Resin laminate

Abstract

To provide a resin laminate which is used for a transparent substrate material or a protective material, can suppress curling under an environment of 23 °C and 50% RH, and is excellent in surface hardness. Another object of the present invention is to provide a resin laminate which can be prevented from curling in an environment of 23 °C. and 50% RH after antireflection coating and which is excellent in surface hardness.SOLUTION: According to the present invention, it is possible to provide a resin laminate including a layer containing a polycarbonate-based resin (A) containing a polycarbonate resin as a main component and a layer containing a thermoplastic resin (B) laminated on at least one surface of the layer, in which the curl shape of the resin laminate after being left in a 23 °C. 50% RH environment is such that the layer containing the thermoplastic resin (B) is concave and 11m ≤ radius of curvature R ≤ 1225m.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin laminate that is suitable for use as a transparent substrate material or protective material and includes a polycarbonate-based resin layer and a thermoplastic resin layer, and preferably has excellent curl resistance after lamination of an anti-reflection layer. [Background technology]

[0002] Polycarbonate resin sheets have excellent transparency, impact resistance, and heat resistance, and are used for soundproof partition walls, carports, signs, glazing materials, lighting fixtures, office equipment, electronic device displays, and touch panel front panels. However, they have the disadvantage of being easily scratched due to their low surface hardness, which limits their applications. In order to overcome this drawback, Patent Document 1 proposes a method of coating the surface with an ultraviolet curable resin or the like, and a method of applying a hard coat to a substrate made by co-extrusion of polycarbonate resin and acrylic resin. However, when a hard coat is applied to the surface of a polycarbonate resin, the required pencil hardness cannot be met, and in some cases, the polycarbonate resin cannot be used for applications requiring high surface hardness. Therefore, a laminate of an acrylic resin and a polycarbonate resin has a certain degree of improved surface hardness, and has been widely used for displays, touch panel front panels, and the like of electronic devices. Furthermore, Patent Document 2 discloses a laminate in which a resin having structural units of (meth)acrylic acid ester and aliphatic vinyl is laminated on a polycarbonate resin in order to suppress the degree of curling after being left in a high-temperature, high-humidity environment.

[0003] In recent years, anti-reflection coatings have been applied to plastic surfaces to reduce sunlight reflections on the screens of in-car navigation systems and smartphones. Anti-reflection coatings are formed by depositing metal while heating to form multiple metal films such as SiOx and TiOx. However, due to the difference in linear expansion coefficients between the resin laminate and the metal films, the plastic surface can curl significantly into a convex shape at room temperature, which has been a serious drawback in electronic device applications such as LCD display covers and touch panel front panels. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-103169 [Patent Document 2] WO2011 / 145630 publication Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin laminate that can be used as a transparent substrate material or protective material, can suppress curling in an environment of 23°C and 50% RH, and has excellent surface hardness. Another object of the present invention is to provide a resin laminate that can suppress curling in an environment of 23°C and 50% RH after anti-reflection coating, and has excellent surface hardness. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following aspects of the present invention. Specifically, the present invention is as follows.

[0007] [1] A resin laminate comprising a layer containing a polycarbonate-based resin (A) mainly composed of a polycarbonate resin, and a layer containing a thermoplastic resin (B) laminated on at least one surface of the layer, wherein the resin laminate, after being left in an environment of 23°C and 50% RH, has a curl shape with a concave shape toward the layer containing the thermoplastic resin (B) of 11 m≦radius of curvature R≦1225 m. [2] The resin laminate according to [1] above, wherein the surface of the layer containing the thermoplastic resin (B) is subjected to one or more of a hard coat treatment, an anti-reflection treatment, an anti-fouling treatment, an anti-fingerprint treatment, an anti-static treatment, a weather resistance treatment, and an anti-glare treatment. [3] The resin laminate according to the above [1] or [2], wherein an anti-reflection layer is further laminated on the surface of the layer containing the thermoplastic resin (B), and the curl shape of the resin laminate after being left in an environment of 23°C and 50% RH is such that the curl shape of the layer containing the thermoplastic resin (B) is concave or convex with a radius of curvature R≧21 m. [4] A resin laminate comprising a layer containing a polycarbonate-based resin (A) containing a polycarbonate resin as a main component, a layer containing a thermoplastic resin (B) laminated on at least one surface of the layer containing resin (A), and an anti-reflection layer laminated on the surface of the layer containing resin (B), wherein the resin laminate curls after being left in an environment of 23°C and 50% RH, with the anti-reflection layer side being concave or convex, and the radius of curvature of the resin laminate is R≧21 m. [5] The resin laminate according to [4] above, wherein one or more of a hard coat treatment, an anti-reflection treatment, an anti-fouling treatment, an anti-fingerprint treatment, an anti-static treatment, a weather resistance treatment, and an anti-glare treatment is applied between the layer containing the thermoplastic resin (B) and the anti-reflection layer. [6] The resin laminate according to any one of the above [1] to [5], wherein the surface on the side of the layer containing the thermoplastic resin (B) has a pencil hardness of HB or higher. [7] The resin laminate according to any one of the above [1] to [6], wherein the polycarbonate resin (A) has a weight average molecular weight of 15,000 to 75,000. [8] The resin laminate according to any one of the above [1] to [7], wherein the layer containing the polycarbonate resin (A) and / or the layer containing the thermoplastic resin (B) contains an ultraviolet absorber. [9] A transparent substrate material comprising the resin laminate according to any one of [1] to [8] above.

[10] A transparent protective material comprising the resin laminate according to any one of [1] to [8] above.

[11] A front surface protection plate for a touch panel, comprising the resin laminate according to any one of the above [1] to [8]. [Effects of the Invention]

[0008] According to the present invention, a resin laminate is provided that exhibits excellent surface hardness and suppresses curling in a 23°C, 50% RH environment (preferably after anti-reflection coating), and the resin laminate is used as a transparent substrate material or a transparent protective material. Specifically, the resin laminate is suitable for use in portable display devices such as mobile phone terminals, portable electronic toys, personal digital assistants, and mobile PCs, as well as stationary display devices such as notebook PCs, desktop PC LCD monitors, LCD televisions, and in-vehicle car navigation systems. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, the present invention will be described in detail by way of examples and working examples, but the present invention is not limited to the illustrated examples and working examples, and can be carried out by any method as long as it does not significantly deviate from the content of the present invention.

[0010] <Polycarbonate resin (A)> The polycarbonate-based resin (A) used in the present invention is a polycarbonate-based resin (A) primarily composed of polycarbonate resin. Here, "primarily composed of polycarbonate resin" means that the polycarbonate resin content exceeds 50% by mass. The polycarbonate-based resin (A) preferably contains 75% or more by mass of polycarbonate resin, more preferably 90% or more by mass of polycarbonate resin, and even more preferably consists essentially of polycarbonate resin. The polycarbonate-based resin (A) contains a carbonate bond in the molecular main chain. That is, the polycarbonate-based resin (A) is not particularly limited as long as it contains an -[OR-OCO]- unit (where R represents an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further represents a linear or branched structure). However, it is particularly preferred to use a polycarbonate containing a structural unit of the following formula (3). The use of such a polycarbonate allows for the production of a resin laminate with excellent impact resistance. [ka] Specifically, aromatic polycarbonate resins (for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000, commercially available from Mitsubishi Engineering Plastics Corporation) can be used as the polycarbonate resin (A). The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably from 120 to 160°C, more preferably from 125 to 155°C, and particularly preferably from 130 to 150°C. In recent years, there has been an increasing demand for bending front panels as well, and therefore, it is preferable to synthesize the polycarbonate resin (A) using a monohydric phenol represented by the following general formula (4) as an end terminator. [ka] (In the formula, R1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R2 to R5 each represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent, and the substituent is halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

[0011] The monohydric phenol of general formula (4) is more preferably a monohydric phenol represented by the following general formula (5). [ka] (In the formula, R1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)

[0012] The number of carbon atoms in R1 in general formula (4) or general formula (5) is more preferably within a specific numerical range. Specifically, the upper limit of the number of carbon atoms in R1 is preferably 36, more preferably 22, and particularly preferably 18. The lower limit of the number of carbon atoms in R1 is preferably 8, and more preferably 12.

[0013] Among the monohydric phenols (end terminators) represented by general formula (4) or general formula (5), it is particularly preferable to use either or both of parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester as the end terminator.

[0014] When a monohydric phenol (terminal terminator) having an alkyl group with 16 carbon atoms is used as R1 in general formula (4) or general formula (5), the glass transition temperature, melt fluidity, moldability, drawdown resistance, and solvent solubility of the monohydric phenol during polycarbonate resin production are excellent, and this is particularly preferred as a terminal terminator for use in the polycarbonate resin of the present invention.

[0015] On the other hand, if the number of carbon atoms in R1 in general formula (4) or general formula (5) is too large, the solubility of the monohydric phenol (end-stopper) in organic solvents tends to decrease, which may result in a decrease in productivity during the production of polycarbonate resin. For example, when the carbon number of R1 is 36 or less, the productivity and economy of producing a polycarbonate resin are high. When the carbon number of R1 is 22 or less, the monohydric phenol has particularly excellent solubility in organic solvents, and the productivity and economy of producing a polycarbonate resin can be significantly increased. If the number of carbon atoms in R1 in general formula (4) or general formula (5) is too small, the glass transition temperature of the polycarbonate resin will not be a sufficiently low value, and thermoformability may decrease.

[0016] Other resins contained in the polycarbonate resin (A) include polyester resins. The polyester resin may contain terephthalic acid as a dicarboxylic acid component as a main component, and may contain a dicarboxylic acid component other than terephthalic acid. For example, a polyester resin obtained by polycondensation of a glycol component containing 80 to 60 (molar ratio) of ethylene glycol as a main component and 20 to 40 (molar ratio, total 100) of 1,4-cyclohexanedimethanol and a dicarboxylic acid component, so-called "PETG," is preferred. The polycarbonate resin (A) may also contain a polyestercarbonate resin having an ester bond and a carbonate bond in the polymer skeleton.

[0017] In the present invention, the weight-average molecular weight of the polycarbonate-based resin (A) affects the impact resistance and molding conditions of the resin laminate. That is, if the weight-average molecular weight is too small, the impact resistance of the resin laminate decreases, which is undesirable. If the weight-average molecular weight is too high, an excessive heat source may be required when laminating layers containing the polycarbonate-based resin (A), which is undesirable. Furthermore, some molding methods require high temperatures, which expose the polycarbonate-based resin (A) to high temperatures, which may adversely affect its thermal stability. The weight-average molecular weight of the polycarbonate-based resin (A) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and even more preferably 25,000 to 65,000.

[0018] <Method for measuring weight-average molecular weight of polycarbonate resin (A)> The weight-average molecular weight of the polycarbonate resin (A) can be measured based on the description in paragraphs 0061 to 0064 of JP-A No. 2007-179018. Details of the measurement method are shown below. [Table 1]

[0019] After performing measurements using polystyrene (PS) as a standard polymer, the relationship between elution time and the molecular weight of polycarbonate (PC) is determined using the universal calibration method to create a calibration curve. Then, the elution curve (chromatogram) of PC is measured under the same conditions as for the calibration curve, and each average molecular weight is calculated from the elution time (molecular weight) and the peak area (number of molecules) at that elution time. If the number of molecules at molecular weight Mi is Ni, the weight-average molecular weight can be expressed as follows. The following conversion formula was also used: (Weight average molecular weight) Mw=Σ(NiMi 2 ) / Σ(NiMi) (conversion formula) MPC=0.47822MPS 1.01470 It should be noted that MPC indicates the molecular weight of PC, and MPS indicates the molecular weight of PS.

[0020] The method for producing the polycarbonate resin (A) used in the present invention can be appropriately selected depending on the monomer used, such as the known phosgene method (interfacial polymerization method) or transesterification method (melt method).

[0021] <Thermoplastic resin (B)> The thermoplastic resin (B) used in the present invention mainly comprises a high-hardness resin. In this specification, a high-hardness resin is a resin that is harder than the polycarbonate-based resin (A) that serves as the base material, and refers to a resin with a pencil hardness of HB or higher. The pencil hardness of the high-hardness resin is preferably HB to 5H, more preferably H to 4H, and particularly preferably 2H to 4H. The high-hardness resin used in the present invention may be one type or two or more types. The high-hardness resin is preferably at least one selected from the following resins (B1) to (B6), more preferably at least one selected from the resins (B1) to (B3), and particularly preferably resin (B1).

