Extruded resin laminated film and method for producing same

Abstract

The present disclosure provides a method for producing an extruded resin laminated film that undergoes little optical distortion and little change in the orientation axis thereof. A laminate having a (meth)acrylic-resin-containing layer laminated on at least one surface of a polycarbonate-containing layer is co-extruded from a T die in a molten state and is cooled using three or more cooling rolls, and the resultant extruded resin laminated film is taken off using a take-off roll. The laminate is interposed between a first cooling roll and a second cooling roll without creating a bank, an elastic metal roll being used as the first cooling roll, and a rigid metal roll being used as the second cooling roll. The overall temperature of the laminate when detached from the final cooling roll ranges from –40°C to –5°C relative to the glass transition temperature of the polycarbonate-containing layer. V2 is the circumferential velocity of the second cooling roll, V3 is the circumferential velocity of the third cooling roll, and V4 is the circumferential velocity of the take-off roll. Both V3 / V2 and V4 / V2 are set at 0.980-1.000.

Description

Extruded resin laminate film and its manufacturing method

[0001] The present disclosure relates to an extruded resin laminate film and a method for producing the same.

[0002] In flat panel displays such as liquid crystal displays, and displays such as touch panel displays that combine such flat panel displays with touch panels (also called touch screens), a transparent resin protective film may be provided on the front side from the viewpoints of preventing surface scratches, ease of processing, and weight reduction. In this specification, this protective film is also referred to as a "liquid crystal display protective film." This protective film is required to have properties such as gloss, scratch resistance, and impact resistance.

[0003] In recent years, displays with curved surfaces have been proposed from the viewpoint of design and the like. Transparent resin films used as protective films for such applications are subjected to curved surface processing by thermoforming, such as press molding, vacuum forming, and pressure forming. Optical distortion (phase difference) occurs in these transparent resin films due to stress during thermal bending, and in displays using such films, rainbow unevenness may be observed when the displayed image is viewed through a polarizing filter, such as polarized sunglasses.

[0004] In recent years, in-vehicle head-up display (HUD) devices have been put into practical use to improve safety and other aspects. HUD devices include a display system such as a liquid crystal display, an optical system, and a housing that houses these components. The housing has an opening to ensure an optical path, and a transparent resin cover member is attached to this opening to prevent foreign matter such as dust from entering the housing and to facilitate processability. Unlike touch panel protective films, this cover member is rarely touched by people and does not require rigidity, so a transparent resin film with a thickness of 1.0 mm or less can be used. In particular, polycarbonate monolayer films are often used from the perspectives of heat resistance and impact resistance, but in HUD devices using such films, optical distortion (phase difference) and variations in its orientation axis may result in rainbow unevenness when the displayed image is viewed through a polarized filter such as polarized sunglasses.

[0005] JP 2007-185956 A, International Publication No. 2011 / 145630, JP 2009-248416 A, JP 2016-22616 A, International Publication No. 2015 / 093037 (Patent No. 6266021 A)

[0006] For the above applications, a resin laminate film including a polycarbonate layer, which has excellent heat resistance and impact resistance, and a (meth)acrylic resin layer, which has excellent gloss, transparency, and scratch resistance, has been investigated. This resin laminate film is preferably produced by coextrusion molding. In this case, strain stress may remain in the resulting resin laminate film due to differences in the properties of the two resins. The strain stress remaining in the resin laminate film is called "residual stress," and a resin laminate film having this residual stress may warp due to thermal changes.

[0007] As a method for reducing residual stress in a resin laminate film and suppressing the occurrence of warpage, Patent Document 1 discloses a method for optimizing the rotation speed of a cooling roll used in extrusion molding (claim 1). Patent Document 2 discloses a method for using a resin obtained by copolymerizing a (meth)acrylic acid ester with an aromatic vinyl monomer and then hydrogenating the aromatic double bonds as a (meth)acrylic resin to be laminated with polycarbonate (claim 2).

[0008] Furthermore, in order to solve the above problems, improvements in the heat resistance and moisture resistance of (meth)acrylic resins have been investigated. For example, Patent Document 3 discloses a method of using, as a (meth)acrylic resin to be laminated with polycarbonate, a (meth)acrylic resin having methyl methacrylate (MMA) units and units selected from methacrylic acid units, acrylic acid units, maleic anhydride units, N-substituted or unsubstituted maleimide units, glutaric anhydride units, and glutarimide units, and having a glass transition temperature (Tg) of 110°C or higher (Claim 1).

[0009] Patent Document 4 is an example of a document related to a low-optical distortion laminate film for curved surface processing. This document discloses a multilayer film in which acrylic resin-containing layers (B-1 layer and B-2 layer) are laminated on both sides of a polycarbonate-containing layer (A layer), the total thickness is 50 to 300 μm, the thickness of A layer is 5 to 35% of the total thickness, and the in-plane retardation Re at an incident angle of 0° with a wavelength of 590 nm is 30 nm or less (Claim 1). This document also discloses a method for producing a low-optical distortion laminate film by sandwiching and pressing molten resin discharged from an extruder between a metal roll and an elastic metal roll (Claim 6). However, the present inventors' investigations revealed that it is difficult to stably produce a low-distortion laminate film using the above method alone.

[0010] In Patent Document 5, the present inventors disclose a method for producing an extruded resin plate in which a methacrylic resin layer is laminated on at least one side of a polycarbonate layer, in which production conditions such as the relationship between the peripheral speeds of multiple cooling rolls and a take-up roll, and the temperature of the entire resin at the time of peeling from the last cooling roll, are optimized during co-extrusion molding of the extruded resin plate (claim 1). While this method can reduce optical distortion, the present inventors have discovered a method for more effectively reducing optical distortion. However, this document does not disclose any control of the orientation axis of optical distortion.

[0011] The present disclosure has been made in consideration of the above circumstances, and aims to provide an extruded resin laminate film that includes a polycarbonate-containing layer and a (meth)acrylic resin-containing layer, has small changes in optical distortion (retardation) and in the orientation axis of in-plane optical distortion, and is suppressed from warping due to thermal changes, and a method for producing the same.

[0012] The present disclosure provides the following extruded resin laminate films [1] to

[11] , methods for producing the same, and extruded resin laminate films with cured coatings. [1] A method for producing an extruded laminate resin film having a laminate structure in which a (meth)acrylic resin-containing layer is laminated on at least one surface of a polycarbonate-containing layer, the method comprising the steps of co-extruding a thermoplastic resin laminate having the laminate structure in a molten state from a T-die, using three or more adjacent cooling rolls, sandwiching the thermoplastic resin laminate in the molten state between an nth cooling roll (n≧1) and an n+1th cooling roll, and cooling the thermoplastic resin laminate by repeating the operation of wrapping the thermoplastic resin laminate around the n+1th cooling roll a plurality of times starting from n=1, and taking up the extruded laminate resin film obtained after cooling with a take-up roll, wherein the thermoplastic resin laminate is sandwiched between a first cooling roll and a second cooling roll without forming a bank, wherein the first cooling roll is an elastic metal roll having an elastic outer cylinder made of a thin metal film on its outer periphery, and the second cooling roll is a rigid metal roll, and the total temperature (TT) of the thermoplastic resin laminate when peeled from the last cooling roll is set to −40 to −5° C. relative to the glass transition temperature of the polycarbonate-containing layer, a peripheral speed ratio (V3 / V2) between the peripheral speed (V3) of the third cooling roll and the peripheral speed (V2) of the second cooling roll, and a peripheral speed ratio (V4 / V2) between the peripheral speed (V4) of the take-up roll and the peripheral speed (V2) of the second cooling roll, are both set to 0.980 to 1.000; the extruded resin laminate film has a total thickness of 0.1 to 0.8 mm, a thickness of the (meth)acrylic resin-containing layer is 0.04 mm or more, a ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness is 50% or less, an in-plane retardation value of at least a part in the width direction is 50 nm or less, an absolute value of an angle of the slow axis of the in-plane retardation when an angle of an axis parallel to the extrusion direction is 0° is 10° or less, and an amount of warpage of a square test piece having a side length of 10 cm after heating at 90°C for 10 minutes is 5 mm or less.

[0013] [2] The extruded resin laminate film has a laminate structure in which the (meth)acrylic resin-containing layer containing the (meth)acrylic resin (A) having a syndiotacticity (rr) of 56% or more, expressed in triads, is laminated on at least one surface of the polycarbonate-containing layer. [3] The extruded resin laminate film of [2], wherein the (meth)acrylic resin (A) has a methyl methacrylate unit content of 90% by mass or more and a glass transition temperature of 122°C or more. [4] The extruded resin laminate film of any of [1] to [3], wherein the (meth)acrylic resin-containing layer contains multilayer-structured rubber particles.

[0014] [5] The method for producing an extruded laminated resin film according to [1], wherein the (meth)acrylic resin-containing layer contains 5 to 90% by mass of a (meth)acrylic resin and 95 to 10% by mass of a copolymer containing structural units derived from an aromatic vinyl compound and structural units derived from maleic anhydride, and has a glass transition temperature of 122° C. or higher. [6] The method for producing an extruded laminated resin film according to [5], wherein the copolymer contains 50 to 85% by mass of structural units derived from the aromatic vinyl compound and 15 to 50% by mass of structural units derived from maleic anhydride. [7] The method for producing an extruded laminated resin film according to [6], wherein the copolymer contains 50 to 84% by mass of structural units derived from the aromatic vinyl compound, 15 to 49% by mass of structural units derived from maleic anhydride, and 1 to 35% by mass of structural units derived from a (meth)acrylic acid ester.

[0015] [8] An extruded resin laminate film having a (meth)acrylic resin-containing layer laminated on at least one surface of a polycarbonate-containing layer, wherein the extruded resin laminate film has a total thickness of 0.1 to 0.8 mm, the thickness of the (meth)acrylic resin-containing layer is 0.04 mm or more, and a ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness is 50% or less, the (meth)acrylic resin-containing layer has a glass transition temperature of 122°C or more, an in-plane retardation value of at least a part in the width direction is 50 nm or less, the absolute value of the angle of the slow axis of the in-plane retardation when the angle of an axis parallel to the extrusion direction is 0° is 10° or less, and the amount of warpage of a square test piece having a side length of 10 cm after heating at 90°C for 10 minutes is 5 mm or less.

[0016] [9] The extruded resin laminate film of [8], wherein the difference between the glass transition temperature of the polycarbonate-containing layer and the glass transition temperature of the (meth)acrylic resin-containing layer is 28°C or less.

