Resin laminate

Abstract

Provided is a resin laminate having at least one layer containing a polycarbonate resin (A) and another layer containing a thermoplastic resin (B) on the surface of the layer containing the polycarbonate resin (A), wherein the viscosity of the polycarbonate resin (A) is 3,700 to 15,000 [Pa・S] at a shear rate of 6.080 x 10[1 / S] measured at 260°C, and the thermoplastic resin (B) contains a styrene copolymer (C).

Description

Technical Field

[0001] This invention relates to a resin laminate comprising a layer containing a polycarbonate-based resin and a layer containing at least a styrene copolymer. More specifically, it relates to a resin laminate used in transparent substrate materials and protective materials. Background Technology

[0002] Acrylic resins possess excellent surface hardness, transparency, scratch resistance, and weather resistance. On the other hand, polycarbonate resins exhibit superior impact resistance. Therefore, laminates with acrylic and polycarbonate resin layers offer excellent surface hardness, transparency, scratch resistance, weather resistance, and impact resistance, making them suitable for display windows in automotive parts, home appliances, electronic devices, and portable information terminals.

[0003] In recent years, with the diversification of design requirements, display devices, such as front panels, have sought products with improved design flexibility through thermoforming methods such as vacuum forming or pressure forming. Considering the aforementioned superior performance, attempts have been made to apply laminates with acrylic and polycarbonate resin layers to front panels. However, when thermoforming these laminates, the sheet needs to be heated to a temperature at which the polycarbonate resin can fully elongate. Due to excessive heating of the acrylic resin, sometimes the interface between the acrylic and polycarbonate resin layers peels off, the surface whitens, or cracks appear.

[0004] As a resin with high heat resistance, a copolymer resin formed from styrene and maleic anhydride is known. Patent documents 1 and 2 disclose a resin molded article formed by incorporating a copolymer resin formed from styrene and maleic anhydride into a methacrylic resin. In addition, patent document 3 discloses a laminate having a layer containing a methacrylic resin and a copolymer resin formed from styrene and maleic anhydride, and a layer containing a polycarbonate resin.

[0005] However, in laminates having layers containing methacrylic resin and a copolymer resin formed from styrene and maleic anhydride, and layers containing polycarbonate resin, "transparent spots" originating from the copolymer resin formed from styrene and maleic anhydride ( Figure 1 A layer containing polycarbonate resin is inserted near the interface between the layer containing methacrylic acid resin and the copolymer resin formed from styrene and maleic anhydride and the layer containing polycarbonate resin. Figure 2 The interface becomes cluttered, producing stripes ("interface stripes") in the flow direction.

[0006] When there are many interface streaks, they look like surface scratches, which can be a fatal defect for transparent substrate materials and transparent protective materials.

[0007] Patent document 4 discloses adding a specific lubricant to a resin mixture containing methacrylic acid resin and a copolymer resin formed from styrene and maleic anhydride to suppress gel formation during melt molding. The "transparent spots" from the copolymer resin formed from styrene and maleic anhydride are generated during copolymer polymerization and are also present in the raw materials; therefore, even with the addition of a specific lubricant, "interface streaks" will still occur during laminate molding. Furthermore, even when the resin mixture containing methacrylic acid resin and the copolymer resin formed from styrene and maleic anhydride is passed through a polymer filter, the problem of "interface streaks" occurring during resin laminate molding persists.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2008-225452

[0011] Patent Document 2: Japanese Patent Application Publication No. 2011-116928

[0012] Patent Document 3: WO2015 / 050051 Publication

[0013] Patent Document 4: WO2016 / 132743 Summary of the Invention

[0014] The technical problem that the invention aims to solve

[0015] The technical problem to be solved by the present invention is to provide a resin laminate with high heat resistance and good appearance.

[0016] Technical solutions for solving technical problems

[0017] In order to solve the above-mentioned technical problems, the inventors of this invention have conducted repeated and meticulous research, and as a result, discovered that the above-mentioned technical problems can be solved by using the following invention. Specifically, the invention is as follows.

[0018] [1] A resin laminate having at least one side of a layer containing a polycarbonate resin (A) having a layer containing a thermoplastic resin (B), wherein the viscosity of the polycarbonate resin (A) at a shear rate of 6.080 × 10 [1 / S] measured at 260°C is 3,700 to 15,000 [Pa·S], and the thermoplastic resin (B) contains a styrene copolymer (C).

[0019] [2] The resin laminate as described in [1] above, wherein the thermoplastic resin (B) contains a styrene copolymer (C) and a methacrylic resin (D).

[0020] [3] The resin laminate as described in [2] above, wherein the thermoplastic resin (B) is a polymer alloy of the styrene copolymer (C) and the methacrylic resin (D).

[0021] [4] The resin laminate as described in any one of [1] to [3] above, wherein the viscosity of the thermoplastic resin (B) is 100 to 3,600 [Pa·S] when the shear rate is 6.080 × 10 [1 / S] as measured at 260°C.

[0022] [5] The resin laminate as described in any one of [1] to [4] above, wherein the melt flow rate of the polycarbonate resin (A) at 300°C and 1.2 kg load is 1.0 to 5.0 g / 10 min.

[0023] [6] The resin laminate as described in [2] or [3] above, wherein, based on a total of 100 parts by mass of the content of the styrene copolymer (C) and the methacrylic resin (D) in the thermoplastic resin (B), the content of the styrene copolymer (C) is 15 to 85 parts by mass and the content of the methacrylic resin (D) is 85 to 15 parts by mass.

[0024] [7] The resin laminate as described in any one of [1] to [6] above, wherein the styrene copolymer (C) is a copolymer containing 68 to 84% by mass of vinyl aromatic monomer units (c1) and 16 to 32% by mass of cyclic anhydride monomer units (c2).

[0025] [8] The resin laminate as described in [7] above, wherein the vinyl aromatic monomer unit (c1) contained in the styrene copolymer (C) is styrene.

[0026] [9] The resin laminate as described in [7] or [8] above, wherein the cyclic anhydride monomer unit (c2) contained in the styrene copolymer (C) is maleic anhydride.

[0027]

[10] The resin laminate as described in any one of [1] to [9] above, wherein at least one of the layers containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B) contains an ultraviolet absorber.

[0028]

[11] The resin laminate as described in any one of [1] to

[10] above, wherein one or both sides of the resin laminate are subjected to at least one of fingerprint-resistant treatment, anti-reflective treatment, anti-glare treatment, weather-resistant treatment, antistatic treatment and anti-fouling treatment.

[0029]

[12] The resin laminate as described in any one of [1] to

[11] above, wherein when a 297 mm × 210 mm prototype is visually inspected in a dark room with a three-wavelength fluorescent lamp in the lit state and an illuminance of 1,200 to 2,000 lux, the number of interface stripes is 5 or less.

[0030]

[13] A transparent substrate material comprising any one of the resin stacks described in [1] to

[12] above.

[0031]

[14] A transparent protective material comprising any one of the resin laminates described in any one of [1] to

[12] above.

[0032]

[15] A front protective plate for a touch panel, comprising the resin laminate described in any one of [1] to

[12] above.

[0033]

[16] A front panel for car navigation, OA equipment or portable electronic devices, comprising any of the resin laminates described in any one of [1] to

[12] .

[0034] Invention Effects

[0035] This invention provides a resin laminate with high heat resistance and a good appearance. Specifically, the resin laminate of this invention can be used as a transparent substrate material and a transparent protective material. Specifically, it can be suitable for use as a front panel protector in portable display devices such as mobile terminals, portable electronic game devices, portable information terminals, and mobile PCs, as well as in display devices such as laptop PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs. Attached Figure Description

[0036] Figure 1 These are microscope images of "transparent spots" from a copolymer resin formed from styrene and maleic anhydride.

[0037] Figure 2 This is a microscopic photograph of the "transparent spots" on the cross-section of the resin laminate where the interface stripes are generated.