[0022] <Resin (B1)> The resin (B1) includes a vinyl copolymer (C) and a styrene copolymer (D) described below. Each of these components will be explained below.

[0023] <Vinyl copolymer (C)> The vinyl copolymer (C) contained in the resin (B1) comprises (meth)acrylic acid ester monomer units (c1) represented by the following general formula (6) and aliphatic vinyl monomer units (c2) represented by the following general formula (7), characterized in that the total proportion of the (meth)acrylic acid ester monomer units (c1) and the aliphatic vinyl monomer units (c2) is 90 to 100 mol % based on the total of all monomer units in the vinyl copolymer (C), the proportion of the (meth)acrylic acid ester monomer units (c1) is 60 to 80 mol % based on the total of all monomer units in the vinyl copolymer (C), and the proportion of the aliphatic vinyl monomer units (c2) is 40 to 20 mol % based on the total of all monomer units in the vinyl copolymer (C).

[0024] [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 18 carbon atoms.)

[0025] [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.)

[0026] In the (meth)acrylic acid ester monomer unit (c1) represented by the general formula (6), R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, an isobornyl group, etc. Among the (meth)acrylic acid ester monomer units (c1), preferred are (meth)acrylic acid ester monomer units in which R2 is a methyl group and / or an ethyl group, and more preferred are methyl methacrylate monomer units in which R1 is a methyl group and R2 is a methyl group.

[0027] The aliphatic vinyl monomer unit (c2) represented by the general formula (7) includes a unit in which R3 is a hydrogen atom or a methyl group, and R4 is a cyclohexyl group or a cyclohexyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. Of the aliphatic vinyl monomer units (c2), a preferred one is a unit in which R3 is a hydrogen atom and R4 is a cyclohexyl group.

[0028] The vinyl copolymer (C) used in the present invention is mainly composed of (meth)acrylic acid ester monomer units (c1) represented by the general formula (6) and aliphatic vinyl monomer units (c2) represented by the general formula (7). The vinyl copolymer (C) may contain one or more types of the (meth)acrylic acid ester monomer units (c1), and may contain one or more types of the aliphatic vinyl monomer units (c2). The total proportion of the (meth)acrylic acid ester monomer units (c1) and the aliphatic vinyl monomer units (c2) is 90 to 100 mol%, preferably 95 to 100 mol%, and more preferably 98 to 100 mol%, based on the total of all monomer units in the vinyl copolymer (C). That is, the vinyl copolymer (C) may contain monomer units other than the (meth)acrylic acid ester monomer units (c1) and the aliphatic vinyl monomer units (c2) in an amount of 10 mol % or less based on the total of all monomer units. Examples of monomer units other than the (meth)acrylic acid ester monomer units (c1) and the aliphatic vinyl monomer units (c2) include monomer units derived from aromatic vinyl monomers containing unhydrogenated aromatic double bonds in vinyl copolymers (C) obtained by polymerizing a (meth)acrylic acid ester monomer with an aromatic vinyl monomer and then hydrogenating the aromatic double bonds derived from the aromatic vinyl monomer. The proportion of the (meth)acrylic acid ester monomer units (c1) represented by general formula (6) is 60 to 80 mol%, preferably 70 to 80 mol%, based on the total of all monomer units in the vinyl copolymer (C). The proportion of the aliphatic vinyl monomer units (c2) represented by general formula (7) is 40 to 20 mol%, preferably 30 to 20 mol%, based on the total of all monomer units in the vinyl copolymer (C). If the proportion of (meth)acrylic acid ester monomer units (c1) relative to the total of all monomer units in the vinyl copolymer (C) is less than 60 mol%, adhesion to the polycarbonate resin (A) and surface hardness may decrease, making it impractical. If it exceeds 80 mol%, the laminate may warp due to water absorption, making it impractical. If the proportion of aliphatic vinyl monomer units (c2) relative to the total of all monomer units in the vinyl copolymer (C) is less than 20 mol%, the glass transition temperature may be low and heat-resistant dimensional stability may be poor, making it impractical. On the other hand, if it exceeds 40 mol%, solvent resistance may be poor and making it impractical.

[0029] The method for producing the vinyl copolymer (C) is not particularly limited, but it is preferably obtained by polymerizing at least one (meth)acrylic acid ester monomer and at least one aromatic vinyl monomer, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. (Meth)acrylic acid refers to methacrylic acid and / or acrylic acid. Specific examples of the aromatic vinyl monomer used in this case include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Among these, styrene is preferred.

[0030] The polymerization of the (meth)acrylic acid ester monomer and the aromatic vinyl monomer can be carried out by a known method, such as bulk polymerization or solution polymerization. The bulk polymerization method is carried out by continuously supplying a monomer composition containing the above-mentioned monomers and a polymerization initiator to a complete mixing tank and continuously polymerizing the monomers at 100 to 180°C. The above-mentioned monomer composition may contain a chain transfer agent as needed.

[0031] The polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylperoxy normal octoate, t-butylperoxyisopropyl monocarbonate, and di-t-butyl peroxide, as well as azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile). These can be used alone or in combination of two or more.

[0032] A chain transfer agent is used as needed, and examples thereof include α-methylstyrene dimer.

[0033] Examples of solvents used in solution polymerization include hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane; ester solvents such as ethyl acetate and methyl isobutyrate; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; and alcohol solvents such as methanol and isopropanol.

[0034] The solvent used in the hydrogenation reaction after polymerization of the (meth)acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the polymerization solvent described above, and examples thereof include hydrocarbon solvents such as cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as methanol and isopropanol.

[0035] After polymerizing the (meth)acrylic acid ester monomer and the aromatic vinyl monomer as described above, the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated to obtain the vinyl copolymer (C) used in the present invention. The hydrogenation method is not particularly limited, and known methods can be used. For example, the hydrogenation can be carried out in a batch or continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250°C. By setting the temperature at 60°C or higher, the reaction time is not excessive, and by setting the temperature at 250°C or lower, scission of molecular chains and hydrogenation of ester moieties are reduced.

[0036] Examples of catalysts used in hydrogenation reactions include solid catalysts in which metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals, are supported on porous supports such as carbon, alumina, silica, silica-alumina, and diatomaceous earth.

[0037] In the vinyl copolymer (C), preferably, 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated. That is, the proportion of unhydrogenated aromatic double bonds in the monomer units derived from the aromatic vinyl monomer is preferably 30% or less. If it exceeds 30%, the transparency of the vinyl copolymer resin (C) may decrease. It is more preferably less than 10%, and even more preferably less than 5%.

[0038] The weight-average molecular weight of the vinyl copolymer (C) is not particularly limited, but from the viewpoints of strength and moldability, it is preferably 50,000 to 400,000, and more preferably 70,000 to 300,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC) and is calculated as a weight-average molecular weight in terms of standard polystyrene.

[0039] The vinyl copolymer (C) can be blended with other resins as long as the transparency is not impaired, such as methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co)polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and various elastomers.

[0040] The glass transition temperature of the vinyl copolymer (C) is preferably in the range of 110 to 190°C, more preferably in the range of 110 to 160°C. When the glass transition temperature is 110°C or higher, the laminate provided by the present invention is less likely to deform or crack in a hot or humid heat environment, and when it is 190°C or lower, it exhibits excellent processability, such as continuous thermal shaping using a mirrored roll or a shaping roll, or batch thermal shaping using a mirrored mold or a shaping mold. The glass transition temperature in the present invention is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0041] <Styrene copolymer (D)> The styrene copolymer (D) contained in the resin (B1) contains vinyl aromatic monomer units (d1), cyclic acid anhydride monomer units (d2), and methacrylic acid ester monomer units (d3), and is characterized in that the total proportion of the vinyl aromatic monomer units (d1), the cyclic acid anhydride monomer units (d2), and the methacrylic acid ester monomer units (d3) is 90 to 100 mol% based on the total of all monomer units in the styrene copolymer (D), the proportion of the vinyl aromatic monomer units (d1) is 60 to 90 mol% based on the total of all monomer units in the styrene copolymer (D), the proportion of the cyclic acid anhydride monomer units (d2) is 10 to 20 mol% based on the total of all monomer units in the styrene copolymer (D), and the proportion of the methacrylic acid ester monomer units (d3) is 0 to 20 mol% based on the total of all monomer units in the styrene copolymer (D).

[0042] The vinyl aromatic monomer unit (d1) of the styrene copolymer (D) is not particularly limited, and any known aromatic vinyl monomer can be used. From the viewpoint of easy availability, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, etc. are listed. Among these, styrene is particularly preferred from the viewpoint of compatibility. Two or more of these aromatic vinyl monomers may be mixed.

[0043] Examples of the cyclic acid anhydride monomer unit (d2) of the styrene copolymer (D) include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferred from the viewpoint of compatibility with acrylic resins. Two or more of these unsaturated dicarboxylic acid anhydride monomers may be mixed.

[0044] Examples of the methacrylate ester monomer unit (d3) of the styrene copolymer (D) include acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, and (meth)acrylic esters. Examples of (meth)acrylic esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. Among these, methyl methacrylate (MMA) is preferred from the viewpoint of compatibility with acrylic resins. Two or more of these acrylic compound monomers may be mixed.

[0045] In the styrene copolymer (D) used in the present invention, the total proportion of the vinyl aromatic monomer units (d1), the cyclic acid anhydride monomer units (d2), and the methacrylic acid ester monomer units (d3) is 90 to 100 mol %, preferably 95 to 100 mol %, and more preferably 98 to 100 mol %, based on the total of all monomer units in the styrene copolymer (D). That is, the styrene copolymer (D) may contain monomer units other than the vinyl aromatic monomer units (d1), the cyclic acid anhydride monomer units (d2), and the methacrylic acid ester monomer units (d3) in an amount of 10 mol% or less based on the total of all monomer units. Examples of the monomer units other than the vinyl aromatic monomer units (d1), the cyclic acid anhydride monomer units (d2), and the methacrylic acid ester monomer units (d3) include N-substituted maleimide monomers. Examples of N-substituted maleimide monomers include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide, and N-phenylmaleimide is preferred from the viewpoint of compatibility with acrylic resins. Two or more of these N-substituted maleimide monomers may be mixed.

[0046] The proportion of the vinyl aromatic monomer units (d1) is 60 to 90 mol%, preferably 65 to 90 mol%, more preferably 70 to 90 mol%, even more preferably 72 to 88 mol%, and particularly preferably 74 to 86 mol%, based on the total of all monomer units in the styrene copolymer (D). The proportion of the cyclic acid anhydride monomer units (d2) is 10 to 20 mol%, preferably 12 to 18 mol%, and more preferably 14 to 16 mol%, based on the total of all monomer units in the styrene copolymer (D). The proportion of the methacrylic acid ester monomer units (d3) is 0 to 20 mol%, preferably 0 to 15 mol%, and more preferably 0 to 10 mol%, based on the total of all monomer units in the styrene copolymer (D). If the proportion of the vinyl aromatic monomer units (d1) to the total of all monomer units in the styrene copolymer (D) is less than 60 mol%, compatibility with the vinyl copolymer (C) will be poor. If it exceeds 90 mol%, sufficient heat resistance will not be imparted. If the proportion of the cyclic acid anhydride monomer units (d2) to the total of all monomer units in the styrene copolymer (D) is less than 10 mol%, heat resistance will be insufficient. If it exceeds 20 mol%, compatibility with the vinyl copolymer (C) will be poor.

[0047] The method for producing the styrene copolymer (D) is not particularly limited, and can be appropriately selected from known methods such as solution polymerization and bulk polymerization.

[0048] The weight-average molecular weight of the styrene copolymer (D) is not particularly limited, but from the viewpoint of compatibility with the vinyl copolymer (C), it is preferably 50,000 to 400,000, more preferably 70,000 to 300,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC) and is calculated as a standard polystyrene.

[0049] The glass transition temperature of the styrene copolymer (D) is preferably in the range of 100 to 190°C, more preferably in the range of 115 to 185°C, and particularly preferably in the range of 125 to 185°C. When the glass transition temperature is 100°C or higher, the laminate provided by the present invention is less likely to deform or crack in a hot or humid heat environment. Furthermore, when the glass transition temperature is 190°C or lower, the laminate has excellent processability, such as continuous thermal shaping using a mirrored roll or a shaping roll, or batch-type thermal shaping using a mirrored mold or a shaping mold. The glass transition temperature in the present invention is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0050] The styrene copolymer (D) is a binary copolymer containing vinyl aromatic monomer units (d1) and cyclic acid anhydride monomer units (d2), or a ternary copolymer containing vinyl aromatic monomer units (d1), cyclic acid anhydride monomer units (d2), and methacrylic acid ester monomer units (d3). By using the styrene copolymer (D) in combination with the vinyl copolymer (C), a resin laminate having higher hardness than when the styrene copolymer (D) alone is used and having better shape stability under high temperature and high humidity conditions than when the vinyl copolymer (C) alone is used can be obtained.

