Laminate for thermoforming, and article including said laminate

Abstract

The present invention provides: a laminate for thermoforming which is capable of imparting excellent surface hardness and IPA crack resistance; and an article including the laminate.　A laminate for thermoforming according to the present disclosure sequentially includes a first polycarbonate resin layer, a second polycarbonate resin layer, and a curable hard coat precursor layer. The ratio of a constituent unit of formula 1 in the first polycarbonate resin contained in the first polycarbonate resin layer is 70 mol% or more, and the ratio of a constituent unit of formula 2 in the second polycarbonate resin contained in the second polycarbonate resin layer is 50 mol% or more. In formula 2, W represents a single bond, an alkylene group having 1-6 carbon atoms, an arylene group having 6-10 carbon atoms, or a cyclic alkylene group having 3-8 carbon atoms.

Description

Thermoforming laminate and article including said laminate

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to thermoformable laminates and articles including the laminates.

[0002] BACKGROUND ART Various techniques have been developed to date for applying a coating layer such as a hard coat layer to a laminate containing a polycarbonate resin layer.

[0003] For example, Patent Document 1 discloses a polycarbonate resin laminate with a hard coat layer, in which a specific penetration layer (layer B) and a specific hard coat layer (layer C) are laminated in this order on at least one surface of a polycarbonate resin substrate layer (layer A) having a thickness of 1 mm to 20 mm.

[0004] Patent Document 2 discloses a film with a hard coat layer, which has a hard coat layer containing metal oxide particles and an ultraviolet-curable resin on a film substrate containing a polycarbonate-based resin or the like.

[0005] Patent No. 7121201 JP 2022-171369 A

[0006] For example, a laminate sheet having a polycarbonate resin substrate and an uncured hard coat layer applied thereto may be applied to a support member by a thermoforming method, but the article thus obtained may not have sufficient surface hardness despite having a hard coat layer.

[0007] Furthermore, for example, if an acrylic resin layer or a rubber-blended acrylic resin layer is applied between the polycarbonate resin substrate and the uncured hard coat layer, the surface hardness can be improved, but cracks may occur in a crack test using isopropyl alcohol (sometimes referred to as "IPA").

[0008] Accordingly, an object of the present disclosure is to provide a thermoforming laminate that can impart excellent surface hardness and IPA crack resistance, and an article including the laminate.

[0009] Aspect 1: A thermoformable laminate comprising a first polycarbonate resin layer, a second polycarbonate resin layer, and a curable hard coat precursor layer in that order, wherein the first polycarbonate resin contained in the first polycarbonate resin layer contains structural units of the following formula 1 at a ratio of 70 mol % or more, and the second polycarbonate resin contained in the second polycarbonate resin layer contains structural units of the following formula 2 at a ratio of 50 mol % or more: In Formula 2, W represents a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a cyclic alkylene group having 3 to 8 carbon atoms. Aspect 2: The laminate according to Aspect 1, wherein the first polycarbonate resin layer contains an elastomer. Aspect 3: The laminate according to Aspect 1 or 2, wherein the structural unit of Formula 2 is a structural unit derived from at least one selected from the group consisting of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, and 2,2'-methyl-4,4'-biphenyldiol. Aspect 4: The laminate according to any one of Aspects 1 to 3, wherein the curable hard coat precursor layer contains an ultraviolet-curable resin composition. Aspect 5: The laminate according to any one of Aspects 1 to 4, wherein the curable hard coat precursor layer has a curing reaction rate of 2% or more and 50% or less. Aspect 6: The laminate according to any one of Aspects 1 to 5, wherein the second polycarbonate resin layer has a thickness of 10 to 100 μm. Aspect 7: The laminate according to any one of Aspects 1 to 6, wherein the curable hard coat precursor layer has a thickness of 1 to 20 μm. Aspect 8: The laminate according to any one of Aspects 1 to 7, comprising at least one layer selected from the group consisting of a design layer and an adhesive layer. Aspect 9: A method for producing an article, comprising: applying an adhesive layer to a surface of the first polycarbonate resin layer opposite to the second polycarbonate resin layer in the laminate according to any one of Aspects 1 to 8, laminating the laminate to a support member via the adhesive layer using a thermoforming method, and curing the curable hard coat precursor layer of the laminate to form a hard coat layer, thereby obtaining an article. Aspect 10: An article, wherein the laminate according to any one of aspects 1 to 8 includes an adhesive layer, the laminate is adhered to a support member via the adhesive layer, and the curable hard coat precursor layer is cured to form a hard coat layer. Aspect 11: The article according to aspect 10, which has a three-dimensional shape.

[0010] According to the present disclosure, it is possible to provide a thermoforming laminate that can impart excellent surface hardness and IPA crack resistance, and an article including the laminate.

[0011] 3A is a cross-sectional view of a thermoformable laminate according to an embodiment of the present disclosure; FIG. 3B is a cross-sectional view of an article including a thermoformable laminate according to an embodiment of the present disclosure; FIG. 3C is a photograph of a test sample bent in an IPA crack test; and FIG. 3D is a photograph of the test sample after the IPA crack test, showing the test sample in a cracked state.

[0012] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0013] The thermoformable laminate of the present disclosure comprises, in order, a first polycarbonate resin layer, a second polycarbonate resin layer, and a curable hard coat precursor layer, wherein the proportion of structural units of the following formula 1 in the first polycarbonate resin contained in the first polycarbonate resin layer is 70 mol % or more, and the proportion of structural units of the following formula 2 in the second polycarbonate resin contained in the second polycarbonate resin layer is 50 mol % or more: In formula 2, W represents a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a cyclic alkylene group having 3 to 8 carbon atoms.

[0014] Without being limited by theory, it is believed that the principle of action by which the thermoforming laminate of the present disclosure (sometimes simply referred to as the "laminate") can impart excellent surface hardness and IPA crack resistance is as follows.

[0015] Polycarbonate resin substrates subjected to thermoforming generally tend to have low surface hardness because they are easily deformed by heating. Therefore, even if a hard coat layer or a polycarbonate resin layer with higher hardness is applied to such substrates, it is thought that the surface hardness cannot be sufficiently improved due to the influence of the substrate.

[0016] On the other hand, when a polymethyl methacrylate (PMMA) resin layer or a rubber-containing acrylic resin layer, which have excellent surface hardness, is applied to such a substrate, it is possible to improve the surface hardness, but cracks tend to occur easily in the IPA crack test. Furthermore, even when a hard coat layer is further applied to such a laminate structure, the IPA crack resistance does not improve. The reason for this is thought to be that the acrylic resin layer containing PMMA resin or the like is easily affected by IPA.

[0017] The thermoformable laminate of the present disclosure includes a specific second polycarbonate resin layer between a first polycarbonate resin layer that can serve as a substrate and a curable hard coat precursor layer that can serve as a hard coat layer. It is believed that this specific second polycarbonate resin layer is an optimal resin layer that provides a good balance between enabling thermoforming and improving the surface hardness and IPA crack resistance of the hard coat layer. In other words, if only improving the surface hardness is sufficient, this may be solved by applying an acrylic resin layer containing PMMA resin or the like. However, when improving both the surface hardness and IPA crack resistance while enabling thermoforming, it is believed that the balance of the layer arrangement, in which the specific second polycarbonate resin layer is disposed between the first polycarbonate resin layer and the curable hard coat precursor layer, worked well.

[0018] The definitions of terms used in this disclosure are as follows:

[0019] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0020] 1, the thermoformable laminate of the present disclosure includes, in order, at least a first polycarbonate resin layer 105, a second polycarbonate resin layer 103, and a curable hard coat precursor layer 101. Here, the term "in order" means that when focusing on the three components of the first polycarbonate resin layer, the second polycarbonate resin layer, and the curable hard coat precursor layer, the laminate includes these components in this order, and other layers such as a design layer may be interposed between these components, for example, between the first polycarbonate resin layer and the second polycarbonate resin layer.

[0021] First, each layer constituting the thermoforming laminate of the present disclosure will be described below.

[0022] <First Polycarbonate Resin Layer> The first polycarbonate resin layer constituting the laminate of the present disclosure can be used, for example, as the base material of a thermoformable laminate. The first polycarbonate resin layer can be, for example, a layer containing 50% by mass or more, 70% by mass or more, or 90% by mass or more of the first polycarbonate resin relative to the total amount of resin components of the layer, or a layer consisting solely of the first polycarbonate resin. Here, the first polycarbonate resin can be a polycarbonate resin in which the proportion of the structural unit of the following formula 1 is 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 98 mol% or more, and 100 mol% or less, or less than 100 mol%. From the viewpoint of thermoformability, it is more preferable that the proportion of the structural unit of the following formula 1 in the first polycarbonate resin is 100%. The first polycarbonate resin can be one of these resins used alone or in combination of two or more:

[0023] The first polycarbonate resin is typically an aromatic polycarbonate resin, which can be obtained, for example, by reacting a dihydric phenol with a carbonate precursor by a solution method or a melt method, such as interfacial polycondensation, melt transesterification, solid-phase transesterification of a carbonate prepolymer, and ring-opening polymerization of a cyclic carbonate compound.