[0038] Figure 3 This is a schematic diagram illustrating an example of a resin laminate manufacturing apparatus according to an embodiment. Detailed Implementation

[0039] The present invention will be described in detail below with examples of manufacturing and embodiments, but the present invention is not limited to the examples of manufacturing and embodiments shown. Any method can be used as long as it does not depart from the scope of the present invention.

[0040] <Polycarbonate Resin (A)>

[0041] The polycarbonate resin (A) used in this invention is a polycarbonate resin (A) with polycarbonate resin as the main component. "With polycarbonate resin as the main component" means that the content of polycarbonate resin is greater than 50% by mass. The polycarbonate resin (A) preferably contains 75% by mass or more of polycarbonate resin, more preferably 90% by mass or more of polycarbonate resin, and even more preferably is substantially composed of polycarbonate resin. The polycarbonate resin (A) contains carbonate bonds in its molecular backbone. That is, it is not particularly limited as long as it contains -[O-R-OCO]- units (where R represents an aliphatic group, an aromatic group, or a group containing both aliphatic and aromatic groups, or a group having a straight-chain structure or a branched structure), but it is particularly preferred to use polycarbonate containing structural units of the following formula (3). By using such polycarbonate, a resin laminate with excellent impact resistance can be obtained.

[0042]

[0043] Specifically, as a polycarbonate resin (A), an aromatic polycarbonate resin (such as Iupilon E-1000, commercially available from Mitsubishi Engineering Plastics Co., Ltd.) can be used.

[0044] In recent years, the demand for bending processing of front panels has gradually increased. Therefore, polycarbonate resin (A) is preferably synthesized using a monohydric phenol represented by the following general formula (4) as a terminator.

[0045]

[0046] (In the formula, R1 represents an alkyl group or an alkenyl group with 8 to 36 carbon atoms, and R2 to R5 represent hydrogen, halogen, or an alkyl group with 1 to 20 carbon atoms or an aryl group with 6 to 12 carbon atoms that may have substituents, wherein the substituents are halogens, alkyl groups with 1 to 20 carbon atoms, or aryl groups with 6 to 12 carbon atoms.)

[0047] The monohydric phenol of general formula (4) is more preferably the monohydric phenol shown in general formula (5) below.

[0048]

[0049] (In the formula, R1 represents an alkyl group with 8 to 36 carbon atoms or an alkenyl group with 8 to 36 carbon atoms.)

[0050] More preferably, the number of carbon atoms in R1 in general formula (4) or general formula (5) is within a specific numerical range. Specifically, as the upper limit of the number of carbon atoms in R1, 36 is preferred, 22 is more preferred, and 18 is particularly preferred. In addition, as the lower limit of the number of carbon atoms in R1, 8 is preferred, and 12 is more preferred.

[0051] In the monohydric phenol (terminator) represented by general formula (4) or general formula (5), it is particularly preferred to use either or both of hexadecyl p-hydroxybenzoate and 2-hexyldecyl p-hydroxybenzoate as the terminator.

[0052] When using, for example, an alkyl group having 16 carbon atoms as R1 in general formula (4) or general formula (5), a monohydric phenol (terminant) with excellent glass transition temperature, melt flowability, moldability, drawdown resistance, and solvent solubility of the monohydric phenol in the manufacture of polycarbonate resin is particularly preferred as a terminant for the polycarbonate resin used in the present invention.

[0053] On the other hand, when the number of carbon atoms in R1 in general formula (4) or general formula (5) increases too much, there is a tendency for the organic solvent solubility of monohydric phenol (terminator) to decrease, and sometimes the productivity of manufacturing polycarbonate resin decreases.

[0054] As an example, when the number of carbon atoms in R1 is 36 or less, the production of polycarbonate resins is highly productive and economical. When the number of carbon atoms in R1 is 22 or less, the organic solvent solubility of the monohydric phenol is particularly excellent, which can make the production of polycarbonate resins very productive and economical.

[0055] When the number of carbon atoms in R1 in general formula (4) or general formula (5) is too small, the glass transition temperature of polycarbonate resin is not a sufficiently low value, and sometimes the thermoformability decreases.

[0056] Other resins included in polycarbonate resin (A) include polyester resins. Among polyester resins, the dicarboxylic acid component can be terephthalic acid as the main component, or it may contain dicarboxylic acid components other than terephthalic acid. For example, a preferred polyester resin is one formed by the condensation polymerization of a diol component containing 20-40 molar ratios of 1,4-cyclohexanediethanol relative to 80-60 molar ratios of ethylene glycol as the main component, and a dicarboxylic acid component, known as "PETG". Furthermore, polycarbonate resin (A) may also include polyester carbonate resins with ester bonds and carbonate bonds in the polymer backbone.

[0057] In this invention, the weight-average molecular weight of the polycarbonate resin (A) affects the molding conditions. Specifically, a low weight-average molecular weight is undesirable because it reduces the impact resistance of the resin laminate. A high weight-average molecular weight sometimes requires excessive heat when laminating the polycarbonate resin (A), which is also undesirable. Furthermore, the molding method may require high temperatures, exposing the polycarbonate resin (A) to high temperatures, which can sometimes negatively affect its thermal stability. The weight-average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 95,000, more preferably 20,000 to 90,000, and even more preferably 25,000 to 85,000.

[0058] <Method for determining the weight-average molecular weight of polycarbonate resin (A)>

[0059] The weight-average molecular weight of polycarbonate resin (A) can be determined based on the description in sections 0061 to 0064 of Japanese Patent Application Publication No. 2007-179018. Details of the determination method are shown below.

[0060] [Table 1]

[0061] Table 1: Determination conditions for weight-average molecular weight

[0062] The device is the "Aliance" manufactured by Waters.

[0063] Shodex K-805L (2 pieces) manufactured by Showa Denko.

[0064] Detector UV detector: 254nm

[0065] chloroform eluent

[0066] After determining the molecular weight of polystyrene (PS) as a standard polymer, a calibration curve was constructed by using a universal calibration method to establish the relationship between elution time and the molecular weight of polycarbonate (PC). Then, the elution curve (chromatogram) of PC was determined under the same conditions as the calibration curve, and the average molecular weight was calculated based on the elution time (molecular weight) and the peak area (number of molecules) at that elution time. When the number of molecules in the molecular weight Mi is set to Ni, the weight-average molecular weight is expressed as follows. Furthermore, the conversion formula is as follows.

[0067] (weight-average molecular weight)

[0068] Mw=Σ(NiMi 2 ) / Σ(NiMi)

[0069] (Conversion formula)

[0070] MPC = 0.47822 MPS 1.01470

[0071] Where MPC represents the molecular weight of PC and MPS represents the molecular weight of PS.

[0072] The glass transition temperature of the polycarbonate resin (A) used in this invention is preferably 100–180°C, more preferably 120–165°C, and particularly preferably 125°C–160°C. The glass transition temperature of the polycarbonate resin (A) in this specification is measured using a differential scanning calorimeter at a heating rate of 10°C / minute, and calculated based on the intersection of the baseline and the tangent at the inflection point.

[0073] The melt flow rate of the aforementioned polycarbonate resin (A) is preferably in the range of 1.0 to 30.0 g / 10 min, more preferably in the range of 1.0 to 5.0 g / 10 min, and even more preferably in the range of 1.5 to 5.0 g / 10 min. When the melt flow rate is in the range of 1 to 30 g / 10 min, the stability of the heat-melt molding is good. The melt flow rate of the polycarbonate resin (A) in this specification is a value measured using a melt indexer under conditions of 300°C and a load of 1.2 kg.

