Laminated sheet, molded body, and front panel for display device

Abstract

Provided is a laminated sheet that has excellent resistance to warping deformation in a high-temperature (high-humidity) environment. The laminated sheet of the present disclosure includes a layer made of a methacrylic resin composition (MR) containing a glutarimide resin and a layer made of a polycarbonate resin composition (PCR), and has a total thickness of 500 to 5,000 μm. The glass transition temperature of the methacrylic resin composition (MR) is Tg MR [℃], the glass transition temperature of the polycarbonate resin composition (PCR) is Tg PCR [℃], the average linear expansion coefficient of the methacrylic resin composition (MR) is α MR [ppm / ℃], and the average linear expansion coefficient of the polycarbonate resin composition (PCR) is α PCR [ppm / ℃], 140≦Tg MR ≦170, 0≦|Tg PCR -Tg MR |≦15 and 0≦α PCR -α MR ≦30, and the saturated water absorption rate of the methacrylic resin composition (MR) at 23° C. is 0 to 3.0 mass %.

Description

[Technical Field]

[0001] The present disclosure relates to a laminate sheet, a molded body, and a front panel for a display device. [Background technology]

[0002] Methacrylic resins are excellent in transparency, scratch resistance, and weather resistance, while polycarbonate resins are excellent in impact resistance. A laminate sheet containing a methacrylic resin-containing layer and a polycarbonate resin-containing layer has the properties of both resins and is suitable for applications requiring high appearance, surface strength, durability, etc., such as electronic devices such as display devices; home appliances; house walls; and furniture. In such applications, the laminate sheet can further have a functional layer such as a hard coat layer (also called a scratch-resistant layer or a scratch-resistant (hard coat) cured coating). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-248416 [Patent Document 2] International Publication No. 2021 / 215435 [Patent Document 3] JP 2009-279806 A [Patent Document 4] JP 2015-34285 A [Patent Document 5] International Publication No. 2016 / 042727 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-128899 Summary of the Invention [Problem to be solved by the invention]

[0004] In the laminate sheet, the thickness of the methacrylic resin-containing layer is preferably designed to be 30 to 200 μm from the viewpoint of the balance between scratch resistance and impact resistance. In such a design, if the total thickness of the laminate sheet is large, the ratio of the thickness of the methacrylic resin-containing layer to the total thickness of the laminate sheet becomes small, and warping may occur in a high-temperature (high-humidity) environment. In this specification, "high temperature (high humidity) environment" is a general term for high temperature environment and high temperature / high humidity environment, and "(high temperature) high humidity environment" is a general term for high humidity environment and high temperature / high humidity environment.

[0005] As a first prior art technique for suppressing warpage of the above-mentioned laminated sheet in a high-temperature (high-humidity) environment, Patent Documents 1 to 4 disclose laminates using, as a methacrylic resin, a methacrylic resin containing a ring structural unit that has excellent heat resistance and moisture resistance (Claim 1 of Patent Document 1, Claim 1 of Patent Document 2, Claim 4 of Patent Document 3, and Paragraph 0037 of Patent Document 4). In this specification, unless otherwise specified, a "ring structural unit" is a structural unit having a ring structure in the main chain. However, according to the research of the present inventors, it has been found that in the laminates disclosed in these documents, when the amount of ring structural units in the ring structural unit-containing methacrylic resin is small, the difference between the glass transition temperature (Tg) of the methacrylic resin-containing layer and the glass transition temperature (Tg) of the polycarbonate resin layer is relatively large, and warping may occur in a high temperature (high humidity) environment.

[0006] Furthermore, compared to general methacrylic resins that do not contain ring structural units, methacrylic resins containing ring structural units tend to have inferior scratch resistance. The laminate sheets disclosed in the above documents preferably have a hard coat layer (also called an scratch-resistant layer or a scratch-resistant (hard coat) cured coating) on ​​the methacrylic resin-containing layer to improve scratch resistance (Claim 1 in Patent Document 1, Claim 9 in Patent Document 2, Claim 1 in Patent Document 3, and Claim 3 in Patent Document 4). However, the adhesion between the methacrylic resin-containing layer containing the ring structural unit-containing methacrylic resin and the hard coat layer may be poor. In Patent Document 4, the surface of a methacrylic resin-containing layer is subjected to a corona discharge treatment, and a coating film containing a silane coupling agent is formed on the surface (Claim 1). This method can improve the adhesion of the hard coat layer, but the poly(meth)acrylimide resin used in Patent Document 4 has relatively high water absorption and tends to have poor dimensional stability in a (high temperature) high humidity environment.

[0007] As a second prior art technique for suppressing warpage of the above-mentioned laminated sheet in a high-temperature (high-humidity) environment, a laminate in which the difference in linear expansion coefficient between the methacrylic resin-containing layer and the polycarbonate resin-containing layer is specified to be small is disclosed (Claim 2 of Patent Document 5, Claims 2 and 5 of Patent Document 6, Abstract). However, according to the research of the present inventors, it has been found that in the laminates disclosed in these documents, if the linear expansion coefficient of the methacrylic resin-containing layer is larger than the linear expansion coefficient of the polycarbonate resin-containing layer, a relatively large residual strain resulting from cooling strain occurs in the methacrylic resin-containing layer during the sheet manufacturing process using a co-extrusion molding method or the like, and when this residual strain is released in a high-temperature (high-humidity) environment, there is a risk of warping of the laminate sheet.

[0008] The present disclosure has been made in consideration of the above circumstances, and aims to provide a laminated sheet having a methacrylic resin-containing layer and a polycarbonate resin-containing layer, which has excellent heat resistance and moisture resistance, and is excellent in resistance to warpage deformation in a high-temperature (high-humidity) environment. Another object of the present disclosure is to provide a laminate sheet having a methacrylic resin-containing layer, a polycarbonate resin-containing layer, and a hard coat layer, which has excellent heat resistance and moisture resistance, excellent resistance to warpage deformation in a high-temperature (high-humidity) environment, and excellent adhesion of the hard coat layer. [Means for solving the problem]

[0009] The present disclosure provides the following laminate sheets [1] to

[10] . [1] One or more methacrylic resin-containing layers made of a methacrylic resin composition (MR) containing a glutarimide resin (G) containing 5 to 63 mass% of methyl methacrylate units, 35 to 75 mass% of glutarimide units represented by the following formula (I), 1 to 48 mass% of α-methylstyrene units, and 1 to 48 mass% of styrene units; and one or more polycarbonate-based resin-containing layers made of a polycarbonate-based resin composition (PCR) containing a polycarbonate-based resin (PC), A laminated sheet having a total thickness of 500 to 5,000 μm, The glass transition temperature of the methacrylic resin composition (MR) is Tg MR [°C], and the glass transition temperature of the polycarbonate resin composition (PCR) is Tg PCR [°C], and the average linear expansion coefficient of the methacrylic resin composition (MR) at 23 to 100°C is α MR [ppm / °C], and the average linear expansion coefficient of the polycarbonate resin composition (PCR) at 23 to 100°C is α PCR [ppm / ℃], 140≦Tg MR ≦170, 0≦|Tg PCR -Tg MR |≦15 and 0≦α PCR -α MR ≦30, A laminated sheet in which the saturated water absorption rate of the methacrylic resin composition (MR) at 23°C is 0 to 3.0% by mass.

[0010] [ka] (In formula (I), two R 1 are each independently a hydrogen atom or a methyl group. 2 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms and containing an aromatic ring.

[0011] [2] 145≦Tg MR A laminated sheet of [1] that satisfies ≦170. [3] 0≦|Tg PCR -TgMR A laminated sheet of [1] or [2] that satisfies |≦10. [4] 0≦α PCR -α MR A laminated sheet according to any one of [1] to [3], which satisfies ≦20. [5] The laminate sheet according to any one of [1] to [4], wherein the surface of the methacrylic resin-containing layer has a wet tension of 38 to 50 mN / m.

[0012] [6] The laminate sheet according to any one of [1] to [5], comprising a co-extrusion molded sheet including the methacrylic resin-containing layer and the polycarbonate resin-containing layer. [7] The laminate sheet according to any one of [1] to [6], further comprising a hard coat layer laminated on the methacrylic resin-containing layer. [8] The laminate sheet according to any one of [1] to [7], further comprising one or more functional layers selected from the group consisting of an anti-reflection layer, an anti-fingerprint layer, an anti-fogging layer, a weather-resistant layer, an anti-static layer, an anti-fouling layer, and an anti-glare layer. [9] A molded article comprising the laminated sheet according to any one of [1] to [8].

[10] A front panel for a display device, comprising the laminate sheet according to any one of [1] to [8]. [Effects of the Invention]

[0013] According to the present disclosure, it is possible to provide a laminate sheet that has a methacrylic resin-containing layer and a polycarbonate resin-containing layer, and that has excellent heat resistance and moisture resistance, as well as excellent resistance to warpage deformation in a high-temperature (high-humidity) environment. The present disclosure also makes it possible to provide a laminate sheet having a methacrylic resin-containing layer, a polycarbonate resin-containing layer, and a hard coat layer, which has excellent heat resistance and moisture resistance, excellent resistance to warpage deformation in a high-temperature (high-humidity) environment, and excellent adhesion of the hard coat layer. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a schematic cross-sectional view of a laminate sheet according to a first and second embodiment of the present invention. [Figure 2]FIG. 2 is a schematic cross-sectional view of a laminate sheet according to a third and fourth embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] Generally, terms such as "film" and "sheet" are used for thin film molded bodies depending on the thickness, but there is no clear distinction between them. In this specification, "sheet" includes "form". In this specification, unless otherwise specified, a "unit" contained in a polymer is a repeating unit contained in the polymer, and is a monomer unit derived from a raw material monomer or a derived unit derived from one or more monomer units. In this specification, (meth)acrylic is a general term for acrylic and methacrylic, and the same applies to (meth)acrylic acid, (meth)acrylonitrile, and the like.

[0016] In this specification, unless otherwise specified, the weight average molecular weight (Mw) of a resin is the weight average molecular weight (Mw) calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). The same applies to the number average molecular weight (Mn).

[0017] [Laminated sheet] The laminate sheet of the present disclosure includes one or more methacrylic resin-containing layers made of a methacrylic resin composition (MR) containing a glutarimide resin (G), and one or more polycarbonate resin-containing layers made of a polycarbonate resin composition (PCR) containing a polycarbonate resin (PC). The laminate sheet of the present disclosure may contain one or more other thermoplastic resin layers in addition to the methacrylic resin-containing layer and the polycarbonate resin-containing layer, if necessary. The laminate sheet of the present disclosure may have one or more functional layers, such as a hard coat layer, an anti-reflection layer, an anti-fingerprint layer, an anti-fogging layer, a weather-resistant layer (e.g., an ultraviolet blocking layer), an antistatic layer, an anti-fouling layer, an anti-glare layer, a colored layer, a printed layer, an adhesive layer, and a pressure-sensitive adhesive layer, as needed. The laminate sheet of the present disclosure may contain layers other than those described above, if necessary. The laminate sheet of the present disclosure has a total thickness of 500 to 5,000 μm.

[0018] FIG. 1 is a schematic cross-sectional view of a laminate sheet according to a first and second embodiment of the present invention. The laminate sheet 1A of the first embodiment is a thermoplastic resin sheet having a two-layer structure of a methacrylic resin-containing layer 11 and a polycarbonate resin-containing layer 21. The laminate sheet 1B of the second embodiment is a thermoplastic resin sheet having a three-layer structure of a first methacrylic resin-containing layer 11A, a polycarbonate resin-containing layer 21, and a second methacrylic resin-containing layer 11B.

[0019] Fig. 2 is a schematic cross-sectional view of a laminate sheet according to a third and fourth embodiment of the present invention, in which the same components as those in Fig. 1 are given the same reference numerals and their explanations will be omitted. The laminate sheet 2A of the third embodiment is a thermoplastic resin sheet with a hard coat layer, in which a hard coat layer 31 is laminated on the methacrylic resin-containing layer 11 of the laminate sheet 1A of the first embodiment shown in Fig. 1. The hard coat layer 31 may be formed on both sides of the laminate sheet 1A. The laminate sheet 2B of the fourth embodiment is a thermoplastic resin sheet with a hard coat layer, in which a hard coat layer 31 is laminated on one of the methacrylic resin-containing layers 11A of the laminate sheet 1B of the second embodiment shown in Fig. 1. The hard coat layer 31 may be formed on both sides of the laminate sheet 1B.