[0024] The first polycarbonate resin may contain 70 mol% or more of the structural unit of Formula 1, and may also contain one or more other structural units, or may not contain any other structural units. The structural unit of Formula 1 can be prepared, for example, using 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A) as the dihydric phenol. The other structural units can be prepared, for example, using 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, or the like as the dihydric phenol.

[0025] Carbonate precursors include, for example, carbonyl halides, carbonate esters, and haloformates, specifically phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0026] The first polycarbonate resin can be produced by using a dihydric phenol and / or a carbonate precursor alone or in combination of two or more thereof. In producing the first polycarbonate resin, a molecular weight modifier, a branching agent, a catalyst, etc. can be used as needed.

[0027] In some embodiments, the first polycarbonate resin can be specified by a viscosity average molecular weight, such as 1.0×10 ４ That's it, 1.3 x 10 ４ That's it, 1.5 x 10４ That's it, 1.8 x 10 ４ That's it, 2.0 x 10 ４ or more, or 2.2 x 10 ４ or more, and 10.0 × 10 ４ Below, 8.0 x 10 ４ Below, 5.0 x 10 ４ Below, 4.5 x 10 ４ Below, 4.0 x 10 ４ Below, 3.5 x 10 ４ Below, 3.2 x 10 ４ Below, 3.0 x 10 ４ or less, or 2.8 x 10 ４ Here, the "viscosity average molecular weight" in the present disclosure refers to the specific viscosity (η ｓｐ ) into the following formulas a and b. In the case of a mixture of two or more polycarbonate resins, the molecular weight of the entire mixture is expressed as: η ｓｐ / c = [η] + 0.45 × [η] ２ c...Formula a [η]=1.23×10 －４ M ０．８３ ...Equation b (where c = 0.7 g / dL, [η] is the intrinsic viscosity.)

[0028] In some embodiments, the first polycarbonate resin can be defined by its glass transition temperature (Tg). From the viewpoint of thermoformability, the glass transition temperature is preferably 100°C or higher, 105°C or higher, 110°C or higher, 115°C or higher, or 120°C or higher, and is preferably 145°C or lower, 140°C or lower, 130°C or lower, 125°C or lower, or 120°C or lower. Here, the glass transition temperature refers to a value measured by differential scanning calorimetry (DSC).

[0029] The first polycarbonate resin layer of the present disclosure may contain various components as appropriate within the range that does not adversely affect the effects of the present disclosure. Examples of such optional components include elastomers, heat stabilizers, release agents, infrared absorbers, ultraviolet absorbers, antioxidants, light stabilizers, foaming agents, reinforcing agents (e.g., talc, mica, clay, wollastonite, calcium carbonate, glass fibers, glass beads, glass balloons, milled fibers, glass flakes, carbon fibers, carbon flakes, carbon beads, carbon milled fibers, metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, and various other components. Examples of optional components include: seed whiskers), flame retardants (e.g., halogen-based flame retardants, phosphate ester-based flame retardants, metal salt-based flame retardants, red phosphorus-based flame retardants, silicone-based flame retardants, fluorine-based flame retardants, and metal hydrate-based flame retardants), colorants (e.g., pigments such as carbon black and titanium oxide, and dyes), light diffusing agents (e.g., acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, and calcium carbonate particles), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., particulate titanium oxide and particulate zinc oxide), impact modifiers such as graft rubber, and photochromic agents. These optional components can be used alone or in combination.

[0030] Among the optional components, from the viewpoint of thermoformability, it is preferable to use an elastomer, and it is more preferable to use the elastomer in combination with the first polycarbonate resin. The elastomers can be used alone or in combination of two or more kinds.

[0031] Among the elastomers, from the viewpoint of thermoformability, thermoplastic elastomers are preferred, and polyester-based thermoplastic elastomers are more preferred. The polyester-based thermoplastic elastomer is preferably a multiblock copolymer comprising a hard segment composed of polybutylene terephthalate units and a soft segment composed of polyester units having an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid as dicarboxylic acid components and a diol having 5 to 15 carbon atoms as a diol component.

[0032] The hard segment composed of the polybutylene terephthalate unit has excellent compatibility with polycarbonate resins, is preferable from the viewpoints of transparency and thermoformability, and can also exhibit good properties in terms of strength, etc. Polybutylene terephthalate may contain other components as copolymerization components to the extent that the effects of the present disclosure are not impaired. The proportion of such copolymerization components is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, of the total components (100 mol%) of both the dicarboxylic acid component and the diol component. The intrinsic viscosity of the polymer that becomes the hard segment is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5.

[0033] The soft segment consisting of polyester units having an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component refers to a segment in which the melting point of the polymer formed from the segment is 100°C or lower, or which is liquid and amorphous at 100°C. The intrinsic viscosity of the polymer that becomes the soft segment is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5. The soft segment used is a soft segment consisting of polyester units having an aromatic dicarboxylic acid and / or an aliphatic carboxylic acid as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component (hereinafter sometimes referred to as "SS-1"). SS-1 is preferred because it provides extremely good transparency.

[0034] From the viewpoint of obtaining better transparency, the soft segment SS-1 preferably contains 60 to 99 mol% of aromatic dicarboxylic acid and 1 to 40 mol% of aliphatic dicarboxylic acid, based on a total of 100 mol% of dicarboxylic acid components. It is more preferable that the aromatic dicarboxylic acid content is 70 to 95 mol% and the aliphatic dicarboxylic acid content is 5 to 30 mol%. It is even more preferable that the aromatic dicarboxylic acid content is 85 to 93 mol% and the aliphatic dicarboxylic acid content is 7 to 15 mol%. It is particularly preferable that the aromatic dicarboxylic acid content is 89 to 92 mol% and the aliphatic dicarboxylic acid content is 8 to 11 mol%.

[0035] The aromatic dicarboxylic acid of SS-1 is preferably at least one selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenylcarboxylic acid, bis(4-carboxyphenyl)methane, and bis(4-carboxyphenyl)sulfone, with terephthalic acid and isophthalic acid being more preferred, and isophthalic acid being particularly preferred from the viewpoint of reducing crystallinity.

[0036] As the aliphatic dicarboxylic acid of SS-1, straight-chain aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as succinic acid, adipic acid, and sebacic acid are preferred, with sebacic acid being particularly preferred.

[0037] As the diol component of SS-1 having 5 to 15 carbon atoms, linear aliphatic diols having 6 to 12 carbon atoms such as hexamethylene glycol, decamethylene glycol, 3-methylpentanediol, and 2-methyloctamethylenediol are more preferred, with hexamethylene glycol being particularly preferred.

[0038] SS-1 is particularly preferred from the viewpoints that it has high compatibility with polycarbonate resins, can produce highly transparent products, and has good surface properties and transparency after thermoforming. More specifically, SS-1 is preferably a polyester composed of isophthalic acid, sebacic acid, and hexamethylene glycol.

[0039] In the present disclosure, the ratio of hard segments to soft segments in the polyester-based thermoplastic elastomer is preferably 20 to 70% by mass of hard segments and 80 to 30% by mass of soft segments, and more preferably 20 to 40% by mass of hard segments and 80 to 60% by mass of soft segments, based on 100% by mass of the elastomer. From the viewpoint of strength, the intrinsic viscosity of the polyester-based thermoplastic elastomer is preferably 0.6 or more, more preferably in the range of 0.8 to 1.5, and even more preferably in the range of 0.8 to 1.2. Here, the intrinsic viscosity is a value measured in o-chlorophenol at 35°C.

[0040] The polyester-based thermoplastic elastomer is preferably contained in the first polycarbonate resin layer in an amount of 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more, 20 parts by mass or less, 18 parts by mass or less, or 15 parts by mass or less, per 100 parts by mass of the polycarbonate resin in the first polycarbonate resin layer, because this allows the glass transition temperature of the first polycarbonate resin layer to be set in a suitable range, thereby improving thermoformability.

[0041] There are no particular limitations on the method for producing the first polycarbonate resin layer, and examples of such a production method include a melt extrusion method and a solution casting method.

[0042] Specific examples of the melt extrusion method include feeding a fixed amount of the first polycarbonate resin into an extruder, heating and melting it, extruding the molten resin from the tip of a T-die onto a mirror-finished roll in the form of a sheet or film, taking it up while cooling it with multiple rolls, and cutting it to an appropriate size or winding it up when it solidifies.

