WO2022131014A1 - Resin composition, plate-shape molded body, laminate, molded product, and molded product production method - Google Patents

Resin composition, plate-shape molded body, laminate, molded product, and molded product production method Download PDF

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Publication number
WO2022131014A1
WO2022131014A1 PCT/JP2021/044412 JP2021044412W WO2022131014A1 WO 2022131014 A1 WO2022131014 A1 WO 2022131014A1 JP 2021044412 W JP2021044412 W JP 2021044412W WO 2022131014 A1 WO2022131014 A1 WO 2022131014A1
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Prior art keywords
resin composition
resin
unit
mass
acrylic
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PCT/JP2021/044412
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French (fr)
Japanese (ja)
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円 山口
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三菱瓦斯化学株式会社
Ｍｇｃフィルシート株式会社
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Priority to CN202180085240.4A priority Critical patent/CN116615335A/en
Priority to JP2022569857A priority patent/JPWO2022131014A1/ja
Priority to KR1020237022905A priority patent/KR20230119165A/en
Publication of WO2022131014A1 publication Critical patent/WO2022131014A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers

Definitions

  • the present invention relates to a resin composition, a flat plate-shaped molded product, a multilayer body, a molded product, and a method for manufacturing a molded product.
  • Patent Document 1 comprises 10 to 70 parts by mass of the following (meth) acrylic acid ester-based polymer (A) and 90 to 30 parts by mass of a styrene-maleic anhydride-based copolymer (B).
  • a resin composition characterized by having a haze of 2 mm thickness measured based on D1003 of 3% or less is disclosed.
  • (Meta) Acrylic acid ester-based polymer (A): Polymer styrene-maleic anhydride consisting of (meth) acrylic acid ester-based monomer unit 60 to 100% by mass and styrene-based monomer unit 40 to 0% by mass.
  • System-based copolymer (B): A copolymer composed of 75 to 95% by mass of a styrene-based monomer unit and 25 to 5% by mass of maleic anhydride.
  • acrylic resin is inferior in material toughness, so that it has transparency and a material. Multilayer films and sheets are produced by coextrusion with a polycarbonate resin having excellent toughness.
  • An object of the present invention is to solve such a problem, and a resin composition capable of suppressing the occurrence of cracks and providing a multilayer body in which flow marks are less likely to occur, and the resin composition. It is an object of the present invention to provide a flat plate-shaped molded product, a multilayer body, and a molded product using the above.
  • ⁇ 2> The resin composition according to ⁇ 1>, wherein the haze when the resin composition is molded into a test piece having a thickness of 1 mm is 5.0% or less.
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the initial glass transition temperature (Tig) measured by differential scanning calorimetry of the resin composition is 140 ° C. or higher.
  • Tig initial glass transition temperature measured by differential scanning calorimetry of the resin composition.
  • the resin composition contains an acrylic resin (a) containing a (meth) acrylic compound unit and a styrene resin (b) as a resin containing an aromatic vinyl compound unit.
  • ⁇ 5> The resin composition according to ⁇ 4>, wherein the acrylic resin (a) contains at least one of a cyclic acid anhydride unit, an imide unit, and a glutarimide unit.
  • ⁇ 6> The resin composition according to ⁇ 4>, wherein the acrylic resin (a) contains a cyclic acid anhydride unit and / or an N-substituted maleimide unit.
  • ⁇ 7> The resin composition according to ⁇ 5> or ⁇ 6>, wherein the acrylic resin (a) contains an N-substituted maleimide unit.
  • the acrylic resin (a) contains 37 to 96% by mass of the (meth) acrylic compound unit, 1 to 60% by mass of the aromatic vinyl compound unit, and 3 of maleic anhydride and / or N-substituted maleimide units. -74% by mass (however, the total of (meth) acrylic compound unit, aromatic vinyl compound unit, and maleic anhydride and / or N-substituted maleimide unit does not exceed 100% by mass), ⁇ 4>- The resin composition according to any one of ⁇ 8>.
  • ⁇ 10> The resin composition according to any one of ⁇ 4> to ⁇ 9>, wherein the styrene resin (b) contains a cyclic acid anhydride unit.
  • the styrene resin (b) contains 68 to 84% by mass of an aromatic vinyl compound unit and 16 to 32% by mass of a cyclic acid anhydride unit (however, an aromatic vinyl compound unit and a cyclic acid anhydride unit).
  • ⁇ 12> The resin composition according to any one of ⁇ 4> to ⁇ 11>, wherein the styrene resin (b) contains a styrene unit.
  • the content of the acrylic resin (a) is 15 to 85 parts by mass based on the total content of 100 parts by mass of the acrylic resin (a) and the styrene resin (b), and the content of the styrene resin (b) is 15 to 85 parts by mass.
  • the resin composition according to any one of ⁇ 4> to ⁇ 13> which has a content of 15 to 85 parts by mass.
  • ⁇ 16> A flat plate-shaped molded product formed from the resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 17> The flat plate-shaped molded product according to ⁇ 16>, which has a thickness of 10 to 5,000 ⁇ m.
  • ⁇ 18> A multilayer body including the flat plate-shaped molded body according to ⁇ 16> or ⁇ 17>.
  • ⁇ 19> A multilayer body having the flat plate-shaped molded body according to ⁇ 16> or ⁇ 17> and a layer containing a polycarbonate resin.
  • a hard coat layer wherein the hard coat layer is laminated in the order of a layer containing the polycarbonate resin, the flat plate-shaped molded body, and the hard coat layer.
  • one or more of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, anti-static treatment, anti-fouling treatment and anti-blocking treatment are applied to one or both sides of the multilayer body.
  • ⁇ 22> A molded product formed from the multilayer body according to any one of ⁇ 18> to ⁇ 21>, which has a portion having a radius of curvature of 50 mmR or less.
  • ⁇ 23> A method for producing a molded product, which comprises thermally bending the multilayer body according to any one of ⁇ 23> and ⁇ 18> to ⁇ 21> at 133 to 143 ° C.
  • a resin composition capable of suppressing the generation of cracks and providing a multilayer body in which flow marks are less likely to occur and a flat plate-shaped molded body, a multilayer body and a molded product using the resin composition are provided. It became possible. In particular, even when molded at a high temperature of about 135 ° C., it has become possible to make it difficult for cracks to occur in the multilayer body.
  • FIG. 1 is a schematic diagram showing the configuration of an example of an antireflection film.
  • the present embodiment will be described in detail.
  • the following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
  • "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
  • various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
  • the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the notation that does not describe substitution and non-substitution is preferably non-substitution.
  • the "(meth) acrylic compound” represents both an acrylic compound and / or a methacrylic compound, and a methacrylic compound is preferable.
  • the acrylic resin also contains a methacrylate (co) polymer in addition to the acrylate (co) polymer.
  • plate-shaped molded article and “multilayer” in the present specification are intended to include those in the shape of a film or a sheet, respectively.
  • the “film” and the “sheet” refer to a molded product having a thickness thin and generally flat with respect to the length and width, respectively. Further, the “film” and “sheet” in the present specification may be a single layer or a multilayer.
  • “part by mass” indicates a relative amount of a component
  • “mass%” indicates an absolute amount of a component. If the standards shown in this specification differ from year to year in terms of measurement method, etc., they shall be based on the standards at the time of filing unless otherwise specified.
  • the resin composition of the present embodiment is a resin composition containing a resin containing a (meth) acrylic compound unit and an aromatic vinyl compound unit, and the (meth) acrylic compound unit and the aromatic vinyl in the resin composition.
  • the total of the compound units is 55% by mass or more
  • the initial glass transition temperature (Tig) measured by the differential scanning calorimetry of the resin composition is 135 ° C. or more
  • the resin composition is molded into an ISO test piece having a thickness of 3 mm.