[0020] [Methacrylic resin composition (MR)] (Glutarimide resin (G)) The methacrylic resin composition (MR) contains one or more glutarimide resins (G) containing 5 to 63 mass% of methyl methacrylate (MMA) units, 35 to 75 mass% of glutarimide (GI) units, 1 to 48 mass% of α-methylstyrene (αMSt) units, and 1 to 48 mass% of styrene (St) units.

[0021] In the present disclosure, a glutarimide (GI) unit is a unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure represented by the following formula (I):

[0022] [ka]

[0023] In formula (I), two R 1 are each independently a hydrogen atom or a methyl group, and two R 1 Preferably, both R are methyl groups. 2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms and containing an aromatic ring, and is preferably a methyl group, an n-butyl group, a cyclohexyl group, or a benzyl group, more preferably a methyl group, an n-butyl group, or a benzyl group, and particularly preferably a methyl group.

[0024] The glutarimide resin (G) can be produced by known methods described in, for example, WO 2005 / 108438, JP 2010-254742 A, JP 2008-273140 A, and JP 2008-274187 A.

[0025] The first production method includes an imide cyclization reaction step in which an imidizing agent is added to a precursor resin having two adjacent methyl methacrylate (MMA) units to cause a reaction. Examples of the imidizing agent include ammonia; aliphatic hydrocarbon group-containing amines such as methylamine (also called monomethylamine), ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, and n-hexylamine; aromatic hydrocarbon group-containing amines such as aniline, toluidine, trichloroaniline, and n-methylbenzylamine; alicyclic hydrocarbon group-containing amines such as cyclohexylamine and n-methylcyclohexylamine; and urea compounds such as urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea. Among these, methylamine is preferred.

[0026] In the imide cyclization reaction step, some of the methyl methacrylate (MMA) units may be hydrolyzed to form carboxy groups. In this case, it is preferable to return the carboxy groups to the original methyl methacrylate (MMA) units by an esterification reaction using a known esterifying agent. Examples of the esterifying agent include dimethyl carbonate and trimethyl acetate. In this reaction, a tertiary amine such as trimethylamine, triethylamine, or tributylamine may be used in combination as a catalyst.

[0027] In the second production method, a precursor resin having an acid anhydride unit (glutaric anhydride unit) represented by the following formula (IIa) is reacted with a compound represented by the general formula R 2 An example of such a method is to add an imidizing agent represented by NH2 and allow the reaction to proceed.

[0028] [ka] (In the formula, R 1 , R 2 is as defined above.)

[0029] In the first and second production methods, the reaction between the precursor resin and the imidizing agent can be carried out in a continuous manner, in which the precursor resin is melted using an extruder or the like, and the imidizing agent is added to the melt to carry out the reaction, or in a batch manner, in which a precursor resin solution is prepared using a solvent that can dissolve the precursor resin but is unreactive in the imidization reaction, and the imidizing agent is added to the solution to carry out the reaction.

[0030] In the continuous method, for example, a precursor resin is introduced into a raw material inlet of an extruder, and the precursor resin is melted to fill the cylinder. Then, an imidizing agent is injected into the extruder using an addition pump, and the imidization reaction can proceed in the extruder. In the cylinder of the extruder, the region between the injection position of the imidizing agent and the resin discharge port (die portion) is also called the "reaction zone in the extruder." Examples of the extruder include a single-screw extruder, a twin-screw extruder, a multi-screw extruder, and a combination thereof. From the viewpoint of promoting mixing of the imidizing agent with the precursor resin, a twin-screw extruder is preferred. Examples of the type of twin-screw extruder include a non-intermeshing co-rotating type, an intermeshing co-rotating type, a non-intermeshing counter-rotating type, and an intermeshing counter-rotating type. The intermeshing co-rotating type is preferred from the viewpoint of promoting mixing of the imidizing agent with the precursor resin, as it is capable of high-speed rotation. Since the imidization reaction proceeds well and a glutarimide resin (G) having the desired properties can be stably obtained, the resin temperature (also referred to as the reaction temperature) in the reaction zone of the extruder is preferably 180 to 300°C, more preferably 200 to 290°C, and the reaction time in the reaction zone of the extruder is preferably 10 to 600 seconds, more preferably 30 to 300 seconds. The resin pressure inside the extruder is preferably from atmospheric pressure to 50 MPa, more preferably from 1 MPa to 30 MPa. The extruder preferably has a vent hole that can reduce the pressure to below atmospheric pressure in order to remove unreacted imidizing agent and by-products such as methanol.

[0031] Instead of an extruder, a horizontal twin-screw reactor (e.g., "Bivolac" manufactured by Sumitomo Heavy Industries, Ltd.) and a vertical twin-screw stirring tank (e.g., "Superblend" manufactured by Sumitomo Heavy Industries, Ltd.) that can handle high viscosity materials can also be suitably used.

[0032] A third production method includes a step of intramolecular cyclization of a copolymer having a unit represented by the following formula (III): In this method, it is preferable to carry out the reaction under heating at an appropriate temperature in order to promote the intramolecular cyclization reaction.

[0033] [ka] (In the formula, R 1 , R 2 is as defined above. Me represents a methyl group.

[0034] From the viewpoint of the transparency and thermal decomposition resistance of the glutarimide resin (G), the content of methyl methacrylate (MMA) units in the glutarimide resin (G) is 5 to 63 mass%. The lower limit is more preferably 6 mass%, even more preferably 10 mass%, particularly preferably 15 mass%, and most preferably 20 mass%. The upper limit is more preferably 60 mass%, particularly preferably 55 mass%, and most preferably 50 mass%.

[0035] From the viewpoints of the heat resistance, thermal decomposition resistance, low water absorbency, moldability, dimensional stability of the laminate sheet, and adhesion of the hard coat layer, which is optionally included, of the glutarimide resin (G), the content of glutarimide (GI) units in the glutarimide resin (G) is 35 to 75% by mass. The lower limit is more preferably 38% by mass, even more preferably 40% by mass, particularly preferably 45% by mass, and most preferably 50% by mass. The upper limit is more preferably 73% by mass, even more preferably 70% by mass, particularly preferably 65% ​​by mass, and most preferably 60% by mass.

[0036] From the viewpoints of the heat resistance, rigidity, thermal decomposition resistance, productivity (polymerizability), suppression of inhibition of the glutarimidation reaction by intramolecular cyclization, and dimensional stability of the laminate sheet, the content of α-methylstyrene (αMSt) units in the glutarimide resin (G) is 1 to 48 mass%. The lower limit is more preferably 3 mass%, even more preferably 5 mass%, particularly preferably 7 mass%, and most preferably 10 mass%. The upper limit is more preferably 40 mass%, even more preferably 35 mass%, even more preferably 30 mass%, particularly preferably 25 mass%, and most preferably 20 mass%.

[0037] From the viewpoints of the thermal decomposition resistance and melt fluidity of the glutarimide resin (G), suppression of inhibition of the glutarimidation reaction due to intramolecular cyclization, and the appearance of the laminate sheet, the content of styrene (St) units in the glutarimide resin (G) is 1 to 48 mass%. The lower limit is more preferably 3 mass%, particularly preferably 5 mass%, and most preferably 7 mass%. The upper limit is more preferably 45 mass%, even more preferably 40 mass%, even more preferably 35 mass%, even more preferably 30 mass%, even more preferably 25 mass%, even more preferably 20 mass%, particularly preferably 15 mass%, and most preferably 10 mass%.

[0038] From the viewpoint of suppressing inhibition of the glutarimidation reaction by intramolecular cyclization, the total content of α-methylstyrene (αMSt) units and styrene (St) units in the glutarimide resin (G) is preferably 2 to 40% by mass. The lower limit is more preferably 5% by mass, particularly preferably 10% by mass, and most preferably 15% by mass. The upper limit is more preferably 35% by mass, particularly preferably 30% by mass, and most preferably 25% by mass.

[0039] From the viewpoints of the balance between the heat resistance and low water absorbency of the glutarimide resin (G) and the dimensional stability of the laminate sheet, the content of α-methylstyrene (αMSt) units relative to 100% by mass of the total of α-methylstyrene (αMSt) units and styrene (St) units is preferably 30 to 95% by mass. The lower limit is more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The upper limit is more preferably 90% by mass, even more preferably 85% by mass, even more preferably 80% by mass, particularly preferably 75% by mass, and most preferably 70% by mass.

[0040] The glutarimide resin (G) may contain other ring structural units besides the glutarimide (GI) unit, as needed, such as an acid anhydride unit, a maleimide unit, a lactone ring unit, and a glutaric anhydride unit.

[0041] Examples of the acid anhydride unit include a maleic anhydride (Mah) unit and an itaconic anhydride unit.

[0042] The maleimide unit (unsubstituted or N-substituted maleimide unit) is a unit having an unsubstituted or N-substituted 2,5-pyrrolidinedione structure, and examples thereof include units represented by the following formula:

[0043] [ka]

[0044] In the above formula, two R 11 are each independently a hydrogen atom or a methyl group. 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms and containing an aromatic ring, and is preferably a methyl group, an n-butyl group, a cyclohexyl group, or a benzyl group, more preferably a methyl group, an n-butyl group, or a benzyl group, and particularly preferably a methyl group.

[0045] Examples of methods for producing a copolymer containing maleimide units include a method of polymerizing a monomer mixture containing a monomer containing a maleimide unit, and a method of reacting maleic anhydride units in a polymerization reaction product of a monomer mixture containing maleic anhydride with an imidizing agent. For the latter method, see JP-B No. 61-026924, JP-B No. 7-042332, JP-A No. 9-100322, and JP-A No. 2001-329021.

[0046] Examples of monomers containing a maleimide unit include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide (ChMI); and N-arylmaleimides such as N-phenylmaleimide (PhMI), N-methylphenylmaleimide, and N-chlorophenylmaleimide. Of these, N-cyclohexylmaleimide (ChMI) and N-phenylmaleimide (PhMI) are preferred.

[0047] A lactone ring unit is a unit containing a >CH-OC(=O)- group in the ring structure. The unit containing a >CH-OC(=O)- group in the ring structure preferably has 4 to 8, more preferably 5 to 6, and most preferably 6, ring constituent elements. Examples of units containing a >CH-OC(=O)- group in the ring structure include lactonediyl units such as β-propiolactonediyl unit, γ-butyrolactonediyl unit, and δ-valerolactonediyl unit. In the formula, ">C" means that the carbon atom C has two bonds.

[0048] For example, the δ-valerolactonediyl unit includes a unit represented by the following formula: [ka]

[0049] In the above formula, R 21 , R 22 , and R 23are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an organic group having 1 to 5 carbon atoms. Examples of the organic group include a linear or branched alkyl group, a linear or branched aryl group, a -OCOCH3 group, and a -CN group. The organic group may contain a heteroatom such as an oxygen atom. Preferably, R 22 is a methyl group, and R 21 and R 23 is a hydrogen atom.

[0050] The lactone ring unit can be obtained by intramolecular cyclization of a hydroxy group and an ester group, for example, by intramolecular cyclization of a 2-(hydroxyalkyl)acrylate unit and a methyl (meth)acrylate unit. See JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, JP-A-2002-254544, and JP-A-2005-146084.

[0051] The glutaric anhydride unit is a unit having a 2,6-dioxodihydropyrandiyl structure, and examples thereof include units represented by the following formula: [ka]

[0052] In the above formula, two R 31 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and are preferably a methyl group.

[0053] The glutaric anhydride unit can be obtained by intramolecular cyclization of two adjacent (meth)acrylic acid units, or intramolecular cyclization of a (meth)acrylic acid unit and a methyl (meth)acrylate unit, etc. See JP-A-2007-197703 and JP-A-2010-96919, etc.

[0054] From the viewpoints of suppressing inhibition of the glutarimidation reaction due to intramolecular cyclization and the appearance of the laminate sheet, the content (total amount if multiple types of ring structural units are present) of ring structural units other than glutarimide (GI) units in the glutarimide resin (G) is preferably 0 to 48% by mass, with the upper limit being more preferably 45% by mass, even more preferably 40% by mass, even more preferably 35% by mass, even more preferably 30% by mass, even more preferably 20% by mass, particularly preferably 15% by mass, and most preferably 10% by mass.