[0074] The viscosity of the polycarbonate resin (A) at a shear rate of 6.080 × 10¹⁰ [1 / S] measured at 260°C is preferably in the range of 3,700 to 15,000 [Pa·S], more preferably in the range of 3,900 to 12,000 [Pa·S], and particularly preferably in the range of 4,100 to 10,000 [Pa·S]. The viscosity of the polycarbonate resin (A) at a shear rate of 6.080 × 10¹⁰ [1 / S] measured at 260°C in this specification is the value measured using a capillary rheometer with a diameter of 1.0 mm, a length of 10.0 mm, and an L / D of 10, at a furnace temperature of 260°C.

[0075] The manufacturing method of the polycarbonate resin (A) used in this invention can be appropriately selected from known methods such as the phosgene method (interfacial polymerization method) and the transesterification method (melt method) depending on the monomer used.

[0076] <Thermoplastic Resin (B)>

[0077] The thermoplastic resin (B) used in this invention contains a styrene copolymer (C), and preferably also contains a methacrylic resin (D). The constituent elements are described below.

[0078] <Styrene copolymer (C)>

[0079] The styrene copolymer (C) contained in the thermoplastic resin (B) of the present invention is not particularly limited, but it is preferred to use a styrene copolymer containing vinyl aromatic monomer units (c1) and cyclic anhydride monomer units (c2) and the total proportion of vinyl aromatic monomer units (c1) and cyclic anhydride monomer units (c2) is 50 to 100% by mass relative to the total of all monomer units in the above-mentioned styrene copolymer (C).

[0080] The vinyl aromatic monomer unit (c1) of the aforementioned styrene copolymer (C) is not particularly limited, and any known aromatic vinyl monomer can be used. From the viewpoint of ease of acquisition, examples include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, etc. Among these, styrene is particularly preferred from the viewpoint of compatibility. Two or more of these aromatic vinyl monomers may also be mixed.

[0081] Examples of cyclic anhydride monomer units (c2) in the aforementioned styrene copolymer (C) include maleic acid, itaconic acid, citraconic acid, aconitic acid, etc., with maleic anhydride being preferred from the viewpoint of compatibility with acrylic resins. Two or more of these unsaturated dicarboxylic acid anhydride monomers may also be mixed.

[0082] In the styrene copolymer (C) used in this invention, the total ratio of the vinyl aromatic monomer unit (c1) and the cyclic anhydride monomer unit (c2) relative to the total of all monomer units in the styrene copolymer (C) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 98 to 100% by mass.

[0083] That is, the styrene copolymer (C) described above may contain monomer units other than the vinyl aromatic monomer unit (c1) and the cyclic anhydride monomer unit (c2) in a range of less than 50% by mass relative to the total of all monomer units. Examples of monomer units other than the vinyl aromatic monomer unit (c1) and the cyclic anhydride monomer unit (c2) include, for example, methacrylate monomer units and N-substituted maleimide monomers.

[0084] Examples of methacrylate monomer units in styrene copolymers (C) include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, and other alkyl methacrylates; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate, and other cycloalkyl methacrylates; phenyl methacrylate and other aryl methacrylates; benzyl methacrylate and other aryl methacrylates, etc. From the viewpoint of compatibility with methacrylic resins, methyl methacrylate is preferred. Two or more of these methacrylate monomers may also be mixed.

[0085] Examples of N-substituted maleimide monomers in styrene copolymers (C) include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-tribromophenylmaleimide, and N-arylmaleimide. From the viewpoint of compatibility with methacrylic resins, N-phenylmaleimide is preferred. Two or more of these N-substituted maleimide monomers may also be mixed.

[0086] The proportion of the vinyl aromatic monomer unit (c1) relative to the total of all monomer units in the styrene copolymer (C) is preferably 68-84% by mass, more preferably 70-83% by mass, and particularly preferably 74-82% by mass. The proportion of the cyclic anhydride monomer unit (c2) relative to the total of all monomer units in the styrene copolymer (C) is preferably 16-32% by mass, more preferably 17-30% by mass, and particularly preferably 18-26% by mass.

[0087] When the thermoplastic resin (B) contains styrene copolymer (C) and methacrylic resin (D), the compatibility of the aforementioned vinyl aromatic monomer unit (c1) with methacrylic resin (D) sometimes deteriorates when the ratio of the aforementioned vinyl aromatic monomer unit (c1) to the total of all monomer units in the aforementioned styrene copolymer (C) is other than 68-84% by mass. Furthermore, the compatibility of the aforementioned cyclic anhydride monomer unit (c2) with methacrylic resin (D) sometimes deteriorates when the ratio of the aforementioned cyclic anhydride monomer unit (c2) to the total of all monomer units in the styrene copolymer (C) is other than 16-32% by mass.

[0088] The styrene copolymer (C) is preferably a binary copolymer or multi-component copolymer containing vinyl aromatic monomer units (c1) and cyclic anhydride monomer units (c2). By using methacrylic resin (D) in combination, the hardness is higher than that of using only styrene copolymer (C), and a resin laminate with excellent thermoforming properties can be obtained compared with using only methacrylic resin (D).

[0089] From the viewpoint of the formability of the resin laminate, the weight-average molecular weight of the above-mentioned styrene copolymer (C) is preferably 10,000 to 200,000, more preferably 20,000 to 150,000, and particularly preferably 40,000 to 120,000. The above-mentioned weight-average molecular weight is the weight-average molecular weight converted from standard polystyrene, determined by gel permeation chromatography (GPC).

[0090] The glass transition temperature of the styrene copolymer (C) is preferably in the range of 120 to 190°C, and more preferably in the range of 128 to 170°C. With a glass transition temperature of 120°C or higher, the resin laminate provided by the present invention is less prone to deformation or cracking in a thermal environment. Furthermore, with a glass transition temperature of 190°C or lower, processability is excellent, whether using continuous hot forming with mirror rollers or forming rollers, or intermittent hot forming with mirror molds or forming molds. The glass transition temperature of the styrene copolymer (C) in this specification is measured using a differential scanning calorimeter at a heating rate of 10°C / min, and calculated based on the intersection of the baseline and the tangent at the inflection point.

[0091] There are no particular limitations on the manufacturing method of the above-mentioned styrene copolymer (C), and well-known methods such as solution polymerization, monolithic polymerization, and suspension polymerization can be appropriately selected.

[0092] <Methacrylic Resin (D)>

[0093] The thermoplastic resin (B) of the present invention preferably contains methacrylic resin (D) without particular limitation, but resins containing structural units derived from methacrylic ester monomers are preferred examples.

[0094] Examples of methacrylate monomers for the aforementioned methacrylate resin (D) include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, and other alkyl methacrylates; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate, and other cycloalkyl methacrylates; phenyl methacrylate and other aryl methacrylates; benzyl methacrylate and other aryl methacrylates. From the viewpoint of availability, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred, with methyl methacrylate being the most preferred.

[0095] Furthermore, from the viewpoint of heat resistance, the aforementioned methacrylic resin (D) preferably contains 50% by mass or more structural units derived from methacrylate monomers, more preferably 70% by mass or more, and even more preferably 95% by mass or more. When the methacrylic resin (D) contains 50% by mass or more structural units derived from methacrylate monomers, its hardness increases, which is therefore preferable.

[0096] In addition, the aforementioned methacrylic resin (D) may also contain structural units from monomers other than methacrylates. Examples of monomers other than methacrylates include acrylate monomers, vinyl aromatic monomers, cyclic anhydride monomers, N-substituted maleimide monomers, glutaric anhydride monomers, glutarimide monomers, and lactone ring monomers.

[0097] Examples of acrylate monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluene acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate.

[0098] Examples of vinyl aromatic monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and tert-butylstyrene.

[0099] Examples of cyclic acid anhydride monomers include maleic acid, itaconic acid, citraconic acid, aconitic acid, etc.

[0100] Examples of N-substituted maleimide monomers include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-tribromophenylmaleimide, and other N-arylmaleimides.