  • the impact strength of the unnotched Sharpy is 10.0 kJ / m 2 or more
  • the thickness of the ISO test piece is changed from 4 mm to 3 mm in JIS K 711-1.
  • melt viscosity of the resin composition at a shear rate of 240 ° C. and 1220 seconds -1 is 500 Pa ⁇ s or less.
  • a multilayer body having a layer formed from the resin composition of the present embodiment (flat plate-shaped molded product of the present embodiment) and a layer containing a polycarbonate resin (hereinafter, may be referred to as “polycarbonate resin layer”) may be used.
  • Thermal bending can be performed even at about 125 ° C., but when the temperature is 135 ° C. or higher, the thermal bending time can be effectively shortened, stress relaxation of the resin is accelerated, and springback is less likely to occur, which is preferable.
  • the above mechanism is presumed to be as follows. That is, by raising the glass transition temperature of the resin composition and making it equal to or higher than a predetermined Charpy impact strength, the occurrence of cracks can be effectively suppressed. Further, by lowering the melt viscosity of the resin composition, the generation of flow marks can be effectively suppressed. That is, when the resin composition of the present embodiment and another resin (for example, a polycarbonate resin) are extruded in multiple layers, there is a point where the resin composition of the present embodiment and the other resin components merge. At this time, if the difference in the melt viscosity of the resin is too large, a flow failure is likely to occur. In the present embodiment, it is presumed that by bringing the melt viscosity of the resin composition close to the melt viscosity of the resin co-extruded with the acrylic resin, flow failure can be effectively suppressed and flow marks can be suppressed.
  • the resin composition of the present embodiment contains a resin containing a (meth) acrylic compound unit and an aromatic vinyl compound unit, and the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit in the resin composition is 55. It is mass% or more. Inclusion of (meth) acrylic compound units tends to further improve pencil hardness and impact resistance, and inclusion of aromatic vinyl compound units improves refractive index and other resins such as aromatic polycarbonate resins. It is possible to effectively suppress interference fringes when a multilayer body with a layer is formed. Further, by setting the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit in the resin composition to 55% by mass or more, the pencil hardness and high refractive index of the resin are achieved while maintaining the transparency. To.
  • the (meth) acrylic compound unit means a structural unit composed of the (meth) acrylic compound in the resin
  • the aromatic vinyl compound unit is a structural unit composed of the aromatic vinyl compound in the resin.
  • the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit is a blend of the acrylic resin (a) containing the (meth) acrylic compound unit and the styrene resin (b) containing the aromatic vinyl compound unit. It may be a product, or it may be a copolymer containing a (meth) acrylic compound unit and an aromatic vinyl compound unit.
  • the resin composition of the present embodiment preferably contains both an acrylic resin (a) containing a (meth) acrylic compound unit and a styrene resin (b) containing an aromatic vinyl compound unit.
  • the (meth) acrylic compound is not particularly specified as long as it contains a (meth) acrylic group, but a compound represented by the formula (a1) is preferable.
  • Ra 1 is a hydrogen atom or a methyl group
  • Ra 2 is an aliphatic group.
  • Ra 1 is a hydrogen atom or a methyl group, and a methyl group is preferable.
  • Ra 2 is an aliphatic group, preferably a linear or branched aliphatic group, and 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), an alkenyl group (including a cycloalkenyl group), and the like, and an alkyl group is preferable, and a linear or branched alkyl is preferable. Groups are more preferred, and straight chain alkyl groups are even more preferred.
  • the number of carbon atoms of the aliphatic group of Ra 2 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and further preferably 1 or 2. It is preferably 1, and even more preferably 1.
  • the (meth) acrylic compound represented by the formula (a1) is preferably an alkyl (meth) acrylate (preferably alkyl methacrylate), and more preferably a methyl (meth) acrylate (preferably methyl methacrylate).
  • alkyl (meth) acrylate preferably alkyl methacrylate
  • methyl (meth) acrylate preferably methyl methacrylate
  • the aromatic vinyl compound is a compound having a vinyl group and an aromatic ring group, and a compound copolymerizable with the (meth) acrylic compound can be widely adopted.
  • L 1 is a single bond or a divalent linking group, preferably a single bond or a divalent linking group having a formula of 100 to 500, and a single bond or a divalent link having a formula of 100 to 300. It is more preferably a group, and even more preferably a single bond.
  • L 1 is a divalent linking group, it is preferably an aliphatic hydrocarbon group or a group consisting of a combination of an aliphatic hydrocarbon group and —O—.
  • the formula amount means the mass (g) per mole of the portion corresponding to L 1 of the aromatic vinyl compound.
  • Ar 1 is an aromatic ring group, preferably a substituted or unsubstituted benzene ring group or a naphthalene ring (preferably a benzene ring), and more preferably an unsubstituted benzene ring group.
  • the aromatic vinyl compound preferably contains an aromatic vinyl compound represented by the formula (b1). Equation (b1) (In the formula (b1), Ra 3 is a substituent and na is an integer of 0 to 6).
  • Ra 3 is a substituent, which is a halogen atom (preferably a chlorine atom, a fluorine atom or a bromine atom), a hydroxyl group, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and an aryl.
  • a group preferably a phenyl group
  • an alkenyl group preferably an alkenyl group having 2 to 5 carbon atoms
  • an alkoxy group preferably an alkoxy group having 1 to 5 carbon atoms
  • an aryloxy group preferably a phenoxy group.
  • na is preferably an integer of 5 or less, more preferably an integer of 4 or less, further preferably an integer of 3 or less, further preferably an integer of 2 or less, and an integer of 1 or less. Is even more preferable, and 0 is even more preferable.
  • the aromatic vinyl compound is preferably a compound having a molecular weight of 104 to 600, and more preferably a compound having a molecular weight of 104 to 400.
  • Specific examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene and methoxystyrene.
  • styrene-based monomers such as monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.
  • the mass ratio of the (meth) acrylic compound unit and the aromatic vinyl compound unit contained in the resin composition of the present embodiment will be described.
  • the mass ratio of the (meth) acrylic compound unit to the aromatic vinyl compound unit is 25 parts by mass or more of the aromatic vinyl compound unit with respect to 100 parts by mass of the (meth) acrylic compound unit. It is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 70 parts by mass or more, and further preferably 75 parts by mass or more. ..
  • the value By setting the value to the lower limit or more, the occurrence of interference fringes when laminated with the polycarbonate resin layer can be effectively suppressed by improving the refractive index.
  • the mass ratio of the (meth) acrylic compound unit to the aromatic vinyl compound unit is preferably 250 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic compound unit. It is more preferably parts by mass or less, more preferably 190 parts by mass or less, further preferably 180 parts by mass or less, and even more preferably 175 parts by mass or less. By setting the value to the upper limit or less, the impact strength and scratch resistance of the flat plate-shaped molded product formed from the resin composition of the present embodiment tend to be further improved.
  • the (meth) acrylic compound unit and the aromatic vinyl compound unit may contain only one kind or two or more kinds, respectively. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the resin composition of the present embodiment preferably contains an acrylic resin (a) containing a (meth) acrylic compound unit.
  • the ratio of the (meth) acrylic compound unit in the acrylic resin (a) is preferably more than 50% by mass, more preferably 55% by mass or more, and more preferably 60% by mass in all the constituent units excluding the terminal group.
  • the above is more preferable, 65% by mass or more is further preferable, and 70% by mass or more is further preferable.
  • the upper limit of the ratio of the (meth) acrylic compound unit in the acrylic resin (a) is preferably 100% by mass, preferably 90% by mass or less, and preferably 85% by mass in all the constituent units excluding the terminal group. It is more preferably mass% or less.
