Resin composition, plate-like molding, and multilayer body

Abstract

To provide a resin composition which has a low glass transition temperature while maintaining excellent appearance, transparency and a molecular weight that a polycarbonate resin originally has, and a plate-like molding and a multilayer body using the resin composition.SOLUTION: A resin composition contains 0.05 to 5 pts.mass of a compound (1) and / or a compound (2) with respect to 100 pts.mass of a polycarbonate resin.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a resin composition, a flat plate-shaped molded body, and a multi-layer body, and in particular to a resin composition containing a polycarbonate resin as a main component. [Background technology]

[0002] Polycarbonate resin is a thermoplastic resin that has excellent mechanical strength, transparency, heat resistance, thermal stability, etc., and is widely used in fields such as electricity, electronics, machinery, and automobiles. For example, Patent Document 1 discloses a polycarbonate resin composition containing 100 parts by weight of an aromatic polycarbonate resin (A) and 0.05 to 3.0 parts by weight of trimethylolpropane tribenzoate (B). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2022-017013 Summary of the Invention [Problem to be solved by the invention]

[0004] Polycarbonate resins generally have a glass transition temperature of about 152° C., but there are cases where a polycarbonate resin having a lower glass transition temperature is required. Here, the inventors have investigated Patent Document 1 and found that the polycarbonate resin composition described in Patent Document 1 has a low glass transition temperature. However, the inventors have also investigated and found that the resulting molded article has poor appearance, a small molecular weight, and other properties inherent to the polycarbonate resin are inferior. The present invention has an object to solve the above problems, and to provide a resin composition having a low glass transition temperature while maintaining the excellent appearance, transparency, and molecular weight inherent to polycarbonate resins, as well as a flat plate-shaped molded body and a multilayer body using the resin composition. [Means for solving the problem]

[0005] Means for Solving the Problems The present inventors have conducted research in light of the above-mentioned problems and have found that by blending a specific compound with a polycarbonate resin, it is possible to provide a resin composition having a low glass transition temperature while maintaining the excellent appearance, transparency, and molecular weight that are inherent to polycarbonate resin. Specifically, the above problems were solved by the following means. <1> A resin composition comprising 100 parts by mass of a polycarbonate resin and 0.05 to 5 parts by mass of the following compound (1) and / or compound (2): [ka] <2> The resin composition has a glass transition temperature of 150° C. or lower as measured by differential scanning calorimetry. <1> The resin composition according to claim 1. <3> The resin composition has a glass transition temperature of 130° C. or higher as measured by differential scanning calorimetry. <1> or <2> The resin composition according to claim 1. <4> The resin composition has a YI value of 4.0 or less when molded to a thickness of 3 mm. <1> ~ <3> 10. The resin composition according to claim 9 . <5> Further comprising an antioxidant and / or a mold release agent, <1> ~ <4> 10. The resin composition according to claim 9 . <6> The resin composition has a glass transition temperature of 150° C. or lower as measured by differential scanning calorimetry, a glass transition temperature of 130° C. or higher as measured by differential scanning calorimetry, and a YI value of 4.0 or lower when the resin composition is molded to a thickness of 3 mm, and further contains an antioxidant and / or a mold release agent. <1> The resin composition according to claim 1. <7> <1> ~ <6> 1. A flat plate-like molded product formed from the resin composition according to any one of claims 1 to 9. <8> The thickness is 10 to 5,000 μm. <7> The flat plate-like molded article according to claim 1. <9> <7> or <8> 2. A multilayer body having the flat plate-like molded body according to claim 1 and a layer containing an acrylic resin. <10> The total thickness of the multilayer body is 10 to 10,000 μm. <9> The multilayer body according to claim 1. <11> Further, the hard coat layer is formed by laminating the flat plate-like molded body, the layer containing an acrylic resin, and the hard coat layer in this order. <9> or <10> The multilayer body according to claim 1. Effect of the Invention

[0006] The present invention makes it possible to provide a resin composition having a low glass transition temperature while maintaining the excellent appearance, transparency, and molecular weight inherent to polycarbonate resin, as well as a flat plate-shaped molded body and a multilayer body using the resin composition. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a diagram showing a schematic layer structure of the multilayer body of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] 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 this specification, "(meth)acrylate" refers to both or either of acrylate and methacrylate. The flat plate-like molded body and the multi-layered body in this specification are intended to include those in the shape of a film or a sheet. The terms "film" and "sheet" refer to molded bodies that are thin relative to their length and width and are generally flat. In this specification, the terms "film" and "sheet" may be either single-layer or multi-layer. 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. The drawings attached to this specification are schematic diagrams, and may not be drawn to scale or correspond to reality.

