JP7749564B2 - Resin laminate, and transparent substrate material and transparent protective material using the same - Google Patents

Description

The present invention relates to a resin laminate used as a transparent substrate material or protective material. More specifically, it relates to a resin laminate that has excellent thermoformability at low temperatures, suppresses the occurrence of interference fringes, and has a good appearance.

Acrylic resins have excellent surface hardness, transparency, scratch resistance, and weather resistance. On the other hand, polycarbonate resins have excellent impact resistance. For this reason, laminates having an acrylic resin layer and a polycarbonate resin layer have excellent surface hardness, transparency, scratch resistance, weather resistance, and impact resistance, and are used in display windows for automobile parts, home appliances, electronic devices, and portable information terminals.

In recent years, with the diversification of design needs, there has been a demand for products with enhanced design, such as the front panels of display devices, achieved through thermoforming processes such as vacuum forming and pressure forming. Due to the excellent performance described above, laminates comprising acrylic resin layers and polycarbonate resin layers have been attempted for use as front panels. However, when thermoforming a laminate comprising acrylic resin layers and polycarbonate resin layers, the sheet must be heated to a temperature at which the polycarbonate resin is sufficiently elongated. This results in excessive heat being applied to the acrylic resin, which can lead to delamination at the interface between the acrylic resin layer and the polycarbonate resin layer, resulting in whitening of the surface and cracking. On the other hand, lowering the molding temperature to prevent whitening and cracking can result in "springback," in which the mold shape is not reproduced.

Patent Document 1 discloses a molding resin sheet made of a polycarbonate resin having specific terminal groups and an acrylic resin, as a molding resin sheet suitable for thermoforming, such as vacuum forming or pressure forming. Such a resin sheet is less likely to whiten or crack when bent during thermoforming. However, applying a hard coat to the surface of the acrylic resin layer of such a resin sheet poses the problem of cracking during thermoforming.

Patent Document 2 discloses a laminate of an alloy layer of styrene-maleic anhydride copolymer and methacrylic resin and a polycarbonate resin layer, which can be thermoformed at a temperature of 160°C. Such a laminate does not cause any problems when thermoformed at a temperature of 160°C. However, a resin laminate having a hard coat layer on the surface of the alloy layer of styrene-maleic anhydride copolymer and methacrylic resin of such a laminate has the problem that cracks occur in the bent portions of the resin laminate when thermoformed at a temperature of 160°C.

International Publication No. 2016/060100 International Publication No. 2015/133530

The objective of the present invention is to provide a resin laminate that has excellent thermoformability at low temperatures, has a good appearance, and suppresses the occurrence of interference fringes.

The inventors have conducted extensive research to solve the above problems and have completed the present invention. Specifically, the present invention is as follows:

[1] A resin laminate having a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate-based resin (A), and having a hard coat layer on at least one surface of the layer containing the thermoplastic resin (B),
The polycarbonate resin (A) has a glass transition temperature of 115°C to 140°C,
the thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), and the content of the methacrylic resin (C) is 15 to 70 parts by mass and the content of the styrene copolymer (D) is 85 to 30 parts by mass, based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D);
the styrene copolymer (D) is a copolymer containing 68 to 84 mass% of vinyl aromatic monomer units (d1) and 16 to 32 mass% of cyclic acid anhydride monomer units (d2), and has a weight average molecular weight of 50,000 to 130,000;
The resin laminate is such that, after being thermoformed to a radius of 50 mm using a hot press machine at a mold temperature of 120°C, cracks and springback do not occur in the bent portions.
[2] The resin laminate according to the above [1], wherein the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 15°C.
[3] The resin laminate according to the above [1] or [2], wherein the thermoplastic resin (B) is a polymer alloy of the methacrylic resin (C) and the styrene copolymer (D).
[4] The resin laminate according to any one of the above [1] to [3], wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene.
[5] The resin laminate according to any one of the above [1] to [4], wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride.
[6] The resin laminate according to any one of [1] to [5] above, wherein the polycarbonate resin (A) has a terminal structure derived from a monohydric phenol represented by the following general formula (1) and a structural unit derived from a dihydric phenol:
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R ₂ to R ₅ each represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent, and the substituent is halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)
[7] The resin laminate according to any one of [1] to [6] above, wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.4 to 4.0 mm.
[8] The resin laminate according to any one of the above [1] to [7], wherein at least one of the layer containing the polycarbonate-based resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer contains an ultraviolet absorber.
[9] The resin laminate according to any one of the above [1] to [8], wherein the hard coat layer is an acrylic hard coat.
[10] The resin laminate according to any one of [1] to [9] above, wherein one or both surfaces of the resin laminate are subjected to at least one of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, and anti-fouling treatment.
[11] A thermoformed product obtained by heat bending the resin laminate according to any one of [1] to [10] above.
[12] A transparent substrate material comprising the resin laminate according to any one of [1] to [10] above or the thermoformed article according to [11] above.
[13] A transparent protective material comprising the resin laminate according to any one of [1] to [10] above or the thermoformed article according to [11] above.
[14] A touch panel front protection plate comprising the resin laminate according to any one of [1] to [10] above or the thermoformed article according to [11] above.
[15] A front panel for a car navigation system, an office automation device, or a portable electronic device, comprising the resin laminate according to any one of [1] to [12] above, or the thermoformed article according to [11] above.
[16] A method for producing a thermoformed product, comprising a step of hot bending a resin laminate at a mold temperature of 100 ° C to 135 ° C,
the resin laminate has a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate-based resin (A), and has a hard coat layer on at least one surface of the layer containing the thermoplastic resin (B);
The polycarbonate resin (A) has a glass transition temperature of 115°C to 140°C,
the thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), and the content of the methacrylic resin (C) is 15 to 70 parts by mass and the content of the styrene copolymer (D) is 85 to 30 parts by mass, based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D);
In the above production method, the styrene copolymer (D) is a copolymer containing 68 to 84 mass% of vinyl aromatic monomer units (d1) and 16 to 32 mass% of cyclic acid anhydride monomer units (d2), and has a weight average molecular weight of 50,000 to 130,000.

According to the present invention, there is provided a resin laminate that is excellent in thermoforming at low temperatures and that can be used to form thermoformed articles in which the occurrence of interference fringes is suppressed. That is, the resin laminate of the present invention suppresses the occurrence of whitening and cracking during thermoforming, and a molded article having a good appearance can be obtained.
The resin laminate can be used as a transparent substrate material or a transparent protective material, specifically, as a front panel for protecting portable display devices such as mobile phone terminals, portable electronic toys, personal digital assistants, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD televisions.

The present invention will be explained in detail below using manufacturing examples and examples, but the present invention is not limited to the manufacturing examples and examples exemplified, and can be modified in any way as long as it does not significantly deviate from the content of the present invention.

<Polycarbonate Resin (A)>
The polycarbonate-based resin (A) used in the present invention is a polycarbonate-based resin (A) primarily composed of polycarbonate resin. Here, "primarily composed of polycarbonate resin" means that the polycarbonate resin content exceeds 50% by mass. The polycarbonate-based resin (A) preferably contains 75% or more by mass of polycarbonate resin, more preferably 90% or more by mass of polycarbonate resin, and even more preferably consists essentially of polycarbonate resin. The polycarbonate-based resin (A) contains a carbonate bond in the molecular main chain. That is, the polycarbonate-based resin (A) is not particularly limited as long as it contains an -[O-R-OCO]- unit (where R represents an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further represents a linear or branched structure). However, it is particularly preferred to use a polycarbonate containing a structural unit of the following formula (2). The use of such a polycarbonate enables the production of a resin laminate with excellent impact resistance.

