Laminate and cured product obtained by curing 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

Laminate and cured product obtained by curing the same

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

[0002] Thermoforming films (also called functional films or decorative films) are suitably used to impart desired properties (for example, scratch resistance, chemical resistance, designability, 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 glass transition temperature (Tg) of Layer A is 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).

[0007] Japanese Patent Application Laid-Open No. 2021-146687

[0008] However, it has been found that after molding the thermoforming sheet described in Patent Document 1, if adhesives or the like 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.

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

[0010] [1] A laminate comprising: 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 disposed between the substrate layer (a) and the curable resin layer (b), wherein the shear rate of the (meth)acrylic resin is 122 sec －１ a melt viscosity at 230°C measured by FT-IR spectroscopy is 2200 to 10000 Pa·s, and the thickness of the acrylic layer (c) is 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 weight average molecular weight of the (meth)acrylic resin is 140000 to 300000. [4] The laminate according to any one of the above [1] to [3], wherein the intermediate glass transition temperature (Tmg) of the base layer (a) is 100 to 140°C. [5] The polycarbonate resin is a polycarbonate resin containing bisphenol A, a carbonate binder, and a carboxylic acid ester represented by the following formula (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 ２and (6) the monohydric phenol end-terminator represented by formula (1) comprises at least one member selected from the group consisting of 2-hexyldecyl parahydroxybenzoate, hexadecyl parahydroxybenzoate, dodecyl parahydroxybenzoate, and 2-ethylhexyl parahydroxybenzoate. [7] The laminate according to any one of the above [1] to [4], wherein the (meth)acryloyl polymer is a bisphenol A polycarbonate obtained by reacting a monohydric phenol end-terminator represented by formula (1) with a monohydric phenol end-terminator represented by formula (2): [8] The laminate according to any one of the above items [1] to [6], comprising a repeating unit represented by the following formula (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, and 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]. [9] The laminate according to any one of [1] to [8] above, which is used in TOM molding.

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

[11] The cured product according to

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

[12] A laminate comprising: 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 disposed between the substrate layer (a) and the curable resin layer (b), which laminate does not undergo chemical cracking in an alcohol wipe test.

[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.

[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), the acrylic layer (c), and the curable resin layer (b) in this order. At this time, the shear rate of the (meth)acrylic resin is 122 sec －１ The melt viscosity at 230° C. measured by a method of the present invention 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 the case of conventional laminates, in order to achieve both hardness and moldability, the laminate is left uncured before molding and then cured after molding to form a hard coat layer. When the molded laminate or its cured product is wiped and cleaned with a solvent such as alcohol, cracks may occur. The reasons for this include, for example, that the laminate or cured product after molding is curved, bent, etc., making it prone to cracks due to stress, and that the laminate or cured product has a laminated structure, making it prone to chemical cracks due to solvent penetration from its cross section. In this case, for example, in the laminate, the cracks are likely to occur in the acrylic layer (c) among 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 10,000 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 necessarily 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 curves and bends 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. Note that this effect can also be exerted 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 it is possible to achieve both hardness and moldability. 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. Vacuum forming is a forming method in which forming is performed under vacuum conditions, and examples thereof include in-mold forming and three-dimensional decoration (TOM) forming. However, because vacuum forming is typically applied to three-dimensional shapes with unevenness, the laminate tends to have a large degree of curvature and bending after forming. For this reason, the laminate after forming tends to be more susceptible to cracking due to wiping and cleaning with a solvent. The laminate according to the present invention can prevent cracking due to wiping and cleaning with a solvent, even when vacuum forming is performed. Furthermore, as described above, when a laminate including a curable resin layer (b) is applied to a molded product (when molding), it is preferable not to cure 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 contained in the curable resin layer (b), which can cause unintended curing of the curable resin layer (b) during vacuum forming. As a result, cracks can occur in the curable resin layer (b) after molding from this perspective as well. 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. The three-dimensional decoration (TOM) molding includes (1) a vacuum process in which a lower chamber with an opening at the top and in which a molded product having a textured surface is placed, an upper chamber with an opening 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 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 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. That is, three-dimensional decorative (TOM) molding involves heating a laminate to soften it under vacuum conditions, pushing a molded product up from below the laminate to bring them into contact (the laminate is tightly laminated by the molded product due to its own weight), and then creating a pressure difference in the upper chamber under atmospheric pressure to apply pressure from the upper chamber to the lower chamber to complete the lamination. This allows for the production of a three-dimensionally decorated molded product including a molded product with a textured surface and a laminate placed on the textured surface. Note that three-dimensional decorative (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. Furthermore, three-dimensional decorative (TOM) molding may further include a trimming step of removing a portion of the laminate placed on the textured surface and a curing step of curing the laminate after the lower chamber de-vacuuming step. When using conventional laminates, attempting to perform three-dimensional decorative (TOM) molding often results in the laminate being unable to be laminated to a molded product with a textured surface with high conformability, and even if lamination is possible, cracks may occur in the laminate. In particular, when a laminate after molding is subjected to wiping cleaning using a solvent, cracks tend to occur. However, the laminate according to the present invention can be laminated with high conformability to a molded article having an uneven surface. Furthermore, even when the resulting laminate is subjected to wiping cleaning using a solvent, cracks are unlikely to occur.