[0051] In the present invention, the mass ratio of the vinyl copolymer (C) to the styrene copolymer (D) is preferably 5 to 95 parts by mass of the vinyl copolymer (C) and 95 to 5 parts by mass of the styrene copolymer (D), based on 100 parts by mass of the total content of the vinyl copolymer (C) and the styrene copolymer (D). More preferably, the mass ratio is 15 to 85 parts by mass of the vinyl copolymer (C) and 85 to 15 parts by mass of the styrene copolymer (D), even more preferably, the mass ratio is 25 to 75 parts by mass of the vinyl copolymer (C) and 75 to 25 parts by mass of the styrene copolymer (D), and particularly preferably, the mass ratio is 40 to 60 parts by mass of the vinyl copolymer (C) and 60 to 40 parts by mass of the styrene copolymer (D). By maintaining this mass ratio, an excellent resin (B1) can be obtained that maintains transparency, has excellent warp resistance and heat resistance even when exposed to high temperature and high humidity, has a high refractive index, and has a good appearance.

[0052] The temperature at which the vinyl copolymer (C) and the styrene copolymer (D) are alloyed is preferably in the range of 230 to 320°C, more preferably in the range of 240 to 300°C. If the alloying temperature is lower than 230°C, compatibility tends to be poor and haze tends to increase. On the other hand, if the alloying temperature exceeds 320°C, the vinyl copolymer (C) and / or the styrene copolymer (D) will be thermally decomposed.

[0053] In the present invention, the method for producing the resin (B1) is not particularly limited, and a known method can be applied, in which the necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then melt-kneaded using a machine such as a Banbury mixer, a roll, a Brabender mixer, a single-screw extruder, a twin-screw extruder, or a pressure kneader. One of the characteristics of resin (B1) is that it has a relatively high glass transition temperature, preferably in the range of 110 to 185°C, more preferably in the range of 115 to 160°C, and particularly preferably in the range of 120 to 140°C. Because the glass transition temperature of resin (B1) is relatively high and has a small difference from the glass transition temperature of the polycarbonate-based resin (A), there is the advantage that even if the glass transition temperature is brought close to that of the polycarbonate-based resin (A) during hot press molding or hot bending, there is little problem with poor appearance of the layer containing resin (B1). The difference between the glass transition temperature of the polycarbonate-based resin (A) and the glass transition temperature of resin (B1) is preferably in the range of 0 to 35°C, more preferably in the range of 0 to 25°C, and particularly preferably in the range of 0 to 20°C.

[0054] <Resin (B2)> Resin (B2) contains the vinyl copolymer (C) and can be blended with other resins as long as transparency is not impaired. The mass ratio of the vinyl copolymer (C) is preferably 30 to 100 parts by mass per 100 parts by mass of the total resin (B2). More preferably, the vinyl copolymer (C) is 40 to 100 parts by mass, even more preferably, 90 to 100 parts by mass, and particularly preferably, 98 to 100 parts by mass. By maintaining this mass ratio, resin (B2) can be obtained that maintains transparency, has excellent warpage resistance and heat resistance even when exposed to high temperature and high humidity, and has a good appearance.

[0055] <Resin (B3)> The resin (B3) contains a methacrylic resin (E) and a styrene copolymer (F). Each component will be described below.

[0056] <Methacrylic resin (E)> The methacrylic resin (E) contained in the resin (B3) may have a structural unit derived from a methacrylic acid ester monomer.

[0057] Examples of the methacrylic acid ester monomer of the methacrylic resin (E) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, and cyclohexyl methacrylate; methacrylic acid cycloalkyl esters such as cycloheptyl, cyclooctyl methacrylate, and tricyclo[5.2.1.02,6]dec-8-yl methacrylate; aryl methacrylates such as phenyl methacrylate; and aralkyl methacrylates such as benzyl methacrylate. From the viewpoint of availability, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred, and methyl methacrylate is most preferred.

[0058] From the viewpoint of heat resistance, the methacrylic resin (E) preferably contains 80 mol % or more, more preferably 90 mol % or more, and even more preferably 95 mol % or more of structural units derived from methacrylic acid ester monomers. When the methacrylic resin (E) contains 80 mol % or more of structural units derived from methacrylic acid ester monomers, compatibility with the styrene copolymer (F) is improved, which is preferable. On the other hand, when the structural units derived from methacrylic acid ester monomers are less than 80 mol %, the methacrylic resin may not be compatible with the styrene copolymer (F) and may become cloudy.

[0059] The methacrylic resin (E) may contain structural units derived from other monomers than methacrylic acid esters. Examples of such other monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-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, trimethyl acrylate, and methyl acrylate. Examples of suitable acrylic acid esters include trifluoroethyl, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate. From the viewpoint of availability, preferred are acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate. Methyl acrylate and ethyl acrylate are more preferred, and methyl acrylate is the most preferred. The total content of structural units derived from these other monomers in the methacrylic resin (E) is preferably 20 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less.

[0060] The lower limit of the triad syndiotacticity (rr) of the methacrylic resin (E) is preferably 50 mol% or more, more preferably 51% mol or more, and even more preferably 52% mol or more. When the lower limit of the content of such a structure is 50 mol% or more, the resin has excellent heat resistance.

[0061] Here, the syndiotacticity (rr) expressed as a triad (hereinafter sometimes referred to simply as "syndiotacticity (rr)") is the proportion of two chains (diads) in a chain of three consecutive structural units (triad) that are both racemo (denoted as rr). Note that in chains (diads) of structural units in a polymer molecule, those 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 syndiotacticity (rr) (%) of the methacrylic resin (E) in deuterated chloroform at 30°C is 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.

[0062] The weight-average molecular weight of the methacrylic resin (E) is determined by the ease of mixing (dispersion) with the styrene copolymer (F) and the ease of production of the resin (B3). In other words, if the weight-average molecular weight of the methacrylic resin (E) is too large, the difference in melt viscosity between the methacrylic resin (E) and the styrene copolymer (F) will be too great, resulting in poor mixing (dispersion) of the two, which may result in poor transparency of the resin (B3) or inability to continue stable melt-kneading. Conversely, if the weight-average molecular weight of the methacrylic resin (E) is too small, the strength of the resin (B3) will decrease, resulting in problems such as reduced impact resistance of the resin laminate. The weight-average molecular weight of the methacrylic resin (E) is preferably in the range of 50,000 to 700,000, more preferably 60,000 to 500,000, and even more preferably 70,000 to 200,000. The weight-average molecular weight is the weight-average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0063] The glass transition temperature of the methacrylic resin (E) is preferably 100°C or higher, more preferably 105°C or higher, and even more preferably 108°C or higher. When the glass transition temperature is 100°C or higher, the laminate provided by the present invention is less likely to deform or crack in a thermal environment. In this specification, the glass transition temperature of the methacrylic resin (E) is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0064] The melt flow rate of the methacrylic resin (E) is preferably in the range of 1 to 10 g / 10 min. The lower limit of the melt flow rate is more preferably 1.2 g / 10 min or more, and even more preferably 1.5 g / 10 min or more. The upper limit of the melt flow rate is more preferably 7.0 g / 10 min or less, and even more preferably 4.0 g / 10 min or less. A melt flow rate in the range of 1 to 10 g / 10 min provides good stability in hot melt molding. The melt flow rate of the methacrylic resin (E) in this specification is a value measured using a melt indexer at a temperature of 230°C under a load of 3.8 kg.

[0065] <Styrene copolymer (F)> The styrene copolymer (F) contained in the resin (B3) contains vinyl aromatic monomer units (f1) and cyclic acid anhydride monomer units (f2), and is characterized in that the total proportion of the vinyl aromatic monomer units (f1) and the cyclic acid anhydride monomer units (f2) is 92 to 100 mass% based on the total of all monomer units in the styrene copolymer (F).

[0066] The vinyl aromatic monomer unit (f1) of the styrene copolymer (F) is not particularly limited, and any known aromatic vinyl monomer can be used. From the viewpoint of easy availability, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, etc. are listed. Among these, styrene is particularly preferred from the viewpoint of compatibility. Two or more of these aromatic vinyl monomers may be mixed.

[0067] Examples of the cyclic acid anhydride monomer unit (f2) of the styrene copolymer (F) include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferred from the viewpoint of compatibility with methacrylic resins. Two or more of these unsaturated dicarboxylic acid anhydride monomers may be mixed.

[0068] In the styrene copolymer (F) used in the present invention, the total proportion of the vinyl aromatic monomer units (f1) and the cyclic acid anhydride monomer units (f2) is 92 to 100 mass%, preferably 95 to 100 mass%, and more preferably 98 to 100 mass%, based on the total of all monomer units in the styrene copolymer (F). That is, the styrene copolymer (F) may contain monomer units other than the vinyl aromatic monomer units (f1) and the cyclic acid anhydride monomer units (f2) in an amount of 8% by mass or less based on the total amount of all monomer units. Examples of the monomer units other than the vinyl aromatic monomer units (f1) and the cyclic acid anhydride monomer units (f2) include methacrylic acid ester monomer units and N-substituted maleimide monomers. Examples of the methacrylate ester monomer units in the styrene copolymer (F) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate. Examples of methacrylic acid esters include methacrylic acid cycloalkyl esters such as 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, and tricyclo[5.2.1.02,6]dec-8-yl methacrylate; methacrylic acid aryl esters such as phenyl methacrylate; and methacrylic acid aralkyl esters such as benzyl methacrylate. Methyl methacrylate is preferred from the viewpoint of compatibility with methacrylic resins. Two or more of these methacrylic acid ester monomers may be mixed. Examples of the N-substituted maleimide monomer in the styrene copolymer (F) include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide, and N-phenylmaleimide is preferred from the viewpoint of compatibility with methacrylic resins. Two or more of these N-substituted maleimide monomers may be mixed.

[0069] The proportion of the vinyl aromatic monomer units (f1) is 68 to 84 mass%, preferably 70 to 82 mass%, more preferably 74 to 80 mass%, and even more preferably 76 to 79 mass%, based on the total of all monomer units in the styrene copolymer (F). The proportion of the cyclic acid anhydride monomer units (f2) is 16 to 32 mass%, preferably 18 to 30 mass%, more preferably 20 to 26 mass%, and even more preferably 21 to 24 mass%, based on the total of all monomer units in the styrene copolymer (F). If the proportion of the vinyl aromatic monomer units (f1) to the total of all monomer units in the styrene copolymer (F) is outside the range of 68 to 84 mass%, the compatibility with the methacrylic resin (E) will be poor. Also, if the proportion of the cyclic acid anhydride monomer units (f2) to the total of all monomer units in the styrene copolymer (F) is outside the range of 16 to 32 mass%, the compatibility with the methacrylic resin (E) will be poor.

[0070] The weight-average molecular weight of the styrene copolymer (F) is not particularly limited, but from the viewpoint of compatibility with the methacrylic resin (E), it is preferably 30,000 to 400,000, more preferably 40,000 to 300,000, and particularly preferably 50,000 to 200,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC) and is calculated as a standard polystyrene.

[0071] The glass transition temperature of the styrene copolymer (F) is preferably in the range of 120 to 190°C, more preferably in the range of 130 to 170°C. When the glass transition temperature is 120°C or higher, the laminate provided by the present invention is less likely to deform or crack in a thermal environment. Furthermore, when the glass transition temperature is 190°C or lower, the laminate has excellent processability, such as continuous thermal shaping using a mirrored roll or a shaping roll, or batch thermal shaping using a mirrored mold or a shaping mold. In this specification, the glass transition temperature of the styrene copolymer (F) is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0072] The melt flow rate of the styrene copolymer (F) is preferably in the range of 1 to 10 g / 10 min, more preferably in the range of 4 to 9 g / 10 min, and even more preferably in the range of 6 to 8 g / 10 min. When the melt flow rate is in the range of 1 to 10 g / 10 min, the stability of hot melt molding is good. In this specification, the melt flow rate of the styrene copolymer (F) is a value measured using a melt indexer at a temperature of 230°C under a load of 3.8 kg.

[0073] The method for producing the styrene copolymer (F) is not particularly limited, and can be appropriately selected from known methods such as solution polymerization, bulk polymerization, and suspension polymerization.