The polycarbonate resin (A) is preferably synthesized using a monohydric phenol represented by the following general formula (1) as a terminal terminator.
(wherein R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms;
R ₂ to R ₅ each represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent, and the substituent is halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

The monohydric phenol of general formula (1) is more preferably a monohydric phenol represented by the following general formula (3).
(wherein _R1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms).

The number of carbon atoms in _R1 in general formula (1) or general formula (3) is more preferably within a specific numerical range. Specifically, the upper limit of the number of carbon atoms in _R1 is preferably 36, more preferably 22, and particularly preferably 18. The lower limit of the number of carbon atoms in _R1 is preferably 8, and more preferably 12.

Among the monohydric phenols (end terminators) represented by general formula (1) or general formula (3), it is particularly preferred to use either or both of parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester as the end terminator.

When a monohydric phenol (terminal terminator) having an alkyl group with 16 carbon atoms is used as R ₁ in general formula (1) or general formula (3), the glass transition temperature, melt fluidity, moldability, drawdown resistance, and solvent solubility of the monohydric phenol during polycarbonate resin production are excellent, and this is particularly preferred as a terminal terminator for use in the polycarbonate resin of the present invention.

On the other hand, if the number of carbon atoms in _R1 in general formula (1) or general formula (3) is too large, the solubility of the monohydric phenol (end-stopper) in organic solvents tends to decrease, which may result in a decrease in productivity during the production of polycarbonate resins.
For example, when the carbon number of _R1 is 36 or less, the productivity and economy of producing a polycarbonate resin are high. When the carbon number of _R1 is 22 or less, the monohydric phenol has particularly excellent solubility in organic solvents, and the productivity and economy of producing a polycarbonate resin can be significantly increased.
If the number of carbon atoms in R ₁ in general formula (1) or general formula (3) is too small, the glass transition temperature of the polycarbonate resin will not be sufficiently low, and thermoformability may decrease.

Other resins contained in the polycarbonate-based resin (A) include polyester-based resins. The polyester-based resin may contain terephthalic acid as the primary dicarboxylic acid component, but may also contain dicarboxylic acid components other than terephthalic acid. For example, a polyester-based resin obtained by polycondensation of a glycol component containing 80 to 60 parts by weight (molar ratio) of ethylene glycol and 20 to 40 parts by weight (molar ratio, total 100) of 1,4-cyclohexanedimethanol, the primary component, and a dicarboxylic acid component, known as "PETG," is preferred. The polycarbonate-based resin (A) may also contain polyestercarbonate-based resins having ester bonds and carbonate bonds in the polymer backbone.

In the present invention, the weight-average molecular weight of the polycarbonate-based resin (A) affects the impact resistance and molding conditions of the resin laminate. In other words, if the weight-average molecular weight is too low, the impact resistance of the resin laminate will decrease, which is undesirable. If the weight-average molecular weight is too high, an excessive heat source may be required when laminating layers containing the polycarbonate-based resin (A), which is undesirable. Furthermore, some molding methods require high temperatures, which expose the polycarbonate-based resin (A) to high temperatures, which may adversely affect its thermal stability. The weight-average molecular weight of the polycarbonate-based resin (A) is preferably 10,000 to 75,000, more preferably 15,000 to 60,000, and even more preferably 20,000 to 50,000.

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

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

The glass transition temperature of the polycarbonate-based resin (A) used in the present invention is preferably 115 to 140°C, more preferably 115 to 135°C, even more preferably 115 to 130°C, and particularly preferably 115°C or higher but lower than 130°C. Note that the glass transition temperature of the polycarbonate-based resin (A) in this specification is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C/min and calculated at the intersection of the baseline and the tangent at the inflection point.

The melt flow rate of the polycarbonate resin (A) is preferably in the range of 1 to 30 g/10 min, more preferably in the range of 8 to 20 g/10 min, and even more preferably in the range of 11 to 15 g/10 min. A melt flow rate in the range of 1 to 30 g/10 min provides good stability in hot melt molding. Note that the melt flow rate of the polycarbonate resin (A) in this specification is measured using a melt indexer at a temperature of 300°C under a load of 1.2 kg.

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

<Thermoplastic resin (B)>
The thermoplastic resin (B) used in the present invention contains a methacrylic resin (C) and a styrene copolymer (D). Each of the components will be described below.

<Methacrylic resin (C)>
The methacrylic resin (C) contained in the thermoplastic resin (B) according to the present invention may be a resin containing a structural unit derived from a methacrylic acid ester monomer.

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

Furthermore, from the viewpoint of heat resistance, the above-mentioned methacrylic resin (C) preferably contains 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, of structural units derived from methacrylic acid ester monomers. When the methacrylic resin (C) contains 80% by mass or more of structural units derived from methacrylic acid ester monomers, compatibility with the styrene copolymer (D) is favorable, which is preferable. On the other hand, when the structural units derived from methacrylic acid ester monomers are less than 80% by mass, the resin may not be compatible with the styrene copolymer (D) and may become cloudy.

The methacrylic resin (C) may also contain structural units derived from monomers other than methacrylic acid esters. Examples of such other monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, and thiazolinone. Examples of acrylic acid esters include trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate, and from the viewpoint of availability, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate are preferred, with methyl acrylate and ethyl acrylate being more preferred, and methyl acrylate being most preferred. The total content of structural units derived from these other monomers in the methacrylic resin (C) is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

The lower limit of the triad syndiotacticity (rr) of the methacrylic resin (C) is preferably 50 mol% or more, more preferably 51% or more, and even more preferably 52% or more. Having a lower limit of the content of such structures of 50 mol% or more results in excellent heat resistance.

Here, the syndiotacticity (rr) expressed as a triad (hereinafter sometimes simply referred to as "syndiotacticity (rr)") is the proportion of two chains (diads) in a chain of three consecutive structural units (triad) that are both racemo (denoted as rr). Note that in the chains (diads) of structural units in a polymer molecule, those with the same steric configuration are called meso and those with the opposite configuration are called racemo, and are denoted as m and r, respectively.
The syndiotacticity (rr) (%) of the methacrylic resin (C) can be calculated by measuring ^{a 1} H-NMR spectrum in deuterated chloroform at 30°C, measuring the area (X) of the region from 0.6 to 0.95 ppm and the area (Y) of the region from 0.6 to 1.35 ppm from the spectrum when tetramethylsilane (TMS) is set to 0 ppm, and then using the formula: (X/Y) × 100.

The weight-average molecular weight of the methacrylic resin (C) is determined by the ease of mixing (dispersion) with the styrene copolymer (D) and the ease of manufacturing the thermoplastic resin (B). In other words, if the weight-average molecular weight of the methacrylic resin (C) is too high, the difference in melt viscosity with the styrene copolymer (D) will be too great, resulting in poor mixing (dispersion) of the two, which can lead to problems such as poor transparency of the thermoplastic resin (B) or inability to continue stable melt-kneading. Conversely, if the weight-average molecular weight of the methacrylic resin (C) is too low, the strength of the thermoplastic resin (B) will decrease, resulting in problems such as reduced impact resistance of the resin laminate. The weight-average molecular weight of the methacrylic resin (C) is preferably in the range of 50,000 to 700,000, more preferably 60,000 to 500,000, and even more preferably 70,000 to 200,000. The weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

The glass transition temperature of the methacrylic resin (C) is preferably 100°C or higher, more preferably 105°C or higher, and even more preferably 108°C or higher. A glass transition temperature of 100°C or higher means that the resin laminate provided by the present invention is less likely to deform or crack in a thermal environment. Note that the glass transition temperature of the methacrylic resin (C) in this specification is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C/min, and calculated at the intersection of the baseline and the tangent at the inflection point.

