Laminate and cured product formed by cureing laminate

Abstract

The present invention relates to a laminate which is less susceptible to cracking even when wiped and cleaned using a solvent such as an alcohol. A laminate comprising a substrate layer (a) containing a polycarbonate resin, a curable resin layer (b) containing a (meth) acryloyl polymer having an acryloyl equivalent of 200-600 g / mol, and an acrylic layer (c) containing a (meth) acrylic resin disposed between the substrate layer (a) and the curable resin layer (b), the (meth) acrylic resin has a melt viscosity of 2200-10000 Pa * s at 230 DEG C as measured at a shear rate of 122 sec <-1 >, and the thickness of the acrylic layer (c) is 10-120 [mu] m.

Description

TECHNICAL FIELD

[0001] The present application relates to a laminate and a cured product formed by curing the laminate. BACKGROUND

[0002] A thermoforming film (also referred to as a functional film, a decorative film) can impart a moderate desired property (e.g., scratch resistance, chemical resistance, design sense, etc.) to the surface of a molded product.

[0003] In the case where a thermoforming film is applied to a molded product, various molding methods are employed. As the molding method, for example, vacuum molding, pressure air molding, film insert molding, in-mold molding, and three-dimensional decoration (TOM) molding are suitably employed.

[0004] In the case where, for example, a scratch-resistant property is imparted to a molded product, the thermoforming film needs to have high hardness. To this end, the thermoforming film is made in the form of a laminate provided with a hard coat layer formed by curing a resin. However, the higher the hardness of the thermoforming film, the lower the moldability, and the less the conformability to the molded product. That is, there is a trade-off relationship between the hardness and the moldability of the thermoforming film.

[0005] Methods for making the hardness and the moldability of a thermoforming film both excellent have been studied. For example, Patent Literature 1 describes an invention relating to a thermoforming sheet formed by sequentially laminating at least an A layer containing a polycarbonate resin, a B layer containing an acrylic resin, and a C layer formed of an uncured product of an acrylate-based active energy beam-curable resin composition. In this case, it is characterized in that the glass transition temperature (Tg) of the A layer is 100°C or higher and 145°C or lower.

[0006] Patent Literature 1 also describes the content that, according to the invention, by making the C layer, which corresponds to a hard coat layer, be in an uncured state during application to a molded product, high moldability can be achieved, and by curing the C layer by performing post-exposure using an active energy beam after the thermoforming sheet is applied to the molded product (after molding), a high-hardness hard coat layer can be obtained.

[0007] Prior Art Documents Patent Literature Patent Literature 1: Japanese Patent Application Publication No. 2021-146687 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION However, the inventors have recognized that, after the thermoforming sheet described in Patent Literature 1 is formed, if a solvent such as an alcohol is used to wipe and clean a bonding agent or the like that can adhere to the surface of the thermoforming sheet, the thermoforming sheet can develop cracks.

[0009] Accordingly, the present application provides a laminate which is less likely to be cracked even when cleaned by wiping with a solvent such as alcohol.

[0010] Technical solution for solving the technical problem The present application is, for example, the application described below.

[0011] [1] A laminate comprising: a base layer (a) containing a polycarbonate resin, a curable resin layer (b) containing a (meth)acryl polymer having an acryl group equivalent of 200 to 600 g / mol, and an acrylic layer (c) containing a (meth)acryl resin disposed between the base layer (a) and the curable resin layer (b), a melt viscosity of the (meth)acryl resin at 230°C measured at a shear rate of 122 sec ﹣1 -1 is 2200 to 10000 Pa·s, a thickness of the acrylic layer (c) is 10 to 120 μm.

[0012] [2] The laminate according to the above [1], wherein the melt viscosity of the (meth)acryl resin is 3000 to 6000 Pa·s.

[0013] [3] The laminate according to the above [1] or [2], wherein the weight average molecular weight of the (meth)acryl resin is 140000 to 300000.

[0014] [4] The laminate according to any one of the above [1] to [3], wherein a glass transition midpoint temperature (Tmg) of the base layer (a) is 100 to 140°C.

[0015] [5] The laminate according to any one of the above [1] to [4], wherein the polycarbonate resin is a bisphenol A type polycarbonate formed by reacting bisphenol A, a carbonate bonding agent, and a monohydric phenol chain terminator 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 is hydrogen, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which can be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms which can 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 can be substituted with an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0016] [6] The stack as described in [5] above, wherein the monophenol chain terminator of formula (1) above comprises at least one selected from 2-hexyldecyl p-hydroxybenzoate, hexadecyl p-hydroxybenzoate, dodecyl p-hydroxybenzoate and 2-ethylhexyl p-hydroxybenzoate.

[0017] [7] A laminate as described in any one of [1] to [6] above, wherein the (meth)acrylamide polymer comprises a repeating unit as shown in formula (2) below. 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 that can be substituted by at least one of the following substituents: epoxy group, hydroxyl group, or (meth)acryloyl group.

[0018] [8] The stack as described in [7] above, wherein the (meth)acrylamide polymer comprises at least one of the repeating units shown in formulas (2-a) to (2-c). [9] The laminate as described in any one of [1] to [8] above, wherein the laminate is used in TOM molding.

[0019]

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

[0020]

[11] The cured material as described in

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

[0021]

[12] A laminate comprising: Substrate layer (a) containing polycarbonate resin A curable resin layer (b) containing a (meth)acrylamide polymer with an acrylamide equivalent of 200–600 g / mol, and An acrylic layer (c) containing (meth)acrylic resin is disposed between the above-mentioned substrate layer (a) and the above-mentioned curable resin layer (b). The laminate did not exhibit chemical cracking during alcohol wiping tests.

[0022] Invention Effects According to the present invention, it is possible to provide a laminate that is not prone to cracking even when wiped and cleaned with solvents such as alcohols. Detailed Implementation

[0023] The following provides a detailed description of specific embodiments for carrying out the present invention.

[0024] 1. Laminated body The laminate of the present invention comprises a substrate layer (a) containing polycarbonate resin, a curable resin layer (b) containing a (meth)acrylamide polymer with an acrylamide equivalent of 200-600 g / mol, and an acrylic layer (c) containing (meth)acrylic resin disposed between the substrate layer (a) and the curable resin layer (b). That is, the laminate is stacked in the order of substrate layer (a), acrylic layer (c), and curable resin layer (b).

[0025] In this case, at 122 seconds ﹣1 The melt viscosity of the above (meth)acrylic resin at 230°C, as measured by the shear rate, is 2200–10000 Pa·s, and the thickness of the above acrylic layer (c) is 10–120 μm.

[0026] The laminate described above is not prone to cracking even when cleaned with solvents such as alcohols. Furthermore, the cured product obtained by curing the laminate is also not prone to cracking even when cleaned with solvents such as alcohols.

[0027] In conventional laminates, where a hard coating is formed to achieve a balance of hardness and formability, curing occurs before molding but not after. Cracks may appear when the laminate or its cured product is cleaned with solvents such as alcohols. This is likely because, for example, the laminate and cured product are molded products, making them prone to cracking due to stress from bending or folding; or because the laminate and cured product have a layered structure, they are susceptible to chemical cracking due to solvent penetration through their cross-sections. In this case, for example, in a laminate, the aforementioned cracks are more likely to occur in the acrylic layer (c) of the substrate layer (a), the acrylic layer (c), and the curable resin layer (b).

[0028] In contrast, according to the laminate of the present invention, by subjecting the (meth)acrylic resin in the laminate, particularly the (meth)acrylic resin constituting the acrylic layer (c), to 122 seconds... ﹣1The melt viscosity at 230°C, measured by shear rate, is 2200–10000 Pa·s. By maintaining the acrylic layer (c) thickness at 10–120 μm, cracking caused by solvent cleaning can be prevented. While the exact reason is not fully understood, it is believed to be due to the solvent resistance of (meth)acrylic resin, the high mechanical strength of the acrylic layer (c) sufficient to withstand bending and folding after molding, and the fact that the acrylic layer (c) is located between the substrate layer (a) and the curable resin layer (b), allowing for flexible and high-strength bonding between the two. It should be noted that the cured product formed after the laminate is cured also exhibits this effect.

[0029] It should be noted that, in this specification, the solvent used for wiping and cleaning is preferably an alcohol, and isopropanol is preferred from the perspective of making it easier to clean the binders and other substances that may adhere to the surface of the laminate after molding. Furthermore, in this specification, "crack" refers to cracks, fissures, or crazing that appear in the structural layers of the laminate, and is preferably a chemical crack caused by the solvent.