[0055] The glutarimide resin (G) may contain one or more other vinyl monomer units other than those mentioned above, as needed. Examples of the other vinyl monomer units include (meth)acrylic acid ester monomer units other than methyl methacrylate (MMA) units, aromatic vinyl monomer units other than α-methylstyrene (αMSt) units and styrene (St) units, vinyl cyanide monomer units, amides such as (meth)acrylamide, and various polyfunctional monomers.

[0056] Examples of (meth)acrylic acid ester monomers other than methyl methacrylate (MMA) include methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate. Examples of aromatic vinyl monomers other than α-methylstyrene (αMSt) and styrene (St) include o-, m-, or p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, o-, m-, or p-ethylstyrene, p-tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylbenzylbenzene, isopropenylhexylbenzene, and isopropenyloctylbenzene. Examples of vinyl cyanide monomers include (meth)acrylonitrile and vinylidene cyanide.

[0057] The content of other vinyl monomer units in the glutarimide resin (G) (the total amount when multiple types are present) is preferably 0 to 20% by mass from the viewpoint of heat resistance and rigidity, with the upper limit being more preferably 15% by mass, and particularly preferably 10% by mass.

[0058] From the viewpoints of the mechanical strength, melt fluidity, and moldability of the methacrylic resin composition (MR), the weight-average molecular weight (Mw) of the glutarimide resin (G) is preferably 40,000 to 250,000. The lower limit is more preferably 50,000, even more preferably 55,000, even more preferably 60,000, particularly preferably 65,000, and most preferably 70,000. The upper limit is more preferably 200,000, even more preferably 180,000, particularly preferably 150,000, and most preferably 100,000.

[0059] From the viewpoint of stability in hot melt molding, the melt flow rate (MFR) of the glutarimide resin (G) is preferably 0.8 to 20 g / 10 min. The lower limit is more preferably 0.9 g / 10 min, particularly preferably 1.0 g / 10 min. The upper limit is more preferably 15 g / 10 min, even more preferably 10 g / 10 min, particularly preferably 8.0 g / 10 min, and most preferably 5.0 g / 10 min. In this specification, the MFR of the glutarimide resin (G) is a value measured in accordance with JIS K7210 using a melt indexer at a temperature of 230° C. under a load of 3.8 kg.

[0060] The acid value of the glutarimide resin (G) is preferably 0.01 to 0.30 mmol / g, more preferably 0.05 to 0.28 mmol / g. The acid value is a value proportional to the content of carboxylic acid units and carboxylic anhydride units in the glutarimide resin (G). The acid value can be calculated, for example, by the method described in JP-A-2005-23272. When the acid value is within the above range, a good balance of heat resistance, mechanical properties, and moldability is achieved.

[0061] The content of the glutarimide resin (G) in the methacrylic resin composition (MR) (total amount when multiple types are used) is preferably 51 to 100% by mass, and the lower limit is more preferably 55% by mass, even more preferably 60% by mass, even more preferably 65% ​​by mass, even more preferably 70% by mass, even more preferably 75% by mass, particularly preferably 80% by mass, especially preferably 85% by mass, and most preferably 90% by mass.

[0062] (Other methacrylic resins (M)) In order to improve melt flowability, the methacrylic resin composition (MR) may contain one or more methacrylic resins (M) other than the glutarimide resin (G). The content of the other methacrylic resin (M) in the methacrylic resin composition (MR) (total amount when multiple types are present) is preferably 0 to 49 mass%, with the upper limit being more preferably 45 mass%, even more preferably 40 mass%, particularly preferably 35 mass%, and most preferably 30 mass%.

[0063] The methacrylic resin (M) is a homopolymer or copolymer containing one or more methacrylic acid ester units and, if necessary, one or more other monomer units. Examples of methacrylic acid esters include alkyl methacrylates such as methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, and tricyclo[5.2.1.0] methacrylate; 2,6 methacrylic acid cycloalkyl esters such as dec-8-yl; methacrylic acid aryl esters such as phenyl methacrylate; and methacrylic acid aralkyl esters such as benzyl methacrylate. From the viewpoint of availability, MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, and the like are preferred, with MMA being particularly preferred.

[0064] The content of methacrylic acid ester units in the methacrylic resin (M) (total amount when multiple types are present) is preferably 50 to 100% by mass, with the lower limit being more preferably 60% by mass, even more preferably 70% by mass, even more preferably 80% by mass, still more preferably 90% by mass, particularly preferably 95% by mass, and most preferably 98% by mass. From the viewpoint of heat resistance, the content of MMA units in the methacrylic resin (M) is preferably 50 to 100% by mass, and the lower limit is more preferably 60% by mass, even more preferably 70% by mass, even more preferably 80% by mass, still more preferably 90% by mass, particularly preferably 95% by mass, and most preferably 98% by mass.

[0065] Other monomers include acrylic esters; unsaturated carboxylic acids such as (meth)acrylic acid, maleic anhydride, maleic acid, and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; conjugated dienes such as butadiene, isoprene, and myrcene; aromatic vinyl monomers such as styrene (St), α-methylstyrene, p-methylstyrene, and m-methylstyrene; (meth)acrylamide, (meth)acrylonitrile; vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

[0066] Examples of acrylic acid esters include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate. From the viewpoint of availability, MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate are preferred, MA and ethyl acrylate are more preferred, and MA is particularly preferred.

[0067] The content of other monomer units in the methacrylic resin (M) (total amount when multiple types are present) is preferably 0 to 50% by mass, with the upper limit being more preferably 40% by mass, even more preferably 30% by mass, even more preferably 20% by mass, still more preferably 10% by mass, particularly preferably 5% by mass, and most preferably 2% by mass.

[0068] The stereoregularity of the methacrylic resin (M) is not particularly limited, and methacrylic resins having stereoregularity such as isotactic, heterotactic, and syndiotactic may be used. As the methacrylic resin (M), a modified methacrylic resin (excluding glutarimide resin (G)) that has been modified by introducing a ring structure into the main chain may be used in place of a general methacrylic resin (also called an unmodified methacrylic resin) that does not have a ring structural unit in the main chain. A methacrylic resin having no ring structural unit in the main chain can be produced by (co)polymerizing a monomer (mixture) containing methyl methacrylate (MMA) and, if necessary, one or more other monomers, by a known method. Methods for producing a methacrylic resin having a ring structural unit in the main chain include a method of copolymerizing, by a known method, multiple types of monomers including methyl methacrylate (MMA), a monomer having a ring structure, and, if necessary, other monomers; and a method of (co)polymerizing, by a known method, a methacrylic resin containing an MMA unit but no ring structural unit, and then introducing a ring structure into the main chain to form a ring structural unit. Examples of polymerization methods for methacrylic resins include radical polymerization methods such as suspension polymerization, (continuous) bulk polymerization, solution polymerization, and emulsion polymerization; and anionic polymerization.

[0069] From the viewpoints of heat resistance, melt fluidity, and moldability, the methacrylic resin (M) may include a methacrylic resin (M-HS) having a methyl methacrylate (MMA) unit content of 90 to 100 mass% and a syndiotacticity (rr) expressed in triad form (hereinafter also simply referred to as "syndiotacticity (rr)" or "rr ratio") of 56 to 99%. The lower limit of the rr ratio is more preferably 57%, particularly preferably 58%. The upper limit is more preferably 95%, even more preferably 90%, even more preferably 85%, particularly preferably 80%, and most preferably 77%.

[0070] Here, the syndiotacticity (rr) of a triad is the proportion of two diads (diads) in a triad of three consecutive units that are both racemo (denoted as rr). Note that diads in polymer molecules with the same configuration are called meso, and those with the opposite configuration are called racemo, and are denoted as m and r, respectively. The rr ratio of methacrylic resin (M) is in deuterated chloroform at 30°C. 1 The H-NMR spectrum is measured, and from the spectrum, the area (X) of the region from 0.6 to 0.95 ppm and the area (Y) of the region from 0.6 to 1.35 ppm are measured when tetramethylsilane (TMS) is set to 0 ppm, and the chromaticity can be calculated using the formula: (X / Y) × 100.

[0071] From the viewpoints of the mechanical strength, melt fluidity, and molding processability of the methacrylic resin composition (MR), the weight-average molecular weight (Mw) of the methacrylic resin (M) is preferably 40,000 to 500,000. The lower limit is more preferably 50,000, even more preferably 60,000, particularly preferably 70,000, and most preferably 80,000. The upper limit is more preferably 400,000, even more preferably 300,000, particularly preferably 200,000, and most preferably 150,000.

[0072] From the viewpoint of stability in hot melt molding, the melt flow rate (MFR) of the methacrylic resin (M) is preferably 1 to 20 g / 10 min. The lower limit is more preferably 1.2 g / 10 min, particularly preferably 1.5 g / 10 min. The upper limit is more preferably 15 g / 10 min, particularly preferably 10 g / 10 min.

[0073] The method for producing the methacrylic resin composition (MR) containing the glutarimide resin (G) and the methacrylic resin (M) is not particularly limited, and examples thereof include a method of polymerizing the methacrylic resin (M) in the presence of the glutarimide resin (G); and a method of melt-kneading the glutarimide resin (G) and the methacrylic resin (M). The melt-kneading can be carried out using a known mixing or kneading device such as an extruder, a kneader-ruder, a mixing roll, a Banbury mixer, etc. Examples of the extruder include a single-screw extruder, a twin-screw extruder, a multi-screw extruder, and combinations thereof, with a twin-screw extruder being preferred.

[0074] (optional ingredient) The methacrylic resin composition (MR) may contain one or more other polymers in addition to those mentioned above. Examples of such other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; styrene resins such as polystyrene, high-impact polystyrene, methyl methacrylate-styrene copolymer (MS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-maleic anhydride-methyl methacrylate copolymer (SMM resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene (ABS resin), acrylonitrile-ethylene-propylene-diene-styrene (AES resin), acrylic-acrylonitrile-styrene (AAS) resin, acrylonitrile-chlorinated ethylene-styrene (ACS) resin, and methacrylic butadiene styrene (MBS) resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomer; and polyurethanes. Other thermoplastic resins include polyphenylene oxide, polyphenylene sulfide, modified polyphenylene ether, polyether ether ketone, polysulfone, polyimide, polyetherimide, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, ethylene-vinyl acetate copolymer, polyvinylidene fluoride, phenoxy resins, and ethylene-based ionomers; silicone-modified resins, silicone rubber; acrylic thermoplastic elastomers such as acrylic multilayer copolymer particles, diblock copolymers or triblock copolymers containing methyl methacrylate polymer blocks and n-butyl acrylate polymer blocks; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM; thermosetting resins such as epoxy resins, phenolic resins, melamine resins, and silicone resins; and biodegradable resins. The content of other polymers in the methacrylic resin composition (MR) (total amount when multiple types are used) is preferably 0 to 10% by mass, and the upper limit is more preferably 5% by mass.

[0075] The methacrylic resin composition (MR) may contain one or more additives as needed, such as fillers, light diffusing agents, matting agents, colorants such as dyes, pigments, organic dyes, and fluorescent materials, antioxidants, heat deterioration inhibitors, ultraviolet absorbers, stabilizers such as heat stabilizers and light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, flame retardant assistants, and plasticizers. Examples of fillers (which may function as a light diffusing agent or a matting agent) include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate. The content of fillers in the methacrylic resin composition (MR) (the total amount when multiple types of fillers are used) is preferably 0 to 3% by mass. The upper limit is more preferably 2.0% by mass, and particularly preferably 1.5% by mass. The content of additives other than the filler, light diffusing agent, and matting agent in the methacrylic resin composition (MR) (the total amount if multiple additives are used) is preferably 0 to 7% by mass, with the upper limit being more preferably 5% by mass, and particularly preferably 4% by mass, from the viewpoint of suppressing poor appearance.

[0076] The timing of addition of the other additives is not particularly limited, and may be any timing, such as before, during, or after the production of the glutarimide resin (G) (for example, before, during, or after the polymerization of the precursor, or after the cyclization reaction), before, during, or after the production of the methacrylic resin (M), or during the production of the methacrylic resin composition (MR).

[0077] [Polycarbonate resin composition (PCR)] The polycarbonate resin composition (PCR) contains one or more polycarbonate resins (PC). The polycarbonate resin (PC) is preferably obtained by copolymerizing one or more dihydric phenols with one or more carbonate precursors. Production methods include an interfacial polymerization method in which an aqueous solution of a dihydric phenol is reacted with an organic solvent solution of a carbonate precursor at the interface, and a transesterification method in which a dihydric phenol is reacted with a carbonate precursor under high temperature, reduced pressure, and solvent-free conditions.