[10] The extruded resin laminate film of [8] or [9], wherein the (meth)acrylic resin-containing layer contains an infrared absorbing agent, and the extruded resin laminate film has a total light transmittance of 80% or more and a transmittance at a wavelength of 1500 nm of 60% or less, and is for a head-up display device.

[11] An extruded resin laminate film with an abrasion-resistant layer, comprising the extruded resin laminate film of any of [8] to

[10] , and an abrasion-resistant layer on at least one surface thereof.

[0017] According to the present disclosure, it is possible to provide an extruded resin laminate film that includes a polycarbonate-containing layer and a (meth)acrylic resin-containing layer, has small changes in optical distortion (retardation) and in-plane optical distortion orientation axis, and is suppressed from warping due to thermal changes, and a method for producing the same.

[0018] It is a schematic cross-sectional view of an extruded resin laminate film of a first embodiment according to the present invention. It is a schematic cross-sectional view of an extruded resin laminate film of a second embodiment according to the present invention. It is a schematic view of a manufacturing apparatus for an extruded resin laminate film of an embodiment according to the present invention.

[0019] [Extruded Resin Laminate Film] The extruded resin laminate film of the present disclosure has a laminate structure in which a layer containing a (meth)acrylic resin (PM) ((meth)acrylic resin-containing layer) is laminated on at least one side of a layer containing a polycarbonate (PC) (polycarbonate-containing layer). In this specification, "(meth)acrylic" is a general term for acrylic and methacrylic. Generally, the terms "film," "sheet," and "plate" are used for thin film molded bodies depending on their thickness, but no clear distinction is made between them. For convenience, the term "film" is used herein for thin film molded bodies with a thickness of less than 1.0 mm. The extruded resin laminate film of the present disclosure has a total thickness of 0.1 to 0.8 mm, and the thickness of the (meth)acrylic resin-containing layer is 0.04 mm or more. The ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness is 50% or less. Polycarbonate (PC) has excellent heat resistance and impact resistance, while (meth)acrylic resin has excellent gloss, transparency, and scratch resistance. Therefore, the extruded resin laminate film of the present disclosure, which is formed by laminating these resins, has excellent gloss, transparency, heat resistance, impact resistance, and scratch resistance. Furthermore, since the extruded resin laminate film of the present disclosure is produced by an extrusion molding method, it has excellent productivity.

[0020] ((Meth)acrylic Resin-Containing Layer) The (meth)acrylic resin-containing layer contains one or more (meth)acrylic resins (PM). The (meth)acrylic resin (PM) is a homopolymer or copolymer containing structural units derived from one or more (meth)acrylic acid hydrocarbon esters (hereinafter simply referred to as (meth)acrylic acid esters). The hydrocarbon group in the (meth)acrylic acid ester may be an acyclic aliphatic hydrocarbon group such as a methyl group, an ethyl group, or a propyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group such as a phenyl group. From the viewpoint of transparency, the content of (meth)acrylic acid ester monomer units in the (meth)acrylic resin (PM) is preferably 90% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and may even be 100% by mass.

[0021] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Examples of such acrylates include 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, trifluoromethyl (meth)acrylate, trifluoroethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and 3-dimethylaminoethyl (meth)acrylate.

[0022] Among these, methacrylic acid esters are preferred, and from the viewpoint of availability, MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, and the like are preferred, with MMA being particularly preferred.

[0023] The (meth)acrylic resin (PM) may contain structural units derived from one or more other monomers other than (meth)acrylic acid esters. Examples of other monomers other than (meth)acrylic acid esters include (meth)acrylic acid; (meth)acrylic acid metal salts; vinyl-based monomers such as vinyl chloride and vinyl acetate; (meth)acrylonitrile; (meth)acrylamide; styrene-based monomers such as styrene, α-methylstyrene, and vinyltoluene; and acid anhydrides such as maleic anhydride. The content of structural units derived from other monomers other than (meth)acrylic acid esters in the (meth)acrylic resin (PM) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

[0024] The (meth)acrylic resin (PM) is obtained by polymerizing one or more (meth)acrylic acid esters and, if necessary, other monomers. When multiple types of monomers are used, the multiple types of monomers are usually mixed to prepare a monomer mixture, and then polymerization is carried out. Polymerization methods for the (meth)acrylic resin (PM) include radical polymerization and anionic polymerization. Radical polymerization methods include suspension polymerization, bulk polymerization, solution polymerization, and emulsion polymerization. Among these, suspension polymerization and bulk polymerization are preferred from the viewpoint of productivity and thermal decomposition resistance. Anionic polymerization methods include bulk polymerization and solution polymerization. Various properties of the (meth)acrylic resin (PM) (such as Tg, Mw, Mw / Mn, MFR, and flexural modulus) can be adjusted by adjusting polymerization conditions such as polymerization temperature, polymerization time, the type and amount of chain transfer agent, and the type and amount of polymerization initiator. As a method for producing the (meth)acrylic resin (A) having a high rr ratio, which will be described later, an anionic polymerization method is preferred.

[0025] The weight average molecular weight (Mw) of the (meth)acrylic resin (PM) is preferably 30,000 to 500,000. When the Mw is 30,000 or more, the (meth)acrylic resin-containing layer has excellent scratch resistance and heat resistance, and when the Mw is 500,000 or less, the (meth)acrylic resin-containing layer has excellent formability.

[0026] In this specification, the glass transition temperature of the (meth)acrylic resin (PM) or a composition containing it is represented by Tg(M), the glass transition temperature of the (meth)acrylic resin (A) having a high rr ratio (described later) is represented by Tg(A), and the glass transition temperature of polycarbonate (PC) is represented by Tg(PC). Unless otherwise specified, the glass transition temperature is determined by the method described in the [Examples] section. Tg(M) is not particularly limited, and it is preferable that the difference between Tg(M) and Tg(PC) is small. In this case, the extruded resin laminate film of the present disclosure is less susceptible to the influence of external environmental temperature, and warping is suppressed even when exposed to high temperatures. In this case, even when the extruded resin laminate film of the present disclosure is subjected to heat bending, changes in the optical distortion and the orientation axis of in-plane optical distortion can be suppressed. Furthermore, the extruded resin laminate film of the present disclosure is easy to thermoform, and the surface properties of the secondary molded product obtained after thermoforming can be improved. Furthermore, when a cured coating is formed on the extruded resin laminate film of the present disclosure, curing can be performed at a higher temperature, thereby increasing the surface hardness of the cured coating and improving adhesion to the extruded resin laminate film. The difference between the glass transition temperature (Tg(PC)) of the polycarbonate (PC) and the glass transition temperature (Tg(M)) of the (meth)acrylic resin (PM) is preferably 28°C or less, more preferably 25°C or less, and particularly preferably 20°C or less. The lower limit of Tg(M) is preferably 120°C, more preferably 122°C, particularly preferably 125°C, and most preferably 127°C or more. The upper limit of Tg(M) is preferably 160°C, more preferably 155°C, and particularly preferably 150°C.

[0027] <(Meth)acrylic Resin (A)> In one embodiment of the present invention, the extruded laminate resin film may have a laminate structure in which a (meth)acrylic resin-containing layer containing a (meth)acrylic resin (A) having a syndiotacticity (rr) in triad notation (hereinafter sometimes abbreviated simply as "syndiotacticity (rr)" or "rr ratio") of 56% or more is laminated on at least one surface of a polycarbonate-containing layer.

[0028] The (meth)acrylic resin (A) having an rr ratio of 56% or more may be a single (meth)acrylic resin having an rr ratio of 56% or more, or a mixture of multiple (meth)acrylic resins having different rr ratios and an overall rr ratio of 56% or more. When the (meth)acrylic resin (A) is a mixture of multiple (meth)acrylic resins, it is sufficient that the entire mixture has suitable properties for the (meth)acrylic resin (A) in terms of various properties other than the rr ratio (such as Tg, Mw, Mw / Mn, MFR, and flexural modulus). Multiple (meth)acrylic resins with different properties may be combined to obtain a (meth)acrylic resin (A) having desired properties.

[0029] A (meth)acrylic resin (A) having an rr ratio of 56% or more has a higher glass transition temperature (Tg) and higher heat resistance than general (meth)acrylic resins. From the viewpoint of improving the glass transition temperature Tg(A) of the (meth)acrylic resin (A), the rr ratio of the (meth)acrylic resin (A) is 56% or more, preferably 63% or more, and more preferably 65% ​​or more. The upper limit of the rr ratio of the (meth)acrylic resin (A) is not particularly limited, and from the viewpoint of moldability and surface hardness, it is preferably 99%, more preferably 95%, particularly preferably 90%, and most preferably 85%. Tg(A) is preferably 122°C or more, more preferably 125°C or more, and particularly preferably 127°C or more. The upper limit of Tg(A) is usually about 130°C. Tg(A) can be controlled by adjusting the molecular weight, rr ratio, etc.

[0030] While typical (meth)acrylic resins have relatively low glass transition temperatures (Tg), resulting in a relatively large difference in Tg between them and polycarbonate (PC), (meth)acrylic resin (A) having an rr ratio of 56% or more has a relatively high glass transition temperature (Tg), resulting in a relatively small difference in Tg between them and polycarbonate. Therefore, the extruded resin laminate film of this embodiment using (meth)acrylic resin (A) is less susceptible to the effects of external environmental temperature, and warping is suppressed even when exposed to high temperatures. In this case, even when the extruded resin laminate film of this embodiment is subjected to hot bending, changes in the optical distortion and the orientation axis of in-plane optical distortion can be suppressed. Furthermore, the extruded resin laminate film of this embodiment is easily thermoformed, and the surface properties of the secondary molded product obtained after thermoforming can be improved. Furthermore, when a cured coating is formed on the extruded resin laminate film of this embodiment, curing can be performed at a higher temperature, thereby increasing the surface hardness of the cured coating and improving adhesion to the extruded resin laminate film. The difference between the glass transition temperature (Tg(PC)) of the polycarbonate (PC) and the glass transition temperature (Tg(A)) of the (meth)acrylic resin (A) is preferably 28°C or less, more preferably 25°C or less, and particularly preferably 20°C or less.

[0031] The rr ratio is the proportion of two chains (diads) in a chain (triad) of three consecutive structural units that are both racemo (denoted as rr). In addition, in the chain (diad) 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. In this specification, unless otherwise specified, the "rr ratio" is determined by the method described in the [Examples] section.

[0032] The preferred monomer unit composition of the (meth)acrylic resin (A) is the same as that of the (meth)acrylic resin (PM). The (meth)acrylic resin (A) is preferably a single methacrylic resin or a mixture of multiple methacrylic resins. The (meth)acrylic resin (A) preferably has a methyl methacrylate (MMA) unit content of 90% by mass or more.