[0074] The styrene copolymer (F) is a binary copolymer or a multi-component copolymer containing a vinyl aromatic monomer unit (f1) and a cyclic acid anhydride monomer unit (f2). By using the styrene copolymer (F) in combination with the methacrylic resin (E), a resin laminate having higher hardness than when the styrene copolymer (F) alone is used and having better thermoformability than when the methacrylic resin (E) alone is used can be obtained.

[0075] In the present invention, the mass ratio of the methacrylic resin (E) to the styrene copolymer (F) is preferably 5 to 70 parts by mass of the methacrylic resin (E) and 95 to 30 parts by mass of the styrene copolymer (F), based on 100 parts by mass of the total content of the methacrylic resin (E) and the styrene copolymer (F). More preferably, the mass ratio is 10 to 65 parts by mass of the methacrylic resin (E) and 90 to 35 parts by mass of the styrene copolymer (F). Even more preferably, the mass ratio is 15 to 60 parts by mass of the methacrylic resin (E) and 85 to 40 parts by mass of the styrene copolymer (F). Especially preferably, the mass ratio is 20 to 55 parts by mass of the methacrylic resin (E) and 80 to 45 parts by mass of the styrene copolymer (F). By maintaining this mass ratio, an excellent resin (B3) can be obtained that maintains transparency, has excellent heat resistance, a high refractive index, and a good appearance.

[0076] The glass transition temperature of resin (B3) is preferably in the range of 120 to 165°C, more preferably in the range of 120 to 155°C. When the glass transition temperature is 120°C or higher, the laminate provided by the present invention is less likely to deform or crack in a thermal environment. Furthermore, when the glass transition temperature is 165°C or lower, excellent processability is achieved, such as continuous thermal shaping using a mirrored roll or a shaping roll, or batchwise thermal shaping using a mirrored mold or a shaping mold. In this specification, the glass transition temperature of resin (B3) is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0077] The melt flow rate of resin (B3) is preferably in the range of 1 to 10 g / 10 min, more preferably in the range of 1.5 to 7 g / 10 min, and even more preferably in the range of 2 to 5 g / 10 min. A melt flow rate in the range of 1 to 10 g / 10 min provides good stability in hot melt molding. In this specification, the melt flow rate of resin (B3) is a value measured using a melt indexer at a temperature of 230°C under a load of 3.8 kg.

[0078] In the present invention, the method for producing the resin (B3) is not particularly limited, and a known method can be applied, in which the necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then melt-kneaded using a machine such as a Banbury mixer, a roll, a Brabender mixer, a single-screw extruder, a twin-screw extruder, or a pressure kneader.

[0079] The glass transition temperature of resin (B3) is relatively high and the difference therebetween is small, so that even if the glass transition temperature is brought close to that of polycarbonate resin (A) during hot press molding or hot bending, there is little problem of poor appearance occurring in the layer containing resin (B3). The difference between the glass transition temperature of polycarbonate resin (A) and that of resin (B3) is preferably in the range of 0 to 30°C, more preferably 0 to 20°C.

[0080] <Resin (B4)> Resin (B4) is a copolymer containing a structural unit (G) represented by the following general formula (8) and, optionally, a structural unit (H) represented by the following general formula (9): Resin (B4) may or may not contain structural unit (H), but preferably does contain structural unit (H). [ka] [ka]

[0081] The proportion of the structural unit (G) in all structural units of the resin (B4) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and particularly preferably 70 to 100 mol%, The proportion of the structural unit (H) in all structural units of the resin (B4) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 30 mol%.

[0082] The total content of the structural units (G) and (H) relative to the resin (B4) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and especially preferably 98 to 100 mol %.

[0083] Resin (B4) may contain structural units other than structural units (G) and (H). When other structural units are contained, the amount thereof is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on the total structural units of resin (B4). Examples of other structural units include structural units represented by the following general formula (10). [ka]

[0084] The method for producing resin (B4) is not particularly limited, but it can be produced by the same method as the method for producing polycarbonate resin (A) described above, except that bisphenol C is used as the monomer.

[0085] Specific examples of the resin (B4) include Iupilon KH3410UR, KH3520UR, and KS3410UR (manufactured by Mitsubishi Engineering-Plastics Corporation).

[0086] The weight average molecular weight of the resin (B4) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000. The weight average molecular weight of the resin (B4) can be measured by the same method as the method for measuring the weight average molecular weight of the polycarbonate resin (A) described above.

[0087] The glass transition temperature of resin (B4) is preferably 105 to 150°C, more preferably 110 to 140°C, and particularly preferably 110 to 135°C. When the glass transition temperature is 105°C or higher, the laminate provided by the present invention is less likely to deform or crack in a thermal environment. Furthermore, when the glass transition temperature is 150°C or lower, the laminate has excellent processability, such as continuous thermal shaping using a mirrored roll or a shaping roll, or batch thermal shaping using a mirrored mold or a shaping mold. In this specification, the glass transition temperature of resin (B4) is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0088] <Resin (B5)> Resin (B5) is a copolymer (I) containing 6 to 77% by mass of (meth)acrylic acid ester structural units (i1), 15 to 71% by mass of styrene structural units (i2), and 8 to 23% by mass of unsaturated dicarboxylic acid structural units (i3), or an alloy of copolymers (I), or an alloy of copolymer (I) with a resin other than copolymer (I). Examples of resins other than copolymer (I) include methyl methacrylate-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polymethyl methacrylate, and copolymers of methyl methacrylate and methyl acrylate or ethyl acrylate. Commercially available products can also be used, such as Mitsubishi Chemical Corporation's ACRYPET, Sumitomo Chemical Co., Ltd.'s SUMIPEX, Kuraray Co., Ltd.'s PARAPET, and Arkema's ALTOGLAS. When alloying, alloys of resins with higher Tg are preferred to avoid a decrease in the Tg of high-hardness resins.

[0089] Examples of (meth)acrylic acid ester monomers constituting the (meth)acrylic acid ester structural unit (i1) include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc., with methyl methacrylate being particularly preferred. Two or more of these (meth)acrylic acid ester monomers may be used in combination. The content of the (meth)acrylic acid ester structural unit (i1) is from 6 to 77% by mass, and preferably from 20 to 70% by mass, based on the total mass of the resin (B5).

[0090] The styrene structural unit (i2) is not particularly limited, and any known styrene-based monomer can be used. From the viewpoint of easy availability, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, etc. are preferred. Among these, styrene is particularly preferred from the viewpoint of compatibility. Two or more of these styrene-based monomers may be used in combination. The content of the styrene structural unit (i2) is from 15 to 71 mass % and preferably from 20 to 66 mass % based on the total mass of the resin (B5).

[0091] Examples of unsaturated dicarboxylic acid anhydride monomers constituting the unsaturated dicarboxylic acid structural unit (i3) include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferred from the viewpoint of compatibility with styrene-based monomers. Two or more of these unsaturated dicarboxylic acid anhydride monomers may be used in combination. The content of the unsaturated dicarboxylic acid structural unit (i3) is from 8 to 23 mass %, and preferably from 10 to 23 mass %, based on the total mass of the resin (B5).

[0092] The total content of the (meth)acrylic acid ester structural units (i1), styrene structural units (i2), and unsaturated dicarboxylic acid structural units (i3) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and particularly preferably 98 to 100 mol %, based on all structural units of the resin (B5). That is, the resin (B5) may contain structural units other than the (meth)acrylic acid ester structural unit (i1), the styrene structural unit (i2), and the unsaturated dicarboxylic acid structural unit (i3). The amount thereof is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on the total structural units of the resin (B5).

[0093] Other structural units include, for example, N-phenylmaleimide. The method for producing the resin (B5) is not particularly limited, but examples thereof include bulk polymerization and solution polymerization.

[0094] Specific examples of the resin (B5) include Resistify R100, R200, and R310 (manufactured by Denka Co., Ltd.), Delpet 980N (manufactured by Asahi Kasei Co., Ltd.), and hw55 (manufactured by Daicel-Evonik).

[0095] The weight-average molecular weight of the resin (B5) is not particularly limited, but is preferably 50,000 to 300,000, and more preferably 80,000 to 200,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC) and is calculated as a weight-average molecular weight in terms of standard polystyrene.

[0096] The glass transition temperature of resin (B5) is preferably 90 to 150°C, more preferably 100 to 150°C, and particularly preferably 115 to 150°C. A glass transition temperature of 90°C or higher means that the laminate provided by the present invention is less likely to deform or crack in a thermal environment. Furthermore, a glass transition temperature of 150°C or lower provides excellent processability, such as continuous thermal shaping using a mirrored roll or a shaping roll, or batch-type thermal shaping using a mirrored mold or a shaping mold. The glass transition temperature of resin (B5) in this specification is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0097] <Resin (B6)> Resin (B6) is a copolymer (J) containing 5 to 20 mass% of styrene structural units (j1), 60 to 90 mass% of (meth)acrylic acid ester structural units (j2), and 5 to 20 mass% of N-substituted maleimide structural units (j3), or an alloy of copolymer (J) with a resin other than copolymer (J).

[0098] The styrene structural unit (j1) is not particularly limited, and any known styrene-based monomer can be used. However, from the viewpoint of easy availability, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, etc. are preferred. Among these, styrene is particularly preferred from the viewpoint of compatibility. The copolymer (J) may contain two or more of these styrene structural units. The content of the styrene structural unit is 5 to 20 mass%, preferably 5 to 15 mass%, and more preferably 5 to 10 mass%, based on the total mass of the resin (B6).

[0099] Examples of the (meth)acrylic acid ester structural unit (j2) include structural units derived from acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate, with structural units derived from methyl methacrylate being particularly preferred. Furthermore, the copolymer (J) may contain two or more of these (meth)acrylic acid ester structural units. The content of the (meth)acrylic acid ester structural units is 60 to 90% by mass, preferably 70 to 90% by mass, and more preferably 80 to 90% by mass, based on the total mass of the resin (B6).

[0100] Examples of the N-substituted maleimide structural unit (j3) in resin (B6) include structural units derived from N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide. From the viewpoint of compatibility with acrylic resins, structural units derived from N-phenylmaleimide are preferred. Copolymer (J) may contain two or more of these N-substituted maleimide structural units. The content of the N-substituted maleimide structural unit is 5 to 20% by mass, preferably 5 to 15% by mass, and more preferably 5 to 10% by mass, based on the total mass of resin (B6).

[0101] The total content of the styrene structural unit (j1), the (meth)acrylic acid ester structural unit (j2), and the N-substituted maleimide structural unit (j3) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and particularly preferably 98 to 100 mol %, relative to the resin (B6). Resin (B6) may contain structural units other than the above structural units. If other structural units are contained, the amount thereof is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on the total structural units of resin (B6).

[0102] Examples of other structural units include structural units derived from the following general formula (11) and structural units derived from the following general formula (12). [ka] (wherein R1 is a hydrogen atom or a methyl group; R2 is an alkyl group having 1 to 18 carbon atoms). [ka] (wherein R3 is a hydrogen atom or a methyl group; R4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms).

[0103] The method for producing the resin (B6) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.

[0104] A specific example of the resin (B6) is Delpet PM120N (manufactured by Asahi Kasei Chemical Corporation).

[0105] The weight average molecular weight of the resin (B6) is preferably 50,000 to 250,000, and more preferably 100,000 to 200,000. The weight average molecular weight is measured by gel permeation chromatography (GPC) and is calculated as a weight average molecular weight in terms of standard polystyrene.

[0106] The glass transition temperature of resin (B6) is preferably 110 to 150°C, more preferably 115 to 140°C, and particularly preferably 115 to 135°C. A glass transition temperature of 110°C or higher means that the laminate provided by the present invention is less likely to deform or crack in a thermal environment. Furthermore, a glass transition temperature of 150°C or lower provides excellent processability, such as continuous thermal shaping using a mirrored roll or a shaping roll, or batch-type thermal shaping using a mirrored mold or a shaping mold. The glass transition temperature of resin (B6) in this specification is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C / min and calculated by the midpoint method.

[0107] <Hard coat layer> Although an additional layer may be present between the hard coat layer of the present invention and the layer containing thermoplastic resin (B), the hard coat layer is preferably laminated on the surface or both surfaces of the layer containing thermoplastic resin (B). The hard coat layer is preferably an acrylic hard coat. In this specification, "acrylic hard coat" refers to a coating film formed by polymerizing a monomer, oligomer, or prepolymer containing a (meth)acryloyl group as a polymerizable group to form a crosslinked structure. The acrylic hard coat preferably contains 2 to 98% by mass of a (meth)acrylic monomer, 2 to 98% by mass of a (meth)acrylic oligomer, and 0 to 15% by mass of a surface modifier. Furthermore, the acrylic hard coat preferably contains 0.001 to 7 parts by mass of a photopolymerization initiator per 100 parts by mass of the total of the (meth)acrylic monomer, (meth)acrylic oligomer, and surface modifier.