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

<Styrene copolymer (D)>
The styrene copolymer (D) contained in the thermoplastic resin (B) according to the present invention is characterized in that it contains vinyl aromatic monomer units (d1) and cyclic acid anhydride monomer units (d2), and the total proportion of the vinyl aromatic monomer units (d1) and the cyclic acid anhydride monomer units (d2) is 92 to 100 mass% based on the total of all monomer units in the styrene copolymer (D).

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

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

In the styrene copolymer (D) used in the present invention, the total proportion of the vinyl aromatic monomer units (d1) and the cyclic acid anhydride monomer units (d2) is 92 to 100 mass%, preferably 95 to 100 mass%, and more preferably 98 to 100 mass%, based on the total of all monomer units in the styrene copolymer (D).
That is, the styrene copolymer (D) may contain a monomer unit other than the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) in an amount of 8% by mass or less based on the total amount of all monomer units. Examples of the monomer unit other than the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) include a methacrylic acid ester monomer unit and an N-substituted maleimide monomer.
Examples of the methacrylate ester monomer units in the styrene copolymer (D) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate. methacrylic acid esters such as 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, and tricyclo[5.2.1.02,6]dec-8-yl methacrylate; aryl methacrylates such as phenyl methacrylate; and aralkyl methacrylates such as benzyl methacrylate, among which methyl methacrylate is preferred from the viewpoint of compatibility with methacrylic resins. Two or more of these methacrylic acid ester monomers may be mixed.
Examples of the N-substituted maleimide monomer in the styrene copolymer (D) include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide, and N-phenylmaleimide is preferred from the viewpoint of compatibility with the methacrylic resin. Two or more of these N-substituted maleimide monomers may be mixed.

The proportion of the vinyl aromatic monomer units (d1) is 68 to 84 mass%, preferably 70 to 82 mass%, more preferably 74 to 80 mass%, and even more preferably 76 to 79 mass%, based on the total of all monomer units in the styrene copolymer (D). The proportion of the cyclic acid anhydride monomer units (d2) is 16 to 32 mass%, preferably 18 to 30 mass%, more preferably 20 to 26 mass%, and even more preferably 21 to 24 mass%, based on the total of all monomer units in the styrene copolymer (D).
If the proportion of the vinyl aromatic monomer units (d1) relative to the total of all monomer units in the styrene copolymer (D) is outside the range of 68 to 84 mass%, the compatibility with the methacrylic resin (C) will be poor. Also, if the proportion of the cyclic acid anhydride monomer units (d2) relative to the total of all monomer units in the styrene copolymer (D) is outside the range of 16 to 32 mass%, the compatibility with the methacrylic resin (C) will be poor.

From the viewpoint of thermoformability at low temperatures, the weight-average molecular weight of the styrene copolymer (D) is preferably 50,000 to 130,000, more preferably 55,000 to 100,000, and particularly preferably 60,000 to 90,000. The weight-average molecular weight is the weight-average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

The glass transition temperature of the styrene copolymer (D) is preferably in the range of 120 to 190°C, and more preferably in the range of 130 to 170°C. A glass transition temperature of 120°C or higher means that the resin laminate provided by the present invention is less likely to deform or crack in a thermal environment. Furthermore, a glass transition temperature of 190°C or lower provides excellent processability, such as continuous thermal shaping using a mirrored roll or shaping roll, or batch thermal shaping using a mirrored mold or shaping mold. The glass transition temperature of the styrene copolymer (D) in this specification is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C/min, and calculated at the intersection of the baseline and the tangent at the inflection point.

The melt flow rate of the styrene copolymer (D) is preferably in the range of 1 to 10 g/10 min, more preferably in the range of 3 to 8 g/10 min, and even more preferably in the range of 4 to 7 g/10 min. A melt flow rate in the range of 1 to 10 g/10 min provides good stability in hot melt molding. Note that the melt flow rate of the styrene copolymer (D) in this specification is a value measured using a melt indexer at a temperature of 230°C under a load of 3.8 kg.

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

The styrene copolymer (D) is a binary or multi-component copolymer containing vinyl aromatic monomer units (d1) and cyclic acid anhydride monomer units (d2). By combining it with methacrylic resin (C), a resin laminate can be obtained that has higher hardness than when only the styrene copolymer (D) is used and has better thermoformability than when only the methacrylic resin (C) is used.

In the present invention, the mass ratio of the methacrylic resin (C) to the styrene copolymer (D) is preferably 15 to 70 parts by mass of the methacrylic resin (C) and 85 to 30 parts by mass of the styrene copolymer (D), based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D). More preferably, the mass ratio is 20 to 65 parts by mass of the methacrylic resin (C) and 80 to 35 parts by mass of the styrene copolymer (D), and even more preferably, the mass ratio is 20 to 55 parts by mass of the methacrylic resin (C) and 80 to 45 parts by mass of the styrene copolymer (D). By maintaining this mass ratio, an excellent thermoplastic resin (B) can be obtained that maintains transparency, has excellent heat resistance, a high refractive index, excellent thermoformability at low temperatures, and a good appearance.

The glass transition temperature of the thermoplastic resin (B) is preferably in the range of 120 to 165°C, and more preferably in the range of 120 to 155°C. A glass transition temperature of 120°C or higher means that the resin laminate provided by the present invention is less likely to deform or crack in a thermal environment. Furthermore, a glass transition temperature of 165°C or lower provides excellent processability, such as continuous thermal shaping using a mirrored roll or shaping roll, or batch thermal shaping using a mirrored mold or shaping mold. The glass transition temperature of the thermoplastic resin (B) in this specification is the temperature measured using a differential scanning calorimeter at a heating rate of 10°C/min, and calculated at the intersection of the baseline and the tangent at the inflection point.

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

In the present invention, there are no particular limitations on the method for producing thermoplastic resin (B). Known methods can be used, such as premixing the necessary components using a mixer such as a tumbler, Henschel mixer, or super mixer, and then melt-kneading the components using a machine such as a Banbury mixer, roll, Brabender, single-screw extruder, twin-screw extruder, or pressure kneader.

The thermoplastic resin (B) used in the present invention has a relatively high glass transition temperature, and the difference between this and the glass transition temperature of the polycarbonate-based resin (A) is small. This has the advantage that even if the glass transition temperature is brought close to that of the polycarbonate-based resin (A) during hot press molding or hot bending, there is little problem with poor appearance in the layer containing the thermoplastic resin (B). The difference between the glass transition temperature of the polycarbonate-based resin (A) and the glass transition temperature of the thermoplastic resin (B) is preferably in the range of 0 to 15°C, and more preferably in the range of 0 to 10°C.

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

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

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

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

(Meth)acrylate monomers having at least one (meth)acryloyloxy group and one hydroxyl group per molecule that are used in the urethane reaction include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

Polyisocyanates used in the urethane reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (e.g., hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.

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

Polyester polyols include those obtained by the dehydration condensation reaction of the above-mentioned polyols with polycarboxylic acids. Specific polycarboxylic acid compounds include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may also be anhydrides. Furthermore, polyether polyols include polyalkylene glycols as well as polyoxyalkylene-modified polyols obtained by the reaction of the above-mentioned polyols or phenols with alkylene oxides.

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

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

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

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

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

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

There are no particular limitations on the method for forming the hard coat layer, but it can be formed, for example, by applying a hard coat liquid to a layer located below the hard coat layer and then photopolymerizing it.

There are no particular limitations on the method for applying the hard coat liquid (polymerizable composition), and any known method can be used. Examples include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and spraying.

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

The irradiation intensity of the lamp is a factor that determines the degree of polymerization of the resulting polymer and is appropriately controlled depending on the performance of the target product. When a typical cleavage-type initiator having an acetophenone group is blended, the irradiance is preferably in the range of 0.1 to 300 mW/ ^cm² . In particular, it is preferable to use a metal halide lamp with an irradiance of 10 to 40 mW/ ^cm² .

