Multilayer body and molded article

Abstract

To provide a multilayer body comprising a polycarbonate resin, with a minimal decrease in the molecular weight of the polycarbonate resin even after a hot and humid test, and to provide a molded article.SOLUTION: A multilayer body comprises a thermoplastic resin layer (Y) on at least one side of an aromatic polycarbonate resin layer (X). The layer (X) comprises 0.05-10 pts.mass of a plasticizer comprising two to five groups represented by the formula (B) in one molecule, relative to 100 pts.mass of the aromatic polycarbonate resin. (In the formula (B), R independently represent a methyl group, an ethyl group or a phenyl group, n represents an integer of 0-3, and Ar is a benzene ring or naphthalene ring).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a multilayer body and a molded article, and in particular to a multilayer body having a polycarbonate resin layer. [Background technology]

[0002] In addition to its excellent transparency, polycarbonate resin is easier to process and more impact resistant than glass, and there is no risk of toxic gases compared to other plastic materials, so it is widely used in a variety of fields and is also used as a thermoforming material for vacuum forming, pressure forming, and other processes.

[0003] On the other hand, polycarbonate resin generally has a low surface hardness, and therefore the surface of a molded product made of polycarbonate resin tends to be easily scratched. Therefore, when polycarbonate resin is made into a film, a layer containing an acrylic resin or a hard coat layer (protective layer) is formed on the surface to prevent the product surface from being scratched. For example, Patent Document 1 discloses a molding resin sheet which is a laminated sheet having a coating layer mainly composed of an acrylic resin (B) on one side of a base layer mainly composed of a polycarbonate resin composition (A) consisting of a polymer alloy of an aromatic polycarbonate (A1) and another resin (A2), and which is characterized in that the absolute value of the difference in glass transition temperature between the polycarbonate resin composition (A) and the acrylic resin (B) is within 30°C. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-196153 A Summary of the Invention [Problem to be solved by the invention]

[0005] Here, in a multilayer body having a layer containing an aromatic polycarbonate resin and a layer containing another thermoplastic resin, if there is a large difference in glass transition temperature between the layer containing an aromatic polycarbonate resin and the layer containing another thermoplastic resin, cracks may occur in the multilayer body when the multilayer body is hot-molded, or the multilayer body may return to its original shape after hot bending (springback). Therefore, in order to lower the glass transition temperature of the layer containing aromatic polycarbonate resin, it is considered to add a plasticizer to lower the glass transition temperature of the layer containing aromatic polycarbonate resin. However, it has been found that when a plasticizer is blended into polycarbonate resin, the molecular weight of the polycarbonate resin may be reduced by a wet heat test or the like. When the molecular weight of the polycarbonate resin is reduced in this way, the mechanical strength and the like that the polycarbonate resin originally has cannot be fully exhibited. The present invention has an object to solve the above problems, and to provide a multilayer body and a molded article using a polycarbonate resin that undergoes only a small decrease in molecular weight even after a wet heat test. [Means for solving the problem]

[0006] As a result of the investigation by the present inventors under the above-mentioned circumstances, the above-mentioned problems were solved by blending a specific plasticizer in a layer containing an aromatic polycarbonate resin. Specifically, the above-mentioned problems were solved by the following means. <1> A multilayer body having a layer (Y) containing a thermoplastic resin other than an aromatic polycarbonate resin on at least one surface of a layer (X) containing an aromatic polycarbonate resin, the layer (X) containing 0.05 to 10 parts by mass of a plasticizer containing 2 to 5 groups represented by formula (B) in one molecule per 100 parts by mass of the aromatic polycarbonate resin. [ka] (In formula (B), R each independently represents a methyl group, an ethyl group, or a phenyl group, n represents an integer of 0 to 3, and Ar represents a benzene ring or a naphthalene ring.) <2> The layer (Y) has a glass transition temperature of 130°C to 150°C as measured by differential scanning calorimetry. <1> The multilayer body according to claim 1. <3> In the formula (B), Ar is a benzene ring. <1> or <2> The multilayer body according to claim 1. <4> The other thermoplastic resin includes an acrylic resin (y1). <1> ~ <3> 13. The multilayer body according to any one of claims 1 to 12. <5> The other thermoplastic resin comprises 30 to 90 parts by mass of an acrylic resin (y1) and 10 to 70 parts by mass of a styrene resin (y2). <1> ~ <4> 13. The multilayer body according to any one of claims 1 to 12. <6> The acrylic resin (y1) is (meth)acrylic compound units; Contains at least one of a cyclic acid anhydride unit, an N-substituted maleimide unit, and a lactone ring unit; <4> or <5> The multilayer body according to claim 1. <7> the acrylic resin (y1) contains 60 to 96 mass% of (meth)acrylic compound units and 4 to 40 mass% in total of at least one of cyclic acid anhydride units, N-substituted maleimide units, and lactone ring units; <4> or <5> The multilayer body according to claim 1. <8> The styrene resin (y2) contains 68 to 84 mass% of aromatic vinyl compound units and 16 to 32 mass% of cyclic acid anhydride units. <5> ~ <7> 13. The multilayer body according to any one of claims 1 to 12. <9> a difference between a glass transition temperature of the layer (X) measured by differential scanning calorimetry and a glass transition temperature of the layer (Y) measured by differential scanning calorimetry is 0 to 15°C; <1> ~ <8> 13. The multilayer body according to any one of claims 1 to 12. <10> The plasticizer containing 2 to 5 groups represented by the formula (B) in one molecule includes a plasticizer represented by the formula (B-1). <1> ~ <9> 13. The multilayer body according to any one of claims 1 to 12. [ka] (In formula (B-1), R each independently represents a methyl group, an ethyl group, or a phenyl group, n represents an integer of 0 to 3, L represents an n1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n1 represents an integer of 2 to 5.) <11> The thickness of the layer (Y) is 10 to 250 μm, and the total thickness of the multilayer body is 400 to 4,000 μm. <1> ~ <10> 13. The multilayer body according to any one of claims 1 to 12. <12> Further, the multilayer body has a hard coat layer on one or both sides thereof. <1> ~ <11> 13. The multilayer body according to any one of claims 1 to 12. <13> Furthermore, one or both surfaces of the multilayer body are subjected to one or more of an anti-fingerprint treatment, an anti-reflection treatment, an anti-glare treatment, a weather resistance treatment, an antistatic treatment, an anti-soiling treatment, and an anti-blocking treatment. <1> ~ <12> 13. The multilayer body according to any one of claims 1 to 12. <14> The layer (X) and / or the layer (Y) contain an antioxidant and / or a release agent; <1> ~ <13> 13. The multilayer body according to any one of claims 1 to 12. <15> the layer (Y) has a glass transition temperature of 130°C to 150°C as measured by differential scanning calorimetry, the other thermoplastic resin comprises 30 to 90 parts by mass of an acrylic resin (y1) and 10 to 70 parts by mass of a styrene resin (y2), the difference between the glass transition temperature of the layer (X) as measured by differential scanning calorimetry and the glass transition temperature of the layer (Y) as measured by differential scanning calorimetry is 0 to 15°C, and the plasticizer containing 2 to 5 groups represented by formula (B) in one molecule comprises a plasticizer represented by formula (B-1). <1> The multilayer body according to claim 1. [ka] (In formula (B-1), R each independently represents a methyl group, an ethyl group, or a phenyl group, n represents an integer of 0 to 3, L represents an n1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n1 represents an integer of 2 to 5.) <16> <1> ~ <15> A molded article formed from the multilayer body according to any one of claims 1 to 5. Effect of the Invention

