Thermoforming laminate, and laminated molded product containing the laminate

Abstract

The present invention provides thermoforming laminates and laminated products that can provide excellent surface hardness, formability, and IPA crack resistance. [Solution] The thermoforming laminate of the present disclosure comprises, in order, a first polycarbonate resin layer and a second polycarbonate resin layer, wherein the proportion of constituent units of the following formula 1 in the first polycarbonate resin contained in the first polycarbonate resin layer is 90 mol% or more, and the proportion of constituent units of the following formula 2 in the second polycarbonate resin contained in the second polycarbonate resin layer is 15 mol% or more and 95 mol% or less: JPEG2026090812000015.jpg1878 JPEG2026090812000016.jpg3376

Description

Technical Field

[0001] The present disclosure relates to a laminate for thermoforming and a laminated molded article including the laminate.

Background Art

[0002] Since polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability, it is used as an engineering plastic in a wide range of fields such as housings for electric and electronic devices, interior and exterior parts of automobiles, building materials, furniture, musical instruments, and sundries. Furthermore, compared with inorganic glass, it has a low specific gravity, can be lightweight, and has excellent productivity, so it is used for window applications such as automobiles. Furthermore, sheets and films using polycarbonate resin are widely used as various display devices and protective parts for automobile interiors by performing additional secondary processing such as coating treatment, lamination, and surface modification.

[0003] However, the pencil hardness of polycarbonate resin measured in accordance with the paint general test method - Part 5: Mechanical properties of paint films - Section 4: Scratch hardness (pencil method) described in JIS K5600-5-4 for polycarbonate resin without coating treatment is only about 2B, and there is a problem that once a scratch occurs, it is very noticeable. For example, Patent Document 1 discloses a method of laminating an acrylic resin layer on a polycarbonate resin film in order to improve the above surface characteristics. Furthermore, Patent Document 2 discloses a method of performing a hard coat treatment on the acrylic resin layer.

[0004] On the other hand, Patent Document 3 proposes a method of laminating a special high-hardness polycarbonate resin instead of the acrylic resin.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] When an acrylic resin layer is applied to a polycarbonate resin substrate, surface hardness and formability can coexist, but cracks may occur in a crack test using isopropyl alcohol (sometimes referred to as "IPA"). In addition, when a high-hardness resin layer other than acrylic is applied to a polycarbonate resin substrate, IPA crack resistance and formability can coexist, but sufficient surface hardness may not be obtained. Therefore, an object of the present disclosure is to provide a thermoformable laminate capable of coexisting excellent surface hardness, formability, and IPA crack resistance, and a laminated molded article including the laminate. [Means for Solving the Problems]

[0007] <Aspect 1> It sequentially includes a first polycarbonate resin layer and a second polycarbonate resin layer, The proportion of the structural unit of the following formula 1 in the first polycarbonate resin contained in the first polycarbonate resin layer is 90 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 15 mol% or more and 95 mol% or less, Thermoformable laminate: [Chemical formula] [Chemical formula] In formula 2, Ring Z is a condensed polycyclic arene ring, R 1 and R 2Each of these independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0008] <Aspect 2> The thermoforming laminate according to embodiment 1, wherein in the constituent unit of formula 2, ring Z is a naphthalene ring. <Aspect 3> The thermoforming laminate according to embodiment 1 or 2, wherein the proportion of constituent units of the following formula 3 in the second polycarbonate resin contained in the second polycarbonate resin layer is 40 mol% or more. [ka] In formula 3, W represents a single bond, an alkylene group with 1 to 6 carbon atoms, an arylene group with 6 to 10 carbon atoms, or a cyclic alkylene group with 3 to 8 carbon atoms.

[0009] <Aspect 4> The thermoforming laminate according to embodiment 3, wherein the constituent unit of formula 3 is a constituent 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, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2'-methyl-4,4'-biphenyldiol, and 2,2-bis(4-hydroxyphenyl)propane. <Aspect 5> A thermoforming laminate according to any one of embodiments 1 to 4, wherein when the thickness of the first polycarbonate resin layer is A (μm) and the thickness of the second polycarbonate layer is B (μm), A / B > 1.0. <Pattern 6> The thermoforming laminate according to any one of embodiments 1 to 5, wherein the thickness of the second polycarbonate resin layer is 10 to 100 μm. <Aspect 7> The viscosity-average molecular weight of the second polycarbonate resin contained in the second polycarbonate resin layer is 1.0 × 10 4 The above is 10.0 × 10 4 A thermoforming laminate according to any one of the following embodiments 1 to 6. <Aspect 8> A thermoforming laminate comprising a hard coat layer laminated on the side of the second polycarbonate resin layer of the thermoforming laminate according to any one of the configurations 1 to 7 that is opposite to the first polycarbonate resin layer. <Aspect 9> The thermoforming laminate according to embodiment 8, wherein the thickness of the hard coat layer is 1 to 20 μm. <Aspect 10> The thermoforming laminate according to embodiment 8 or 9, wherein the hard coat layer comprises an ultraviolet-curable resin composition. <Aspect 11> The thermoforming laminate according to any one of the embodiments 8 to 10, wherein the hard coat layer is a curable hard coat precursor layer, and the curing reaction rate of the curable hard coat precursor layer is 2% or more and 50% or less. <Aspect 12> A laminated molded product obtained by thermoforming a thermoformable laminate according to any one of claims 1 to 10 to give it a three-dimensional shape. <Aspect 13> A laminated product obtained by thermoforming the thermoformable laminate described in form 11 to impart a three-dimensional shape, and then performing a hardening treatment on the hardened hard coat precursor layer to form a hard coat layer. <Aspect 14> Automotive interior and exterior parts using laminated molded products as described in Embodiment 12 or Embodiment 13. <Aspect 15> A display panel using a laminated molded product as described in Embodiment 12 or Embodiment 13. [Effects of the Invention]

[0010] According to this disclosure, it is possible to provide a thermoforming laminate that can impart excellent surface hardness, formability, and IPA crack resistance, and a laminated molded product containing the laminate. [Brief explanation of the drawing]

[0011] [Figure 1] This is a cross-sectional view of a thermoforming laminate according to one embodiment of the present disclosure. [Figure 2] This is a cross-sectional view of a laminated product including a thermoformable laminate according to one embodiment of the present disclosure. [Figure 3] Figure 3(a) is a photograph of the test sample in a bent state during the IPA crack test, and Figure 3(b) is a photograph of the test sample with cracks after the IPA crack test. [Modes for carrying out the invention]

[0012] The embodiments of this disclosure will be described in detail below. This disclosure is not limited to the embodiments described below, and can be implemented in various ways within the scope of the essence of the invention.

[0013] The thermoforming laminate of this disclosure comprises, in order, a first polycarbonate resin layer, a second polycarbonate resin layer, and optionally a hard coat layer, wherein the proportion of constituent units of the following formula 1 in the first polycarbonate resin layer is 90 mol% or more, and the proportion of constituent units of the following formula 2 in the second polycarbonate resin layer is 15 mol% or more and 95 mol% or less:

[0014] [ka]

[0015] [ka]

[0016] In formula 2, Ring Z is a condensed polycyclic arene ring, R 1 and R 2 Each of these independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0017] While not limited by principle, we believe that the operating principle by which the thermoforming laminate (sometimes simply referred to as "laminated") of this disclosure can impart excellent surface hardness and IPA crack resistance is as follows.

[0018] Polycarbonate resin substrates used in thermoforming generally have a tendency to deform easily when heated, resulting in low surface hardness. Therefore, even when a hard coat layer or a conventional, higher-hardness polycarbonate resin layer is applied to such a substrate, it is thought that the surface hardness could not be sufficiently improved due to the influence of the substrate.

[0019] On the other hand, applying a polymethyl methacrylate (PMMA) resin layer, which has excellent surface hardness, to such a substrate can improve surface hardness, but it tends to crack easily in IPA crack tests. Furthermore, applying a hard coat layer to such a laminated structure did not improve IPA crack resistance. We believe this is because the acrylic resin layer containing PMMA resin is susceptible to the effects of IPA, and cracks occur in the PMMA layer as IPA penetrates from the edges, etc.

[0020] The thermoformable laminate of this disclosure includes a specific second polycarbonate resin layer on a first polycarbonate resin layer that can serve as a base material. This specific second polycarbonate resin layer is considered to be an optimally balanced resin layer that enables thermoformability, provides excellent surface hardness, and improves IPA crack resistance.

[0021] The definitions of terms used in this disclosure are as follows: In this disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0022] Laminates for thermoforming As shown in Figure 1, the thermoforming laminate of the present disclosure includes, in order, at least a first polycarbonate resin layer 105 and a second polycarbonate resin layer 103. Here, "in order" means that, when focusing on the two components, the first polycarbonate resin layer and the second polycarbonate resin 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. Furthermore, a curable hard coat precursor layer 101 may be laminated on the side of the second polycarbonate layer opposite to the first polycarbonate layer.