[0043] A specific example of the solution casting method is to cast a solution (concentration: 5% to 40%) of the first polycarbonate resin in methylene chloride onto a mirror-polished stainless steel plate from a T-die, peel off the sheet or film while passing the sheet or film through a stepwise temperature-controlled oven, remove the solvent from the peeled sheet or film, and then cool and wind it up.

[0044] The thickness of the first polycarbonate resin layer is not particularly limited and can be appropriately set depending on the intended use of the thermoformable laminate, etc. For example, from the viewpoint of thermoformability, etc., the thickness of the first polycarbonate resin layer is preferably 20 μm or more, 50 μm or more, 70 μm or more, 100 μm or more, or 120 μm or more, and is preferably 3,000 μm or less, 2,500 μm or less, 2,000 μm or less, 1,500 μm or less, 1,000 μm or less, 800 μm or less, 500 μm or less, or 300 μm or less.

[0045] <Second Polycarbonate Resin Layer> The second polycarbonate resin layer constituting the laminate of the present disclosure may be, for example, a layer containing 50% by mass or more, 70% by mass or more, or 90% by mass or more of the second polycarbonate resin relative to the total amount of the resin components of the layer, or a layer consisting solely of the second polycarbonate resin. Here, the second polycarbonate resin may be a polycarbonate resin in which the proportion of the structural unit of the following formula 2 is 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 98 mol% or more, 100 mol% or less, less than 100 mol%, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, or 50 mol% or less. The proportion of the structural unit of the following formula 2 in the second polycarbonate resin may be 100%. The second polycarbonate resin may be used alone or in combination of two or more: In formula 2, W represents a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a cyclic alkylene group having 3 to 8 carbon atoms.

[0046] The second polycarbonate resin is also typically an aromatic polycarbonate resin, and like the first polycarbonate resin, such an aromatic polycarbonate resin can be obtained, for example, by reacting a dihydric phenol with a carbonate precursor by a solution method or a melt method.

[0047] The second polycarbonate resin may contain 50 mol% or more of the structural unit of the above formula 2, and may contain one or more other structural units, or may not contain any other structural units. By using a second polycarbonate resin containing 50 mol% or more of the structural unit of the above formula 2, a second polycarbonate resin layer can be obtained that has thermoformability and excellent surface hardness and IPA crack resistance. In some embodiments, the hardness of the second polycarbonate resin layer is higher than the hardness of the first polycarbonate resin layer. By using such a second polycarbonate resin layer, the surface hardness and IPA crack resistance of the entire thermoformed laminate can be further improved.

[0048] From the viewpoints of thermoformability, surface hardness, and IPA crack resistance, the structural unit of formula 2 preferably contains a structural unit derived from at least one selected from the group consisting of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, and 2,2'-methyl-4,4'-biphenyldiol, and more preferably contains a structural unit derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane.

[0049] The second polycarbonate resin may contain other structural units in addition to the structural unit of Formula 2. Examples of other structural units include structural units derived from at least one selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)sulfide, and bis(4-hydroxyphenyl)sulfone. In particular, from the viewpoints of thermoformability, surface hardness, and IPA crack resistance, when the second polycarbonate resin contains other structural units, it is preferable that such structural units include structural units derived from 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), i.e., structural units of Formula 1 described above. From the viewpoints of thermoformability, surface hardness, and IPA crack resistance, the proportion of other structural units (for example, the structural units of the above-mentioned formula 1) is preferably 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 2 mol% or less, or 0 mol% or more, or more than 0 mol%.

[0050] In some embodiments, the second polycarbonate resin can be specified by a viscosity average molecular weight, similar to that of the first polycarbonate resin. ４ That's it, 1.3 x 10 ４ That's it, 1.5 x 10 ４ That's it, 1.8 x 10 ４ That's it, 2.0 x 10 ４ or more, or 2.2 x 10 ４ or more, and 10.0 × 10 ４ Below, 8.0 x 10 ４ Below, 5.0 x 10 ４ Below, 4.5 x 10 ４ Below, 4.0 x 10 ４ Below, 3.5 x 10 ４ Below, 3.2 x 10 ４ Below, 3.0 x 10 ４ or less, or 2.8 x 10４ It can be as follows:

[0051] In some embodiments, the second polycarbonate resin can be defined by its glass transition temperature (Tg). From the viewpoint of thermoformability, the glass transition temperature is preferably 105°C or higher, 110°C or higher, 115°C or higher, 120°C or higher, or 125°C or higher, and is preferably 150°C or lower, 145°C or lower, 140°C or lower, 135°C or lower, or 130°C or lower.

[0052] The second polycarbonate resin layer may also contain the above-mentioned optional components as appropriate, similar to the first polycarbonate resin layer.

[0053] There are no particular limitations on the method for applying the second polycarbonate resin layer to the surface of the first polycarbonate resin layer, and examples of such methods include thermocompression bonding and coextrusion.

[0054] Any method can be adopted as the thermocompression bonding method. Examples of such methods include a method in which a first polycarbonate resin layer and a second polycarbonate resin layer, each formed into a film or sheet, are thermocompression bonded together using a laminator or a press, and a method in which a film or sheet-like second polycarbonate resin layer is thermocompression bonded to a film or sheet-like first polycarbonate resin layer immediately after extrusion. Among these, from the viewpoint of productivity, etc., a method in which a film or sheet-like second polycarbonate resin layer is thermocompression bonded continuously to a film or sheet-like first polycarbonate resin layer immediately after extrusion is advantageous.

[0055] The conditions for thermocompression bonding can be appropriately adjusted depending on the thicknesses of the first and second polycarbonate resin layers, the state of the bonding surfaces, etc. Specific examples of such conditions include a temperature equal to or higher than the glass transition temperature of the second polycarbonate resin layer, for example, a temperature of from the glass transition temperature of the second polycarbonate resin layer −10° C. to the glass transition temperature +150° C., preferably from the glass transition temperature −5° C. to the glass transition temperature +100° C., and a pressure of 0.05 to 5 kg / cm. ２ about 0.1 to 1 kg / cm ２The pressure can be as low as 100 kJ / s.

[0056] There are no particular limitations on the method for producing the film- or sheet-like second polycarbonate resin layer used in the thermocompression bonding method, and examples of such production methods include melt extrusion and solution casting.

[0057] Specific examples of the melt extrusion method include feeding a fixed amount of the second polycarbonate resin into an extruder, heating and melting it, extruding the molten resin from the tip of a T-die onto a mirror-finished roll in the form of a sheet or film, taking it up while cooling it with multiple rolls, and cutting it to an appropriate size or winding it up when it solidifies.

[0058] A specific example of the solution casting method is to cast a solution (concentration: 5% to 40%) of the second polycarbonate resin in methylene chloride onto a mirror-polished stainless steel plate from a T-die, peel off the sheet or film while passing the sheet or film through a stepwise temperature-controlled oven, remove the solvent from the peeled sheet or film, and then cool and wind it up.

[0059] The coextrusion method, which is a method for applying a second polycarbonate resin layer to the surface of a first polycarbonate resin layer, can be carried out, for example, by melt-extruding the second polycarbonate resin in an auxiliary extrusion step at a temperature ranging from its glass transition temperature to glass transition temperature +230°C, preferably glass transition temperature +50°C to glass transition temperature +200°C, and melt-extruding the first polycarbonate resin in a main extrusion step at a temperature ranging from its glass transition temperature to glass transition temperature +230°C, preferably glass transition temperature +50°C to glass transition temperature +200°C, followed by extrusion lamination using a known method such as a multi-manifold method or a feedblock method.

[0060] The thickness of the second polycarbonate resin layer is not particularly limited and can be appropriately set depending on the required performance (e.g., thermoformability, surface hardness, and IPA crack resistance), etc. For example, from the viewpoint of thermoformability, surface hardness, and IPA crack resistance, the thickness of the second polycarbonate resin layer is preferably 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more, and is preferably 100 μm or less, 90 μm or less, 80 μm or less, or 70 μm or less.

