. This resulted in a monolayer film consisting of an acrylic layer (c) containing Delpet 80NB.

[0193] (2) Manufacturing of laminates A curable resin layer (b) was formed on the acrylic layer (c) in the same manner as in Example 1 so that the film thickness after drying would be 4 μm, thereby producing a laminate in which the acrylic layer (c) and the curable resin layer (b) were laminated.

[0194] Comparative Example 4 A laminate of a substrate layer (a) and a curable resin layer (b) was produced.

[0195] (1) Preparation of a monolayer film consisting of a substrate layer (a) Using pellets of T-1380, a polycarbonate resin obtained in the same manner as in Example 1, a single-layer film (thickness: 200 μm) made of a substrate layer (a) was produced. Specifically, the pellets were continuously introduced and extruded using a T-die melt extruder consisting of a vented twin-screw extruder TEX30α (manufactured by The Japan Steel Works, Ltd.) with a barrel diameter of 32 mm and a screw L / D of 31.5, at a cylinder temperature of 280°C. The pellets were extruded into a sheet form through a T-die connected to the extruder, and cooled while transferring a mirror surface using three mirror-finished rolls set at temperatures of 120°C, 120°C, and 120°C from the upstream side, to obtain a monolayer film consisting of a base layer (a) containing T-1380, a polycarbonate resin.

[0196] (2) Manufacture of laminate When a curable resin layer (b) was formed on the base material layer (a) in the same manner as in Example 1, the base material layer (a) was dissolved in the paint solvent and the surface appearance deteriorated.

[0197]

Table 1

[0198] 3. Evaluation Various evaluations were carried out on the laminates produced in Examples 1 to 2 and Comparative Examples 1 to 3 in which the curable resin composition could be laminated without problems.

[0199] <TOM formability> TOM forming was performed using the laminate, and the cracks were evaluated.

[0200] The laminate was cut into a size of 330 mm × 330 mm, and an adhesive layer was bonded to the base material layer (a) side. A spare lens for safety goggles (manufactured by TRUSCO: product number TSG-005SP) was used as the adherend. The laminate with the adhesive layer and the adherend were set in the upper and lower boxes in an NGF-0709-S (manufactured by Busch Vacuum Co., Ltd.) which is a TOM forming machine. After reducing the pressure in the upper and lower boxes to 0.1 kPa, the laminate with the adhesive layer was heated to 140°C. Then, a TOM formed body was obtained by introducing compressed air of 0.3 MPa only into the upper box.

[0201] The TOM formability was evaluated as follows. The evaluation was carried out by 5 experts and judged by a majority vote. The obtained results are shown in Table 2 below. 〇: No cracks in the laminate ×: Large cracks are visible in the laminate

[0202] <Alcohol wiping test> An alcohol wiping test was carried out on the cured product obtained by curing the laminate.

[0203] The cured product was manufactured as follows. That is, the curable resin layer (b) of the laminate was irradiated with ultraviolet light using a conveyor-type UV irradiator ECS-401GX (manufactured by Eye Graphics Co., Ltd.). At this time, the ultraviolet light irradiation was 700 mJ / cm 2 (UV illuminometer manufactured by Oak Corporation, measurement wavelength 360 nm) As a result, a cured product was produced in which the curable resin layer (b) of the laminate was cured.

[0204] The cured product was cut into a 50 mm x 100 mm piece and wrapped around a mandrel rod (radius: 32 mm) so that the cured film of the curable resin layer (b) formed a convex surface. Gauze soaked in isopropyl alcohol (IPA) was pressed against the surface of the laminate (the cured film of the curable resin layer (b)) for 10 seconds, and then the gauze was removed. This alcohol wiping test was performed five times.

[0205] The alcohol wipe test was evaluated as follows. The evaluation was carried out by five experts and judged by majority vote. The results are shown in Table 2 below. ⊚: No cracks were observed in any of the five alcohol wiping tests. ○: Cracks occurred only once out of five alcohol wiping tests. ×: Cracks occurred in two or more of the five alcohol wiping tests.

[0206] <Pencil hardness> The laminate was cured and the resulting cured product was evaluated for pencil strength.

[0207] The cured product produced in the alcohol wiping test was subjected to pencil hardness measurement of the cured film surface of the curable resin layer (b) according to the conditions of JIS K 5600-5-4:1999, and evaluated as the hardest pencil grit that did not cause scratches. The results are shown in Table 2 below.

[0208] The pencil hardness increases in the following order: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, and 9H.

[0209] [Table 2]

[0210] The results in Table 2 show that the laminates of Examples 1 and 2 did not develop chemical cracks in the alcohol wiping test.

Claims

1. a substrate layer (a) containing a polycarbonate resin; a curable resin layer (b) containing a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol; an acrylic layer (c) containing a (meth)acrylic resin and disposed between the substrate layer (a) and the curable resin layer (b); A laminate comprising: Shear rate of the (meth)acrylic resin: 122 sec －１ The melt viscosity at 230°C measured by is 2200 to 10000 Pa s, The acrylic layer (c) has a thickness of 10 to 120 μm.

2. 2. The laminate according to claim 1, wherein the melt viscosity of the (meth)acrylic resin is 3000 to 6000 Pa·s.

3. 2. The laminate according to claim 1, wherein the (meth)acrylic resin has a weight average molecular weight of 140,000 to 300,000.

4. The laminate according to claim 1, wherein the intermediate glass transition temperature (Tmg) of the substrate layer (a) is 100 to 140°C.

5. The polycarbonate resin is a copolymer of bisphenol A, a carbonate binder, and a compound represented by the following formula (1): 【Chemical 1】 [In the above formula (1), R １ is an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, R ２ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

2. The laminate according to claim 1, which is a bisphenol A polycarbonate obtained by reacting a monohydric phenol end terminator represented by the formula:

6. 6. The laminate according to claim 5, wherein the monohydric phenol end-terminator represented by formula (1) comprises at least one selected from the group consisting of 2-hexyldecyl parahydroxybenzoate, hexadecyl parahydroxybenzoate, dodecyl parahydroxybenzoate, and 2-ethylhexyl parahydroxybenzoate.

7. The (meth)acryloyl polymer is represented by the following formula (2): 【Chemistry 2】 [In the above formula (2), m is a single bond or an alkylene group having 1 to 4 carbon atoms; n is hydrogen or an alkyl group having 1 to 4 carbon atoms; p is a single bond or an alkylene group having 1 to 2 carbon atoms; q is hydrogen or an alkyl group having 1 to 12 carbon atoms which may be substituted with at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, and a (meth)acryloyl group. The laminate according to claim 1 , comprising a repeating unit represented by the formula:

8. The (meth)acryloyl polymer is represented by the following formulas (2-a) to (2-c): 【Chemistry 3】 The laminate according to claim 7, comprising at least one repeating unit represented by:

9. The laminate according to claim 1 , which is used in TOM molding.

10. A cured product obtained by curing the laminate according to any one of claims 1 to 9, comprising: a substrate layer (a); a cured film of the curable resin layer (b); and an acrylic layer (c).

11. The cured product according to claim 10 , wherein the pencil strength of the cured film surface of the curable resin layer (b) is H or more.

12. a substrate layer (a) containing a polycarbonate resin; a curable resin layer (b) containing a (meth)acryloyl polymer having an acrylic equivalent of 200 to 600 g / mol; an acrylic layer (c) containing a (meth)acrylic resin and disposed between the substrate layer (a) and the curable resin layer (b); A cured product obtained by curing a laminate comprising: A hardened product that shows no chemical cracks when wiped with alcohol.

Images