[0101] From an availability point of view, acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate are preferred, methyl acrylate and ethyl acrylate are more preferred, and methyl acrylate is most preferred. Structural units from monomers other than these methacrylates may also be mixed in two or more forms. The total content of structural units from monomers other than these methacrylates in the methacrylic resin (D) is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 5% by mass or less.

[0102] The lower limit of the syndiotactic regularity (rr) of the ternary group of methacrylic resin (D) is preferably 50 mol% or more, more preferably 51 mol% or more, and even more preferably 52 mol% or more. With a lower limit of 50 mol% or more for the content of this structure, articles with excellent heat resistance can be produced.

[0103] In this context, the syndiotactic regularity (rr) represented by the triad (hereinafter sometimes simply referred to as "syndiotactic regularity (rr)") is the proportion of two racemic (denoted as rr) chains in a chain of three consecutive structural units (triad). Within the chains of structural units (diad) in a polymer molecule, chains with identical stereoconfigurations are called meso, and chains with opposite stereoconfigurations are called racemo, denoted as m and r, respectively.

[0104] The syntactic regularity (rr) (%) of methacrylic acid resin (D) can be determined in deuterated chloroform at 30°C. 1 The H-NMR spectrum was used to measure the area (X) of the 0.6–0.95 ppm region and the area (Y) of the 0.6–1.35 ppm region when tetramethylsilane (TMS) was set to 0 ppm. The result was calculated using the formula: (X / Y)×100.

[0105] From the viewpoint of the moldability of the resin laminate, the weight-average molecular weight of the above-mentioned methacrylic resin (D) is preferably in the range of 10,000 to 700,000, more preferably in the range of 30,000 to 500,000. Even more preferably, it is in the range of 50,000 to 300,000. The above-mentioned weight-average molecular weight is the weight-average molecular weight converted from standard polystyrene, determined by gel permeation chromatography (GPC).

[0106] The glass transition temperature of the aforementioned methacrylic resin (D) is preferably 100°C or higher, more preferably 105°C or higher, and even more preferably 108°C or higher. With a glass transition temperature of 100°C or higher, the resin laminate provided by this invention is less prone to deformation or cracking in thermal environments. The glass transition temperature of the methacrylic resin (D) in this specification is measured using a differential scanning calorimeter at a heating rate of 10°C / minute, and calculated based on the intersection of the baseline and the tangent at the inflection point.

[0107] The glass transition temperature of the aforementioned thermoplastic resin (B) is preferably in the range of 115–165°C, and more preferably in the range of 120–160°C. With a glass transition temperature of 115°C or higher, the resin laminate is less prone to deformation or cracking in a thermal environment. Furthermore, with a temperature below 165°C, processability is excellent, whether using continuous hot forming with mirror rollers or forming rollers, or intermittent hot forming with mirror molds or forming molds. The glass transition temperature of the thermoplastic resin (B) in this specification is measured using a differential scanning calorimeter at a heating rate of 10°C / min, and calculated based on the intersection of the baseline and the tangent at the inflection point.

[0108] The viscosity of the thermoplastic resin (B) at a shear rate of 6.080 × 10¹⁰ [1 / S] measured at 260°C is preferably in the range of 100 to 3,600 [Pa·S], more preferably in the range of 200 to 3,000 [Pa·S], and particularly preferably in the range of 500 to 1,500 [Pa·S]. The viscosity of the thermoplastic resin (B) at a shear rate of 6.080 × 10¹⁰ [1 / S] measured at 260°C in this specification is the value obtained using a capillary rheometer with a diameter of 1.0 mm, a length of 10.0 mm, and an L / D ratio of 10, under furnace temperature conditions of 260°C.

[0109] In this invention, there are no particular limitations on the manufacturing method of the thermoplastic resin (B). For example, a mixer such as a drum mixer, Henschel mixer, or super mixer can be used to premix the necessary components, and then melt-mix them using equipment such as a Banbury mixer, roller mixer, Brabender mixer, single-screw extruder, twin-screw extruder, or pressure kneader.

[0110] In this invention, when using methacrylic resin (D), regarding the mass ratio of the styrene copolymer (C) to the methacrylic resin (D), based on a total mass of 100 parts by mass of styrene copolymer (C) and methacrylic resin (D), it is preferable that the styrene copolymer (C) is 15 to 85 parts by mass and the methacrylic resin (D) is 85 to 15 parts by mass. More preferably, the styrene copolymer (C) is 30 to 70 parts by mass and the methacrylic resin (D) is 70 to 30 parts by mass. Even more preferably, the styrene copolymer (C) is 40 to 60 parts by mass and the styrene copolymer (D) is 60 to 40 parts by mass. Within this mass ratio, an excellent thermoplastic resin (B) can be produced that maintains transparency while exhibiting excellent heat resistance, high refractive index, and good appearance.

[0111] <Resin Laminate>

[0112] In this invention, the thickness of the layer containing thermoplastic resin (B) affects the surface hardness and impact resistance of the resin laminate. Specifically, if the layer containing thermoplastic resin (B) is too thin, the surface hardness is low, which is not preferred. If the layer containing thermoplastic resin (B) is too thick, the impact resistance deteriorates, which is also not preferred. The thickness of the layer containing thermoplastic resin (B) is preferably 10–250 μm, more preferably 20–200 μm, and even more preferably 30–150 μm.

[0113] In this invention, when a hard coating is included, it is difficult to form if the combined thickness of the layer containing polycarbonate resin (A), the layer containing thermoplastic resin (B), and the hard coating is too thin or too thick. The overall thickness of the resin laminate is preferably 0.05 to 4.0 mm, more preferably 0.3 to 3.5 mm, and even more preferably 0.5 to 3.0 mm.

[0114] One or both sides of the resin laminate of the present invention may be treated with one or more of the following: fingerprint resistance treatment, anti-reflective treatment, anti-fouling treatment, antistatic treatment, weather resistance treatment, and anti-glare treatment. The methods for anti-reflective treatment, anti-fouling treatment, antistatic treatment, weather resistance treatment, and anti-glare treatment are not particularly limited, and known methods may be used. Examples include methods such as coating with anti-reflective coatings, vapor-depositing dielectric films, and coating with antistatic coatings.

[0115] <Any Additives>

[0116] In this invention, the layer containing polycarbonate resin (A) forming the substrate layer and / or the layer containing thermoplastic resin (B) forming the surface layer may contain components other than the main components mentioned above.

[0117] For example, the UV absorber can be mixed into the layer containing polycarbonate resin (A) and / or the layer containing thermoplastic resin (B). Additionally, in this invention, the hard coating may also contain the UV absorber. If the UV absorber content is too high, depending on the molding method, the excess UV absorber may sometimes disperse due to the applied high temperature, contaminating the molding environment and causing adverse effects. Therefore, the UV absorber content is preferably 0-5% by mass, more preferably 0-3% by mass, and even more preferably 0-1% by mass. Examples of benzophenone-based ultraviolet absorbers include: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, etc.; 2-(2-hydroxy-5-methylphenyl)benzotriazole; 2-(2-hydroxy-3,5-dihydroxybenzophenone... Benzotriazole-based UV absorbers include tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)benzotriazole, and (2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol; benzoate-based UV absorbers include phenyl salicylate and 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; hindered amine-based UV absorbers include bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; and 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-trimethylphenyl Azides, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine Triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine and other triazine-based ultraviolet absorbers, 2-[2-(6-hydroxybenzo[1,3]dioxane-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxane-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]dioxane-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate,3-[2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl]propyl methacrylate, 4-[2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl]butyl methacrylate, 4-[2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl]butyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl]butyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl]propyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl]butyl ... 2-[2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl methacrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl methacrylate, 2 ... 4-[3-{2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl}propionyloxy]butyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl methacrylate, 2-(methacryloyloxy)ethyl Examples of benzotriazole-based UV absorbers include 2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazole-5-carboxylic acid ester, 2-(acryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazole-5-carboxylic acid ester, 4-(methacryloyloxy)butyl 2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazole-5-carboxylic acid ester, and 4-(acryloyloxy)butyl 2-(6-hydroxybenzo[1,3]dioxacyclopenten-5-yl)-2H-benzotriazole-5-carboxylic acid ester, etc. There are no particular limitations on the mixing method; methods such as total mixing (compounding), dry mixing of the masterbatch, and total dry mixing can be used.