[0023] First, each layer constituting the thermoforming laminate of this disclosure will be described below. <First polycarbonate resin layer> The first polycarbonate resin layer constituting the laminate of this disclosure can be used, for example, as a base material for a thermoformable laminate. The first polycarbonate resin layer can also be, for example, a layer containing 50% or more, 70% or more, or 90% or more by mass of the first polycarbonate resin relative to the total amount of resin components in the layer, or a layer consisting solely of the first polycarbonate resin. Here, the first polycarbonate resin can be one in which the proportion of constituent units of the following formula 1 is 90 mol% or more, 95 mol% or more, 98 mol% or more, 100 mol% or less, or less than 100 mol%. From the viewpoint of thermoformability, etc., it is more preferable that the proportion of constituent units of the following formula 1 in the first polycarbonate resin is 100 mol%. The first polycarbonate resin can be used alone or in combination of two or more types:

[0024] [ka]

[0025] The first polycarbonate resin is typically an aromatic polycarbonate resin, which can be obtained, for example, by reacting a divalent phenol with a carbonate precursor using a solution method or a melt method. Examples of such reaction methods include interfacial polycondensation, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0026] The first polycarbonate resin may contain 90 mol% or more of the structural unit of the above formula 1, and may contain one or more other structural units, or may not contain 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. Other structural units can be prepared, for example, using, as the dihydric phenol, 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, etc.

[0027] Examples of the carbonate precursor include carbonyl halide, carbonate ester, and haloformate, and specifically, phosgene, diphenyl carbonate, and dihaloformate of dihydric phenol.

[0028] The first polycarbonate resin can be produced from the dihydric phenol and / or the carbonate precursor alone or in combination of two or more. In the production of the first polycarbonate resin, a molecular weight regulator, a branching agent, a catalyst, etc. can be used as necessary.

[0029] In some embodiments, the first polycarbonate resin can be defined by the viscosity average molecular weight. Such molecular weight can be 1.0×10 4 or more, or 1.3×10 4 or more, or 1.5×10 4 or more, or 1.8×10 4 or more, or 2.0×10 4 or more, or 2.2×10 4 or more, and can also be 10.0×10 4 or less, or 8.0×10 4 or less, or 5.0×10 4 or less, or 4.5×10 4 or less, or 4.0×104 Below, 3.5 × 10 4 Below, 3.2 × 10 4 Below, 3.0 × 10 4 The following, or 2.8 × 10 4 The following is possible. Here, "viscosity-average molecular weight" in this disclosure refers to the specific viscosity (η) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. sp This was obtained by inserting ) into the following formulas a and b. Furthermore, if the polycarbonate resin is a mixture of two or more types, the molecular weight of the entire mixture is expressed: η sp / c=[η]+0.45×[η] 2 c …Formula a [η] = 1.23 × 10 -4 M 0.83 …Formula b (However, c = 0.7 g / dL, and [η] is the intrinsic viscosity.)

[0030] In some embodiments, the first polycarbonate resin can be defined by its glass transition temperature (Tg). From the viewpoint of thermoformability, such 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 preferably 180°C or lower, 170°C or lower, 160°C or lower, 155°C or lower, or 150°C or lower. Here, the glass transition temperature refers to the value measured by differential scanning calorimetry (DSC).

[0031] The first polycarbonate resin layer of this disclosure may contain various components as appropriate, provided that they do not adversely affect the effects of this disclosure. Such optional components include, for example, elastomers, heat stabilizers, mold 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 each Examples of components include: various types of whiskers, flame retardants (e.g., halogenated flame retardants, phosphate ester flame retardants, metal salt flame retardants, red phosphorus flame retardants, silicone flame retardants, fluorine flame retardants, and metal hydrate flame retardants), colorants (e.g., pigments such as carbon black and titanium dioxide, and dyes), light diffusing agents (e.g., acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, and calcium carbonate particles), fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antimicrobial agents, photocatalytic antifouling agents (e.g., granular titanium dioxide and granular zinc oxide), impact modifiers represented by graft rubber, and photochromic agents. Any component can be used individually or in combination of two or more.

[0032] Among the optional components, elastomers are preferred from the viewpoint of thermoformability, and it is more preferable to use elastomers mixed with the first polycarbonate resin. Elastomers can be used alone or in combination of two or more types.

[0033] Among elastomers, thermoplastic elastomers are preferred from the viewpoint of thermoformability, and polyester-based thermoplastic elastomers are more preferred. The polyester-based thermoplastic elastomer is preferably a multi-block copolymer composed of a hard segment consisting of polybutylene terephthalate units and a soft segment consisting of polyester units in which aromatic dicarboxylic acids and aliphatic dicarboxylic acids are the dicarboxylic acid components and diols having 5 to 15 carbon atoms are the diol components.

[0034] The hard segments composed of polybutylene terephthalate units exhibit excellent compatibility with polycarbonate resins, are preferable from the viewpoint of transparency and thermoformability, and can also exhibit good properties in terms of strength. Polybutylene terephthalate may contain other components as copolymer components as long as it does not impair the effects of this disclosure. The proportion of such copolymer components is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, for both the dicarboxylic acid component and the diol component, out of 100 mol% of the total components. The intrinsic viscosity of the polymer forming the hard segments is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5.

[0035] The soft segment, which consists of polyester units with aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component, refers to a segment from which the polymer formed has a melting point of 100°C or less, or is liquid and amorphous at 100°C. The intrinsic viscosity of the polymer that forms 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 with aromatic dicarboxylic acids and / or aliphatic carboxylic acids 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.

[0036] From the viewpoint of obtaining better transparency, it is preferable that the soft segment SS-1 contains 60-99 mol% aromatic dicarboxylic acids and 1-40 mol% aliphatic dicarboxylic acids out of a total of 100 mol% of dicarboxylic acid components. It is more preferable that the aromatic dicarboxylic acid content is 70-95 mol% and the aliphatic dicarboxylic acid content is 5-30 mol%. It is even more preferable that the aromatic dicarboxylic acid content is 85-93 mol% and the aliphatic dicarboxylic acid content is 7-15 mol%. It is particularly preferable that the aromatic dicarboxylic acid content is 89-92 mol% and the aliphatic dicarboxylic acid content is 8-11 mol%.

[0037] 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.

[0038] As the aliphatic dicarboxylic acid of SS-1, linear 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.

[0039] 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, and hexamethylene glycol is particularly preferred.

[0040] SS-1 is particularly preferred because it has high compatibility with polycarbonate resin, can be obtained with high transparency, and exhibits good surface properties and transparency after thermoforming. More specifically, a polyester composed of isophthalic acid, sebaciic acid, and hexamethylene glycol is preferred as SS-1.

[0041] In this disclosure, the ratio of hard segments to soft segments in a polyester thermoplastic elastomer is preferably 20-70% by mass of hard segments and 80-30% by mass of soft segments, and more preferably 20-40% by mass of hard segments and 80-60% by mass of soft segments, based on 100% by mass of elastomer. From the viewpoint of strength, the intrinsic viscosity of the polyester thermoplastic elastomer is preferably 0.6 or higher, 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, intrinsic viscosity is the value measured in o-chlorophenol at 35°C.

[0042] Since the glass transition temperature of the first polycarbonate resin layer can be set to a suitable range, and as a result, thermoformability can be improved, it is preferable that the polyester thermoplastic elastomer is included 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 polycarbonate resin in the first polycarbonate resin layer.

[0043] There are no particular limitations on the method for manufacturing the first polycarbonate resin layer. Examples of such manufacturing methods include melt extrusion and solution casting (casting).

[0044] Specific methods of the melt extrusion method include, for example, supplying a fixed amount of the first polycarbonate resin to an extruder and heating and melting it, extruding the molten resin in a sheet or film form from the tip of a T-die onto a mirror-finish roll, taking it up while cooling it with multiple rolls, and cutting or winding it to an appropriate size once it has solidified.

[0045] A specific method of the solution casting method involves, for example, casting a solution (concentration 5% to 40%) of a first polycarbonate resin dissolved in methylene chloride onto a mirror-polished stainless steel plate using a T-die. The sheet or film is then peeled off while passing through a temperature-controlled oven in stages, and after removing the solvent from the peeled sheet or film, it is cooled and wound up.

[0046] There are no particular restrictions on the thickness of the first polycarbonate resin layer, and it can be set appropriately depending on the intended use of the thermoformable laminate. For example, from the viewpoint of thermoformability, 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 also 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. The thickness can be measured using a micrometer.

[0047] <Second polycarbonate resin layer> The second polycarbonate resin layer constituting the laminate of this disclosure may be, for example, a layer containing 50% or more, 70% or more, or 90% or more by mass of the second polycarbonate resin relative to the total amount of resin components in such 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 constituent units of the following formula 2 is 15 mol% or more, 18 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, or 35 mol% or more, 95 mol% or less, less than 95 mol%, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 45 mol% or less, or 40 mol% or less. The second polycarbonate resin may be used alone or in combination of two or more types:

[0048] [ka]

[0049] In formula 2, Ring Z is a condensed polycyclic arene ring, R 1 and R 2 Each of these independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0050] The second polycarbonate resin is also typically an aromatic polycarbonate resin, and like the first polycarbonate resin, such aromatic polycarbonate resins can be obtained, for example, by reacting a divalent phenol with a carbonate precursor using a solution method or a melt method.

[0051] The second polycarbonate resin may contain 15 mol% to 95 mol% of the constituent units of Formula 2, and may also contain one or more other constituent units, or may not contain any other constituent units. By using a second polycarbonate resin containing 15 mol% to 95 mol% of the constituent units of Formula 2, a second polycarbonate resin layer can be obtained that is thermoformable and has excellent surface hardness and IPA crack resistance. In some embodiments, the hardness of the second polycarbonate resin layer is higher than that of the first polycarbonate resin layer. By employing such a second polycarbonate resin layer, excellent thermoformability, surface hardness, and IPA crack resistance can be achieved for the entire thermoformed laminate.