[0030] Therefore, according to one embodiment of the present invention, a laminate that does not develop chemical cracks due to an alcohol wiping test can be provided. The laminate comprises a substrate layer (a) containing a polycarbonate resin; a curable resin layer (b) containing a (meth)acrylamide polymer with an acrylamide equivalent of 200 to 600 g / mol; and an acrylic layer (c) containing an acrylic resin disposed between the substrate layer (a) and the curable resin layer (b).

[0031] Furthermore, since the curable resin layer (b) of the laminated body of the present invention can remain uncured before molding and cure after molding, it is possible to achieve both excellent hardness and formability. In particular, since the curable resin layer (b) has the composition of the present invention, it has excellent stereoforming properties.

[0032] In one embodiment of the present invention, the laminate is used for vacuum forming. Vacuum forming is a forming method performed under vacuum conditions, including in-mold forming and three-dimensional decorative (TOM) forming.

[0033] However, since vacuum forming is often applied to three-dimensional shapes with uneven surfaces, the resulting laminates tend to have greater degrees of bending and folding. Therefore, the laminates are more prone to cracking when cleaned with solvents.

[0034] The laminate according to the present invention can prevent cracks from being generated by wiping with solvents, even when vacuum forming is performed.

[0035] Furthermore, as described above, when a laminate containing a curable resin layer (b) is applied to a molded article (during molding), it is preferable that the curable resin layer (b) does not cure during molding, but cures after molding.

[0036] However, when molding is performed under vacuum conditions, free radicals may be generated by oxygen atoms contained in the curable resin layer (b), leading to unexpected curing of the curable resin layer (b) during the vacuum molding process.

[0037] As a result, even from this perspective, cracks may appear in the cured resin layer (b) after molding.

[0038] According to the present invention, even when the lamination is formed under vacuum conditions, the molded body can be formed without cracking, and cracking of the curable resin layer (b) of the above-mentioned lamination can be prevented.

[0039] In one embodiment of the present invention, the laminate of the present invention is used for three-dimensional decorative (TOM) molding. The three-dimensional decorative (TOM) molding includes: (1) a vacuum process in which a vacuum condition is achieved after forming an airtight state between a lower chamber with a molded article having an uneven surface and an upper chamber with a heater and an upper chamber having a lower opening; (2) a heating process in which the laminate of the present invention is heated using the heater; (3) a contact process in which the molded article having an uneven surface is brought into contact with the heated laminate; (4) a vacuum environment unsealing process in which the upper chamber reaches atmospheric pressure; and (5) a vacuum environment unsealing process in which the lower chamber reaches atmospheric pressure.

[0040] In other words, three-dimensional decorative molding (TOM) involves heating and softening a laminate under vacuum conditions, then lifting the molded part from the bottom of the laminate upwards until they come into contact (the laminate, due to its own weight, comes into close contact with the molded part and is laminated). Atmospheric pressure is then created in the upper chamber to generate a pressure difference, which is used to pressurize the upper chamber towards the lower chamber to complete the lamination process. This results in a three-dimensional decorative molded part comprising a molded part with uneven surfaces and a laminate disposed on those uneven surfaces.

[0041] It should be noted that the three-dimensional decoration (TOM) molding may also include an upper chamber pressurization process, which introduces compressed air into the upper chamber after the upper chamber vacuum environment unsealing process. In addition, it may also include a trimming process, which removes a portion of the laminate disposed on the uneven surface, and a curing process, which solidifies the laminate, after the lower chamber vacuum environment unsealing process.

[0042] When using existing laminates, it is impossible to achieve high conformability in laminating the laminate with molded articles having uneven surfaces for three-dimensional decoration (TOM) molding. Even if lamination is possible, cracks may occur in the laminate. In particular, if the laminate is cleaned with a solvent after molding, cracks are prone to occur. However, the laminate according to the present invention can achieve high conformability in lamination with molded articles having uneven surfaces. Moreover, cracks are less likely to occur even when the resulting laminate is cleaned with a solvent.

[0043] <Substrate layer (a)> The substrate layer (a) contains polycarbonate resin. In addition, the substrate layer (a) may also contain other resins, plasticizers, additives, etc.

[0044] [Polycarbonate resin] As a polycarbonate resin, any compound containing carbonate bonds in its main molecular chain, i.e., -[O-R-OCO]- units (R can contain aliphatic groups, aromatic groups, or both aliphatic and aromatic groups, and can have a straight-chain structure or a branched structure), is acceptable, without any particular limitation.

[0045] In one embodiment, the polycarbonate resin is preferably a polycarbonate formed by reacting bisphenol, a carbonate binder, and a chain terminator.

[0046] (Bisphenol) Examples of bisphenols include, but are not specifically limited to, 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, 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-tert-butylphenyl)propane, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane (Bisphenol PH:BPPH), 1,1-bis(4-hydroxyphenyl)-2-methylpropane (Bisphenol IBT), 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)propane Bisphenol compounds are compounds in which two phenolic groups are bonded together via a "-C(R)2-" bond. The compounds contain 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). Each R is independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, an alkyl group with 1 to 20 substituted or unsubstituted carbon atoms, an alkoxy group with 1 to 5 substituted or unsubstituted carbon atoms, an aryl group with 6 to 12 substituted or unsubstituted carbon atoms, or a carbocyclic group with 5 to 20 carbon atoms formed by the bonding of two R groups. Bisphenolic compounds containing two phenolic groups linked by a "-S-" bond, such as heterocyclic groups; bis(4-hydroxyphenyl) sulfide containing two phenolic groups linked by a "-O-" bond, such as bis(4-hydroxyphenyl) ether; bisphenolic compounds containing two phenolic groups linked by a "-SO-" bond, such as bis(4-hydroxyphenyl) sulfoxide; bisphenolic compounds containing two phenolic groups linked by a "-CO-" bond, such as bis(4-hydroxyphenyl) ketone; bis(4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(2-hydroxyphenyl) sulfone, bis(4-hydroxy-3-methylphenyl) sulfone containing two phenolic groups linked by a "-SO2-" bond; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,Bisphenolic compounds containing two phenolic groups linked by fluorene, such as 9-bis(4-hydroxy-3-ethylphenyl)fluorene; bisphenolic compounds containing two phenolic groups linked by phenylene dialkylene, such as 4,4'-[1,4-benzenedi(1-methylethylidene)]bisphenol and 4,4'-[1,3-phenylene di(1-methylethylidene)]bisphenol; bisphenolic compounds containing two phenolic groups linked by adamantylene, such as 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane; and bisphenolic compounds containing two phenolic groups linked by polyalkylsiloxane, such as α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane and α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane. These bisphenols can be used alone or in combination of two or more.

[0047] The bisphenol is preferably a bisphenol compound containing two phenolic groups bonded by "-C(R)2-", and is more preferably bisphenol A.

[0048] The content of bisphenol relative to all structural units of polycarbonate is preferably 1 mol% or more, more preferably 2 to 100 mol%, further preferably 5 to 100 mol%, and particularly preferably 10 to 100 mol%.

[0049] Furthermore, the content of bisphenol relative to the total molar number of polycarbonate structural units and end groups is preferably 2 to 99.8 mol%, more preferably 5 to 99 mol%.

[0050] (Compounds that derive other structural units) Polycarbonate can be formed by further reacting compounds that derive other structural units. By using the aforementioned compounds that derive other structural units, the physical properties of polycarbonate (e.g., median glass transition temperature (Tmg), viscosity-average molecular weight, etc.) can be adjusted.

[0051] Organosiloxanes are examples of compounds from which other structural units are derived.

[0052] Examples of organosiloxanes include α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane and α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane. These organosiloxanes can be used alone or in combination of two or more.

[0053] The content of organosiloxane relative to 1 mole of bisphenol is preferably 50 moles or less, more preferably 0.1 to 40 moles.

[0054] (carbonate binder) Examples of carbonate binders include, but are not specifically limited to, carbonyl compounds such as phosgene, triphosgene, carbon monoxide, carbon dioxide, and diester carbonate.

[0055] Examples of the aforementioned dicarbonate compounds include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and ditert-butyl carbonate, as well as substituted diphenyl carbonates such as diphenyl carbonate, di-p-toluene carbonate, phenyl-p-toluene carbonate, and di-p-chlorophenyl carbonate.

[0056] The carbonate binder preferably includes at least one of phosgene, triphosgene, diphenyl carbonate, and substituted diphenyl carbonate, and more preferably includes at least one of phosgene and diphenyl carbonate. It should be noted that the carbonate binder can be used alone or in combination of two or more.

[0057] (Chain terminator) Chain terminators have the function of adjusting the median glass transition temperature (Tmg) and viscosity-average molecular weight of polycarbonate.