[0078] Examples of dihydric phenols include 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfide, and bis(4-hydroxyphenyl)sulfone, with bisphenol A being preferred. Examples of carbonate precursors include carbonyl halides such as phosgene; carbonate esters such as diphenyl carbonate; and haloformates such as dihaloformates of dihydric phenols.

[0079] From the viewpoints of the impact resistance and heat resistance of the laminate sheet, the moldability of the polycarbonate-based resin (PC), and the productivity of the laminate sheet of the present disclosure, the weight-average molecular weight (Mw) of the polycarbonate-based resin (PC) is preferably 10,000 to 100,000. The lower limit is more preferably 20,000. The upper limit is more preferably 90,000, particularly preferably 80,000, and most preferably 70,000.

[0080] Commercially available polycarbonate resins (PC) may be used, such as SD Polyca (registered trademark) manufactured by Sumika Polycarbonate Co., Ltd., Iupilon / Novarex (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, Toughlon (registered trademark) manufactured by Idemitsu Kosan Co., Ltd., and Panlite (registered trademark) manufactured by Teijin Limited.

[0081] The polycarbonate resin composition (PCR) may contain one or more other polymers as needed. The other polymers may be methacrylic resins and / or polymers similar to those contained in the methacrylic resin composition (MR). The content of polycarbonate resin (PC) in the polycarbonate resin composition (PCR) (total amount when multiple types are used) is preferably 85 to 100 mass %, with the lower limit being more preferably 90 mass %, and particularly preferably 95 mass %. The content of other polymers in the polycarbonate resin composition (PCR) (total amount when multiple types are used) is preferably 15 to 0 mass %, with the upper limit being more preferably 10 mass %, and particularly preferably 5 mass %. The polycarbonate resin composition (PCR) may contain various additives as needed, and examples of the additives and the amounts added are the same as those for the methacrylic resin composition (MR).

[0082] The glass transition temperature (Tg) of a typical polycarbonate resin (PC) is about 150°C. Examples of polycarbonate resin compositions (PCR) that can achieve a lower Tg than when polycarbonate resin (PC) is used alone, for example, a Tg of 145°C or lower, include a first embodiment containing an alloy or copolymer of polycarbonate resin (PC) and an aromatic polyester, and a second embodiment containing polycarbonate resin (PC) and a plasticizer. In the second embodiment, the polycarbonate resin composition (PCR) preferably contains 85 to 99 parts by mass of polycarbonate resin (PC) and 15 to 1 part by mass of plasticizer.

[0083] Examples of aromatic polyesters include polycondensates of aromatic dicarboxylic acid components and diol components. Representative aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentyl acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, and p-oxybenzoic acid. One or more of these can be used. Representative diol components include ethylene glycol, diethylene glycol, triethylene glycol, and cyclohexanedimethanol. Other diol components include propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, trimethylol, and methoxypolyalkylene glycol. These can be used alone or in combination.

[0084] A typical example of an aromatic polyester is polyethylene terephthalate (PET), which is a polycondensation product of terephthalic acid and ethylene glycol. Copolymer polyesters using terephthalic acid and ethylene glycol with other dicarboxylic acid components and / or other diol components are also preferred. Other typical examples of aromatic polyesters include polybutylene terephthalate (PBT), which is a polycondensation product of terephthalic acid or dimethyl terephthalate with 1,4-butanediol. Copolymer polyesters using terephthalic acid and 1,4-butanediol with other dicarboxylic acid components and / or other diol components are also preferred. Among these, copolymer polyesters (PCTG) in which cyclohexanedimethanol (1,4-CHDM) is used in combination with a portion of the ethylene glycol in PET, preferably 55 to 75 mol %, more preferably 50 to 75 mol %, and copolymer polyesters (PCTG) in which isophthalic acid is used in combination with a portion of the terephthalic acid in PBT, preferably 10 to 30 mol %, and combinations thereof are preferred. These copolymer polyesters can be completely miscible and polymer-alloyed by melt-blending with polycarbonate resins. Furthermore, this polymer-alloying can effectively lower the glass transition temperature.

[0085] The plasticizer is not particularly limited, and examples thereof include phosphate ester compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl)phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate; phosphite compounds corresponding to these phosphate ester compounds; phthalate ester compounds such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis(2-ethylhexyl phthalate), diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, and ethyl phthalyl ethyl glycolate; and trimellitate esters such as tris(2-ethylhexyl) trimellitate. ester compounds; aliphatic dibasic acid ester compounds such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis(butyldiglycol) adipate, bis(2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, and diethyl succinate; polyester compounds containing the aliphatic dibasic acid units contained in these aliphatic dibasic acid ester compounds; ricinoleic acid ester compounds such as methyl acetyl ricinoleate; acetate ester compounds such as triacetin and octyl acetate; and sulfonamide compounds such as N-butylbenzenesulfonamide. Among these, phosphate ester compounds, particularly cresyl diphenyl phosphate (CDP) and tricresyl phosphate (TCP), are preferred because they have good compatibility with polycarbonate resins (PC) and the transparency of the resin after compatibility is good.

[0086] From the viewpoint of stability in hot melt molding, the MFR of the polycarbonate resin composition (PCR) is preferably 1 to 30 g / 10 min. The lower limit is more preferably 3 g / 10 min, and particularly preferably 5 g / 10 min. The upper limit is more preferably 20 g / 10 min, and particularly preferably 10 g / 10 min. In this specification, the MFR of a polycarbonate resin composition (PCR) is a value measured using a melt indexer under conditions of a temperature of 300°C and a load of 1.2 kg.

[0087] (Other thermoplastic resin layer) The laminate sheet of the present disclosure may optionally contain one or more other thermoplastic resin layers in addition to the methacrylic resin-containing layer and the polycarbonate resin-containing layer. The location of the other thermoplastic resin layer is not particularly limited, and it may be a surface layer or an inner layer. In other words, the laminate sheet of the present disclosure includes a thermoplastic resin sheet (also referred to as the thermoplastic resin sheet of the present disclosure) having a laminate structure that includes one or more methacrylic resin-containing layers and one or more polycarbonate resin-containing layers, and further includes one or more other thermoplastic resin layers as needed. The thermoplastic resin sheet is preferably a coextruded sheet.

[0088] The thermoplastic resin sheet of the present disclosure preferably has a laminate structure in which at least one methacrylic resin-containing layer is the outermost layer in a laminate that includes one or more methacrylic resin-containing layers and one or more polycarbonate resin-containing layers, and optionally one or more other thermoplastic resin layers. From the viewpoint of resistance to warpage deformation of the laminate sheet in a high-temperature (high-humidity) environment, the thermoplastic resin sheet of the present disclosure preferably has a symmetrical structure in cross section. The laminate sheet of the present disclosure preferably has, for example, a three-layer structure of a first methacrylic resin-containing layer / a polycarbonate resin-containing layer / a second methacrylic resin-containing layer. The first methacrylic resin-containing layer and the second methacrylic resin-containing layer preferably have the same composition and thickness.

[0089] (Relationship between physical properties of methacrylic resin-containing layer and polycarbonate resin-containing layer) As explained in the section [Problem to be solved by the invention], depending on the relationship between the physical properties of the methacrylic resin-containing layer and the polycarbonate resin-containing layer, during the sheet manufacturing process using a co-extrusion molding method or the like, a relatively large residual strain resulting from cooling strain may occur in the methacrylic resin-containing layer, and if this residual strain is released in a high-temperature (high-humidity) environment, warping may occur in the laminated sheet. A preferred relationship between the physical properties of the methacrylic resin-containing layer and the polycarbonate resin-containing layer will be described below.

[0090] <Glass transition temperature (Tg)> The glass transition temperature of the methacrylic resin composition (MR) is Tg MR [°C], and the glass transition temperature of the polycarbonate resin composition (PCR) is Tg PCR [℃]. From the viewpoint of the heat resistance of the methacrylic resin composition (MR) and the dimensional stability of the laminate sheet, the laminate sheet of the present disclosure has a Tg MR The lower limit is more preferably 142°C, and particularly preferably 145°C.

[0091] From the viewpoint of reducing residual strain in the laminate sheet and improving warpage resistance of the laminate sheet in a high-temperature (high-humidity) environment, the laminate sheet of the present disclosure has a temperature Tg PCR -Tg MR |≦15. The upper limit is more preferably 12°C, even more preferably 10°C, particularly preferably 8°C, and most preferably 5°C.

[0092] From the viewpoint of the heat resistance of the methacrylic resin composition (MR), the glass transition temperature (Tg) of the glutarimide resin (G) contained in the methacrylic resin composition (MR) is preferably 140 to 170° C. The lower limit is more preferably 142° C., and particularly preferably 145° C. From the viewpoint of the heat resistance of the methacrylic resin composition (MR), the glass transition temperature (Tg) of the methacrylic resin (M) other than the glutarimide resin (G) that can be contained in the methacrylic resin composition (MR) is preferably 100 to 150° C. The lower limit is more preferably 105° C., particularly preferably 110° C., and most preferably 115° C. Glass transition temperature (Tg PCR ) is preferably 120 to 160°C. The lower limit is more preferably 130°C, and particularly preferably 140°C. In this specification, unless otherwise specified, the "glass transition temperature (Tg)" can be measured in accordance with JIS K7121 by the method described in the section "Examples" below.

[0093] <Linear expansion coefficient> The average linear expansion coefficient of the methacrylic resin composition (MR) at 23 to 100°C is α MR [ppm / °C], and the average linear expansion coefficient of the polycarbonate resin composition (PCR) at 23 to 100°C is α PCR [ppm / ℃]. The laminated sheet of the present disclosure has a structure in which 0≦α PCR -α MR Satisfy the condition of ≦30.

[0094] In general, the residual strain of the polycarbonate-based resin-containing layer tends to be smaller than that of the methacrylic-based resin-containing layer. MR ) is the average linear expansion coefficient (α PCR ) or less, residual strain resulting from cooling strain generated in the methacrylic resin-containing layer during the sheet manufacturing process by co-extrusion molding or the like can be reduced, and warping of the laminated sheet when this residual strain is released in a high-temperature (high-humidity) environment can be suppressed.

[0095] The laminate sheet of the present disclosure is suitable as a front panel (protective plate, cover member, etc.) for display devices such as panel displays such as liquid crystal displays, and touch panel displays that combine a panel display such as a liquid crystal display with a touch panel. Even if the laminate sheet warps slightly, the laminate sheet of the present disclosure that satisfies the above relationship can be placed on a display device so that one methacrylic resin-containing layer is the uppermost layer among one or more methacrylic resin-containing layers and one or more polycarbonate resin-containing layers. In this case, the laminate sheet of the present disclosure warps upward in a convex direction, and the display device can be well protected without applying pressure to the display device.

[0096] From the viewpoint of warpage resistance of the laminated sheet under high temperature (high humidity) environment, the average linear expansion coefficient (α MR ) is preferably 50 to 68 ppm / °C. The upper limit is more preferably 65 ppm / °C, particularly preferably 63 ppm / °C, and most preferably 60 ppm / °C. From the viewpoint of resistance to warpage deformation of the laminate sheet in a high-temperature (high-humidity) environment, the average linear expansion coefficient of the glutarimide resin (G) contained in the methacrylic resin-containing layer at 23 to 100° C. is preferably 50 to 68 ppm / ° C. The upper limit is more preferably 65 ppm / ° C., particularly preferably 63 ppm / ° C., and most preferably 60 ppm / ° C. From the viewpoint of warpage resistance of laminated sheets under high temperature (high humidity) environments, the average linear expansion coefficient (α PCR ) is preferably 50 to 80 ppm / °C. The upper limit is more preferably 75 ppm / °C, particularly preferably 72 ppm / °C, and most preferably 70 ppm / °C. The average coefficient of linear expansion at 23 to 100° C. can be measured in accordance with JIS K7197 by the method described in the section [Examples] below.

[0097] <Saturated water absorption rate> From the viewpoint of moisture resistance of the methacrylic resin composition (MR) and suppression of warping of the laminated sheet due to moisture absorption, the saturated water absorption rate (c MR ) is 0 to 3.0% by mass. The upper limit is preferably 2.7% by mass, more preferably 2.5% by mass, and particularly preferably 2.3% by mass. The lower limit can be 0.1%, 0.2%, or 0.3% by mass.