[0052] In formula (2) above, the fused polycyclic arene ring represented by ring Z can be a fused bicyclic arene ring (for example, a fused bicyclic arene ring with 10 to 16 carbon atoms, such as a naphthalene ring or an indene ring), or a fused tricyclic arene ring (for example, an anthracene ring or a phenanthrene ring). A naphthalene ring or an anthracene ring is preferred as ring Z, and a naphthalene ring is more preferred. The two rings Z connected to the carbon atom at position 9 of the fluorene ring may be of different types, but are usually the same.

[0053] Furthermore, the substitution position of ring Z relative to the 9th position of the fluorene ring is not particularly limited. For example, if ring Z is a naphthalene ring, substitution may occur at either the 1st or 2nd position of the naphthalene ring relative to the 9th position of the fluorene ring, with substitution at the 2nd position being preferred.

[0054] The substitution positions of the oxygen atom (-O-) and ester bond [-OC(=O)-] that form the carbonate bond for linking the 9,9-bis-condensed polycyclic arylfluorene skeleton are not particularly limited as long as they are positions other than the bond between ring Z and the fluorene ring. For example, when ring Z is a naphthalene ring, the substitution is usually made at one of the positions 5 to 8 of the naphthyl group bonded to the 9th position of the fluorene ring at position 1 or 2. It is preferable that the 1st or 2nd position of the naphthalene ring is substituted for the 9th position of the fluorene ring (substitution in the relationship of 1-naphthyl or 2-naphthyl), and that the substitution is made at the 1,5th and 2,6th positions, with the substitution at the 2,6th position being more preferable.

[0055] In equation (2) above, R 1 and R 2Each of these independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0056] Examples of halogen atoms include fluorine, chlorine, and bromine atoms.

[0057] Examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl groups. Preferably, alkyl groups have 1 to 6 carbon atoms.

[0058] Examples of alkoxy groups having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and octoxy groups. Alkoxy groups having 1 to 6 carbon atoms are preferred.

[0059] Examples of cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl groups and cyclooctyl groups. Cycloalkyl groups having 6 to 12 carbon atoms are preferred.

[0060] Preferred cycloalkoxy groups with 6 to 20 carbon atoms include cyclohexyloxy groups and cyclooctyloxy groups. Cycloalkoxy groups with 6 to 12 carbon atoms are preferred.

[0061] Examples of alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl, and pentenyl groups. Alkenyl groups having 2 to 6 carbon atoms are preferred.

[0062] Examples of aryl groups with 6 to 14 carbon atoms include the phenyl group and the naphthyl group.

[0063] Examples of aryloxy groups with 6 to 14 carbon atoms include phenyloxy groups and naphthyloxy groups.

[0064] Examples of aralkyl groups with 7 to 20 carbon atoms include the benzyl group and the phenylethyl group.

[0065] Examples of aralkyloxy groups with 7 to 20 carbon atoms include the benzyloxy group and the phenylethyloxy group.

[0066] Among them, R 1 and R 2 The group is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, with a hydrogen atom being particularly preferred.

[0067] The second polycarbonate resin may further contain other constituent units. These other constituent units are those shown in formula 3 below.

[0068] [ka]

[0069] In formula 3, W represents a single bond, an alkylene group with 1 to 6 carbon atoms, an arylene group with 6 to 10 carbon atoms, or a cyclic alkylene group with 3 to 8 carbon atoms.

[0070] Examples of the constituent units shown in Formula 3 above include those 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-hydroxy-3-methylphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2'-methyl-4,4'-biphenyldiol, 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.

[0071] In particular, from the viewpoint of improving surface hardness and IPA crack resistance while maintaining thermoformability, it is preferable to include 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, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and 2,2'-methyl-4,4'-biphenyldiol, and more preferably to include a structural unit derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane. Furthermore, from the viewpoint of chemical resistance, it may also include a structural unit derived from 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), i.e., the structural unit of formula 1 described above.

[0072] From the viewpoint of thermoformability, surface hardness, and IPA crack resistance, the proportion of other constituent units other than the constituent units of Formula 2 is preferably 85 mol% or less, 82 mol% or less, 80 mol% or less, 70 mol% or less, or 65 mol% or less, 5 mol% or more, more than 5 mol%, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 55 mol% or more, or 60 mol% or more.

[0073] In some embodiments, the second polycarbonate resin can be defined by its viscosity-average molecular weight, similar to that of the first polycarbonate resin. Such a molecular weight may be 1.0 × 10⁻⁶. 4 The above is 1.3 × 10 4 The above is 1.5 × 10 4 The above is 1.8 × 10 4 The above is 2.0 × 10 4 The above, or 2.2 × 10 4 It can be set to the above, and also 10.0 × 10 4 Below, 8.0 × 10 4 Below, 5.0 × 10 4 Below, 4.5 × 10 4 Below, 4.0 × 10 4 Below, 3.5 × 10 4 Below, 3.2 × 10 4 Below, 3.0 × 10 4 Below, 2.8 × 10 4 Below, 2.6 × 10 4 Below, 2.5 × 10 4 Below, 2.4 × 10 4 The following, or 2.2 × 10 4 The following is possible:

[0074] In some embodiments, the second polycarbonate resin can be defined by its glass transition temperature (Tg). From the viewpoint of thermoformability, such glass transition temperature is preferably 105°C or higher, 110°C or higher, 115°C or higher, 120°C or higher, 125°C or higher, 130°C or higher, 135°C or higher, 140°C or higher, 145°C or higher, or 150°C or higher, and preferably 200°C or lower, 190°C or lower, 185°C or lower, 180°C or lower, 175°C or lower, 170°C or lower, 165°C or lower, or 160°C or lower.

[0075] The second polycarbonate resin layer, like the first polycarbonate resin layer, can also be appropriately blended with the aforementioned optional components.

[0076] There are no particular limitations on the method for applying the second polycarbonate resin layer to the surface of the first polycarbonate resin layer. Examples of such methods include thermocompression bonding and co-extrusion.

[0077] Any method can be used as the heat-pressing method. Examples of such methods include a method of heat-pressing a first polycarbonate resin layer and a second polycarbonate resin layer, each molded into a film or sheet, using a laminating machine or press machine, and a method of heat-pressing a second polycarbonate resin layer, also in film or sheet form, onto a first polycarbonate resin layer, also in film or sheet form, immediately after extrusion. Among these, from the viewpoint of productivity, the method of heat-pressing a second polycarbonate resin layer, also in film or sheet form, continuously onto a first polycarbonate resin layer, also in film or sheet form, immediately after extrusion, is advantageous.

[0078] The conditions for heat-compression bonding can be appropriately adjusted depending on the thickness of the first polycarbonate resin layer and the second polycarbonate resin layer, the condition of the bonding surface, etc. Specific examples of such conditions include a temperature of the glass transition temperature of the second polycarbonate resin layer or higher, for example, -10°C to +150°C, preferably -5°C to +100°C, and a bonding pressure of 0.05 to 5 kg / cm². 2 To a certain extent, preferably 0.1 to 1 kg / cm³ 2 It can raise the level of pressure.

[0079] There are no particular limitations on the method for manufacturing the second polycarbonate resin layer, which is in the form of a film or sheet, used in the thermocompression bonding method. Examples of such manufacturing methods include the melt extrusion method and the solution casting method (flow casting method).

[0080] Specific methods of the melt extrusion method include, for example, supplying a fixed amount of a second polycarbonate resin to an extruder and heating and melting it, extruding the molten resin in a sheet or film form from the tip of a T-die onto a mirror-finish roll, taking it up while cooling it with multiple rolls, and cutting or winding it to an appropriate size once it has solidified.

[0081] A specific method of solution casting involves, for example, casting a solution (concentration 5% to 40%) of a second polycarbonate resin dissolved in methylene chloride onto a mirror-polished stainless steel plate using a T-die. The sheet or film is then peeled off while passing through a temperature-controlled oven in stages. After removing the solvent from the peeled sheet or film, it is cooled and wound up.

[0082] The co-extrusion method, which is a method for applying a second polycarbonate resin layer to the surface of a first polycarbonate resin layer, can be performed by, for example, melt-extruding the second polycarbonate resin in an auxiliary extrusion at 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 at its glass transition temperature to glass transition temperature + 230°C, preferably glass transition temperature + 50°C to glass transition temperature + 200°C, and then extruding and laminating using a known method such as a multi-manifold system or a feed block system.

[0083] There are no particular restrictions on the thickness of the second polycarbonate resin layer, and it can be set appropriately according to the required performance (e.g., thermoformability, surface hardness, and IPA crack resistance). 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 also preferably 100 μm or less, 90 μm or less, 80 μm or less, or 70 μm or less. The thickness can be measured using a micrometer.

[0084] Furthermore, when the thickness of the first polycarbonate resin layer is A (μm) and the thickness of the second polycarbonate layer is B (μm), it is preferable that A / B > 1.0, more preferably that A / B ≥ 1.1, and even more preferably that A / B ≥ 1.2. There is no particular upper limit to A / B, but it is preferable that A / B ≤ 10, more preferably that A / B ≤ 7, and even more preferably that A / B ≤ 5. Within the above range, excellent moldability, surface hardness, and IPA crack resistance are obtained.