  • the acrylic resin (a) may contain only one type of (meth) acrylic compound unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the acrylic resin (a) may contain a monomer unit other than the (meth) acrylic compound unit.
  • examples of other monomers include monomers other than the (meth) acrylic compound and which can be copolymerized with the (meth) acrylic compound.
  • Specific examples of other monomer units include aromatic vinyl compound units, cyclic acid anhydride units, imide structural units, lactone ring structural units, and aliphatic vinyl compound units.
  • a preferred example of the other monomer unit is at least one selected from an aromatic vinyl compound unit, a cyclic acid anhydride unit, a lactone ring structure unit, and an N-substituted maleimide unit.
  • Another preferred example of the other monomer unit is at least one of a cyclic acid anhydride unit, an imide unit, a glutarimide unit, and a lactone ring structure unit.
  • Another preferred example of the other monomer unit is to include a cyclic acid anhydride unit and / or an N-substituted maleimide unit.
  • Another preferred example of the other monomer unit is to include an aromatic vinyl compound unit and an N-substituted maleimide unit.
  • Another preferred example of the other monomer unit is to include an aromatic vinyl compound unit, an N-phenylmaleimide unit, and an N-cyclohexylmaleimide unit.
  • the acrylic resin (a) contains an aromatic vinyl compound unit
  • the content thereof is preferably 1% by mass or more, and more preferably 3% by mass or more, in all the constituent units excluding the terminal group in the acrylic resin (a).
  • the content thereof is preferably 49% by mass or less in all the constituent units excluding the terminal group in the acrylic resin (a). It is more preferably 25% by mass or less, more preferably 25% by mass or less, 20% by mass or less, 10% by mass or less, and 7% by mass or less.
  • the cyclic acid anhydride unit examples include a maleic anhydride unit and a glutaric anhydride unit, and the maleic anhydride unit is preferable.
  • the cyclic acid anhydride unit particularly the maleic acid unit, the effect of improving the compatibility with the styrene resin (b) and the effect of improving the heat resistance are more effectively exhibited.
  • the acrylic resin (a) contains a cyclic acid anhydride unit, the content thereof is preferably 1% by mass or more, preferably 4% by mass, based on all the constituent units excluding the terminal group in the acrylic resin (a). The above is more preferable. By setting the value to the lower limit or more, the heat resistance tends to be further improved.
  • Examples of the imide structural unit include N-substituted maleimide units and glutarimide units.
  • Examples of the N-substituted maleimide unit include N-phenylmaleimide unit, N-cyclohexylmaleimide unit, N-benzylmaleimide, and N- (4-carboxyphenyl) maleimide), N-phenylmaleimide unit, and / or N-cyclohexyl.
  • Maleimide units are preferred.
  • the description in paragraphs 0030 to 0034 of JP-A-2018-009144 can be referred to, and the contents thereof are incorporated in the present specification.
  • As the glutarimide unit the description in paragraphs 0040 to 0047 of JP-A-2018-009144 can be referred to, and the contents thereof are incorporated in the present specification.
  • the acrylic resin (a) contains an N-substituted maleimide unit, particularly an N-phenylmaleimide unit, and / or an N-cyclohexylmaleimide, so that the acrylic resin (a) has heat resistance and a styrene resin (b). Compatibility is exhibited more effectively.
  • the acrylic resin (a) contains an N-substituted maleimide unit or a glutarimide unit (preferably an N-substituted maleimide unit)
  • the content thereof is 5 mass in all the constituent units excluding the terminal group in the acrylic resin (a).
  • % Or more more preferably 10% by mass or more.
  • the acrylic resin (a) contains an N-substituted maleimide unit or a glutarimide unit (preferably an N-substituted maleimide unit), the content thereof is the content of all the constituent units excluding the terminal group in the acrylic resin (a). It is preferably 49% by mass or less, more preferably 30% by mass or less, and further, 25% by mass or less, 20% by mass or less, and 10% by mass or less. By setting the value to the upper limit or less, the impact resistance and the scratch resistance tend to be further improved.
  • the acrylic resin (a) may contain only one type of N-substituted maleimide unit or glutarimide unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the acrylic resin (a) may contain only one type of lactone ring unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the (meth) acrylic compound unit (preferably methylmethacrylate unit) is 37 to 96% by mass, and the aromatic vinyl compound unit (preferably styrene) is 1 to 60% by mass. %, And a unit consisting of one or more of a cyclic acid anhydride unit, an imide unit, and a lactone ring structure unit (preferably maleic anhydride and / or an N-substituted maleimide unit, more preferably an N-substituted maleimide unit).
  • the total of substituted maleimide units does not exceed 100% by mass.
  • the total of the acid and / or N-substituted maleimide units) is preferably 90% by mass or more, more preferably 95% by mass or more, and 99% by mass of all the constituent units excluding the terminal group of the acrylic resin (a). % Or more is more preferable.
  • the second embodiment of the acrylic resin (a) is a blend of the acrylic resin of the first embodiment and an acrylic resin (ax) containing 90% by mass or more of a (meth) acrylic compound unit.
  • the blend ratio (mass ratio) of the acrylic resin of the first embodiment and the acrylic resin (ax) containing 90% by mass or more of the (meth) acrylic compound unit is preferably 1 to 10: 1, preferably 2 to 9. It is more preferably 1: 1, further preferably 3 to 8: 1, further preferably 3 to 7: 1, and even more preferably 4 to 6: 1.
  • the initial glass transition temperature (Tig) of the acrylic resin (a) is preferably 120 ° C. or higher, more preferably 125 ° C. or higher, further preferably 130 ° C. or higher, and 133 ° C. or higher. You may. By setting the value to the lower limit or more, the effect of preventing crack generation during thermal bending molding tends to be further improved.
  • the initial glass transition temperature (Tig) of the acrylic resin (a) is preferably 170 ° C. or lower, more preferably 160 ° C. or lower, further preferably 150 ° C. or lower, and 140 ° C. or lower. May be. By setting the value to the upper limit or less, the effect of suppressing springback during hot bending tends to be further improved.
  • the initial glass transition temperature (Tig) of the acrylic resin (a) is Tig of the mixture.
  • the method for measuring the glass transition temperature follows the method described in Examples described later (hereinafter, the same applies to the weight average molecular weight, pencil hardness, and the glass transition temperature, weight average molecular weight, and pencil hardness of the styrene resin (b)). ..
  • the weight average molecular weight of the acrylic resin (a) is preferably 50,000 or more, more preferably 70,000 or more, further preferably 100,000 or more, and 120,000 or more. It is more preferably 150,000 or more, and even more preferably 150,000 or more. By setting the value to the lower limit or more, the impact strength of the obtained flat plate-shaped molded product can be further improved.
  • the weight average molecular weight of the acrylic resin (a) is preferably 300,000 or less, more preferably 250,000 or less, further preferably 225,000 or less, and 210,000 or less. It is more preferably 200,000 or less, and even more preferably 200,000 or less. By setting the value to the upper limit or less, the melt viscosity of the resin composition can be effectively lowered.
  • the pencil hardness of the acrylic resin (a) is preferably HB or higher, and more preferably H or higher. By setting the value to the lower limit or more, the surface hardness of the obtained flat plate-shaped molded product can be further increased. Further, the pencil hardness of the acrylic resin (a) is preferably 2H or less, and more preferably H or less.