[0098] From the viewpoints of the moisture resistance of the methacrylic resin composition (MR) and suppressing warping of the laminate sheet due to moisture absorption, the saturated water absorption of the glutarimide resin (G) contained in the methacrylic resin composition (MR) at 23°C is preferably 0 to 3.0% by mass. The upper limit is more preferably 2.7% by mass, particularly preferably 2.5% by mass, and most preferably 2.3% by mass. The lower limit can be 0.1%, 0.2%, or 0.3% by mass.

[0099] From the viewpoints of the moisture resistance of the methacrylic resin composition (MR) and suppressing warping of the laminate sheet due to moisture absorption, the saturated water absorption at 23°C of the methacrylic resin (M) other than the glutarimide resin (G) that can be contained in the methacrylic resin composition (MR) is preferably 0 to 3.0% by mass. The upper limit is more preferably 2.7% by mass, and particularly preferably 2.5% by mass. The lower limit can be 0.1%, 0.2%, or 0.3% by mass.

[0100] The saturated water absorption rate (c PCR ) is preferably 0 to 1.0 mass %. From the viewpoint of suppressing warpage of laminated sheets due to moisture absorption, the saturated water absorption rate (c MR ) and saturated water absorption rate (c PCR ) and the absolute value of the difference |c MR -c PCRis preferably 0 to 4.5% by mass. The upper limit is more preferably 4.0% by mass, even more preferably 3.5% by mass, still more preferably 3.0% by mass, particularly preferably 2.5% by mass, and most preferably 2.0% by mass. The saturated water absorption at 23°C can be measured by the method described in the section [Examples] below.

[0101] (Thickness of each layer and total thickness) From the viewpoints of impact resistance and productivity, the total thickness of the thermoplastic resin sheet of the present disclosure and the total thickness of the laminate sheet of the present disclosure are 500 to 5,000 μm. The lower limit is preferably 600 μm, more preferably 700 μm, even more preferably 800 μm, even more preferably 900 μm, still more preferably 1,000 μm, particularly preferably 1,500 μm, and most preferably 2,000 μm. The upper limit is preferably 4,500 μm, more preferably 4,000 μm.

[0102] From the viewpoints of abrasion resistance, weather resistance, and impact resistance, the thickness of the methacrylic resin-containing layer is preferably 30 to 200 μm. The lower limit is more preferably 40 μm, and particularly preferably 50 μm. The upper limit is more preferably 180 μm, even more preferably 150 μm, even more preferably 120 μm, even more preferably 100 μm, particularly preferably 90 μm, and most preferably 80 μm.

[0103] From the viewpoints of impact resistance and productivity, the thickness of the polycarbonate resin-containing layer is preferably 300 to 4,900 μm. The lower limit is more preferably 400 μm, even more preferably 500 μm, even more preferably 800 μm, even more preferably 1,000 μm, even more preferably 1,500 μm, even more preferably 1,800 μm, particularly preferably 2,000 μm, and most preferably 2,500. The upper limit is more preferably 4,500 μm, even more preferably 4,000 μm, particularly preferably 3,500 μm, and most preferably 3,000.

[0104] From the viewpoints of abrasion resistance, weather resistance, and impact resistance, the ratio of the thickness of the methacrylic resin-containing layer to the total thickness of the thermoplastic resin sheet of the present disclosure or the laminate sheet of the present disclosure is preferably 1 to 20%. The lower limit is more preferably 1.5%, particularly preferably 2%. The upper limit is more preferably 17%, even more preferably 15%, even more preferably 13%, even more preferably 10%, even more preferably 8%, particularly preferably 5%, and most preferably 3%.

[0105] From the viewpoint of impact resistance and weather resistance, the ratio of the thickness of the polycarbonate-based resin-containing layer to the total thickness of the thermoplastic resin sheet of the present disclosure or the total thickness of the laminate sheet of the present disclosure is preferably 80 to 99%. The lower limit is more preferably 83%, even more preferably 85%, even more preferably 90%, particularly preferably 92%, and most preferably 95%. The upper limit is more preferably 98.5%, particularly preferably 98%.

[0106] (Total light transmittance (Tt)) From the viewpoint of appearance quality, the total light transmittance (Tt) of each of the methacrylic resin-containing layer, the polycarbonate resin-containing layer, the thermoplastic resin sheet of the present disclosure, and the laminate sheet of the present disclosure is preferably 80 to 100%, and the lower limit is more preferably 85%, particularly preferably 87%, and most preferably 90%. The total light transmittance (Tt) can be measured in accordance with JIS K7105 by the method described in the section [Examples] below.

[0107] The thermoplastic resin sheet of the present disclosure can be produced by known multilayer molding methods such as coextrusion molding (also called multilayer extrusion molding), multilayer blow molding, and multilayer injection molding. A single-layer sheet consisting of one of the methacrylic resin-containing layer and the polycarbonate resin-containing layer may be prepared, and the other resin layer may be laminated on this single-layer sheet. Examples of the lamination method for the other resin layer include insert molding; a method of applying a solution containing the material of the other resin layer onto a single-layer sheet consisting of one resin layer and drying it; a method of laminating a single-layer sheet consisting of one resin layer onto a single-layer sheet consisting of the other resin layer via an adhesive layer; and a multi-layer press molding method of thermocompression bonding a single-layer sheet consisting of one resin layer and a single-layer sheet consisting of the other resin layer. The same manufacturing method as above can be applied to the case where the thermoplastic resin sheet of the present disclosure includes a resin layer other than the methacrylic resin-containing layer and the polycarbonate resin-containing layer.

[0108] From the viewpoint of productivity, a co-extrusion molding method is preferred, and a T-die method using an extruder equipped with a T-die is preferred. The constituent resin compositions of each layer are melt-kneaded using an extruder and co-extruded in the desired laminate structure in the form of a sheet from a T-die with a wide discharge port. Examples of extruders include single-screw extruders, twin-screw extruders, multi-screw extruders, and combinations thereof. Examples of lamination methods include a feedblock method in which lamination is performed before entering the T-die, and a multi-manifold method in which lamination is performed inside the T-die. The multi-manifold method is preferred from the viewpoint of improving the interfacial smoothness between layers.

[0109] To remove foreign matter, each molten resin is preferably melt-filtered using a filter before extrusion. By using melt-filtered molten resins for production, a sheet with fewer defects due to foreign matter and gels can be obtained. The filter material for the filter is appropriately selected based on the operating temperature, viscosity, filtration accuracy, etc. Examples include nonwoven fabrics made of glass fiber, etc.; sheets made of phenolic resin-impregnated cellulose; sintered metal fiber nonwoven sheets; sintered metal powder sheets; wire mesh; and combinations thereof. Among these, from the viewpoint of heat resistance and durability, a filter formed by stacking multiple sintered metal fiber nonwoven sheets is preferred. The filtration accuracy of the filter is not particularly limited, but is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less.

[0110] The molten thermoplastic resin laminate coextruded from the T-die is pressed and cooled using a plurality of cooling rolls, such as rigid metal rolls and elastic metal rolls. The rigid metal roll is a roll having no elasticity and made of a metal such as stainless steel, and examples thereof include a drilled roll and a spiral roll. The surface of the rigid metal roll may be a mirror finish or may have a pattern or irregularities. The metal elastic roll is a roll having an elastic outer cylinder made of a thin metal film on its outer periphery. The metal elastic roll is composed of, for example, a metal shaft roll made of stainless steel or the like, a metal thin film (elastic outer cylinder) made of stainless steel or the like covering the outer surface of the shaft roll, and a fluid sealed between the shaft roll and the metal thin film (elastic outer cylinder), and can exhibit elasticity in the presence of the fluid. Examples of the fluid include water and oil. The thickness of the metal thin film of the metal elastic roll is not particularly limited, but is preferably about 2 to 8 mm. The metal thin film preferably has flexibility and bendability, and preferably has a seamless structure without welded joints. A metal elastic roll equipped with such a metal thin film is not only excellent in durability, but also easy to use because it can be handled in the same way as a normal mirror-finished roll if the metal thin film is mirror-finished, and can become a roll to which the shape can be transferred if a pattern, irregularities, etc. are imparted to the metal thin film. By using a roll having an uneven surface (also called an embossing roll or a graining roll) as one or more cooling rolls, a thermoplastic resin sheet having unevenness on at least one surface can be produced.

[0111] The thermoplastic resin sheet obtained after cooling is taken up by a pair of take-up rolls. The above steps of extrusion, cooling, and taking-up are carried out continuously. The configuration of the manufacturing apparatus can be appropriately modified in design without departing from the spirit of the present invention. In this specification, the heated and molten state is mainly referred to as a "thermoplastic resin laminate" and the solidified state is mainly referred to as a "thermoplastic resin laminate sheet", but there is no clear boundary between the two.

[0112] (functional layer) The laminate sheet of the present disclosure may have one or more functional layers, such as a hard coat layer, an anti-reflection layer, an anti-fingerprint layer, an anti-fogging layer, a weather-resistant layer (e.g., an ultraviolet blocking layer), an antistatic layer, an anti-fouling layer, an anti-glare layer, a colored layer, a printed layer, an adhesive layer, and a pressure-sensitive adhesive layer, as needed.

[0113] The laminate sheet of the present disclosure may include a hard coat layer laminated on at least one surface of the thermoplastic resin sheet of the present disclosure. The hard coat layer is a functional layer having scratch resistance. In addition to scratch resistance, the hard coat layer may have other functions such as anti-reflection or anti-glare properties. The thickness of the hard coat layer is preferably 1 to 100 μm in terms of the surface hardness and appearance of the laminate sheet. The lower limit is more preferably 2 μm, even more preferably 3 μm, particularly preferably 4 μm, and most preferably 5 μm. The upper limit is more preferably 80 μm, even more preferably 70 μm, even more preferably 60 μm, even more preferably 50 μm, even more preferably 40 μm, even more preferably 30 μm, particularly preferably 20 μm, and most preferably 10 μm. At least one hard coat layer is preferably laminated on the methacrylic resin-containing layer.

[0114] Materials for the hard coat layer include inorganic, organic, organic-inorganic, and silicone materials, and from the viewpoint of productivity, organic and organic-inorganic materials are preferred.

[0115] The inorganic hard coat layer can be formed by depositing an inorganic material such as a metal oxide such as SiO2, Al2O3, TiO2, or ZrO2 by vapor phase deposition such as vacuum deposition or sputtering. The organic hard coat layer can be formed by applying a curable composition containing one or more curable compounds and curing the composition by heating or irradiating with ionizing radiation. The curable compounds include monomers, oligomers, prepolymers, and curable resins. Examples of the curable compound that is cured by heating include thermosetting resins such as polyester resin, epoxy resin, polyurethane resin, aminoalkyd resin, melamine resin, guanamine resin, urea resin, and thermosetting acrylic resin. Examples of curable compounds that are cured by irradiation with ionizing radiation include oligomers and prepolymers having a radically polymerizable unsaturated group in the molecule, such as epoxy (meth)acrylate-based, urethane (meth)acrylate-based, polyether-based urethane (meth)acrylate, caprolactone-based urethane (meth)acrylate, polyester (meth)acrylate-based, and polyether (meth)acrylate-based oligomers and prepolymers. Ionizing radiation is electromagnetic waves and charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, and specific examples include electromagnetic waves such as ultraviolet (UV) rays, electron beams (EB), X-rays, and gamma rays; and charged particle beams such as alpha rays, beta rays, and ion beams.

[0116] The organic-inorganic hard coat layer can be formed, for example, by applying an ultraviolet-curable hard coat coating material containing inorganic ultrafine particles such as silica ultrafine particles having photopolymerizable functional groups introduced on the surface and a curable organic component, and then polymerizing the curable organic component with the photopolymerizable functional groups of the inorganic ultrafine particles by ultraviolet irradiation. This method results in a network-like crosslinked film in which the inorganic ultrafine particles are dispersed in the organic matrix while being chemically bonded to the organic matrix.

[0117] The silicone-based hard coat layer can be formed, for example, by polycondensing partial hydrolysates of carbon functional alkoxysilane, alkyltrialkoxysilane, tetraalkoxysilane, etc., or materials obtained by blending these with colloidal silica.

[0118] Examples of methods for applying the curable composition include spin coating, dip coating, roll coating, gravure coating, flow coating, rod coating, blade coating, spray coating, die coating, bar coating, slide coating, meniscus coating, flexographic printing, screen printing, beat coating, and spraying.