[0022] <Substrate Layer (a)> The substrate layer (a) contains a polycarbonate resin. The substrate layer (a) 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., a -[O-R-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-bis(4-hydroxy-3-methylphenyl)ethane, and bisphenol A. t-butylphenyl)propane, 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: B PPH), 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, Bisphenols with two phenol groups such as 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), and bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP; BPBP) have "-C(R)" groups. ２Bisphenol compounds in which two phenol groups are linked by "-S-" (wherein each R is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a carbocyclic group having 5 to 20 carbon atoms or a heterocyclic group having 5 to 12 elements formed by the bonding of two R); bisphenol compounds in which two phenol groups are linked by "-S-" such as bis(4-hydroxyphenyl) sulfide; Bisphenol compounds in which two phenolic groups are linked by "-O-", such as 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 "-SO", such as bis(4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(2-hydroxyphenyl) sulfone, and bis(4-hydroxy-3-methylphenyl) sulfone. ２ bisphenol compounds in which two phenol 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 phenol groups are linked by a phenylene, such as 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol and 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol; bisphenol compounds in which two phenol groups are linked by an adamantyl group, such as 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane; and bisphenol compounds in which two phenol groups are linked by a polyalkylsiloxane, such as α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane and α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymerized siloxane. These bisphenols may be used alone or in combination of two or more.

[0026] Of these, bisphenols are those in which the two phenolic groups are "-C(R) ２ It is preferable to include a bisphenol compound linked with "-", and it is preferable to include 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] (Compound for Derivation of Other Structural Units) The polycarbonate may be formed by further reacting a compound for derivation of other structural units. By using the compound for derivation of other structural units, the physical properties of the polycarbonate (e.g., the mid-glass transition temperature (Tmg), the 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, and examples thereof include carbonyl compounds such as phosgene, triphosgene, carbon monoxide, carbon dioxide, and carbonate 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 Capper) The end capper 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]

[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 the "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):

[0041] In the above formula (1-a), R１ 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 １ When the upper limit of the carbon number of R is appropriate, the solubility of the monohydric phenol end-terminator 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 number of carbon atoms is appropriate, the glass transition point of the polycarbonate resin will not be too high, and the polycarbonate 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) １is 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) ２ are 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 parahydroxybenzoic acid 2-hexyldecyl ester, parahydroxybenzoic acid hexadecyl ester, parahydroxybenzoic acid dodecyl ester, and parahydroxybenzoic acid 2-ethylhexyl ester, more preferably includes at least one of parahydroxybenzoic acid 2-hexyldecyl ester and parahydroxybenzoic acid hexadecyl ester, and even more preferably includes parahydroxybenzoic acid 2-hexyldecyl ester.

[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):