  • the ratio of the aromatic vinyl compound unit (preferably the styrene-based monomer unit) in the styrene resin (b) is preferably more than 50% by mass and 55% by mass or more in all the constituent units excluding the terminal group. Is more preferably 60% by mass or more, further preferably 65% by mass or more, and even more preferably 70% by mass or more. By setting the value to the lower limit or more, the refractive index is improved, and the interference fringes when laminated with the polycarbonate resin layer tend to be effectively suppressed.
  • the upper limit of the ratio of the aromatic vinyl compound unit in the styrene resin (b) is 100% by mass in all the constituent units excluding the terminal group.
  • the styrene resin (b) may contain only one aromatic vinyl compound unit, or may contain two or more aromatic vinyl compound units. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the styrene resin (b) may contain a monomer unit other than the aromatic vinyl compound unit and an aromatic vinyl compound unit other than the styrene-based monomer unit.
  • the other monomer include monomers other than the aromatic vinyl compound and which can be copolymerized with the aromatic vinyl compound.
  • Specific examples of the other monomer unit include a cyclic acid anhydride unit, an N-substituted maleimide unit, and a cyanide alkenyl unit, and a cyclic acid anhydride unit is preferable.
  • cyclic acid anhydride unit examples include maleic anhydride unit and glutaric anhydride, and maleic anhydride unit is preferable.
  • the glass transition temperature of the obtained styrene resin (b) can be increased.
  • the styrene resin (b) contains a cyclic acid anhydride unit, the content thereof is preferably 16% by mass or more, preferably 20% by mass, based on all the constituent units excluding the terminal group in the styrene resin (b). The above is more preferable.
  • the content thereof is preferably 32% by mass or less in all the constituent units excluding the terminal group in the styrene resin (b). It is more preferably mass% or less.
  • the value By setting the value to be equal to or higher than the lower limit and not higher than the upper limit, the compatibility with the acrylic resin tends to be further improved. Further, by setting the value to the lower limit or more, the heat resistance of the entire resin composition can be improved.
  • the styrene resin (b) may contain only one type of cyclic acid anhydride unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the styrene resin (b) may contain 68 to 84% by mass of an aromatic vinyl compound unit (preferably styrene unit) and 16 to 32% by mass of a cyclic acid anhydride unit (preferably maleic anhydride unit). It is more preferable to contain 70 to 83% by mass of the aromatic vinyl compound unit and 17 to 30% by mass of the cyclic acid anhydride unit. However, the total of the aromatic vinyl compound unit and the cyclic acid anhydride unit does not exceed 100% by mass.
  • the total of the aromatic vinyl compound unit and the cyclic acid anhydride unit is preferably 90% by mass or more, more preferably 95% by mass or more of all the constituent units excluding the terminal group of the styrene resin (b). It is more preferably 99% by mass or more.
  • the initial glass transition temperature (Tig) of the styrene resin (b) is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, further preferably 140 ° C. or higher, and 143 ° C. or higher. Is even more preferable. By setting the value to the lower limit or more, it is possible to effectively suppress the occurrence of cracks during thermal bending molding.
  • the initial glass transition temperature (Tig) of the styrene resin (b) is preferably 180 ° C. or lower, more preferably 160 ° C. or lower, and even more preferably 155 ° C. or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
  • the weight average molecular weight of the styrene resin (b) is preferably 20,000 or more, more preferably 25,000 or more, still more preferably 30,000 or more, and 40,000 or more. It is more preferably 60,000 or more, and even more preferably 60,000 or more. By setting the value to the lower limit or more, the impact strength of the obtained flat plate-shaped molded product can be further improved.
  • the weight average molecular weight of the styrene resin (b) is preferably 150,000 or less, more preferably 130,000 or less, still more preferably 120,000 or less, and 100,000 or less. It is more preferably 80,000 or less, and it may be 70,000 or less. By setting the value to the upper limit or less, the melt viscosity of the resin composition can be effectively lowered.
  • the content of the acrylic resin (a) is 15 to 85 parts by mass based on the total content of 100 parts by mass of the acrylic resin (a) and the styrene resin (b), and the styrene resin (
  • the content of b) is preferably 15 to 85 parts by mass, the content of the acrylic resin (a) is 20 to 80 parts by mass, and the content of the styrene resin (b) is 80 to 20 parts by mass.
  • the content of the acrylic resin (a) is 30 to 70 parts by mass, and the content of the styrene resin (b) is 70 to 30 parts by mass.
  • the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit in the resin composition is 55% by mass or more, preferably 60% by mass or more, preferably 65. It is more preferably 7% by mass or more, further preferably 70% by mass or more, and further preferably 73% by mass or more. By setting the value to the lower limit or higher, high pencil hardness and high refractive index tend to be exhibited more effectively. Further, in the resin composition, the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less. Is more preferable, and 80% by mass or less is further preferable.
  • the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit occupies 90% by mass or more of the resin composition. It is more preferable to occupy 94% by mass or more, and even more preferably 97% by mass or more.
  • the upper limit value may be 99.9% by mass of the resin composition.
  • examples of the resin component other than the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit include a polycarbonate resin and a polyarylate resin.
  • the resin composition of the present embodiment preferably contains an antioxidant.
  • the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant.
  • a phosphorus-based antioxidant and a phenol-based antioxidant are preferable.
  • Phosphorus-based antioxidants are particularly preferable because they are excellent in hue of molded products.
  • a phosphite-based antioxidant is preferable, and a phosphite compound represented by the following formula (1) or (2) is preferable.
  • R 11 and R 12 independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • R 13 to R 17 independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
  • RA independently represents an alkyl group having 1 to 10 carbon atoms.
  • RB independently represent 1 to 10 carbon atoms. Represents an alkyl group of 10.
  • the antioxidant can be referred to in paragraphs 0057 to 0061 of JP-A-2017-031313, the contents of which are incorporated in the present specification.
  • the resin composition of the present embodiment preferably contains a mold release agent.
  • a mold release agent By including a mold release agent, the moldability of the flat plate-shaped molded product can be improved.
  • the type of the release agent is not particularly specified, but for example, an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a number average molecular weight of 100 to 100. Examples thereof include 5,000 polyethers and polysiloxane-based silicone oils.
  • the content of the release agent is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and 0.01 part by mass or more with respect to 100 parts by mass of the resin composition. It is more preferable to have.
  • the upper limit value is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and further preferably 0.2 parts by mass or less. Only one type of release agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.
  • the resin composition of the present embodiment includes a thermoplastic resin other than the above, an ultraviolet absorber, a heat stabilizer, a flame retardant, a flame retardant aid, a colorant, an antistatic agent, a fluorescent whitening agent, and a protective agent. It may contain a fogging agent, a fluidity improving agent, a plasticizer, a dispersant, an antibacterial agent, an anti-blocking agent, an impact improving agent, a sliding improving agent, a hue improving agent, an acid trapping agent and the like. One of these components may be used, or two or more thereof may be used in combination. When contained, the content of the above components is preferably 0.1 to 5% by mass in total of the resin composition.
  • the resin composition of the present embodiment has an initial glass transition temperature (Tig) of 135 ° C. or higher, preferably 136 ° C. or higher, more preferably 137 ° C. or higher, and more preferably 138 ° C. or higher by differential scanning calorimetry. It is more preferably 139 or more, and even more preferably 140 ° C. or higher.
  • the upper limit of the initial glass transition temperature (Tig) is not particularly determined, but is practically 145 ° C or lower, and may be 144 ° C or lower, further may be 143 ° C or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
  • the intermediate glass transition temperature (Tmg) measured by differential scanning calorimetry is preferably 139 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 141 ° C. or higher. , 142 ° C. or higher is more preferable, and 143 ° C. or higher is even more preferable.