[0033] The weight-average molecular weight (Mw) of the (meth)acrylic resin (A) is not particularly limited, but is preferably 30,000 to 200,000, more preferably 50,000 to 150,000, and particularly preferably 60,000 to 120,000. When the Mw of the (meth)acrylic resin (A) having an rr ratio of 56% or more is 30,000 to 20,0000, the (meth)acrylic resin-containing layer is easily formed, and the resulting extruded resin laminate film has high strength and is less likely to crack. The molecular weight distribution (the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), Mw / Mn) of the (meth)acrylic resin (A) is not particularly limited, but is preferably 1.01 to 5.0, more preferably 1.05 to 3.5. Unless otherwise specified, Mw and Mn in this specification are values ​​measured using gel permeation chromatography (GPC) in terms of standard polystyrene.

[0034] The melt flow rate (MFR) of the (meth)acrylic resin (A) is preferably 0.1 to 20 g / 10 min, more preferably 0.5 to 15 g / 10 min, and particularly preferably 1.0 to 10 g / 10 min. Unless otherwise specified, the MFR of the (meth)acrylic resin (A) is a value measured in accordance with JIS K7210 using a melt indexer at a temperature of 230°C under a load of 3.8 kg.

[0035] The flexural modulus of the (meth)acrylic resin (A) is not particularly limited, but is preferably 3200 MPa or less, more preferably 3150 MPa or less, particularly preferably 3100 MPa or less, and most preferably 3000 MPa or less. The flexural modulus can be measured in accordance with JIS K7171.

[0036] <Multilayered Rubber Particles (RP)> In another embodiment of the present invention, the (meth)acrylic resin (PM) and the (meth)acrylic resin-containing layer may contain multilayered rubber particles (RP). The (meth)acrylic resin (PM) has excellent gloss, transparency, surface hardness, and the like, but depending on the application, higher impact resistance may be required. Adding multilayered rubber particles (RP) to the (meth)acrylic resin (PM) can improve the impact resistance of the (meth)acrylic resin-containing layer. For example, the impact resistance of an extruded resin laminate film for resin glazing can be improved. For example, cracking during thermoforming or handling of an extruded resin laminate film for a decorative film as a paint replacement material can be suppressed.

[0037] Generally, as the concentration of the multilayered rubber particles (RP) in the (meth)acrylic resin-containing layer increases, the toughness tends to increase relatively, while the surface hardness tends to decrease relatively. From the viewpoint of the balance between surface hardness and impact resistance, the (meth)acrylic resin (PM) content in the (meth)acrylic resin-containing layer is preferably 94 to 75% by mass, more preferably 92 to 80% by mass, and particularly preferably 92 to 88% by mass, and the multilayered rubber particles (RP) content is preferably 6 to 25% by mass, more preferably 8 to 20% by mass, and particularly preferably 8 to 12% by mass.

[0038] The multilayered rubber particles (RP) are preferably acrylic multilayered rubber particles containing one or more graft copolymer layers containing one or more acrylic acid alkyl ester copolymers. Examples of such acrylic multilayered rubber particles include those disclosed in JP 2004-352837 A and the like. The acrylic multilayered rubber particles preferably contain a crosslinked polymer layer containing an acrylic acid alkyl ester unit having 6 to 12 carbon atoms. The number of layers in the multilayered rubber particles (RP) is not particularly limited, and may be two or three or more layers. The upper limit of the number of layers is not particularly limited, and is typically about four layers. The multilayered rubber particles (RP) are preferably core-shell multilayered particles with three or more layers, including an innermost layer (RP-a), one or more intermediate layers (RP-b), and an outermost layer (RP-c).

[0039] The constituent polymer of the innermost layer (RP-a) contains MMA units and graftable or crosslinkable monomer units, and may further contain one or more other monomer units as necessary. The content of MMA units in the constituent polymer of the innermost layer (RP-a) is preferably 80 to 99.99% by mass, more preferably 85 to 99% by mass, and particularly preferably 90 to 98% by mass. The proportion of the innermost layer (RP-a) in the multilayered particle (RP) having three or more layers is preferably 0 to 15% by mass, more preferably 7 to 13% by mass. Having the proportion of the innermost layer (RP-a) within this range can enhance the heat resistance of the (meth)acrylic resin-containing layer.

[0040] The constituent polymer of the intermediate layer (RP-b) contains an acrylic acid alkyl ester unit having 6 to 12 carbon atoms and a graftable or crosslinkable monomer unit, and may further contain one or more other monomer units as necessary. The content of the acrylic acid alkyl ester unit in the constituent polymer of the intermediate layer (RP-b) is preferably 70 to 99.8% by mass, more preferably 75 to 90% by mass, and particularly preferably 78 to 86% by mass. The proportion of the intermediate layer (RP-b) in the multilayered rubber particle (RP) having three or more layers is preferably 40 to 60% by mass, more preferably 45 to 55% by mass. By having the proportion of the intermediate layer (RP-b) within this range, the surface hardness of the (meth)acrylic resin-containing layer can be increased, making the (meth)acrylic resin-containing layer less likely to crack.

[0041] The constituent polymer of the outermost layer (RP-c) contains MMA units and may further contain one or more other monomer units as necessary. The content of MMA units in the constituent polymer of the outermost layer (RP-c) is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and particularly preferably 90 to 100% by mass. The proportion of the outermost layer (RP-c) in the multilayered particle (RP) having three or more layers is preferably 35 to 50% by mass, more preferably 37 to 45% by mass. By having the proportion of the outermost layer (RP-c) within this range, the surface hardness of the (meth)acrylic resin-containing layer can be increased, making the (meth)acrylic resin-containing layer less likely to crack.

[0042] The particle size of the multilayered rubber particles (RP) is not particularly limited, and is preferably 0.05 to 0.3 μm, more preferably 0.08 to 0.25 μm, and particularly preferably 0.08 to 0.13 μm. The particle size can be measured by known methods such as electron microscope observation and dynamic light scattering measurement. Measurement by electron microscope observation can be performed, for example, by selectively staining a specific layer of the multilayered rubber particles (RP) using an electron staining method, measuring the particle sizes of multiple particles using a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and calculating the average value. Dynamic light scattering is a measurement method that utilizes the principle that the larger the particle size, the greater the Brownian motion of the particles.

[0043] The multilayered rubber particles (RP) can be used in the form of a latex or powder containing the multilayered rubber particles (RP) and dispersion particles (D) to prevent deterioration in handleability due to adhesion between the multilayered rubber particles (RP) and deterioration in impact resistance due to poor dispersion during melt-kneading. The dispersion particles (D) are, for example, made of a (co)polymer of one or more monomers, primarily MMA, and can have a particle size relatively smaller than that of the multilayered rubber particles (RP).

[0044] The particle size of the dispersing particles (D) is preferably as small as possible from the viewpoint of improving dispersibility, and from the viewpoint of production reproducibility by emulsion polymerization, it is preferably 40 to 120 nm, more preferably 50 to 100 nm. The amount of the dispersing particles (D) added is preferably 10 to 50 mass%, more preferably 20 to 40 mass%, based on the total amount of the multilayer-structured rubber particles (RP) and the dispersing particles (D), from the viewpoint of the dispersibility improving effect.

[0045] <(Meth)acrylic Resin Composition (MR)> In another embodiment of the present invention, the (meth)acrylic resin-containing layer can contain a (meth)acrylic resin composition (MR) (hereinafter also simply referred to as resin composition (MR)) containing a (meth)acrylic resin (PM) and an SMA resin. Examples of the "SMA resin" include a binary copolymer containing structural units derived from one or more aromatic vinyl compounds (II) and structural units derived from one or more acid anhydrides (III) including maleic anhydride (MAh), and a terpolymer containing structural units derived from one or more aromatic vinyl compounds (II), structural units derived from one or more acid anhydrides (III) including maleic anhydride (MAh), and structural units derived from a (meth)acrylic acid ester.

[0046] From the viewpoint of setting the glass transition temperature (Tg(M)) to 122°C or higher, the content of the (meth)acrylic resin (PM) in the resin composition (MR) is preferably 5 to 90 mass%, more preferably 5 to 55 mass%, and particularly preferably 10 to 50 mass%, and the content of the SMA resin in the resin composition (MR) is preferably 95 to 10 mass%, more preferably 95 to 45 mass%, and particularly preferably 90 to 50 mass%.

[0047] Examples of the aromatic vinyl compound (II) include styrene (St); nuclear-alkyl-substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, and 4-tert-butylstyrene; and α-alkyl-substituted styrenes such as α-methylstyrene and 4-methyl-α-methylstyrene. Among these, styrene (St) is preferred from the viewpoint of availability. From the viewpoints of the transparency and moisture resistance of the resin composition (MR), the content of aromatic vinyl compound (II) monomer units in the SMA resin is preferably 50 to 85% by mass, more preferably 55 to 82% by mass, and particularly preferably 60 to 80% by mass. From the viewpoint of availability, at least maleic anhydride (MAh) is used as the acid anhydride (III), and other acid anhydrides such as citraconic anhydride and dimethylmaleic anhydride can be used as necessary. From the viewpoint of the transparency and heat resistance of the resin composition (MR), the content of the acid anhydride (III) monomer unit in the SMA resin is preferably 15 to 50 mass%, more preferably 18 to 45 mass%, and particularly preferably 20 to 40 mass%.

[0048] As the (meth)acrylic acid ester, MMA is preferred from the viewpoints of the heat resistance and transparency of the SMA resin. From the viewpoints of the bending processability and transparency of the extruded resin laminate film, the content of (meth)acrylic acid ester monomer units in the SMA resin is preferably 1 to 35 mass%, more preferably 3 to 30 mass%, and particularly preferably 5 to 26 mass%. In this case, the content of aromatic vinyl compound (II) monomer units is preferably 50 to 84 mass%, and the content of acid anhydride (III) monomer units is preferably 15 to 49 mass%.

[0049] The SMA resin may have structural units derived from other monomers in addition to the aromatic vinyl compound (II), acid anhydride (III), and (meth)acrylic acid ester. The content of other monomer units in the SMA resin is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less. The other monomers can be selected from the group of monomers excluding the aromatic vinyl compound (II) and acid anhydride (III) from the examples of other monomers given in the description of the (meth)acrylic resin (PM).