[0058] Chain terminators can be exemplified, but are not particularly limited to, monohydric phenol chain terminators represented by the following formula (1) and monohydric phenol compounds without unsaturated groups. In the above equation (1), R 1 It is an alkyl group or an alkenyl group having 8 to 36 carbon atoms; R 2 Each of the following components is independently hydrogen, a halogen atom, or an alkyl group with 1 to 20 carbon atoms that can be substituted with a halogen atom or an aryl group with 6 to 12 carbon atoms; or an aryl group with 6 to 12 carbon atoms that can be substituted with a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms. It should be noted that in this specification, "alkyl" and "alkenyl" can be linear or branched, preferably linear.

[0059] More preferably, the monohydric phenol chain terminator represented by formula (1) is represented by the following general formula (1-a). In the above equation (1-a), R 1 It is an alkyl group or an alkenyl group with 8 to 36 carbon atoms.

[0060] R in equation (1) or equation (1-a) 1 The number of carbon atoms is more preferably within a specific numerical range. Specifically, as R 1 The upper limit for the number of carbon atoms is preferably 36, more preferably 22, and particularly preferably 18. Furthermore, as R... 1 The lower limit of the number of carbon atoms is preferably 8, and more preferably 12.

[0061] If R 1If the upper limit of the number of carbon atoms is appropriate, the organic solvent solubility of the monophenol chain terminator shown in formula (1) can be improved, thereby increasing the productivity in the polycarbonate resin manufacturing process and improving the transparency of the polycarbonate resin, etc., and is therefore preferred. As an example, when R 1 When the number of carbon atoms is less than 36, a polycarbonate resin with high transparency can be obtained, and the productivity in the manufacturing process is very high, resulting in good economic benefits; while when R... 1 When the number of carbon atoms is less than 22, the organic solvent solubility of the monophenol chain terminator shown in formula (1) is particularly good, which can greatly improve the productivity in the polycarbonate resin manufacturing process and improve economic benefits.

[0062] If R 1 An appropriate lower limit for the number of carbon atoms can prevent the glass transition temperature of polycarbonate resin from becoming too high, thus ensuring suitable thermoformability, and is therefore preferred. For example, when using R... 1 In the case of a monohydric phenol chain terminator of formula (1) with 16 carbon atoms, the monohydric phenol chain terminator of formula (1) has excellent glass transition median temperature, melt flowability, formability, anti-dripping properties, and solvent solubility in the polycarbonate resin manufacturing process, and is particularly preferred as a chain terminator for polycarbonate resin.

[0063] In one implementation, R in equations (1) and (1-a) 1 Preferably, it is a dodecyl alkyl, tridecyl alkyl, tetradecyl alkyl, pentadecyl alkyl, hexadecyl alkyl, heptadecanyl alkyl, or octadecyl alkyl; more preferably, it is a tetradecyl alkyl, pentadecyl alkyl, hexadecyl alkyl, or heptadecanyl alkyl, or 2-hexyldecyl; and even more preferably, it is a hexadecyl alkyl or 2-hexyldecyl.

[0064] In one implementation, R in equation (1) 2 Each is independent, preferably hydrogen, halogen atom, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, or phenyl; more preferably hydrogen, fluorine atom, chlorine atom, methyl, ethyl, or phenyl; and even more preferably hydrogen, fluorine atom, chlorine atom, methyl, or ethyl. In another embodiment, preferably all R... 2 Both are hydrogen.

[0065] In one embodiment, the monophenol chain terminator represented by formula (1) preferably comprises at least one selected from 2-hexyldecyl p-hydroxybenzoate, hexadecyl p-hydroxybenzoate, dodecyl p-hydroxybenzoate, and 2-ethylhexyl p-hydroxybenzoate, more preferably at least one selected from 2-hexyldecyl p-hydroxybenzoate and hexadecyl p-hydroxybenzoate, and even more preferably 2-hexyldecyl p-hydroxybenzoate.

[0066] It should be noted that the monohydric phenol chain terminator shown in formula (1) above can be used alone or in combination of two or more.

[0067] The amount of the monohydric phenol chain terminator shown in formula (1) relative to 1 mole of bisphenol is preferably 0.02 to 0.07 moles, more preferably 0.025 to 0.06 moles.

[0068] The amount of the monophenol chain terminator shown in formula (1) relative to 1 mole of carbonate binder is preferably 0.02 to 0.07 moles, more preferably 0.025 to 0.06 moles.

[0069] Examples of monohydric phenolic compounds without unsaturated groups include phenol, p-cresol, o-cresol, 2,4-xylenol, p-tert-butylphenol, p-hexylphenol, p-heptylphenol, p-octylphenol, and p-cumylphenol. These monohydric phenolic compounds can be used alone or in combination of two or more.

[0070] The amount of the monohydric phenolic compound without unsaturated groups relative to 1 mole of the chain terminator shown in formula (1) is preferably 0.5 moles or less, more preferably 0.2 moles or less, and even more preferably 0.1 moles or less.

[0071] The amount of a monohydric phenolic compound without unsaturated groups relative to 1 mole of bisphenol is preferably 0.02 to 0.07 moles, more preferably 0.025 to 0.06 moles.

[0072] In one embodiment, the polycarbonate resin is preferably a bisphenol A type polycarbonate obtained by reacting bisphenol A, a carbonate binder, and a monophenol chain terminator as shown in formula (1) below. The aforementioned bisphenol A type polycarbonate can be further reacted with bisphenols other than bisphenol A, compounds that derive other structural units, monophenolic compounds without unsaturated groups, etc.

[0073] It should be noted that the above-mentioned compounds can be used as carbonate binders, monohydric phenol chain terminators as shown in formula (1), bisphenols other than bisphenol A, compounds that derive other structural units, and monohydric phenol compounds without unsaturated groups.

[0074] In one embodiment, the content of the structural units derived from bisphenol A in the bisphenol A type polycarbonate, except for the chain-end structures of the bisphenol A type polycarbonate, is preferably 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, and particularly preferably 98 to 100% by mass.

[0075] The above-mentioned polycarbonate resins can be used alone or in combination of two or more.

[0076] The median glass transition temperature (Tmg) of the polycarbonate resin is preferably 100–140°C, more preferably 125–140°C, further preferably 128–140°C, and even more preferably 128–135°C. When the median glass transition temperature (Tmg) of the polycarbonate resin is within the above range, it is easier to control the median glass transition temperature (Tmg) of the substrate layer (a), and therefore it is preferred. It should be noted that in this specification, "median glass transition temperature (Tmg)" is a value obtained by analyzing the DSC curve obtained by differential scanning calorimetry (DSC). Specifically, when the intersection of line A (extending the baseline from the low-temperature side of the DSC curve to the high-temperature side), tangent B at the inflection point, and line C (extending the baseline from the high-temperature side to the low-temperature side) and tangent B is defined as the glass transition initiation temperature (Tig), and the intersection of tangent B and line C is defined as the glass transition end temperature (Teg), the midpoint between the glass transition initiation temperature (Tig) and the glass transition end temperature (Teg) is defined as the glass transition median temperature (Tmg). It should be noted that, generally, when referring to glass transition temperature, the glass transition initiation temperature (Tig) is used, and the glass transition initiation temperature (Tig) is lower than the glass transition median temperature (Tmg). The glass transition median temperature (Tmg) is measured according to the method described in the embodiments.

[0077] The viscosity-average molecular weight of the polycarbonate resin is preferably 14,000 or more, more preferably 16,000 or more, further preferably 20,000 or more, particularly preferably 24,000 or more, and extremely preferably 26,000 or more. Furthermore, the viscosity-average molecular weight of the polycarbonate resin is preferably 40,000 or less, more preferably 38,000 or less, further preferably 36,000 or less, particularly preferably 34,000 or less, and extremely 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, further preferably 18,000 to 36,000, particularly preferably 20,000 to 34,000, and extremely preferably 24,000 to 32,000. It should be noted that in this specification, "viscosity-average molecular weight" is measured according to the method described in the examples. Additionally, when the polycarbonate resin is a mixture of two or more polycarbonate resins with different molecular weights, the viscosity-average molecular weight of the mixture is used.

[0078] The content of polycarbonate resin relative to the total mass of the substrate layer (a) is preferably 96% by mass or more, more preferably 98% by mass or less, and even more preferably 100% by mass.

[0079] [Plasticizer] The substrate layer (a) may also contain a plasticizer. The plasticizer has the function of adjusting the median glass transition temperature (Tmg) of the substrate layer (a).

[0080] Examples of plasticizers include, but are not limited to, polyesters, polyethers, aromatic phosphonates, and aromatic esters.

[0081] Examples of the aforementioned polyesters include aliphatic polyesters such as polycaprolactone (PCL) and aromatic polyesters such as polyethylene terephthalate modified resin and polycaprolactone-polyethylene terephthalate modified resin.