[0007] According to the present invention, it is possible to provide a multi-layer body and a molded article using a polycarbonate resin in which the molecular weight of the polycarbonate resin decreases little even after a wet heat test. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing the configuration of an example of an antireflection film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an embodiment of the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment. In this specification, the use of "to" means that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, various physical properties and characteristic values ​​are those at 23° C. unless otherwise specified. In the description of groups (atomic groups) in this specification, when the description does not indicate whether the group is substituted or unsubstituted, the description also includes groups (atomic groups) that have a substituent as well as groups (atomic groups) that have no substituent. For example, the term "alkyl group" includes not only alkyl groups that have no substituent (unsubstituted alkyl groups), but also alkyl groups that have a substituent (substituted alkyl groups). In this specification, when the description does not indicate whether the group is substituted or unsubstituted, the description is preferably unsubstituted. In this specification, the term "(meth)acrylic compound" refers to both or either of an acrylic compound and a methacrylic compound, with a methacrylic compound being preferred. Furthermore, the acrylic resin includes not only an acrylate (co)polymer but also a methacrylate (co)polymer. In this specification, the layer (X), layer (Y) and multilayer body each include those in the form of a film or sheet. The terms "film" and "sheet" refer to a generally flat molded product having a small thickness relative to its length and width, respectively. In this specification, "parts by mass" indicates the relative amount of a component, and "% by mass" indicates the absolute amount of a component. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards as of January 1, 2022, unless otherwise stated. Figure 1 is a schematic diagram and may not be to scale. In this specification, the term "polycarbonate resin" means an aromatic polycarbonate resin, unless otherwise specified.

[0010] The multilayer body of the present embodiment is a multilayer body having a layer (Y) containing a thermoplastic resin other than an aromatic polycarbonate resin (hereinafter, sometimes simply referred to as "another thermoplastic resin layer (Y)" or "layer (Y)") on at least one surface of a layer (X) containing an aromatic polycarbonate resin (hereinafter, sometimes simply referred to as "polycarbonate resin layer (X)" or "layer (X)"), and the layer (X) is characterized in that it contains 0.05 to 10 parts by mass of a plasticizer containing 2 to 5 groups represented by formula (B) in one molecule per 100 parts by mass of the aromatic polycarbonate resin. [ka] (In formula (B), R each independently represents a methyl group, an ethyl group, or a phenyl group, n represents an integer of 0 to 3, and Ar represents a benzene ring or a naphthalene ring.)

[0011] By adopting such a configuration, the decrease in molecular weight of the polycarbonate resin after the wet heat test can be effectively suppressed. As described above, when a plasticizer is blended, the glass transition temperature of the polycarbonate resin can be lowered, but the molecular weight may decrease after the wet heat test. In the present invention, the glass transition temperature of the polycarbonate resin is lowered while the decrease in molecular weight after the wet heat test is effectively suppressed by using a plasticizer containing a group represented by formula (B). The reason for this is presumed to be that the group represented by formula (B) has an ester structure, and therefore is unlikely to cause hydrolysis. In addition, the group represented by formula (B) has a benzene ring or a naphthalene ring, and therefore is likely to be compatible with aromatic polycarbonate resins. Furthermore, in order to sufficiently lower the glass transition temperature of the polycarbonate resin, it is necessary to have a plasticizer content of at least a predetermined amount. However, if the content is too high, the viscosity decreases, making it difficult to form the resin into a sheet. The multi-layer body of the present embodiment has been achieved by taking the above points into consideration and selecting an appropriate plasticizer.

[0012] <Layer (X) Containing Aromatic Polycarbonate Resin> The polycarbonate resin layer (X) contains 0.05 to 10 parts by mass of a plasticizer containing 2 to 5 groups represented by formula (B) in one molecule, based on 100 parts by mass of polycarbonate resin. [ka] (In formula (B), R each independently represents a methyl group, an ethyl group, or a phenyl group, n represents an integer of 0 to 3, and Ar represents a benzene ring or a naphthalene ring.)

[0013] The polycarbonate resin layer (X) contains an aromatic polycarbonate resin. In the present embodiment, the aromatic polycarbonate resin is preferably a bisphenol-type polycarbonate resin. The bisphenol-type polycarbonate resin means that, for example, 80 mol % or more, preferably 90 mol % or more, more preferably 95 mol % or more of the structural units constituting the polycarbonate resin are carbonate structural units derived from bisphenol (preferably bisphenol A) and / or its derivatives. The bisphenol type polycarbonate resin is preferably a bisphenol A type polycarbonate resin.

[0014] The molecular weight of the polycarbonate resin is not particularly limited, but is preferably 20,000 or more in terms of viscosity average molecular weight calculated from the solution viscosity measured at 25°C using methylene chloride as a solvent. The viscosity average molecular weight is preferably 35,000 or less, more preferably 32,000 or less, and even more preferably 30,000 or less. By setting the viscosity average molecular weight to the lower limit or more, the strength of the obtained flat plate-shaped molded product can be increased. By setting the viscosity average molecular weight to the upper limit or less, moldability tends to be improved. Here, the viscosity average molecular weight [Mv] is calculated by using methylene chloride as a solvent, measuring the intrinsic viscosity [η] (unit: dL / g) at 25°C using an Ubbelohde viscometer, and calculating the viscosity average molecular weight according to the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 The intrinsic viscosity [η] is the value calculated from the specific viscosity [η sp ] was measured and the value was calculated according to the following formula.

number

[0015] For details of the polycarbonate resin, reference can be made to paragraphs 0011 to 0020 of JP 2012-144604 A and paragraphs 0014 to 0035 of JP 2019-002023 A, as long as they do not deviate from the spirit of this embodiment, and the contents of these are incorporated into this specification.

[0016] The content of the polycarbonate resin in the polycarbonate resin layer (X) is preferably 90% by mass or more, more preferably 92% by mass or more, even more preferably 94% by mass or more, still more preferably 96% by mass or more, and even more preferably 97% by mass or more, based on 100% by mass of the polycarbonate resin layer (X). When the polycarbonate resin layer (X) contains two or more kinds of polycarbonate resins, the total amount thereof preferably falls within the above range.

[0017] Next, a plasticizer containing 2 to 5 groups represented by formula (B) in one molecule (hereinafter sometimes referred to as "plasticizer (B)") will be described. The plasticizer (B) has a group represented by the following formula: [ka] (In formula (B), R each independently represents a methyl group, an ethyl group, or a phenyl group, n represents an integer of 0 to 3, and Ar represents a benzene ring or a naphthalene ring.)

[0018] R is a substituent of Ar and may replace any hydrogen atom on the benzene ring or the naphthalene ring. R represents a methyl group, an ethyl group, or a phenyl group, and is preferably a methyl group. n represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. Ar is a benzene ring or a naphthalene ring, and is preferably a benzene ring.

[0019] The plasticizer (B) preferably does not contain a hydroxyl group. The plasticizer (B) also preferably does not contain a phosphate ester group. The plasticizer (B) also preferably is not a metal-containing compound such as calcium stearate or zinc stearate. By adopting such a constitution, there is a tendency that the decrease in molecular weight of the polycarbonate resin after the moist heat resistance test can be more effectively suppressed. The plasticizer (B) also preferably does not contain a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and more preferably does not contain a linear aliphatic hydrocarbon group having 3 or more carbon atoms.