  • the upper limit of the intermediate glass transition temperature (Tmg) is not particularly determined, but is practically 149 ° C. or lower, and may be 148 ° C. or lower, and further may be 147 ° C. or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
  • the glass transition temperature (Tig, Tmg) is measured according to the method described in Examples described later. In order to increase the initial glass transition temperature (Tig), it is exemplified to adjust the raw material monomer of the resin. Another example is to increase the molecular weight of the resin.
  • the glass transition temperature of the resin is generally determined by the raw material monomer and the molecular weight, and can be appropriately selected by those skilled in the art.
  • the resin composition of the present embodiment has a melt viscosity of 500 Pa ⁇ s or less at a shear rate of 240 ° C. and 1220 seconds -1 .
  • the melt viscosity is preferably 495 Pa ⁇ s or less, more preferably 490 Pa ⁇ s or less, further preferably 485 Pa ⁇ s or less, and even more preferably 480 Pa ⁇ s or less.
  • the lower limit of the melt viscosity is preferably 250 Pa ⁇ s or more, more preferably 300 Pa ⁇ s or more, further preferably 350 Pa ⁇ s or more, and further preferably 375 Pa ⁇ s or more. , 400 Pa ⁇ s or more is even more preferable.
  • melt viscosity is measured according to the description of Examples described later.
  • adjustment of the molecular weight of the resin and addition of a low molecular weight compound that does not adversely affect the resin can be mentioned.
  • the resin composition of the present embodiment is preferably excellent in transparency.
  • the haze when the resin composition of the present embodiment is molded to a thickness of 1 mm is preferably 5.0% or less, more preferably 2.0% or less, and 1.0. % Or less, more preferably 0.4% or less, and even more preferably 0.2% or less.
  • the lower limit is ideally 0%, but 0.01% or more is practical. Haze is measured according to the description of Examples described later.
  • the resin composition of the present embodiment preferably has a high pencil hardness (hardness). Specifically, the resin composition of the present embodiment is molded to a thickness of 1 mm, and the pencil hardness measured with a pencil hardness tester at a load of 750 g according to JIS K5600-5-4: 1999 is obtained. , F or more is preferable, and H or more is more preferable. By setting the pencil hardness to F or higher, the hardness of the entire multilayer body can be increased, and the scratch resistance can be improved. The upper limit is not particularly set, but 3H or less is practical. Pencil hardness is measured according to the description of Examples described later.
  • the resin composition of the present embodiment is preferably excellent in impact strength.
  • the impact strength without notch was 10.0 kJ / m 2 or more. Yes, 10.2 kJ / m 2 or more is preferable, and 10.5 kJ / m 2 or more is more preferable.
  • the upper limit of the Charpy impact strength is not particularly determined, but it is practically 20.0 kJ / m 2 or less, and even if it is 13.0 kJ / m 2 or less, the required performance is sufficiently satisfied. Examples of methods for increasing the Charpy impact strength include blending a known high impact resistant resin such as polymethylmethacrylate, adopting a resin having a high molecular weight, and blending a shock resistant modifier such as rubber. Will be done.
  • the resin composition of the present embodiment is preferably processed into a flat plate-shaped molded product and used. That is, the flat plate-shaped molded product of the present embodiment is formed from the resin composition of the present embodiment.
  • the flat plate-shaped molded product of the present embodiment has excellent moisture and heat resistance. Examples of the flat plate-shaped molded body include a plate, a film, and a sheet. Further, the flat plate-shaped molded body may be included in a multilayer body laminated on another base material or the like, as described in detail later. Further, the flat plate-shaped molded body of the present embodiment may be subjected to bending or the like after being incorporated into a part of the multilayer body.
  • the lower limit of the thickness of the flat plate-shaped molded product is, for example, 1 ⁇ m or more, preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 50 ⁇ m or more, and further preferably 80 ⁇ m or more. It is more preferable, and it may be 100 ⁇ m or more. By setting the value to the lower limit or more, molding tends to be easier and the hardness tends to be improved.
  • the upper limit of the thickness of the flat plate-shaped molded product is not particularly limited, but is preferably 5,000 ⁇ m or less, more preferably 2,000 ⁇ m or less, and further preferably 1,000 ⁇ m or less. It is more preferably 500 ⁇ m or less, and even more preferably 300 ⁇ m or less.
  • the flat plate-shaped molded product is thinner than the total thickness of the flat plate-shaped molded product and the polycarbonate resin layer.
  • the flat plate-shaped molded body of the present embodiment is molded by injection molding, extrusion molding with a T-die, or the like.
  • the flat plate-shaped molded body of the present embodiment conforms to JIS K5600-5-4: 1999, and the pencil hardness measured with a pencil hardness tester at a load of 750 g is preferably F or more, preferably H or more. Is more preferable.
  • the pencil hardness is measured according to the description of Examples described later.
  • the multilayer body of the present embodiment includes the flat plate-shaped molded body of the present embodiment. Such a multilayer body has excellent surface hardness. Further, the multilayer body of the present embodiment is preferably a multilayer body having the flat plate-shaped molded body of the present embodiment and a layer containing a polycarbonate resin (polycarbonate resin layer). The polycarbonate resin layer usually serves as a substrate for the multilayer body. The multilayer body of the present embodiment further preferably includes a hard coat layer. It is preferable that the hard coat layer is laminated in the order of the layer containing the polycarbonate resin, the flat plate-shaped molded product, and the hard coat layer. Further, the hard coat layer may be provided on the polycarbonate resin layer side as well.
  • FIG. 1 is a schematic view showing an example of an antireflection film, in which 1 is a substrate (polycarbonate resin layer), 2 is a flat plate-shaped molded product, 3 is a hard coat layer, and 4 is an antireflection layer. ing.
  • 1 is a substrate (polycarbonate resin layer)
  • 2 is a flat plate-shaped molded product
  • 3 is a hard coat layer
  • 4 is an antireflection layer. ing.
  • the base material 1, the flat plate-shaped molded body 2, the hard coat layer 3, and the antireflection layer 4 are laminated in the above-mentioned order, but have other layers as long as the gist of the present embodiment is not deviated. May be.
  • the multilayer body has another layer, one side or both sides of the multilayer body are subjected to fingerprint resistance treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment, antifouling treatment and the like. It is preferable that any one or more of the anti-blocking treatments are applied.
  • An example of the outermost surface of the multilayer body at this time is a hard coat layer.
  • the anti-blocking treatment refers to a treatment that enables the films to be easily peeled off even if they are in close contact with each other, and examples thereof include adding an anti-blocking agent and providing irregularities on the surface of the multilayer body.
  • the multilayer body of the present embodiment may have other layers in addition to the above. Specifically, an adhesive layer, an adhesive layer, an antifouling layer and the like are exemplified.
  • the base material 1 will be described.
  • the type of the base material 1 is not particularly specified, and a known base material can be used as long as it satisfies the performance required for the multilayer body of the present embodiment.
  • a resin base material is preferable, a polyolefin resin, a polyester resin, a polycarbonate resin, an acrylic resin, and a polystyrene resin are more preferable, and it is further preferable to contain a polycarbonate resin. These may form a composite base material of one kind alone or two or more kinds.
  • the base material 1 is preferably a layer containing a polycarbonate resin (polycarbonate resin layer).
  • the proportion of the polycarbonate resin in the polycarbonate resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
  • the polycarbonate resin is preferably an aromatic polycarbonate resin, and more preferably a bisphenol A type polycarbonate resin.
  • the bisphenol A type polycarbonate resin refers to a resin having a carbonate constituent unit derived from bisphenol A and its derivative, and preferably has a constituent unit represented by the following formula (B-1). * In the formula represents the bond position.
  • X 1 represents the following structure.