[0082] It should be noted that, as a polycaprolactone-modified polyethylene terephthalate resin, examples include ethylene glycol-modified polyethylene terephthalate (PETG) and ethylene glycol-modified polycyclohexamethylene terephthalate (PCTG).

[0083] PETG is a product of PET (terephthalic acid unit of dicarboxylic acid unit and ethylene glycol unit of diol unit) in which some ethylene glycol units are replaced by 1,4-cyclohexanediethanol units. The content of 1,4-cyclohexanediethanol units relative to all diol units is preferably less than 50 mol%, more preferably 30 to 40 mol%.

[0084] PCTG is a product in which some of the diol units in PCT (the terephthalic acid unit of the dicarboxylic acid unit and the 1,4-cyclohexanediethanol unit of the diol unit) are replaced by ethylene glycol units. The content of ethylene glycol units relative to all diol units is preferably less than 50 mol%, more preferably 30 to 40 mol%.

[0085] The number-average molecular weight of the polyester is preferably 10,000 to 100,000, more preferably 20,000 to 60,000. It should be noted that, in this specification, the value of "number-average molecular weight" is obtained by gel permeation chromatography.

[0086] Examples of the aforementioned polyethers include those having at least one unit selected from ethylene glycol, propylene glycol, butanediol, trimethylene glycol, and tetramethylene glycol. Specifically, the polyether can be a homopolymer or a copolymer. In the case of a copolymer, it can be any of random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and combinations thereof. Specific examples of polyethers include block copolymers of polyethylene glycol, polypropylene glycol, polybutanediol, and polyethylene glycol and polypropylene glycol.

[0087] The number average molecular weight of the polyether is preferably 500-4000, more preferably 600-3000, and even more preferably 800-2000.

[0088] Examples of the aforementioned aromatic phosphonate compounds include triphenyl phosphate, tricresyl phosphate, tri(xyl) phosphate, toluene diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis(tert-butylphenyl)phenyl phosphate, tri(tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis(isopropylphenyl)diphenyl phosphate, tri(isopropylphenyl) phosphate, resorcinol bis(diphenyl) phosphate, resorcinol poly(bis(2,6-xylyl)) phosphate, resorcinol bis(bis(xylyl)) phosphate, bisphenol A bis(diphenyl) phosphate, and biphenyl bis(diphenyl) phosphate. It should be noted that the molecular weight of the aromatic phosphonate compound is preferably 200–1000, more preferably 400–800.

[0089] Examples of the aforementioned aromatic ester compounds include diethylene glycol dibenzoate, glyceryl tribenzoate, trimethylolpropane tribenzoate, and pentaerythritol tetrabenzoate. It should be noted that the molecular weight of the aromatic ester compound is preferably 200–1000, more preferably 400–800.

[0090] The plasticizer preferably contains polyester or aromatic phosphonate compounds, more preferably polyester, and even more preferably at least one of polycaprolactone (PCL), glycol-modified polyethylene terephthalate (PETG), and glycol-modified polycyclohexamethylene terephthalate (PCTG), and particularly preferably polycaprolactone (PCL). The above plasticizers can be used alone or in combination of two or more.

[0091] The content of plasticizer relative to the total mass of substrate layer (a) is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 0.1 to 2% by mass. When the content of plasticizer is 4% by mass or less, the substrate layer (a) can contain polycarbonate resin with a content of 96% by mass or more.

[0092] [additive] The substrate layer (a) may also contain additives.

[0093] Examples of additives, but not limited to, include antioxidants, anti-esterification agents, mold release agents, heat stabilizers, flame retardants, flame retardant additives, ultraviolet absorbers, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, anti-blocking agents, impact modifiers, slip improvers, color improvers, and acid collectors. These additives can be used alone or in combination of two or more.

[0094] The additive content relative to the total mass of the substrate layer (a) is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 0.1% to 2% by mass. When the additive content is 4% by mass or less, the substrate layer (a) can contain polycarbonate resin with a content of 96% by mass or more.

[0095] [Composition of substrate layer (a)] The median glass transition temperature (Tmg) of the substrate layer (a) is preferably 100–140°C, more preferably 110–140°C, further preferably 120–140°C, particularly preferably 120–135°C, and most preferably 125–135°C. The median glass transition temperature (Tmg) of the substrate layer (a) can be controlled by appropriately adjusting the structure of the polycarbonate resin (e.g., the type and content of the structural units of the polycarbonate resin, the type of chain terminator used, the viscosity-average molecular weight, etc.) and the type and content of the plasticizer added to the substrate layer (a).

[0096] The thickness of the substrate layer (a) is preferably 10-800 μm, more preferably 20-500 μm, even more preferably 30-400 μm, even more preferably 50-300 μm, and even more preferably 60-200 μm.

[0097] <Curing resin layer (b)> The curable resin layer (b) contains a (meth)acrylamide polymer with an acrylamide equivalent of 200–600 g / mol. Since the curable resin layer (b) is in an uncured state, it exhibits excellent formability, particularly stereoforming ability, when forming the laminate of the present invention. Therefore, in the case of stereoforming, for example, the conformability of the curable resin layer (b) is better, and the cured resin layer (b) is less prone to cracking after molding. Furthermore, the cured product obtained by curing the laminate has high hardness, and its scratch resistance, chemical resistance, etc., are also improved. It should be noted that in this specification, "(meth)acrylamide" refers to methacrylamide and / or acrylamide. Similarly, "(meth)propenyl" and "(meth)acrylate" also refer to methpropenyl and / or propenyl, methacrylate and / or acrylate.

[0098] [(Meth)acrylamide polymer] (Methacrylamide) polymers preferably contain repeating units as shown in formula (2) below. In the above formula (2), m is a single bond or an alkylene group with 1 to 4 carbon atoms, preferably methylene or ethylene, and more preferably methylene.

[0099] 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.

[0100] p is a single bond or an alkylene group having 1 to 2 carbon atoms, preferably a single bond or a methylene group, more preferably a single bond.

[0101] q is hydrogen or an alkyl group having 1 to 12 carbon atoms that can be substituted by at least one of the substituents selected from epoxy, hydroxyl, and (meth)acryloyl groups. It is preferably an alkyl group having 1 to 4 carbon atoms that can be substituted by at least one of the substituents selected from epoxy and (meth)acryloyl groups. More preferably, it is an alkyl group having 1 to 2 carbon atoms that can be substituted by at least one of the substituents selected from epoxy and (meth)acryloyl groups.

[0102] In one embodiment, the (meth)acrylamide polymer preferably comprises at least one of the repeating units shown in formulas (2-a) to (2-c). or The content of the repeating unit shown in formula (2-a) relative to the total molar number of (meth)acrylamide polymer is preferably 30 to 85 mol%, more preferably 40 to 80 mol%.

[0103] The content of the repeating unit shown in formula (2-b) relative to the total molar number of (meth)acrylamide polymer is preferably 5 to 30 mol%, more preferably 10 to 25 mol%.

[0104] The content of the repeating unit shown in formula (2-c) relative to the total molar number of (meth)acrylamide polymer is preferably 10 to 40 mol%, more preferably 10 to 35 mol%.

[0105] The above-mentioned (meth)acrylamide polymers can be used alone or in combination of two or more.

[0106] The molar ratio of the repeating unit shown in formula (2-a) to the repeating unit shown in formula (2-b) is preferably 4.5 to 5.5: 1.5 to 2.5.

[0107] The molar ratio of the repeating unit shown in formula (2-a) to the repeating unit shown in formula (2-c) is preferably 4.5 to 5.5: 2.5 to 3.5.

[0108] The molar ratio of the repeating unit shown in formula (2-b) to the repeating unit shown in formula (2-c) is preferably 1.5 to 2.5: 2.5 to 3.5.

[0109] The acryloyl equivalent of the (meth)acryloyl polymer is 200–600 g / mol, and from the perspective of further improving the hardness of the cured product, it is preferably 200–500 g / mol, more preferably 200–400 g / mol, and even more preferably 200–300 g / mol. It should be noted that in this specification, the (meth)acryloyl equivalent (g / mol) refers to the molecular weight of each (meth)acryloyl group, which can be calculated using the methods described in the examples.

[0110] The weight-average molecular weight of the (meth)acrylamide polymer is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, further preferably 15,000 to 100,000, and particularly preferably 20,000 to 50,000. It should be noted that in this specification, "weight-average molecular weight" is calculated using the methods described in the examples.

[0111] The content of (meth)acrylamide polymer relative to the total mass of the curable resin layer (b) 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.