[0085] <Hard court layer> As described above, the thermoforming laminate may sequentially include a first polycarbonate resin layer, a second polycarbonate resin layer, and optionally a hard coat layer. Including a hard coat layer improves surface hardness and IPA crack resistance, as well as chemical resistance. Therefore, it is preferable to include a hard coat layer in molded articles that require high surface hardness, IPA crack resistance, and chemical resistance.

[0086] As the hard coat layer, a hard coat layer formed from a thermosetting resin composition or an ultraviolet-curing resin composition can be used. In particular, it is preferable that the hard coat layer contains an ultraviolet-curing resin composition.

[0087] Furthermore, since a hardening treatment can be applied to a support member having a three-dimensional shape after thermoforming, it is preferable to include a hard coat layer using the hardening type hard coat precursor layer shown below.

[0088] <Hardening type hard coat precursor layer> The thermoformable laminate of this disclosure may include a curable hard coat precursor layer for the purpose of further improving surface hardness and chemical resistance. The thermoformable laminate can be applied to a support member having a three-dimensional shape, for example, and a curing treatment can be performed after thermoforming. Therefore, such a "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, that is, a state in which it has not cured to the extent that it exhibits the desired hard coat performance (for example, a state in which it has not fully cured).

[0089] 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 also 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 becomes semi-cured, reducing its tackiness, which improves workability, and also improves the flexibility of the curable hard coat precursor layer itself, allowing it to conform well 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 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 later. If the three-dimensional shape of the support member to which the thermoformable laminate is applied is gentle, the curable hard coat precursor layer can be cured before applying the thermoformable laminate to the support member.

[0090] The curable hard coat precursor layer may be a single layer or a multilayer structure. The curable hard coat precursor layer may be applied to the entire surface of the thermoforming laminate or to a portion thereof.

[0091] There are no particular restrictions on the materials that constitute the curable hard coat precursor layer. Examples 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 of two or more. Among these, (meth)acrylic resins and silicone resins are preferred from the viewpoint of adhesion, thermoformability, surface hardness, and IPA crack resistance. The resin material may be an active energy ray (e.g., ultraviolet rays, X-rays, electron beams) curable resin or a thermosetting resin. From the viewpoint of productivity, it is preferable that the curable hard coat precursor layer 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 this range, productivity can be improved, and properties such as thermoformability, surface hardness, and IPA crack resistance can be further enhanced. An example of a composition containing resin material is described below.

[0092] ((meth)acrylic resin composition) Examples of (meth)acrylic resins 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 viewpoint of adhesion, thermoformability, surface hardness, and IPA crack resistance. In addition, monofunctional monomers can be used as appropriate in addition to polyfunctional monomers when obtaining (meth)acrylic resins. The monomers used can be used alone or in combination of two or more types.

[0093] In some embodiments, the curable hard coat precursor layer of the present disclosure comprises 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 capable of initiating a polymerization reaction by generating radicals or the like when exposed to ultraviolet light can be used. The photopolymerization initiator can be used alone or in combination of two or more.

[0094] There are no particular restrictions on the type of photopolymerization initiator; for example, acylphosphine oxide-based photopolymerization initiators, phenylglyoxylate-based photopolymerization initiators, benzyl ketal-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, and α-aminoalkylphenone-based photopolymerization initiators can be cited.

[0095] There are no particular restrictions on the content of the photopolymerization initiator. For example, the amount can be 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, or 10 parts by mass or less, 9.0 parts by mass or less, or 8.5 parts by mass or less, per 100 parts by mass of the total monomer components in the resin composition that forms the curable hard coat precursor layer.

[0096] (Silicone resin composition) Examples of silicone resin compositions that can constitute a 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.

[0097] (1) Inorganic oxide particles surface-modified with hydrolyzable silane compounds having active energy ray-reactive groups Inorganic oxide particles include, for example, 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 silica, alumina, zirconia, titania, and cerium oxide. Since the inorganic oxide particles are surface-modified with hydrolyzable silane compounds having active energy ray reactive groups, such reactive silica particles can undergo a crosslinking reaction and be fixed in the polymer matrix by active energy ray irradiation during the curing of the composition. Inorganic oxide particles surface-modified with hydrolyzable silane compounds having active energy ray reactive groups can be used alone or in combination of two or more types.

[0098] In some embodiments, the average particle diameter of inorganic oxide particles is preferably 80 nm or less, and more preferably 50 nm or less, from the viewpoint of transparency and other factors. The lower limit of the average particle diameter can be 10 nm or more, 15 nm or more, or 20 nm or more. In this disclosure, the average particle diameter can be measured by a particle size distribution analyzer using the dynamic light scattering photon correlation method.

[0099] Preferred inorganic oxide particles are silica particles, with silica particles having an average particle diameter of 50 nm or less being more preferred. The silica particles may be non-porous, hollow, or porous.

[0100] Examples of hydrolyzable silane compounds having an active energy ray reactive group include silane coupling agents containing a (meth)acrylic group. Specific examples 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, and γ-acryloxypropylmethyldiethoxysilane. Examples include 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. Hydrolyzable silane compounds having an active energy ray reactive group can be used alone or in combination of two or more.

[0101] The amount of surface modification of the hydrolyzable silane compound having an active energy ray reactive group can be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, 10% by mass or less, 8% by mass or less, or 5% by mass or less, relative to the particles.

[0102] One method for surface modification using a hydrolyzable silane compound having an active energy ray reactive group is to hydrolyze the hydrolyzable silane compound having an active energy ray reactive group in the presence of silica particles.

[0103] 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, as described later. By having the particles as primary particles, a film with good appearance, such as transparency, can be obtained.

[0104] Specifically, this can involve physically dispersing inorganic oxide particles in a (meth)acrylic group-containing compound using a dispersant or dispersion equipment, or adding a (meth)acrylic group-containing compound to a solution in which inorganic oxide particles are dispersed, and then removing the original dispersant by distillation.

[0105] (2) Compounds containing three or more (meth)acrylic groups Compounds containing three or more (meth)acrylic groups, together with the surface-modified inorganic oxide particles and compounds containing one or two (meth)acrylic groups, form the main components of the curable material and create the matrix of the film obtained after curing. Compounds containing three or more (meth)acrylic groups are components that disperse the inorganic oxide particles and also act as binder components, and these compounds result in a cured product 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 types.

[0106] Compounds containing three or more (meth)acrylic groups are compounds having three or more (meth)acrylic groups in their molecule. Specific examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methoxylate pentaerythritol tetra(meth)acrylate, ethoxylate pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, and triacrylated isocyanurates. Other examples include polymer components such as trifunctional or more urethane(meth)acrylates, polyester(meth)acrylates, and hydrolysis condensates of hydrolyzable silane compounds having active energy ray reactive groups.

[0107] (3) Compounds containing one or two (meth)acrylic groups Compounds containing one or two (meth)acrylic groups, together with the surface-modified inorganic oxide particles and compounds containing three or more (meth)acrylic groups, form the main components of the curable components and create the matrix of the film obtained after curing. Compounds containing one or two (meth)acrylic groups can be used alone or in combination of two or more.

[0108] Compounds containing one or two (meth)acrylic groups can be components for reducing the viscosity of the composition, as well as components for improving adhesion to polycarbonate resin layers and the like.

[0109] To reduce the viscosity of the composition, the viscosity of a compound containing one or two (meth)acrylic groups at 25°C is preferably 100 mPa·s or less, and more preferably 50 mPa·s or less. There is no particular limit to the lower limit of viscosity, and it can be 1 mPa·s or more. Here, such viscosity can be measured by a rotational viscometer.

[0110] From the viewpoint of improving adhesion, compounds containing one or two (meth)acrylic groups are preferably those that have functional groups such as hydroxyl groups or epoxy groups within the molecule.

[0111] 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.

[0112] From the viewpoint of adhesion, hardness, etc., the amount of component (1) blended is 25 to 70 parts by mass, preferably 35 to 60 parts by mass, out of a total of 100 parts by mass of components (1), (2), and (3); the amount of component (2) blended is 20 to 70 parts by mass, preferably 30 to 55 parts by mass, out of a total of 100 parts by mass of components (1), (2), and (3); and the amount of component (3) blended is 5 to 30 parts by mass, preferably 10 to 20 parts by mass, out of a total of 100 parts by mass of components (1), (2), and (3).

[0113] (4) Radical-based photopolymerization initiators As radical photopolymerization initiators, for example, common ones such as acetophenone-based, benzoin-based, acylphosphine oxide-based, benzophenone-based, and thioxanthone-based ones can be selected. Specifically, benzophenone, benzyl, Michlar's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2- Examples include hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, a mixture of 2-[2-oxo-2-phenylacetoxyethoxy]ethyl oxyphenylacetate and 2-(2-hydroxyethoxy)ethyl oxyphenylacetate, acylphosphine oxide derivatives, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethylbenzoyldiphenylphosphine. Radical photopolymerization initiators can be used alone or in combination of two or more.

[0114] In particular, from the viewpoint of curing properties, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl 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.

[0115] The amount of radical photopolymerization initiator added 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 components (1), (2), and (3) described above, from the viewpoint of curability and adhesion.

[0116] 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.

[0117] Various components can be appropriately blended into the curable hard coat precursor layer, provided that they do 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, defoamers, antifouling agents (e.g., surfactants), dispersants, silane coupling agents, surface modifiers, dyes, pigments, and fillers (e.g., organic and inorganic fillers). These optional components can be used individually or in combination of two or more.