[0050] SMA resins are obtained by polymerizing an aromatic vinyl compound (II), an acid anhydride (III), optionally a (meth)acrylic acid ester, and optionally other monomers. In this polymerization, typically, a monomer mixture is prepared by mixing multiple types of monomers, and then polymerization is carried out. The polymerization method is not particularly limited, and from the viewpoint of productivity, radical polymerization methods such as bulk polymerization and solution polymerization are preferred. Commercially available SMA resins may be used. Examples include "Resify (registered trademark)" manufactured by Denki Kagaku Kogyo Co., Ltd. and "XIRAN (registered trademark)" manufactured by Polyscope.

[0051] The Mw of the SMA resin is preferably 40,000 to 300,000. When the Mw is 40,000 or more, the (meth)acrylic resin-containing layer has excellent scratch resistance and impact resistance, and when the Mw is 300,000 or less, the (meth)acrylic resin-containing layer has excellent formability.

[0052] The resin composition (MR) can be obtained, for example, by mixing a (meth)acrylic resin (PM) and an SMA resin. Examples of mixing methods include melt mixing and solution mixing. In the melt mixing method, a melt mixer such as a single-screw or multi-screw kneader, an open roll, a Banbury mixer, or a kneader can be used, and melt mixing can be performed under an inert gas atmosphere such as nitrogen gas, argon gas, or helium gas, as necessary. In the solution mixing method, the (meth)acrylic resin (PM) and the SMA resin can be dissolved in an organic solvent such as toluene, tetrahydrofuran, or methyl ethyl ketone and mixed.

[0053] <Infrared Absorbent> The (meth)acrylic resin-containing layer may contain one or more infrared absorbents. In this case, the extruded resin laminate film of the present disclosure can block at least a portion of infrared rays. For example, when the extruded resin laminate film of the present disclosure is used as a cover member for the housing of a head-up display (HUD) device, the temperature inside the housing can be prevented from rising due to infrared rays contained in external light, which can damage the display system and optical system inside the housing. When the (meth)acrylic resin-containing layer contains an infrared absorbent, from the viewpoint of infrared shielding effect, the extruded resin laminate film of the present disclosure preferably has a transmittance at a wavelength of 1500 nm of 60% or less, more preferably 50% or less. When the (meth)acrylic resin-containing layer contains an infrared absorbent, the extruded resin laminate film of the present disclosure preferably has a total light transmittance (Tt) of 80% or more. When used as a cover member for the housing of a head-up display (HUD) device, the total light transmittance (Tt) is preferably 80% or more, and the transmittance at a wavelength of 1500 nm is preferably 60% or less.

[0054] As the infrared absorbing agent, a known one can be used. ｙ O ｚ (wherein W is tungsten, O is oxygen, and 2.2≦z / y≦2.999), tungsten oxide fine particles represented by the general formula M ｘ W ｙ O ｚ (wherein M is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals, and rare earth elements; W is tungsten; O is oxygen; and 0.001≦x / y≦1, 2.2≦z / y≦3), ３ (wherein X is at least one metal element selected from the group consisting of Ni, Co, Fe, and Mn), ｍ(wherein X is at least one metal element selected from the group consisting of Y, Sr, Ca, and lanthanoids, and 4.0≦m≦6.2), indium tin oxide (ITO) fine particles, and at least one fine particle selected from the group consisting of antimony tin oxide (ATO) fine particles are preferred.

[0055] The concentration of the infrared absorber contained in the (meth)acrylic resin-containing layer can be designed depending on the thickness of the (meth)acrylic resin-containing layer so that the transmittance of the extruded resin laminate film at a wavelength of 1500 nm is 60% or less. Depending on the thickness of the (meth)acrylic resin-containing layer, the concentration is preferably 0.01 to 2.00% by mass, more preferably 0.01 to 1.00% by mass, particularly preferably 0.05 to 0.50% by mass, and most preferably 0.10 to 0.30% by mass. Layers containing the infrared absorber may absorb infrared rays during weather resistance testing, thereby increasing their temperature and accelerating degradation reactions of resins, etc. Adding the infrared absorber to the (meth)acrylic resin-containing layer, which has excellent weather resistance, rather than the polycarbonate-containing layer, which has poor weather resistance, can suppress discoloration (coloration) during weather resistance testing. The timing of adding the infrared absorber may be during or after polymerization of resins such as the (meth)acrylic resin (PM), the (meth)acrylic resin (A), the SMA resin, and the multilayer-structured rubber particles (RP), or may be during or after mixing of multiple types of resins.

[0056] The (meth)acrylic resin-containing layer may optionally contain one or more polymers other than the (meth)acrylic resin. The other polymers are not particularly limited, and examples thereof include other thermoplastic resins such as polyolefins (e.g., polyethylene and polypropylene), polyamides, polyphenylene sulfide, polyether ether ketones, polyesters, polysulfones, polyphenylene oxides, polyimides, polyetherimides, and polyacetals; and thermosetting resins (e.g., phenolic resins, melamine resins, silicone resins, and epoxy resins). The content of the other polymers in the (meth)acrylic resin-containing layer is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

[0057] The (meth)acrylic resin-containing layer may contain various additives other than the infrared absorber, as needed. Examples of additives include antioxidants, heat degradation inhibitors, UV absorbers, light stabilizers, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, light diffusing agents, matting agents, block copolymers, and fluorescent materials. The content of the additives can be appropriately set within a range that does not impair the effects of the present invention. For example, the antioxidant content is preferably 0.01 to 1 part by weight, the UV absorber content is 0.01 to 3 parts by weight, the light stabilizer content is 0.01 to 3 parts by weight, the lubricant content is 0.01 to 3 parts by weight, and the dye / pigment content is 0.01 to 3 parts by weight, relative to 100 parts by weight of the resin constituting the (meth)acrylic resin-containing layer.

[0058] From the viewpoint of stability in hot melt molding, the melt flow rate (MFR) of the constituent resin of the (meth)acrylic resin-containing layer is preferably 1 to 10 g / 10 min, more preferably 1.5 to 7 g / 10 min, and particularly preferably 2 to 4 g / 10 min. Unless otherwise specified herein, the MFR of the constituent resin of the (meth)acrylic resin-containing layer is a value measured using a melt indexer at a temperature of 230°C under a load of 3.8 kg.

[0059] (Polycarbonate-Containing Layer) The polycarbonate-containing layer contains one or more polycarbonates (PC). The polycarbonate (PC) is preferably obtained by copolymerizing one or more dihydric phenols with one or more carbonate precursors. Examples of production methods include an interfacial polymerization method in which an aqueous solution of a dihydric phenol is reacted with an organic solvent solution of a carbonate precursor at an interface, and a transesterification method in which a dihydric phenol is reacted with a carbonate precursor under high temperature, reduced pressure, and solvent-free conditions.

[0060] Examples of dihydric phenols include 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfide, and bis(4-hydroxyphenyl)sulfone, with bisphenol A being preferred. Examples of carbonate precursors include carbonyl halides such as phosgene; carbonate esters such as diphenyl carbonate; and haloformates such as dihaloformates of dihydric phenols.

[0061] The Mw of the polycarbonate (PC) is preferably 10,000 to 100,000, more preferably 20,000 to 70,000. When the Mw is 10,000 or more, the polycarbonate-containing layer has excellent impact resistance and heat resistance, and when the Mw is 100,000 or less, the polycarbonate-containing layer has excellent moldability.

[0062] Commercially available polycarbonate (PC) products may be used, such as "Calibur (registered trademark)" and "SD Polyca (registered trademark)" manufactured by Sumika Styron Polycarbonate Co., Ltd., "Iupilon / Novarex (registered trademark)" manufactured by Mitsubishi Engineering Plastics Corporation, "Toughlon (registered trademark)" manufactured by Idemitsu Kosan Co., Ltd., and "Panlite (registered trademark)" manufactured by Teijin Chemicals Limited.

[0063] The polycarbonate-containing layer may optionally contain one or more other polymers and / or various additives. The other polymers and various additives may be the same as those described above in the description of the (meth)acrylic resin-containing layer. The content of the other polymer in the polycarbonate-containing layer is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The content of the additives can be appropriately set within a range that does not impair the effects of the present invention. Per 100 parts by mass of polycarbonate (PC), the content of the antioxidant is preferably 0.01 to 1 part by mass, the content of the ultraviolet absorber is 0.01 to 3 parts by mass, the content of the light stabilizer is 0.01 to 3 parts by mass, the content of the lubricant is 0.01 to 3 parts by mass, and the content of the dye / pigment is preferably 0.01 to 3 parts by mass. When other polymers and / or additives are added to the polycarbonate (PC), the addition may be performed during or after polymerization of the polycarbonate (PC).

[0064] The glass transition temperature Tg(PC) of the polycarbonate-containing layer is preferably 120 to 160°C, more preferably 135 to 155°C, and particularly preferably 140 to 150°C. From the viewpoint of stability in hot melt molding, the MFR of the constituent resin of the polycarbonate-containing layer is preferably 1 to 30 g / 10 min, more preferably 3 to 20 g / 10 min, and particularly preferably 5 to 10 g / 10 min. In this specification, unless otherwise specified, the MFR of the constituent resin of the polycarbonate-containing layer is a value measured using a melt indexer at a temperature of 300°C and under a load of 1.2 kg.

[0065] (Thickness Relationship) The extruded resin laminate film of the present disclosure has a total thickness of 0.1 to 0.8 mm. If the total thickness is too thin, defects such as cracks may occur during thermoforming, while if it is too thick, moldability may be impaired, such as difficulty in forming fine shapes during thermoforming. In the extruded resin laminate film of the present disclosure, the thickness of the (meth)acrylic resin-containing layer is 0.04 mm or more from the viewpoints of scratch resistance and impact resistance. In the extruded resin laminate film of the present disclosure, the ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness is 50% or less, preferably 49% or less, more preferably 45% or less, and particularly preferably 40% or less, from the viewpoint of suppressing warpage due to thermal changes. In the extruded resin laminate film of the present disclosure, the thickness of the (meth)acrylic resin-containing layer is 0.4 mm or less.

[0066] (Laminate Structure) The extruded resin laminate film of the present disclosure may have other resin layers, as long as a (meth)acrylic resin-containing layer is laminated on at least one side of the polycarbonate-containing layer. Examples of the laminate structure of the extruded resin laminate film of the present disclosure include a two-layer structure of a polycarbonate-containing layer and a (meth)acrylic resin-containing layer, a three-layer structure of a (meth)acrylic resin-containing layer, a polycarbonate-containing layer and a (meth)acrylic resin-containing layer, a three-layer structure of a (meth)acrylic resin-containing layer, a polycarbonate-containing layer and another resin layer, and a three-layer structure of another resin layer, a (meth)acrylic resin-containing layer and a polycarbonate-containing layer.