[0112] [Multifunctional acrylate compounds] The curable resin layer (b) may also contain a polyfunctional acrylate compound. The polyfunctional acrylate compound can increase the hardness of the cured product by reacting, for example, with the (meth)acryloyl group, epoxy group, hydroxyl group, etc., present in the (meth)acryloyl polymer. It should be noted that, in this specification, "polyfunctional" means having two or more functions, preferably three or more functions, more preferably three to eight functions, and even more preferably three to six functions.

[0113] Examples of polyfunctional acrylate compounds include, but are not limited to, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0114] The content of the polyfunctional acrylate compound relative to the total amount of the (meth)acrylamide polymer and 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.

[0115] [Inorganic particles] The cured resin layer (b) may also contain inorganic particles. Inorganic particles can improve the hardness and scratch resistance of the cured product.

[0116] Examples of inorganic particles include, but are not limited to, silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, and diamond.

[0117] Inorganic particles can be surface-treated. Through surface treatment, the inorganic particles can be dispersed in a stable state within the curable resin layer (b). In this case, the surface treatment agent used can be, but is not particularly limited to, silane compounds, alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, etc. These surface treatment agents can be used alone or in combination of two or more. Through surface treatment, polymerizable groups (preferably vinyl or (meth)propylene) can be introduced onto the surface of the inorganic particles.

[0118] The aforementioned inorganic particles can be used alone or in combination of two or more.

[0119] The average particle size of the inorganic particles is preferably 5–95 nm, more preferably 8–70 nm, and from the perspective of improving the scratch resistance of the resulting cured product, it is further preferably 20–60 nm, and particularly preferably 30–60 nm. It should be noted that in this specification, "particle size" refers to the maximum distance between two points on the outer surface of the particle. Furthermore, the "average particle size" can be measured using the method described in the examples.

[0120] The content of inorganic particles relative to the total mass of the cured resin layer (b) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

[0121] [Leveling agent] The cured resin layer (b) may also contain a leveling agent. The leveling agent has the functions of improving leveling (making the coating smooth), fingerprint wiping resistance, stain resistance, and abrasion resistance of the cured product.

[0122] Examples of leveling agents include, but are not limited to, fluorinated leveling agents and silicone leveling agents.

[0123] As fluorinated leveling agents, compounds containing perfluoropolyether bonds can be cited as examples. Commercially available fluorinated leveling agents include, for example, MEGAFACE 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, and 240GFTX-218 (manufactured by Neos Corporation).

[0124] Examples of silicone-based leveling agents include polyether-modified polydimethylsiloxanes containing acryloyl groups. Commercially available silicone-based leveling agents can be used, such as BYK-UV3500 and BYK-UV3505 (manufactured by BYK Chemicals Japan).

[0125] Among these factors, fluorine-based leveling agents are preferred for improving the fingerprint removability of the cured material. It should be noted that the aforementioned leveling agents can be used alone or in combination of two or more.

[0126] The leveling agent content relative to the total mass of the cured resin layer (b) is preferably 0.001 to 10% by mass, more preferably 0.001 to 5% by mass, even more preferably 0.01 to 4% by mass, and particularly preferably 0.1 to 3% by mass.

[0127] [Photopolymerization initiator] The curable resin layer (b) may also contain a photopolymerization initiator. The photopolymerization initiator has the function of promoting the curing reaction during the curing process of the curable resin layer (b).

[0128] Examples of photopolymerization initiators include, but are not limited to, 1-hydroxy-cyclohexyl benzophenone (Irgacure-184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (Irgacure 1173), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Irgacure TPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2,2'-dimethoxy-2-phenylacetophenone (Irgacure-651), oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone (EsacureONE), and 1-hydroxy-cyclohexyl benzophenone (Omnirad 184). From the perspective of improving heat resistance, it is preferable to include at least one of oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone (EsacureONE) and 1-hydroxycyclohexylbenzophenone (Omnirad 184), and more preferably 1-hydroxycyclohexylbenzophenone (Omnirad 184). It should be noted that the above-mentioned photopolymerization initiator can be used alone or in combination of two or more.

[0129] The content of the photopolymerization initiator relative to the total mass of the curable resin layer (b) is preferably 1 to 10% by mass, more preferably 1 to 6% by mass, even more preferably 2 to 5% by mass, and particularly preferably 2 to 4% by mass.

[0130] [Light stabilizer] The curable resin layer (b) may also contain a light stabilizer. The light stabilizer has functions such as improving the weather resistance of the cured product.

[0131] Examples of light stabilizers include, but are not limited to, hindered amine light stabilizers.

[0132] Examples of hindered amine-based light stabilizers include bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (adeKa stab LA-81), tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylic acid ester (adeKa STAB LA-52), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylic acid ester (adeKastab LA-57), 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (adeKa stab LA-82), and bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) sebacate (Tinuvin). 123), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin770DF), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) butylmalonic acid (Tinuvin144), etc.

[0133] The light stabilizer preferably includes a hindered amine-based light stabilizer. It should be noted that the above-mentioned light stabilizers can be used alone or in combination of two or more.

[0134] The content of light stabilizer relative to the total mass of the curable resin layer (b) is preferably 0.1 to 15% by mass, more preferably 0.1 to 7% by mass, even more preferably 0.3 to 5% by mass, and particularly preferably 0.3 to 3% by mass.

[0135] [Polymerization inhibitor] The hard coating (b) may also contain a polymerization inhibitor. The polymerization inhibitor has the function of inhibiting the polymerization reaction of the curable resin layer (b) under the influence of light and heat, and improving the storage stability of the laminate.

[0136] Examples of polymerization inhibitors include, but are not limited to, phenothiazine, 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-oxopyridine-1-oxo radical, and 2-mercaptobenzimidazole.

[0137] The polymerization inhibitor preferably includes at least one of phenothiazine, p-methoxyphenol, and hydroquinone, and more preferably includes phenothiazine. It should be noted that the above-mentioned polymerization inhibitors can be used alone or in combination of two or more.

[0138] The content of the polymerization inhibitor relative to the total mass of the cured resin layer (b) is preferably 0.001 to 5% by mass, more preferably 0.01 to 4% by mass, and even more preferably 0.01 to 3% by mass.

[0139] [additive] The curable resin layer (b) may also contain additives.

[0140] Examples of additives include, but are not specifically limited to, heat stabilizers, antioxidants, flame retardants, flame retardant additives, ultraviolet absorbers, mold release agents, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, and antibacterial agents. These additives can be used alone or in combination of two or more.

[0141] [Composition of the curable resin layer (b)] The curable resin layer (b) is in an uncured state, for example, the (meth)acrylamide polymer has polymerizable functional groups ((meth)acrylyl, epoxy, hydroxyl, etc.). The curable resin layer (b) is easy to conform to the mold, and the cured resin layer (b) is not prone to cracking after molding, thus exhibiting excellent formability, especially stereoforming properties. However, for example, without impairing the effects of the present invention, the (meth)acrylamide polymer in the curable resin layer (b) can also have a cross-linked structure by subjecting some of the (meth)acrylyl groups to a curing reaction during the molding process.

[0142] 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.

[0143] <Acrylic layer (c)> An acrylic layer (c) is disposed between a substrate layer (a) and a curable resin layer (b).

[0144] The acrylic layer (c) contains (meth)acrylic resin. The acrylic layer (c) may also contain additives, etc.

[0145] [(Meth)acrylic resin] There are no particular restrictions on (meth)acrylic resins, as long as they are polymers of (meth)acrylates.

[0146] Examples of the aforementioned (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. These (meth)acrylates can be used alone or in combination of two or more.

[0147] (Meth)acrylic resin can also be a copolymer of (meth)acrylate and other polymerizable monomers.

[0148] Other polymerizable monomers include (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, and acrylonitrile. These other polymerizable monomers can be used alone or in combination of two or more.

[0149] (Meth)acrylic resins can be homopolymers or copolymers. Furthermore, (meth)acrylic resins can also be crosslinked using crosslinking agents.

[0150] From the perspectives of high transparency and excellent moldability, (meth)acrylic resin preferably includes polymethyl methacrylate (PMMA) resin. It should be noted that the aforementioned (meth)acrylic resin can be used alone or in combination of two or more types.

[0151] (Meth)acrylic resin at 122 seconds ﹣1 The melt viscosity at 230°C, measured at a shear rate of 2200–10000 Pa·s, preferably 2500–8000 Pa·s, more preferably 2800–7000 Pa·s, and even more preferably 3000–6000 Pa·s, is 2200–10000 Pa·s. When the melt viscosity of the (meth)acrylic resin is within the above range, it can achieve the effect of preventing cracks caused by solvent wiping and cleaning, and reducing the occurrence of appearance defects. It should be noted that in this specification, "at 122 sec..." ﹣1 The melt viscosity at 230°C, measured at the shear rate, can be specifically measured using the method described in the examples.