[0118] In this invention, in addition to the aforementioned ultraviolet absorber, various additives may be mixed into the polycarbonate resin (A) layer forming the substrate layer and / or the thermoplastic resin (B) layer forming the surface layer. Examples of such additives include antioxidants, anti-coloring agents, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers, and inorganic fillers, etc. The mixing method is not particularly limited; methods such as mixing all quantities, dry mixing of the masterbatch, or dry mixing of all quantities can be used.

[0119] The materials contained in the layers containing polycarbonate resin (A) and / or thermoplastic resin (B) of the present invention, such as polycarbonate resin (A) and thermoplastic resin (B), are preferably purified by filtration. Purification by filtration or lamination thereby yields a resin laminate with fewer appearance defects, such as foreign matter and imperfections. The filtration method is not particularly limited; melt filtration, solution filtration, or combinations thereof can be used.

[0120] There are no particular restrictions on the filters used; any known filter can be used, selected appropriately based on the operating temperature, viscosity, and filtration precision of each material. As for the filter material, there are no particular limitations; nonwoven fabrics or rovings made of polypropylene, cotton, polyester, viscose rayon, or glass fiber, cellulose impregnated with phenolic resin, sintered metal fiber nonwoven fabrics, sintered metal powders, braker plates, or combinations thereof can all be used. Especially when considering heat resistance, durability, and pressure resistance, sintered metal fiber nonwoven fabrics are preferred.

[0121] For polycarbonate resin (A) and thermoplastic resin (B), the filtration accuracy is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less. Furthermore, since the coating is applied to the outermost layer of the resin laminate, the filtration accuracy of the hard coating is 20 μm or less, preferably 10 μm or less, and more preferably 2 μm or less.

[0122] For the filtration of polycarbonate resins (A) and thermoplastic resins (B), polymer filters, such as those used for melt filtration of thermoplastic resins, are preferred. Polymer filters are classified according to their structure into disc filters, candle filters, packed disc filters, cylindrical filters, etc., with disc filters having a particularly large effective filtration area being preferred.

[0123] <Method for manufacturing resin laminates>

[0124] One aspect of the present invention relates to a method for manufacturing a resin laminate, which is formed by laminating a layer containing a thermoplastic resin (B) onto at least one side of a layer containing a polycarbonate resin (A). The method for manufacturing the resin laminate of the present invention is not particularly limited. Examples include: a method of laminating separately formed layers containing thermoplastic resin (B) and polycarbonate resin (A) and then heating and pressing them together; a method of bonding separately formed layers containing thermoplastic resin (B) and polycarbonate resin (A) using an adhesive; a method of co-extruding a layer containing thermoplastic resin (B) and a layer containing polycarbonate resin (A); and a method of in-mold molding a layer containing polycarbonate resin (A) using a pre-formed layer containing thermoplastic resin (B) to achieve integral integration. From the viewpoint of manufacturing cost and productivity, the co-extrusion method is preferred.

[0125] As a method of co-extrusion molding, for example, the manufacturing method can be described as follows: using separate extruders, heating and melting a layer containing polycarbonate resin (A) and a layer containing thermoplastic resin (B), extruding them separately from the slit-shaped nozzle of a T-die to form a laminate, and then using cooling rollers to seal and cure them.

[0126] Figure 3 This is a schematic diagram illustrating an example of a resin laminate manufacturing apparatus according to an embodiment. Figure 3 In the process, molten polycarbonate resin (A) and thermoplastic resin (B) co-extruded from die 1 are sandwiched between the first cooling roller 2 and the second cooling roller 3, wound onto the second cooling roller 3, and then wound onto at least one rear cooling roller 4. Afterward, they are fed to the clamping roller 5, thereby obtaining a resin laminate.

[0127] exist Figure 3 In the manner shown, firstly, polycarbonate resin (A) and thermoplastic resin (B) are heated and melted using separate extruders (not shown), and then co-extruded from die 1 for co-extrusion molding to form a laminate.

[0128] The temperature at which the extruder heats and melts the resin is preferably 80–150°C higher than the glass transition temperature (Tg) of both the polycarbonate resin (A) and the thermoplastic resin (B). Generally, the temperature conditions of the main extruder for extruding the polycarbonate resin (A) are typically 200–320°C, preferably 220–310°C, while the temperature conditions of the auxiliary extruder for extruding the thermoplastic resin (B) are typically 180–280°C, preferably 190–270°C.

[0129] As a method for co-extruding two molten resins, known methods such as feed block method and multi-channel method can be used.

[0130] For example, in the case of a feed block method, the molten resin after being stacked using the feed blocks is introduced into a sheet forming mold such as a T-mold, formed into a sheet, and then flows into a forming roller (polishing roller) with a mirror-finished surface to form a bank. The mirror finish and cooling are then performed during the process of passing through the forming roller.

[0131] In the multi-channel method, the molten resin after being stacked in the multi-channel mold is formed into a sheet inside the mold, and then the surface is processed and cooled by forming rollers.

[0132] In either case, the temperature of mold 1 is usually 230-290°C, with 250-280°C being the preferred setting.

[0133] Next, the sheet or film laminate co-extruded from mold 1 is wound onto at least three cooling rollers for cooling and curing. Specifically, the molten laminate is sandwiched between the first cooling roller 2 and the second cooling roller 3, wound onto the second cooling roller, and then wound onto at least one rear cooling roller 4. It is then fed into a pair of clamping rollers 5 arranged vertically to obtain the resin laminate.

[0134] As forming (cooling) rollers, there are rigid rollers and elastic rollers, and any type can be used. In one embodiment, the cooling rollers (2, 3, 4) are rigid rollers. In order to achieve a mirror finish on the surface of the resin laminate, it is preferable to perform a mirror finish on the rigid rollers.

[0135] To achieve a mirror finish, the polycarbonate resin (A) surface is preferably sandwiched between the first cooling roller 2 and the second cooling roller 3, wound onto the second cooling roller 3, and then wound around using at least one rear cooling roller 4. The temperatures of the first cooling roller 2 and the second cooling roller 3 are typically 70–160°C, and preferably set to 80–150°C.

[0136] The circumferential speed of the roller is, for example, 0.5 to 30.0 m / min, wherein it is preferably set to 0.8 to 6.0 m / min.

[0137] The speed ratio between the rear cooling roller 4 and the clamping roller 5 is, for example, the speed of the rear cooling roller (m / min) / the speed of the clamping roller (m / min) = 0.5 to 2.0, wherein it is preferably set to 0.7 to 1.5.

[0138] <Defects during laminate molding>

[0139] When thermoplastic resin (B) is co-extruded onto at least one side of a layer containing polycarbonate resin (A), the interface becomes disordered when contaminants such as cellulose or unmeltable foreign matter are present near the interface between the layer containing polycarbonate resin (A) and the layer containing thermoplastic resin (B). Streaks (“interface streaks”) are generated in the flow direction.

[0140] Especially for styrene copolymers (C), "transparent spots" are generated during copolymerization and are also present in the raw materials. Figure 1 ) penetrates into the layer containing polycarbonate resin (A) Figure 2 When the interface becomes cluttered, it often produces "interface stripes".

[0141] "Interface stripes" can be visually inspected in a dark room with a three-wavelength fluorescent lamp in the lit state and an illuminance of 1,200 to 2,000 lux.