[0067] 1 and 2 are schematic cross-sectional views of extruded resin laminate films according to first and second embodiments of the present invention. In the figures, reference numerals 16X and 16Y denote extruded resin laminate films, reference numeral 21 denotes a polycarbonate-containing layer, and reference numerals 22, 22A, and 22B denote (meth)acrylic resin-containing layers. The extruded resin laminate film 16X of the first embodiment has a two-layer structure of a polycarbonate-containing layer 21 and a (meth)acrylic resin-containing layer 22. The extruded resin laminate film 16Y of the second embodiment has a three-layer structure of a first (meth)acrylic resin-containing layer 22A, a polycarbonate-containing layer 21, and a second (meth)acrylic resin-containing layer 22B. The configuration of the extruded resin laminate film can be modified as needed.

[0068] (Cured Coating) A cured coating can be provided on at least one surface of the extruded resin laminate film of the present disclosure. The cured coating can function as an abrasion-resistant layer or a low-reflectivity layer for improving visibility. The cured coating can be formed by a known method. In applications such as protective films for liquid crystal displays and cover members for HUDs, it is preferable to provide an abrasion-resistant layer on the outermost surface of the extruded resin laminate film from the viewpoint of preventing scratches. The extruded resin laminate film with an abrasion-resistant layer of the present disclosure is provided with an abrasion-resistant layer on at least one surface of the extruded resin laminate film of the present disclosure described above.

[0069] Materials for the cured coating include inorganic, organic, organic-inorganic, and silicone-based materials, with organic and organic-inorganic materials being preferred from the viewpoint of productivity.

[0070] The inorganic hardened coating is, for example, SiO ２ , Al ２ O ３ , TiO ２ , and ZrO ２These can be formed by forming a film of an inorganic material such as a metal oxide by vapor-phase deposition such as vacuum deposition or sputtering. Organic cured coatings can be formed, for example, by applying a coating material containing a resin such as a melamine resin, an alkyd resin, a urethane resin, or an acrylic resin and then heat-curing it, or by applying a coating material containing a polyfunctional acrylic resin and then UV-curing it. Organic-inorganic cured coatings can be formed, for example, by applying a UV-curable hard coat coating containing inorganic ultrafine particles such as silica ultrafine particles with photopolymerization-reactive functional groups introduced onto their surfaces and a curable organic component, and then polymerizing the curable organic component with the photopolymerization-reactive functional groups of the inorganic ultrafine particles by UV irradiation. This method results in a network-like crosslinked coating film in which the inorganic ultrafine particles are dispersed in an organic matrix while chemically bonded to the organic matrix. Silicone cured coatings can be formed, for example, by polycondensation of partial hydrolysates of carbon functional alkoxysilanes, alkyltrialkoxysilanes, tetraalkoxysilanes, etc., or materials in which these are combined with colloidal silica. In the above method, examples of the coating method for the material include dip coating, various roll coating methods such as gravure roll coating, flow coating, rod coating, blade coating, spray coating, die coating, and bar coating.

[0071] The thickness of the scratch-resistant (hard coat) cured coating (scratch-resistant layer) is preferably 2 to 30 μm, more preferably 5 to 20 μm. If it is too thin, the surface hardness will be insufficient, and if it is too thick, cracks may occur due to bending during the manufacturing process. The thickness of the low-reflectivity cured coating (low-reflectivity layer) is preferably 80 to 200 nm, more preferably 100 to 150 nm. If it is too thin or too thick, the low-reflectivity performance may be insufficient.

[0072] [Method for producing extruded resin laminate film] The method for producing the extruded resin laminate film of the present disclosure having the above-described configuration will be described below. The extruded resin laminate film of the present disclosure is produced by a production method including coextrusion molding. (Step (X)) The constituent resins of the polycarbonate-containing layer and the (meth)acrylic resin-containing layer are each heated and melted, and are coextruded in a molten state from a T-die having a wide discharge opening in the form of a thermoplastic resin laminate in which the (meth)acrylic resin-containing layer is laminated on at least one side of the polycarbonate-containing layer.

[0073] The molten resin for the polycarbonate-containing layer and the molten resin for the (meth)acrylic resin-containing layer are preferably melt-filtered through a filter before lamination. By using the melt-filtered molten resins to form a multilayer film, an extruded resin laminate film with fewer defects caused by foreign matter and gels can be obtained. The filter material is appropriately selected based on the operating temperature, viscosity, filtration accuracy, etc. Examples include nonwoven fabrics made of polypropylene, polyester, rayon, cotton, glass fiber, etc.; sheets made of phenolic resin-impregnated cellulose; sintered metal fiber nonwoven sheets; sintered metal powder sheets; wire mesh; and combinations thereof. Among these, from the viewpoint of heat resistance and durability, a filter made of multiple laminated sintered metal fiber nonwoven sheets is preferred. The filtration accuracy of the filter is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm or less, and particularly preferably 5 μm or less.

[0074] Examples of lamination methods include a feed block method in which lamination is performed before flowing into a T-die, and a multi-manifold method in which lamination is performed inside a T-die. The multi-manifold method is preferred from the viewpoint of improving the interfacial smoothness between layers of the extruded resin laminate film.

[0075] The molten thermoplastic resin laminate coextruded from a T-die is cooled using multiple cooling rolls. In the manufacturing method of the present disclosure, three or more adjacent cooling rolls are used, and the molten thermoplastic resin laminate is sandwiched between the nth (n≧1) cooling roll and the (n+1)th cooling roll, and the operation of wrapping the molten thermoplastic resin laminate around the (n+1)th cooling roll is repeated multiple times starting from n=1. For example, when three cooling rolls are used, the number of repetitions is two.

[0076] Examples of cooling rolls include rigid metal rolls and elastic metal rolls. Rigid metal rolls are inelastic rolls made of metals such as stainless steel, and include drilled rolls and spiral rolls. The surface of the rigid metal roll may be a mirror finish or may have a pattern or irregularities. Elastic metal rolls are rolls having an elastic outer cylinder made of a thin metal film on the outer periphery. For example, elastic metal rolls consist of a metal shaft roll made of stainless steel or the like, a thin metal film (elastic outer cylinder) made of stainless steel or the like covering the outer surface of the shaft roll, and a fluid sealed between the shaft roll and the thin metal film (elastic outer cylinder), and can exhibit elasticity in the presence of the fluid. Examples of fluids include water and oil. The thickness of the thin metal film of the elastic metal roll is not particularly limited, but is preferably about 2 to 8 mm. The thin metal film preferably has flexibility and bendability, and preferably has a seamless structure without welded joints. The metal elastic roll provided with such a metal thin film is excellent in durability, and can be handled in the same way as a normal mirror-finished roll if the metal thin film is mirror-finished. If a pattern, irregularities, or the like is imparted to the metal thin film, the roll can be made to transfer the shape, making it easy to use.

[0077] In the manufacturing method of the present disclosure, a metal elastic roll having an elastic outer sleeve made of a metal thin film on the outer periphery is used as the first cooling roll (also referred to as the first cooling roll), a metal rigid roll is used as the second cooling roll (also referred to as the second cooling roll), and the third cooling roll (also referred to as the third cooling roll) is not particularly limited, and a metal elastic roll or a metal rigid roll can be used.

[0078] The extruded resin laminate film obtained after cooling is taken up by a take-up roll. The above co-extrusion, cooling, and take-up steps are carried out continuously. In this specification, the heated and molten state is mainly referred to as a "thermoplastic resin laminate," and the solidified state is referred to as an "extruded resin laminate film," but there is no clear boundary between the two.

[0079] FIG. 3 shows a schematic diagram of a manufacturing apparatus including a T-die 11, first to third cooling rolls 12-14, and a pair of take-up rolls 15 as one embodiment. The thermoplastic resin laminate co-extruded from the T-die 11 is cooled using the first to third cooling rolls 12-14 and taken up by the pair of take-up rolls 15. In the illustrated example, the third cooling roll 14 is the "cooling roll around which the thermoplastic resin laminate is finally wrapped (also referred to as the last cooling roll)." Fourth and subsequent cooling rolls may be installed adjacent to the rear of the third cooling roll 14. In this case, the cooling roll around which the thermoplastic resin laminate is finally wrapped becomes the "last cooling roll." Note that, although transport rolls can be installed between multiple adjacent cooling rolls and take-up rolls as needed, the transport rolls are not included in the "cooling rolls." Note that the configuration of the manufacturing apparatus can be appropriately modified in design within the scope of the present invention.

[0080] <Regarding Retardation> "Retardation" is the phase difference between light in the direction of the molecular main chain and light in the direction perpendicular thereto. Generally, polymers can be formed into any shape by heating and melting them, but it is known that the stress generated during the heating and cooling process causes the molecules to orient, resulting in retardation. Therefore, in order to control retardation, it is necessary to control the molecular orientation. Molecular orientation is caused, for example, by stress during molding near the glass transition temperature (Tg) of the polymer. In this specification, "retardation" refers to in-plane retardation unless otherwise specified. Retardation may also be abbreviated as Re.

[0081] <Regarding Retardation Axis> The axis of in-plane retardation depends on the molecular orientation direction. When the orientation birefringence and photoelastic coefficient of a resin are positive values, the direction perpendicular to the molecular orientation direction is the fast axis, and the direction parallel to the molecular orientation direction is the slow axis. Conversely, when the orientation birefringence and photoelastic coefficient of a resin are negative values, the direction perpendicular to the molecular orientation direction is the slow axis, and the direction parallel to the molecular orientation direction is the fast axis. In other words, the fast axis and the slow axis are perpendicular to each other. Furthermore, the molecular orientation direction depends on the tensile direction, and generally, the direction parallel to the extrusion direction is the fast axis or the slow axis. Furthermore, generally, the orientation birefringence and photoelastic coefficient of polycarbonate are positive values, and the orientation birefringence and photoelastic coefficient of a (meth)acrylic resin are negative values.

[0082] In the case of the extruded resin laminate film of the present disclosure, the direction parallel to the extrusion direction is the slow axis due to the large influence of the orientation birefringence and photoelastic coefficient of the polycarbonate. Therefore, unless otherwise specified, in this specification, the retardation axis (Re axis) indicates the slow axis of in-plane retardation. Furthermore, in this specification, the angle of the retardation axis (Re axis) indicates the absolute value of the angle of the slow axis of in-plane retardation when the angle of the axis parallel to the extrusion direction is set to 0°.