[0061] <Curable Hard Coat Precursor Layer> The thermoformable laminate of the present disclosure includes a curable hard coat precursor layer. The thermoformable laminate can be applied to, for example, a support member having a three-dimensional shape, and then subjected to a curing treatment after thermoforming. Therefore, the term "curable hard coat precursor layer" refers to a hard coat layer in which the curable resin component constituting the hard coat layer is in an uncured or semi-cured state, i.e., a state in which the hard coat layer has not been cured to the extent that it exhibits the desired hard coat performance (e.g., a state in which the hard coat layer has not been completely cured). Specifically, the curing reaction rate of the curable hard coat precursor layer (i.e., the curing reaction rate of the curable resin component) is preferably 2% or more, 3% or more, 4% or more, or 5% or more, and preferably 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less. When the curing reaction rate is within this range, the curable hard coat precursor layer reaches a semi-cured state, reducing tackiness and improving workability. Furthermore, the flexibility of the curable hard coat precursor layer itself is improved, allowing it to suitably conform to complex shapes during thermoforming. The curing reaction rate of the curable hard coat precursor layer can be adjusted, for example, by the amount of ultraviolet light irradiation, and can also be determined by the ATR method using FT-IR measurement before and after the curing reaction of the precursor layer, as described below. When the three-dimensional shape of the support member to which the thermoforming laminate is applied is gentle, the curable hard coat precursor layer can be subjected to a curing treatment before applying the thermoforming laminate to the support member.

[0062] The curable hard coat precursor layer may have a single layer structure or a multilayer structure, and may be applied to the entire surface of the thermoforming laminate, or may be applied to a part of the surface.

[0063] The material constituting the curable hard coat precursor layer is not particularly limited, and examples thereof include resin materials such as (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. The resin materials can be used alone or in combination. Among these, (meth)acrylic resins and silicone resins are preferred from the viewpoints of adhesion, thermoformability, surface hardness, and IPA crack resistance. The resin material may be an active energy ray (e.g., ultraviolet light, X-rays, or electron beam) curable resin or a thermosetting resin. From the viewpoint of productivity, the curable hard coat precursor layer preferably contains an ultraviolet-curable resin composition. Furthermore, the content of the resin material in the curable hard coat precursor layer is preferably in the range of 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, 100% by mass or less, less than 100% by mass, 95% by mass or less, or 90% by mass or less, based on the total solid content of the curable hard coat precursor layer. Within such a range, productivity is excellent and performance such as thermoformability, surface hardness, and IPA crack resistance can be further improved. An example of a composition containing a resin material will be described below.

[0064] ((Meth)acrylic resin composition) Examples of the (meth)acrylic resin include (meth)acrylic resins that can be prepared using various polyfunctional (meth)acrylate monomers such as polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, phosphazene (meth)acrylate, melamine (meth)acrylate, and amino (meth)acrylate. Among these, urethane (meth)acrylate is preferred from the viewpoints of adhesion, thermoformability, surface hardness, and IPA crack resistance. In addition, when obtaining a (meth)acrylic resin, a monofunctional monomer can also be used as appropriate in addition to the polyfunctional monomer. The monomers used can be used alone or in combination of two or more.

[0065] In some embodiments, the curable hard coat precursor layer of the present disclosure includes an ultraviolet-curable resin composition. Such a composition may typically include a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and any known material that can generate radicals or the like by ultraviolet light to initiate a polymerization reaction can be used. The photopolymerization initiator can be used alone or in combination of two or more types.

[0066] The type of photopolymerization initiator is not particularly limited, and examples thereof include acylphosphine oxide-based photopolymerization initiators, phenylglyoxylic acid ester-based photopolymerization initiators, benzyl ketal-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, and α-aminoalkylphenone-based photopolymerization initiators.

[0067] The content of the photopolymerization initiator is not particularly limited, and may be, for example, 0.10 parts by mass or more, 0.50 parts by mass or more, 1.0 parts by mass or more, 2.0 parts by mass or more, or 3.0 parts by mass or more relative to 100 parts by mass of all monomer components in the resin composition that forms the curable hard coat precursor layer, and may be 10 parts by mass or less, 9.0 parts by mass or less, or 8.5 parts by mass or less.

[0068] (Silicone-Based Resin Composition) Examples of silicone-based resin compositions that can constitute the curable hard coat precursor layer include compositions containing (1) inorganic oxide particles surface-modified with a hydrolyzable silane compound having an active energy ray-reactive group, (2) a compound containing three or more (meth)acrylic groups, (3) a compound containing one or two (meth)acrylic groups, and (4) a radical-based photopolymerization initiator.

[0069] (1) Inorganic oxide particles surface-modified with a hydrolyzable silane compound having an active energy ray-reactive group. Examples of inorganic oxide particles include oxide particles of Si, Ti, Al, Zn, Zr, In, Sn, Sb, Ce, or Fe, or composite oxide particles thereof. Specific examples of metal oxide particles include particles of silica, alumina, zirconia, titania, and cerium oxide. Since the inorganic oxide particles are surface-modified with a hydrolyzable silane compound having an active energy ray-reactive group, the reactive silica particles undergo a crosslinking reaction upon irradiation with active energy rays during curing of the composition, and can be fixed in the polymer matrix. The inorganic oxide particles surface-modified with a hydrolyzable silane compound having an active energy ray-reactive group can be used alone or in combination of two or more types.

[0070] In some embodiments, the average particle size of the inorganic oxide particles is preferably 80 nm or less, more preferably 50 nm or less, from the viewpoint of transparency, etc. The lower limit of the average particle size can be 10 nm or more, 15 nm or more, or 20 nm or more. In the present disclosure, the average particle size can be measured using a particle size distribution analyzer using dynamic light scattering photon correlation spectroscopy.

[0071] The inorganic oxide particles are preferably silica particles, and more preferably silica particles having an average particle size of 50 nm or less. The silica particles may be non-porous, hollow, or porous.

[0072] Examples of hydrolyzable silane compounds having an active energy ray reactive group include silane coupling agents containing a (meth)acrylic group. Specific examples thereof include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldichlorosilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldimethylchlorosilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyltrichlorosilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, Examples of the hydrolyzable silane compound having an active energy ray reactive group include silane, γ-acryloxypropylmethyldichlorosilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyldimethylethoxysilane, γ-acryloxypropyldimethylchlorosilane, γ-acryloxymethyltrimethoxysilane, γ-acryloxymethyltriethoxysilane, γ-acryloxymethyltrichlorosilane, γ-acryloxymethylmethyldimethoxysilane, γ-acryloxymethylmethyldiethoxysilane, γ-acryloxymethylmethyldichlorosilane, γ-acryloxymethyldimethylmethoxysilane, γ-acryloxymethyldimethylethoxysilane, and γ-acryloxymethyldimethylchlorosilane. The hydrolyzable silane compound having an active energy ray reactive group can be used alone or in combination of two or more types.

[0073] The surface modification amount of the hydrolyzable silane compound having an active energy ray reactive group can be 0.1 mass% or more, 0.5 mass% or more, or 1 mass% or more, and 10 mass% or less, 8 mass% or less, or 5 mass% or less, relative to the particles.

[0074] Examples of methods for surface modification with a hydrolyzable silane compound having an active energy ray reactive group include a method in which a hydrolyzable silane compound having an active energy ray reactive group is hydrolyzed in the presence of silica particles.

[0075] It is preferable to use inorganic oxide particles dispersed as primary particles in a compound containing three or more (meth)acrylic groups and / or a compound containing one or two (meth)acrylic groups, which will be described later. By having the inorganic oxide particles exist as primary particles, a coating having good appearance, such as transparency, can be obtained.

[0076] Specifically, examples of such a method include a method in which inorganic oxide particles are physically dispersed in a (meth)acrylic group-containing compound using a dispersant or a dispersing device, and a method in which a (meth)acrylic group-containing compound is added to a solution in which inorganic oxide particles are dispersed, and then the original dispersant is distilled off.

[0077] (2) Compounds containing three or more (meth)acrylic groups Compounds containing three or more (meth)acrylic groups are the main components of the curable components together with the above-mentioned surface-modified inorganic oxide particles and compounds containing one or two (meth)acrylic groups, and form the matrix of the coating obtained after curing. The compounds containing three or more (meth)acrylic groups are components that disperse the above-mentioned inorganic oxide particles and also serve as binder components, and this compound allows for the production of cured products with excellent abrasion resistance and high hardness. Compounds containing three or more (meth)acrylic groups can be used alone or in combination of two or more.

[0078] The compound containing three or more (meth)acrylic groups is a compound having three or more (meth)acrylic groups in the molecule. Specific examples thereof include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, and triacrylated isocyanurate. Other examples include polymer components such as trifunctional or higher urethane(meth)acrylate, polyester(meth)acrylate, and hydrolysis condensate of hydrolyzable silane compounds having active energy ray reactive groups.

[0079] (3) Compound containing one or two (meth)acrylic groups The compound containing one or two (meth)acrylic groups is the main component of the curable component together with the surface-modified inorganic oxide particles and the compound containing three or more (meth)acrylic groups, and forms the matrix of the coating obtained after curing. The compound containing one or two (meth)acrylic groups can be used alone or in combination of two or more.