[0119] From the viewpoint of adhesion of the hard coat layer, the wetting tension of the surface of the thermoplastic resin sheet of the present disclosure on which the hard coat layer is formed (preferably the surface of the methacrylic resin-containing layer) is preferably 38 to 50 mN / m. The lower limit is more preferably 39 mN / m, particularly preferably 40 mN / m. The upper limit is more preferably 45 mN / m, particularly preferably 43 mN / m. In order to adjust the surface wetting tension, the surface of the thermoplastic resin sheet of the present disclosure on which the hard coat layer is formed (preferably the surface of the methacrylic resin-containing layer) may be subjected to surface treatments such as discharge treatments such as low-temperature plasma treatment and corona discharge treatment; chemical treatments such as acid treatment, alkali treatment, and organic solvent treatment; ozone spraying; ultraviolet irradiation; and flame treatment. The discharge treatment can increase the number of polar groups such as carbonyl groups, carboxyl groups, and hydroxyl groups, while the chemical treatment can increase the number of polar groups such as amino groups, hydroxyl groups, and carbonyl groups. The wet tension can be measured in accordance with JIS K6768 by the method described in the section [Examples] below.

[0120] In order to improve the adhesion of the hard coat layer, an undercoat layer such as an anchor layer or a primer layer may be disposed between the thermoplastic resin sheet of the present disclosure and the hard coat layer.

[0121] Examples of the resin constituting the undercoat layer include (meth)acrylic resins, nitrocellulose resins, polyurethane resins (including cured products of two-component curing type curable compositions consisting of a main agent containing a polyol compound and a curing agent containing an isocyanate compound), acrylic urethane resins (including cured products of two-component curing type curable compositions consisting of a main agent containing an acrylic polyol compound and a curing agent containing an isocyanate compound), polyester resins, styrene-maleic acid resins, and chlorinated polypropylene resins, and (meth)acrylic resins are preferred.

[0122] The undercoat layer may optionally contain a colorant such as a pigment. For example, a laminate sheet of the present disclosure including an undercoat layer containing a yellow pigment can exhibit a golden appearance (metallic appearance). The undercoat layer may optionally contain other additives such as an antistatic agent. The laminate sheet of the present disclosure, which includes an undercoat layer formed using a curing agent containing an isocyanate compound, can have improved heat resistance, weather resistance, water resistance, and the like. From the viewpoint of improving the adhesion of the hard coat layer, the thickness of the undercoat layer is preferably 0.1 to 3 μm.

[0123] The undercoat layer can be formed, for example, by applying a resin composition or curable composition for forming an undercoat layer, which contains a solvent such as methyl ethyl ketone, toluene, or ethyl acetate as needed, to the hard coat-forming surface of the thermoplastic resin sheet of the present disclosure, and drying and / or curing the composition at about 80 to 100°C for 30 seconds to 1 minute.

[0124] Functional layers such as antireflection layers, antifingerprint layers, antifogging layers, weather-resistant layers (e.g., ultraviolet-shielding layers), antistatic layers, antifouling layers, antiglare layers, colored layers, and printed layers can be formed by known methods. Methods for forming antireflection layers include applying a reflection-reducing coating material and depositing a dielectric thin film having a single layer or multilayer structure. Methods for forming antistatic layers include applying an antistatic coating material. In order to improve interlayer adhesion, a known adhesive layer or pressure-sensitive adhesive layer may be disposed between any two adjacent layers, if necessary.

[0125] As described above, according to the present disclosure, it is possible to provide a laminated sheet that has a methacrylic resin-containing layer and a polycarbonate resin-containing layer, and that has excellent heat resistance and moisture resistance, and excellent resistance to warpage deformation in high-temperature (high-humidity) environments. The present disclosure also makes it possible to provide a laminate sheet having a methacrylic resin-containing layer, a polycarbonate resin-containing layer, and a hard coat layer, which has excellent heat resistance and moisture resistance, excellent resistance to warpage deformation in a high-temperature (high-humidity) environment, and excellent adhesion of the hard coat layer.

[0126] [Molded body] The molded article of the present disclosure includes the laminate sheet of the present disclosure described above. Examples of the molded body of the present disclosure include a secondary molded body obtained by shaping the laminated sheet of the present disclosure by known methods, such as curving, folding, cutting, and three-dimensional molding; and a laminated body (decorated molded body, etc.) in which the laminated sheet of the present disclosure is laminated on a substrate.

[0127] Examples of methods for secondary forming of laminated sheets include press forming, vacuum forming, pressure forming, and vacuum pressure forming.

[0128] Methods for manufacturing laminates such as decorated molded bodies include adhesive bonding, lamination, pressure forming, vacuum forming, vacuum pressure forming, three-dimensional surface decorative molding (Three Dimension Overlay Method: TOM molding), insert molding, and in-mold molding. When the substrate is made of a resin, a method of applying the laminate sheet of the present disclosure to the surface of the substrate under heating by press molding, vacuum molding, pressure molding, or vacuum pressure molding; an injection molding simultaneous lamination method, etc. are preferred. The simultaneous injection molding and lamination method is a method in which a laminate sheet of the present disclosure is inserted between a pair of male and female injection molds, and then a molten thermoplastic resin is injection molded into the mold (on one side of the sheet). This method allows the lamination of the laminate sheet to be carried out simultaneously with the production of an injection-molded article. The laminate sheet inserted into the mold may be flat, or may have a three-dimensional shape obtained by preforming using vacuum forming, pressure forming, or the like. The preforming of the laminate sheet may be carried out in a separate molding machine, or may be carried out within the mold of the injection molding machine used in the simultaneous injection molding and lamination method. The method in which a molten resin is injected into one side of a preformed laminate sheet is called an insert molding method.

[0129] [Application] The laminated sheet of the present disclosure can be used for any purpose. The laminated sheet of the present disclosure is suitable as an electronic device component such as a front panel (protective plate, cover member, etc.) of a display device such as a panel display such as a liquid crystal display, and a touch panel display that combines a panel display such as a liquid crystal display with a touch panel. The laminate sheet of the present disclosure is suitable as a front panel (protective plate, cover member, etc.) of a display device such as a liquid crystal display or a touch panel display used in, for example, ATMs of financial institutions such as banks; vending machines; televisions; digital information devices such as mobile phones (including smartphones), personal computers, personal digital assistants (PDAs) such as tablet personal computers, digital audio players, portable game consoles, copy machines, fax machines, and car navigation systems.

[0130] The laminate sheet of the present disclosure or a molded article containing the same is suitable for glazing applications such as window glass for moving bodies such as trains, electric trains, and automobiles, ships, and aircraft; and window glass for buildings. The laminate sheet of the present disclosure or a molded article containing the same is suitable for vehicle window glass such as a windshield, rear glass, roof glass, and side glass. The laminate sheet of the present disclosure or a molded article (decorative molded article, etc.) containing the same is suitable for automobile interior parts and automobile exterior parts such as side visors, rear visors, head wings, headlight covers, and bumpers. The laminate sheet of the present disclosure or a molded article containing the same is also suitable for building components other than window glass, housings for home appliances, and the like. [Example]

[0131] Examples and comparative examples according to the present invention will be described. [Evaluation items and evaluation methods] The evaluation items and evaluation methods are as follows. (polymerization conversion rate) The polymerization conversion rate was determined by gas chromatography analysis. A Shimadzu Gas Chromatograph GC-14A was connected to a GL Sciences InertCap1 column (film thickness 0.4 μm, inner diameter 0.25 mmφ, length 60 m). Analysis was performed under the following conditions, and the polymerization conversion rate was calculated from the obtained data. Injection temperature: 250℃, Detector temperature: 250℃, Temperature profile: Hold at 60°C for 5 minutes → Heat to 250°C at a rate of 10°C / min → Hold at 250°C for 10 minutes.

[0132] (Unit composition of precursor resin of glutarimide resin) Measurement mode: Under the condition of the reverse gate decoupling method, 13 The C-NMR spectrum was measured, and the unit composition of the precursor resin of the glutarimide resin was determined from the ratio of the integral values ​​of the peaks derived from each unit. Specifically, the peak derived from the carbon of the carbonyl group of the methyl methacrylate (MMA) unit, the peak derived from the carbon of the phenyl group of the α-methylstyrene (αMSt) unit, and / or the peak derived from the carbon of the phenyl group of the styrene (St) unit were identified, and the unit composition was determined from the ratio of the integral values ​​of each peak.

[0133] (Unit composition of glutarimide resin) Using a nuclear magnetic resonance spectrometer (Bruker "ULTRA SHIELD 400 PLUS"), the glutarimide resin obtained from the precursor resin was analyzed. 1 H-NMR measurements were carried out. The peaks (δ = around 3.5 to 3.8 ppm) derived from the O-CH3 protons of the methyl methacrylate (MMA) unit and the NR of the glutarimide (GI) unit 2 The peak (δ=approximately 3.0 to 3.3 ppm) due to the protons bound to the hydroxyl group was identified. The integral values ​​of the two peaks were determined, and the glutarimide cyclization rate (mol %) was calculated based on the following formula. [Glutarimide cyclization rate] (mol%) = [S G / (S M +S G )] x 100 In the above formula, S M is the integral value of the peak derived from the MMA unit, and S G is the integral value of the peak derived from the glutarimide unit. The glutarimide cyclization rate (mol %) was converted to glutarimide cyclization rate (mass %) using the molecular weight of each unit. The unit composition of the glutarimide resin was determined from the unit composition of the precursor resin and the glutarimide cyclization rate (mass %).

[0134] (Syndiotacticity of the triad (rr) (rr ratio)) A sample solution was prepared by dissolving a methacrylic resin (M) in deuterated chloroform. The obtained sample solution was analyzed using a nuclear magnetic resonance spectrometer (Bruker "ULTRA SHIELD 400 PLUS") at room temperature (20 to 25°C) with 64 accumulations. 1 The H-NMR spectrum was measured. From the spectrum, the area (X) of the region from 0.6 to 0.95 ppm and the area (Y) of the region from 0.6 to 1.35 ppm were measured when tetramethylsilane (TMS) was set to 0 ppm, and the syndiotacticity (rr) expressed in triad form was calculated using the formula: (X / Y) × 100.

[0135] (Weight average molecular weight (Mw)) The weight-average molecular weight (Mw) of the resin was determined by gel permeation chromatography (GPC). The measurement device used was a GPC device "HLC-8320" manufactured by Tosoh Corporation. The separation column used consisted of "TSKguardcolumSuperHZ-H," "TSKgelHZM-M," and "TSKgelSuperHZ4000" columns connected in series, all manufactured by Tosoh Corporation. A differential refractive index detector (RI detector) was used as the detector. A sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 mL of tetrahydrofuran. The column oven temperature was set to 40°C. Tetrahydrofuran was used as the eluent, and the eluent flow rate was set to 0.35 mL / min. 20 μL of the sample solution was injected into the instrument, and a chromatogram was measured. GPC measurements were performed on 10 standard polystyrenes with molecular weights ranging from 400 to 5,000,000, and a calibration curve showing the relationship between retention time and molecular weight was created. Based on this calibration curve, the Mw, Mn, and Mw / Mn of the resin to be measured, converted to standard polystyrene, were determined.

[0136] (glass transition temperature (Tg)) The methacrylic resin (composition) was dissolved in chloroform and reprecipitated with methanol. The reprecipitated resin (composition) was vacuum dried at 100°C for 12 hours or more. The vacuum-dried resin (composition) was measured using a differential scanning calorimeter (Shimadzu Corporation, "DSC-50") in accordance with JIS K7121. 10 mg of resin (composition) was placed in an aluminum pan and set in the above-mentioned apparatus. After nitrogen replacement for 30 minutes or more, the sample was heated from room temperature (20-25°C) to 250°C at a rate of 20°C / min in a 10 ml / min nitrogen stream, held for 5 minutes, and then cooled to room temperature (first scan). The sample was then heated to 200°C at a rate of 10°C / min (second scan), and a DSC curve was measured. The midpoint glass transition temperature determined from the DSC curve obtained in the second scan was taken as the glass transition temperature (Tg).

[0137] (Melt flow rate (MFR)) The methacrylic resin (composition) was dissolved in chloroform and reprecipitated with methanol. The reprecipitated resin (composition) was vacuum dried at 100°C for 12 hours or more. The melt flow rate (MFR) of the vacuum-dried resin (composition) was measured at 230°C under a load of 3.8 kg in accordance with JIS K7210.