[0083] <Cooling Roll> In the manufacturing method disclosed herein, a metal elastic roll is used as the first cooling roll and a metal rigid roll is used as the second cooling roll, and a thermoplastic resin laminate is sandwiched between these cooling rolls without forming a bank. A bank is a resin pool formed in the gap between the first and second cooling rolls. Conventionally, in extrusion resin film molding, metal rigid rolls are generally used as the first and second cooling rolls. In this case, to control the film thickness and obtain a good surface condition, molding is carried out while forming a bank between the first and second cooling rolls. In this conventional method, the bank contacts both the first and second cooling rolls. The surface of the bank is at a temperature near the glass transition temperature, generating a certain elongation stress, which affects the Re value and Re axis. Within the bank, a flow occurs perpendicular to the film surface, and the cross section maintains a constant state while swirling. The direction of this vortex is thought to have a significant impact on changes in the Re axis because the vortex maintains fluidity. As a result of extensive research based on this idea, the inventors have found that a suitable production method for reducing changes in the Re value and Re axis is to use an elastic metal roll as the first cooling roll and a rigid metal roll as the second cooling roll, without forming a bank between these cooling rolls.

[0084] <Re Value and Re Axis Angle> The present inventors have found that by optimizing the manufacturing conditions during extrusion molding, molecular orientation can be controlled, thereby controlling the Re value and Re axis angle of the extruded resin laminate film to be small. According to the present disclosure, an extruded resin laminate film having the following optical properties can be provided. The Re value of at least a portion of the extruded resin laminate film in the width direction of the present disclosure is 50 nm or less, and preferably 30 nm or less. The absolute value of the angle of the Re slow axis of the extruded resin laminate film of the present disclosure, when the angle of the axis parallel to the extrusion direction is 0°, is 10° or less, preferably 7° or less, more preferably 6° or less, particularly preferably 5° or less, and most preferably 4° or less.

[0085] <Total Temperature (TT) of Thermoplastic Resin Laminate When Peeling from the Last Chill Roll> In the manufacturing method of the present disclosure, the total temperature (TT) of the thermoplastic resin laminate when peeling from the last chill roll (the third chill roll in FIG. 3 ) is set to a range of −40 to −5°C relative to the glass transition temperature (Tg(PC)) of the polycarbonate-containing layer. The temperature (TT) is preferably −25 to −10°C relative to Tg(PC)). If the temperature TT is too low relative to Tg(PC), the shape of the last chill roll (the third chill roll in FIG. 3 ) may be transferred to the extruded resin laminate film, resulting in significant warpage. On the other hand, if the temperature TT at the time of contact with the last chill roll (the third chill roll in FIG. 3 ) is too high, the change in the Re axis of the extruded resin laminate film may be significant. The temperature (TT) is measured by the method described in the Examples section below.

[0086] <Relationship Between Peripheral Speed ​​Ratio, Re Value, and Re Axis> In this specification, unless otherwise specified, the "peripheral speed ratio" refers to the ratio of the peripheral speed of any other cooling roll or take-up roll to the second cooling roll. The peripheral speed of the second cooling roll is represented as V2, the peripheral speed of the third cooling roll as V3, and the peripheral speed of the take-up roll as V4. In the manufacturing method of the present disclosure, the overall temperature (TT) of the thermoplastic resin laminate when peeled from the last cooling roll (the third cooling roll in FIG. 3) is adjusted to a range of -40°C to -5°C relative to the glass transition temperature (Tg(PC)) of the polycarbonate-containing layer.

[0087] The inventors have conducted various evaluations of the relationship between the peripheral speed ratio (V3 / V2) of the third chill roll relative to the second chill roll and the peripheral speed ratio (V4 / V2) of the take-up roll relative to the second chill roll, and the Re value. As a result, it was found that changes in the peripheral speed ratio (V3 / V2) and the peripheral speed ratio (V4 / V2) have a significant effect on the Re value. It was also found that in order to stably maintain the Re value of at least a portion of the width direction at 50 nm or less, it is necessary to set both the peripheral speed ratio (V3 / V2) and the peripheral speed ratio (V4 / V2) to 0.980 to 1.000. The peripheral speed ratio (V3 / V2) and the peripheral speed ratio (V4 / V2) are preferably 0.980 to 0.999. Regarding the change in the Re axis, it was found that the influence of changes in the peripheral speed ratio (V3 / V2) and the peripheral speed ratio (V4 / V2) was small as long as the overall temperature (TT) of the thermoplastic resin laminate was within a range of −40°C to −5°C relative to the glass transition temperature (Tg(PC)) of the polycarbonate-containing layer.

[0088] <Relationship between Temperature (TT), Peripheral Speed ​​Ratio, Re Value, and Re Axis Direction> It was found that when molding was performed under conditions where the overall temperature (TT) of the thermoplastic resin laminate when peeled from the final cooling roll (the third cooling roll in FIG. 3 ) was outside the range of −40 to −5° C. relative to Tg(PC), there was a tendency for the change in the Re axis to be large. When the thermoplastic resin laminate was peeled from the final cooling roll while the resin temperature was high, the resin was not sufficiently restrained, and therefore the resin was affected by the peripheral speed ratio (V4 / V2) not only in the extrusion direction but also in the width direction, which is thought to be why there was a tendency for the change in the Re axis to be large.

[0089] <In-plane retardation value (Re value)> In extruded resin laminate films for curved surface processing (for hot bending) used as protective films for curved liquid crystal displays and touch panel displays, etc., a small Re value is preferred, taking into consideration the optical distortion that occurs during hot bending. Specifically, the Re value of at least a portion of the extruded resin laminate film in the width direction is preferably 50 nm or less, more preferably 30 nm or less. If the Re value exceeds 50 nm, optical distortion is caused by the stress during hot bending, and when the displayed image is viewed through a polarizing filter such as polarized sunglasses, rainbow unevenness patterns may occur, reducing visibility.

[0090] In extruded resin laminate films used as cover members for in-vehicle head-up display (HUD) devices, etc., a small Re value is preferable from the viewpoint of reducing optical distortion. Specifically, the Re value of at least a portion of the width direction of the extruded resin laminate film is preferably 50 nm or less, more preferably 30 nm or less. Furthermore, the absolute value of the angle of the slow axis of Re, when the angle of the axis parallel to the extrusion direction is 0°, is preferably 10° or less, more preferably 7° or less, even more preferably 6° or less, particularly preferably 5° or less, and most preferably 4° or less. If the Re value exceeds 50 nm and the absolute value of the angle of the slow axis of Re exceeds 10°, rainbow unevenness or the like may occur when the displayed image is viewed through a polarized filter such as polarized sunglasses, and visibility may be reduced.

[0091] <Warpage of Extruded Resin Laminate Film> In the manufacturing method of the present disclosure, the difference in glass transition temperature between the polycarbonate-containing layer and the (meth)acrylic resin-containing layer is relatively small, the ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness is 50% or less, and the overall temperature (TT) of the thermoplastic resin laminate when peeled from the final cooling roll is −40 to −5°C lower than the glass transition temperature of the polycarbonate-containing layer. Manufacturing under these conditions can provide an extruded resin laminate film with minimal warpage due to thermal changes. Specifically, an extruded resin laminate film can be provided in which a square test piece with a side length of 10 cm exhibits a warpage of 5 mm or less after heating at 90°C for 10 minutes.

[0092] As described above, the present disclosure provides an extruded resin laminate film and a method for producing the same, which includes a polycarbonate-containing layer and a (meth)acrylic resin-containing layer, exhibiting small changes in optical distortion (retardation) and in-plane optical distortion axis orientation, and suppressed warpage due to thermal changes. The extruded resin laminate film of the present disclosure has a (meth)acrylic resin-containing layer laminated on at least one side of the polycarbonate-containing layer, and therefore exhibits excellent gloss, transparency, heat resistance, impact resistance, and scratch resistance. The extruded resin laminate film of the present disclosure exhibits low warpage due to thermal changes, thereby suppressing changes in optical distortion and in-plane optical distortion axis orientation, even when subjected to curved surface processing (bending). The extruded resin laminate film of the present disclosure exhibits low warpage due to thermal changes, and therefore can withstand heating during processes such as forming a cured coating that functions as an abrasion-resistant layer and during thermoforming, thereby exhibiting excellent productivity, durability, and thermoforming processability. The extruded resin laminate film of the present disclosure is suitable for use as a protective film for liquid crystal displays and touch panel displays, and as a cover member for head-up displays (HUDs). The extruded resin laminate film of the present disclosure has small changes in the optical distortion (phase difference) and the orientation axis of in-plane optical distortion, and therefore, in the above-mentioned applications, good visibility can be obtained even when the display screen is viewed through a polarized filter such as polarized sunglasses. The extruded resin laminate film of the present disclosure has small changes in the optical distortion (phase difference) and the orientation axis of in-plane optical distortion, and is less susceptible to warping due to thermal changes, and therefore, even when curved (bending) is performed, good visibility can be obtained even when the display screen is viewed through a polarized filter such as polarized sunglasses.

[0093] [Applications] The extruded resin laminate film of the present disclosure can be used for any application. The extruded resin laminate film of the present disclosure is suitable as a protective film for curved liquid crystal displays, touch panel displays, and the like. For example, it is suitable as a protective film for curved liquid crystal displays, touch panel displays, and the like used in ATMs of financial institutions such as banks; vending machines; digital information devices such as mobile phones (including smartphones), personal digital assistants (PDAs) such as tablet personal computers, digital audio players, portable game consoles, copiers, fax machines, and car navigation systems. The extruded resin laminate film of the present disclosure is also suitable as a cover member for an in-vehicle head-up display (HUD) device.

[0094] Examples and comparative examples according to the present invention will be described. [Evaluation items and evaluation methods] The evaluation items and evaluation methods are as follows. (Copolymer composition of SMA resin) The copolymer composition of SMA resin was measured using a nuclear magnetic resonance spectrometer ("GX-270" manufactured by JEOL Ltd.) according to the following procedure. １３ The sample solution was prepared by dissolving 1.5 g of SMA resin in 1.5 ml of deuterated chloroform, and the sample was analyzed under the conditions of room temperature and 4000 to 5000 cycles. １３ The C-NMR spectrum was measured and the following values ​​were determined: [Integrated intensity of the carbon peak (near 127, 134, and 143 ppm) of the benzene ring (carbon number: 6) in the styrene unit] / 6; [Integrated intensity of the carbon peak (near 170 ppm) of the carbonyl moiety (carbon number: 2) in the maleic anhydride unit] / 2; [Integrated intensity of the carbon peak (near 175 ppm) of the carbonyl moiety (carbon number: 1) in the MMA unit] / 1. The molar ratios of styrene units, maleic anhydride units, and MMA units in the sample were determined from the area ratios of the above values. The mass composition of each monomer unit in the SMA resin was determined from the obtained molar ratio and the mass ratio of each monomer unit (styrene unit:maleic anhydride unit:MMA unit = 104:98:100).