[0080] The compound containing one or two (meth)acrylic groups is a component for reducing the viscosity of the composition and can also be a component for improving adhesion to a polycarbonate resin layer or the like.

[0081] In order to reduce the viscosity of the composition, the viscosity of the compound containing one or two (meth)acrylic groups at 25°C is preferably 100 mPa s or less, particularly 50 mPa s or less. There is no particular restriction on the lower limit of the viscosity, and it can be 1 mPa s or more. Here, such viscosity can be measured using a rotational viscometer.

[0082] From the viewpoint of improving adhesion, the compound containing one or two (meth)acrylic groups preferably has a functional group such as a hydroxyl group or an epoxy group in the molecule.

[0083] Examples of compounds containing one or two (meth)acrylic groups include hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, diacrylated isocyanurate, and ethylene oxide-modified bisphenol A di(meth)acrylate.

[0084] From the viewpoint of adhesion, hardness, and the like, the blending amount of the above-mentioned component (1) is 25 to 70 parts by mass, preferably 35 to 60 parts by mass, per 100 parts by mass of the total of the components (1), (2), and (3); the blending amount of the component (2) is 20 to 70 parts by mass, preferably 30 to 55 parts by mass, per 100 parts by mass of the total of the components (1), (2), and (3); and the blending amount of the component (3) can be 5 to 30 parts by mass, preferably 10 to 20 parts by mass, per 100 parts by mass of the total of the components (1), (2), and (3).

[0085] (4) Radical Photopolymerization Initiator The radical photopolymerization initiator can be selected from, for example, ordinary ones such as acetophenone, benzoin, acylphosphine oxide, benzophenone, and thioxanthone. Specific examples include benzophenone, benzil, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzil dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4 ... Examples of the radical photopolymerization initiator include 2-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, a mixture of oxyphenylacetic acid 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, acylphosphine oxide derivatives, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethylbenzoyldiphenylphosphine. The radical photopolymerization initiator can be used alone or in combination of two or more.

[0086] Among these, from the viewpoint of curability, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethylbenzoyldiphenylphosphine are preferred.

[0087] From the viewpoints of curability, adhesion, and the like, the amount of the radical photopolymerization initiator to be blended is preferably 1 to 8 parts by mass, and more preferably 2 to 6 parts by mass, per 100 parts by mass of the total of the above-mentioned components (1), (2), and (3).

[0088] The curable hard coat precursor layer can be applied by known wet coating methods such as roll coating, spin coating, bar coating, and microgravure coating.

[0089] Various components can be appropriately blended into the curable hard coat precursor layer within a range that does not adversely affect the effects of the present disclosure. Examples of such optional components include heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, leveling agents, antifoaming agents, antifouling agents (e.g., surfactants), dispersants, silane coupling agents, surface modifiers, dyes, pigments, and fillers (e.g., organic fillers and inorganic fillers). The optional components can be used alone or in combination of two or more.

[0090] The thickness of the curable hard coat precursor layer is not particularly limited and can be appropriately set so as to exhibit the desired performance (e.g., surface hardness, abrasion resistance) depending on the application. Such a thickness can be, for example, 10 nm or more, 50 nm or more, 100 nm or more, 500 nm or more, 1 μm or more, 3 μm or more, or 5 μm or more. The upper limit of the thickness is not particularly limited and can be, for example, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less. Since the thermoformable laminate of the present disclosure includes a specific second polycarbonate resin layer between the first polycarbonate resin layer and the curable hard coat precursor layer, sufficient surface hardness can be exhibited after curing even if the curable hard coat precursor layer is thin. From the viewpoints of productivity, thermoformability, surface hardness, and IPA crack resistance, the thickness is preferably in the range of 1 to 20 μm. The thickness of the curable hard coat precursor layer can correspond to the thickness of the hard coat layer after curing.

[0091] The thickness of each layer in the thermoforming laminate of the present disclosure can be determined using a Digimatic caliper (ABS Digimatic Caliper CD-AX, manufactured by Mitutoyo Corporation) or a high-precision Digimatic micrometer (MDH-25MB, manufactured by Mitutoyo Corporation), and / or an optical microscope or a scanning electron microscope. For example, for a relatively thin layer such as a hard coat layer, an optical microscope or a scanning electron microscope is used to measure the cross section of the laminate in the thickness direction, and the thickness can be determined as the average value of the thicknesses of at least five arbitrary locations in the target layer of the laminate structure, for example, the hard coat layer. The thickness of the first polycarbonate resin layer that can be used as the substrate can be determined by measuring the thickness at any five or more locations in the laminate using a Digimatic caliper (ABS Digimatic Caliper CD-AX, manufactured by Mitutoyo Corporation) or a high-precision Digimatic micrometer (MDH-25MB, manufactured by Mitutoyo Corporation), calculating the average value, and then subtracting from this value the thicknesses of other layers (such as a hard coat layer) obtained using an optical microscope or a scanning electron microscope.

[0092] The pencil hardness of the surface of the hard coat layer after curing by irradiating the curable hard coat precursor layer with active energy rays such as ultraviolet rays is preferably H or more or 2H or more. There is no particular upper limit to the pencil hardness, and it can be 5H or less, 4H or less, or 3H or less. When the pencil hardness is in this range, it is possible to improve the abrasion resistance and scratch resistance.

[0093] Here, the pencil hardness refers to a value obtained by curing a precursor layer of a laminate having a curable hard coat precursor layer to prepare a test piece, and measuring the pencil hardness of the coating film (hard coat layer) on the test piece in accordance with JIS K5600-5-4-1999. Examples of curing conditions include an integrated light dose of 2,000 mJ / cm. ２ UV irradiation can be employed.

[0094] <Optional Layers> The thermoforming laminate of the present disclosure may further include one or more optional layers depending on the intended use, etc., to the extent that the effects of the present disclosure are not adversely affected. Examples of optional layers include a design layer, an adhesive layer, an anchor coat layer (sometimes referred to as a "primer layer"), an antistatic layer, a conductive layer, and a release liner. The optional layers can be used alone or in combination of two or more. For example, the design layer and adhesive layer will be described in detail below, but the optional layers are not limited to these.

[0095] (Design Layer) In some embodiments, the thermoforming laminate of the present disclosure can include a design layer. The design layer may be applied anywhere on the thermoforming laminate, but is preferably applied between the first polycarbonate resin layer (105) and the second polycarbonate resin layer (103) of the thermoforming laminate (100), and / or between the second polycarbonate resin layer (103) and the curable hard coat precursor layer (101), as shown in FIG. 1. When the design layer is applied in such a position, it can be protected by the second polycarbonate resin layer and / or the curable hard coat precursor layer or hard coat layer. The design layer may be formed over the entire surface to which it is applied, or may be formed partially. A thermoforming laminate including a design layer can also be referred to as a decorative sheet.

[0096] The design layer is not particularly limited as long as it is a layer that can exhibit design (decoration). Examples of the design layer include a colored layer that exhibits a special color or metallic color, and a design layer that can impart a pattern (for example, wood grain, stone grain), logo, picture, etc. The design layer may be of one type, or a combination of multiple types of design layers.

[0097] The thickness of the design layer may vary, for example, 1 μm or more, 2 μm or more, or 5 μm or more, and may be 50 μm or less, 30 μm or less, 10 μm or less, 8 μm or less, or 5 μm or less.

[0098] (Adhesive Layer) Various adhesive layers can be applied to the thermoforming laminate of the present disclosure. The adhesive layer may have a single layer configuration or a laminate configuration. The adhesive layer may be applied to the entire surface of the laminate, or may be applied partially. The adhesive layer is typically used when bonding the thermoforming laminate of the present disclosure to an adherend (support member), as shown in FIG.

[0099] There are no particular limitations on the adhesive that can form the adhesive layer. Examples of adhesives that can be used include commonly used (meth)acrylic, polyolefin, polyurethane, polyester, and rubber-based adhesives, such as solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, and UV-curable adhesives. The adhesives can be used alone or in combination. The adhesive layer can be applied by a known wet coating method or the like.

[0100] Various components can be appropriately blended into the adhesive layer as long as they do not adversely affect the effects of the present disclosure. Examples of such optional components include heat stabilizers, light stabilizers, UV absorbers, antioxidants, antistatic agents, flame retardants, dispersants, tackifiers, dispersants, plasticizers, leveling agents, defoamers, antifouling agents (e.g., surfactants), silane coupling agents, surface modifiers, dyes, pigments, and fillers (e.g., organic fillers and inorganic fillers). The optional components can be used alone or in combination of two or more.

[0101] The thickness of the adhesive layer is not limited to the following, but can be, for example, 5 μm or more, 10 μm or more, or 20 μm or more, and can be 200 μm or less, 100 μm or less, or 80 μm or less.