[0108] The hard coat layer more preferably contains 5 to 50 mass% of a (meth)acrylic monomer, 50 to 95 mass% of a (meth)acrylic oligomer, and 1 to 10 mass% of a surface modifier, and particularly preferably contains 20 to 40 mass% of a (meth)acrylic monomer, 60 to 80 mass% of a (meth)acrylic oligomer, and 2 to 5 mass% of a surface modifier. The amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass, particularly preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of the (meth)acrylic monomer, (meth)acrylic oligomer, and surface modifier.

[0109] Any (meth)acrylic monomer can be used as long as it has a (meth)acryloyl group as a functional group in the molecule, and may be a monofunctional monomer, a difunctional monomer, or a trifunctional or higher functional monomer. Examples of monofunctional monomers include (meth)acrylic acid and (meth)acrylic acid esters, and specific examples of bifunctional and / or trifunctional or higher (meth)acrylic monomers include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di(meth)acrylate, dicyclopentaerythritol 2-hydroxybenzoate, ... Examples of the alkyl acrylate include butyl di(meth)acrylate, polyethylene glycol diacrylate, 1,4-butanediol oligoacrylate, neopentyl glycol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, and pentaerythritol tetraacrylate. The hard coat layer may contain one or more types of (meth)acrylic monomers.

[0110] Examples of the (meth)acrylic oligomer include difunctional or higher polyfunctional urethane (meth)acrylate oligomers (hereinafter also referred to as polyfunctional urethane (meth)acrylate oligomers), difunctional or higher polyfunctional polyester (meth)acrylate oligomers (hereinafter also referred to as polyfunctional polyester (meth)acrylate oligomers), difunctional or higher polyfunctional epoxy (meth)acrylate oligomers (hereinafter also referred to as polyfunctional epoxy (meth)acrylate oligomers), etc. The hard coat layer may contain one or more types of (meth)acrylic oligomers. Examples of polyfunctional urethane (meth)acrylate oligomers include urethane reaction products of a (meth)acrylate monomer having at least one (meth)acryloyloxy group and hydroxyl group in one molecule and a polyisocyanate; and urethane reaction products of an isocyanate compound obtained by reacting a polyol with a polyisocyanate and a (meth)acrylate monomer having at least one (meth)acryloyloxy group and hydroxyl group in one molecule.

[0111] Examples of the (meth)acrylate monomer having at least one (meth)acryloyloxy group and one hydroxyl group per molecule used in the urethanization reaction include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0112] Examples of polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.

[0113] Polyols used in the urethanization reaction generally include aromatic, aliphatic, and alicyclic polyols, as well as polyester polyols, polyether polyols, etc. Typical aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerin, and hydrogenated bisphenol A.

[0114] Examples of polyester polyols include those obtained by the dehydration condensation reaction of the above-mentioned polyols with polycarboxylic acids. Specific examples of polycarboxylic acid compounds include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides. Examples of polyether polyols include polyalkylene glycols and polyoxyalkylene-modified polyols obtained by the reaction of the above-mentioned polyols or phenols with alkylene oxides.

[0115] Multifunctional polyester (meth)acrylate oligomers can be obtained by a dehydration condensation reaction using (meth)acrylic acid, a polycarboxylic acid, and a polyol. Examples of polycarboxylic acids used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may also be anhydrides. Examples of polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0116] Multifunctional epoxy (meth)acrylate oligomers are obtained by the addition reaction of polyglycidyl ethers with (meth)acrylic acid. Examples of polyglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

[0117] The surface modifier used in the present invention is an agent that changes the surface performance of the hard coat layer, such as a leveling agent, an antistatic agent, a surfactant, a water- and oil-repellent agent, inorganic particles, or organic particles. Examples of leveling agents include polyether-modified polyalkylsiloxanes, polyether-modified siloxanes, polyester-modified hydroxyl group-containing polyalkylsiloxanes, polyether-modified polydimethylsiloxanes having alkyl groups, modified polyethers, and silicon-modified acrylics.

[0118] Examples of antistatic agents include glycerin fatty acid ester monoglycerides, glycerin fatty acid ester organic acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, cationic surfactants, and anionic surfactants. Examples of inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, and glass particles. Examples of organic particles include acrylic particles and silicon particles. Examples of surfactants and water / oil repellents include fluorine-containing surfactants and water / oil repellents such as oligomers containing fluorine-containing groups and lipophilic groups, and oligomers containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups.

[0119] The hard coat layer may contain a photopolymerization initiator. In this specification, the photopolymerization initiator refers to a photoradical generator.

[0120] Examples of monofunctional photopolymerization initiators that can be used in the present invention include acetophenone-based initiators such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocur 2959: manufactured by Merck]; α-hydroxy-α,α'-dimethylacetophenone [Darocur 1173: manufactured by Merck]; methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], and 1-hydroxy-cyclohexylphenyl ketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and other halogenated ketones, acylphosphinoxides, and acylphosphonates.

[0121] The method for forming the hard coat layer is not particularly limited, but for example, the hard coat layer can be formed by applying a hard coat liquid onto a layer located below the hard coat layer and then photopolymerizing the liquid.

[0122] The method for applying the hard coat liquid (polymerizable composition) is not particularly limited, and known methods can be used, such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and spraying.

[0123] The lamp used for light irradiation in photopolymerization has an emission distribution with a light wavelength of 420 nm or less, and examples thereof include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc. Among these, high-pressure mercury lamps or metal halide lamps are preferred because they efficiently emit light in the active wavelength region of the initiator and do not emit much short-wavelength light that would reduce the viscoelastic properties of the resulting polymer due to crosslinking, or much long-wavelength light that would heat and evaporate the reaction composition.

[0124] The irradiation intensity of the lamp is a factor that determines the degree of polymerization of the resulting polymer, and is appropriately controlled depending on the performance of the target product. When a typical cleavage-type initiator having an acetophenone group is blended, the irradiance is 0.1 to 300 mW / cm. 2 In particular, when a metal halide lamp is used, the illuminance is set to 10 to 40 mW / cm. 2 It is preferable to set the following.

[0125] Photopolymerization reactions are inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to perform light irradiation using a method that can eliminate reaction inhibition by oxygen. One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to prevent contact with oxygen, and then irradiate the reactive composition with light through the film. Alternatively, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen has been replaced with an inert gas such as nitrogen gas or carbon dioxide gas.

[0126] When light irradiation is performed in an inert atmosphere, a certain amount of inert gas is always introduced to maintain a low oxygen concentration in the atmosphere. The introduction of this inert gas generates an airflow on the surface of the reactive composition, causing monomer evaporation. To suppress the level of monomer evaporation, the airflow velocity of the inert gas is preferably 1 m / sec or less, more preferably 0.1 m / sec or less, relative to the laminate coated with the hard coat liquid moving under the inert gas atmosphere. By setting the airflow velocity within the above range, monomer evaporation due to the airflow can be substantially suppressed.

[0127] In order to improve the adhesion of the hard coat layer, the coated surface may be pretreated by known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition.

[0128] The hard coat layer is exposed to UV light (254 nm) with an irradiation output of 20 mW / cm 2 When irradiated with ultraviolet light using a metal halide lamp, the pencil hardness is preferably 2H or more.

[0129] The thickness of the hard coat layer is preferably 1 μm or more and 40 μm or less, and more preferably 2 μm or more and 10 μm or less. A thickness of 1 μm or more can provide sufficient hardness. Furthermore, a thickness of 40 μm or less can suppress the occurrence of cracks during bending. The thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and measuring from the coating interface to the surface.

[0130] <Resin laminate> In the present invention, the thickness of the layer containing thermoplastic resin (B) affects the surface hardness and impact resistance of the resin laminate. That is, if the thickness of the layer containing thermoplastic resin (B) is too thin, the surface hardness will be low, which is undesirable. If the thickness of the layer containing thermoplastic resin (B) is too thick, the impact resistance will be poor, which is undesirable. The thickness of the layer containing thermoplastic resin (B) is preferably 10 to 250 μm, more preferably 20 to 200 μm, and even more preferably 30 to 150 μm.

[0131] In the present invention, molding becomes difficult if the total thickness of the layer containing the polycarbonate-based resin (A) and the layer containing the thermoplastic resin (B) is too thin or too thick. The total thickness of the layer containing the polycarbonate-based resin (A) and the layer containing the thermoplastic resin (B) is preferably 0.04 to 4.0 mm, more preferably 0.05 to 3.5 mm, and even more preferably 0.5 to 3.0 mm.

[0132] Furthermore, a resin laminate comprising a layer containing a polycarbonate-based resin (A) and a layer containing a thermoplastic resin (B), or a resin laminate having a surface on the side of the layer containing a polycarbonate-based resin (A), a layer containing a thermoplastic resin (B), and a layer containing a thermoplastic resin (B) and having been subjected to one or more of a hard coat treatment, an anti-reflection treatment, an anti-fouling treatment, an anti-fingerprint treatment, an anti-static treatment, a weather-resistant treatment, and an anti-glare treatment, is left in an environment of 23°C and 50% RH, and the curl shape of the resin laminate after being left in an environment of 23°C and 50% RH is preferably such that the concave curl on the side of the layer containing thermoplastic resin (B) is 11 m ≦ radius of curvature R ≦ 1225 m, more preferably such that the concave curl on the side of the layer containing thermoplastic resin (B) is 12 m ≦ radius of curvature R ≦ 613 m, even more preferably such that the concave curl on the side of the layer containing thermoplastic resin (B) is 13 m ≦ radius of curvature R ≦ 408 m, and particularly preferably such that the concave curl on the side of the layer containing thermoplastic resin (B) is 13 m ≦ radius of curvature R ≦ 306 m. If the layer containing thermoplastic resin (B) is concave and the radius of curvature R<11 m, a resin laminate in which an anti-reflection layer is further laminated on the surface of the layer containing thermoplastic resin (B) will exhibit significant concave warpage after being left in an environment of 23°C and 50% RH, making subsequent processing difficult. Also, if the layer containing thermoplastic resin (B) is concave and the radius of curvature R>1225 m, or the layer containing thermoplastic resin (B) is convex, a resin laminate in which an anti-reflection layer is further laminated on the surface of the layer containing thermoplastic resin (B) will exhibit significant convex warpage after being left in an environment of 23°C and 50% RH, making subsequent processing difficult.

[0133] (i) a resin laminate of a layer containing a polycarbonate-based resin (A) and a layer containing a thermoplastic resin (B), or (ii) a resin laminate in which the surface of the layer containing a polycarbonate-based resin (A), the layer containing a thermoplastic resin (B), and the layer containing a thermoplastic resin (B) has been subjected to one or more of hard coat treatment, anti-reflection treatment, anti-fouling treatment, anti-fingerprint treatment, anti-static treatment, weather resistance treatment, and anti-glare treatment, and an anti-reflection layer is further laminated on the surface of the layer containing a thermoplastic resin (B). The resin laminate thus obtained preferably has a curl shape after being left in a 23°C, 50% RH environment, with the thermoplastic resin (B) containing layer side being concave or convex, with a radius of curvature R≧21 m, more preferably a curvature radius R≧22 m, even more preferably a curvature radius R≧24 m, and particularly preferably a curvature radius R≧25 m. If the curl shape after being left in a 23°C, 50% RH environment, with the thermoplastic resin (B) containing layer side being concave or convex, with a radius of curvature R<21 m, the resin laminate will have a large concave or convex warp, making subsequent processing difficult.