[0020] The plasticizer (B) preferably has two or more groups represented by the formula (B) in one molecule, more preferably has three or more groups, and preferably has five or less groups, more preferably has four or less groups. By setting the number of groups to be equal to or more than the lower limit and equal to or less than the upper limit, the effect of the present embodiment tends to be more effectively exhibited.

[0021] The molecular weight of the plasticizer (B) is preferably 200 or more, more preferably 250 or more, even more preferably 300 or more, even more preferably 350 or more, and even more preferably 400 or more. By making it equal to or more than the lower limit, it is difficult to thermally decompose when added, and the effect of suppressing gas generation and roll staining during pelletization and sheet molding tends to be improved. In addition, the molecular weight of the plasticizer (B) is preferably 1200 or less, more preferably 1000 or less, even more preferably 900 or less, even more preferably 800 or less, and even more preferably 700 or less. By making it equal to or less than the upper limit, it tends to be possible to lower the glass transition temperature and viscosity even with a small amount of blending.

[0022] The plasticizer (B) preferably contains a plasticizer represented by formula (B-1). [ka] (In formula (B-1), R each independently represents a methyl group, an ethyl group, or a phenyl group, n represents an integer of 0 to 3, L represents an n1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n1 represents an integer of 2 to 5.)

[0023] In formula (B-1), R and n have the same meanings as R and n in formula (B), and the preferred ranges are also the same. L represents an n1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms. The number of carbon atoms constituting the n1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably 2 or more, more preferably 3 or more, and is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less. n1 is an integer of 2 to 5, preferably 2 to 4, and more preferably 3 or 4.

[0024] The content of the plasticizer (B) in the polycarbonate resin layer (X) is 0.05 parts by mass or more, preferably 0.08 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 0.7 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin. By making it equal to or more than the lower limit, the glass transition temperature and viscosity can be effectively lowered. In addition, the upper limit of the content of the plasticizer (B) is 10 parts by mass or less, preferably 9 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 7 parts by mass or less, even more preferably 6 parts by mass or less, even more preferably 4 parts by mass or less, and particularly more preferably 2.5 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin. By making it equal to or less than the upper limit, the Charpy impact strength does not decrease, and excellent toughness tends to be maintained. The polycarbonate resin layer (X) may contain only one type of plasticizer (B), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0025] The polycarbonate resin layer (X) or the resin composition (x) for forming the polycarbonate resin layer (X) (hereinafter, sometimes simply referred to as "resin composition (x)") may contain, in addition to the above-mentioned components, a thermoplastic resin other than polycarbonate resin, an antioxidant, a release agent, an ultraviolet absorber, a heat stabilizer, a flame retardant, a flame retardant assistant, a colorant, an antistatic agent, a fluorescent brightener, an antifogging agent, a flow improver, a plasticizer, a dispersant, an antibacterial agent, an antiblocking agent, an impact improver, a sliding improver, a hue improver, an acid trapping agent, etc. These components may be used alone or in combination of two or more. When contained, the content of the above components is preferably 0.1 to 5% by mass in total of the polycarbonate resin layer (X) or the resin composition (x).

[0026] The polycarbonate resin layer (X) or the resin composition (x) particularly preferably contains an antioxidant and / or a release agent.

[0027] Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. Among them, in the present embodiment, phosphorus-based antioxidants and phenol-based antioxidants (more preferably hindered phenol-based antioxidants) are preferred. Phosphorus-based antioxidants are particularly preferred because they provide excellent color to the molded product.

[0028] The phosphorus-based antioxidant is preferably a phosphite-based antioxidant, and more preferably a phosphite compound represented by the following formula (1) or (2). [ka] (In formula (1), R 11 and R 12 each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. [ka] (In formula (2), R 13 ~R 17 each independently represents a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.

[0029] In the above formula (1), R 11 , R 12 Each of the alkyl groups represented by the following formula (1) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. 11 , R 12 When is an aryl group, it is preferably an aryl group represented by any one of the following formulae (1-a), (1-b), and (1-c), in which * represents the bonding position.

[0030] [ka] (In formula (1-a), R A Each of R independently represents an alkyl group having 1 to 10 carbon atoms. Beach independently represents an alkyl group having 1 to 10 carbon atoms.

[0031] For the hindered phenol-based antioxidant, reference can be made to the descriptions in paragraph 0063 of JP2018-090677A and paragraph 0076 of JP2018-188496A, the contents of which are incorporated herein by reference.

[0032] In addition to the above, the antioxidants can be found in paragraphs 0057 to 0061 of JP2017-031313A, the contents of which are incorporated herein by reference.

[0033] The content of the antioxidant is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.010 parts by mass or more, and even more preferably 0.050 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin layer (X) or the resin composition (x). The upper limit of the content of the antioxidant is preferably 0.500 parts by mass or less, more preferably 0.300 parts by mass or less, even more preferably 0.200 parts by mass or less, even more preferably 0.150 parts by mass or less, even more preferably 0.100 parts by mass or less, and particularly more preferably 0.080 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin layer (X) or the resin composition (x).

[0034] By setting the content of the antioxidant to the above lower limit or more, a molded article with a lower hue (YI value) can be obtained. By setting the content of the antioxidant to the above upper limit or less, a molded article with good wet heat stability can be obtained. The antioxidant may be used alone or in combination of two or more. When two or more antioxidants are used, the total amount is preferably within the above range.

[0035] Next, the release agent contained in the polycarbonate resin layer (X) will be described. The type of release agent is not particularly limited, but examples thereof include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polyethers having a number average molecular weight of 100 to 5,000, and polysiloxane-based silicone oils.

[0036] For details about the release agent, please refer to paragraphs 0035 to 0039 of WO 2015 / 190162, the contents of which are incorporated herein by reference.

[0037] The content of the release agent is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.010 parts by mass or more, and even more preferably 0.050 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin layer (X) or the resin composition (x). The upper limit is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and even more preferably 0.1 parts by mass or less. The release agent may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0038] The polycarbonate resin layer (X) or the resin composition (x) preferably has a low onset glass transition temperature (Tg) measured by differential scanning calorimetry. Specifically, the onset glass transition temperature (Tg) of the polycarbonate resin layer (X) is preferably 150°C or lower, more preferably 149°C or lower, even more preferably 148°C or lower, even more preferably 146°C or lower, and even more preferably 144°C or lower. The lower limit of the onset glass transition temperature is preferably 120°C or higher, more preferably 125°C or higher, even more preferably 126°C or higher, even more preferably 128°C or higher, even more preferably 130°C or higher, even more preferably more than 130°C, and may be 131°C or higher. The onset glass transition temperature (Tg) is measured according to the method described in the Examples section below.

[0039] In this embodiment, it is preferable that the polycarbonate resin layer (X) or the resin composition (x) has a polycarbonate resin with a small decrease in molecular weight after a moist heat resistance test. Specifically, it is preferable that the difference in weight average molecular weight before and after the polycarbonate resin layer (X) or the resin composition (x) for forming the polycarbonate resin layer (X) is subjected to a wet heat treatment for 450 hours under conditions of 85° C. and a relative humidity of 85% is not more than 3000. It is preferable that the lower limit of the difference in weight average molecular weight is 0 in absolute value.

[0040] <Layer (Y) Containing Thermoplastic Resin Other Than Polycarbonate Resin> The multilayer body of the present embodiment has a layer (Y) containing a thermoplastic resin other than a polycarbonate resin on at least one surface of an aromatic polycarbonate resin layer (X), and the glass transition temperature of the layer (Y) measured by differential scanning calorimetry is 130°C to 150°C.