[0138] (Total light transmittance (Tt)) The methacrylic resin composition was press-molded to obtain a sheet having a thickness of 3 mm. The total light transmittance (Tt) of this sheet was measured using a haze meter ("HM-150" manufactured by Murakami Color Research Institute) in accordance with JIS K7361-1.

[0139] (1% thermogravimetric reduction temperature) Using a thermogravimetric analyzer (Shimadzu Corporation, "TGA-50"), approximately 5 mg of the methacrylic resin composition was heated from room temperature (20-25°C) to 500°C at a heating rate of 10°C / min in a nitrogen atmosphere to obtain a TG curve. The temperature at which the weight loss rate was 1% relative to 100% weight at 200°C was determined as the 1% thermal weight loss temperature.

[0140] (saturated water absorption rate) The methacrylic resin (composition) was press-molded and cut into a square test piece measuring 50 mm on a side and 3 mm thick. The test piece was vacuum-dried at 80°C and 5 mmHg for 24 hours and then allowed to cool in a desiccator. Once the test piece had reached room temperature (20-25°C), it was removed from the desiccator and its mass (also referred to as the dry mass or initial mass) (W0) was immediately measured. Next, the test piece was immersed in distilled water at 23°C. The test piece was taken out of the water, the water adhering to the surface was wiped off, and the mass of the test piece (also called the water absorption mass) was measured. The immersion of the test piece in distilled water and the measurement of the water absorption mass of the test piece were repeated, and the water absorption mass of the test piece at the time when the mass change rate of the test piece became within 0.02% of the previous water absorption mass was defined as the saturated water absorption mass (W S ) was decided. The saturated water absorption was calculated using the following formula. [Saturated water absorption rate (%)]=[(W S -W0) / W0] × 100

[0141] (Charpy impact strength (unnotched)) The methacrylic resin composition was press-molded and cut into test pieces measuring 80 mm in length, 10 mm in width, and 4 mm in thickness. The Charpy impact strength of these test pieces (without notches) was measured at 23°C and 50% relative humidity in accordance with JIS K7111-1 / 1eU. The measurement was performed 10 times, and the average value was used as the data.

[0142] (wet tension) The methacrylic resin composition was press-molded to obtain a sheet having a thickness of 3 mm. The wet tension was measured using a mixture for wet tension testing (manufactured by Wako Pure Chemical Industries, Ltd.) at 23°C and a relative humidity of 50% in accordance with JIS K6768.

[0143] (average linear expansion coefficient) A methacrylic resin (composition) or a polycarbonate resin (composition) was press-molded and then machined to obtain a square prism-shaped test piece with a base measuring 5 mm on each side and a height of 10 mm. The test piece was vacuum-dried at 80°C and 5 mmHg for 24 hours and then allowed to cool in a desiccator. After reaching room temperature (20-25°C), the test piece was removed from the desiccator and its linear expansion coefficient (ppm / °C) was measured in accordance with JIS K7197. Thermomechanical analysis (TMA) measurements were performed in a compression mode under conditions of a nitrogen gas flow rate of 150 mL / min, a test load of 49 mN, a heating rate of 5°C / min, and a temperature range of 23 to 130°C. The average displacement of the test specimens at 23 to 100°C was calculated as the average linear expansion coefficient (ppm / °C) at 23 to 100°C.

[0144] (exterior) The appearance of the laminated sheet was visually observed to check for transparency, flow patterns due to poor flow, and foaming due to thermal decomposition of the resin. Evaluation was made according to the following criteria. A (good): High transparency, no flow pattern or bubbles observed. C (poor): Low transparency and / or flow patterns and / or bubbles were observed.

[0145] (Pencil hardness) A rectangular test piece with a long side of 110 mm and a short side of 65 mm was cut out from the laminate sheet. The short side direction was parallel to the extrusion flow direction, and the long side direction was perpendicular to the extrusion flow direction. Using a moving-table pencil scratch tester (Model P) (manufactured by Toyo Seiki Co., Ltd.), the presence or absence of scratches was confirmed by pressing a pencil lead against the surface of the methacrylic resin-containing layer of the test piece at an angle of 45 degrees and a load of 500 g. The hardness of the pencil lead was gradually increased, and the hardness of the lead one level softer than the point at which scratches occurred was taken as the pencil scratch hardness and evaluated according to the following criteria. A (good): Pencil hardness is 3H to 9H, B (Acceptable): Pencil hardness is H~2H, C (poor): Pencil hardness is 6B~F.

[0146] (Warping in high temperature (high humidity) environments) A first rectangular test piece with a long side of 110 mm and a short side of 65 mm and a second rectangular test piece with a long side of 200 mm and a short side of 100 mm were cut out from the laminated sheet. The direction parallel to the extrusion flow direction was the short side direction, and the direction perpendicular to the extrusion flow direction was the long side direction.

[0147] The first test piece was placed on a glass platen so that one methacrylic resin-containing layer was the uppermost layer among one or more methacrylic resin-containing layers and one or more polycarbonate resin-containing layers, and was left to stand for 24 hours in an environment of a temperature of 23°C and a relative humidity of 50%. Thereafter, the maximum gap between the test piece and the platen was measured using a gap gauge, and this value was taken as the initial warpage. Next, the first test piece placed on the glass surface plate was placed in an environmental tester set at a temperature of 85°C and a relative humidity of 85%, and left to stand for 72 hours. The test piece placed on the glass surface plate was removed from the environmental tester and left to stand for 4 hours in a 25°C environment. Thereafter, the amount of warpage was measured in the same manner as the initial measurement, and this value was taken as the amount of warpage under a high-temperature, high-humidity environment. The amount of warpage change under a high-temperature, high-humidity environment, defined by the following formula, was determined and evaluated according to the following criteria. [Warpage change under high temperature and humidity environment] = [Warpage under high temperature and humidity environment] - [Initial warpage] A (Good): The absolute value of the warpage change under high temperature and humidity conditions is 0 to 0.5 mm. C (Poor): The absolute value of the warpage change under high temperature and high humidity conditions exceeds 0.5 mm.

[0148] The initial amount of warpage of the second test piece was also determined in the same manner as above. Next, the second test piece placed on a glass surface plate was heated for 5 hours in an oven controlled at a temperature within the range of 125°C ± 3°C. Thereafter, the amount of warpage was measured in the same manner as the initial measurement, and this value was taken as the amount of warpage in a high-temperature environment. The amount of warpage change in a high-temperature environment, defined by the following formula, was calculated and evaluated according to the following criteria. [Warpage change under high temperature environment = [Warpage under high temperature environment] - [Initial warpage] A (Good): Warpage change under high temperature environment is 0 to 0.3 mm. B (Acceptable): Warpage change under high temperature environment is between -0.3 mm and 0 mm or 0.3 mm or more. C (Poor): The amount of warpage change under high temperature conditions is less than -0.3 mm.

[0149] In addition, for all test specimens, when the test specimen placed on the surface plate had an upward convex warp, the sign of the amount of warp was defined as "plus," and when the test specimen had a downward convex warp, the sign of the amount of warp was defined as "minus."

[0150] (Adhesion of hard coat layer) 16 parts by mass of 4-hydroxybutyl acrylate ("4-HBA" manufactured by Osaka Organic Chemical Industry Co., Ltd.), 32 parts by mass of urethane acrylate ("NK Oligo UA-53H-80BK" manufactured by Shin-Nakamura Chemical Co., Ltd.), 48 parts by mass of a condensate of pentaerythritol and acrylic acid ("Viscoat #300" manufactured by Osaka Organic Chemical Industry Co., Ltd.), 4 parts by mass of ethoxylated glycerin triacrylate ("A-GLY-9E" manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2.4 parts by mass of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907" manufactured by BASF) as a photopolymerization initiator were mixed. The resulting mixture was diluted with a mixed solvent of methyl isobutyl ketone (MIBK) and propylene glycol monomethyl ether (PGM) (MIBK:PGM = 50:50 (mass ratio)) to obtain a UV-curable composition (HC-1) with a solid content concentration of 42.0 mass %.

[0151] A UV-curable composition (HC-1) was applied to one of the methacrylic resin-containing layers of the laminate sheet so that the thickness after curing would be 6 μm. The resulting coating film was dried at 70°C and then irradiated with ultraviolet (UV) light at an illuminance of 150 mW / cm using an ultraviolet (UV) irradiation device equipped with a high-pressure mercury lamp H04-L41 manufactured by Eye Graphics. 2 , cumulative irradiation dose 368mJ / cm 2 Under the conditions, the coating film was irradiated with ultraviolet (UV) rays to cure it, thereby forming a hard coat layer. The adhesion of the hard coat layer to the methacrylic resin-containing layer was evaluated in accordance with JIS-K5600-5-6, except that the number of cut lines in each direction of the grid pattern was set to 11, forming 100 test cells. Using a cutter knife, 11 cuts were made in the hard coat layer at 1 mm intervals in two mutually perpendicular linear directions to a depth reaching the methacrylic resin-containing layer, resulting in a grid-like cut with a total of 100 squares of 1 mm square. An adhesive tape (Cellotape (registered trademark)) was firmly pressed onto the grid using a spatula, and then the adhesive tape was quickly peeled off in an angle of approximately 60° from the edge. The number of peeled squares out of the 100 grids was determined and evaluated according to the following criteria. A (good): 0 to 9 peeled pieces C (Poor): The number of peeled pieces is 10 or more.

[0152] (Secondary formability) A mold was prepared, which was made up of a combination of a convex mold (male mold) and a concave mold (female mold), and which was capable of curving the laminated sheet into an arc-shaped cross section with a curvature radius of 50 mm. The laminate sheet was preheated at 90°C for 2 minutes and set in a mold so that one methacrylic resin-containing layer contained in the laminate sheet was in contact with the convex mold. Press molding was performed for 3 minutes at a mold temperature of 140°C, and then the molded product was allowed to cool naturally. The surface condition and overall shape of the resulting molded product were visually observed, and the moldability was evaluated according to the following criteria. A (good): No surface roughness or molding return was observed, and a secondary molded article with a smooth surface and curved as designed was obtained. B (Acceptable): Some surface roughness and / or return to molding was observed. C (poor): Significant surface roughness and / or return to molding was observed.

[0153] [material] The following materials were prepared or manufactured:

[0154] <Methacrylic resin (M) or styrene copolymer (S)> (MMA99.7-MA0.3) Methyl methacrylate-methyl acrylate copolymer, "Parapet HR" manufactured by Kuraray Co., Ltd., Mw = 90,000, methyl methacrylate (MMA) unit / methyl acrylate (MA) unit (mass ratio) = 99.3 / 0.7, rr ratio = 51%, Tg = 117°C, MFR = 2.4 g / 10 min, saturated water absorption = 2.0%.

[0155] (MMA74-St15-Mah9) Methyl methacrylate-styrene-maleic anhydride copolymer, "PLEXIGLAS hw55 Clear" manufactured by Polypla-Evonik, Mw = 141,000, methyl methacrylate (MMA) unit / styrene (St) unit / maleic anhydride (Mah) unit (mass ratio) = 74 / 15 / 9, Tg = 121°C, saturated water absorption = 2.2%.

[0156] (St74-Mah26) Styrene-maleic anhydride copolymer, "XIRAN 3500" manufactured by POLYSCOPE (Mw = 80,000, styrene (St) unit / maleic anhydride (Mah) unit (mass ratio) = 74 / 26, Tg = 159°C, saturated water absorption = 0.3%).

[0157] <Polycarbonate resin (PC)> (PC-1) Sumika Polycarbonate Co., Ltd. "SD Polyca 300 Series", Mw = 50,000, Tg = 150°C, saturated water absorption = 0.3%, linear expansion coefficient 69.3 ppm / °C.