[0134] A resin laminate of a layer containing a polycarbonate-based resin (A) and a layer containing a thermoplastic resin (B), or a resin laminate of a layer containing a polycarbonate-based resin (A), a layer containing a thermoplastic resin (B), and a layer containing a thermoplastic resin (B) on the surface of the layer containing the thermoplastic resin (B), which has been subjected to one or more of a hard coat treatment, an anti-reflection treatment, an anti-fouling treatment, an anti-fingerprint treatment, an anti-static treatment, a weather resistance treatment, and an anti-glare treatment, is left in an environment of 85°C and 85% RH for 120 hours, and then curls to a shape that is concave on the layer containing the thermoplastic resin (B) side with a radius of curvature R≧10 m, or It is preferable that the radius of curvature R is 31 m or more when the layer side containing thermoplastic resin (B) is convex, and it is more preferable that the radius of curvature R is 11 m or more when the layer side containing thermoplastic resin (B) is convex, and it is even more preferable that the radius of curvature R is 12 m or more when the layer side containing thermoplastic resin (B) is concave, or it is even more preferable that the radius of curvature R is 12 m or more when the layer side containing thermoplastic resin (B) is convex, and it is particularly preferable that the radius of curvature R is 13 m or more when the layer side containing thermoplastic resin (B) is convex, and it is particularly preferable that the radius of curvature R is 123 m or more when the layer side containing thermoplastic resin (B) is concave. If the radius of curvature R of the layer containing thermoplastic resin (B) is concave and less than 10 m, or if the radius of curvature R of the layer containing thermoplastic resin (B) is convex and less than 31 m, a resin laminate in which an anti-reflection layer is further laminated on the surface of the layer containing thermoplastic resin (B) of the resin laminate will show significant concave or convex warping after being left in an environment of 85°C and 85% RH for 120 hours, and shape changes will occur in a high-temperature, high-humidity environment, potentially resulting in quality problems.

[0135] (i) a resin laminate of a layer containing a polycarbonate-based resin (A) and a layer containing a thermoplastic resin (B), or (ii) a resin laminate in which the surface of the layer containing a polycarbonate-based resin (A), the layer containing a thermoplastic resin (B), and the layer containing a thermoplastic resin (B) has been subjected to one or more of hard coat treatment, anti-reflection treatment, anti-fouling treatment, anti-fingerprint treatment, anti-static treatment, weather resistance treatment, and anti-glare treatment, and an anti-reflection layer is further laminated on the surface of the layer containing a thermoplastic resin (B). For the resin laminate, after leaving it in an environment of 85°C and 85% RH for 120 hours, the curl shape is preferably such that the layer side containing the thermoplastic resin (B) is concave or convex with a radius of curvature R≧15 m, more preferably such that the layer side containing the thermoplastic resin (B) is concave or convex with a radius of curvature R≧18 m, even more preferably such that the layer side containing the thermoplastic resin (B) is concave or convex with a radius of curvature R≧20 m, and particularly preferably such that the layer side containing the thermoplastic resin (B) is concave or convex with a radius of curvature R≧23 m. If the radius of curvature R<15 m on the concave or convex side of the layer containing thermoplastic resin (B), a resin laminate in which an anti-reflection layer is further laminated on the surface of the layer containing thermoplastic resin (B) of the resin laminate will have large concave or convex warpage after being left in an environment of 85°C and 85% RH for 120 hours, and the shape will change in a high-temperature, high-humidity environment, which may result in quality problems.

[0136] In the present invention, the layer containing the thermoplastic resin (A) and / or the layer containing the thermoplastic resin (B) may contain components other than the above-mentioned main components. For example, an ultraviolet absorber can be mixed into the layer containing thermoplastic resin (A) and / or the layer containing thermoplastic resin (B). In the present invention, an ultraviolet absorber may also be incorporated into the hard coat layer. If the content of the ultraviolet absorber is too low, light resistance becomes insufficient. If the content is too high, depending on the molding method, excess ultraviolet absorber may scatter due to high temperatures, contaminating the molding environment and causing problems. The content of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass.Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone; Benzotriazole-based UV absorbers such as 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)benzotriazole, and (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol; benzoate-based UV absorbers such as phenyl salicylate and 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate; bis(2,2,6 hindered amine ultraviolet absorbers such as 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy and triazine-based ultraviolet absorbers such as 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, and 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine.The mixing method is not particularly limited, and methods such as compounding the entire amount, dry blending a master batch, and dry blending the entire amount can be used.

[0137] The resin laminate of the present invention can be subjected to one or both surfaces thereof to one or more of anti-fingerprint treatment, anti-reflection treatment, anti-fouling treatment, anti-static treatment, weather resistance treatment, and anti-glare treatment. The method for the anti-reflection treatment, anti-fouling treatment, anti-static treatment, weather resistance treatment, and anti-glare treatment is not particularly limited, and known methods can be used. Examples include a method of applying a reflection-reducing coating, a method of vapor-depositing a dielectric thin film, and a method of applying an anti-static coating.

[0138] <Optional additives> In the present invention, various additives other than the UV absorber can be mixed into the layer containing the polycarbonate resin (A) and / or the layer containing the thermoplastic resin (B). Examples of such additives include antioxidants, anti-coloring agents, anti-static agents, release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers. The mixing method is not particularly limited, and methods such as compounding the entire amount, dry blending a masterbatch, and dry blending the entire amount can be used.

[0139] In the present invention, the materials for the layer containing the polycarbonate-based resin (A), the layer containing the thermoplastic resin (B), and the hard coat, such as the polycarbonate-based resin (A) and the thermoplastic resin (B), are preferably filtered and purified by filtration. By passing the materials through a filter or laminating them, a resin laminate with little appearance defects such as foreign matter or defects can be obtained. There are no particular limitations on the filtration method, and melt filtration, solution filtration, or a combination thereof can be used.

[0140] <Various materials manufacturing methods> One aspect of the present invention relates to a method for producing a resin laminate comprising a layer containing a thermoplastic resin (B) laminated on at least one surface of a layer containing a polycarbonate-based resin (A). The method for producing the resin laminate of the present invention is not particularly limited. For example, there are various methods, such as a method of laminating a layer containing a thermoplastic resin (B) and a layer containing a polycarbonate-based resin (A) that have been separately formed and then thermocompression bonding them together, a method of laminating a layer containing a thermoplastic resin (B) and a layer containing a polycarbonate-based resin (A) that have been separately formed and then bonding them together with an adhesive, a method of co-extrusion molding a layer containing a thermoplastic resin (B) and a layer containing a polycarbonate-based resin (A), and a method of in-mold molding a layer containing a polycarbonate-based resin (A) using a layer containing a thermoplastic resin (B) that has been previously formed to integrate them. From the viewpoint of production cost and productivity, the co-extrusion molding method is preferred. An example of a coextrusion molding method is a manufacturing method in which a layer containing a polycarbonate-based resin (A) and a layer containing a thermoplastic resin (B) are each heated and melted in separate extruders, extruded through the slit-shaped outlet of a T-die, laminated, and then solidified in close contact with a cooling roll. In a manufacturing method according to an embodiment, the layer containing a polycarbonate-based resin (A) and the layer containing a thermoplastic resin (B) in a molten state coextruded from the die are sandwiched between a first cooling roll and a second cooling roll, wrapped around the second cooling roll, and then wrapped around at least one subsequent cooling roll. The resin laminate is then fed through a pinch roll to obtain a resin laminate.

[0141] The temperature at which the resins are heated and melted in the extruder is preferably 80 to 150°C higher than the glass transition temperatures (Tg) of the polycarbonate resin (A) and the thermoplastic resin (B). In general, the temperature condition of the main extruder that extrudes the polycarbonate resin (A) is usually 200 to 290°C, preferably 210 to 280°C, and the temperature condition of the sub-extruder that extrudes the thermoplastic resin (B) is usually 180 to 280°C, preferably 190 to 270°C.

[0142] As a method for co-extruding two kinds of molten resins, known methods such as a feed block method and a multi-manifold method can be used. For example, in the case of the feed block method, the molten resin laminated in the feed block is introduced into a sheet forming die such as a T-die, formed into a sheet, and then flowed into a forming roll (polishing roll) with a mirror-finished surface to form a bank, and the resin is mirror-finished and cooled while passing through the forming roll. In the case of the multi-manifold system, the molten resin laminated in the multi-manifold die is formed into a sheet inside the die, and then the surface is finished and cooled by a forming roll.

[0143] In any case, the die temperature is usually set to 230 to 290°C, preferably 250 to 280°C. The forming roll may be a rigid roll or an elastic roll, and either may be used.

[0144] To achieve a mirror finish on the surface, it is preferable to sandwich the film between a first cooling roll and a second cooling roll, wrap the film around the second cooling roll, and then wrap the polycarbonate resin (A) side around at least one subsequent cooling roll. The temperatures of the first and second cooling rolls are usually set to 70 to 150°C, preferably 80 to 135°C. The roll peripheral speed is set to 0.5 to 30.0 m / min, preferably 0.8 to 6.0 m / min. The speed ratio between the rear-stage cooling roll and the pinch roll is set to pinch roll speed (m / min) / rear-stage cooling roll speed (m / min)=0.5 to 2.0, preferably 0.7 to 1.8.

[0145] In the manufacturing method of the present invention, the layer side of the resin laminate containing thermoplastic resin (B) is preferably heated by an infrastructure heater during the cooling process after the subsequent cooling roll is peeled off after wrapping around the second cooling roll. The temperature to which the layer side of the resin laminate containing thermoplastic resin (B) is heated by the infrastructure heater during the cooling process after the subsequent cooling roll is peeled off is preferably 200°C to 410°C, more preferably 250°C to 405°C, and even more preferably 320°C to 400°C. If the heating temperature by the infrastructure heater is less than 200°C, the heating temperature is weak and the layer containing thermoplastic resin (B) of the resin laminate cannot be corrected into a concave shape. If the heating temperature by the infrastructure heater exceeds 410°C, the heating temperature is strong, causing the layer containing thermoplastic resin (B) of the resin laminate to become concave, resulting in a resin laminate with an anti-reflection layer further laminated thereon, which may result in a quality problem. In the present invention, the "temperature of the rear-stage cooling roll" refers to the temperature of the circulating heat transfer medium at the inlet of the rear-stage cooling roll.

[0146] There are no particular limitations on the filter used, and known filters can be used, and they are appropriately selected depending on the temperature, viscosity, and filtration accuracy of each material.The filter material is not particularly limited, but any of polypropylene, cotton, polyester, viscose rayon, glass fiber nonwoven fabric or roving yarn wound, phenolic resin-impregnated cellulose, sintered metal fiber nonwoven fabric, sintered metal powder, breaker plate, or a combination thereof can be used.In particular, considering heat resistance, durability, and pressure resistance, sintered metal fiber nonwoven fabric is preferable.

[0147] The filtration accuracy of the polycarbonate resin (A) and the thermoplastic resin (B) is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less. The filtration accuracy of the hard coating agent is 20 μm or less, preferably 10 μm or less, and more preferably 2 μm or less, since it is applied to the outermost layer of the resin laminate.

[0148] For filtering the polycarbonate resin (A) and the thermoplastic resin (B), it is preferable to use a polymer filter used in, for example, melt filtering of thermoplastic resins. Polymer filters are classified into leaf disc filters, candle filters, pack disc filters, cylindrical filters, etc. depending on their structure, but leaf disc filters, which have a large effective filtration area, are particularly suitable.

[0149] <Anti-reflection layer> The anti-reflection layer is configured by laminating multiple thin films (preferably 2 to 10 layers, more preferably 3 to 8 layers) with different refractive indices so that light reflected at the interfaces between the thin films is canceled out by interference, thereby reducing reflectance and reducing glare caused by reflected external light.

[0150] The material of the anti-reflection layer is not particularly limited, and known materials can be used, and is appropriately selected depending on the material of the resin laminate. For example, a configuration in which a high refractive index layer and a low refractive index layer are laminated may be used. The high refractive index layer and the low refractive index layer may each include one layer, or may each include two or more layers. When two or more high refractive index layers and two or more low refractive index layers are included, it is preferable that the high refractive index layers and the low refractive index layers are alternately laminated. The materials of the high refractive index layer and the low refractive index layer are not particularly limited, and can be selected taking into consideration the required anti-reflection performance, productivity, etc. The high refractive index layer can be preferably made of a material containing at least one selected from the group consisting of niobium, titanium, zirconium, tantalum, and silicon, such as niobium oxide (Nb2O5), titanium oxide (TiO2), zirconium oxide (ZrO2), tantalum oxide (Ta2O5), and silicon nitride. The low refractive index layer can be preferably made of a material containing silicon, such as silicon oxide (SiO), a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, or a material containing a mixed oxide of Si and Al.

[0151] The processing method of the antireflection layer is not particularly limited, and known methods can be used, which are appropriately selected according to each material. For example, vacuum evaporation method, sputtering method, ion plating method, etc. can be mentioned. To form an antireflection layer on plastic, the vacuum evaporation method or sputtering method that does not require heating as much as possible is preferably used. The total thickness of the antireflection layer is preferably 100 to 600 nm, and more preferably 150 to 550 nm. If the total thickness exceeds 600 nm, there is a risk of reducing reliability and productivity, resulting in cost increase. On the other hand, if it is less than 100 nm, it may be difficult to design antireflection properties.