[0102] The overall thickness of the thermoforming laminate of the present disclosure is not particularly limited, and can be, for example, 50 μm or more, 70 μm or more, 100 μm or more, 120 μm or more, 150 μm or more, 170 μm or more, or 200 μm or more, and can be 5,000 μm or less, 4,000 μm or less, 3,000 μm or less, 2,500 μm or less, 2,000 μm or less, 1,500 μm or less, 1,000 μm or less, 800 μm or less, 500 μm or less, 300 μm or less, or 250 μm or less.

[0103] <<Method for Producing an Article>> The thermoforming laminate of the present disclosure can be used to produce an article (molded article) by various conventionally known molding methods. In these production methods, the constituent materials of the thermoforming laminate described above can be used in the same way.

[0104] In some embodiments, a method for producing an article of the present disclosure includes: (1) applying an adhesive layer to the surface of the first polycarbonate resin layer in the thermoforming laminate described above, opposite the surface of the second polycarbonate resin layer; (2) laminating the thermoforming laminate to a support member via the adhesive layer using a thermoforming method; and (3) curing the curable hard coat precursor layer of the thermoforming laminate to form a hard coat layer, thereby obtaining an article.

[0105] An example of a molding method for an article is the insert molding method, which is a method of in-mold decoration during injection molding. In this method, a thermoforming laminate that has been shaped in advance by vacuum forming, pressure forming, or the like to fit the shape of the cavity of an injection molding mold is set in the mold, and a molten resin is injected into the mold, and the thermoforming laminate is welded to a supporting member (a resin molded article) and integrated with the supporting member to obtain an article.

[0106] Other molding methods include, for example, a molding method in which a thermoforming laminate is attached to the cavity side of a mold under vacuum pressure, molten resin is injected therein, and heat and pressure are applied to bond the thermoforming laminate to a support member (a resin molded product) to obtain an article.

[0107] Other molding methods include lamination by vacuum molding or pressure molding. Heating the thermoforming laminate during thermoforming can be achieved using various methods, such as infrared heaters, electric heaters, high-frequency induction, halogen lamps, microwaves, high-temperature induction heaters (steam, etc.), and lasers. According to these methods, materials other than resin materials can be used for the support member.

[0108] Here, examples of materials for the support member include resin materials (e.g., polyolefin resin, polyester resin, (meth)acrylic resin, polycarbonate resin, acrylonitrile-butadiene-styrene copolymer), inorganic materials (e.g., glass, ceramic, concrete, gypsum, calcium silicate, natural stone, asphalt), rubber materials, cloth materials (e.g., woven fabrics, knitted fabrics, nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, stainless steel), and wood materials including paper.

[0109] The molding method described above is not limited to the following temperatures, but can generally be performed at temperatures of about 140°C to 180°C depending on the process. Therefore, the article can be cooled or allowed to cool as needed. The curable hard coat precursor layer applied to the article can then be cured by irradiating it with active energy rays (ultraviolet rays, visible light, infrared rays, or electron beams). The active energy rays may be polarized or unpolarized. Among active energy rays, ultraviolet rays are preferred in terms of equipment costs, safety, running costs, and the like. When curing is performed by ultraviolet irradiation, a photopolymerization initiator is typically used. Examples of ultraviolet energy ray sources that can be used include high-pressure mercury lamps, halogen lamps, xenon lamps, metal halide lamps, nitrogen lasers, electron beam accelerators, and radioactive elements. The ultraviolet irradiation dose is 100 to 5,000 mJ / cm as the cumulative exposure at an ultraviolet wavelength of 365 nm. ２ The range is preferably 300 to 3,000 mJ / cm ２ When the irradiation amount is within this range, a hard coat layer excellent in properties such as surface hardness can be obtained.

[0110] The oxygen concentration during irradiation with active energy rays is preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less. Such an atmosphere with a low oxygen concentration or an atmosphere free of oxygen can be obtained, for example, by replacing the atmosphere in at least the irradiation section of the irradiation device with an inert gas. Examples of inert gases include nitrogen, helium, neon, and argon.

[0111] In addition, when the three-dimensional shape of the support member to which the thermoforming laminate is applied is gentle, the curable hard coat precursor layer can be subjected to a curing treatment before applying the thermoforming laminate to the support member.

[0112] The article of the present disclosure can typically be obtained by the above-described manufacturing method. In some embodiments, the article of the present disclosure includes the above-described thermoforming laminate including the adhesive layer bonded to a support member via the adhesive layer, and the curable hard coat precursor layer is cured to form a hard coat layer.

[0113] In some embodiments, the article of the present disclosure has a three-dimensional shape. Here, the term "three-dimensional shape" refers to a three-dimensional shape that includes the Z axis in addition to a two-dimensional shape (a planar shape including only the X and Y axes). Here, the "three-dimensional shape" in the present disclosure may also include, for example, a curved shape.

[0114] The use form of the article is not particularly limited, and examples thereof include interior and exterior materials for automobiles, indicator panels for automobiles, electrical appliances, cosmetic cases, interior and exterior parts for building materials, cases for various devices or products, cases for miscellaneous items, switches, keys, keypads, handles, levers, buttons, and housings or exterior parts for home appliances and AV devices (for example, personal computers), mobile phones, and mobile devices.

[0115] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Physical property evaluations in the examples and comparative examples were performed using the following methods, and the results are summarized in Table 1. In the comparative examples, layers other than a polycarbonate resin layer were also used as intermediate layers, and the term "second polycarbonate resin layer" is inappropriate. Therefore, in Table 1, these layers are referred to as layers A to C. Here, layers A, B, and C in Table 1 correspond to layers 105, 103, and 101 in the layer structure shown in FIG. 1 . Furthermore, for example, "A / B" in the layer structure in Table 1 indicates a two-layer structure consisting of layers A and B. The "structural unit of formula 1" and "structural unit of formula 2" in Table 1 refer to the structural units of formula 1 and formula 2, respectively, that constitute the polycarbonate resin. Furthermore, the methods for measuring various physical properties described in the examples are not limited to the laminates and manufacturing methods thereof described in the examples, but can also be similarly performed on the laminates and manufacturing methods described above.

[0116] Examples 1 to 3 and Comparative Examples 1 to 7 In the physical property evaluations shown below, the evaluations of the curing reaction rate and formability of the C layer (curable hard coat precursor layer) are physical property evaluations before the curing treatment for making it function as a hard coat layer, and the evaluations of the surface hardness, IPA cracking, and chemical resistance are physical property evaluations after the curing treatment for making it function as a hard coat layer.

[0117] <Methods for Evaluating Various Physical Properties> (Curing Reaction Rate of Layer C) The curing reaction rate of the curable resin in the curable hard coat precursor layer (Layer C) was measured by the ATR method using FT-IR. More specifically, as a reference, an uncured coating layer that had been dried with hot air in a drying oven at 80°C for 2 minutes was measured, and the curing reaction rate was 1730 cm －１ The peak located near 800 cm (C=O absorption band) －１ The peak intensity ratio was calculated from the peak intensity of the peak (= C-H absorption band) located near the 800 cm peak using the following formulas c and d. The peak intensity ratio was also calculated for the coating layer of the sample for measuring the curing reaction rate using the same procedure: Peak intensity ratio = 800 cm －１ Peak intensity / 1730 cm －１Peak intensity of ...Equation c Curing reaction rate (%) = (1 - peak intensity ratio of coating layer of sample to be measured / peak intensity ratio of coating layer of reference) × 100 ...Equation d

[0118] (Moldability) Using a biaxial stretching tester (manufactured by Toyo Seiki Seisakusho), a test sample was preheated at 140°C for 1 minute and then stretched at the same temperature to a stretch ratio of 1.3 times. The appearance of the test sample was evaluated using the following index. Here, ratings of "A" and "B" can be considered as pass levels, and rating of "C" as fail level: A: No cracks or cloudiness are observed. B: Weak cracks or slight cloudiness are observed. C: Cracks or cloudiness are observed.

[0119] (Surface Hardness: Pencil Hardness) The pencil hardness of the test sample surface was measured in accordance with JIS K5600-5-4-1999. When the test sample had a two-layer or three-layer structure, the surface of the layer other than the A layer (the B layer or the C layer) was evaluated. In particular, when the C layer was laminated, the pencil hardness was measured at an integrated light intensity of 2,000 mJ / cm. ２ The surface of the C layer was evaluated after the C layer was cured by irradiating it with ultraviolet light. A surface hardness of H or higher can be considered to be an acceptable level.