[0158] <Precursor resin (Pre)> (Pre-1) An autoclave equipped with a stirrer was charged with 68.0 parts by mass of purified methyl methacrylate (MMA), 28.0 parts by mass of α-methylstyrene (αMSt), 7.0 parts by mass of styrene (St), 0.05 parts by mass of 2,2'-azobis(2-methylpropionitrile) (AIBN), and 0.01 parts by mass of n-octyl mercaptan (n-OM), and the resulting mixture was dissolved uniformly to obtain a polymerization raw material. Nitrogen gas was blown into the polymerization raw material to adjust the dissolved oxygen concentration to 3 ppm. Next, a continuous flow tank reactor equipped with a brine cooling condenser was prepared, and the inside of the reactor was purged with nitrogen gas. The polymerization raw materials were continuously fed into the reactor at a constant flow rate so that the average residence time was 3 hours, and bulk polymerization was carried out at a polymerization temperature of 140°C. A liquid containing precursor resin (Pre-1) (MMA / αMSt / St copolymer) was continuously discharged from the reactor. The pressure inside the reactor was regulated by a pressure control valve connected to the brine cooling condenser. The liquid discharged from the reactor was then heated to 210°C and fed to a twin-screw extruder adjusted to 230°C. Volatiles, primarily consisting of unreacted monomers, were separated and removed. The resin was extruded into strands and cut with a pelletizer to obtain pellets of precursor resin (Pre-1) (MMA / αMSt / St copolymer). Table 1 shows the polymerization conversion rate and the composition and physical properties of the obtained precursor resin.

[0159] (Pre-2) Precursor resin (Pre-2) (MMA / αMSt / St copolymer) was obtained in the same manner as precursor resin (Pre-1), except that the charged composition was changed to 77.5 parts by mass of purified methyl methacrylate (MMA), 17.5 parts by mass of α-methylstyrene (αMSt), 5.0 parts by mass of styrene (St), 0.04 parts by mass of 2,2'-azobis(2-methylpropionitrile) (AIBN), and 0.053 parts by mass of n-octyl mercaptan (n-OM), and the average residence time during continuous bulk polymerization was changed to 2.5 hours. Table 1 shows the polymerization conversion rate and the composition and physical properties of the obtained precursor resin.

[0160] (Pre-3) Precursor resin (Pre-3) (MMA / αMSt copolymer) was obtained in the same manner as precursor resin (Pre-1), except that the charged composition was changed to 75.0 parts by mass of purified methyl methacrylate (MMA), 25.0 parts by mass of α-methylstyrene (αMSt), 0.004 parts by mass of 2,2'-azobis(2-methylpropionitrile) (AIBN), and 0.02 parts by mass of n-octyl mercaptan (n-OM), the polymerization temperature was changed to 130°C, the heating temperature of the liquid discharged from the reactor was changed to 230°C, and the set temperature of the twin-screw extruder was changed to 240°C. Table 1 shows the polymerization conversion rate and the composition and physical properties of the obtained precursor resin.

[0161] (Pre-4) A precursor resin (Pre-4) (MMA / St copolymer) was obtained in the same manner as in the "Method for producing copolymer (A)" in the section [Examples] of JP-A No. 2003-231785, except that the mass ratio of MMA and St charged into the autoclave was changed. Table 1 shows the polymerization conversion rate and the composition and physical properties of the obtained precursor resin.

[0162] <Glutarimide resin (G)> (G-1)~(G-4), (G-6), (G-7) A twin-screw extruder (TEX30α-77AW-3V, manufactured by Nippon Steel Corporation) was prepared. The extruder had a transport section, a melt-kneading section, a devolatilizing section, and a discharge section. The screw rotation speed was set at 150 rpm and the temperature was set at 210 to 270°C. A precursor resin (Pre) (any of (Pre-1) to (Pre-4)) was fed into the transport section of the twin-screw extruder at a flow rate of 15 kg / hr. Monomethylamine was injected as an imidizing agent through the additive supply port of the twin-screw extruder in an amount that would result in the glutarimide (GI) unit content shown in Table 2. The precursor resin (Pre) and monomethylamine were reacted in the melt-kneading section, which included a kneading block. The by-products and excess monomethylamine were volatilized from the resulting molten resin in the devolatilizing section and discharged through multiple vents. The molten resin was extruded in the form of a strand from a die provided at the end of the discharge section of the twin-screw extruder, cooled in a water tank, and cut with a pelletizer to obtain pelletized glutarimide resin (G) ((G-1) to (G-4), (G-6), and (G-7)). Table 2 shows the type of precursor resin (Pre) and the composition and physical properties of the resulting glutarimide resin (G).

[0163] (G-5) "PLEXIMID TT50" manufactured by Polypla-Evonik, Mw = 76,000, methyl methacrylate (MMA) unit / N-methylglutarimide unit (mass ratio) = 30 / 70, Tg = 150°C, saturated water absorption = 3.8%. The composition and physical properties are shown in Table 2.

[0164] [Table 1]

[0165] [Table 2]

[0166] <Methacrylic resin composition (MR)> (MR-1)~(MR-4), (MR-11)~(MR-17) Glutarimide resins (G-1) to (G-7) and 100 parts by weight of one or more thermoplastic resins selected from the group consisting of methacrylic resins (M) or styrene copolymers (S) ((MMA99.7-MA0.3), (MMA74-St15-Mah9), or (St74-Mah26)) (100 parts by weight total for multiple resins), 0.15 parts by weight of stearyl alcohol (Kao Corporation, "Kalcol 8089") as a lubricant, and 0.90 parts by weight of a high-molecular-weight benzotriazole-based UV absorber (ADEKA Corporation, "LA-31RG") were dry-blended, melt-kneaded at 250°C in a twin-screw extruder with a shaft diameter of 20 mm, and extruded to obtain methacrylic resin compositions (MR-1) to (MR-4) and (MR-11) to (MR-17). The compositions and evaluation results are shown in Table 3.

[0167] [Table 3]

[0168] [Examples E1 to E5, Comparative Examples EC1 to EC8] Using a 65 mmφ single-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a methacrylic resin composition (MR) (any of (MR-1) to (MR-4), (MR-11) to (MR-17)) was melt-kneaded. Using a 150 mmφ single-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a polycarbonate resin (PC-1) was melt-kneaded. These molten resins (compositions) were introduced into a junction block, and a multi-manifold die was used to co-extrude a molten thermoplastic resin laminate having a two-layer or three-layer structure at an extrusion temperature of 250° C. The thickness of each layer was adjusted by adjusting the extrusion rate of each resin (composition). Next, the molten thermoplastic resin laminate was sandwiched between adjacent first and second cooling rolls, wrapped around the second cooling roll, sandwiched between the second and third cooling rolls, and cooled by being wrapped around the third cooling roll. In the two-layer structure, the polycarbonate-based resin-containing layer was in contact with the third cooling roll. After cooling, the resulting laminated sheet was taken up by a pair of take-up rolls. The peripheral speed ratio (V4 / V2) between the peripheral speed of the take-up roll (V4) and the peripheral speed of the second cooling roll (V2) was set to 0.99, and the peripheral speed ratio (V3 / V2) between the peripheral speed of the third cooling roll (V3) and the peripheral speed of the second cooling roll (V2) was adjusted to 1.00. In this manner, a laminate sheet was produced having a two-layer structure of a methacrylic resin-containing layer (first layer) / polycarbonate resin-containing layer (second layer), or a three-layer structure of a first methacrylic resin-containing layer (first layer, first surface layer) / polycarbonate resin-containing layer (second layer) / second methacrylic resin-containing layer (third layer, second surface layer). In the three-layer structure, the first methacrylic resin-containing layer and the second methacrylic resin-containing layer had the same composition and / or thickness. The main manufacturing conditions and evaluation results are shown in Tables 4 and 5. In the examples shown in Table 4, conditions not listed in the table were common conditions.

[0169] [Table 4]

[0170] [Table 5]

[0171] [Summary of results] In Examples E1 to E5, laminate sheets were produced that had a total thickness of 500 to 5,000 μm and included one or more methacrylic resin-containing layers made of a methacrylic resin composition (MR) containing a glutarimide resin (G) containing 5 to 63 mass% of methyl methacrylate (MMA) units, 35 to 75 mass% of glutarimide (GI) units, 1 to 48 mass% of α-methylstyrene (αMSt) units, and 1 to 48 mass% of styrene (St) units, and one or more polycarbonate resin-containing layers made of a polycarbonate resin composition (PCR) containing a polycarbonate resin (PC). All of the laminated sheets obtained in these examples had a Tg MR ≦170, 0≦|Tg PCR -Tg MR |≦15 and 0≦α PCR -α MR The saturated water absorption rate of the methacrylic resin composition (MR) at 23°C was 0 to 3.0 mass%. In all of the laminate sheets obtained in these Examples, the wet tension of the surface of the methacrylic resin-containing layer was 38 to 50 mN / m. All of the laminate sheets obtained in these Examples were excellent in appearance quality, surface hardness, resistance to warpage deformation in a high temperature (high humidity) environment, adhesion of the hard coat layer, and secondary processability.

[0172] The laminated sheet obtained in Comparative Example EC1 had a Tg MR <140, |Tg PCR -TgMR |>15, α PCR -α MR <0. In the laminate sheets obtained in Comparative Examples EC2 and EC3, the saturated water absorption of the methacrylic resin composition (MR) at 23°C exceeded 3.0% by mass. The laminated sheet obtained in Comparative Example EC4 had a Tg MR <140, |Tg PCR -Tg MR |>15, α PCR -α MR <0. The laminated sheet obtained in Comparative Example EC5 had a PCR -α MR <0. The laminated sheet obtained in Comparative Example EC6 had a Tg MR <140. The laminated sheets obtained in Comparative Examples EC7 and EC8 had Tg MR <140, |Tg PCR -Tg MR |>15. The laminated sheets obtained in these comparative examples were poor in one or more of the evaluation items of appearance quality, surface hardness, resistance to warpage deformation in a high temperature (high humidity) environment, adhesion of the hard coat layer, and secondary processability.

[0173] The present invention is not limited to the above-described embodiments and examples, and appropriate design changes are possible without departing from the spirit of the present invention. [Explanation of symbols]

[0174] 1A, 1B, 2A, 2B laminated sheet 11, 11A, 11B Methacrylic resin-containing layer 21 Polycarbonate resin-containing layer 31 Hard coat layer

Claims

1. one or more methacrylic resin-containing layers made of a methacrylic resin composition (MR) containing a glutarimide resin (G) containing 5 to 63 mass% of methyl methacrylate units, 35 to 75 mass% of glutarimide units represented by the following formula (I), 1 to 48 mass% of α-methylstyrene units, and 1 to 48 mass% of styrene units; and one or more polycarbonate-based resin-containing layers made of a polycarbonate-based resin composition (PCR) containing a polycarbonate-based resin (PC), A laminated sheet having a total thickness of 500 to 5,000 μm, The glass transition temperature of the methacrylic resin composition (MR) is Tg ＭＲ [°C], and the glass transition temperature of the polycarbonate resin composition (PCR) is Tg ＰＣＲ [°C], and the average linear expansion coefficient of the methacrylic resin composition (MR) at 23 to 100°C is α ＭＲ [ppm / °C], and the average linear expansion coefficient of the polycarbonate resin composition (PCR) at 23 to 100°C is α ＰＣＲ [ppm / °C], 140≦Tg ＭＲ ≦170, 0≦|Tg ＰＣＲ -Tg ＭＲ |≦15 and 0≦α ＰＣＲ -α ＭＲ ≦30 is satisfied, A laminated sheet, wherein the saturated water absorption rate of the methacrylic resin composition (MR) at 23°C is 0 to 3.0 mass%. 【Chemistry 1】 (In formula (I), two R １ are each independently a hydrogen atom or a methyl group. ２ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms and containing an aromatic ring.

2. 145≦Tg ＭＲ The laminated sheet according to claim 1, which satisfies ≦170.

3. 0≦|Tg ＰＣＲ -Tg ＭＲ The laminate sheet according to claim 1, wherein |≦10 is satisfied.

4. 0≦α ＰＣＲ -α ＭＲ The laminate sheet according to claim 1, wherein the thickness satisfies ≦20.

5. 2. The laminate sheet according to claim 1, wherein the surface of the methacrylic resin-containing layer has a wet tension of 38 to 50 mN / m.

6. The laminate sheet according to claim 1 , comprising a coextrusion-molded sheet including the methacrylic resin-containing layer and the polycarbonate resin-containing layer.

7. The laminate sheet according to claim 1 , further comprising a hard coat layer laminated on the methacrylic resin-containing layer.

8. The laminate sheet according to claim 1, further comprising one or more functional layers selected from the group consisting of an anti-reflection layer, an anti-fingerprint layer, an anti-fogging layer, a weather-resistant layer, an anti-static layer, an anti-fouling layer, and an anti-glare layer.

9. A molded article comprising the laminate sheet according to any one of claims 1 to 8.

10. A front panel for a display device, comprising the laminate sheet according to any one of claims 1 to 8.

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