[0152] <Usage> The resin laminate of the embodiment has excellent processability of the antireflection layer and is preferably used as a transparent substrate material, a transparent protective material, etc. Specifically, it is preferably used as a transparent substrate material and a transparent protective material (for example, the front panel) for portable display devices such as mobile phone terminals, portable electronic game devices, portable information terminals, mobile PCs, and installation-type display devices such as notebook PCs, desktop PC liquid crystal monitors, car navigation liquid crystal monitors, and liquid crystal TVs.

Examples

[0153] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited by these examples in any way.

[0154] The appearance evaluation of the copolymer obtained in the production example and the appearance evaluation of the resin laminates obtained in the examples and comparative examples were carried out as follows.

[0155] <Measurement of total light transmittance> The total light transmittance was measured using a reflection / transmittance meter HR-100 type manufactured by Murakami Color Technology Laboratory Co., Ltd.

[0156] <Haze measurement> The Haze was measured using a COH-400 manufactured by Nippon Denshoku Industries Co., Ltd.

[0157] <Molar ratio of monomer units in copolymer> Using JNM-AL400 manufactured by JEOL Ltd. 1 H-NMR and 13 Calculation was performed from the measured values ​​of C-NMR (400 MHz: solvent was CDCl3).

[0158] <Hydrogenation rate of copolymer> The hydrogenation rate was determined by the rate of decrease in absorbance at 260 nm in UV spectrum measurement before and after the hydrogenation reaction. Various copolymers were dissolved in tetrahydrofuran at arbitrary ratios, and the absorbance A1 at resin concentration C1 before the hydrogenation reaction and the absorbance A2 at resin concentration C2 after the hydrogenation reaction were used to calculate the hydrogenation rate using the following formula: Hydrogenation rate = 100 x [1 - (A2 x C1) / (A1 x C2)]

[0159] <Glass transition temperature> A differential scanning calorimeter DSC6200 manufactured by Seiko Instruments Inc. was used. Under a nitrogen flow of 30 ml / min, the temperature was increased from 30°C to 200°C at 10°C / min, then decreased from 200°C to 30°C at 50°C / min, and again increased from 30°C to 200°C at 10°C / min. The midpoint glass transition temperature (Tmg) in the second temperature increase was used as the glass transition temperature.

[0160] <Refractive index measurement> Measurement was performed using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. The measurement temperature was 20°C, the measurement wavelength was 589 nm, and monobromonaphthalene was used as the intermediate liquid.

[0161] <Evaluation of curl shape (curvature radius R and unevenness direction)> Since the laminate was curled after being left in an environment of 23°C 50% RH and an environment of 85°C 85% RH, the radius of curvature of the curled shape and the direction of the irregularities were evaluated with the layer containing the thermoplastic resin (B) as the convex side, or the layer containing the thermoplastic resin (B) as the concave side (the layer containing the polycarbonate-based resin (A) as the convex side). Radius of curvature (m) = {arc length [m] (= length of the test piece)} 2The formula was defined as / (8 × arrow height [m]). In this case, if the layer containing thermoplastic resin (B) was convex, a "-" sign was used for evaluation, and if the layer containing thermoplastic resin (B) was concave, a "+" sign was used for evaluation.

[0162] <Evaluation of curl shape after leaving in an environment of 23°C and 50% humidity> A test piece was cut into a square measuring 280 mm x 140 mm. The test piece was placed in a two-point support holder and placed in an environmental test chamber set at a temperature of 23°C and a relative humidity of 50% for at least 24 hours to condition it, after which h (= arrow height [m]) was measured. A three-dimensional shape measuring machine equipped with an electric stage was used to measure the arrow height. The removed test piece was placed horizontally with a convex shape upward, scanned at 2 mm intervals, and the bulge in the center was measured as the arrow height, and the radius of curvature [m] = {0.313 (= arc length [m])} 2 The curl shape was evaluated at a speed of 1 / (8×h [m]) for a resin laminate of a layer containing a polycarbonate-based resin (A) and a layer containing a thermoplastic resin (B), a resin laminate in which a hard coat treatment was applied to the surface of the layer containing a polycarbonate-based resin (A), a layer containing a thermoplastic resin (B), and the layer containing a thermoplastic resin (B), or a resin laminate in which an anti-reflection layer was further laminated on the surface of the layer containing a thermoplastic resin (B) of the above resin laminate. (For resin laminates that do not include an anti-reflection layer) ○ (Pass): The layer containing thermoplastic resin (B) is concave and the radius of curvature R is 11 m or less and 1225 m or less. × (Fail): Outside the above range. (In the case of a resin laminate including an anti-reflection layer) ○ (Pass): The layer side containing the thermoplastic resin (B) has a concave or convex curvature radius R≧21 m. × (Fail): Outside the above range.

[0163] <Evaluation of curl shape after leaving in an environment of 85°C and 85% RH> A test specimen was cut into a square measuring 280 mm x 140 mm. The test specimen was placed in a two-point support holder and placed in an environmental test chamber set at 23°C and 50% relative humidity for at least 24 hours to condition it. The holder was then placed in an environmental test chamber set at 85°C and 85% relative humidity and held there for 120 hours. The holder was then moved into an environmental test chamber set at 23°C and 50% relative humidity and held there for 4 hours, after which h (= arrow height [m]) was measured. A three-dimensional shape measuring instrument equipped with an electric stage was used to measure the arrow height. The removed test specimen was placed horizontally with a convex shape upward and scanned at 2 mm intervals. The central bulge was measured as the arrow height, and the radius of curvature [m] was calculated as 0.313 (= arc length [m]). 2 The curl shape was evaluated at a speed of 1 / (8×h [m]) for a resin laminate of a layer containing a polycarbonate-based resin (A) and a layer containing a thermoplastic resin (B), a resin laminate in which a hard coat treatment was applied to the surface of the layer containing a polycarbonate-based resin (A), a layer containing a thermoplastic resin (B), and the layer containing a thermoplastic resin (B), or a resin laminate in which an anti-reflection layer was further laminated on the surface of the layer containing a thermoplastic resin (B) of the above resin laminate.

[0164] <Pencil scratch hardness test> In accordance with JIS K 5600-5-4, pencils of gradually increasing hardness were pressed against the surface of the layer containing the thermoplastic resin (B) at an angle of 45 degrees to the surface with a load of 750 g, and the hardness of the hardest pencil that did not leave a scratch was evaluated as the pencil hardness. (For resin laminates that do not include an anti-reflection layer) ○ (Pass): Pencil hardness HB or higher. × (Fail): Outside the above range. (In the case of a resin laminate including an anti-reflection layer) ○ (Pass): Pencil hardness HB or higher. × (Fail): Outside the above range.

[0165] <Anti-reflection layer lamination (processing method)> Each layer was formed by vacuum deposition on the surface of the layer containing the thermoplastic resin (B) of the resin laminate. SiO2 (refractive index: 1.46) and TiO2 (refractive index: 2.49) were repeatedly layered to form an anti-reflection layer. The layering order and film thickness are as follows: Layer 1 is the layer in contact with the resin laminate, and Layer 6 is the outermost layer in contact with the air layer. 1st layer: TiO28nm 2nd layer: SiO251nm 3rd layer: TiO220nm 4th layer: SiO242nm 5th layer: TiO220nm 6th layer: SiO2 113nm

[0166] For the purposes of the examples and comparative examples, the following materials were used as the polycarbonate resin (A-1), thermoplastic resin (B-1), vinyl copolymer (C-1), and styrene copolymer (D-1), but the materials are not limited to these.

[0167] <Polycarbonate resin (A-1) and styrene copolymer (D-1)> Polycarbonate resin (A-1): Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Corporation (weight average molecular weight: 33,000, glass transition temperature: 147°C, refractive index: 1.586) Styrene copolymer (D-1): XIBOND140 manufactured by Polyscope (weight average molecular weight: 114,000, glass transition temperature: 134°C, (d1) / (d2) = styrene / maleic anhydride = 85 mol% / 15 mol%, refractive index: 1.590)

[0168] Production Example 1 [Production of vinyl copolymer (C-1)] A monomer composition consisting of 75.000 mol% purified methyl methacrylate (Mitsubishi Gas Chemical Company, Inc.) and 24.998 mol% purified styrene (Wako Pure Chemical Industries, Ltd.) as monomer components, and 0.002 mol% t-amylperoxy-2-ethylhexanoate (Arkema Yoshitomi Co., Ltd., trade name: Luperox 575) as a polymerization initiator, was continuously fed into a 10 L complete mixing vessel equipped with a helical ribbon impeller at 1 kg / h. Continuous polymerization was carried out at an average residence time of 2.5 hours and a polymerization temperature of 150 °C. The liquid was continuously withdrawn from the bottom to maintain a constant liquid level in the vessel and introduced into a solvent removal device to obtain pelletized copolymer. The proportion of (meth)acrylic acid ester monomer units (c1) derived from methyl methacrylate in the resulting copolymer was 73 mol%. The weight-average molecular weight (as converted to standard polystyrene) measured by gel permeation chromatography was 124,000. This copolymer was dissolved in methyl isobutyrate (Kanto Chemical Co., Ltd.) to prepare a 10% by mass methyl isobutyrate solution. A 1000 mL autoclave was charged with 500 parts by mass of this 10% by mass methyl isobutyrate solution of the copolymer and 1 part by mass of 10% by mass Pd / C (NE Chemcat Corporation) as a hydrogenation catalyst, and the mixture was maintained at 200°C under a hydrogen pressure of 9 MPa for 15 hours to hydrogenate the aromatic double bonds of the styrene moieties of the copolymer. The hydrogenation reaction rate of the styrene moieties was 99%. Furthermore, the proportion of structural units derived from methyl methacrylate in the resulting vinyl copolymer (C-1) was 73 mol%, and the vinyl copolymer (C-1) had a glass transition temperature of 121°C and a refractive index of 1.494.

[0169] Production Example 2 [Production of Thermoplastic Resin (B-1)] To a total of 100 parts by mass of 40 parts vinyl copolymer (C-1) and 60 parts styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36 (ADEKA Corporation) and 0.2% by mass of stearic acid monoglyceride (product name: H-100, Riken Vitamin Co., Ltd.) were added. The mixture was blended for 20 minutes in a blender. After that, the mixture was melt-kneaded at a cylinder temperature of 240°C using a 26 mm screw diameter twin-screw extruder (Toshiba Machine Co., Ltd., TEM-26SS, L / D ≒ 40) equipped with a 10 μm mesh polymer filter. The extruded strands were pelletized using a pelletizer. Pellets were produced stably. The resulting thermoplastic resin (B-1) had a glass transition temperature of 129°C and a refractive index of 1.551.

[0170] Example 1 [Production of Resin Laminate (K-1)] A resin laminate was molded using a multi-layer extrusion device equipped with a single-screw extruder with a 32 mm shaft diameter, a single-screw extruder with a 65 mm shaft diameter, a feed block connected to all extruders, a 650 mm-wide T-die connected to the feed block, and a multi-manifold die connected to each extruder. The thermoplastic resin (B-1) obtained in Production Example 2 was continuously introduced into the single-screw extruder with a 32 mm shaft diameter and extruded at a cylinder temperature of 240°C and a throughput of 2.6 kg / h. Furthermore, a polycarbonate resin (A-1) (manufactured by Mitsubishi Engineering-Plastics Corporation, product name: Iupilon S-1000) was continuously introduced into the single-screw extruder with a 65 mm shaft diameter and extruded at a cylinder temperature of 280°C and a throughput of 31.8 kg / h. The feed block connected to all extruders was equipped with two-type, two-layer distributor pins, and the thermoplastic resin (B-1) and polycarbonate-based resin (A-1) were introduced and laminated at a temperature of 270 ° C. The extruded material was extruded into a sheet through a T-die connected to the extruder at a temperature of 270 ° C. The material was then cooled while transferring a mirror finish using three mirror-finished rolls set at temperatures of 130 ° C, 140 ° C, and 180 ° C from the upstream side. After peeling off the third cooling roll, the layer containing the thermoplastic resin (B-1) of the resin laminate was heated using an infra-heater set at 340 ° C., resulting in a resin laminate (K-1) having a layer containing the thermoplastic resin (B-1) and a layer containing the polycarbonate-based resin (A-1). The overall thickness of the central part of the resulting resin laminate (K-1) was 1000 μm, and the thickness of the surface layer (the layer containing the thermoplastic resin (B)) was 80 μm. This resin laminate (K-1) had a total light transmittance of 90.9%, haze of 0.7%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +116m (good), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +533m, pencil hardness before laminating the anti-reflection layer: H (good), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: -55m (good), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: -23m, pencil hardness after laminating the anti-reflection layer: H (good), and the overall pass / fail judgment was good.