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

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

To improve the adhesion of the hard coat layer, the coating surface may be pretreated. Examples of pretreatments include well-known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment using a resin composition.

The hard coat layer preferably has a pencil hardness of 2H or more when irradiated with ultraviolet light (254 nm) using a metal halide lamp with an irradiation output of 20 mW/cm ² .

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

<Haze>
The resin laminate of the present invention is not particularly limited, but preferably has a haze of 1.0% or less, more preferably 0.8% or less, and particularly preferably 0.7% or less. If the haze exceeds 1.0%, the resin laminate may appear whitish to the naked eye.

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

In the present invention, molding becomes difficult if the total thickness of the layer containing polycarbonate resin (A), the layer containing thermoplastic resin (B), and the hard coat layer is too thin or too thick. The total thickness of the resin laminate is preferably 0.4 to 4.0 mm, more preferably 0.5 to 3.5 mm, and even more preferably 0.5 to 3.0 mm.

In the present invention, the difference in refractive index between the polycarbonate-based resin (A) and the thermoplastic resin (B) is preferably in the range of 0 to 0.07, more preferably in the range of 0 to 0.06, and even more preferably in the range of 0 to 0.05. If the difference in refractive index between the polycarbonate-based resin (A) and the thermoplastic resin (B) is greater than 0.07, the reflected light intensity at the interface between the layer containing the polycarbonate-based resin (A) and the layer containing the thermoplastic resin (B) will be high, which may result in problems such as interference fringes.

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

<Optional Additives>
In the present invention, the layer containing the polycarbonate-based resin (A) forming the base layer and/or the layer containing the thermoplastic resin (B) forming the surface layer may contain components other than the above-mentioned main components.

For example, an ultraviolet absorber can be mixed into the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and/or the hard coat layer. In the present invention, the hard coat layer may also contain an ultraviolet absorber. If the content of the ultraviolet absorber is too high, depending on the molding method, the excess ultraviolet absorber may scatter due to high temperatures, contaminating the molding environment and causing problems. For this reason, the content of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass. Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone; 2-(2-hydroxy-5-methylphenyl)benzotriazole; benzotriazole-based ultraviolet absorbers such as 2-(2-hydroxy-3-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)benzotriazole, and (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol; benzoate-based ultraviolet absorbers such as phenyl salicylate and 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate; hindered amine-based ultraviolet absorbers such as bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate; ,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-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-based ultraviolet absorbers such as azine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, and 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine; 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl acrylate, 3-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl acrylate, and the like; benzotriazol-5-yl]propyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]propyl acrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]butyl methacrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]butyl acrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl acrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl acrylate butyl methacrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]butyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl acrylate, 2-(methacryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxol Examples of sesamol-type benzotriazole-based ultraviolet absorbers include 2-(acryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 2-(acryloyloxy)ethyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(methacryloyloxy)butyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, and 4-(acryloyloxy)butyl 2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate. The mixing method is not particularly limited, and methods such as compounding the entire amount, dry blending a masterbatch, and dry blending the entire amount can be used.

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

The materials for the layer containing polycarbonate-based resin (A), the layer containing thermoplastic resin (B), and the hard coat layer in the present invention, such as polycarbonate-based resin (A) and thermoplastic resin (B), are preferably filtered and purified by filtration. Purifying or laminating through a filter makes it possible to obtain a resin laminate with minimal appearance defects such as foreign matter and defects. There are no particular restrictions on the filtration method, and melt filtration, solution filtration, or a combination thereof can be used.

There are no particular restrictions on the filter used; known filters can be used, and they are selected appropriately depending on the operating temperature, viscosity, and filtration accuracy of each material. The filter medium is not particularly limited, but any of the following can be used: polypropylene, cotton, polyester, viscose rayon, or glass fiber nonwoven fabric or roving yarn rolls, phenolic resin-impregnated cellulose, sintered metal fiber nonwoven fabric, sintered metal powder, breaker plate, or a combination of these. Sintered metal fiber nonwoven fabric is particularly preferred, considering its heat resistance, durability, and pressure resistance.

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

When filtering polycarbonate resin (A) and thermoplastic resin (B), it is preferable to use a polymer filter, such as one used for melt filtration of thermoplastic resins. Polymer filters are classified according to their structure into leaf disc filters, candle filters, pack disc filters, and cylindrical filters, but leaf disc filters, which have a large effective filtration area, are particularly suitable.

<Heat bending process>
The heat-bending process for the resin laminate of the present invention is not particularly limited. Examples include "heat press molding," in which a convex (male) and concave (female) molds are attached to a press and a heat-softened laminate sheet is sandwiched between the two molds; "vacuum molding," in which the heat-softened laminate sheet and the convex (male) mold are placed under a vacuum to adhere the laminate sheet to the mold and finish it into the desired shape; and "pressure molding," in which the heat-softened laminate sheet and the convex (male) mold are pressed under pressure greater than atmospheric pressure to adhere the laminate sheet to the mold and finish it into the desired shape. The resin laminate of the present invention can be obtained as a heat-formed product that does not undergo springback even when heat-bending is performed at low temperatures (e.g., 100 to 135°C).

<Thermoformed body>
When heat-press molding a laminated sheet using conventional polycarbonate resins (e.g., Iupilon S-2000, Iupilon S-1000, Iupilon E-2000, commercially available from Mitsubishi Engineering Plastics Corporation), it is necessary to heat the sheet at 135 to 145 ° C until the polycarbonate resin is sufficiently elongated. As a result, excessive heat is applied to the thermoplastic resin, which can cause peeling at the interface between the thermoplastic resin layer and the polycarbonate resin layer, resulting in surface whitening and cracking. Furthermore, heating the sheet to 160 ° C can cause the surface to melt or mold scratches to be transferred. On the other hand, when heat-press molding is performed at low temperatures of 100 ° C to 135 ° C to suppress thermoforming defects, "springback" can occur, in which the sheet tries to return to a flat shape from the mold without reproducing the shape of the mold.

In contrast, the resin laminate of an embodiment of the present invention uses a specific polycarbonate-based resin (A), so even when hot press molded at low temperatures of 100°C to 135°C, springback does not occur, and a thermoformed product with excellent design properties can be obtained at low temperatures.

Furthermore, when a resin laminate having a layer containing a thermoplastic resin on a layer containing a polycarbonate resin and a hard coat layer on the surface of the layer containing the thermoplastic resin is subjected to heat press molding at a low temperature of 100°C to 135°C, cracks may occur in the bent portions of the resin laminate.

In contrast, the resin laminate of an embodiment of the present invention uses a specific thermoplastic resin (B). Therefore, even when a resin laminate having a hard coat layer on the surface of a layer containing thermoplastic resin (B) is heat-press molded at a low temperature of 100°C to 135°C, no cracks occur in the bent portions of the resin laminate, and a thermoformed product with excellent design at low temperatures can be obtained.

<Application>
The molded article (e.g., thermoformed article) of the embodiment is a molded article including the resin laminate of the present invention including the various preferred forms and configurations described above. There are no limitations on the shape, pattern, color, dimensions, etc. of the molded article, and they may be set arbitrarily depending on the application.
The resin laminates and thermoformed articles of the embodiments have excellent thermoformability at low temperatures (e.g., 100 to 135°C) and can suppress the occurrence of interference fringes. Therefore, they are suitable for use as transparent substrate materials, transparent protective materials, and the like. Specifically, they can be used as transparent substrate materials and transparent protective materials (e.g., front panels) for portable display devices such as mobile phone terminals, portable electronic toys, personal digital assistants, and mobile PCs, as well as stationary display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD televisions. In particular, they are suitable for use as front panel protective panels for touch panels that require high design quality, and front panels for car navigation systems, office automation equipment, and portable electronic devices.