[0118] There are no particular restrictions on the thickness of the curable hard coat precursor layer, and it can be set appropriately to achieve the desired performance (e.g., surface hardness, wear resistance) according to the application. For example, such a thickness can be 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. There are no particular restrictions on the upper limit of such a thickness, and for example, it can be 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 this 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 achieved after curing even if the thickness of the curable hard coat precursor layer is thin. From the viewpoint of productivity, thermoformability, surface hardness, and IPA crack resistance, such a thickness is preferably in the range of 1 to 20 μm. Furthermore, the thickness of the curable hard coat precursor layer can correspond to the thickness of the hard coat layer after curing.

[0119] The thickness of each layer in the thermoforming laminate of this disclosure can be determined using a digital caliper (ABS digital caliper CD-AX, manufactured by Mitutoyo Corporation) or a high-precision digital micrometer (MDH-25MB, manufactured by Mitutoyo Corporation), and / or an optical microscope or a scanning electron microscope. For example, for relatively thin layers such as a hard coat layer, the thickness can be determined by measuring the cross-section of the laminate in the thickness direction using an optical microscope or a scanning electron microscope and taking the average value of the thickness of at least five arbitrary locations in the target layer of the laminate configuration, such as the hard coat layer. The thickness of the first polycarbonate resin layer that can be used as a base material can be determined by first measuring the thickness at at least five arbitrary points in the laminate using a digital caliper (ABS digital caliper CD-AX, manufactured by Mitutoyo Corporation) or a high-precision digital micrometer (MDH-25MB, manufactured by Mitutoyo Corporation), calculating the average value, and then subtracting the thickness of other layers (such as a hard coat layer) obtained using an optical microscope or scanning electron microscope from this value.

[0120] <Pencil hardness> The pencil hardness of the surface of the thermoformable laminate and laminated product of this disclosure is preferably 3H or higher. There is no particular upper limit to the pencil hardness, and it can be 5H or less, or 4H or less. When the pencil hardness is within this range, wear resistance and scratch resistance can be improved.

[0121] Here, pencil hardness refers to the value obtained by measuring the pencil hardness of the coating (hard coat layer) on thermoformable laminates and laminated products as test specimens, in accordance with JIS K5600-5-4-1999.

[0122] <Any layer> The thermoforming laminate of this disclosure may further comprise one or more layers as appropriate, depending on the intended use, provided that these layers do not adversely affect the effects of this disclosure. Examples of such 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. Any of these layers can be used alone or in combination of two or more. For example, the design layer and the adhesive layer will be described in detail below, but the layers are not limited to these.

[0123] (Design layer) In some embodiments, the thermoformable laminate of the present disclosure may include a decorative layer. The decorative layer may be applied to any part of the thermoformable laminate, but it is preferably applied between the first polycarbonate resin layer (105) and the second polycarbonate resin layer (103) of the thermoformable laminate (100), and / or between the second polycarbonate resin layer (103) and the curable hard coat precursor layer (101), as shown in Figure 1. When the decorative layer is applied to such a location, the decorative layer can be protected by the second polycarbonate resin layer and / or the curable hard coat precursor layer or the hard coat layer. The decorative layer may be formed over the entire surface to which it is applied, or it may be formed partially. The thermoformable laminate having a decorative layer may also be referred to as a decorative sheet.

[0124] There are no particular restrictions on the design layer, as long as it is a layer capable of exhibiting design (decorative) properties. Examples of design layers include colored layers that exhibit special hues or metallic colors, and patterned layers that can be given patterns (e.g., wood grain, stone pattern), logos, or illustrations. The design layer may be of a single type, or it may be a combination of multiple design layers.

[0125] The thickness of the design layer can vary; for example, it can be 1 μm or more, 2 μm or more, or 5 μm or more, and it can also be 50 μm or less, 30 μm or less, 10 μm or less, 8 μm or less, or 5 μm or less.

[0126] (adhesive layer) Various adhesive layers can be applied to the thermoformable laminate of this disclosure. The adhesive layer may be a single layer or a multi-layer structure. The adhesive layer may be applied to the entire surface of the laminate or to a portion of it. Typically, the adhesive layer may be used to bond the thermoformable laminate of this disclosure to an adherend (support member), as shown in Figure 2.

[0127] There are no particular restrictions on the adhesive that can form the adhesive layer. For example, commonly used adhesives such as (meth)acrylic, polyolefin, polyurethane, polyester, and rubber-based adhesives, including solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives, can be used. Adhesives can be used alone or in combination of two or more types. The adhesive layer can be applied by known wet coating methods, etc.

[0128] Various components may be appropriately blended into the adhesive layer, provided that they do 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, dispersants, tackifiers, plasticizers, leveling agents, defoamers, antifouling agents (e.g., surfactants), silane coupling agents, surface modifiers, dyes, pigments, and fillers (e.g., organic and inorganic fillers). Optional components can be used individually or in combination of two or more.

[0129] 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.

[0130] There are no particular limitations on the overall thickness of the thermoforming laminate of this disclosure. For example, it can be 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. It can also 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.

[0131] Method for manufacturing molded products Using the thermoforming laminate of this disclosure, molded products (laminated molded products) can be manufactured by various conventionally known molding methods. In these manufacturing methods, the constituent materials of the thermoforming laminate described above can be used in the same manner.

[0132] One example of a molding method for molded products is the insert molding method, which is an in-mold decoration method in injection molding. In this method, a thermoformable laminate, which has been pre-shaped by vacuum forming or pressure forming to conform to the shape of the injection molding die cavity, is set inside the mold, and molten resin is injected into it, simultaneously with injection molding, welding the thermoformable laminate to the support member (resin molded product) and integrating them to obtain a molded product.

[0133] Other molding methods include, for example, a method in which a thermoforming laminate is attached to the mold cavity side under vacuum pressure, molten resin is injected into it, and heat and pressure are applied to bond the thermoforming laminate to a support member (resin molded product) to obtain a molded product.

[0134] Other molding methods include lamination by vacuum forming or pressure forming. Various methods can be used to heat the thermoforming laminate during thermoforming, such as infrared heaters, electric heaters, high-frequency induction, halogen lamps, microwaves, high-temperature derivatives (such as steam), and lasers. Using such methods, materials other than resin can be used as the material for the support member.

[0135] 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, fabric materials (e.g., woven fabrics, knitted fabrics, nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, stainless steel), and wood-based materials including paper.

[0136] The molding method described above is not limited to the following temperatures, but can generally be subjected to temperatures of approximately 140°C to 180°C depending on the process. Therefore, the molded product can be cooled or allowed to cool as needed. Subsequently, the curable hard coat precursor layer applied to the molded product can be cured by irradiation with active energy rays (ultraviolet light, visible light, infrared light, or electron beams) as needed. The active energy rays may be polarized or unpolarized. Among the active energy rays, ultraviolet light is preferred from the viewpoint of equipment cost, safety, and running cost. When curing by ultraviolet irradiation, a photopolymerization initiator is typically used. Examples of ultraviolet energy sources 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 / cm² as the cumulative exposure dose at an ultraviolet wavelength of 365 nm. 2 A range of 300 to 3,000 mJ / cm² is preferred. 2 This is more preferable. When the irradiation dose is within this range, a hard coat layer with excellent performance, such as surface hardness, can be obtained.

[0137] 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 oxygen-free atmosphere, can be obtained, for example, by replacing the atmosphere in at least the irradiation area within the irradiation apparatus with an inert gas. Examples of inert gases include nitrogen, helium, neon, and argon. Furthermore, if the three-dimensional shape of the support member to which the thermoformable laminate is applied is gentle, the hardening-type hard coat precursor layer can be cured before applying the thermoformable laminate to the support member.

[0138] 《Molded products》 The molded articles (laminated molded articles) of this disclosure can typically be obtained by the manufacturing method described above. In some embodiments, the molded articles of this disclosure are formed by bonding the thermoforming laminate described above to a support member. Alternatively, a curable hard coat precursor layer may harden to form a hard coat layer.

[0139] In some embodiments, the molded articles of this disclosure have a three-dimensional shape. Here, "three-dimensional shape" refers to a three-dimensional shape that adds a Z-axis to a two-dimensional shape (a planar shape with only the X and Y axes). Here, "three-dimensional shape" in this disclosure may also include, for example, curved shapes.

[0140] There are no particular restrictions on the form in which the molded products can be used. Examples 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 equipment or products, cases for general merchandise, switches, keys, keypads, handles, levers, buttons, and housings or exterior parts for home appliances and AV equipment (e.g., personal computers), mobile phones, and mobile devices. [Examples]

[0141] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The physical properties evaluated in the examples and comparative examples were performed by the following methods, and the results are summarized in Table 1. In the comparative examples, layers other than the polycarbonate resin layer are also used as intermediate layers, and the notation "second polycarbonate resin layer" is not appropriate, so in Table 1, they are referred to as layers A to C. Here, layers A, B, and C in Table 1 correspond to layers 105, 103, and 101 according to the lamination configuration in Figure 1, and "A / B" in the layer configuration of Tables 2 and 3, for example, means a two-layer configuration of layer A and layer B. "Constituent units of Formula 1" and "Constituent units of Formula 2" in Tables 2 and 3 refer to the constituent units of Formula 1 and Formula 2 shown above that constitute the polycarbonate resin, respectively. Furthermore, the measurement methods for various physical properties described in the examples are not limited to the laminates and their manufacturing methods described in the examples, but can also be similarly applied to the laminates and their manufacturing methods described above.