[0152] 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, it can achieve the effect of preventing cracks caused by solvent wiping and cleaning, and reducing the occurrence of appearance defects.

[0153] It should be noted that (meth)acrylic resin at 122 seconds ﹣1The melt viscosity and weight-average molecular weight at 230°C, measured at the shear rate, can be adjusted by changing the type of (meth)acrylate used, the type and content of other polymerizable monomers, the polymerization conditions, and whether crosslinking exists.

[0154] The content of (meth)acrylic resin relative to the total mass of acrylic layer (c) is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 90 to 100% by mass.

[0155] [additive] The acrylic layer (c) may also contain additives. Examples of additives include, but are not limited to, UV absorbers, antioxidants, color inhibitors, and inorganic particles. These additives may be used alone or in combination of two or more.

[0156] [Composition of acrylic layer (c)] The thickness of the acrylic layer (c) is 10-120 μm, preferably 20-120 μm, more preferably 30-100 μm, further preferably 30-90 μm, and particularly preferably 40-80 μm.

[0157] 2. Manufacturing method of laminated bodies According to one embodiment of the present invention, a method for manufacturing a laminated body will be provided.

[0158] In one embodiment, the method of manufacturing the laminate includes a step (1) of co-extruding a first resin composition and a third resin composition to form a precursor comprising a substrate layer (a) and an acrylic layer (c), and a step (2) of forming a curable resin layer (b) containing a second resin composition on the acrylic layer (c) in the precursor.

[0159] In this case, the first resin composition comprises a polycarbonate resin.

[0160] The second resin composition comprises a (meth)acrylamide polymer with an acrylamide equivalent of 200 to 600 g / mol.

[0161] The third resin composition comprises (meth)acrylic resin.

[0162] The following describes each process.

[0163] <Process (1)> Step (1) is a step of co-extruding a first resin composition and a third resin composition to form a precursor comprising a substrate layer (a) and an acrylic layer (c).

[0164] [First Resin Composition] The first resin composition comprises polycarbonate resin. In addition, the first resin composition may also contain plasticizers, additives, etc.

[0165] The polycarbonate resin, plasticizer, and additives used are materials as described above.

[0166] The composition of the first resin composition may be adjusted as appropriate to achieve the composition required for the substrate layer (a).

[0167] [Third Resin Composition] The third resin composition contains (meth)acrylic resin. In addition, the third resin composition may also contain additives, etc.

[0168] The composition of the third resin composition may be adjusted as appropriate to achieve the composition required for the acrylic layer (c).

[0169] [Precursor Formation Methods] The precursor is formed by co-extruding a first resin composition and a third resin composition. This allows the formation of a precursor comprising a substrate layer (a) and an acrylic layer (c).

[0170] The melting temperature of the first resin composition is preferably, but not particularly limited to, 230–320°C, and more preferably 260–300°C.

[0171] The cooling temperature of the first resin composition is preferably, but not particularly limited to, 50–200°C, and more preferably 70–150°C.

[0172] The melting temperature of the third resin composition is preferably, but not particularly limited to, 200–300°C, and more preferably 210–280°C.

[0173] The cooling temperature of the third resin composition is preferably, but not particularly limited to, 50–200°C, and more preferably 70–150°C.

[0174] <Process (2)> Step (2) is a step of forming a curable resin layer (b) containing a second resin composition on top of the acrylic layer (c) in the precursor formed by step (1).

[0175] [Second Resin Composition] The second resin composition comprises a (meth)acrylamide polymer with an acrylamide equivalent of 200–600 g / mol. In addition, the second resin composition may also contain polyfunctional acrylate compounds, inorganic particles, leveling agents, photopolymerization initiators, light stabilizers, polymerization inhibitors, additives, diluents, etc.

[0176] It should be noted that, among the diluents mentioned above, acetone, but not limited to, but not limited to, but including, are examples of diluents such as methyl ethyl ketone (MEK), cyclohexanone, etc. These diluents can be used alone or in combination of two or more.

[0177] The composition of the second resin composition may be adjusted as appropriate to achieve the composition required for the curable resin layer (b).

[0178] [Method for forming the curable resin layer (b)] The method for forming the curable resin layer (b) is preferably, but not particularly limited to, coating a second resin composition over an acrylic layer (c) in a precursor.

[0179] Examples of coating methods for the second resin composition include spraying, spin coating, doctor blade coating, gravure coating, and die coating.

[0180] The coating film formed by coating is preferably dried. For example, a curable resin layer (b) can be obtained by drying to evaporate the diluent that may be present in the second resin composition.

[0181] The drying temperature of the coating is preferably 50–200°C, more preferably 70–150°C.

[0182] 3. Cured product According to one embodiment of the present invention, a cured product can be provided. The cured product is a product obtained by curing the aforementioned laminate, comprising a substrate layer (a), a curable resin layer (b), and an acrylic layer (c). It should be noted that, in this specification, "curing of the laminate" refers to the process of curing the curable resin layer (b) of the laminate to obtain a cured film. "Curved film" refers to a cured film (single-layer film) obtained by curing the curable resin layer (b). Furthermore, "cured product" refers to a laminate consisting of two or more layers, including the cured film, derived from each layer of the laminate (such as the substrate layer (a)).

[0183] In one embodiment, the cured product is preferably a cured film having a substrate layer (a), an acrylic layer (c), and a curable resin layer (b) stacked sequentially.

[0184] In this case, the composition of the substrate layer (a) and the acrylic layer (c) is usually equivalent to the composition of the laminate.

[0185] The cured film of the curable resin layer (b) has very high hardness. As a result, the cured product can achieve high scratch resistance, chemical resistance, etc.

[0186] In one embodiment, the pencil hardness of the cured film surface of the curing resin layer (b) is preferably H or higher, more preferably 2H or higher, further preferably 3H or higher, and particularly preferably 3H to 5H. It should be noted that the "pencil hardness of the cured film surface of the curing resin layer (b)" is affected not only by the cured film of the curing resin layer (b) but also by other layers of the cured product (e.g., the composition of the substrate layer (a), the composition of the acrylic layer (c), etc.). Furthermore, in this specification, "pencil hardness" is measured using the method described in the examples.

[0187] Furthermore, in one embodiment, the cured material exhibits high fingerprint removability and weather-resistant adhesion. Additionally, even when cleaned with solvents, the cured material is less prone to cracking.

[0188] Since the cured material can be used as a thermoforming film (functional film, decorative film), it is preferable to mold it to cover the surface of a molded article. That is, in one embodiment, a molded article containing a thermoforming film of the cured material of the present invention disposed on the surface of the molded article is provided.

[0189] The molded articles described above are preferably, but not particularly limited to, molded articles with uneven surfaces. Examples of such molded articles include goggles, sinks, accordions, beds, and vehicle bodies.

[0190] In a preferred embodiment, the molded article is a molded article with an uneven surface, and the molded article is subjected to a three-dimensional decorative molding (TOM molding) process of the above-mentioned stacked body, so that a three-dimensional decorative molded article including a molded article with an uneven surface and a stacked body disposed on the above-mentioned uneven surface can be provided.

[0191] 4. Methods for manufacturing cured products According to one embodiment of the present invention, a method for manufacturing a cured material can be provided. The method for manufacturing a cured material includes a curing step of curing the aforementioned laminate. The method for manufacturing a cured material may also further include a molding step of molding the laminate onto the surface of a molded article.

[0192] [Molding Process] The molding process is a process of forming a laminate on the surface of the molded article. The molding process is preferably stereolithography. Because the curable resin layer (b) of the laminate is in an uncured state, the laminate has high formability, especially stereolithographic formability. As a result, even when stereolithography is performed, the laminate has high conformability, and even if the laminate is cleaned with solvent after molding, cracks are not easily formed.

[0193] (Molded product) Molded articles may be used, but are not specifically limited to, the articles described above.

[0194] (Laminated body) The above-mentioned products can be used as laminates.

[0195] (forming) As for molding, it is preferred, but not particularly limited to, three-dimensional molding, and more preferably, three-dimensional decorative (TOM) molding.

[0196] The above-described three-dimensional decoration (TOM) molding includes (1) a vacuum process in which a lower chamber with an upper opening and a molded article having a concave and convex surface is configured, an upper chamber with a lower opening and a heater is configured, and the laminate of the present invention held by the lower chamber and the upper chamber are formed into an airtight state, thereby achieving a vacuum condition; (2) a heating process in which the laminate is heated using the heater; (3) a contact process in which the molded article having a concave and convex surface is brought into contact with the heated laminate; (4) a vacuum environment unsealing process in which the upper chamber reaches atmospheric pressure conditions; and (5) a vacuum environment unsealing process in which the lower chamber reaches atmospheric pressure conditions.