  • R 5 and R 6 are alkyl groups or hydrogen atoms, preferably at least one of which is a methyl group and more preferably both of which are methyl groups.
  • the formula (B-1) is preferably represented by the following formula (B-2).
  • the content of the structural unit represented by the formula (B-1) in the bisphenol A type polycarbonate resin is preferably 70 mol% or more, preferably 80 mol% or more, in all the structural units excluding both ends. Is more preferable, and 90 mol% or more is further preferable.
  • the upper limit is not particularly limited, and 100 mol% may be a structural unit represented by the formula (B-1).
  • the bisphenol A type polycarbonate a resin in which substantially all the constituent units excluding both ends are composed of the constituent units of the formula (B-1) can be mentioned.
  • substantially all the constituent units excluding both ends mean that it is 99.0 mol% or more of all the constituent units excluding both ends, and 99.5 mol% or more is preferable, and 99.9 mol.
  • the bisphenol A type polycarbonate resin may have a structural unit other than the carbonate structural unit derived from bisphenol A and its derivative.
  • Examples of the dihydroxy compound constituting such another structural unit include aromatic dihydroxy compounds described in paragraph 0014 of JP-A-2018-154819, the contents of which are incorporated in the present specification. ..
  • Examples of the terminal structure of the bisphenol A type polycarbonate resin include an alkyl group-substituted phenoxy group and an alkoxycarbonyl phenoxy group.
  • the number of carbon atoms of the alkyl group of the alkyl group substituted phenoxy group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 5.
  • Examples of the alkyl group-substituted phenoxy group include m-methylphenoxy group, p-methylphenoxy group, m-propylphenoxy group, p-propylphenoxy group and p-tert-butylphenoxy group.
  • the alkoxy group of the alkoxycarbonylphenoxy group preferably has 1 to 20 carbon atoms.
  • alkoxycarbonylphenoxy group an alkoxycarbonylphenoxy group having 1 to 10 carbon atoms is preferable, and a p-tert-butylphenoxy group is more preferable, from the viewpoint of heat resistance.
  • the initial glass transition temperature of the polycarbonate resin is preferably 140 to 155 ° C.
  • the method for producing the bisphenol A type polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
  • an interfacial polymerization method e.g., a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
  • the description of paragraphs 0040 to 0073 of JP-A-2019-035001 and the description of paragraphs 0016 to 0043 of JP-A-2018-103518 can be referred to, and these contents are incorporated in the present specification. Is done.
  • the base material 1 may contain various resin additives, if necessary, as long as the desired physical properties are not significantly impaired.
  • the resin additive include antioxidants, mold release agents, flame retardants, anti-dripping agents, dyes and pigments (including carbon black), antistatic agents, anti-fog agents, anti-blocking agents, and fluidity improvers.
  • examples include plasticizers, dispersants, antibacterial agents and the like.
  • 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.
  • the base material 1 may be a single layer or a multilayer.
  • the thickness of the base material 1 (preferably the polycarbonate resin layer) is not particularly limited, but is, for example, 1 ⁇ m or more, preferably 30 ⁇ m or more, more preferably 35 ⁇ m or more, and more preferably 40 ⁇ m or more. Further, it is more preferably 50 ⁇ m or more, further preferably 100 ⁇ m or more, further preferably 300 ⁇ m or more, particularly preferably 500 ⁇ m or more, and may be 700 ⁇ m or more.
  • the thickness of the base material 1 is preferably 10,000 ⁇ m or less, more preferably 5,000 ⁇ m or less, 3,000 ⁇ m or less, or 2,500 ⁇ m or less.
  • the multilayer body of the present embodiment preferably includes the flat plate-shaped molded body and the base material, but at this time, the relationship between the thickness of the flat plate-shaped molded body and the base material (preferably the polycarbonate resin layer) is , It is preferable that the thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material] ⁇ 1/5 is satisfied. By satisfying this relationship, the flat plate-shaped molded body becomes thin as a whole multilayer body, so that even if the multilayer body is heat-molded, the generation of cracks is more effectively suppressed and the generation of springback is more likely to occur. Effectively suppressed.
  • the thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material] ⁇ 1/6 is more preferable, and the thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material]. Thickness] ⁇ 1/8 is more preferable. Further, 1/35 ⁇ thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material] is preferable, and 1/25 ⁇ thickness of the flat plate-shaped molded body / [flat plate-shaped molded body and the base material]. Total thickness] is more preferable.
  • the flat plate-shaped molded body and the base material satisfy the above-mentioned preferable range of the predetermined thickness, and the multilayer body satisfies the above-mentioned relationship while satisfying the preferable range of the thickness described later.
  • the initial glass transition temperature (Tig) of the flat plate-shaped molded body, the initial glass transition temperature (Tig) of the base material (preferably the polycarbonate resin layer), and the thermal bending molding temperature (° C.) have the following relationship. It is preferable to satisfy.
  • Tig of flat plate-shaped molded product ⁇ Thermal bending temperature (° C)> [Initial glass transition temperature of substrate (Tig) -15 ° C] More preferably, Tig of the flat plate-shaped molded body> thermal bending molding temperature (° C)> [initial glass transition temperature (Tig) of the substrate -15 ° C] More preferably Tig of flat plate-shaped molded product> Thermal bending temperature (° C)> [Initial glass transition temperature of substrate (Tig) -10 ° C] By doing so, the suppression of springback and the suppression of crack generation tend to be further improved.
  • the amount of change in warpage of the multilayer body composed of the flat plate-shaped molded body (acrylic resin layer) and the polycarbonate resin layer before and after the high-humidity heat treatment is preferably less than 700 ⁇ m, and preferably less than 200 ⁇ m. More preferred. Ideally, the lower limit of the amount of change in warpage is 0 ⁇ m, but 1 ⁇ m or more is practical. The amount of change in warpage is measured according to the description of Examples described later.
  • 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 base material (for example, a polycarbonate resin layer).
  • the surface hardness of the multilayer body or the molded product can be increased.
  • the thickness of the hard coat layer is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 2 ⁇ m or more, further preferably 4 ⁇ m or more, and further preferably 5 ⁇ m or more. Is even more preferable. By setting the value to the lower limit or more, the pencil hardness of the entire multilayer body due to the hard coat layer tends to be further improved.
  • the upper limit of the thickness of the hard coat layer is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 12 ⁇ m or less, further preferably 10 ⁇ m or less, and further preferably 8 ⁇ m or less. Is even more preferable. By setting the value to the upper limit or less, the workability at the time of thermal bending tends to be further improved.
  • the hard coat layer is preferably obtained by applying a hard coat material that can be heat-cured or cured by an active energy ray and then curing it.
  • the coating material to be cured using the active energy ray include a resin composition composed of one or more monofunctional or polyfunctional (preferably 2 to 10 functional) (meth) acrylate monomers or oligomers, which is preferable.
  • examples thereof include a resin composition containing a monofunctional or polyfunctional (preferably 2 to 10 functional) urethane (meth) acrylate oligomer. It is preferable to add a photopolymerization initiator as a curing catalyst to these resin compositions.
  • the thermosetting resin paint include polyorganosiloxane-based paints and cross-linked acrylic-based paints.
  • the total thickness of the multilayer body of the present embodiment is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and further preferably 100 ⁇ m or more.
  • the total thickness of the multilayer body is preferably 10,000 ⁇ m or less, more preferably 5,000 ⁇ m or less, and may be 2,000 ⁇ m or less.
  • the multilayer body of the present embodiment uses a main extruder for extruding a resin composition containing a polycarbonate resin and a sub extruder for extruding the resin composition of the present embodiment, and melts the resin under the conditions of the resin to be used.
  • a multilayer body can be formed by guiding the resin to an extrusion die and laminating it inside the die to form a sheet, or by forming the sheet and then laminating.