[0041] The other thermoplastic resin layer (Y) in this embodiment is a layer containing a thermoplastic resin other than a polycarbonate resin. As the other thermoplastic resin, a wide variety of thermoplastic resins capable of forming a resin layer having a glass transition temperature of 130°C to 150°C according to differential scanning calorimetry can be used.

[0042] The onset glass transition temperature of the other thermoplastic resin layer (Y) or the resin composition (y) for forming the other thermoplastic resin layer (Y) (hereinafter sometimes simply referred to as "resin composition (y)") is preferably more than 130°C, more preferably 131°C or more, and even more preferably 132°C or more. By making it equal to or higher than the lower limit, cracks are less likely to occur during hot bending. In addition, the onset glass transition temperature of the other thermoplastic resin layer (Y) or the resin composition (y) is preferably 145°C or less, more preferably 140°C or less, even more preferably 138°C or less, even more preferably 136°C or less, and even more preferably 134°C or less. By making it equal to or lower than the upper limit, springback during hot bending tends to be suppressed.

[0043] In this embodiment, the other thermoplastic resin preferably contains an acrylic resin (y1), more preferably contains at least one thermoplastic resin selected from a styrene resin, a fluorine-based resin such as polyvinylidene fluoride, and an aromatic polyether resin such as polyphenylene ether, and further preferably contains an acrylic resin (y1) and a styrene resin (y2). The other thermoplastic resin layer (Y) is preferably composed of 90% by mass or more (preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 98% by mass or more) of the acrylic resin (y1) and the thermoplastic resin (preferably a styrene resin (y2)).

[0044] The other thermoplastic resin layer (Y) preferably contains 30 to 90 parts by mass of an acrylic resin (y1) and 10 to 70 parts by mass of a styrene resin (y2). By adopting such a constitution, the pencil hardness, heat resistance, and impact resistance tend to be improved more effectively. That is, by blending an acrylic resin, the pencil hardness and impact resistance are improved, and by blending a styrene resin, the heat resistance is improved. When the other thermoplastic resin layer (Y) contains an acrylic resin (y1) and a styrene resin (y2), the blend ratio is preferably 35 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, even more preferably 50 parts by mass or more, and even more preferably 55 parts by mass or more, based on 100 parts by mass of the total content of the acrylic resin (y1) and the styrene resin (y2). By making it equal to or more than the lower limit, the pencil hardness and impact resistance tend to be more effectively improved. In addition, when the acrylic resin (y1) and the styrene resin (y2) are contained, the blend ratio is preferably 85 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, and may be 70 parts by mass or less, based on 100 parts by mass of the total content of the acrylic resin (y1) and the styrene resin (y2). By making it equal to or less than the upper limit, the effect of suppressing the decrease in heat resistance tends to be more improved. When the other thermoplastic resin layer (Y) contains an acrylic resin (y1) and a styrene resin (y2), the acrylic resin (y1) and the styrene resin (y2) may each contain only one kind or two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

[0045] <<Acrylic resin (y1)>> Next, the acrylic resin (y1) will be described. The acrylic resin (y1) preferably contains a (meth)acrylic compound unit, and the proportion thereof is preferably 60% by mass or more of all the structural units excluding the terminal groups. By making the proportion equal to or more than the lower limit, the pencil hardness and impact resistance tend to be improved. Here, the (meth)acrylic compound unit refers to a structural unit composed of a (meth)acrylic compound in the resin (the same applies to the "aromatic vinyl compound unit" described later). The upper limit of the proportion of the (meth)acrylic compound unit in the acrylic resin (y1) is 100% by mass of all the structural units excluding the terminal groups, and is preferably 96% by mass or less. The acrylic resin (y1) may contain only one type of (meth)acrylic compound unit, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0046] The (meth)acrylic compound is not particularly limited as long as it contains a (meth)acrylic group, but a compound represented by formula (a1) is preferred. [ka] (In formula (a1), Ra 1 is a hydrogen atom or a methyl group, and Ra 2 is an aliphatic group. In the above formula (a1), Ra 1 is a hydrogen atom or a methyl group, and a methyl group is preferable. 2is an aliphatic group, preferably a linear or branched aliphatic group, more preferably a linear aliphatic group. Examples of the aliphatic group include an alkyl group (including a cycloalkyl group), an alkynyl group (including a cycloalkynyl group), and an alkenyl group (including a cycloalkenyl group), of which an alkyl group is preferred, a linear or branched alkyl group is more preferred, and a linear alkyl group is even more preferred. Ra 2 The aliphatic group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, even more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom. The (meth)acrylic compound represented by formula (a1) is preferably an alkyl (meth)acrylate (preferably an alkyl methacrylate), and more preferably a methyl (meth)acrylate (preferably a methyl methacrylate). By using methyl methacrylate, the impact strength of the other thermoplastic resin layer (Y) obtained tends to be improved.

[0047] The acrylic resin (y1) preferably contains other monomer units other than the (meth)acrylic compound units. Examples of the other monomer units include cyclic acid anhydride units, N-substituted maleimide units, and lactone ring units, with cyclic acid anhydride units and / or N-substituted maleimide units being preferred, and N-substituted maleimide units being more preferred. The acrylic resin (y1) more preferably contains 60 to 96 mass % of (meth)acrylic compound units and 4 to 40 mass % in total of at least one of cyclic acid anhydride units, N-substituted maleimide units, and lactone ring units (preferably N-substituted maleimide units). In the acrylic resin (y1), the total amount of at least one of the cyclic acid anhydride units, N-substituted maleimide units, and lactone ring units (preferably N-substituted maleimide units) is, when the acrylic resin (y1) is taken as 100% by mass, preferably 6% by mass or more, more preferably 9% by mass or more, and even more preferably 12% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and even more preferably 20% by mass or less. The acrylic resin (y1) may contain at least one of other monomer units, preferably cyclic acid anhydride units, N-substituted maleimide units, and lactone ring units, either alone or in combination. When two or more types are contained, the total amount is preferably within the above range. In the acrylic resin (y1), the total of the (meth)acrylic compound unit and at least one of the cyclic acid anhydride unit, the N-substituted maleimide unit, and the lactone ring unit preferably accounts for 90 mass% or more, more preferably 95 mass% or more, even more preferably 97 mass% or more, and still more preferably 99 mass% or more, when the acrylic resin (y1) is 100 mass%.

[0048] Examples of the cyclic acid anhydride unit include a maleic anhydride unit and a glutaric anhydride unit, and the maleic anhydride unit is preferred. The maleic anhydride constituting the maleic anhydride unit and the glutaric acid constituting the glutaric anhydride unit may each have a substituent, but it is preferred that they have no substituent. Examples of the N-substituted maleimide unit include an N-cyclohexylmaleimide unit, an N-phenylmaleimide unit, an N-methylmaleimide unit, an N-ethylmaleimide unit, an N-isopropylmaleimide unit, an Nt-butylmaleimide unit, an N-dodecylmaleimide unit, an N-benzylmaleimide unit, and an N-naphthylmaleimide unit, and an N-cyclohexylmaleimide unit and an N-phenylmaleimide unit are preferred. Examples of the lactone ring unit include those described in JP-A-2006-171464 and JP-A-2004-168882, the contents of which are incorporated herein by reference.