[0197] Additionally, it may also include an upper chamber pressurization process, which introduces compressed air into the upper chamber after the upper chamber vacuum environment unsealing process. Furthermore, it may also include a finishing process, which removes a portion of the laminate disposed on the uneven surface, after the lower chamber vacuum environment unsealing process.

[0198] [Curing Process] The curing process is the process of curing the laminate. More specifically, it is the process of curing the curable resin layer (b) in the laminate through a curing reaction to obtain a cured film of the curable resin layer (b).

[0199] The curing reaction is preferably, but not particularly limited to, being achieved by irradiating an active energy beam.

[0200] Examples of active energy beams include ultraviolet light, electron beams, and radiation, with ultraviolet light being the preferred choice.

[0201] The irradiation dose of the active energy beam is preferably, but not particularly limited to, 100–5000 mJ / cm², calculated as the cumulative exposure dose at a UV wavelength of 365 nm. 2 More preferably, 300–3000 mJ / cm 2 .

[0202] Example The following examples illustrate the present invention in detail, but the present invention is not limited to these examples.

[0203] 1. Measurement Method (1) Glass transition temperature The glass transition temperature (Tg) of various resins and resin compositions was measured under the following differential scanning calorimetry (DSC) conditions with two rounds of heating and cooling, and the glass transition temperature during the second round of heating was measured.

[0204] The intersection of the straight line extending from the low-temperature baseline to the high-temperature side (line A) and the tangent at the inflection point (tangent B) is defined as the glass transition initiation temperature (Tig). The intersection of the straight line extending from the high-temperature baseline to the low-temperature side (line C) and the tangent at the inflection point (tangent B) is defined as the glass transition end temperature (Teg). The midpoint between the glass transition initiation temperature (Tig) and the glass transition end temperature (Teg) is defined as the glass transition median temperature (Tmg).

[0205] Measurement start temperature: 30℃ Heating rate: 10℃ / min Reaching temperature: 250℃ Cooling rate: 20℃ / min Measuring device: Differential scanning calorimeter "DSC7020" (manufactured by Hitachi Advanced Technology & Science Co., Ltd.) (2) Viscosity-average molecular weight The viscosity-average molecular weight was calculated based on the Schnell viscosity formula.

[0206] Specifically, firstly, the intrinsic viscosity [η] (in dL / g) of the resin was measured using dichloromethane as a solvent. The temperature was set at 25°C. The specific viscosity [η] at various solution concentrations [C] (g / dL) was measured using an Ubbelohde viscometer. sp Measurements were performed. Based on the obtained specific viscosity value and concentration, the intrinsic viscosity was calculated according to the following formula. Then, based on Schnell's viscosity formula, i.e., η = 1.23 × 10⁻⁶, ﹣4 Mv 0.83 The viscosity-average molecular weight [Mv] was calculated.

[0207] (3) Weight-average molecular weight The weight-average molecular weight (Mw) was measured by gel permeation chromatography.

[0208] Specifically, the gel permeation chromatography system used an LC-20AD system (manufactured by Shimadzu Corporation) as the column, connected to an LF-804 (manufactured by Shodex Corporation). The column temperature was set to 40°C. The RI detector used was a RID-10A (manufactured by Shimadzu Corporation). Chloroform was used as the eluent, and the calibration curve was plotted using standard polystyrene (manufactured by Tosoh Corporation, Japan).

[0209] (4) Acryloyl equivalent Acryloyl equivalent is calculated using the formula "molecular weight / number of (meth)acryloyl groups".

[0210] (5) Average particle size The average particle size was calculated by randomly selecting 30 inorganic particles observed by transmission electron microscopy (TEM), taking the maximum distance between two points on the outer surface of each particle as the particle size, and calculating their average value.

[0211] (6) Melt viscosity Melt viscosity was measured using a capillary rheometer. Specifically, the (meth)acrylic resin was pre-dried at 90°C for 4 hours, and then the melt viscosity was measured using a capillary rheometer. Measurements were taken at a temperature of 230°C, a capillary length of 10 mm, a capillary diameter of 1 mm, a reactor diameter of 9.55 mm, and a shear rate of 122 sec. ﹣1 It was carried out under certain conditions.

[0212] The capillary rheometer used was a Capilograph 1D PMD-C (manufactured by Toyo Seiki Co., Ltd.).

[0213] 2. Fabrication of laminated structures [Example 1] A laminate consisting of a substrate layer (a), an acrylic layer (c), and a curable resin layer (b) stacked sequentially was manufactured.

[0214] (1) Preparation of the substrate layer (a) and acrylic layer (c) laminate (precursor) A TEX30α twin-screw extruder (manufactured by Nippon Steel Corporation) with a screw diameter of 32 mm and a screw L / D of 31.5 and equipped with a vent was used to melt-blend polycarbonate resin T-1380 (a bisphenol A (BPA) type polycarbonate resin with p-HBAHE as a chain terminator, viscosity-average molecular weight: 25500, Tig: 126℃, Tmg: 131℃, manufactured by Mitsubishi Gas Chemical Co., Ltd.) at a barrel temperature of 280℃. The granules were obtained by cutting the stock.

[0215] A laminate (precursor) consisting of a substrate layer (a) and an acrylic layer (c) was prepared using the above-mentioned granules and PMMA (polymethyl methacrylate) resin Delpet 80NB (melt viscosity: 3350 Pa·s, weight average molecular weight: 175000, manufactured by Asahi Kasei Corporation).

[0216] Specifically, a multi-layer extrusion unit was used, comprising a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feeding mechanism connected to all extruders, and a 650 mm wide T-die connected to the feeding mechanism. PMMA resin (Delpet 80NB) was continuously introduced into the single-screw extruder with a shaft diameter of 32 mm at a barrel temperature of 280°C, and the granules were continuously introduced into the single-screw extruder with a shaft diameter of 65 mm at the same barrel temperature. In this case, the output rates of both PMMA resin and the granules were controlled to ensure that the thickness of the acrylic layer (c) of the PMMA resin was 60 μm and the thickness of the substrate layer (a) of the granules was 140 μm. The feeding mechanism connected to all extruders has a dual-material, dual-layer feeder, and the feed block connected to the full extruder has two types of dual-layer distribution pins. The material is laminarly stacked and extruded into a sheet shape using a T-die. It is then cooled while performing mirror transfer using three mirror finishing rollers with temperatures set at 100°C, 100°C, and 115°C from the upstream side. This process produces a laminate (precursor) containing a substrate layer (a) of polycarbonate resin T-1380 and an acrylic layer (c) containing PMMA resin Delpet 80NB.

[0217] (2) Fabrication of laminated bodies A laminate is formed by forming a curable resin layer (b) on top of the acrylic layer (c) in a laminate (precursor) of a substrate layer (a) and an acrylic layer (c).

[0218] A curable resin composition was obtained by mixing 70 parts by weight of an acryloyl-containing polymer SMP-360A (acryloyl equivalent: 360 g / mol, manufactured by Kyoei Chemical Co., Ltd.), 30 parts by weight of nano-silica PGM-AC4130Y (average particle size 45 nm, surface treated with acryloyl compounds, PGM dispersion, manufactured by Nissan Chemical Co., Ltd.), 3 parts by weight of photopolymerization initiator Omnirad184 (manufactured by IGM RESINS BV), 1 part by weight of fluorinated leveling agent RS-90 (manufactured by DIC Co., Ltd.), and diluent cyclohexanone. In this case, the amount of cyclohexanone added was set such that the solid component concentration of the curable resin composition reached 25% by weight.

[0219] A curable resin composition was applied to the acrylic layer (c) of a laminate consisting of a substrate layer (a) and an acrylic layer (c) using a doctor blade until the dried film thickness was 4 μm. The resulting coating was then dried at 130°C for 3 minutes to form a curable resin layer (b). This process produced a laminate consisting of a substrate layer (a), an acrylic layer (c), and a curable resin layer (b) stacked sequentially.

[0220] [Example 2] Except that the acrylic layer (c) was replaced with PMMA resin Acrypet VH4-001 (melt viscosity: 2650 Pa·s, weight average molecular weight: 160000, manufactured by Mitsubishi Chemical Corporation), the laminate was prepared in the same manner as in Example 1.

[0221] [Comparative Example 1] Except that the acrylic layer (c) was replaced with PMMA resin Delpet 80HD (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), the laminate was prepared in the same manner as in Example 1.

[0222] [Comparative Example 2] Except that the acrylic layer (c) was replaced with PMMA resin Acrypet VH-001 (melt viscosity: 2060 Pa·s, weight average molecular weight: 114000, manufactured by Mitsubishi Chemical Corporation), the laminate was prepared in the same manner as in Example 1.