[0142] When there are many interface streaks, they look like surface scratches, which can be a fatal defect for transparent substrate materials and transparent protective materials.

[0143] Specifically, for a size of 297mm×210mm, the number of "interface stripes" is preferably 5 or less, more preferably 3 or less, and especially preferably 1 or less.

[0144] Regarding "interfacial stripes," their formation can be suppressed by increasing the viscosity of the polycarbonate resin (A). Specifically, the viscosity of the polycarbonate resin (A) at a shear rate of 6.080 × 10 [1 / S] measured at 260°C is preferably in the range of 3,700 to 15,000 [Pa·S], more preferably in the range of 3,900 to 12,000 [Pa·S], and particularly preferably in the range of 4,100 to 10,000 [Pa·S].

[0145] Furthermore, since the viscosity of the thermoplastic resin (B) is lower than that of the polycarbonate resin (A), the formation of "interfacial streaks" can be suppressed. Specifically, the viscosity of the thermoplastic resin (B) at a shear rate of 6.080 × 10 [1 / S] measured at 260°C is preferably in the range of 100 to 3,600 [Pa·S], more preferably in the range of 200 to 3,000 [Pa·S], and particularly preferably in the range of 500 to 1,500 [Pa·S].

[0146] <Uses>

[0147] The resin laminate of the embodiment is a resin laminate with high heat resistance and good appearance. Therefore, it can be suitable for use as a transparent substrate material and a transparent protective material. Specifically, it can be suitable for use as a transparent substrate material and a transparent protective material (e.g., front panel) for portable display devices such as mobile terminals, portable electronic game devices, portable information terminals, and mobile PCs, as well as display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs.

[0148] Example

[0149] The present embodiment will be described in more detail below with reference to the embodiments, but the present embodiment is not limited to these embodiments.

[0150] <Determination of viscosity of polycarbonate resin (A) and thermoplastic resin (B)>

[0151] Using a capillary rheometer manufactured by Toyo Seiki Co., Ltd., the viscosity was measured at a shear rate of 6.080 × 10 [1 / S] using a capillary tube with a diameter of 1.0 mm, a length of 10.0 mm and an L / D of 10, at a furnace temperature of 260°C.

[0152] <Determination of melt flow rate of polycarbonate resin (A)>

[0153] The measurements were performed using a melt flow indexer manufactured by Toyo Seiki Co., Ltd., at a temperature of 300°C and a load of 1.2 kg.

[0154] <Composition ratio of monomer units in styrene copolymers>

[0155] Using JNM-AL400 manufactured by Nippon Electronics Co., Ltd., according to 1 H-NMR and 13 The values ​​were calculated based on the C-NMR (400MHz: solvent CDCl3) measurements.

[0156] <Glass transition temperature>

[0157] A differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments Co., Ltd. was used. Under a nitrogen flow of 30 ml / min, the temperature was increased from 30°C to 200°C at a rate of 10°C / min, then decreased from 200°C to 30°C at a rate of 50°C / min, and then increased again from 30°C to 200°C at a rate of 10°C / min. The intersection of the baseline during the second heating and the tangent at the inflection point was used as the glass transition temperature.

[0158] <Interface Stripes>

[0159] Visual inspection of a 297mm × 210mm resin laminate was conducted in a dark room equipped with a three-wavelength fluorescent lamp in operation and an illuminance of 1,200–2,000 lux. Interface striations were evaluated. The following criteria were used to determine whether the interface striations were acceptable; 0 was considered acceptable.

[0160] ○: The interface has 5 or fewer stripes.

[0161] ×: The interface has more than 6 stripes.

[0162] <Total Light Transmittance>

[0163] The total light transmittance of the resin laminate was measured using a reflectance / transmittance meter HR-100 (manufactured by Murakami Color Technology Research Institute Co., Ltd.) based on JISK7361-1.

[0164] <Haze>

[0165] The haze of the resin laminate was measured using a reflectance / transmittance meter HR-100 (manufactured by Murakami Color Technology Research Institute Co., Ltd.) based on JIS K7136.

[0166] In the embodiments, the materials described below were used as polycarbonate resins (A-1) to (A-2), thermoplastic resins (B-1) to (B-2), styrene copolymers (C-1) to (C-2), and methacrylic resins (D-1), but the use of these materials is not limited to them. On the other hand, in the comparative examples, polycarbonate resins (E-1) to (E-3) described below were used respectively.

[0167] <Polycarbonate resin (A-1), styrene copolymer (C-1) to (C-2), methacrylic resin (D-1), polycarbonate resin (E-1) to (E-2)>

[0168] Polycarbonate resin (A-1): Iupilon E-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. (weight-average molecular weight: 65,000, viscosity at a shear rate of 6.080 × 10 [1 / S] measured at 260°C: 7,678 [Pa·S], glass transition temperature: 152°C, melt flow rate at 300°C and 1.2 kg load: 3.0 g / 10 min, refractive index: 1.59)

[0169] Styrene copolymer (C-1): XIRANSO23110 manufactured by Polyscope ((C1) / (C2) = styrene / maleic anhydride = 78% by mass / 22% by mass, weight average molecular weight: 74,300, glass transition temperature: 145°C, melt flow rate at 230°C and 3.8 kg load: 5.9 g / 10 min, refractive index: 1.58).

[0170] Styrene copolymer (C-2): SAM-020 manufactured by Fine-blend Polymer ((C1) / (C2) = styrene / maleic anhydride = 83% by mass / 17% by mass, weight average molecular weight: 107,200, glass transition temperature: 129°C)

[0171] Methacrylate resin (D-1): ALTUGLAS (registered trademark) V020 manufactured by Arkema Corporation (weight average molecular weight: 127,000, glass transition temperature: 109°C, melt flow rate at 230°C and 3.8 kg load: 1.8 g / 10 min, methyl methacrylate / methyl acrylate = 96.1 wt% / 3.9 wt%, refractive index: 1.49, mm / mr / rr = 7.4 mol% / 37.4 mol% / 55.2 mol%)

[0172] Polycarbonate resin (E-1): Iupilon E-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. (weight-average molecular weight: 53,000, viscosity at a shear rate of 6.080 × 10 [1 / S] measured at 260°C: 3,495 [Pa·S], glass transition temperature: 151°C, melt flow rate at 300°C and 1.2 kg load: 5.3 g / 10 min, refractive index: 1.59)

[0173] Polycarbonate resin (E-2): Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. (weight-average molecular weight: 48,000, viscosity at a shear rate of 6.080 × 10 [1 / S] measured at 260°C: 2,550 [Pa·S], glass transition temperature: 149°C, melt flow rate at 300°C and 1.2 kg load: 7.5 g / 10 min, refractive index: 1.59)

[0174] <Synthesis of Polycarbonate Resin (A-2)>

[0175] Synthesis Example 1 [Synthesis of Polycarbonate Resin Terminator]

[0176] Based on pages 143-150 of the Organic Chemistry Handbook, 4-hydroxybenzoic acid manufactured by Tokyo Chemical Industry Co., Ltd. and 1-hexadecyl alcohol manufactured by Tokyo Chemical Industry Co., Ltd. were esterified by dehydration reaction to obtain hexadecyl p-hydroxybenzoate (CEPB).

[0177] Synthesis Example 2 [Preparation of Polycarbonate Resin (A-2) Granules]

[0178] 7.1 kg (31.14 mol) of bisphenol A (BPA) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. and 30 g of hydrosulfite were added to 57.2 kg of a 9 w / w sodium hydroxide aqueous solution and dissolved. 40 kg of dichloromethane was added, and the solution temperature was maintained between 15°C and 25°C while stirring. 4.33 kg of phosgene was blown in over 30 minutes. After the phosgene blowing was completed, 6 kg of a 9 w / w sodium hydroxide aqueous solution, 11 kg of dichloromethane, and a solution containing 363 g (1.00 mol) of hexadecyl paraben (CEPB) as a terminator dissolved in 10 kg of dichloromethane were added and stirred vigorously to emulsify the solution. Then, 10 ml of triethylamine as a polymerization catalyst was added to the solution, and polymerization was carried out for approximately 40 minutes.