[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 unsaturated groups, etc. The carbonate binder, monohydric phenol end-stopper represented by formula (1), bisphenols other than bisphenol A, compounds that derive other structural units, monohydric phenol compounds that do not have unsaturated groups, etc. 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, when the intersection of line A and tangent B, which is obtained by extending the low-temperature side baseline of the DSC curve toward the high-temperature side, line B, which is tangent to the inflection point, and line C, which is obtained by extending the high-temperature side baseline toward the low-temperature side, are taken as the starting glass transition temperature (Tig), and the tangent between line B and line C is taken as 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). Generally, glass transition temperature 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, "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 substrate 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 polycaprolactone polyethylene terephthalate-modified resins include glycol-modified polyethylene terephthalate (PETG) and glycol-modified polycyclohexylene dimethylene terephthalate (PCTG). PETG is a PET (a PET consisting of terephthalic acid units, which are dicarboxylic acid units, and ethylene glycol units, which are glycol units) in which some of the ethylene glycol units have been replaced with 1,4-cyclohexanedimethanol units. The content of 1,4-cyclohexanedimethanol units is preferably less than 50 mol%, more preferably 30 to 40 mol%, based on the total glycol units. PCTG is a PCT (a PET consisting of terephthalic acid units, which are dicarboxylic acid units, and 1,4-cyclohexanedimethanol units, which are glycol units) in which some of the glycol units have been replaced with glycol units. The content of 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] Examples of the polyether include polyethers 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 the polyether 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 a polyester or an aromatic phosphonate compound, more preferably contains a 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, relative to 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 include antioxidants, transesterification inhibitors, release agents, heat stabilizers, flame retardants, flame retardant assistants, 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, relative to 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 the polycarbonate resin.

[0073] [Configuration of Substrate 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 attempting to mold the laminate of the present invention, it exhibits 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 exhibits high hardness and may exhibit improved scratch resistance, chemical resistance, and the like. In this specification, "(meth)acryloyl" refers to methacryloyl and / or acryloyl. Similarly, "(meth)acrylic" and "(meth)acrylate" refer to 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]

[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 repeating unit represented by the following formulas (2-a) to (2-c):

[0083]

[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 to 5.5:1.5 to 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 to 5.5:2.5 to 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, still 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] [Polyfunctional Acrylate Compound] 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 difunctional or more, preferably trifunctional or more, more preferably trifunctional to octafunctional, and even more preferably trifunctional to hexafunctional.

[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 here is not particularly limited, but includes silane compounds, alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, and the like. 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 inorganic particle surfaces.

[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% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by 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. The leveling agent 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] Examples of the fluorine-based leveling agent include compounds having a perfluoropolyether bond. Commercially available fluorine-based leveling agents can be used, such as Megafac RS-56, RS-75, RS-76-E, RS-76-NS, RS-78, and RS-90 (manufactured by DIC Corporation), KY-1203, X-71-1203E, KY-1207, and KY-1211 (manufactured by Shin-Etsu Chemical Co., Ltd.), Optool UD120 (manufactured by Daikin Industries, Ltd.), and Ftergent 710FL, 220P, 208G, 601AD, 602A, 650A, 228P, and 240GFTX-218 (manufactured by Neos Corporation).

[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 KK).

[0105] Among 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. The photopolymerization initiator has a 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-hydroxycyclohexylphenylketone (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 (Esacure ONE), 1-hydroxycyclohexylphenylketone (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] Examples of hindered amine light stabilizers include bis(1-undecanoxy-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-pentamethyi-4-piperidylbutane-1,2,3,4-tetracarboxylate (ADK STAB LA-58). methyl-4-piperidyl methacrylate (ADEKA STAB 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.

[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. The polymerization inhibitor has functions such as 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 additives.

[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, so it has excellent moldability, particularly three-dimensional moldability. However, for example, within a range that does not impair the effects 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. The acrylic layer (c) may further contain additives and the like.

[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 with 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] Shear rate of (meth)acrylic resin: 122 sec －１ The melt viscosity at 230°C measured at 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" is used. －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 being able to prevent cracks that occur during wiping cleaning with a solvent and being less likely to cause poor appearance can be obtained.

[0133] The shear rate of the (meth)acrylic resin was 122 sec －１The melt viscosity and weight average molecular weight at 230°C measured by the method described above 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, based on the total mass of the acrylic layer (c).

[0135] [Additives] The acrylic layer (c) may further contain additives. Examples of additives include, but are not limited to, ultraviolet absorbers, antioxidants, coloring inhibitors, and inorganic particles. 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, even more preferably 30 to 90 μm, and particularly preferably 40 to 80 μm.

[0136] 2. Method for Producing Laminated Body According to one aspect of the present invention, there is provided a method for producing a laminated body.

[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, and the third resin composition contains a (meth)acrylic resin.

[0139] Each step will be described below.

[0140] <Step (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. In addition, the first resin composition may further contain a plasticizer, an additive, and the like.