The present embodiment will be explained in more detail below using examples, but the present embodiment is not limited to these examples.

<Composition ratio of monomer units in styrene copolymer>
Calculations were made from the measured values of ¹ H-NMR and ¹³ C-NMR (400 MHz: solvent: CDCl ₃ ) using a JNM-AL400 manufactured by JEOL Ltd.

<Glass transition temperature>
A differential scanning calorimeter DSC6200 manufactured by Seiko Instruments Inc. was used. Under a nitrogen flow of 30 ml/min, the temperature was increased from 30°C to 200°C at 10°C/min, then decreased from 200°C to 30°C at 50°C/min, and again increased from 30°C to 200°C at 10°C/min. The intersection of the baseline and the tangent at the inflection point during the second temperature increase was used as the glass transition temperature.

<Appearance of pellets>
During the production of the pellets, the appearance of the pellets was visually evaluated and judged as pass or fail according to the following criteria, with ◯ being considered as pass.
○: Transparent ×: Translucent or cloudy

<Refractive index>
Test specimens were prepared using an injection molding machine and cut into pieces measuring 40 mm in length, 10 mm in width, and 3 mm in thickness. The refractive index of the specimens was measured using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. The measurement temperature was 20°C, the measurement wavelength was 589 nm, and monobromonaphthalene was used as the intermediate liquid.

<Total light transmittance>
The total light transmittance of the resin laminate was measured in accordance with JIS K7361-1 using a reflectance/transmittance meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.).

<Haze>
The haze of the resin laminate was measured in accordance with JIS K7136 using a reflectance/transmittance meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.).

<Pencil hardness>
In accordance with JIS K 5600-5-4, pencils of gradually increasing hardness were pressed against the surface of the hard coat layer on the layer containing thermoplastic resin (B) near the center of the resin laminate at an angle of 45 degrees and with a load of 750 g, and the hardness of the hardest pencil that did not leave a scratch was evaluated as the pencil hardness.

<Interference fringes>
Black tape (black vinyl tape, model number 117BLA, manufactured by 3M Japan Co., Ltd.) was attached to the layer containing polycarbonate resin (A) or the layer containing thermoplastic resin (B) of the resin laminate, and a three-wavelength fluorescent lamp (Technica Inverter Light 60 AL-60231) was used to illuminate the surface of the layer containing thermoplastic resin (B), and interference fringes were evaluated. The pass/fail judgment of the interference fringes was made according to the following criteria, with ◯ being considered a pass.
○: No interference fringes are visible or the interference fringes are weak. ×: The interference fringes are strongly visible.

<Heat press molding processability>
A convex (male) mold and a concave (female) mold were prepared to bend a 1 mm thick resin laminate to a radius of 50 mm. The resin laminate was preheated at 90°C for 1 minute before molding, placed in the mold so that the hard coat surface was convex, and pressed at a mold temperature of 80°C, 120°C, or 160°C for 3 minutes, followed by natural cooling to produce a hot-press molded product.

<Appearance of the hot press molded product>
The appearance of the hot press molded article was visually evaluated and judged as pass/fail according to the following criteria, with ◯ being considered as pass.
○: No visible scratches or mold marks on the heat-pressed molded product ×: No visible scratches or mold marks on the heat-pressed molded product

<Cracks in bending parts>
The heat-press molded article was visually evaluated for cracks at the bent portions. The cracks at the bent portions were judged as pass or fail according to the following criteria, with ◯ being considered as pass.
○: No cracks are visible in the bent portion of the heat-pressed molded product. ×: Cracks are visible in the bent portion of the heat-pressed molded product.

<Spring back>
The above hot press molded article was fitted to a cylinder of 50 mm R, and the spring back was judged to be pass or fail according to the following criteria, with ◯ being considered pass.
○: Follows the cylinder (no spring back)
×: Not aligned with the cylinder (spring back occurs)
"◯" indicates a value within 50±2 mmR, and "×" indicates anything other than that.

For the examples, the following materials were used as polycarbonate resin (A-1), thermoplastic resins (B-1) to (B-2), methacrylic resin (C-1), styrene copolymer (D-1), and hard coat (H-1), but these materials are not limited to these. For the comparative examples, the following polycarbonate resin (F-1), thermoplastic resins (G-1) to (G-11), and styrene copolymers (E-1) to (E-3) were used.

<Methacrylic Resin (C-1), Styrene Copolymer (D-1), Styrene Copolymers (E-1) and (E-2), and Polycarbonate Resin (F-1)>
Methacrylic resin (C-1): ALTUGLAS (registered trademark) V020 manufactured by Arkema Inc. (weight average molecular weight: 127,000, glass transition temperature: 109°C, melt flow rate at 230°C under a load of 3.8 kg: 1.8 g/10 min, methyl methacrylate/methyl acrylate = 96.1 mass%/3.9 mass%, refractive index: 1.49, mm/mr/rr = 7.4 mol%/37.4 mol%/55.2 mol%)
Styrene copolymer (D-1): XIRANSO 23110 manufactured by Polyscope ((d1)/(d2) = 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 under a load of 3.8 kg: 5.9 g/10 min, refractive index: 1.58)
Styrene copolymer (E-1): XIRANSO 26080 manufactured by Polyscope ((d1)/(d2) = styrene/maleic anhydride = 75% by mass/25% by mass, weight average molecular weight: 47,600, glass transition temperature: 150°C, melt flow rate at 230°C under a load of 3.8 kg: 8.3 g/10 min, refractive index: 1.58)
Styrene copolymer (E-2): XIBOND140 manufactured by Polyscope ((d1)/(d2) = styrene/maleic anhydride = 85% by mass/15% by mass, weight average molecular weight: 134,000, glass transition temperature: 129°C, melt flow rate at 230°C under a load of 3.8 kg: 6.9 g/10 min, refractive index: 1.59)
Styrene copolymer (E-3): XIBOND180 manufactured by Polyscope ((d1)/(d2) = styrene/maleic anhydride = 67% by mass/33% by mass, weight average molecular weight: 50,100, glass transition temperature: 157°C, melt flow rate at 230°C under a load of 3.8 kg: 1.0 g/10 min, refractive index: 1.59)
Polycarbonate resin (F-1): Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Corporation (weight average molecular weight: 33,000, glass transition temperature: 147°C, melt flow rate at 300°C under a load of 1.2 kg: 7.5 g/10 min, refractive index: 1.59)

<Synthesis of Polycarbonate Resin (A-1)>
Synthesis Example 1 [Synthesis of polycarbonate resin end capping agent]
Based on Organic Chemistry Handbook, pp. 143-150, esterification was carried out by dehydration using 4-hydroxybenzoic acid manufactured by Tokyo Chemical Industry Co., Ltd. and 1-hexadecanol manufactured by Tokyo Chemical Industry Co., Ltd. to obtain hexadecyl parahydroxybenzoate (CEPB).