[0009] The resin composition of the present embodiment is characterized in that it contains 0.05 to 5 parts by mass of the following compound (1) and / or compound (2) per 100 parts by mass of polycarbonate resin. By adopting such a constitution, it is possible to obtain a resin composition having a low glass transition temperature while maintaining the excellent appearance, transparency, and molecular weight inherent to polycarbonate resin. [ka]

[0010] In general, by blending a plasticizer into a polycarbonate resin, the glass transition temperature of the polycarbonate resin can be lowered. For example, by blending trimethylolpropane tribenzoate described in Patent Document 1, the glass transition temperature of the polycarbonate resin can be lowered. However, it was found that blending trimethylolpropane tribenzoate significantly reduces the molecular weight and increases the yellowness. In this embodiment, it has been found that the above problem can be solved by selecting compound (1) and / or compound (2) from among many plasticizers. The details of this embodiment will be described below.

[0011] The resin composition of the present embodiment contains a polycarbonate resin. The polycarbonate resin is not particularly limited as long as it contains a -[OR-OCO]- structural unit (R is a hydrocarbon group (e.g., an aliphatic group, an aromatic group, or one containing both an aliphatic group and an aromatic group, and further one having a straight-chain structure or a branched structure)) that contains a carbonate bond in the molecular main chain, and various polycarbonate resins can be used.

[0012] In this embodiment, polycarbonate resin is preferred, and bisphenol-type polycarbonate resin is more preferred. The bisphenol-type polycarbonate resin means that 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.

[0013] 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

[0014] The onset glass transition temperature (Tg) of the polycarbonate resin used in this embodiment is preferably 160° C. or lower, more preferably 155° C. or lower, even more preferably 154° C. or lower, even more preferably 153° C. or lower, even more preferably 152° C. or lower, and even more preferably 151° C. or lower. The onset glass transition temperature (Tg) of the polycarbonate resin used in this embodiment may be, for example, 148° C. or higher, or even 149° C. or higher, or 150° C. or higher. The onset glass transition temperature is measured as described in the Examples section below.

[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 resin composition of this embodiment is preferably 90 mass% or more, more preferably 92 mass% or more, even more preferably 94 mass% or more, still more preferably 96 mass% or more, and even more preferably 97 mass% or more, based on 100 mass% of the resin composition. When the resin composition of the present embodiment contains two or more types of polycarbonate resins, the total amount is preferably within the above range.

[0017] The resin composition of the present embodiment contains the compound (1) and / or the compound (2). By containing the compound (1) and / or the compound (2), a resin composition having a low glass transition temperature can be obtained. From the viewpoint of lowering the YI value of the plate-like molded article, it is preferred that the composition contains the compound (1). The resin composition of the present embodiment contains 0.05 to 5 parts by mass of the following compound (1) and / or compound (2) relative to 100 parts by mass of polycarbonate resin. Preferably, the total amount of compound (1) and compound (2) relative to 100 parts by mass of polycarbonate resin is preferably 0.1 parts by mass or more, more preferably 0.4 parts by mass or more, even more preferably 0.6 parts by mass or more, even more preferably 1.2 parts by mass or more, and even more preferably 1.5 parts by mass or more. By making it equal to or more than the lower limit, the glass transition temperature of the resin composition can be further lowered. Moreover, the total amount of compound (1) and compound (2) relative to 100 parts by mass of polycarbonate resin is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and may be 2.5 parts by mass or less. By making it equal to or less than the upper limit, the glass transition temperature can be made appropriate.

[0018] In addition to the above components, the resin composition of the present embodiment may contain thermoplastic resins other than polycarbonate resins, antioxidants, release agents, ultraviolet 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 total content of the above components is preferably 0.1 to 5% by mass of the resin composition.

[0019] The resin composition of the present embodiment particularly preferably contains an antioxidant and / or a mold release agent. 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.

[0020] 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.

[0021] 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.

[0022] [ka] (In formula (1-a), R A each independently represents an alkyl group having 1 to 10 carbon atoms. B each independently represents an alkyl group having 1 to 10 carbon atoms.

[0023] 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.

[0024] 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.

[0025] 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 resin composition. 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 resin composition.

[0026] 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.

[0027] Next, the release agent contained in the resin composition 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.

[0028] 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.

[0029] 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 resin composition. 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.

[0030] The resin composition of this embodiment preferably has a low onset glass transition temperature (Tig) measured by differential scanning calorimetry. Specifically, the onset glass transition temperature (Tig) of the resin composition of this embodiment 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 130°C or higher, even more preferably more than 130°C, and may be 131°C or higher. The onset glass transition temperature (Tig) is measured according to the method described in the Examples section below.