[0171] Example 2 [Production of Resin Laminate (K-2)] A resin laminate (K-2) having a layer containing a thermoplastic resin (B-1) and a layer containing a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (K-1) in Example 1, except that after the third cooling roll was peeled off, the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an infrastructure heater set at 360° C. The overall thickness of the central part of the obtained resin laminate (K-2) was 1000 μm, and the surface layer thickness was 80 μm. This resin laminate (K-2) had a total light transmittance of 90.9%, haze of 0.7%, curl shape after being left in a 23°C 50% RH environment before laminating the anti-reflection layer: +45m (good), curl shape after being left in an 85°C 85% RH environment before laminating the anti-reflection layer: +48m, pencil hardness before laminating the anti-reflection layer: H (good), curl shape after being left in a 23°C 50% RH environment after laminating the anti-reflection layer: +208m (good), curl shape after being left in an 85°C 85% RH environment after laminating the anti-reflection layer: -38m, pencil hardness after laminating the anti-reflection layer: H (good), and an overall pass / fail judgment of good.

[0172] Example 3 [Production of Resin Laminate (K-3)] A resin laminate (K-3) having a layer containing a thermoplastic resin (B-1) and a layer containing a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (K-1) in Example 1, except that after the third cooling roll was peeled off, the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an infrastructure heater set at 380° C. The overall thickness of the central part of the obtained resin laminate (K-3) was 1000 μm, and the surface layer thickness was 80 μm. This resin laminate (K-3) had a total light transmittance of 90.9%, haze of 0.7%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +40m (good), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +36m, pencil hardness before laminating the anti-reflection layer: H (good), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: +135m (good), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: -90m, pencil hardness after laminating the anti-reflection layer: H (good), and an overall pass / fail judgment of good.

[0173] Example 4 [Production of Resin Laminate (K-4)] A resin laminate (K-4) having a layer containing a thermoplastic resin (B-1) and a layer containing a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (K-1) in Example 1, except that after the third cooling roll was peeled off, the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an infrastructure heater set at 400° C. The overall thickness of the central part of the obtained resin laminate (K-4) was 1000 μm, and the surface layer thickness was 80 μm. This resin laminate (K-4) had a total light transmittance of 91.0%, haze of 0.7%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +13m and rated as good, curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +13m, pencil hardness before laminating the anti-reflection layer: H and rated as good, curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: +25m and rated as good, curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: +33m, pencil hardness after laminating the anti-reflection layer: H and rated as good, and the overall pass / fail judgment was good.

[0174] Example 5 [Production of Resin Laminate (K-5)] A coating composition containing 60 parts by mass of a hexafunctional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.), 35 parts by mass of PEG200# diacrylate (product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.), and 5 parts by mass of an oligomer containing a fluorine-containing group, a hydrophilic group, a lipophilic group, and a UV-reactive group (product name: RS-90, manufactured by DIC Corporation) to which 1% by mass of a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxycyclohexylphenyl ketone] manufactured by BASF Ltd.) was added was applied to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-1) obtained in Example 1 using a bar coater, and the coating composition was then heated at 20 mW / cm in a metal halide lamp (20 mW / cm in a 100-mass total). 2 ) for 5 seconds to cure the hard coat, thereby producing a resin laminate (K-5). The thickness of the hard coat layer was 6 μm. This resin laminate (K-5) had a total light transmittance of 91.0%, haze of 0.6%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +211m (good), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +170m, pencil hardness before laminating the anti-reflection layer: 3H (good), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: -42m (good), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: -26m, pencil hardness after laminating the anti-reflection layer: 3H (good), and the overall pass / fail judgment was good.

[0175] Example 6 [Production of Resin Laminate (K-6)] The same coating material as in Example 5 was applied with a bar coater to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-2) obtained in Example 2, and the hard coat was cured in the same manner as in Example 5 to produce a resin laminate (K-6). The film thickness of the hard coat layer was 6 μm. This resin laminate (K-6) had a total light transmittance of 91.0%, haze of 0.6%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +52m (good), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +39m, pencil hardness before laminating the anti-reflection layer: 3H (good), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: +942m (good), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: -47m, pencil hardness after laminating the anti-reflection layer: 3H (good), and an overall pass / fail judgment of good.

[0176] Example 7 [Production of Resin Laminate (K-7)] The same coating material as in Example 5 was applied with a bar coater to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-3) obtained in Example 3, and the hard coat was cured in the same manner as in Example 5 to produce a resin laminate (K-7). The film thickness of the hard coat layer was 6 μm. This resin laminate (K-7) had a total light transmittance of 91.0%, haze of 0.6%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +47m (good), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +31m (good), pencil hardness before laminating the anti-reflection layer: 3H (good), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: +340m, curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: -159m, pencil hardness after laminating the anti-reflection layer: 3H (good), and the overall pass / fail judgment was good.

[0177] Example 8 [Production of resin laminate (K-8)] The same coating material as in Example 5 was applied with a bar coater to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-4) obtained in Example 4, and the hard coat was cured in the same manner as in Example 5 to produce a resin laminate (K-8). The film thickness of the hard coat layer was 6 μm. This resin laminate (K-8) had a total light transmittance of 91.0%, haze of 0.6%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +14m (good), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +12m, pencil hardness before laminating the anti-reflection layer: 3H (good), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: +26m (good), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: -29m, pencil hardness after laminating the anti-reflection layer: 3H (good), and an overall pass / fail judgment of good.

[0178] Comparative Example 1 [Production of Resin Laminate (L-1)] A resin laminate (L-1) having a layer containing a thermoplastic resin (B-1) and a layer containing a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (K-1) of Example 1, except that the infrastructure heater was not used after the third cooling roll was peeled off. The overall thickness of the central part of the obtained resin laminate (L-1) was 1000 μm, and the surface layer thickness was 80 μm. This resin laminate (L-1) had a total light transmittance of 90.9%, haze of 0.7%, a curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer of -47 m (X), a curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer of -25 m, a pencil hardness of H (OK) before laminating the anti-reflection layer of -20 m (X), a curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer of -7 m, a pencil hardness of H (OK) after laminating the anti-reflection layer of -20 m (X), a curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer of -7 m, a pencil hardness of H (OK) after laminating the anti-reflection layer of -20 m (X), and an overall pass / fail judgment of -50 m.

[0179] Comparative Example 2 [Production of Resin Laminate (L-2)] A resin laminate (L-2) having a layer containing a thermoplastic resin (B-1) and a layer containing a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (K-1) in Example 1, except that after the third cooling roll was peeled off, the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an infrastructure heater set at 420° C. The overall thickness of the central part of the obtained resin laminate (L-2) was 1000 μm, and the surface layer thickness was 80 μm. This resin laminate (L-2) had a total light transmittance of 90.9%, haze of 0.7%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +10m (×), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +9m, pencil hardness before laminating the anti-reflection layer: H (◯), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: +14m (×), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: +14m, pencil hardness after laminating the anti-reflection layer: H (◯), and the overall pass / fail judgment was ×.

[0180] Comparative Example 3 [Production of Resin Laminate (L-3)] The same coating material as in Example 5 was applied with a bar coater to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (L-1) obtained in Comparative Example 1, and the hard coat was cured in the same manner as in Example 5 to produce a resin laminate (L-3). The film thickness of the hard coat layer was 6 μm. This resin laminate (L-3) had a total light transmittance of 91.0%, haze of 0.6%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: -40m (×), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: -28m, pencil hardness before laminating the anti-reflection layer: 3H (○), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: -18m (×), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: -7m, pencil hardness after laminating the anti-reflection layer: 3H (○), and an overall pass / fail judgment of ×.

[0181] Comparative Example 4 [Production of Resin Laminate (L-4)] The same coating material as in Example 5 was applied with a bar coater to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (L-2) obtained in Comparative Example 2, and the hard coat was cured in the same manner as in Example 5 to produce a resin laminate (L-4). The film thickness of the hard coat layer was 6 μm. This resin laminate (L-4) had a total light transmittance of 91.0%, haze of 0.6%, curl shape after being left in a 23°C, 50% RH environment before laminating the anti-reflection layer: +10m (×), curl shape after being left in an 85°C, 85% RH environment before laminating the anti-reflection layer: +9m, pencil hardness before laminating the anti-reflection layer: 3H (◯), curl shape after being left in a 23°C, 50% RH environment after laminating the anti-reflection layer: +15m (×), curl shape after being left in an 85°C, 85% RH environment after laminating the anti-reflection layer: +13m, pencil hardness after laminating the anti-reflection layer: 3H (◯), and the overall pass / fail judgment was ×.

[0182] [Table 2]

[0183] As described above, by satisfying the conditions of the present invention, an advantageous effect can be achieved in that a resin laminate having excellent curl resistance after lamination of an anti-reflection layer can be obtained.

[0184] That is, as shown in Table 2, when Examples 1 to 8, in which the curl shape after being left in an environment of 23°C and 50% RH before lamination of the antireflection layer was concave toward the layer containing thermoplastic resin (B) and the radius of curvature R was in the range of 11 m≦radius of curvature R≦1225 m, were compared with Comparative Examples 1 and 3, in which the curl shape before lamination of the antireflection layer was convex toward the layer containing thermoplastic resin (B), Examples 1 to 8 had better curl resistance after being left in an environment of 23°C and 50% RH after lamination of the antireflection layer. Furthermore, when comparing Examples 1 to 8 with Comparative Examples 2 and 4, in which the curled shape after being left in an environment of 23°C and 50% RH before laminating the anti-reflection layer was in the range of a concave curvature radius R<11 m on the layer side containing thermoplastic resin (B), Examples 1 to 8 had better curl resistance after being left in an environment of 23°C and 50% RH after laminating the anti-reflection layer.

Claims

1. A resin laminate comprising a layer containing a polycarbonate-based resin (A) having a polycarbonate resin as a main component, and a layer containing a thermoplastic resin (B) laminated on at least one surface of the layer, wherein the resin laminate, after being left in an environment of 23°C and 50% RH, has a curl shape in which the layer containing the thermoplastic resin (B) is concave with a radius of curvature R of 11 m≦R≦1225 m.

2. 2. The resin laminate according to claim 1, wherein the surface of the layer containing the thermoplastic resin (B) is subjected to one or more of a hard coat treatment, an anti-reflection treatment, an anti-fouling treatment, an anti-fingerprint treatment, an anti-static treatment, a weather resistance treatment, and an anti-glare treatment.

3. 3. The resin laminate according to claim 1 or 2, wherein an anti-reflection layer is further laminated on a surface of the layer containing the thermoplastic resin (B), and the resin laminate curls after being left in an environment of 23°C and 50% RH, with a radius of curvature R≧21 m, with the layer containing the thermoplastic resin (B) side being concave or convex.

4. A resin laminate comprising: a layer containing a polycarbonate-based resin (A) containing a polycarbonate resin as a main component; a layer containing a thermoplastic resin (B) laminated on at least one surface of the layer containing resin (A); and an anti-reflection layer laminated on the surface of the layer containing resin (B), wherein the resin laminate curls after being left in an environment of 23°C and 50% RH, with the anti-reflection layer side being concave or convex, and the radius of curvature of the resin laminate is R≧21 m.

5. 5. The resin laminate according to claim 4, wherein one or more of a hard coat treatment, an anti-reflection treatment, an anti-fouling treatment, an anti-fingerprint treatment, an anti-static treatment, a weather resistance treatment, and an anti-glare treatment is applied between the layer containing the thermoplastic resin (B) and the anti-reflection layer.

6. 6. The resin laminate according to claim 1, wherein the surface on the side of the layer containing the thermoplastic resin (B) has a pencil hardness of HB or more.

7. 7. The resin laminate according to claim 1, wherein the polycarbonate resin (A) has a weight average molecular weight of 15,000 to 75,000.

8. 8. The resin laminate according to claim 1, wherein the layer containing the polycarbonate resin (A) and / or the layer containing the thermoplastic resin (B) contains an ultraviolet absorber.

9. A transparent substrate material comprising the resin laminate according to any one of claims 1 to 8.

10. A transparent protective material comprising the resin laminate according to any one of claims 1 to 8.

11. A touch panel front protection plate comprising the resin laminate according to any one of claims 1 to 8.

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