[0142] Examples 1-9 and Comparative Examples 1-6 In the physical property evaluations shown below, if the constituent includes a C layer, the evaluation of the curing reaction rate and moldability of the C layer (curable hard coat precursor layer) is a physical property evaluation before the curing treatment to enable it to function as a hard coat layer, while the evaluation of surface hardness, IPA cracking, and chemical resistance is a physical property evaluation after the curing treatment to enable it to function as a hard coat layer.

[0143] <Methods for evaluating various physical properties> (viscosity average molecular weight) The viscosity-average molecular weight of polycarbonate resin is first calculated using the following formula: the specific viscosity (η) SP The viscosity was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SP The viscosity-average molecular weight Mv was calculated from the following formula. ηSP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 -4 Mv 0.83 c = 0.7

[0144] (Glass transition temperature: Tg) The glass transition temperature (Tg) is measured using a 2910 DSC manufactured by T.A. Instruments Japan Co., Ltd., at a heating rate of 20°C / min.

[0145] (Moldability) Using a biaxial stretching test apparatus (manufactured by Toyo Seiki Co., Ltd.), the test sample was preheated at 160°C for 1 minute, and then stretched to a ratio of 1.3 times at the same temperature. The appearance of the test sample was evaluated according to the following index. Here, "A" and "B" ratings are considered acceptable, and "C" ratings are considered unacceptable: A: No cracks or clouding are observed. B: Slight clouding or weak cracks are observed. C: Cracks or cloudiness are observed.

[0146] (Surface hardness: Pencil hardness) The pencil hardness of the test sample surface was measured in accordance with JIS K5600-5-4-1999. Here, if the test sample had a two- or three-layer structure, the surface of the layer other than layer A (layer B or layer C) was evaluated, and in particular, if layer C was laminated, an integrated light intensity of 2,000 mJ / cm² was used. 2 The surface of the C layer was evaluated after curing it by UV irradiation. Furthermore, a surface hardness of 3H or higher can be considered acceptable.

[0147] (IPA crack) As shown in Figure 3(a), the test sample was bent using a clip so that layer A was facing inward, and in this state, the test sample was immersed in isopropyl alcohol for 10 seconds at room temperature. 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 index. Here, an "A" rating can be considered an acceptable level, and "B" and "C" ratings can be considered unacceptable levels (for example, Figure 3(b) corresponds to a "C" rating). For test samples with a layered C configuration, the cumulative light intensity was 2,000 mJ / cm². 2 The C layer was cured by UV irradiation, and then the test sample was bent using a clip. A correlation between curing and bending, and bending and then curing, had been confirmed beforehand, and this test can address conditions where further deformation stress is applied even after curing following molding. A: No cracks were found. B: Fine cracks have appeared. C: Severe cracking occurs.

[0148] (Chemical resistance) At room temperature, filter paper soaked in acetone was placed in contact with the surface of the test sample and left for 30 minutes. Afterward, the surface of the test sample was wiped with a Kimwipe, and the appearance of the test sample was evaluated according to the following criteria. Here, an "A" rating is considered a passing level, while "B" and "C" ratings are considered failing levels. A: No change. B: Surface gloss is slightly reduced. C: The surface is not glossy.

[0149] (C layer hardening reaction rate) The curing reaction rate of the curable resin in the curable hard coat precursor layer (C layer) was measured using FT-IR and the ATR method. More specifically, an uncured coating layer dried with hot air in an 80°C drying oven for 2 minutes was measured as a reference, and the measurement was performed at 1730 cm². -1 The nearby peak (C=O absorption zone) and 800cm -1The peak intensity ratio was calculated from the peak intensities of nearby peaks (=CH absorption bands) using the following formulas c and d. The peak intensity ratio was also calculated for the coating layer of the sample being measured for curing reaction rate using the same procedure: Peak intensity ratio = 800 cm -1 Peak intensity / 1730cm -1 Peak intensity of ... equation c Curing reaction rate (%) = (1 - Peak intensity ratio of the coating layer of the sample being measured / Peak intensity ratio of the coating layer of the reference) × 100 ... Equation d

[0150] <Example 1> (Molding material A) (Resin G) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 14,876 parts of deionized water and 6,612 parts of 25% sodium hydroxide aqueous solution were added. 3,140 parts of BPA and 6.28 parts of hydrosulfite were dissolved as diol compounds. Then, 14,050 parts of methylene chloride were added, and 1,500 parts of phosgene were blown in over 70 minutes at 16-24°C while stirring. Subsequently, 1,102 parts of 25% sodium hydroxide aqueous solution were added, followed by a solution of 88.84 parts of p-tert-butylphenol dissolved in 251 parts of methylene chloride. The mixture was then stirred to create an emulsified state. Under this stirring, 2.78 parts of triethylamine were added when the reaction mixture was at 28°C. The reaction was then terminated after stirring was continued for 1 hour at 26-31°C. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with deionized water. Once the washing solution became neutral, it was washed with hydrochloric acid-acidified water. Subsequently, the mixture was repeatedly washed with deionized water until the conductivity of the aqueous phase was almost the same as that of the deionized water. It was then placed in a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a polycarbonate resin powder. After dehydration, it was dried at 100°C for 12 hours in a hot air circulating dryer to obtain a white, powdery polycarbonate resin H. This resin G corresponds to the resin material for the first polycarbonate resin layer of this disclosure. After pre-drying the polycarbonate resin G powder, it was extruded into pellets using a twin-screw extruder at a cylinder temperature of 260°C to obtain molding material A for layer A.

[0151] (Molding material B) (Resin A) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 24,983 parts by mass of deionized water and 7,649 parts by mass of 25% sodium hydroxide aqueous solution were added. 1,598 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemical Co., Ltd.), 2,707 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (BPA; manufactured by Nippon Steel Chemical & Material Co., Ltd.), and 8.6 parts by mass of hydrosulfite were dissolved as diol compounds. Then, 19,662 parts by mass of methylene chloride was added, and 2,000 parts by mass of phosgene were blown in over 80 minutes at 16-24°C under stirring. Subsequently, a solution of 1,233 parts by mass of 25% sodium hydroxide aqueous solution and 106.4 parts by mass of p-tert-butylphenol dissolved in 1,064 parts by mass of methylene chloride was added and stirred to achieve an emulsified state. Under such stirring, 3.9 parts by mass of triethylamine were added to the reaction solution at 28°C, and stirring was continued for 1 hour at a temperature of 26-31°C to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with deionized water. When the washing solution became neutral, hydrochloric acid was added. Subsequently, the solution was repeatedly washed with deionized water until the conductivity of the aqueous phase was approximately the same as that of deionized water, thereby obtaining a methylene chloride solution of polycarbonate. Next, the obtained methylene chloride solution was added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flake-like solid. The obtained solid was dried at 120°C for 24 hours to obtain a white flake-like polycarbonate resin A. This resin A corresponds to the resin material for the second polycarbonate resin layer of this disclosure. After pre-drying the polycarbonate resin A flakes, they were extruded into pellets using a twin-screw extruder at a cylinder temperature of 320°C to obtain molding material B for layer B.

[0152] (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 320°C (molding material B), screw rotation speed of 50 rpm (molding material A) and 42 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a test sample with a laminated structure of approximately 300 mm in width and approximately 200 μm in thickness, having a two-layer structure of A layer / B layer (A layer approximately 110 μm, B layer approximately 90 μm).

[0153] <Example 2> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) (Resin B) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 21818 parts by mass of deionized water and 8533 parts by mass of 25% sodium hydroxide aqueous solution were added. 2548 parts by mass of BNF, 2689 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 10.48 parts by mass of hydrosulfite were dissolved as diol compounds. Then, 20606 parts by mass of methylene chloride were added, and 2000 parts by mass of phosgene were blown in over 70 minutes at 16-24°C under stirring. Subsequently, a solution of 1292 parts by mass of 25% sodium hydroxide aqueous solution and 150.3 parts by mass of p-tert-butylphenol dissolved in 1503 parts by mass of methylene chloride was added and stirred to create an emulsified state. Under this stirring, 4.08 parts by mass of triethylamine were added to the reaction mixture at 28°C, and stirring was continued for 1 hour at a temperature of 26-31°C to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with deionized water. When the washing solution became neutral, hydrochloric acid was added. Then, the solution was repeatedly washed with deionized water until the conductivity of the aqueous phase was approximately the same as that of the deionized water, to obtain a methylene chloride solution of polycarbonate. Next, the obtained methylene chloride solution was added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flake-like solid. The obtained solid was dried at 120°C for 24 hours to obtain a white flake-like polycarbonate resin B. This resin B corresponds to the resin material for the second polycarbonate resin layer of this disclosure. After pre-drying the polycarbonate resin B flakes, they were extruded into pellets using a twin-screw extruder at a cylinder temperature of 320°C to obtain molding material B for layer B.

[0154] (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 310°C (molding material B), screw rotation speed of 50 rpm (molding material A) and 42 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a test sample with a laminated structure of approximately 300 mm in width and approximately 200 μm in thickness, having a two-layer structure of A layer / B layer (A layer approximately 110 μm, B layer approximately 90 μm).