[0179] The polymerization solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid, and the solution was repeatedly washed with pure water until the pH of the washings became neutral. The organic solvent was removed by distillation from the purified polycarbonate resin solution, thereby obtaining polycarbonate resin powder.

[0180] Using a twin-screw extruder with a screw diameter of 35mm, the obtained polycarbonate resin powder was melt-mixed at a barrel temperature of 260℃, extruded into strips, and then granulated using a granulator.

[0181] The polycarbonate resin (A-2) has the following properties: weight-average molecular weight: 59,000; viscosity at a shear rate of 6.080 × 10 [1 / S] measured at 260 °C: 4,156 [Pa·S]; glass transition temperature: 132 °C; melt flow rate at 300 °C and 1.2 kg load: 4.9 g / 10 min; and refractive index: 1.59.

[0182] Synthesis Example 3 <Synthesis of Polycarbonate Resin (E-3)>

[0183] In Synthesis Example 2, the amount of CEPB was 443 g (1.22 mol), and otherwise polymerized and granulated in the same manner as in Synthesis Example 2 to obtain a polycarbonate resin (E-3).

[0184] The polycarbonate resin (E-3) has the following properties: weight-average molecular weight: 47,000; viscosity at a shear rate of 6.080 × 10 [1 / S] measured at 260 °C: 1,714 [Pa·S]; glass transition temperature: 127 °C; melt flow rate at 300 °C and 1.2 kg load: 12.1 g / 10 min; and refractive index: 1.59.

[0185] Manufacturing Example 1 [Manufacturing of Granules of Thermoplastic Resin (B-1)]

[0186] A total of 100 parts by weight of styrene copolymer (C-1) and methacrylic resin (D-1) were mixed using a blender. 500 ppm of phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) and 0.2% by weight of glyceryl monostearate (product name: H-100, manufactured by Riken Vitamin Co., Ltd.) were added. The mixture was then melt-blended at a barrel temperature of 240°C using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D≈40) with a 10 μm mesh polymer filter. The resulting product was extruded into strands and granulated using a granulator. Granulation of the thermoplastic resin (B-1) was achieved stably.

[0187] The viscosity of the thermoplastic resin (B-1) granules at a shear rate of 6.080 × 10 [1 / S] measured at 260℃ is 906 [Pa·S], the glass transition temperature is 127℃, and the refractive index is 1.54.

[0188] Manufacturing Example 2 [Preparation of Granules of Thermoplastic Resin (B-2)]

[0189] Relative to 100 parts by mass of a total of 50 parts by mass of styrene copolymer (C-2) and 50 parts by mass of methacrylic resin (D-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of glyceryl monostearate were added, and the mixture was mixed and granulated in the same manner as in Manufacturing Example 1. The granules of thermoplastic resin (B-2) could be stably manufactured.

[0190] The viscosity of the thermoplastic resin (B-2) granules at a shear rate of 6.080 × 10 [1 / S] measured at 260℃ is 765 [Pa·S], and the glass transition temperature is 122℃.

[0191] Example 1 [Manufacturing of Resin Laminate (F-1)]

[0192] A resin laminate is formed using a multi-layer extrusion apparatus comprising a single-screw extruder with a screw diameter of 32 mm, a single-screw extruder with a screw diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block. Thermoplastic resin (B-1) obtained in Manufacturing Example 1 is continuously fed into the single-screw extruder with a screw diameter of 32 mm and extruded at a barrel temperature of 240°C and an ejection rate of 2.0 kg / h. Polycarbonate resin (A-1) is continuously fed into the single-screw extruder with a screw diameter of 65 mm and extruded at a barrel temperature of 290°C and an ejection rate of 66.6 kg / h. The feed block connected to all extruders has two types of two-layered distribution pins, and thermoplastic resin (B-1) and polycarbonate resin (A-1) are fed into the feed block at a temperature of 280°C for lamination.

[0193] The resin is extruded into a sheet using a T-die connected to its front end at a temperature of 270°C. Simultaneously, a mirror surface is transferred from the upstream side using three mirror-finishing rollers at temperatures of 115°C, 120°C, and 185°C, while the sheet is cooled to obtain a resin laminate of thermoplastic resin (B-1) and polycarbonate resin (A-1). The resulting resin laminate (F-1) has an overall thickness of 2000 μm in the central portion and a surface layer (containing the thermoplastic resin (B)) thickness of 60 μm.

[0194] The resin laminate (F-1) has 1 interface stripe, which is 0 (qualified), total light transmittance: 90.5%, and haze: 0.2%.

[0195] Example 2 [Manufacturing of Resin Laminate (F-2)]

[0196] Thermoplastic resin (B-2) was used instead of thermoplastic resin (B-1), and the same procedure was followed as for the resin laminate (F-1) of Example 1 to obtain a resin laminate (F-2) of thermoplastic resin (B-2) and polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (F-2) was 2000 μm, and the thickness of the surface layer (B-2) was 60 μm.

[0197] The interface stripes of this resin laminate (F-2) are 0, which is 0 (qualified). The total light transmittance is 90.3%, and the haze is 0.2%.

[0198] Example 3 [Manufacturing of Resin Laminate (F-3)]

[0199] A resin laminate was formed using a multi-layer extrusion apparatus consisting of a single-screw extruder with a screw diameter of 32 mm, a single-screw extruder with a screw diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block. Thermoplastic resin (B-1) obtained in Manufacturing Example 1 was continuously fed into the single-screw extruder with a screw diameter of 32 mm and extruded at a barrel temperature of 240°C and an ejection rate of 2.0 kg / h. Meanwhile, polycarbonate resin (A-2) obtained in Synthesis Example 2 was continuously fed into the single-screw extruder with a screw diameter of 65 mm and extruded at a barrel temperature of 280°C and an ejection rate of 66.6 kg / h. The feed block connected to all extruders had two types of two-layered distribution pins, and thermoplastic resin (B-1) and polycarbonate resin (A-2) were introduced at a temperature of 280°C for lamination.

[0200] The resin is extruded into a sheet using a T-die connected to its front end at a temperature of 270°C. Simultaneously, a mirror finish is transferred from the upstream side using three mirror-finishing rollers at temperatures of 80°C, 95°C, and 170°C, while the sheet is cooled to obtain a resin laminate of thermoplastic resin (B-1) and polycarbonate resin (A-2). The resulting resin laminate (F-3) has an overall thickness of 2000 μm in the central portion and a surface layer (containing the thermoplastic resin (B)) thickness of 60 μm.

[0201] The resin laminate (F-3) has 3 interface stripes, which is 0 (qualified), total light transmittance: 90.5%, and haze: 0.2%.

[0202] Example 4 [Manufacturing of Resin Laminate (F-4)]

[0203] Thermoplastic resin (B-2) was used instead of thermoplastic resin (B-1), and the same procedure was followed as for the resin laminate (F-3) of Example 3 to obtain a resin laminate (F-4) of thermoplastic resin (B-2) and polycarbonate resin (A-2). The resulting resin laminate (F-4) has an overall thickness of 2000 μm in the central portion and a surface layer (B-2) thickness of 60 μm.

[0204] The resin laminate (F-4) has the following characteristics: 1 interface stripe (qualified); total light transmittance: 90.3%; haze: 0.2%.

[0205] Comparative Example 1 [Manufacturing of Resin Laminate (G-1)]

[0206] Using polycarbonate resin (E-1) instead of polycarbonate resin (A-1), the same procedure was followed as for the resin laminate (F-1) in Example 1 to obtain a resin laminate (G-1) of thermoplastic resin (B-1) and polycarbonate resin (E-1). The overall thickness of the central portion of the obtained resin laminate (G-1) was 2000 μm, and the thickness of the surface layer (B-1) was 60 μm.