Synthesis Example 2 [Production of polycarbonate resin (A-1) pellets]
7.1 kg (31.14 mol) of bisphenol A (hereinafter referred to as BPA) manufactured by Nippon Steel Sumitomo Chemical Co., Ltd. and 30 g of hydrosulfite were dissolved in 57.2 kg of 9 wt.% aqueous sodium hydroxide solution. 40 kg of dichloromethane was added to the solution, and while stirring, 4.33 kg of phosgene was blown in over 30 minutes while maintaining the solution temperature in the range of 15°C to 25°C. After the phosgene blow-in was completed, 6 kg of 9 wt.% aqueous sodium hydroxide solution, 11 kg of dichloromethane, and a solution of 443 g (1.22 mol) of parahydroxybenzoic acid hexadecyl ester (CEPB) as a terminal terminator dissolved in 10 kg of methylene chloride were added and emulsified with vigorous stirring. Thereafter, 10 ml of triethylamine was added as a polymerization catalyst to the solution, and polymerization was carried out for approximately 40 minutes.
The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the organic phase was repeatedly washed with pure water until the pH of the washings became neutral. The organic solvent was evaporated and distilled off from this purified polycarbonate resin solution to obtain a polycarbonate resin powder.
The obtained polycarbonate resin powder was melt-kneaded at a cylinder temperature of 260° C. using a twin-screw extruder with a screw diameter of 35 mm, extruded into a strand shape, and pelletized with a pelletizer.
The polycarbonate resin (A-1) had a weight average molecular weight of 29,000, a glass transition temperature of 127° C., a melt flow rate at 300° C. under a load of 1.2 kg of 12.1 g/10 min, and a refractive index of 1.59.

Production Example 1 [Production of pellets of thermoplastic resin (B-1)]
25 parts by mass of methacrylic resin (C-1) and 75 parts by mass of styrene copolymer (D-1) for a total of 100 parts by mass, phosphorus-based additive PEP-36 (manufactured by ADEKA Corporation) 500 ppm, and stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin Co., Ltd.) 0.2% by mass was added, and after 20 minutes of mixing in a blender, a 26 mm screw diameter twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D ≒ 40) equipped with a polymer filter having a mesh size of 10 μm was used, and the mixture was melt-kneaded at a cylinder temperature of 240 ° C., extruded into strands, and pelletized with a pelletizer. Pellets of thermoplastic resin (B-1) were stably produced.
The pellets of thermoplastic resin (B-1) had an appearance of ◯ (transparent), a glass transition temperature of 134° C., and a refractive index of 1.56.

Production Example 2 [Production of pellets of thermoplastic resin (B-2)]
To a total of 100 parts by mass of 50 parts by mass of methacrylic resin (C-1) and 50 parts by mass of styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (B-2) could be stably produced.
The pellets of thermoplastic resin (B-2) had an appearance of ◯ (transparent), a glass transition temperature of 122° C., and a refractive index of 1.54.

Comparative Production Example 1 [Production of Pellets of Thermoplastic Resin (G-1)]
To a total of 100 parts by mass of 75 parts by mass of methacrylic resin (C-1) and 25 parts by mass of styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-1) could be stably produced.
The pellets of thermoplastic resin (G-1) had an appearance of ◯ (transparent), a glass transition temperature of 114° C., and a refractive index of 1.52.

Comparative Production Example 2 [Production of Pellets of Thermoplastic Resin (G-2)]
To a total of 100 parts by mass of 25 parts by mass of methacrylic resin (C-1) and 75 parts by mass of styrene copolymer (E-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-2) could be stably produced.
The pellets of thermoplastic resin (G-2) had an appearance of ◯ (transparent), a glass transition temperature of 136° C., and a refractive index of 1.56.

Comparative Production Example 3 [Production of Pellets of Thermoplastic Resin (G-3)]
To a total of 100 parts by mass of 50 parts by mass of methacrylic resin (C-1) and 50 parts by mass of styrene copolymer (E-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-3) could be stably produced.
The pellets of thermoplastic resin (G-3) had an appearance of ◯ (transparent), a glass transition temperature of 124° C., and a refractive index of 1.54.

Comparative Production Example 4 [Production of Pellets of Thermoplastic Resin (G-4)]
To a total of 100 parts by mass of 75 parts by mass of methacrylic resin (C-1) and 25 parts by mass of styrene copolymer (E-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-4) could be stably produced.
The pellets of thermoplastic resin (G-4) had an appearance of ◯ (transparent), a glass transition temperature of 115° C., and a refractive index of 1.51.

Comparative Production Example 5 [Production of Pellets of Thermoplastic Resin (G-5)]
To 100 parts by mass of methacrylic resin (C-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-5) could be stably produced.
The pellets of thermoplastic resin (G-5) had an appearance of ◯ (transparent), a glass transition temperature of 109° C., and a refractive index of 1.49.

Comparative Production Example 6 [Production of Pellets of Thermoplastic Resin (G-6)]
To 100 parts by mass of the styrene copolymer (D-1), 500 ppm of the phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of the thermoplastic resin (G-6) could be stably produced.
The pellets of thermoplastic resin (G-6) had an appearance of ◯ (transparent), a glass transition temperature of 145° C., and a refractive index of 1.58.

Comparative Production Example 7 [Production of Pellets of Thermoplastic Resin (G-7)]
To 100 parts by mass of the styrene copolymer (E-1), 500 ppm of the phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of the thermoplastic resin (G-7) could be stably produced.
The pellets of thermoplastic resin (G-7) had an appearance of ◯ (transparent), a glass transition temperature of 150° C., and a refractive index of 1.58.

Comparative Production Example 8 [Production of Pellets of Thermoplastic Resin (G-8)]
To a total of 100 parts by mass of 25 parts by mass of methacrylic resin (C-1) and 75 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-8) could be stably produced.
The appearance of the thermoplastic resin (G-8) pellets was x (semi-transparent).

Comparative Production Example 9 [Production of Pellets of Thermoplastic Resin (G-9)]
To a total of 100 parts by mass of 50 parts by mass of methacrylic resin (C-1) and 50 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-9) could be stably produced.
The appearance of the pellets of thermoplastic resin (G-9) was: × (semi-transparent).

Comparative Production Example 10 [Production of pellets of thermoplastic resin (G-10)]
To a total of 100 parts by mass of 25 parts by mass of methacrylic resin (C-1) and 75 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-10) could be stably produced.
The appearance of the pellets of thermoplastic resin (G-10) was: × (cloudy).

Comparative Production Example 11 [Production of Pellets of Thermoplastic Resin (G-11)]
To a total of 100 parts by mass of 50 parts by mass of methacrylic resin (C-1) and 50 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-11) could be stably produced.
The appearance of the pellets of thermoplastic resin (G-11) was poor (cloudy).