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

[0143] The composition of the first resin composition is appropriately adjusted 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 appropriately adjusted 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] <Step (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. In addition, the second resin composition may further contain a polyfunctional acrylate compound, inorganic particles, a leveling agent, a photopolymerization initiator, a light stabilizer, a polymerization inhibitor, an additive, a dilution solvent, etc.

[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 appropriately adjusted 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 of applying the second resin composition 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, by drying, the dilution solvent that may be contained in the second resin composition is evaporated, and the curable resin layer (b) can be obtained.

[0158] The temperature for drying the coating is preferably 50 to 200°C, 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 configurations of the substrate layer (a) and the acrylic layer (c) are usually the same as those in the laminate.

[0161] The cured film of the curable resin layer (b) has high hardness. As a result, the cured product may have high scratch resistance, chemical resistance, and the like. In one embodiment, the pencil hardness of the surface of the cured film 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 surface of the cured film 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), the configuration of the acrylic layer (c), etc.). In this specification, "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. Method for Producing a 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 step] 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 Article) The molded article is not particularly limited, but for example, the above-mentioned molded articles can be used.

[0169] (Laminate) As the laminate, the above-mentioned materials are used.

[0170] (Molding) The molding method 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 includes: (1) a vacuum process in which a lower chamber with an open top in which a molded product having a textured surface is placed, a lower chamber with an open bottom 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 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. Furthermore, after the upper chamber de-vacuum process, an upper chamber pressurization process in which compressed air is introduced into the upper chamber may be further included. Furthermore, after the lower chamber de-vacuum process, a trimming process in which a portion of the laminate placed on the textured surface is removed may be further included.

[0171] [Curing Step] 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:

[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 various resins and resin compositions was measured by performing two cycles of temperature increase and decrease under the following differential scanning calorimetry (DSC) conditions, 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 starting 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 ending glass transition temperature (Teg). The midpoint between the starting glass transition temperature (Tig) and the ending glass transition temperature (Teg) was defined as the intermediate glass transition temperature (Tmg).

[0177] Measurement starting temperature: 30°C, heating rate: 10°C / min, final temperature: 250°C, cooling rate: 20°C / min. Measurement device: differential scanning calorimeter "DSC7020" (manufactured by Hitachi High-Tech Science Corporation).

[0178] (2) Viscosity-average molecular weight The viscosity-average molecular weight was calculated using Schnell's viscosity formula. 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:

[0179] Next, the viscosity average molecular weight [Mv] was calculated using Schnell's 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, an LC-20AD system (manufactured by Shimadzu Corporation) was used as the gel permeation chromatography apparatus, and an LF-804 (manufactured by Shodex) was connected to the column. The column temperature was set to 40°C. An RID-10A (manufactured by Shimadzu Corporation) was used as the RI detector. Chloroform was used as the eluent, and a calibration curve was created using standard polystyrene (manufactured by 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 Diameter The average particle diameter was determined by randomly selecting 30 inorganic particles observed with a transmission electron microscope (TEM), determining the maximum distance between two points on the outer surface of each particle as the particle diameter, and calculating the average value of these distances.

[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 capillograph used was a Capillograph 1D PMD-C (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

[0184] 2. Production of Laminate [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) Production of Laminate (Precursor) of Substrate Layer (a) and Acrylic Layer (c) T-1380 polycarbonate resin (bisphenol A (BPA) 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] 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), a laminate (precursor) of a base material layer (a) and an acrylic layer (c) was produced. Specifically, a multi-layer extrusion device having 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 was used, and 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. At this time, the PMMA resin was controlled so that the thickness of the acrylic layer (c) was 60 μm, and the pellets were controlled so that the thickness of the base layer (a) was 140 μm. The feed block connected to all extruders was equipped with a two-type, two-layer distribution pin, and the laminar flow was laminated and extruded into a sheet with a T-die, and cooled while transferring the mirror surface with three mirror-finished rolls set at temperatures of 100 ° C., 100 ° C., and 115 ° C. from the upstream side. A laminate (precursor) of a base layer (a) containing T-1380, which is a polycarbonate resin, and an acrylic layer (c) containing Delpet 80NB, which is a PMMA resin, was produced.

[0186] (2) Production of Laminate A laminate was produced by forming the curable resin layer (b) on the acrylic layer (c) of a laminate (precursor) of the base material layer (a) and the acrylic layer (c).