[0049] The onset glass transition temperature (Tg) of the acrylic resin (y1) is preferably 100° C. or higher, more preferably 105° C. or higher, even more preferably 110° C. or higher, even more preferably 115° C. or higher, and even more preferably 120° C. or higher. By setting the onset glass transition temperature (Tg) to the lower limit or higher, the effect of suppressing crack generation during thermal bending tends to be further improved. The onset glass transition temperature (Tg) of the acrylic resin (y1) may be, for example, 130° C. or lower, or even 125° C. or lower. When the other thermoplastic resin layer (Y) contains two or more kinds of acrylic resins (y1), the onset glass transition temperature (Tg) of the acrylic resin (y1) refers to the Tg of the mixture.

[0050] The weight average molecular weight of the acrylic resin (y1) is preferably 50,000 or more, more preferably 60,000 or more, even more preferably 70,000 or more, even more preferably 80,000 or more, and even more preferably 90,000 or more. By making it equal to or more than the lower limit, the impact strength of the other thermoplastic resin layer (Y) obtained can be further improved. The weight average molecular weight of the acrylic resin (y1) is preferably 300,000 or less, more preferably 250,000 or less, even more preferably 200,000 or less, even more preferably 170,000 or less, and even more preferably 150,000 or less. By making it equal to or less than the upper limit, the melt viscosity of the resin composition can be effectively reduced, and the molding of the multilayer body becomes easy. The weight average molecular weight is measured by the method described in the examples below. When the acrylic resin (y1) is a mixture of two or more kinds, the weight average molecular weight is the sum of the weight average molecular weights of the acrylic resins (y1) multiplied by the mass fraction. The same applies to the weight average molecular weight below.

[0051] <<Styrene resin (y2)>> Next, the styrene resin (y2) will be described. The styrene resin (y2) is a resin containing aromatic vinyl compound units, and preferably contains aromatic vinyl compound units and cyclic acid anhydride units, and more preferably contains 68 to 84 mass% aromatic vinyl compound units and 16 to 32 mass% cyclic acid anhydride units. More specifically, when the styrene resin (y2) is taken as 100% by mass, the proportion of cyclic acid anhydride units is preferably 20% by mass or more, more preferably 23% by mass or more, and even more preferably 24% by mass or more, and is preferably 30% by mass or less, more preferably 28% by mass or less, and even more preferably 27% by mass or less. In the styrene resin (y2), the total of the aromatic vinyl compound units and the cyclic acid anhydride units preferably accounts for 90 mass% or more, more preferably 95 mass% or more, even more preferably 97 mass% or more, and still more preferably 99 mass% or more, when the styrene resin (y2) is 100 mass%. The styrene resin (y2) may contain only one type of aromatic vinyl compound unit and one type of cyclic acid anhydride unit, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0052] Examples of the aromatic vinyl compound unit in the styrene resin (y2) include styrene-based monomer units such as a styrene unit, an α-methylstyrene unit, an o-methylstyrene unit, and a p-methylstyrene unit, and it is preferable that the styrene unit is contained.

[0053] Examples of the cyclic acid anhydride unit in the styrene resin (y2) include maleic anhydride unit and glutaric anhydride unit, and maleic anhydride unit is preferred. Maleic anhydride constituting the maleic anhydride unit and glutaric acid constituting the glutaric anhydride unit may each have a substituent, but it is preferred that they do not have a substituent.

[0054] The styrene resin (y2) may contain other monomer units in addition to the aromatic vinyl compound unit and the cyclic acid anhydride unit. Examples of the other monomer units include N-substituted maleimide units, (meth)acrylic compound units, and alkenyl cyanide units.

[0055] The onset glass transition temperature (Tg) of the styrene resin (y2) is preferably 130°C or higher, more preferably 135°C or higher, and even more preferably 140°C or higher. By setting it to the lower limit or higher, the effect of suppressing cracks during hot bending tends to be further improved. Furthermore, the onset glass transition temperature (Tg) of the styrene resin (y2) is preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 160°C or lower. By setting it to the upper limit or lower, the effect of suppressing springback during hot bending tends to be further improved.

[0056] The weight average molecular weight of the styrene resin (y2) is preferably 10,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, and even more preferably 40,000 or more. By making it equal to or more than the lower limit, the impact strength of the other thermoplastic resin layer (Y) obtained can be further improved. In addition, the weight average molecular weight of the styrene resin (y2) is preferably 200,000 or less, more preferably 100,000 or less. By making it equal to or less than the upper limit, the melt viscosity of the resin composition can be effectively reduced.

[0057] The other thermoplastic resin layer (Y) may contain, in addition to the above components, other thermoplastic resins, antioxidants, release agents, UV absorbers, heat stabilizers, flame retardants, flame retardant assistants, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, hue improvers, acid trapping agents, etc. These components may be used alone or in combination of two or more. When contained, the content of the above components is preferably 0.1 to 5% by mass in total of the other thermoplastic resin layer (Y). In particular, in this embodiment, the other thermoplastic resin layer (Y) or the resin composition (y) may contain an antioxidant and / or a release agent. The details of the antioxidant and / or the release agent are the same as those of the antioxidant and / or the release agent described in the section on the polycarbonate resin layer (X), and the preferred ranges are also the same.

[0058] The other thermoplastic resin layer (Y) may be a single layer or may be a multi-layer. The thickness of the other thermoplastic resin layer (Y) is not particularly limited, but the lower limit is, for example, 1 μm or more, preferably 10 μm or more, more preferably 20 μm or more, even more preferably 50 μm or more, even more preferably 60 μm or more, even more preferably 80 μm or more, even more preferably 90 μm or more, and may be 100 μm or more. By making it equal to or more than the lower limit, molding becomes easier and hardness tends to be improved. In addition, the upper limit of the thickness of the other thermoplastic resin layer (Y) is not particularly limited, but it is preferably 5,000 μm or less, more preferably 2,000 μm or less, even more preferably 1,000 μm or less, even more preferably 500 μm or less, even more preferably 300 μm or less, even more preferably 250 μm or less, and particularly more preferably 150 μm or less.

[0059] <Hard coat layer> The multilayer body of the present embodiment may have a hard coat layer. The hard coat layer is usually a layer having a higher surface hardness than the polycarbonate resin layer, and by including such a hard coat layer, the surface hardness of the multi-layer body or molded article can be increased.

[0060] The hard coat layer is preferably provided on the surface of the layer (Y) opposite to the surface of the layer (X). The hard coat layer may also be provided on the polycarbonate resin layer (X), and it is preferable to have a hard coat layer on the surface of the layer (X). Note that, between the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y), and between the other thermoplastic resin layer (Y) and the hard coat layer, other layers may be provided within the scope of the present embodiment. In this embodiment, it is preferable that the polycarbonate resin layer (X), the other thermoplastic resin layer (Y), and the hard coat layer are laminated in this order in succession.

[0061] The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more. By making it equal to or greater than the lower limit, the pencil hardness of the entire multilayer body due to the hard coat layer tends to be improved. The upper limit of the thickness of the hard coat layer is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 12 μm or less, even more preferably 10 μm or less, and even more preferably 8 μm or less. By making it equal to or less than the upper limit, the processability during hot bending tends to be improved.