[0223] [Comparative Example 3] A laminate consisting of an acrylic layer (c) and a curable resin layer (b) was manufactured.

[0224] (1) Preparation of a monolayer film composed of an acrylic layer (c) A monolayer film (200 μm thick) consisting of an acrylic layer (c) was prepared using Delpet 80NB.

[0225] Specifically, a T-die melt extruder, specifically a TEX30α twin-screw extruder (manufactured by Nippon Steel Corporation) with a screw diameter of 32mm and a screw L / D ratio of 31.5 and equipped with a vent, was used. PMMA resin Delpet 80NB was continuously introduced and extruded at a barrel temperature of 280°C. The PMMA resin output was controlled to ensure a 200μm thickness for the acrylic layer (c). The extruded material was extruded into a sheet using a T-die connected to the extruder. The sheet was then cooled while performing a mirror transfer process using three mirror-finishing rollers set to temperatures of 90°C, 90°C, and 100°C from the upstream side, resulting in a single-layer film of the acrylic layer (c) of Delpet 80NB.

[0226] (2) Fabrication of laminated bodies On top of the acrylic layer (c), a curable resin layer (b) with a dried film thickness of 4 μm was formed in the same manner as in Example 1, and a laminate of the acrylic layer (c) and the curable resin layer (b) was produced.

[0227] [Comparative Example 4] A laminate of a base material layer (a) and a curable resin layer (b) was produced.

[0228] (1) Preparation of a single-layer film composed of the base material layer (a) Using the polycarbonate resin pellets T-1380 obtained in the same manner as in Example 1, a single-layer film (200 μm thick) composed of the base material layer (a) was prepared.

[0229] Specifically, a T-die melt extruder equipped with a vent port of a twin-screw extruder TEX30α (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 32 mm and a screw L / D = 31.5 was used. The above pellets were continuously introduced and extruded under the condition of a barrel temperature of 280°C. In this case, the discharge amount of the above pellets was controlled so that the thickness of the base material layer (a) of the above pellets was 140 μm. It was extruded into a sheet shape using a T-die connected to the extruder and cooled under the condition of mirror transfer using three mirror-finished rolls with temperatures set at 120°C, 120°C, and 120°C from the upstream side, and a single-layer film of the base material layer (a) containing polycarbonate resin T-1380 was produced.

[0230] (2) Manufacture of the laminate On the base material layer (a), a curable resin layer (b) was formed in the same manner as in Example 1. As a result, the base material layer (a) was dissolved by the coating solvent and the surface appearance deteriorated.

[0231] [Table 1] 3. Evaluation Various evaluations were carried out on the laminates manufactured in Examples 1 to 2 and Comparative Examples 1 to 3, which could be laminated with the curable resin composition without any problems.

[0232] <TOM moldability> TOM molding was carried out using the laminate, and the cracks were evaluated.

[0233] The laminate was cut to a size of 330mm × 330mm, and a bonding layer was attached to the substrate layer (a) side. A spare lens for goggles (manufactured by TRUSCO, model TSG-005SP) was used for the cover. The laminate with the bonding layer and the cover were assembled in the upper and lower chambers of a TOM molding machine NGF-0709-S (manufactured by Fuse Vacuum Co., Ltd.). After depressurizing the pressure in the upper and lower chambers to 0.1 kPa, the laminate with the bonding layer was heated to 140°C. Then, by introducing compressed air at 0.3 MPa only into the upper chamber, a TOM molded body was obtained.

[0234] The formability of TOM was evaluated as described below. The evaluation was conducted by five experts, and the judgment was made according to the majority rule principle. The results are shown in Table 2 below.

[0235] ○: The laminated body has no cracks. ×: Large cracks are visible in the laminated body. <Alcohol Wipe Test> An alcohol wiping test was performed on the cured product obtained by curing the laminate.

[0236] The cured product was manufactured as described below.

[0237] That is, ultraviolet light was applied to the curable resin layer (b) of the laminate using a conveyor-type UV irradiation device, ECS-401GX (manufactured by Eye Graphics). In this case, the ultraviolet irradiation was at 700 mJ / cm². 2 The experiment was conducted under conditions of (UV illuminometer manufactured by ORC Corporation, measuring wavelength 360nm). This resulted in a cured product formed by curing the curable resin layer (b) of the laminate.

[0238] The cured material was cut into 50mm × 100mm pieces and wound around a mandrel (radius: 32mm) with the cured film of the curing resin layer (b) convex. A gauze soaked in isopropyl alcohol (IPA) was pressed onto the surface of the laminate (the cured film of the curing resin layer (b)) for 10 seconds, and then the gauze was removed. This alcohol wiping test was performed five times.

[0239] The alcohol wiping test was evaluated as described below. The evaluation was conducted by five experts, and the judgment was made according to the majority rule principle. The results are shown in Table 2 below.

[0240] ◎: No cracks were observed in any of the five alcohol wiping tests.

[0241] ○: Cracks appeared only once in five alcohol wiping tests.

[0242] ×: Cracks appeared in more than two out of five alcohol wiping tests.

[0243] <Pencil Hardness> The pencil strength of the cured product obtained by curing the laminate was evaluated.

[0244] For the cured products prepared in the alcohol wiping test, the pencil hardness of the cured film surface of the cured resin layer (b) was measured according to the conditions of JIS K 5600-5-4:1999, and evaluated using the hardest pencil that did not cause scratches. The results are shown in Table 2 below.

[0245] It should be noted that the hardness of pencils increases in the following order: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H.

[0246] [Table 2] As shown in Table 2, the laminates of Examples 1 and 2 did not develop chemical cracks due to the alcohol wiping test.

Claims

1. A laminated body, characterized in that, Include: Substrate layer (a) containing polycarbonate resin A curable resin layer (b) containing a (meth)acrylamide polymer with an acrylamide equivalent of 200–600 g / mol, and An acrylic layer (c) containing (meth)acrylic resin is disposed between the substrate layer (a) and the curable resin layer (b). The (meth)acrylic resin at 122 sec ﹣1 The melt viscosity at 230℃, measured by shear rate, is 2200–10000 Pa·s. The thickness of the acrylic layer (c) is 10–120 μm.

2. The laminated body as described in claim 1, characterized in that, The melt viscosity of the (meth)acrylic resin is 3000-6000 Pa·s.

3. The laminate as described in claim 1, characterized in that, The weight-average molecular weight of the (meth)acrylic resin is 140,000 to 300,000.

4. The laminate as described in claim 1, characterized in that, The median glass transition temperature Tmg of the substrate layer (a) is 100–140 °C.

5. The laminate as described in claim 1, characterized in that, The polycarbonate resin is a bisphenol A type polycarbonate formed by reacting bisphenol A, a carbonate binder, and a monohydric phenol chain terminator as shown in formula (1) below. In the above formula (1), R 1 It is an alkyl group or an alkenyl group with 8 to 36 carbon atoms. R 2 Each of the following is independently hydrogen, a halogen atom, or an alkyl group having 1 to 20 carbon atoms that is optionally 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 that is optionally substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

6. The laminate as described in claim 5, characterized in that, The monophenol chain terminator represented by formula (1) comprises at least one selected from 2-hexyldecyl p-hydroxybenzoate, hexadecyl p-hydroxybenzoate, dodecyl p-hydroxybenzoate, and 2-ethylhexyl p-hydroxybenzoate.

7. The laminate as described in claim 1, characterized in that, The (meth)acrylamide polymer comprises repeating units as shown in formula (2) below. In the above equation (2), m is a single bond or an alkylene group having 1 to 4 carbon atoms. n is either 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 a hydrogen or an alkyl group having 1 to 12 carbon atoms that is optionally substituted with at least one of an epoxy group, a hydroxyl group, or a (meth)acryloyl group.

8. The laminate as described in claim 7, characterized in that, The (meth)acrylamide polymer comprises at least one of the repeating units shown in formulas (2-a) to (2-c) below. 。 9. The laminate as claimed in claim 1, characterized in that, The laminate is used in TOM molding.

10. A cured product, characterized in that, The cured material is obtained by curing the laminate according to any one of claims 1 to 9, comprising a substrate layer (a), a curable resin layer (b), and an acrylic layer (c).

11. The cured product as described in claim 10, characterized in that, The pencil hardness of the cured film surface of the curable resin layer (b) is above H.

12. A laminated body, characterized in that, Include: Substrate layer (a) containing polycarbonate resin A curable resin layer (b) containing a (meth)acrylamide polymer with an acrylamide equivalent of 200–600 g / mol, and An acrylic layer (c) containing (meth)acrylic resin is disposed between the substrate layer (a) and the curable resin layer (b). The laminate did not exhibit chemical cracking during the alcohol wiping test.

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