Example 1 [Production of resin laminate (I-1)]
A resin laminate was molded using a multi-layer extrusion device having a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all extruders, a multi-layer extruder having a 650 mm wide T-die connected to the feed block, and a multi-manifold die connected to each extruder. The thermoplastic resin (B-1) obtained in Production Example 1 was continuously introduced into the single-screw extruder with a shaft diameter of 32 mm and extruded under conditions of a cylinder temperature of 240 ° C and a discharge rate of 2.0 kg / h. Furthermore, the polycarbonate-based resin (A-1) obtained in Synthesis Example 2 was continuously introduced into the single-screw extruder with a shaft diameter of 65 mm and extruded under conditions of a cylinder temperature of 280 ° C and a discharge rate of 31.8 kg / h. The feed block connected to all extruders was equipped with a two-type, two-layer distributor pin, and the thermoplastic resin (B-1) and the polycarbonate-based resin (A-1) were introduced and laminated at a temperature of 270 ° C.
The extruded material was extruded into a sheet through a T-die connected to the end of the die and heated to 270°C, and cooled while transferring a mirror surface using three mirror-finish rolls whose temperatures, starting from the upstream side, were set to 110°C, 105°C, and 165°C, to obtain a resin laminate of thermoplastic resin (B-1) and polycarbonate-based resin (A-1). The overall thickness of the central part of the obtained resin laminate was 1000 μm, and the thickness of the surface layer (layer containing thermoplastic resin (B)) was 60 μm.
Furthermore, on the surface of the thermoplastic resin (B-1) of the resin laminate obtained above, a hexafunctional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 60 parts by weight, PEG200# diacrylate (product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) 35 parts by weight, and a fluorine-containing group, hydrophilic group, lipophilic group, UV-reactive group-containing oligomer (product name: RS-90, manufactured by DIC Corporation) 5 parts by weight, for a total of 100 parts by weight, to which 1% by weight of a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxy-cyclohexyl phenyl ketone] manufactured by BASF Corporation) was added, was applied with a bar coater, and the hard coat was cured by irradiating it with a metal halide lamp (20 mW / cm 2 ) for 5 seconds to produce a resin laminate (I-1). The hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-1) had a total light transmittance of 90.8%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Example 2 [Production of resin laminate (I-2)]
Except for using the thermoplastic resin (B-2) instead of the thermoplastic resin (B-1), a resin laminate (I-2) of a hard coat layer (H-1), a thermoplastic resin (B-2), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The overall thickness of the central part of the obtained resin laminate (I-2) was 1006 μm, the surface layer (B-2) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-2) had a total light transmittance of 90.8%, a haze of 0.2%, a pencil hardness of 3H, and interference fringes of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 1 [Production of Resin Laminate (J-1)]
Except for using the thermoplastic resin (G-1) instead of the thermoplastic resin (B-1), a resin laminate (J-1) of a hard coat layer (H-1), a thermoplastic resin (G-1), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The overall thickness of the central part of the obtained resin laminate (J-1) was 1006 μm, the surface layer (G-1) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-1) had a total light transmittance of 91.0%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 2 [Production of Resin Laminate (J-2)]
Except for using the thermoplastic resin (G-2) instead of the thermoplastic resin (B-1), a resin laminate (J-2) of a hard coat layer (H-1), a thermoplastic resin (G-2), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The overall thickness of the central part of the obtained resin laminate (J-2) was 1006 μm, the surface layer (G-2) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-2) had a total light transmittance of 90.9%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 3 [Production of Resin Laminate (J-3)]
Except for using the thermoplastic resin (G-3) instead of the thermoplastic resin (B-1), a resin laminate (J-3) of a hard coat layer (H-1), a thermoplastic resin (G-3), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The overall thickness of the central part of the obtained resin laminate (J-3) was 1006 μm, the surface layer (G-3) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-3) had a total light transmittance of 91.2%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 4 [Production of Resin Laminate (J-4)]
Except for using the thermoplastic resin (G-4) instead of the thermoplastic resin (B-1), a resin laminate (J-4) of a hard coat layer (H-1), a thermoplastic resin (G-4), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The overall thickness of the central part of the obtained resin laminate (J-4) was 1006 μm, the surface layer (G-4) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-4) had a total light transmittance of 91.2%, a haze of 0.2%, a pencil hardness of 3H, and interference fringes of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 5 [Production of Resin Laminate (J-5)]
Except for using the thermoplastic resin (G-5) instead of the thermoplastic resin (B-1), a resin laminate (J-5) of a hard coat layer (H-1), a thermoplastic resin (G-5), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The total thickness of the central part of the obtained resin laminate (J-5) was 1006 μm, the surface layer (G-5) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-5) had a total light transmittance of 91.4%, a haze of 0.3%, a pencil hardness of 3H, and interference fringes of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 6 [Production of Resin Laminate (J-6)]
Except for using the thermoplastic resin (G-6) instead of the thermoplastic resin (B-1), a resin laminate (J-6) of a hard coat layer (H-1), a thermoplastic resin (G-6), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The overall thickness of the central part of the obtained resin laminate (J-6) was 1006 μm, the surface layer (G-6) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-6) had a total light transmittance of 90.5%, a haze of 0.2%, a pencil hardness of H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent parts of the hot press moldability were poor, and the spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 7 [Production of resin laminate (J-7)]
Except for using the thermoplastic resin (G-7) instead of the thermoplastic resin (B-1), a resin laminate (J-7) of a hard coat layer (H-1), a thermoplastic resin (G-7), and a polycarbonate-based resin (A-1) was obtained in the same manner as the resin laminate (I-1) of Example 1. The overall thickness of the central part of the obtained resin laminate (J-7) was 1006 μm, the thickness of the surface layer (G-7) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm.
This resin laminate (J-7) had a total light transmittance of 90.6%, a haze of 0.2%, a pencil hardness of H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was good.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 8 [Production of Resin Laminate (J-8)]
A resin laminate (J-8) of a hard coat layer (H-1), a thermoplastic resin (B-1), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (I-1) of Example 1, except that polycarbonate-based resin (F-1) was used instead of polycarbonate-based resin (A-1) and cooling was changed to transferring a mirror surface using three mirror-finishing rolls set at temperatures of 130°C, 140°C, and 185°C from the upstream side. The overall thickness of the central part of the obtained resin laminate (J-8) was 1006 μm, the surface layer (B-1) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-8) had a total light transmittance of 90.8%, a haze of 0.2%, a pencil hardness of 3H, and interference fringes of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 9 [Production of Resin Laminate (J-9)]
Except for using the thermoplastic resin (B-2) instead of the thermoplastic resin (B-1), a resin laminate (J-9) of a hard coat layer (H-1), a thermoplastic resin (B-2), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-9) was 1006 μm, the surface layer (B-2) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-9) had a total light transmittance of 90.8%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 10 [Production of Resin Laminate (J-10)]
Except for using the thermoplastic resin (G-1) instead of the thermoplastic resin (B-1), a resin laminate (J-10) of a hard coat layer (H-1), a thermoplastic resin (G-1), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-10) was 1006 μm, the surface layer (G-1) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-10) had a total light transmittance of 91.0%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 11 [Production of Resin Laminate (J-11)]
Except for using the thermoplastic resin (G-2) instead of the thermoplastic resin (B-1), a resin laminate (J-11) of a hard coat layer (H-1), a thermoplastic resin (G-2), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-11) was 1006 μm, the surface layer (G-2) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-11) had a total light transmittance of 90.9%, a haze of 0.2%, a pencil hardness of 3H, and interference fringes of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 12 [Production of resin laminate (J-12)]
Except for using the thermoplastic resin (G-3) instead of the thermoplastic resin (B-1), a resin laminate (J-12) of a hard coat layer (H-1), a thermoplastic resin (G-3), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-12) was 1006 μm, the surface layer (G-3) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-12) had a total light transmittance of 91.2%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 13 [Production of resin laminate (J-13)]
Except for using the thermoplastic resin (G-4) instead of the thermoplastic resin (B-1), a resin laminate (J-13) of a hard coat layer (H-1), a thermoplastic resin (G-4), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-13) was 1006 μm, the surface layer (G-4) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-13) had a total light transmittance of 91.2%, a haze of 0.2%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 14 [Production of resin laminate (J-14)]
Except for using the thermoplastic resin (G-5) instead of the thermoplastic resin (B-1), a resin laminate (J-14) of a hard coat layer (H-1), a thermoplastic resin (G-5), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-14) was 1006 μm, the surface layer (G-5) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-14) had a total light transmittance of 91.4%, a haze of 0.3%, a pencil hardness of 3H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were good, and spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 15 [Production of resin laminate (J-15)]
Except for using the thermoplastic resin (G-6) instead of the thermoplastic resin (B-1), a resin laminate (J-15) of a hard coat layer (H-1), a thermoplastic resin (G-6), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-15) was 1006 μm, the surface layer (G-6) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-15) had a total light transmittance of 90.5%, a haze of 0.2%, a pencil hardness of H, and interference fringes of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

Comparative Example 16 [Production of resin laminate (J-16)]
Except for using the thermoplastic resin (G-7) instead of the thermoplastic resin (B-1), a resin laminate (J-16) of a hard coat layer (H-1), a thermoplastic resin (G-7), and a polycarbonate-based resin (F-1) was obtained in the same manner as the resin laminate (J-8) of Comparative Example 8. The overall thickness of the central part of the obtained resin laminate (J-16) was 1006 μm, the surface layer (G-7) thickness was 60 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (J-7) had a total light transmittance of 90.6%, a haze of 0.2%, a pencil hardness of H, and an interference pattern of ◯.
When hot press molding was performed at a mold temperature of 80°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 120°C, the appearance of the hot press molded product was good, cracks at the bent portions of the hot press molded product were poor, and the spring back of the hot press molded product was poor.
When hot press molding was performed at a mold temperature of 160°C, the appearance of the hot press molded product was poor, cracks at the bent portions of the hot press molded product were poor, and spring back of the hot press molded product was excellent.