[0031] The resin composition of the present embodiment preferably has excellent transparency. Specifically, the resin composition of the present embodiment has a total light transmittance of preferably 80.0% or more, and more preferably 85.0% or more, when molded to a thickness of 3 mm. The upper limit of the total light transmittance may be 100%. Furthermore, the resin composition of the present embodiment preferably has a haze of 2.0% or less, more preferably 1.5% or less, and even more preferably 1.0% or less when molded to a thickness of 3 mm. The lower limit of the haze may be 0%. The resin composition of the present embodiment is preferably resistant to yellowing. Specifically, the YI value when the resin composition of the present embodiment is molded to a thickness of 3 mm is preferably 4.3 or less, more preferably 4.0 or less, even more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit of the YI value is ideally 0, but practically 0.1 or more. The total light transmittance, haze, and YI value are measured according to the description in the examples described later.

[0032] <Flat-shaped molded body> The resin composition of the present embodiment is preferably processed into a plate-shaped molded article for use. That is, the plate-shaped molded article of the present embodiment is formed from the resin composition of the present embodiment. Examples of the flat-plate-shaped molded article include a plate, a film, a sheet, and the like. In addition, the flat-plate-shaped molded article may be included in a multilayer body laminated on another substrate, etc., as described in detail below. In addition, the flat-plate-shaped molded article of this embodiment may be incorporated into a part of the multilayer body and then be subjected to bending processing or the like. The thickness of the flat molded body is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 50 μm or more, and may be 100 μm or more. By making it above the lower limit, molding becomes easier and the hardness tends to improve. In addition, there is no particular limit to the upper limit of the thickness of the flat molded body, but it is practical to make it 5,000 μm or less. The plate-like molded article of this embodiment is molded by injection molding, extrusion molding using a T-die, or the like.

[0033] <Multilayer body> The flat-plate molded article of the present embodiment can be used as a multilayer body. The multilayer body of the present embodiment preferably has the flat-plate molded article of the present embodiment and a layer containing an acrylic resin (acrylic resin layer). The thickness of the multilayer body is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and is preferably 10,000 μm or less, more preferably 5,000 μm or less, and may be 2,000 μm or less. The multilayer body of the present embodiment preferably further includes a hard coat layer. By providing the hard coat layer, the surface hardness of the multilayer body tends to be further improved. The hard coat layer is preferably laminated in the order of the flat plate-shaped molded body, the layer containing an acrylic resin, and the hard coat layer. 1 is a schematic diagram showing an example of the multilayer body of this embodiment, in which, as described above, 1 indicates the multilayer body, 2 indicates a flat plate-like molded body (polycarbonate resin film or sheet), 3 indicates an acrylic resin layer, and 4 indicates a hard coat layer. As long as the flat plate-like molded body 2, the acrylic resin layer 3, and the hard coat layer 4 are laminated in the above order, they may have other layers without departing from the spirit of this embodiment, but it is preferable that they do not have other layers, that is, they are adjacent to each other.

[0034] Next, the acrylic resin layer will be described The acrylic resin layer included in the multilayer body of the present embodiment is a layer containing an acrylic resin.

[0035] The acrylic resin layer in this embodiment preferably has a glass transition temperature of 130° C. to 150° C. according to differential scanning calorimetry. The onset glass transition temperature of the acrylic resin layer or the resin composition for forming the acrylic resin layer 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 thermal bending. In addition, the onset glass transition temperature of the acrylic resin layer or the resin composition for forming the acrylic resin layer 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 thermal bending tends to be suppressed.

[0036] In this embodiment, the acrylic resin layer 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 and a styrene resin. The acrylic resin layer 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 and the thermoplastic resin (preferably a styrene resin).

[0037] The acrylic resin layer 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). This composition tends to more effectively improve the pencil hardness, heat resistance, and impact resistance. That is, by blending the acrylic resin, the pencil hardness and impact resistance are improved, and by blending the styrene resin, the heat resistance is improved. When the acrylic resin layer contains acrylic resin (y1) and 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 acrylic resin layer contains the acrylic resin (y1) and the 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.

[0038] <<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.

[0039] 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 obtained acrylic resin layer tends to be improved.

[0040] 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%.

[0041] 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.

[0042] 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 acrylic resin layer 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.

[0043] 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 obtained acrylic resin layer 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.

[0044] <<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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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 obtained acrylic resin layer 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.