[0120] (IPA crack) As shown in Figure 3(a), the test sample was bent using a clip so that the A layer was on the inside, and in this state, the test sample was immersed in isopropyl alcohol at room temperature for 10 seconds. After immersion, the surface of the test sample was wiped with a Kimwipe, and the appearance of the test sample was evaluated using the following criteria. Here, an "A" rating can be considered a pass level, and "B" and "C" ratings can be considered a fail level (for example, Figure 3(b) corresponds to a "C" rating). Note that for test samples configured with a C layer laminated, an integrated light dose of 2,000 mJ / cm ２After curing the C layer by irradiating it with ultraviolet light, the test sample was bent using a clip. It has been confirmed in advance that there is a correlation between bending after curing and bending after curing, and this test can correspond to a state in which further deformation stress is applied even after molding and curing: A: No cracks occurred. B: Fine cracks occurred. C: Severe cracks occurred.

[0121] (Chemical Resistance) At room temperature, a filter paper soaked in acetone was brought into contact with the surface of a test sample and allowed to stand for 30 minutes. The surface of the test sample was then wiped with a Kimwipe, and the appearance of the test sample was evaluated using the following criteria. Here, an "A" rating is considered to be a pass level, and "B" and "C" ratings are considered to be fail levels: A: No change. B: Slight decrease in surface gloss. C: No surface gloss.

[0122] Preparation Example 1 (Production of Polyester-Based Thermoplastic Elastomer) 100 parts by weight of dimethyl isophthalate, 13 parts by weight of dimethyl sebacate, and 80 parts by weight of hexamethylene glycol were subjected to a transesterification reaction using a dibutyltin diacetate catalyst, followed by polycondensation under reduced pressure to obtain an amorphous polyester (soft segment) with an intrinsic viscosity of 1.06 and no endothermic peak due to crystalline melting as measured by DSC. 32 parts by weight of polybutylene terephthalate pellets (hard segment) with an intrinsic viscosity of 0.98 were added to 100 parts by weight of this polyester, and the mixture was further reacted at 240°C for 45 minutes. Then, 0.03 parts by weight of phenylphosphonic acid was added to terminate the reaction. The resulting polymer had a melting point of 190°C and an intrinsic viscosity of 0.93.

[0123] Comparative Example 1 (Molding Material A) Polycarbonate resin pellets (Teijin's Panlite (registered trademark) L1250WP (bisphenol A homopolycarbonate resin (viscosity average molecular weight 23,900)) and the thermoplastic elastomer obtained in Preparation Example 1 above were each pre-dried in advance and mixed in a V-type blender so that 10 parts by mass of the elastomer was mixed per 100 parts by mass of the polycarbonate resin pellets. The mixture was then extruded using a twin-screw extruder at a cylinder temperature of 260°C to form pellets, thereby obtaining molding material A for layer A. Molding material A had a glass transition temperature of 110°C. In Table 1, the resin type of molding material A (bisphenol A polycarbonate resin and elastomer component) is represented as "PC-AE." This "PC-AE" corresponds to the resin material for the first polycarbonate resin layer of the present disclosure.

[0124] (Extrusion) Molding material A was extruded from a 650 mm wide T-die using a single-screw extruder with a screw diameter of 40 mm under conditions of a cylinder temperature of 260°C and a screw rotation speed of 109 rpm using a feed block system, and the molten resin was cooled by being sandwiched between a metal roll and a metal sleeve roll. After that, the edge was trimmed and the extrusion was taken up at a take-up speed of 10.3 m / min to prepare a test sample with a single layer configuration having a width of approximately 400 mm and a thickness of approximately 200 μm.

[0125] Comparative Example 2 (Molding Material A) The molding material A of Comparative Example 1 was used in the same manner.

[0126] (Molding material B) Polymethyl methacrylate resin pellets (ACRYPET (trademark) VH-001, manufactured by Mitsubishi Chemical Corporation) were pre-dried in advance, mixed in a V-blender, and then extruded into pellets using a twin-screw extruder at a cylinder temperature of 260°C, to obtain molding material B for layer B. The glass transition temperature of molding material B was 110°C. In Table 1, the resin type of molding material B (polymethyl methacrylate resin) is represented as "PMMA".

[0127] (Co-extrusion) Molding material A and molding material B were each extruded from a 650 mm wide T-die using a single-screw extruder with a screw diameter of 40 mm under conditions of a cylinder temperature of 260 ° C. (molding material A), 250 ° C. (molding material B), and a screw rotation speed of 109 rpm (molding material A), 11 rpm (molding material B) by a feed block method. The molten resin was then compressed between a metal roll and a metal sleeve roll and cooled, after which the edges were trimmed and the roll was taken up at a take-up speed of 10.3 m / min to produce a test sample having a laminated structure with a width of approximately 400 mm and a thickness of approximately 200 μm and a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0128] Comparative Example 3 (Molding Material A) Polycarbonate resin pellets (Teijin's Panlite (registered trademark) L1250WP (bisphenol A homopolycarbonate resin (viscosity average molecular weight 23,900)) were pre-dried in advance, mixed in a V-type blender, and then extruded using a twin-screw extruder at a cylinder temperature of 260°C to form pellets, thereby obtaining molding material A for layer A. Molding material A had a glass transition temperature of 150°C. In Table 1, the resin type of molding material A (bisphenol A polycarbonate resin) is represented as "PC-A". This "PC-A" corresponds to the resin material for the first polycarbonate resin layer of the present disclosure.

[0129] (Molding Material B) Polymethyl methacrylate resin pellets (Mitsubishi Chemical's ACRYPET™ VH-001) and rubber component-containing acrylic (Mitsubishi Chemical's ACRYPET™ IRG-304) were each pre-dried in advance and mixed in a V-blender to obtain 70 parts by mass of polymethyl methacrylate resin pellets and 30 parts by mass of rubber component-containing acrylic. The mixture was then extruded using a twin-screw extruder at a cylinder temperature of 260°C to form pellets, thereby obtaining molding material B for layer B. The glass transition temperature of molding material B was 108°C. In Table 1, the resin type of molding material B (polymethyl methacrylate resin and rubber component) is represented as "PMMA-R".

[0130] (Co-extrusion) Molding material A and molding material B were each extruded from a 650 mm wide T-die using a single-screw extruder with a screw diameter of 40 mm under conditions of a cylinder temperature of 260 ° C. (molding material A), 250 ° C. (molding material B), and a screw rotation speed of 109 rpm (molding material A), 11 rpm (molding material B) by a feed block method. The molten resin was then compressed between a metal roll and a metal sleeve roll and cooled, after which the edges were trimmed and the roll was taken up at a take-up speed of 10.3 m / min to produce a test sample having a laminated structure with a width of approximately 400 mm and a thickness of approximately 200 μm and a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0131] Comparative Example 4 (Molding Material A) The molding material A of Comparative Example 2 was used in the same manner.

[0132] (Molding material B) Polycarbonate resin pellets (Teijin Panlite (registered trademark) SH-1126Z (polycarbonate resin of 50 mol % bisphenol A and 50 mol % bisphenol C (viscosity average molecular weight 20,200)) were pre-dried in advance and mixed in a V-type blender, and then extruded using a twin-screw extruder at a cylinder temperature of 260°C to form pellets, thereby obtaining molding material B for layer B. Molding material B had a glass transition temperature of 130°C. In Table 1, the resin type of molding material B (polycarbonate resin of 50 mol % bisphenol A and 50 mol % bisphenol C) is represented as "PC-AC". This "PC-AC" corresponds to the resin material for the second polycarbonate resin layer of the present disclosure.

[0133] (Co-extrusion) Molding material A and molding material B were each extruded from a 650 mm wide T-die using a single-screw extruder with a screw diameter of 40 mm under conditions of a cylinder temperature of 260 ° C. (molding material A), 250 ° C. (molding material B), and a screw rotation speed of 109 rpm (molding material A), 11 rpm (molding material B) by a feed block method. The molten resin was then compressed between a metal roll and a metal sleeve roll and cooled, after which the edges were trimmed and the roll was taken up at a take-up speed of 10.3 m / min to produce a test sample having a laminated structure with a width of approximately 400 mm and a thickness of approximately 200 μm and a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0134] Comparative Example 5 (Molding Material A) The molding material A of Comparative Example 2 was used in the same manner.

[0135] (Paint C) For the paint to form layer C, 100 parts by mass of urethane acrylate ultraviolet curing resin "Folseed (trademark) No. 371C (trade name)" (solid content 40%, manufactured by Chugoku Paint Co., Ltd.), 5 parts by mass of Irgacure (trademark) 184 (photopolymerization initiator, manufactured by Ciba Specialty Chemical Co., Ltd.), and 3 parts by mass of hindered amine compound "TINUVIN (trademark) 292 (trade name)" (manufactured by BASF) were diluted with methyl isobutyl ketone to a solid content concentration of the ultraviolet curing resin in the paint of 30%, and the mixture was thoroughly stirred to prepare a paint.