[0062] The hard coat layer is preferably obtained by applying a hard coat material that can be cured by heat or active energy rays, and then curing the applied material. An example of a coating material that is cured using active energy rays is a resin composition consisting of one or more monofunctional or polyfunctional (preferably difunctional to decafunctional) (meth)acrylate monomers or oligomers, and preferably a resin composition containing a monofunctional or polyfunctional (preferably difunctional to decafunctional) urethane (meth)acrylate oligomer. A photopolymerization initiator is preferably added to these resin compositions as a curing catalyst. Examples of thermosetting resin coatings include polyorganosiloxane-based and crosslinked acrylic-based coatings. Some of these resin compositions are commercially available as hard coating agents for acrylic or polycarbonate resin films or sheets, and may be selected appropriately taking into account suitability for the coating line. For the hard coat layer, the descriptions in paragraphs 0045 to 0055 of JP 2013-020130 A, paragraphs 0073 to 0076 of JP 2018-103518 A, and paragraphs 0062 to 0082 of JP 2017-213771 A can be referred to, the contents of which are incorporated herein by reference.

[0063] <Layer structure and properties of multilayer bodies> The multilayer body of the present embodiment is a multilayer body having a layer (Y) containing a thermoplastic resin other than an aromatic polycarbonate resin on at least one surface of a layer (X) containing an aromatic polycarbonate resin. The relationship between the thickness of the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y) is preferably {thickness of the other thermoplastic resin layer (Y) / [total thickness of the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y)]}<1 / 5. By satisfying this relationship, the other thermoplastic resin layer (Y) becomes thin as a whole multilayer body, so that even if the multilayer body is heated and molded, the occurrence of cracks is more effectively suppressed, and the occurrence of springback is more effectively suppressed. More specifically, in order to suppress springback, it is more effective to relieve the residual stress against bending remaining in the whole multilayer body when the multilayer body is folded. In this embodiment, {thickness of the other thermoplastic resin layer (Y) / [total thickness of the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y)]}<1 / 6 is more preferable, and {thickness of the other thermoplastic resin layer (Y) / [total thickness of the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y)]}<1 / 8 is even more preferable. Also, it is preferable that the thickness of the other thermoplastic resin layer (Y) / the total thickness of the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y) is 1 / 35, and more preferable that the thickness of the other thermoplastic resin layer (Y) / the total thickness of the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y) is 1 / 25. In particular, in this embodiment, it is more preferable that the polycarbonate resin layer (X) and the other thermoplastic resin layer (Y) satisfy the above-mentioned relationship while satisfying the above-mentioned preferred range of the predetermined thickness, and that the multilayer body satisfies the preferred range of the thickness described later. By adopting such a configuration, the effects of the present invention are more effectively achieved.

[0064] In the multilayer body of the present embodiment, the difference (absolute value) between the glass transition temperature of the layer (X) measured by differential scanning calorimetry and the glass transition temperature of the layer (Y) measured by differential scanning calorimetry is preferably 0 to 15°C, more preferably 0 to 13°C. By setting the difference in the glass transition temperatures in this range, the occurrence of springback in the multilayer body tends to be more effectively suppressed. The upper limit of the difference in the glass transition temperatures (absolute value) is more preferably 12°C or less, further preferably 11°C or less. In addition, although it does not matter whether the glass transition temperature of the layer (X) or the glass transition temperature of the layer (Y) is larger, it is generally the case that the glass transition temperature of the layer (X) is equal to or greater than the glass transition temperature of the layer (Y). The above glass transition temperature is Tg (onset glass transition temperature) measured according to the description in the Examples below.

[0065] Furthermore, the multilayer body of the present embodiment may be subjected to one or more of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, anti-soiling treatment, and anti-blocking treatment on one or both sides of the multilayer body.

[0066] Furthermore, the multilayer body of the present embodiment preferably has a low refractive index layer. More preferably, the low refractive index layer is on the hard coat layer, on the side opposite to the other thermoplastic resin layer (Y). That is, the multilayer body can be used as an anti-reflection film.

[0067] FIG. 1 is a schematic diagram showing an example of an anti-reflection film, in which 1 indicates a polycarbonate resin layer (X), 2 indicates another thermoplastic resin layer (Y), 3 indicates a hard coat layer, and 4 indicates an anti-reflection layer. In FIG. 1, a polycarbonate resin layer (X) 1, another thermoplastic resin layer (Y) 2, a hard coat layer 3, and an anti-reflection layer 4 are laminated in the order mentioned above, but other layers may be included within the scope of the present embodiment. In the case where the multilayer body has other layers, one or both sides of the multilayer body may be subjected to one or more of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, anti-soiling treatment, and anti-blocking treatment. In addition, a hard coat layer is an example of the outermost surface of the multilayer body. In addition, the anti-blocking treatment refers to a treatment that allows films to be easily peeled off even when they are in close contact with each other, and examples of the treatment include adding an anti-blocking agent and providing unevenness on the surface of the multilayer body. Furthermore, the multilayer body of the present embodiment may have other layers in addition to the above. Specific examples include an adhesive layer, a pressure-sensitive adhesive layer, and an antifouling layer.

[0068] The total thickness of the multilayer body of the present embodiment is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 100 μm or more, even more preferably 400 μm or more, and even more preferably 500 μm or more. The greater the total thickness, the more rigid the multilayer body tends to be. The total thickness of the multilayer body is preferably 10,000 μm or less, more preferably 5,000 μm or less, even more preferably 4,000 μm or less, and may be 3,000 μm or less. By setting the total thickness to such a value, when the multilayer body is molded, the resin is cooled to the inside of the multilayer body when the multilayer sheet is pressed between rolls and the resin is cooled, so that the moldability of the multilayer body can be improved.

[0069] Next, the pencil hardness of the multilayer body will be described. The multilayer body of the present embodiment preferably has a high (hard) pencil hardness. The pencil hardness measured from the other thermoplastic resin layer (Y) side is preferably F or more, more preferably H or more. There is no particular upper limit, but 3H or less is practical. In particular, in the multilayer body of the present embodiment, when a hard coat layer is provided, the pencil hardness measured from the other thermoplastic resin layer (Y) side is preferably H or more, more preferably 2H or more, and even more preferably 3H or more. There is no particular upper limit, but 4H or less is practical. The pencil hardness is measured as described in the Examples section below.

[0070] <Method of manufacturing multi-layer body> The multilayer body of the present embodiment can be formed by using a main extruder that extrudes the resin composition (x) for forming the polycarbonate resin layer (X) and a sub-extruder that extrudes the resin composition (y) for forming another thermoplastic resin layer (Y), melting the resins under the conditions for each resin used, introducing them into an extrusion die, laminating them inside the die and forming them into a sheet, or forming them into a sheet and then laminating them, thereby forming the multilayer body.

[0071] <Molded products and methods for manufacturing molded products> Next, a molded article using the multilayer body of this embodiment and a method for producing the molded article will be described. The molded article of this embodiment is a molded article formed from the multilayer body of this embodiment. The multilayer body of the present embodiment also has excellent resistance to thermal bending, and is therefore suitable for applications having curved portions, for example, for use in molded articles having a portion with a radius of curvature of 50 mmR or less (preferably a radius of curvature of 40 to 50 mmR). The molded article of this embodiment is preferably obtained by subjecting the multilayer body of this embodiment to hot bending molding at, for example, 133° C. or lower, or, for example, 100° C. or higher. The multilayer body of this embodiment has excellent hot bending resistance, and is therefore particularly useful when it is made into a molded article having a portion with a radius of curvature of 50 mmR or lower. In particular, since the thermoforming temperature can be set relatively low, relaxation after thermoforming of each layer of the multilayer body (polycarbonate resin layer (X), other thermoplastic resin layer (Y), etc.) is more likely to occur, making thermoforming easier. That is, it is preferable that the multilayer body of the present embodiment does not generate springback at the bent portion after being thermoformed to 50 mmR in a press. Moreover, it is preferable that the multilayer body of the present embodiment does not develop cracks in the bent portions after being thermoformed to a radius of 50 mm using a heat press. In this embodiment, the heat bending temperature is preferably 115° C. or higher, more preferably 118° C. or higher, and is preferably 131° C. or lower, from the viewpoint of preventing springback and cracks.