[0155] <Example 3> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) The molding material B from Example 2 was used in the same manner. (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 310°C (molding material B), screw rotation speed of 64 rpm (molding material A) and 28 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a test sample with a laminated structure of approximately 300 mm in width and approximately 200 μm in thickness, having a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0156] <Example 4> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) (Resin C) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 24,982 parts by mass of deionized water and 7,648 parts by mass of 25% sodium hydroxide aqueous solution were added. 1,390 parts by mass of BNF, 3,159 parts by mass of BPC, and 9.15 parts by mass of hydrosulfite were dissolved as diol compounds. Then, 19,663 parts by mass of methylene chloride were added, and 2,000 parts by mass of phosgene were blown in over 70 minutes at 16-24°C under stirring. Subsequently, a solution of 1,234 parts by mass of 25% sodium hydroxide aqueous solution and 69.3 parts by mass of p-tert-butylphenol dissolved in 693 parts by mass of methylene chloride was added and stirred to emulsify. Under this stirring, 3.9 parts by mass of triethylamine were added to the reaction mixture at 28°C, and stirring was continued for 1 hour at a temperature of 26-31°C to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with deionized water. When the washing solution became neutral, hydrochloric acid was added. Subsequently, the mixture was repeatedly washed with deionized water until the conductivity of the aqueous phase was approximately the same as that of the deionized water, thereby obtaining a polycarbonate methylene chloride solution. Next, the obtained methylene chloride solution was added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flake-like solid. The obtained solid was dried at 120°C for 24 hours to obtain a white flake-like polycarbonate resin C. This resin C corresponds to the resin material for the second polycarbonate resin layer of this disclosure. After pre-drying the polycarbonate resin C flakes, they were extruded into pellets using a twin-screw extruder at a cylinder temperature of 320°C to obtain molding material B for layer B.

[0157] (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 310°C (molding material B), screw rotation speed of 50 rpm (molding material A) and 42 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a test sample with a laminated structure of approximately 300 mm in width and approximately 200 μm in thickness, having a two-layer structure of A layer / B layer (A layer approximately 110 μm, B layer approximately 90 μm).

[0158] <Comparative Example 1> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) Polymethyl methacrylate resin pellets (Mitsubishi Chemical Corporation's Acrypet® VH-001) were pre-dried to obtain molding material B for layer B. The glass transition temperature of molding material B was 110°C. In Tables 2 and 3, the resin type of molding material B (polymethyl methacrylate resin) is denoted as "PMMA". (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 280°C (molding material A) and 250°C (molding material B), screw rotation speed of 64 rpm (molding material A) and 28 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a test sample with a laminated structure of approximately 300 mm in width and approximately 200 μm in thickness, having a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0159] <Comparative Example 2> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) (Resin F) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 10,663 parts of deionized water and 6,015 parts of 25% sodium hydroxide aqueous solution were added. 2,921 parts of BPC and 5.84 parts of hydrosulfite were dissolved as diol compounds. Then, 12,588 parts of methylene chloride were added, and 1,500 parts of phosgene were blown in over 70 minutes at 16-24°C under stirring. Subsequently, 911 parts of 25% sodium hydroxide aqueous solution and 0.58 parts of triethylamine were added, followed by a solution of 51.26 parts of p-tert-butylphenol dissolved in 277 parts of methylene chloride. The mixture was then stirred to create an emulsified state. Under this stirring, 2.30 parts of triethylamine were added when the reaction mixture was at 28°C. The reaction was then terminated after stirring was continued for 1 hour at 26-31°C. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with deionized water. Once the washing solution became neutral, it was washed with hydrochloric acid-acidified water. Subsequently, the mixture was repeatedly washed with deionized water until the conductivity of the aqueous phase was almost the same as that of the deionized water. It was then placed in a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a resin powder. After dehydration, it was dried at 100°C for 12 hours in a hot air circulating dryer to obtain a white, powdery polycarbonate resin. After pre-drying the polycarbonate resin F powder, it was extruded into pellets using a twin-screw extruder at a cylinder temperature of 250°C to obtain molding material B for layer B.

[0160] (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 280°C (molding material A) and 250°C (molding material B), screw rotation speed of 64 rpm (molding material A) and 28 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a test sample with a laminated structure of approximately 300 mm in width and approximately 200 μm in thickness, having a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0161] <Comparative Example 3> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) Polycarbonate resin pellets (Teijin Panlite® SH-1126Z (polycarbonate resin containing 50 mol% bisphenol A (BPA) and 50 mol% bisphenol C (BPC) (viscosity-average molecular weight 20,200))) were pre-dried to obtain molding material B for layer B. The glass transition temperature of molding material B was 130°C. In Table 2, the resin type of this molding material B is denoted as "PC-AC". (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 280°C (molding material A) and 260°C (molding material B), screw rotation speed of 64 rpm (molding material A) and 28 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a test sample with a laminated structure of approximately 300 mm in width and approximately 200 μm in thickness, having a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm).

[0162] <Comparative Example 4> (Molding material A) (Resin D) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 21818 parts by mass of deionized water and 8533 parts by mass of 25% sodium hydroxide aqueous solution were added. 2548 parts by mass of BNF, 2689 parts by mass of BPC, and 10.48 parts by mass of hydrosulfite were dissolved as diol compounds. Then, 20606 parts by mass of methylene chloride were added, and 2000 parts by mass of phosgene were blown in over 70 minutes at 16-24°C under stirring. Subsequently, a solution of 1234 parts by mass of 25% sodium hydroxide aqueous solution and 72.73 parts by mass of p-tert-butylphenol dissolved in 727 parts by mass of methylene chloride was added and stirred to emulsify. Under this stirring, 4.08 parts by mass of triethylamine was added to the reaction mixture at 28°C, and stirring was continued for 1 hour at a temperature of 26-31°C to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with deionized water. When the washing solution became neutral, hydrochloric acid was added. Subsequently, the mixture was repeatedly washed with deionized water until the conductivity of the aqueous phase was approximately the same as that of the deionized water, thereby obtaining a polycarbonate methylene chloride solution. Next, the obtained methylene chloride solution was dropped dropwise into warm water maintained at 50-80°C to evaporate and remove the solvent, obtaining a flake-like solid. The obtained solid was dried at 120°C for 24 hours to obtain a white flake-like polycarbonate resin C. This resin D corresponds to the resin material for the second polycarbonate resin layer of this disclosure. After pre-drying the polycarbonate resin D powder, it was extruded into pellets using a twin-screw extruder at a cylinder temperature of 320°C to obtain molding material A for layer A.

[0163] Molding material A was extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under conditions of cylinder temperature of 320 °C and screw rotation speed of 46 rpm. After the molten resin was compressed between metal rolls and cooled, the edges were trimmed and the material was wound at a winding speed of 1.0 m / min to produce a test sample consisting solely of layer A with a width of approximately 300 mm and a thickness of approximately 200 μm.

[0164] <Example 5> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) The molding material B from Example 4 was used in the same manner. (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 300°C (molding material B), screw rotation speed of 50 rpm (molding material A) and 42 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a laminate with a width of approximately 300 mm and a thickness of approximately 200 μm, having a two-layer structure of A layer / B layer (A layer approximately 110 μm, B layer approximately 90 μm). (Paint C) As a coating to form layer C, 100 parts by mass of the urethane acrylate-based UV-curable resin "Forseed (trademark) No. 371C (product name)" (solids content 40%, manufactured by Chugoku Marine Paints and Marine Paints), 5 parts by mass of Irgacure (trademark) 184 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals), and 3 parts by mass of the hindered amine compound "TINUVIN (trademark) 292 (product name)" (manufactured by BASF) were diluted with methyl isobutyl ketone until the solids content concentration of the UV-curable resin in the coating was 30%, and the mixture was thoroughly stirred to prepare the coating. (Coating) Paint C was applied to the side of layer B of a laminate fabricated by co-extrusion, opposite to layer A, using a bar coater (#8). The layer was then dried with hot air in a 100°C drying oven for 5 minutes to form layer C with a thickness of approximately 5 μm. A test sample was then prepared with a laminated structure in which layers A / B / C were stacked in this order. The curing reaction rate of the acrylate in this case was 3%.

[0165] <Example 6> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) After pre-drying the same polycarbonate resin D powder as in Comparative Example 4, it was extruded into pellets using a twin-screw extruder at a cylinder temperature of 300°C to obtain molding material B for layer B. (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder having a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 320°C (molding material B), screw rotation speed of 50 rpm (molding material A) and 42 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a laminate with a width of approximately 300 mm and a thickness of approximately 200 μm, having a two-layer structure of A layer / B layer (A layer approximately 110 μm, B layer approximately 90 μm). (Paint C) Paint C from Example 5 was used in the same manner. (Coating) Paint C was applied to the side of layer B of a laminate fabricated by co-extrusion, opposite to layer A, using a bar coater (#8). The layer was then dried with hot air in a 100°C drying oven for 5 minutes to form layer C with a thickness of approximately 5 μm. A test sample was then prepared with a laminated structure in which layers A / B / C were stacked in this order. The curing reaction rate of the acrylate in this case was 3%.