[0207] The resin laminate (G-1) has 43 interface stripes, which is × (unacceptable); total light transmittance is 90.5%; and haze is 0.2%.

[0208] Comparative Example 2 [Manufacturing of Resin Laminate (G-2)]

[0209] Polycarbonate resin (E-1) was used instead of polycarbonate resin (A-1), and thermoplastic resin (B-2) was used instead of thermoplastic resin (B-1). Otherwise, the process was the same as for the resin laminate (F-1) in Example 1, resulting in a resin laminate (G-2) of thermoplastic resin (B-2) and polycarbonate resin (E-1). The overall thickness of the central portion of the resulting resin laminate (G-2) was 2000 μm, and the thickness of the surface layer (B-2) was 60 μm.

[0210] The resin laminate (G-2) has 27 interface stripes, which is × (unacceptable); total light transmittance is 90.3%; and haze is 0.2%.

[0211] Comparative Example 3 [Manufacturing of Resin Laminate (G-3)]

[0212] Using polycarbonate resin (E-2) instead of polycarbonate resin (A-1), the same procedure was followed as for the resin laminate (F-1) in Example 1 to obtain a resin laminate (G-3) of thermoplastic resin (B-1) and polycarbonate resin (E-2). The total thickness of the central portion of the obtained resin laminate (G-3) was 2000 μm, and the thickness of the surface layer (B-1) was 60 μm.

[0213] The resin laminate (G-3) has 51 interface stripes, which is × (unacceptable); total light transmittance is 90.5%; and haze is 0.2%.

[0214] Comparative Example 4 [Manufacturing of Resin Laminate (G-4)]

[0215] Polycarbonate resin (E-2) was used instead of polycarbonate resin (A-1), and thermoplastic resin (B-2) was used instead of thermoplastic resin (B-1). Otherwise, the process was the same as for the resin laminate (F-1) in Example 1, resulting in a resin laminate (G-4) of thermoplastic resin (B-2) and polycarbonate resin (E-2). The overall thickness of the central portion of the resulting resin laminate (G-4) was 2000 μm, and the thickness of the surface layer (B-2) was 60 μm.

[0216] The resin laminate (G-4) has 38 interface stripes, which is × (unacceptable); total light transmittance is 90.3%; and haze is 0.2%.

[0217] Comparative Example 5 [Manufacturing of Resin Laminate (G-5)]

[0218] Using polycarbonate resin (E-3) instead of polycarbonate resin (A-2), and otherwise operating in the same manner as the resin laminate (F-3) of Example 3, a resin laminate (G-5) of thermoplastic resin (B-1) and polycarbonate resin (E-3) was obtained. The overall thickness of the central portion of the obtained resin laminate (G-5) was 2000 μm, and the thickness of the surface layer (B-1) was 60 μm.

[0219] The resin laminate (G-5) has 80 interface stripes, which is × (unacceptable); total light transmittance is 90.5%; and haze is 0.2%.

[0220] Comparative Example 6 [Preparation of Resin Laminate (G-6)]

[0221] Polycarbonate resin (E-3) was used instead of polycarbonate resin (A-2), and thermoplastic resin (B-2) was used instead of thermoplastic resin (B-1). Otherwise, the process was the same as for the resin laminate (F-3) in Example 3, resulting in a resin laminate (G-6) of thermoplastic resin (B-2) and polycarbonate resin (E-3). The overall thickness of the central portion of the obtained resin laminate (G-6) was 2000 μm, and the thickness of the surface layer (B-2) was 60 μm.

[0222] The resin laminate (G-6) has 62 interface stripes, which is × (unacceptable); total light transmittance is 90.3%; and haze is 0.2%.

[0223] [Table 2]

[0224]

[0225] As described above, by satisfying the conditions of the present invention, the advantageous effect of obtaining a resin laminate with high heat resistance and good appearance can be achieved.

[0226] That is, as shown in Table 2, regarding the resin laminate, Examples 1 to 4, which are laminates of polycarbonate resin (A) with a specific viscosity and thermoplastic resin (B) containing styrene copolymer (C), are compared with Comparative Examples 1 to 6, which are laminates of polycarbonate resin (E) with a different viscosity and thermoplastic resin (B) containing styrene copolymer (C). In Examples 1 to 4, the interface stripes of the resin laminate can be suppressed, and a resin laminate with a good appearance that maintains good total light transmittance and haze is obtained.

[0227] Symbol Explanation

[0228] 1: Mold; 2: First cooling roller; 3: Second cooling roller; 4: Rear cooling roller; 5: Clamping roller.

Claims

1. A resin laminate, characterized in that: The resin laminate has at least one layer containing a thermoplastic resin (B) on at least one side of the layer containing a polycarbonate resin (A). The viscosity of the polycarbonate resin (A) at a shear rate of 6.080 × 10 [1 / S] measured at 260 °C is 3,700 to 15,000 [Pa·S]. The thermoplastic resin (B) contains a styrene copolymer (C).

2. The resin laminate as described in claim 1, characterized in that: The thermoplastic resin (B) contains a styrene copolymer (C) and a methacrylic resin (D).

3. The resin laminate as described in claim 2, characterized in that: The thermoplastic resin (B) is a polymer alloy of the styrene copolymer (C) and the methacrylic resin (D).

4. The resin laminate as described in any one of claims 1 to 3, characterized in that: The viscosity of the thermoplastic resin (B) at a shear rate of 6.080 × 10 [1 / S] measured at 260°C is 100 to 3,600 [Pa·S].

5. The resin laminate as described in any one of claims 1 to 3, characterized in that: The melt flow rate of the polycarbonate resin (A) at 300°C and 1.2 kg load is 1.0 to 5.0 g / 10 minutes.

6. The resin laminate as described in claim 2 or 3, characterized in that: In the thermoplastic resin (B), based on a total of 100 parts by mass of the styrene copolymer (C) and the methacrylic resin (D), the content of the styrene copolymer (C) is 15 to 85 parts by mass, and the content of the methacrylic resin (D) is 85 to 15 parts by mass.

7. The resin laminate as described in any one of claims 1 to 3, characterized in that: The styrene copolymer (C) is a copolymer containing 68-84% by mass of vinyl aromatic monomer units (C1) and 16-32% by mass of cyclic anhydride monomer units (C2).

8. The resin laminate as described in claim 7, characterized in that: The vinyl aromatic monomer unit (c1) contained in the styrene copolymer (C) is styrene.

9. The resin laminate as described in claim 7, characterized in that: The cyclic anhydride monomer unit (c2) contained in the styrene copolymer (C) is maleic anhydride.

10. The resin laminate as described in any one of claims 1 to 3, characterized in that: At least one of the layers containing the polycarbonate resin (A) and the thermoplastic resin (B) contains an ultraviolet absorber.

11. The resin laminate as described in any one of claims 1 to 3, characterized in that: The resin laminate has been subjected to at least one of the following treatments: fingerprint resistance treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, and antifouling treatment on one or both sides.

12. The resin laminate as described in any one of claims 1 to 3, characterized in that: When visually inspecting a 297mm × 210mm prototype sample in a dark room with a three-wavelength fluorescent lamp in the lit state and an illuminance of 1,200–2,000 lux, the number of interface stripes is less than 5.

13. A transparent substrate material, characterized in that: The resin laminate comprising any one of claims 1 to 12.

14. A transparent protective material, characterized in that: The resin laminate comprising any one of claims 1 to 12.

15. A front protective plate for a touch panel, characterized in that: The resin laminate comprising any one of claims 1 to 12.

16. A front panel for car navigation, office automation (OA) equipment, or portable electronic devices, characterized in that: The resin laminate comprising any one of claims 1 to 12.

Images