[0072] <Application> The multilayer body and molded article of the present embodiment can be suitably used for optical parts, design products, anti-reflective molded articles, and the like. The multilayer body and molded article of the present embodiment are preferably used for display devices, electric and electronic devices, OA devices, mobile information terminals, machine parts, home appliances, vehicle parts, various containers, lighting equipment, and other parts. Among these, they are particularly preferably used for housings of various displays, electric and electronic devices, OA devices, mobile information terminals, and home appliances, lighting equipment, and vehicle parts (particularly, vehicle interior parts), surface films of smartphones and touch panels, optical materials, and optical disks. In particular, the molded article of the present embodiment is preferably used as a sensor film for a touch panel or an anti-reflection molded article for various displays. EXAMPLES

[0073] The present invention will be described in more detail below with reference to examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0074] 1.Raw materials <Polycarbonate resin> A1: E-2000F, bisphenol A polycarbonate resin, manufactured by Mitsubishi Gas Chemical Co., Ltd., Tg: 150°C, viscosity average molecular weight: 27,000 A2: S-3000F, bisphenol A polycarbonate resin, manufactured by Mitsubishi Gas Chemical Co., Ltd., Tg: 147°C, viscosity average molecular weight: 21,000

[0075] <Plasticizer> B1: Glyceryl tribenzoate (Sigma-Aldrich) [ka] B2: Pentaerythritol tetrabenzoate (Sigma-Aldrich) [ka] B3: Trimethylolpropane tribenzoate (ADEKA Cizer PN-7000 manufactured by ADEKA Corporation) [ka] B4: Diethylene glycol dibenzoate (Eastman Benzoflex 2-45) [ka] B5: PX-200, manufactured by Daihachi Chemical Industry Co., Ltd., phosphoric acid condensation ester [ka] B6: Pentaerythritol tetrastearate (NOF Corporation, Unistar H-476) [ka]

[0076] <Other thermoplastic resins> C1: SAM-020: Manufactured by Fine-blend Polymer, styrene: maleic anhydride = 83% by mass: 17% by mass, Tg: 129°C, weight average molecular weight: 107,200 C2: XIRANSO26080, manufactured by Polyscope, styrene resin, XIRANSO26080, styrene:maleic anhydride = 74% by mass: 26% by mass, Tg: 150°C, weight average molecular weight: 47,600 C3: SK540N, manufactured by Asahi Kasei Corporation, acrylic resin, Delpet SK540N, mass ratio of N-cyclohexylmaleimide:N-phenylmaleimide:MMA = 7 mass%:8 mass%:85 mass%, Tg: 124°C, weight average molecular weight: 128,000 C4: 80HD, Asahi Kasei Corporation, PMMA resin, Delpet 80HD, Tg: 108°C, weight average molecular weight: 124,600

[0077] <Antioxidants> D1: Tris(2,4-di-tert-butylphenyl)phosphite (phosphorus antioxidant, ADEKA Corporation, Adekastab 2112) <Release agent> E1: Glycerin monostearate (Rikemal S-100A, manufactured by Riken Vitamin Co., Ltd.)

[0078] 2. Examples 1 to 17 and Comparative Examples 1 to 4 <Production of Resin Composition (Pellets)> A resin composition (x) (pellets) for forming a polycarbonate resin layer (X) and a resin composition (y) (pellets) for forming another thermoplastic resin layer (Y) were produced according to the following method. Each of the components described above was weighed out so as to obtain the amount of addition shown in Table 1 or 2 (each component in Table 1 and 2 is expressed in parts by mass). After that, the mixture was mixed in a tumbler for 15 minutes, and then melt-kneaded in a vented twin-screw extruder with a screw diameter of 32 mm ("TEX30α" manufactured by Japan Steel Works, Ltd.), and pellets were obtained by strand cutting. The resin composition (x) (pellets) for forming the polycarbonate resin layer (X) was melt-kneaded at 260 to 300°C while changing the temperature as needed depending on the resin viscosity, and the resin composition (y) (pellets) for forming the other thermoplastic resin layer (Y) was melt-kneaded at 260°C.

[0079] <Measurement of onset glass transition temperature (Tg)> The glass transition temperatures of the raw material resin and the resin composition were measured by carrying out two cycles of temperature increase and decrease according to the differential scanning calorimetry (DSC) measurement conditions described below, and the glass transition temperatures during the second temperature increase cycle were measured. The starting glass transition temperature was determined as the intersection point of a straight line extending the low-temperature side baseline to the high-temperature side and a tangent to the inflection point, the ending glass transition temperature was determined as the intersection point of a straight line extending the high-temperature side baseline to the low-temperature side and a tangent to the inflection point, and the midpoint between the starting glass transition temperature and the ending glass transition temperature was determined as the intermediate glass transition temperature, and the starting glass transition temperature was determined as Tg. Measurement starting temperature: 30°C, heating rate: 10°C / min, final temperature: 250°C, heating rate: 20°C / min. Units shown are °C. The measurement was performed using a differential scanning calorimeter (DSC, Hitachi High-Tech Science Corporation, "DSC7020").

[0080] <Method of measuring weight average molecular weight (Mw) and method of calculating molecular weight change (ΔMw)> The weight average molecular weight (Mw) of the resin composition (pellet) was measured by gel permeation chromatography. Specifically, the gel permeation chromatography apparatus used was an LC-20AD system (manufactured by Shimadzu Corporation), and the column used was an LF-804 (manufactured by Shodex Corporation). The column temperature was set to 40°C. The detector used was an RI detector RID-10A (manufactured by Shimadzu Corporation). Chloroform was used as the eluent, and a calibration curve was created using standard polystyrene (manufactured by Tosoh Corporation). If the above-mentioned gel permeation chromatography apparatus, column, and detector are difficult to obtain, measurement can be performed using other apparatus having equivalent performance.

[0081] The molecular weight change (ΔMw) was measured as follows. The weight average molecular weight of the obtained pellets (resin composition (x)) was measured initially and after 450 hours of wet heat treatment under conditions of 85°C and 85% relative humidity. The difference in weight average molecular weight before and after the wet heat treatment was calculated. Evaluation was performed as follows. A: (Initial weight average molecular weight) - (weight average molecular weight after wet heat treatment) is 3000 or less B: (Initial weight average molecular weight) - (weight average molecular weight after wet heat treatment) is more than 3000

[0082] <Manufacturing of multi-layer body without hard coat (HC)> A multi-layer body was formed 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 the extruders, and a T-die with a width of 650 mm connected to the feed block. The resin composition (y) used to form the layer (Y) in each of the examples and comparative examples shown in Table 1 or Table 2 was introduced into the single screw extruder with a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 250 ° C. and a discharge rate of 1.8 kg / h. In addition, the resin composition (x) used to form the polycarbonate resin layer (X) in each of the examples and comparative examples shown in Table 1 or Table 2 was continuously introduced into the single screw extruder with a shaft diameter of 65 mm, and the cylinder temperature was changed from 240 ° C. to 290 ° C. depending on the resin viscosity, and the discharge rate was extruded at 32.4 kg / h. The feed block connected to all the extruders was equipped with a two-type two-layer distribution pin, and extruded and laminated. The extruded material was extruded into a sheet shape through a T-die connected to the upstream side, and cooled while transferring a mirror surface through three mirror-finishing rolls whose temperatures were set to 130°C, 140°C, and 180°C from the upstream side, to obtain each multilayer body. The total thickness of the central part of the obtained multilayer body was 2000 μm, and the thickness of the layer (Y) was 60 μm.