[0166] <Example 7> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) The molding material B from Example 6 was used in the same manner. (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 320°C (molding material B), screw rotation speed of 64 rpm (molding material A) and 28 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a laminate with a width of approximately 300 mm and a thickness of approximately 200 μm, having a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm). (Paint C) Paint C from Example 5 was used in the same manner. (Coating) Paint C was applied to the side of layer B of a laminate fabricated by co-extrusion, opposite to layer A, using a bar coater (#8). The layer was then dried with hot air in a 100°C drying oven for 5 minutes to form layer C with a thickness of approximately 5 μm. A test sample was then prepared with a laminated structure in which layers A / B / C were stacked in this order. The curing reaction rate of the acrylate in this case was 3%.

[0167] <Example 8> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) The molding material B from Example 6 was used in the same manner. (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 320°C (molding material B), screw rotation speed of 71 rpm (molding material A) and 21 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a laminate with a width of approximately 300 mm and a thickness of approximately 200 μm, having a two-layer structure of A layer / B layer (A layer approximately 155 μm, B layer approximately 45 μm). (Paint C) Paint C from Example 5 was used in the same manner. (Coating) Paint C was applied to the side of layer B of a laminate fabricated by co-extrusion, opposite to layer A, using a bar coater (#8). The layer was then dried with hot air in a 100°C drying oven for 5 minutes to form layer C with a thickness of approximately 5 μm. A test sample was then prepared with a laminated structure in which layers A / B / C were stacked in this order. The curing reaction rate of the acrylate in this case was 3%.

[0168] <Example 9> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) (Resin E) In a reactor equipped with a thermometer, stirrer, and reflux condenser, 24,982 parts by mass of deionized water and 7,649 parts by mass of 25% sodium hydroxide aqueous solution were added. 1,390 parts by mass of BNF, 1,579 parts by mass of BPC, 1,405 parts by mass of BPA, and 8.78 parts by mass of hydrosulfite were dissolved as diol compounds. Then, 19,662 parts by mass of methylene chloride were added, and 2,000 parts by mass of phosgene were blown in over 70 minutes at 16-24°C under stirring. Subsequently, a solution of 1,234 parts by mass of 25% sodium hydroxide aqueous solution and 69.4 parts by mass of p-tert-butylphenol dissolved in 694 parts by mass of methylene chloride was added and stirred to create an emulsified state. Under this stirring, 3.8 parts by mass of triethylamine were added to the reaction mixture at 28°C, and stirring was continued for 1 hour at a temperature of 26-31°C to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with deionized water. When the washing solution became neutral, hydrochloric acid was added. Then, the solution was repeatedly washed with deionized water until the conductivity of the aqueous phase was approximately the same as that of the deionized water, to obtain a methylene chloride solution of polycarbonate. Next, the obtained methylene chloride solution was added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flake-like solid. The obtained solid was dried at 120°C for 24 hours to obtain white flake-like polycarbonate resin E. After pre-drying the polycarbonate resin E flakes, they were extruded into pellets using a twin-screw extruder at a cylinder temperature of 310°C to obtain molding material B for layer B.

[0169] (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 300°C (molding material A) and 310°C (molding material B), screw rotation speed of 50 rpm (molding material A) and 42 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a laminate with a width of approximately 300 mm and a thickness of approximately 200 μm, having a two-layer structure of A layer / B layer (A layer approximately 110 μm, B layer approximately 90 μm). (Paint C) Paint C from Example 5 was used in the same manner. (Coating) Paint C was applied to the side of layer B of a laminate fabricated by co-extrusion, opposite to layer A, using a bar coater (#8). The layer was then dried with hot air in a 100°C drying oven for 5 minutes to form layer C with a thickness of approximately 5 μm. A test sample was then prepared with a laminated structure in which layers A / B / C were stacked in this order. The curing reaction rate of the acrylate in this case was 3%.

[0170] <Comparative Example 5> (Molding material A) The molding material A from Example 1 was used in the same manner. (Molding material B) The molding material B from Comparative Example 1 was used in the same manner. (Co-extrusion) Molding material A and molding material B were extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under the conditions of cylinder temperature of 280°C (molding material A) and 250°C (molding material B), screw rotation speed of 64 rpm (molding material A) and 28 rpm (molding material B). After cooling the molten resin by compressing it between metal rolls, the edges were trimmed and the material was wound at a winding speed of 2.0 m / min to produce a laminate with a width of approximately 300 mm and a thickness of approximately 200 μm, having a two-layer structure of A layer / B layer (A layer approximately 140 μm, B layer approximately 60 μm). (Paint C) Paint C from Example 5 was used in the same manner. (Coating) Paint C was applied to the side of layer B of a laminate fabricated by co-extrusion, opposite to layer A, using a bar coater (#8). The layer was then dried with hot air in a 100°C drying oven for 5 minutes to form layer C with a thickness of approximately 5 μm. A test sample was then prepared with a laminated structure in which layers A / B / C were stacked in this order. The curing reaction rate of the acrylate in this case was 3%.

[0171] <Comparative Example 6> (Molding material A) The molding material A from Comparative Example 4 was used in the same manner. (Extrusion) Molding material A was extruded from a 350 mm wide T-die using a feed block system with a single-screw extruder with a screw diameter of 25 mm, under conditions of cylinder temperature of 320 °C and screw rotation speed of 46 rpm. After the molten resin was compressed between metal rolls and cooled, the edges were trimmed and the material was wound at a winding speed of 1.0 m / min to produce a sheet consisting solely of layer A with a width of approximately 300 mm and a thickness of approximately 200 μm. (Paint C) Paint C from Example 5 was used in the same manner. (Coating) A sheet consisting solely of layer A was coated with paint C using a bar coater (#8), and then dried with hot air in a 100°C drying oven for 5 minutes to form layer C with a thickness of approximately 5 μm. A test sample with a laminated structure in which layers A / B / C were stacked in this order was prepared. The curing reaction rate of the acrylate in this case was 3%.

[0172] [Table 1]

[0173] [Table 2]

[0174] [Table 3] [Industrial applicability]

[0175] The thermoformable laminates of this disclosure, and laminated molded articles including said laminates, are useful, for example, as components for automotive interior and exterior materials, automotive indicator panels, electrical appliances, cosmetic cases, interior and exterior building materials, cases for various equipment or products, cases for general merchandise, switches, keys, keypads, handles, levers, buttons, and housings or exterior parts for home appliances and AV equipment (e.g., personal computers), mobile phones and mobile devices. [Explanation of symbols]

[0176] 100 Laminates for thermoforming 101 Curable hard coat precursor layer 103, 203 Second polycarbonate resin layer 105, 205 First polycarbonate resin layer 200 Laminated Molded Products 202 Hard Court Layer 207 Adhesive layer 209 Support member

Claims

1. It comprises, in order, a first polycarbonate resin layer and a second polycarbonate resin layer. The proportion of the constituent units of the following formula 1 in the first polycarbonate resin contained in the first polycarbonate resin layer is 90 mol% or more, and The proportion of the constituent units of the following formula 2 in the second polycarbonate resin contained in the second polycarbonate resin layer is 15 mol% or more and 95 mol% or less. Laminates for thermoforming: 【Chemistry 1】 【Chemistry 2】 In formula 2, Ring Z is a condensed polycyclic arene ring, R １ and R ２ Each of these independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

2. The thermoforming laminate according to claim 1, wherein in the constituent unit of formula 2, ring Z is a naphthalene ring.

3. The thermoforming laminate according to claim 1, wherein the proportion of the constituent units of the following formula 3 in the second polycarbonate resin contained in the second polycarbonate resin layer is 40 mol% or more. 【Transformation 3】 In formula 3, W represents a single bond, an alkylene group with 1 to 6 carbon atoms, an arylene group with 6 to 10 carbon atoms, or a cyclic alkylene group with 3 to 8 carbon atoms.

4. The thermoforming laminate according to claim 3, wherein the constituent unit of formula 3 is a constituent 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, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2'-methyl-4,4'-biphenyldiol, and 2,2-bis(4-hydroxyphenyl)propane.

5. The thermoforming laminate according to claim 1, wherein when the thickness of the first polycarbonate resin layer is A (μm) and the thickness of the second polycarbonate layer is B (μm), A / B > 1.

0.

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

7. The viscosity-average molecular weight of the second polycarbonate resin contained in the second polycarbonate resin layer is 1.0 × 10 ４ The above is 10.0 x 10 ４ The thermoforming laminate according to claim 1, which is as follows:

8. A thermoforming laminate according to claim 1, wherein a hard coat layer is laminated on the side of the second polycarbonate resin layer of the thermoforming laminate that is opposite to the first polycarbonate resin layer.

9. The thermoforming laminate according to claim 8, wherein the thickness of the hard coat layer is 1 to 20 μm.

10. The thermoforming laminate according to claim 8, wherein the hard coat layer comprises an ultraviolet-curable resin composition.

11. The thermoforming laminate according to claim 8, wherein the hard coat layer is a curable hard coat precursor layer, and the curing reaction rate of the curable hard coat precursor layer is 2% or more and 50% or less.

12. A laminated molded product obtained by thermoforming a thermoformable laminate according to any one of claims 1 to 10 to give it a three-dimensional shape.

13. A laminated molded product obtained by thermoforming the thermoformable laminate described in claim 11 to impart a three-dimensional shape, and then performing a curing treatment on the curable hard coat precursor layer to form a hard coat layer.

14. Automotive interior and exterior parts using the laminated molded product according to claim 12 or claim 13.

15. A full panel for a display using the laminated molded product according to claim 12 or claim 13.

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