[0136] (Coating) Coating material C was applied to layer A prepared in the same manner as in Comparative Example 1 using a bar coater (#8) and dried with hot air in a drying oven at 100°C for 5 minutes to form layer C having a coating thickness of approximately 5 µm. The curing reaction rate of the acrylate at this time was 3%.

[0137] Comparative Example 6: The coating material C prepared in the same manner as in Comparative Example 5 was applied to the layer B side of a laminate sheet of layers A and B prepared in the same manner as in Comparative Example 2 using a bar coater (#8), and the coated layer was dried with hot air in a drying oven at 100°C for 5 minutes to form a layer C having a coating thickness of approximately 5 µm. The curing reaction rate of the acrylate in this case was 3%.

[0138] Comparative Example 7: The coating material C prepared in the same manner as in Comparative Example 5 was applied to the layer B side of a laminate sheet of layers A and B prepared in the same manner as in Comparative Example 3 using a bar coater (#8), and the coated layer was dried with hot air for 5 minutes in a drying oven at 100°C to form a layer C having a coating thickness of approximately 5 µm. The curing reaction rate of the acrylate in this case was 3%.

[0139] Example 1: The coating material C prepared in the same manner as in Comparative Example 5 was applied to the B layer side of a laminate sheet of A layer and B layer prepared in the same manner as in Comparative Example 4 using a bar coater (#8), and the coating was dried with hot air in a drying oven at 100°C for 5 minutes to form a C layer with a coating thickness of approximately 5 µm. The curing reaction rate of the acrylate at this time was 3%.

[0140] Example 2 (Molding Material A) The molding material A of Comparative Example 2 was used in the same manner.

[0141] (Molding Material B) (Production of Modified Polycarbonate Resin "PC-C") A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 3,845 parts by mass of 48% aqueous sodium hydroxide solution and 18,182 parts by mass of ion-exchanged water, to which 3,984 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 8.37 parts by mass of hydrosulfite were added and dissolved, and then 10,567 parts by mass of methylene chloride was added, and 2,000 parts by mass of phosgene was blown in over approximately 60 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, 897 parts by mass of 48% aqueous sodium hydroxide solution and 69.93 parts by mass of p-tert-butylphenol were added, and stirring was resumed to emulsify, after which 5.39 parts by mass of triethylamine was added, and the mixture was further stirred at 28 to 33 ° C. for 1 hour to complete the reaction. After the reaction was completed, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water, and further washed with water repeatedly until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, to obtain a methylene chloride solution of polycarbonate resin.

[0142] Next, this solution was passed through a filter with 0.3 μm openings and further dropped into warm water in a kneader with an isolation chamber and a foreign matter outlet in the bearing section to flaked the polycarbonate resin while distilling off the methylene chloride, and the liquid-containing flakes were subsequently crushed and dried to obtain a powder. After that, 0.0025 mass% of tris(2,4-di-tert-butylphenyl)phosphite and 0.05 mass% of stearic acid monoglyceride were added to the powder and mixed uniformly. The powder was then melt-kneaded while degassing in a vented twin-screw extruder (KTX-46, manufactured by Kobe Steel, Ltd.) to obtain a modified polycarbonate resin "PC-C" whose structural units were derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane.

[0143] Pellets of this modified polycarbonate resin were pre-dried in advance, mixed in a V-blender, and then extruded into pellets using a twin-screw extruder at a cylinder temperature of 260°C to obtain molding material B for layer B. Molding material B had a glass transition temperature of 120°C. In Table 1, the resin type of molding material B (bisphenol C polycarbonate resin) is represented as "PC-C." This "PC-C" corresponds to the resin material for the second polycarbonate resin layer of the present disclosure.

[0144] (Co-extrusion) Molding materials A and B were each extruded from a 650 mm wide T-die using a single-screw extruder with a screw diameter of 40 mm under conditions of a cylinder temperature of 260 ° C. (molding material A), 250 ° C. (molding material B), and a screw rotation speed of 109 rpm (molding material A), 11 rpm (molding material B) by a feed block method. The molten resin was then compressed between a metal roll and a metal sleeve roll and cooled, after which the edges were trimmed and the sheet was taken up at a take-up speed of 10.3 m / min to produce a laminated sheet having a width of approximately 400 mm and a thickness of approximately 200 μm and having a two-layer structure of an A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0145] (Coating) Coating material C prepared in the same manner as in Comparative Example 5 was applied to the B layer side of the laminated sheet of A layer and B layer using a bar coater (#8), and the coated layer was dried with hot air for 5 minutes in a drying oven at 100°C to form a C layer with a coating thickness of approximately 5 µm. The curing reaction rate of the acrylate at this time was 3%.

[0146] Example 3 (Molding Material A) The molding material A of Comparative Example 3 was used in the same manner.

[0147] (Molding Material B) The molding material B of Comparative Example 4 was used in the same manner.

[0148] (Co-extrusion) Molding materials A and B were each extruded from a 650 mm wide T-die using a single-screw extruder with a screw diameter of 40 mm under conditions of a cylinder temperature of 260 ° C. (molding material A), 250 ° C. (molding material B), and a screw rotation speed of 109 rpm (molding material A), 11 rpm (molding material B) by a feed block method. The molten resin was then compressed between a metal roll and a metal sleeve roll and cooled, after which the edges were trimmed and the sheet was taken up at a take-up speed of 10.3 m / min to produce a laminated sheet having a width of approximately 400 mm and a thickness of approximately 200 μm and having a two-layer structure of an A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0149] (Coating) Coating material C prepared in the same manner as in Comparative Example 5 was applied to the B layer side of the laminated sheet of A layer and B layer using a bar coater (#8), and the coated layer was dried with hot air for 5 minutes in a drying oven at 100°C to form a C layer with a coating thickness of approximately 5 µm. The curing reaction rate of the acrylate at this time was 3%.

[0150]

[0151] The thermoforming laminate of the present disclosure and articles comprising the laminate are useful as components such as, for example, interior and exterior materials for automobiles, indicator panels for automobiles, electrical appliances, cosmetic cases, interior and exterior parts for building materials, cases for various devices or products, cases for miscellaneous items, switches, keys, keypads, handles, levers, buttons, and housings or exterior parts for home appliances and AV devices (for example, personal computers), mobile phones, and mobile devices.

[0152] REFERENCE SIGNS LIST 100 Thermoforming laminate 101 Curable hard coat precursor layer 103, 203 Second polycarbonate resin layer 105, 205 First polycarbonate resin layer 200 Article 202 Hard coat layer 207 Adhesive layer 209 Support member

Claims

1. A thermoforming laminate comprising, in order, a first polycarbonate resin layer, a second polycarbonate resin layer, and a curable hard coat precursor layer, wherein the proportion of the structural unit of the following formula 1 in the first polycarbonate resin contained in the first polycarbonate resin layer is 70 mol % or more, and the proportion of the structural unit of the following formula 2 in the second polycarbonate resin contained in the second polycarbonate resin layer is 50 mol % or more: In formula 2, W represents a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a cyclic alkylene group having 3 to 8 carbon atoms.

2. The laminate according to claim 1, wherein said first polycarbonate resin layer comprises an elastomer.

3. The laminate according to claim 1 or 2, wherein the structural unit of formula 2 is a structural unit derived from at least one member selected from the group consisting of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, and 2,2'-methyl-4,4'-biphenyldiol.

4. The laminate according to claim 1 or 2, wherein the curable hard coat precursor layer comprises an ultraviolet-curable resin composition.

5. The laminate according to claim 1 or 2, wherein the curing reaction rate of the curable hard coat precursor layer is 2% or more and 50% or less.

6. The laminate according to claim 1 or 2, wherein the thickness of the second polycarbonate resin layer is 10 to 100 μm.

7. The laminate according to claim 1 or 2, wherein the thickness of the curable hard coat precursor layer is 1 to 20 μm.

8. The laminate according to claim 1 or 2, which comprises at least one layer selected from the group consisting of a design layer and an adhesive layer.

9. A method for manufacturing an article, comprising: applying an adhesive layer to the surface of the first polycarbonate resin layer opposite to the second polycarbonate resin layer in the laminate described in claim 1 or 2; laminating the laminate onto a support member via the adhesive layer using a thermoforming method; and performing a curing treatment on the curable hard coat precursor layer of the laminate to form a hard coat layer, thereby obtaining an article.

10. An article in which the laminate according to claim 1 or 2 includes an adhesive layer, the laminate is adhered to a support member via the adhesive layer, and the curable hard coat precursor layer has cured to form a hard coat layer.

11. The article of claim 10, having a three-dimensional shape.

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