As described above, by satisfying the conditions of the present invention, it is possible to obtain an advantageous resin laminate that has excellent thermoformability at low temperatures, suppresses the occurrence of interference fringes, and has a good appearance.

That is, as shown in Table 2, when comparing Production Examples 1 and 2 in which a specific methacrylic resin (C) and a specific styrene copolymer (D) were blended with pelletized thermoplastic resin (B) with Production Example 5 in which the specific methacrylic resin (C) was used alone, Production Examples 1 and 2 had a higher refractive index.
Furthermore, when comparing Production Examples 1 and 2 with Production Comparative Examples 8 to 11 in which a specific methacrylic resin (C) and a styrene copolymer (E-2, E-3) other than the specific styrene copolymer (D) were blended at a specific mass ratio, Production Examples 1 and 2 were more transparent and had a better appearance.

As shown in Table 3, for the resin laminate after hard coating, Examples 1 and 2 in which a specific methacrylic resin (C) and a specific styrene copolymer (D) were blended in a specific ratio, and pelletized high refractive index thermoplastic resin (B) and polycarbonate-based resin (A) were laminated together, and a hard coat was formed on one surface of the thermoplastic resin (B). A comparison of Comparative Example 1 in which a specific methacrylic resin (C) and a specific styrene copolymer (D) were blended in a ratio other than the specific ratio, and pelletized thermoplastic resin (G) and polycarbonate-based resin (A) were laminated together, and a hard coat was formed on one surface of the thermoplastic resin (G), showed that the resin laminates of Examples 1 and 2 suppressed cracking in the bent portions of the hot press molded body at a mold temperature of 120 ° C.
Furthermore, when Examples 1 and 2 are compared with Comparative Examples 2 and 3 in which a specific methacrylic resin (C) and a styrene copolymer (E-1) other than the specific weight-average molecular weight are blended in a specific ratio, pelletized thermoplastic resin (G) is laminated with a polycarbonate-based resin (A), and one surface of the thermoplastic resin (G) is hard-coated, the resin laminates of Examples 1 and 2 are more effective in suppressing cracks in the bent portions of the heat-press molded body at a mold temperature of 120°C.
Furthermore, when compared with Comparative Example 5 in which a thermoplastic resin (G) obtained by pelletizing a specific methacrylic resin (C) alone and a specific polycarbonate-based resin (A) are laminated together and one surface of the thermoplastic resin (G) has a hard coat, the resin laminates of Examples 1 and 2 suppressed cracking in the bent portions of the heat-press molded body at a mold temperature of 120°C.

Furthermore, when Examples 1 and 2 are compared with Comparative Examples 6 and 7 in which a thermoplastic resin (G) obtained by pelletizing a specific styrene copolymer (D) alone and a specific polycarbonate-based resin (A) are laminated together, and one surface of the thermoplastic resin (G) has a hard coating, the resin laminates of Examples 1 and 2 have higher pencil hardness and suppress cracking at the bent portions of the hot-press molded body.
Furthermore, when Examples 1 and 2 are compared with Comparative Examples 8 and 9 in which a specific methacrylic resin (C) and a specific styrene copolymer (D) are blended in a specific ratio, pelletized thermoplastic resin (B) is laminated with a polycarbonate-based resin (F), and one surface of the thermoplastic resin (B) is hard-coated, the resin laminates of Examples 1 and 2 suppressed springback of the hot-press molded body at a mold temperature of 120°C.

In addition, in Examples 1 and 2, springback occurred in the hot-press molded body when the mold temperature was 80° C., and the appearance of the hot-press molded body deteriorated and cracks occurred in the bent portions when the mold temperature was 160° C. On the other hand, when the mold temperature was 120° C., the appearance of the hot-press molded body was good, and cracks and springback in the bent portions were suppressed.

Claims (16)

A resin laminate having a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate-based resin (A), and having a hard coat layer on at least one surface of the layer containing the thermoplastic resin (B),
The polycarbonate resin (A) has a glass transition temperature of 115°C to 140°C,
the thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), and the content of the methacrylic resin (C) is 15 to 70 parts by mass and the content of the styrene copolymer (D) is 85 to 30 parts by mass, based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D);
the styrene copolymer (D) is a copolymer containing 68 to 84 mass% of vinyl aromatic monomer units (d1) and 16 to 32 mass% of cyclic acid anhydride monomer units (d2), and has a weight average molecular weight of 50,000 to 130,000;
The resin laminate, which does not develop cracks or spring back at bent portions after being thermoformed to a radius of 50 mm using a heat press machine at a mold temperature of 120°C. The resin laminate described in claim 1, wherein the difference between the glass transition temperature of the polycarbonate-based resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 15°C. A resin laminate described in claim 1 or 2, wherein the thermoplastic resin (B) is a polymer alloy of the methacrylic resin (C) and the styrene copolymer (D). A resin laminate described in any one of claims 1 to 3, wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene. A resin laminate described in any one of claims 1 to 4, wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride. The resin laminate according to any one of claims 1 to 5, wherein the polycarbonate resin (A) has a terminal structure derived from a monohydric phenol represented by the following general formula (1) and a structural unit derived from a dihydric phenol:
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R ₂ to R ₅ each represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent, and the substituent is halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) A resin laminate described in any one of claims 1 to 6, wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.4 to 4.0 mm. The resin laminate described in any one of claims 1 to 7, wherein at least one of the layer containing the polycarbonate-based resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer contains an ultraviolet absorber. A resin laminate described in any one of claims 1 to 8, wherein the hard coat layer is an acrylic hard coat. A resin laminate described in any one of claims 1 to 9, wherein one or both sides of the resin laminate are treated with at least one of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, and anti-fouling treatment. A thermoformed product obtained by heat bending a resin laminate according to any one of claims 1 to 10. A transparent substrate material comprising the resin laminate described in any one of claims 1 to 10 or the thermoformed body described in claim 11. A transparent protective material comprising the resin laminate described in any one of claims 1 to 10 or the thermoformed body described in claim 11. A touch panel front protection plate comprising a resin laminate described in any one of claims 1 to 10 or a thermoformed body described in claim 11. A front panel for a car navigation system, office automation equipment, or portable electronic device, comprising the resin laminate described in any one of claims 1 to 10 or the thermoformed body described in claim 11. A method for producing a thermoformed body, comprising a step of hot bending a resin laminate at a mold temperature of 100°C to 135°C,
the resin laminate has a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate-based resin (A), and has a hard coat layer on at least one surface of the layer containing the thermoplastic resin (B);
The polycarbonate resin (A) has a glass transition temperature of 115°C to 140°C,
the thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), and the content of the methacrylic resin (C) is 15 to 70 parts by mass and the content of the styrene copolymer (D) is 85 to 30 parts by mass, based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D);
the styrene copolymer (D) is a copolymer containing 68 to 84 mass% of vinyl aromatic monomer units (d1) and 16 to 32 mass% of cyclic acid anhydride monomer units (d2), and has a weight average molecular weight of 50,000 to 130,000.