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

[0188] Of the laminate of the base material layer (a) and the acrylic layer (c), the curable resin composition was applied onto 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 a PMMA resin, ACRYPET VH4-001 (melt viscosity: 2650 Pa s, weight average molecular weight: 160,000, manufactured by Mitsubishi Chemical Corporation), was used in place of Delpet 80NB for the acrylic layer (c).

[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 a PMMA resin, ACRYPET VH-001 (melt viscosity: 2060 Pa s, weight average molecular weight: 114000, manufactured by Mitsubishi Chemical Corporation), was used in place of Delpet 80NB for the acrylic layer (c).

[0192] [Comparative Example 3] A laminate of an acrylic layer (c) and a curable resin layer (b) was produced. (1) Preparation of a monolayer film consisting of an acrylic layer (c) Using Delpet 80NB, a monolayer film (thickness: 200 μm) consisting of an acrylic layer (c) was produced. 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 L / D = 31.5 was used, and PMMA resin Delpet 80NB was continuously introduced and extruded at a cylinder temperature of 280 ° C. In this case, the amount of PMMA resin discharged was controlled so that the thickness of the acrylic layer (c) was 200 μm. The resin was extruded into a sheet using a T-die connected to an extruder, and cooled while transferring a mirror surface using three mirror-finishing rolls set at temperatures of 90°C, 90°C, and 100°C from the upstream side, to obtain a single-layer film consisting of an acrylic layer (c) containing Delpet 80NB.

[0193] (2) Production of Laminate 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 comprising a substrate layer (a) Using pellets of T-1380, a polycarbonate resin obtained in the same manner as in Example 1, a monolayer film (thickness: 200 μm) comprising a substrate layer (a) was prepared. Specifically, 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 = 31.5, the pellets were continuously introduced and extruded under conditions of a cylinder temperature of 280 ° C. At this time, the pellets were extruded in a sheet form using a T-die connected to the extruder, and the thickness of the substrate layer (a) was controlled to be 140 μm. A monolayer film comprising a substrate layer (a) containing T-1380, a polycarbonate resin, was obtained by extruding the pellets into a sheet using a T-die connected to the extruder, and cooling the sheet 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.

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

[0197]

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

[0199] <TOM Formability> Tom forming was carried out using the laminate, and cracks were evaluated.

[0200] The laminate was cut to a size of 330 mm x 330 mm, and an adhesive layer was attached to the base layer (a) side. A spare lens for safety goggles (manufactured by TRUSCO Corporation: part number TSG-005SP) was used as the adherend. The laminate with the adhesive layer and the adherend were placed in upper and lower boxes within a TOM molding machine NGF-0709-S (manufactured by Fuse Vacuum Co., Ltd.). The pressure inside the upper and lower boxes was reduced to 0.1 kPa, and the laminate with the adhesive layer was heated to 140°C. Compressed air at 0.3 MPa was then introduced only into the upper box to obtain a TOM molded product.

[0201] The TOM formability 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 the laminate. ×: Large cracks were observed 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 produced as follows: 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 at 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 occurred in any of the five alcohol wipe tests. ◯: Cracks occurred only once out of the five alcohol wipe tests. ×: Cracks occurred in two or more of the five alcohol wipe tests.

[0206] <Pencil Hardness> The pencil strength of the cured product obtained by curing the laminate was evaluated.

[0207] The cured product produced in the alcohol wiping test was subjected to measurement of pencil hardness 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 obtained 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]

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

Claims

1. A laminate comprising: 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 disposed between the substrate layer (a) and the curable resin layer (b), wherein the (meth)acrylic resin is heated at a shear rate of 122 sec －１ the melt viscosity at 230° C. measured by a method according to claim 1 being 2200 to 10000 Pa·s, and the thickness of the acrylic layer (c) being 10 to 120 μm.

2. The laminate according to claim 1, wherein the melt viscosity of the (meth)acrylic resin is 3,000 to 6,000 Pa·s.

3. The laminate according to claim 1, wherein the weight average molecular weight of the (meth)acrylic resin is 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 carboxylic acid represented by the following formula (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 each independently represents 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 which may be substituted with an aryl group having 6 to 12 carbon atoms.

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):

2. The laminate according to claim 1, comprising a repeating unit represented by the following formula (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, and 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].

8. The (meth)acryloyl polymer is represented by the following formulas (2-a) to (2-c): 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 base layer (a), a cured film of a 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 laminate comprising: 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), wherein the laminate shows no chemical cracks when subjected to an alcohol wipe test.

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