[0095] (Weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn)) The Mw of the resin and the molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), were determined by GPC using the following procedure. Tetrahydrofuran was used as the eluent, and two "TSKgel SuperMultipore HZM-M" columns manufactured by Tosoh Corporation and a "SuperHZ4000" column connected in series were used. The GPC apparatus used was an HLC-8320 (product number) manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector). A sample solution was prepared by dissolving 4 mg of resin in 5 ml of tetrahydrofuran. The column oven temperature was set to 40 ° C, and 20 μl of the sample solution was injected at an eluent flow rate of 0.35 ml / min, and the chromatogram was measured. Ten standard polystyrenes with molecular weights ranging from 400 to 5,000,000 were measured by GPC, and a calibration curve showing the relationship between retention time and molecular weight was prepared. Mw and Mw / Mn were determined based on this calibration curve.

[0096] (Syndiotacticity (rr) (rr ratio) in triad notation) A (meth)acrylic resin was dissolved in deuterated chloroform to prepare a sample solution. The obtained sample solution was analyzed using a nuclear magnetic resonance spectrometer (ULTRA SHIELD 400 PLUS manufactured by Bruker) at room temperature with 64 accumulations. １ The H-NMR spectrum was measured. From the spectrum, the area (A0) of the region from 0.6 to 0.95 ppm and the area (AY) of the region from 0.6 to 1.35 ppm, when TMS was set to 0 ppm, were measured, and then the syndiotacticity (rr) expressed in triad form was calculated using the formula: (A0 / AY)×100.

[0097] (Glass transition temperature (Tg)) 10 mg of resin (composition) was placed in an aluminum pan and measured using a differential scanning calorimeter ("DSC-50", manufactured by Rigaku Corporation). After nitrogen substitution for 30 minutes or more, the sample was heated from 25°C to 200°C at a rate of 20°C / min in a nitrogen stream of 10 ml / min, held for 10 minutes, and cooled to 25°C (primary scan). The sample was then heated to 200°C at a rate of 10°C / min (secondary scan), and the glass transition temperature (Tg) was calculated from the results obtained in the secondary scan using the midpoint method. Note that when multiple Tg data are obtained for a resin composition containing two or more resins, the value derived from the resin of the main component was used as the Tg data.

[0098] (Average particle size of multilayered rubber particles (RP)) Ultrathin sections were cut from an extruded resin laminate film containing multilayered rubber particles (RP) using a diamond knife, and the butyl acrylate portion was selectively stained with phosphotungstic acid. After that, images were taken using a transmission electron detector on a scanning electron microscope (SEM) (JEOL Ltd., "JSM-7600"). Thirty multilayered rubber particles (RP) showing an image of the entire particle were randomly selected, and the diameter of the stained portion of each particle was measured, and the average value was taken as the average particle size.

[0099] (Warpage of extruded resin laminate film) A square test piece with a side length of 10 cm was cut from the obtained extruded resin laminate film so as to pass through the center of the width direction of the extruded resin laminate film. All sides were parallel or perpendicular to the extrusion direction. The obtained test piece was left in a heating oven at 90°C for 10 minutes, then removed from the heating oven and left in an environment of 23°C ± 3°C for 10 minutes or more. Thereafter, the test piece was placed on a surface plate with the methacrylic resin-containing layer as the uppermost layer, and the maximum gap between the test piece and the surface plate was measured using a thickness gauge. This value was taken as the warpage.

[0100] (Re Value and Re Axis Angle) From the obtained extruded resin laminate film, a square test piece with a side length of 10 cm was cut out so as to pass through the center in the width direction of the extruded resin laminate film. All sides were parallel or perpendicular to the extrusion direction. After leaving this test piece in an environment of 23°C ± 3°C for 10 minutes or more, the in-plane retardation value (Re value) and the absolute value of the angle of the in-plane retardation slow axis were measured using a "WPA-100(-L)" manufactured by Photonic Lattice Co., Ltd. The test piece was set so that the four sides of the test piece were horizontal or perpendicular to the measurement axis, and the angle of the axis where the extrusion direction was horizontal was defined as 0°.

[0101] (Total Temperature (TT) of Thermoplastic Resin Laminate) The total temperature (TT) of the thermoplastic resin laminate when peeled off from the third cooling roll was measured using an infrared radiation thermometer. The measurement position was the center of the extruded resin laminate film in the width direction.

[0102] (Total Light Transmittance (Tt)) A test piece measuring 50 mm x 50 mm was cut out from the obtained extruded resin laminate film. The total light transmittance (Tt) of the test piece was measured using "HM-150" manufactured by Murakami Color Research Laboratory.

[0103] (Transmittance at a wavelength of 1500 nm) A 50 mm x 50 mm test piece was cut out from the obtained extruded resin laminate film. Using a Shimadzu UV-3600 ultraviolet / visible / near-infrared spectrophotometer manufactured by Shimadzu Corporation, the absorption spectrum of the extruded resin laminate film in the wavelength range of 300 to 3000 nm was measured to determine the transmittance at a wavelength of 1500 nm. The lower the transmittance at a wavelength of 1500 nm, the higher the infrared shielding ability of the extruded resin laminate film.

[0104] [Materials] The materials used are as follows: <(Meth)acrylic resin> (PM1) In accordance with the method described in Production Example 2 of JP 2016-94550 A, a (meth)acrylic resin (PM1) (polymethyl methacrylate, PMMA) having Mw of 101,000, Mw / Mn of 1.87, rr ratio of 52.0%, Tg of 120°C, and MMA unit content of 100 mass% was obtained.

[0105] (A1) In accordance with the method described in Production Example 1 of JP2016-94550A, a (meth)acrylic resin (A1) (polymethyl methacrylate, PMMA) having Mw of 70,000, Mw / Mn of 1.05, rr ratio of 75.0%, Tg of 130°C, and a methyl methacrylate (MMA) unit content of 100 mass% was obtained.

[0106] (A2) 50 parts by mass of the (meth)acrylic resin (PM1) and 50 parts by mass of the (meth)acrylic resin (A1) were melt-kneaded to obtain a (meth)acrylic resin (A2) (polymethyl methacrylate, PMMA) having an rr ratio of 63.5% and a Tg of 125°C.

[0107] (A3) 80 parts by mass of the (meth)acrylic resin (PM1) and 20 parts by mass of the (meth)acrylic resin (A1) were melt-kneaded to obtain a (meth)acrylic resin (A3) (polymethyl methacrylate, PMMA) having an rr ratio of 56.6%, a Tg of 122°C, and a methyl methacrylate (MMA) unit content of 100% by mass.

[0108] <SMA Resin> (SMA1) An SMA resin (styrene-maleic anhydride-MMA copolymer, styrene unit / maleic anhydride unit / MMA unit (mass ratio) = 56 / 18 / 26, Mw = 150,000, Tg = 138°C) was obtained in accordance with the method described in WO 2010 / 013557.

[0109] (SMA2) "XIRAN (registered trademark) 23110" manufactured by POLYSCOPE was prepared.

[0110] <Methacrylic resin composition (MR)> The following two types of methacrylic resin compositions were obtained by melt-kneading a (meth)acrylic resin (PM1) and an SMA resin (SMA1) or (SMA2). The SMA ratio indicates the charge ratio (mass percentage) of the SMA resin to the total amount of the (meth)acrylic resin and the SMA resin. (MR1)(PM1) / (SMA1) resin composition (SMA ratio 70 mass%, Tg = 130°C), (MR2)(PM1) / (SMA2) resin composition (SMA ratio 50 mass%, Tg = 135°C).

[0111] <Multilayered Rubber Particles (RP)> (RP1) An innermost layer (RP-a1), a middle layer (RP-b1), and an outermost layer (RP-c1) made of a copolymer having the following composition were sequentially formed to produce a three-layered acrylic multilayered rubber particle (RP1). The particle diameter was 0.23 μm. Innermost layer (RP-a1): methyl methacrylate (MMA) units / methyl acrylate (MA) units / allyl methacrylate units as a crosslinkable monomer (mass ratio) = 32.91 / 2.09 / 0.07; intermediate layer (RP-b1): butyl acrylate units / styrene units / allyl methacrylate units as a crosslinkable monomer (mass ratio) = 37.00 / 8.00 / 0.90; outermost layer (RP-c1): methyl methacrylate (MMA) units / methyl acrylate (MA) units (mass ratio) = 18.80 / 1.20.

[0112] <Dispersion Particles (D)> (D1) Methacrylic copolymer particles, methyl methacrylate (MMA) unit / methyl acrylate unit (mass ratio) = 90 / 10, particle diameter: 0.11 µm.

[0113] <Multilayered rubber particle-containing powder (RD1)> A latex containing multilayered rubber particles (RP1) and a latex containing dispersing particles (D1) were mixed in a solids mass ratio of 67:33. The resulting mixed latex was frozen at -30°C for 4 hours. The frozen latex was added to 90°C warm water in an amount twice the amount of the frozen latex, dissolved to form a slurry, which was then dehydrated by holding at 90°C for 20 minutes and dried at 80°C to obtain a multilayered rubber particle-containing powder (RD1).

[0114] <Infrared Absorbent> Indium tin oxide (ITO) fine particles ("YMDS-874" manufactured by Sumitomo Metal Mining Co., Ltd.) were prepared as an infrared absorbent.

[0115] <Multilayered rubber particle-containing (meth)acrylic resin composition (MRD1)> 100 parts by mass of the (meth)acrylic resin (A2) and 12 parts by mass of the multilayered rubber particle-containing powder (RD1) were melt-kneaded to obtain a multilayered rubber particle-containing (meth)acrylic resin composition (MRD1).

[0116] <Infrared absorbent-added (meth)acrylic resin (A22)> 98 parts by mass of the (meth)acrylic resin (A2) and 2 parts by mass of the above infrared absorbent were melt-kneaded to obtain an infrared absorbent-added (meth)acrylic resin (A22).

[0117] <Polycarbonate (PC1)> "SD Polyca (registered trademark) PCX" manufactured by Sumika Styron Polycarbonate Co., Ltd. (MFR = 6.7 g / 10 min at a temperature of 300°C under a load of 1.2 kg, Tg = 150°C).