[0050] In addition to the above components, the acrylic resin layer may contain other thermoplastic resins, antioxidants, release agents, ultraviolet 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. The content of the above components, if any, is preferably 0.1 to 5% by mass in total of the acrylic resin layer. In particular, in this embodiment, the acrylic resin layer or the resin composition for forming the acrylic resin layer 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 that may be blended in the resin composition of this embodiment, and the preferred ranges are also the same.

[0051] The acrylic resin layer may be a single layer or a multilayer. The thickness of the acrylic resin layer 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 greater than the lower limit, molding becomes easier and hardness tends to improve. In addition, the upper limit of the thickness of the acrylic resin layer 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.

[0052] Next, the details of the hard coat layer will be described. The hard coat layer that may be included in the multilayer body of the present embodiment is a layer having a higher surface hardness than the flat molded body (polycarbonate resin film or sheet). By including such a hard coat layer, the surface hardness of the multilayer body or molded article can be increased. 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.

[0053] 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.

[0054] The multilayer body of the present embodiment may have other layers in addition to those described above. Specific examples of the other layers include an adhesive layer, a pressure-sensitive adhesive layer, and an antifouling layer.

[0055] The multilayer body may be subjected to at least one of anti-fingerprint treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, anti-soiling treatment, and anti-blocking treatment on at least one surface. An example of the outermost surface of the multilayer body in this case is a hard coat layer. The anti-blocking treatment refers to a treatment that allows films to be easily peeled off even if they are in close contact with each other, and examples of the anti-blocking treatment include adding an anti-blocking agent and providing unevenness on the surface of the multilayer body. The multilayer body of the present embodiment can be formed by using a main extruder that extrudes the resin composition of the present embodiment and a sub-extruder that extrudes the composition for forming an acrylic resin layer, 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.

[0056] The multilayer body of the present embodiment may be used as it is, but can also be processed, particularly by heat processing, to form a molded article. 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 can also be used in applications having curved portions, for example, in molded articles having a portion with a curvature radius of 50 mmR or less (preferably a curvature radius of 40 to 50 mmR).

[0057] <Application> The flat plate-like molded body, multilayer body, and molded article of the present embodiment can be suitably used for optical parts, design products, anti-reflection molded bodies, and the like. The flat molded body, multilayer body, and molded article of this 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 body of this embodiment is preferably used as a sensor film for a touch panel or an anti-reflection molded body for various displays. EXAMPLES

[0058] 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.

[0059] 1. Raw materials Polycarbonate resin E-2000: Polycarbonate resin obtained by interfacial polymerization using bisphenol A as the starting material (Mitsubishi Gas Chemical Company, Inc., E-2000F, viscosity average molecular weight: 27,000, Tg: 150°C) S-3000: Polycarbonate resin obtained by interfacial polymerization using bisphenol A as the starting material (Mitsubishi Gas Chemical Company, Inc., S-3000F, viscosity average molecular weight: 21,000, Tg: 147°C)

[0060] Plasticizers Compound (1): Glyceryl tribenzoate (manufactured by Sigma-Aldrich) [ka] Compound (2): Pentaerythritol tetrabenzoate (Sigma-Aldrich) [ka] Comparative compound: Trimethylolpropane tribenzoate (ADEKA Cizer PN-7000, manufactured by ADEKA Corporation) [ka]

[0061] Antioxidants Tris(2,4-di-tert-butylphenyl)phosphite (phosphorus antioxidant, ADEKA Corporation, Adeka STAB 2112) Release agent Glycerin monostearate (Rikemal S-100A, manufactured by Riken Vitamin Co., Ltd.)

[0062] <Method for measuring viscosity average molecular weight> The intrinsic viscosity [η] (unit: dL / g) of polycarbonate resin was measured using methylene chloride as the solvent. The temperature was 25°C. The specific viscosity [η] at each solution concentration [C] (g / dL) was measured using an Ubbelohde viscometer. sp The intrinsic viscosity was calculated from the obtained specific viscosity value and concentration according to the following formula.

number

[0063] 2. Examples 1 to 8 and Comparative Examples 1 to 4 <Production of Resin Composition (Pellets)> Each of the components described above was weighed out so as to obtain the amount of addition shown in Table 1 or Table 2 (each component in Table 1 or Table 2 is expressed in parts by mass). After mixing for 15 minutes in a tumbler, the mixture was melt-kneaded in a vented twin-screw extruder with a screw diameter of 32 mm ("TEX30α" manufactured by Japan Steel Works, Ltd.) and pelletized by strand cutting. The melt-kneading temperature was 260 to 300°C. The onset glass transition temperature (Tig) and molecular weight change (ΔMw) of the obtained resin composition (pellets) were measured.