  • the molded product of the present embodiment is a molded product formed from the multilayer body of the present embodiment. Since the multilayer body of the present embodiment is also excellent in thermal bending resistance, it is also suitable for applications having a bent portion. For example, it is also preferably used for a molded product having a portion having a radius of curvature of 50 mmR or less (preferably a radius of curvature of 40 to 50 mmR).
  • the molded product of the present embodiment is preferably obtained by thermally bending the multilayer body of the present embodiment at 130 to 150 ° C.
  • the temperature is preferably 133 ° C. or higher.
  • the thermal bending temperature is preferably 147 ° C. or lower, more preferably 144 ° C. or lower, and even more preferably 143 ° C. or lower.
  • the flat plate-shaped molded product, the multilayer body, and the molded product of the present embodiment can be suitably used for optical parts, design products, antireflection molded products, and the like.
  • the flat plate-shaped molded body, multilayer body, and molded product of the present embodiment are suitable for parts such as display devices, electrical and electronic devices, OA devices, personal digital assistants, mechanical parts, home appliances, vehicle parts, various containers, lighting equipment, and the like. Used for.
  • the molded product of this embodiment is preferably used as an antireflection molded product for a touch panel sensor film or various displays.
  • St-MMA-MAH copolymer (C) manufactured by Denka Co., Ltd., R-200, styrene: maleic anhydride: methyl methacrylate 55% by mass: 19% by mass: 26% by mass, weight average molecular weight: 123,000, Tig: 124 ° C
  • -Polycarbonate resin layer (F) Bisphenol A type polycarbonate resin whose terminal group is pt-butylphenoxy group, manufactured by Mitsubishi Engineering Plastics Co., Ltd., E-2000F, weight average molecular weight: 53,000, initial glass transition temperature ( Tig): 149 ° C
  • the glass transition temperature of various resins and resin compositions was increased and decreased in two cycles according to the following differential scanning calorimetry (DSC measurement) conditions, and the glass transition temperature at the time of the second cycle of temperature increase was measured. ..
  • the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line of the turning point is the starting glass transition temperature (Tig), and the straight line extending the baseline on the high temperature side to the low temperature side and the tangent line of the turning point.
  • the intersection of the above was defined as the end glass transition temperature
  • the intermediate point between the start glass transition temperature and the end glass transition temperature was defined as the intermediate glass transition temperature (Tmg).
  • the measurement start temperature was 30 ° C.
  • the temperature rise rate was 10 ° C./min
  • the ultimate temperature was 250 ° C.
  • the temperature decrease rate was 20 ° C./min.
  • the unit is shown in ° C.
  • a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation, "DSC7020") was used.
  • ⁇ Pencil hardness> The pencil hardness of various resins and resin compositions is based on JIS K5600-5-4: 1999 for the flat plate-shaped molded body produced above, and the pencil hardness measured with a pencil hardness tester at a load of 750 g. Asked. The evaluation was conducted by five experts and judged by majority vote.
  • melt viscosity was measured using the above resin composition. Specifically, the pellet was pre-dried at 80 ° C. for 3 hours, and then the melt viscosity was measured using a capillograph. The measurement was performed under the conditions of a temperature of 240 ° C., a capillary length of 10 mm, a capillary diameter of 1 mm, a furnace body diameter of 9.55 mm, and a shear rate of 1220 seconds -1 . The unit is Pa ⁇ s.
  • Capillograph 1D PMD-C manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
  • ⁇ Measurement of haze> Using a haze meter, the haze of the flat plate-shaped molded product obtained above was measured under the condition of a D65 light source with a field of view of 10 °. As the haze meter, "HM-150" manufactured by Murakami Color Technology Research Institute was used. The unit is shown in%.
  • the Charpy impact strength was measured in JIS K7111-1 by changing the thickness of the ISO test piece from 4 mm to 3 mm and performing the same procedure for the others. Specifically, the obtained resin composition (pellet) is subjected to a biaxial injection molding machine with a vent (“PE-100” manufactured by Sodick Co., Ltd., a meshing type co-rotating type with a biaxial screw diameter of 29 mm, and a plunger diameter of 28 mm). A molded product (test piece) having a length of 80 mm, a width of 10 mm, and a thickness of 3 mm was produced by melt-kneading at a cylinder temperature of 260 ° C.
  • Each is a multi-layer extruder having a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block.
  • Multilayers were molded using a multi-layer extruder with a multi-manifold die coupled to the extruder.
  • the resin compositions of Examples or Comparative Examples shown in Tables 1 to 3 were introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 250 ° C.
  • the polycarbonate resin (F) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm, and the cylinder temperature was 280 ° C. and the discharge amount was 32.4 kg / h.
  • the feed block connected to all extruders was equipped with two types and two layers of distribution pins, and was extruded and laminated at a temperature of 270 ° C.
  • a T-die with a temperature of 270 ° C connected to the tip extrudes it into a sheet, and three mirror-finishing rolls with temperatures of 130 ° C, 140 ° C, and 180 ° C are used to cool the mirror while transferring the mirror surface.
  • Got The total thickness of the central portion of the obtained multilayer body was 1000 ⁇ m, and the thickness of the acrylic resin layer was 100 ⁇ m.
  • test piece having a length of 10 cm and a width of 6 cm was cut out from the vicinity of the center of the multilayer body without a hard coat obtained above.
  • the test piece was set in a two-point support type holder and placed in an environmental tester set at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more to adjust the state, and then the warp was measured. The value at this time was taken as the value of the amount of warpage before processing.
  • the test piece was set in a holder and placed in an environmental tester set at a temperature of 85 ° C. and a relative humidity of 85%, and held in that state for 120 hours.
  • the holder was moved into an environmental tester set at a temperature of 23 ° C. and a relative humidity of 50%, and the warp was measured again after holding for 4 hours in that state. The value at this time was taken as the value of the amount of warpage after processing.
  • a three-dimensional shape measuring machine equipped with an electric stage is used, and the taken-out test piece is placed horizontally in a convex state and scanned at 1 mm intervals, and the swelling in the center is measured as the warp. did.
  • the difference in the amount of warpage before and after the treatment that is, (the amount of warpage after treatment)-(the amount of warpage before treatment) was evaluated as the amount of change in warpage.
  • 6-functional urethane acrylate oligomer product name: U6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • PEG200 # diacrylate product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.
  • fluorine-containing group 6-functional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 60 parts by mass
  • PEG200 # diacrylate product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.
  • Photopolymerization initiator (product name: I-184) for a total of 100 parts by mass of 5 parts by weight of hydrophilic group, lipophilic group, UV reactive group-containing oligomer (product name: RS-90, manufactured by DIC Co., Ltd.) [Compound name: 1-hydroxy-cyclohexylphenylketone] manufactured by BASF Co., Ltd.) was applied in an amount of 1% by mass on the surface of the multilayer acrylic resin layer without a hard coat prepared above with a bar coater. A metal halide lamp (20 mW / cm 2 ) was applied for 5 seconds to cure the hard coat. The film thickness of the hard coat layer was 6 ⁇ m.
  • the Tig, Tmg, melt viscosity, haze, pencil hardness and Charpy impact strength without notch in the above table show the measured values of the resin composition containing the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit. ..