[0083] <Production of multi-layer body with hard coat> A coating containing 60 parts by mass of hexafunctional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.), 35 parts by mass of PEG200# diacrylate (product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.), and 5 parts by mass of oligomer containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups (product name: RS-90, manufactured by DIC Corporation) and 1% by mass of a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxycyclohexyl phenyl ketone] manufactured by BASF Ltd.) was applied to the surface of the other thermoplastic resin layer (Y) of the multilayer body without a hard coat prepared above using a bar coater, and then the coating was heated with a metal halide lamp (20 mW / cm 2 ) for 5 seconds to cure the hard coat. The hard coat layer had a thickness of 6 μm.

[0084] <Evaluation of moldability> The moldability of the above multi-layered body was evaluated. The flow marks were evaluated by five experts and judged by majority vote. A: Sheet molding is possible B: Sheet molding not possible C: Sheet molding is possible, but flow marks occur

[0085] <Cracks after heat bending at 130℃> For the multilayer body with hard coat obtained above, a convex (male) and concave (female) mold with a curvature radius of 50 mmR were prepared. The multilayer body coated with the hard coat layer was preheated at 90°C for 1 minute before molding, and placed in the mold so that the surface coated with the hard coat layer was the convex side, and pressed for 5 minutes at a mold temperature of 130°C. The cracks in the bent parts of the obtained hot press molded products were visually evaluated. The evaluation was carried out by five experts and judged by majority vote. A: No cracks were found in the bent parts of the hot press molded product. B: Cracks were found in the bent parts of the hot press molded product.

[0086] <Springback after 130℃ heat bending> For the multilayer body with hard coat obtained above, a convex (male) and concave (female) mold with a curvature radius of 50 mmR were prepared. The multilayer body coated with the hard coat layer was preheated at 90°C for 1 minute before molding, placed in the mold so that the surface coated with the hard coat layer was the convex side, and pressed for 10 minutes at a mold temperature of 130°C. The bend radius R of the obtained hot press molded product was measured using a contour measuring instrument (SURFCOM NEX 040DX-22, manufactured by Tokyo Seimitsu Co., Ltd.). A: The bending radius of the heat-pressed product is less than 55 mmR. B: The bending radius of the heat-pressed product is 55 mmR or more and less than 75 mmR. C: The bending radius of the hot pressed product is 75 mmR or more.

[0087] <Pencil hardness> The surface of the other thermoplastic resin layer (Y) of the multilayer body without a hard coat prepared above and the surface of the hard coat layer of the multilayer body with a hard coat were each measured for pencil hardness under a load of 750 g using a pencil hardness tester in accordance with JIS K5600-5-4: 1999. The evaluation was performed by five experts and judged by majority vote.

[0088] [Table 1]

[0089] [Table 2]

[0090] It was difficult to mold a multilayer body in Comparative Example 2. In Comparative Example 5, flow marks were significantly generated, so evaluation of cracks and the like was not performed. [Explanation of symbols]

[0091] 1 Polycarbonate resin layer (X) 2 Other thermoplastic resin layer (Y) 3 Hard coat layer 4 Anti-reflection layer

Claims

1. A multilayer body having a layer (Y) containing a thermoplastic resin other than an aromatic polycarbonate resin on at least one surface of a layer (X) containing an aromatic polycarbonate resin, The layer (X) is a multilayer body containing 0.05 to 10 parts by mass of a plasticizer containing 2 to 5 groups represented by formula (B) in one molecule, based on 100 parts by mass of an aromatic polycarbonate resin. 【Chemical 1】 (In formula (B), each R independently represents a methyl group, an ethyl group, or a phenyl group; n represents an integer of 0 to 3; and Ar represents a benzene ring or a naphthalene ring.)

2. 2. The multilayer body according to claim 1, wherein the layer (Y) has a glass transition temperature of 130°C to 150°C according to differential scanning calorimetry.

3. 3. The multilayer body according to claim 1, wherein Ar in formula (B) is a benzene ring.

4. The multilayer body according to claim 1 or 2, wherein the other thermoplastic resin comprises an acrylic resin (y1).

5. 3. The multilayer body according to claim 1, wherein the other thermoplastic resin comprises 30 to 90 parts by mass of an acrylic resin (y1) and 10 to 70 parts by mass of a styrene resin (y2).

6. The acrylic resin (y1) is (meth)acrylic compound units; At least one of a cyclic acid anhydride unit, an N-substituted maleimide unit, and a lactone ring unit The multilayer body of claim 4 comprising:

7. 5. The multilayer body according to claim 4, wherein the acrylic resin (y1) contains 60 to 96% by mass of (meth)acrylic compound units and 4 to 40% by mass in total of at least one of cyclic acid anhydride units, N-substituted maleimide units, and lactone ring units.

8. 6. The multilayer body according to claim 5, wherein the styrene resin (y2) contains 68 to 84% by mass of aromatic vinyl compound units and 16 to 32% by mass of cyclic acid anhydride units.

9. 3. The multilayer body according to claim 1, wherein the difference between the glass transition temperature of the layer (X) measured by differential scanning calorimetry and the glass transition temperature of the layer (Y) measured by differential scanning calorimetry is 0 to 15°C.

10. 3. The multilayer body according to claim 1, wherein the plasticizer containing 2 to 5 groups represented by formula (B) in one molecule includes a plasticizer represented by formula (B-1). 【Chemistry 2】 (In formula (B-1), each R independently represents a methyl group, an ethyl group, or a phenyl group; n represents an integer of 0 to 3; L represents an n1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n1 represents an integer of 2 to 5.)

11. 3. The multilayer body according to claim 1, wherein the thickness of the layer (Y) is 10 to 250 μm, and the total thickness of the multilayer body is 400 to 4,000 μm.

12. The multilayer body according to claim 1 or 2, further comprising a hard coat layer on one or both sides of the multilayer body.

13. The multilayer body according to claim 1 or 2, further comprising one or both surfaces thereof subjected to one or more of an anti-fingerprint treatment, an anti-reflection treatment, an anti-glare treatment, a weather resistance treatment, an antistatic treatment, an anti-fouling treatment, and an anti-blocking treatment.

14. The multilayer body according to claim 1 or 2, wherein the layer (X) and / or the layer (Y) contains an antioxidant and / or a release agent.

15. The glass transition temperature of the layer (Y) according to differential scanning calorimetry is 130°C to 150°C, the other thermoplastic resin comprises 30 to 90 parts by mass of an acrylic resin (y1) and 10 to 70 parts by mass of a styrene resin (y2); the difference between the glass transition temperature of the layer (X) measured by differential scanning calorimetry and the glass transition temperature of the layer (Y) measured by differential scanning calorimetry is 0 to 15°C; 2. The multilayer body according to claim 1, wherein the plasticizer containing 2 to 5 groups represented by formula (B) in one molecule includes a plasticizer represented by formula (B-1). 【Chemistry 3】 (In formula (B-1), each R independently represents a methyl group, an ethyl group, or a phenyl group; n represents an integer of 0 to 3; L represents an n1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n1 represents an integer of 2 to 5.)

16. A molded article formed from the multilayer body of claim 1, 2 or 15.

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