[0064] <Measurement of onset glass transition temperature (Tig)> The glass transition temperatures of the raw materials and the resin compositions were measured by carrying out two cycles of temperature increase and decrease according to the differential scanning calorimetry (DSC) measurement conditions shown 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. The starting temperature was 30°C, the heating rate was 10°C / min, the final temperature was 250°C, and the cooling rate was 20°C / min. The units were °C. The measurement was performed using a differential scanning calorimeter (DSC, Hitachi High-Tech Science Corporation, "DSC7020").

[0065] <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. The molecular weight change (ΔMw) was expressed as the difference between the weight average molecular weight of the obtained pellets (resin composition) and the weight average molecular weight of pellets obtained by pelletizing only a polycarbonate resin having the same composition as the above pellets using a similar manufacturing method.

[0066] <Manufacture of Test Specimens> The resin composition (pellets) obtained above was dried in a hot air circulation dryer at 120°C for 4 to 7 hours, and then melted and kneaded at a cylinder temperature of 280°C using a twin-screw injection molding machine with a vent (Sodick's "PE-100", meshing type co-rotating twin-screw with a diameter of 29 mm for the twin-screw and a plunger diameter of 28 mm). Test specimens with three thicknesses of 1 mm, 2 mm, and 3 mm were molded under the condition of a mold temperature of 80°C.

[0067] <Measurement of Total Light Transmittance and Haze> Using a haze meter, under the condition of a D65 light source and a 10° field of view, the total light transmittance (%) and haze (%) of the 3-mm-thick portion of the test specimens obtained above were measured. As the haze meter, "HM-150" manufactured by Murakami Color Research Laboratory was used.

[0068] <Measurement of YI (Yellow Index)> The YI value of the 3-mm-thick portion of the test specimens obtained above was measured under the illumination and light-receiving conditions of the di:0° post-spectral method in accordance with JIS Z 8722. As the spectrocolorimeter, "SD-7000" manufactured by Nippon Denshoku Industries Co., Ltd. was used.

[0069]

Table 1

[0070]

Table 2

[0071] As is clear from the above results, for the resin composition of the present invention, the glass transition temperature could be lowered without causing changes in appearance, molecular weight, etc. (Examples 1 to 8). On the other hand, when none of the compounds (1) and (2) and the comparative compounds were used (Comparative Example 1), the glass transition temperature of the resin composition did not decrease at all. In addition, when comparative compounds similar to compounds (1) and (2) were used (Comparative Examples 2 and 3), the glass transition temperature of the resin composition was reduced, but the molecular weight change was large and the YI was high, resulting in poor appearance. On the other hand, when the compound (1) was blended in an excessively large amount (Comparative Example 4), the glass transition temperature of the resin composition could be lowered, but the change in molecular weight was large. [Explanation of symbols]

[0072] 1 Multilayer body 2. Flat molded body (polycarbonate resin film or sheet) 3 Acrylic resin layer 4 Hard Coat Layer

Claims

1. A resin composition comprising 0.05 to 5 parts by mass of the following compound (1) and / or compound (2) per 100 parts by mass of a polycarbonate resin: 【Chemical 1】

2. The resin composition according to claim 1, wherein the resin composition has a glass transition temperature of 150°C or lower as measured by differential scanning calorimetry.

3. The resin composition according to claim 1 or 2, wherein the resin composition has a glass transition temperature of 130°C or higher as measured by differential scanning calorimetry.

4. The resin composition according to claim 1 or 2, wherein the resin composition has a YI value of 4.0 or less when molded into a thickness of 3 mm.

5. The resin composition according to claim 1 or 2, further comprising an antioxidant and / or a mold release agent.

6. The resin composition has a glass transition temperature of 150°C or lower as measured by differential scanning calorimetry; The resin composition has a glass transition temperature of 130°C or higher as measured by differential scanning calorimetry; the resin composition has a YI value of 4.0 or less when molded into a thickness of 3 mm; The resin composition according to claim 1 , further comprising an antioxidant and / or a mold release agent.

7. A flat plate-like molded article formed from the resin composition according to claim 1, 2 or 6.

8. The plate-like molded article according to claim 7, having a thickness of 10 to 5,000 μm.

9. A multilayer body comprising the flat plate-like molded body according to claim 7 and a layer containing an acrylic resin.

10. 10. The multilayer body according to claim 9, wherein the total thickness of the multilayer body is 10 to 10,000 μm.

11. The multilayer body according to claim 9 , further comprising a hard coat layer, the hard coat layer being formed by laminating the tabular molded body, the layer containing an acrylic resin, and the hard coat layer in this order.

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