[0118] Examples 1-14, Comparative Examples 1-6 (Production of Extruded Resin Laminate Films) Extruded resin laminate films were molded using a manufacturing apparatus such as that shown in FIG. 3. The material for the (meth)acrylic resin-containing layer, melted using a 65 mmφ single-screw extruder (manufactured by Toshiba Machine Co., Ltd.), and polycarbonate (PC1), melted using a 150 mmφ single-screw extruder (manufactured by Toshiba Machine Co., Ltd.), were laminated through a multi-manifold die, and a molten thermoplastic resin laminate was co-extruded from a T-die. The molten thermoplastic resin laminate was then sandwiched between adjacent first and second cooling rolls, wrapped around the second cooling roll, sandwiched between the second and third cooling rolls, and cooled by wrapping around the third cooling roll. The extruded resin laminate film obtained after cooling was taken up by a pair of take-up rolls. The polycarbonate-containing layer was in contact with the third cooling roll. In this manner, an extruded resin laminate film having a two-kind two-layer structure of a (meth)acrylic resin-containing layer-polycarbonate-containing layer laminate structure was obtained.

[0119] In each example, the (meth)acrylic resin-containing layer was made of a (meth)acrylic resin (A1), a multilayered rubber particle-containing (meth)acrylic resin composition (MRD1), an infrared absorber-added (meth)acrylic resin (A22), a (meth)acrylic resin composition (MR1), or a (meth)acrylic resin composition (MR2).

[0120] The following rigid metal rolls and elastic metal rolls were prepared as cooling rolls: (Rigid R) a commercially available rigid metal roll made of stainless steel, (Elastic R) a commercially available elastic metal roll made of stainless steel, a metal shaft roll made of stainless steel, a thin metal film (elastic outer cylinder) made of stainless steel covering the outer surface of the shaft roll, and a fluid sealed between the shaft roll and the thin metal film (elastic outer cylinder).

[0121] In each example, one or more of the following conditions were changed: the combination of the first and second cooling rolls; the peripheral speed ratio (V3 / V2) between the second and third cooling rolls; the peripheral speed ratio (V4 / V2) between the second and take-up rolls; the overall temperature (TT) of the thermoplastic resin laminate when peeled from the final cooling roll (specifically, the third cooling roll); the material of the (meth)acrylic resin-containing layer; the total thickness of the extruded resin laminate film; the thickness of the (meth)acrylic resin-containing layer; and the ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness. In each example, a metal elastic roll was used as the third cooling roll. In each example, it was visually confirmed that no bank was formed between the first and second cooling rolls. The overall temperature (TT) of the thermoplastic resin laminate when peeled from the final cooling roll was adjusted by controlling the temperatures of the second and third cooling rolls. Tables 1 to 3 show the main production conditions and the evaluation results of the resulting extruded resin laminate films. In each example, production conditions not listed in the tables were common conditions.

[0122]

[0123]

[0124]

[0125] [Summary of Results] In Examples 1 to 14, no bank was formed between the first and second cooling rolls, an elastic metal roll was used as the first cooling roll, a rigid metal roll was used as the second cooling roll, the overall temperature (TT) of the thermoplastic resin laminate when peeled from the last cooling roll was set to −40 to −5° C. relative to the glass transition temperature of the polycarbonate-containing layer, and V3 / V2 and V4 / V2 were both set to 0.980 to 1.000, thereby producing extruded resin laminate films in which a (meth)acrylic resin-containing layer was laminated on one side of the polycarbonate-containing layer. The extruded resin laminate films obtained in these examples had a total thickness of 0.1 to 0.8 mm, a (meth)acrylic resin-containing layer thickness of 0.04 mm or more, a ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness of 50% or less, an in-plane retardation value of 50 nm or less in at least a portion of the width direction, an absolute value of the angle of the slow axis of the in-plane retardation when the angle of the axis parallel to the extrusion direction is 0° or less of 10° or less, and an amount of warpage of 5 mm or less after heating a square test piece with a side length of 10 cm at 90°C for 10 minutes. In these examples, extruded resin laminate films were produced in which the change in optical distortion (retardation) and the orientation axis of in-plane optical distortion were small, and warpage due to thermal changes was suppressed.

[0126] In Comparative Example 1 in which V3 / V2 was greater than 1.000 and Comparative Example 2 in which V4 / V2 was greater than 1.000, the extruded resin laminate films obtained had Re values ​​greater than 50 nm and were poor.

[0127] In Comparative Examples 3 and 6, the overall temperature (TT) of the thermoplastic resin laminate when peeled from the roll was set higher than the range of −40 to −5° C. relative to the glass transition temperature of the polycarbonate-containing layer. In Comparative Example 3, the thickness was also set to more than 0.8 mm. The extruded resin laminate films obtained in these Comparative Examples were poor in that the absolute value of the angle of the slow axis of the in-plane retardation, when the angle of the axis parallel to the extrusion direction was set to 0°, exceeded 10°.

[0128] In Comparative Example 4, in which the overall temperature (TT) of the thermoplastic resin laminate when peeled off from the final cooling roll was set to be lower than the range of −40 to −5° C. relative to the glass transition temperature of the polycarbonate-containing layer, the obtained extruded resin laminate film had a warpage of more than 5 mm after a square test piece with a side length of 10 cm was heated at 90° C. for 10 minutes, and was therefore unsatisfactory.

[0129] In Comparative Example 5, in which rigid metal rolls were used as the first and second cooling rolls, the extruded resin laminate film obtained had an Re value of more than 50 nm and was therefore unsatisfactory.

[0130] The present invention is not limited to the above-described embodiments and examples, and appropriate design changes are possible without departing from the spirit of the present invention.

[0131] This application claims priority based on Japanese Patent Application No. 2021-159709, filed on September 29, 2021, the disclosure of which is incorporated herein in its entirety.

[0132] REFERENCE SIGNS LIST 11 T-die 12 First cooling roll (first cooling roll) 13 Second cooling roll (second cooling roll) 14 Third cooling roll (third cooling roll) 15 Take-up roll 16 Extruded resin laminate film

Claims

1. A method for producing an extruded laminated resin film having a laminate structure in which a (meth)acrylic resin-containing layer is laminated on at least one surface of a polycarbonate-containing layer, comprising the steps of: the step of co-extruding a thermoplastic resin laminate having the laminate structure in a molten state from a T-die, using three or more cooling rolls adjacent to each other, sandwiching the thermoplastic resin laminate in the molten state between an n-th cooling roll (n≧1) and an n+1-th cooling roll, and winding the thermoplastic resin laminate around the n+1-th cooling roll, repeating this operation multiple times from n=1, and taking up the extruded resin laminate film obtained after cooling by a take-up roll, The thermoplastic resin laminate is sandwiched between the first cooling roll and the second cooling roll without forming a bank; The first cooling roll is a metal elastic roll having an elastic outer cylinder made of a metal thin film on its outer periphery, and the second cooling roll is a metal rigid roll, the total temperature (TT) of the thermoplastic resin laminate when peeled off from the final cooling roll is set to −40 to −5° C. with respect to the glass transition temperature of the polycarbonate-containing layer; a peripheral speed ratio (V3 / V2) between the peripheral speed (V3) of the third cooling roll and the peripheral speed (V2) of the second cooling roll, and a peripheral speed ratio (V4 / V2) between the peripheral speed (V4) of the take-up roll and the peripheral speed (V2) of the second cooling roll are each set to 0.980 to 1.000; the (meth)acrylic resin-containing layer has a thickness of 0.04 mm or more, the ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness is 50% or less, at least a part of the in-plane retardation value in the width direction is 50 nm or less, the absolute value of the angle of the slow axis of the in-plane retardation when the angle of the axis parallel to the extrusion direction is 0° is 10° or less, and a warpage amount of 5 mm or less after heating a square test piece having a side length of 10 cm at 90° C. for 10 minutes is 5 mm or less.

2. 2. The method for producing an extruded resin laminate film according to claim 1, wherein the extruded resin laminate film has a laminate structure in which the (meth)acrylic resin-containing layer containing the (meth)acrylic resin (A) having a syndiotacticity (rr) of 56% or more in triad notation is laminated on at least one side of the polycarbonate-containing layer.

3. The method for producing an extruded resin laminate film according to claim 2, wherein the (meth)acrylic resin (A) has a methyl methacrylate unit content of 90% by mass or more and a glass transition temperature of 122°C or more.

4. The method for producing an extruded laminated resin film according to claim 1 or 2, wherein the (meth)acrylic resin-containing layer contains multilayered rubber particles.

5. The method for producing an extruded resin laminate film according to claim 1, wherein the (meth)acrylic resin-containing layer contains 5 to 90% by mass of a (meth)acrylic resin and 95 to 10% by mass of a copolymer containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and has a glass transition temperature of 122°C or higher.

6. The method for producing an extruded resin laminate film according to claim 5, wherein the copolymer contains 50 to 85% by mass of structural units derived from the aromatic vinyl compound and 15 to 50% by mass of structural units derived from maleic anhydride.

7. The method for producing an extruded resin laminate film according to claim 6, wherein the copolymer contains 50 to 84 mass% of structural units derived from the aromatic vinyl compound, 15 to 49 mass% of structural units derived from maleic anhydride, and 1 to 35 mass% of structural units derived from a (meth)acrylic acid ester.

8. An extruded resin laminate film having a (meth)acrylic resin-containing layer laminated on at least one surface of a polycarbonate-containing layer, a total thickness of 0.1 to 0.8 mm, a thickness of the (meth)acrylic resin-containing layer of 0.04 mm or more, and a ratio of the total thickness of the (meth)acrylic resin-containing layer to the total thickness of the film of 50% or less; The (meth)acrylic resin-containing layer has a glass transition temperature of 122° C. or higher, The retardation value in at least a part of the plane in the width direction is 50 nm or less, the absolute value of the angle of the slow axis of in-plane retardation when the angle of the axis parallel to the extrusion direction is 0° is 10° or less; An extruded resin laminate film, in which a square test piece having a side length of 10 cm has a warpage of 5 mm or less after heating at 90° C. for 10 minutes.

9. The extruded resin laminate film according to claim 8 , wherein the difference between the glass transition temperature of the polycarbonate-containing layer and the glass transition temperature of the (meth)acrylic resin-containing layer is 28° C. or less.

10. the (meth)acrylic resin-containing layer contains an infrared absorbing agent, 10. The extruded resin laminate film according to claim 8, wherein the extruded resin laminate film has a total light transmittance of 80% or more and a transmittance at a wavelength of 1500 nm of 60% or less, and is for a head-up display device.

11. An extruded resin laminate film with an abrasion-resistant layer, comprising an abrasion-resistant layer on at least one surface of the extruded resin laminate film described in claim 8 or 9.