Abstract

A resin composition which makes it possible to provide a laminate in which the occurrence of cracking is suppressed and flow marks are not prone to occur is provided; a plate-shape molded body, a laminate and a molded product that use the resin composition are also provided. This resin composition contains a resin that contains (meth)acrylic compound units and aromatic vinyl compound units; in the resin composition, the total of the (meth)acrylic compound units and aromatic vinyl compound units is greater than or equal to 55 mass%, the initial glass transition temperature (Tig) of the resin composition measured by differential scanning calorimetry is greater than or equal to 135°C, the un-notched Charpy impact strength when forming the resin composition into a 3 mm-thick ISO test piece is greater than or equal to 10.0 kJ/m2, the un-notched Charpy impact strength is the value obtained by changing the thickness of the ISO test piece from 4 mm to 3 mm and otherwise measuring in the same manner as JIS K 7111-1; the melt viscosity of the resin composition at 240°C and at a shear velocity 1220 s-1 is less than or equal to 500 Pa*s.

Description

樹脂組成物、平板状成形体、多層体、成形品および成形品の製造方法Resin composition, flat plate-shaped molded product, multilayer body, molded product and manufacturing method of molded product
　本発明は、樹脂組成物、平板状成形体、多層体、成形品および成形品の製造方法に関する。 The present invention relates to a resin composition, a flat plate-shaped molded product, a multilayer body, a molded product, and a method for manufacturing a molded product.
　アクリル樹脂は、優れた透明性と成形加工性を有し、表面硬度に優れることから光学材料として多くの用途に使用されている。例えば、特許文献１には、下記の（メタ）アクリル酸エステル系重合体（Ａ）１０～７０質量部と、スチレン－無水マレイン酸系共重合体（Ｂ）９０～３０質量部からなり、ＡＳＴＭ　Ｄ１００３に基づき測定された２ｍｍ厚みのヘイズが３％以下であることを特徴とする樹脂組成物が開示されている。
（メタ）アクリル酸エステル系重合体（Ａ）：（メタ）アクリル酸エステル系単量体単位６０～１００質量％とスチレン系単量体単位４０～０質量％からなる重合体
スチレン－無水マレイン酸系共重合体（Ｂ）：スチレン系単量体単位７５～９５質量％と無水マレイン酸２５～５質量％とからなる共重合体
　一方で、アクリル樹脂は材料靭性に劣るため、透明性と材料靭性に優れたポリカーボネート樹脂との共押出により多層フィルム・シートを作製することが行われている。 Acrylic resin has excellent transparency and moldability, and has excellent surface hardness, so that it is used in many applications as an optical material. For example, Patent Document 1 comprises 10 to 70 parts by mass of the following (meth) acrylic acid ester-based polymer (A) and 90 to 30 parts by mass of a styrene-maleic anhydride-based copolymer (B). A resin composition characterized by having a haze of 2 mm thickness measured based on D1003 of 3% or less is disclosed.
(Meta) Acrylic acid ester-based polymer (A): Polymer styrene-maleic anhydride consisting of (meth) acrylic acid ester-based monomer unit 60 to 100% by mass and styrene-based monomer unit 40 to 0% by mass. System-based copolymer (B): A copolymer composed of 75 to 95% by mass of a styrene-based monomer unit and 25 to 5% by mass of maleic anhydride. On the other hand, acrylic resin is inferior in material toughness, so that it has transparency and a material. Multilayer films and sheets are produced by coextrusion with a polycarbonate resin having excellent toughness.
特開２００８－０５０５３６号公報Japanese Unexamined Patent Publication No. 2008-05536
　ここで、アクリル樹脂を含む層を、ポリカーボネート樹脂を含む層との多層体とし、所望の形状に成形する場合、クラックが発生したり、フローマークが発生してしまったりする場合があることが分かった。特に、１３５℃程度の高温で成形したときに、クラックが発生しやすい場合があることが分かった。
　本発明はかかる課題をと解決することを目的とするものであって、クラックの発生が抑制でき、かつ、フローマークが発生しにくい多層体を提供可能な樹脂組成物、ならびに、前記樹脂組成物を用いた平板状成形体、多層体および成形品を提供することを目的とする。 Here, it was found that when the layer containing the acrylic resin is formed into a multilayer body with the layer containing the polycarbonate resin and molded into a desired shape, cracks may occur or flow marks may occur. rice field. In particular, it was found that cracks may easily occur when molding at a high temperature of about 135 ° C.
An object of the present invention is to solve such a problem, and a resin composition capable of suppressing the occurrence of cracks and providing a multilayer body in which flow marks are less likely to occur, and the resin composition. It is an object of the present invention to provide a flat plate-shaped molded product, a multilayer body, and a molded product using the above.
　上記課題のもと、（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂を用い、かつ、樹脂組成物の初期ガラス転移温度を高く、シャルピー衝撃強さを高く、さらに、溶融粘度を低くすることにより、上記課題を解決しうることを見出した。
　具体的には、下記手段により、上記課題は解決された。
＜１＞（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂を含む樹脂組成物であって、前記樹脂組成物中、前記（メタ）アクリル化合物単位と芳香族ビニル化合物単位の合計が５５質量％以上であり、前記樹脂組成物の示差走査熱量測定により測定した初期ガラス転移温度（Ｔｉｇ）が１３５℃以上であり、前記樹脂組成物を３ｍｍ厚さのＩＳＯ試験片に成形したときのノッチ無しシャルピー衝撃強さが１０．０ｋＪ／ｍ２以上であり、前記ノッチ無しシャルピー衝撃強さは、ＪＩＳ　Ｋ　７１１１－１において、ＩＳＯ試験片の厚さを４ｍｍから３ｍｍに変更し、他は同様に行って測定した値であり、前記樹脂組成物の２４０℃、１２２０秒－１のせん断速度での溶融粘度が５００Ｐａ・ｓ以下である樹脂組成物。
＜２＞前記樹脂組成物を厚さ１ｍｍの試験片に成形したときのヘイズが５．０％以下である、＜１＞に記載の樹脂組成物。
＜３＞前記樹脂組成物の示差走査熱量測定により測定した初期ガラス転移温度（Ｔｉｇ）が１４０℃以上である、＜１＞または＜２＞に記載の樹脂組成物。
＜４＞前記樹脂組成物が、（メタ）アクリル化合物単位を含むアクリル樹脂（ａ）と芳香族ビニル化合物単位を含む樹脂としてスチレン樹脂（ｂ）を含む、＜１＞～＜３＞のいずれか１つに記載の樹脂組成物。
＜５＞前記アクリル樹脂（ａ）が、環状酸無水物単位、イミド単位、および、グルタルイミド単位の少なくとも１種を含む、＜４＞に記載の樹脂組成物。
＜６＞前記アクリル樹脂（ａ）が、環状酸無水物単位、および／または、Ｎ置換マレイミド単位を含む、＜４＞に記載の樹脂組成物。
＜７＞前記アクリル樹脂（ａ）が、Ｎ置換マレイミド単位を含む、＜５＞または＜６＞に記載の樹脂組成物。
＜８＞前記アクリル樹脂（ａ）が、Ｎ－フェニルマレイミド単位、および／または、Ｎ－シクロヘキシルマレイミド単位を含む、＜５＞または＜６＞に記載の樹脂組成物。
＜９＞前記アクリル樹脂（ａ）が、（メタ）アクリル化合物単位を３７～９６質量％、芳香族ビニル化合物単位を１～６０質量％、ならびに、無水マレイン酸および／またはＮ置換マレイミド単位を３～７４質量％含む（ただし、（メタ）アクリル化合物単位、芳香族ビニル化合物単位、ならびに、無水マレイン酸および／またはＮ置換マレイミド単位の合計が１００質量％を超えることは無い）、＜４＞～＜８＞のいずれか１つに記載の樹脂組成物。
＜１０＞前記スチレン樹脂（ｂ）が環状酸無水物単位を含む、＜４＞～＜９＞のいずれか１つに記載の樹脂組成物。
＜１１＞前記スチレン樹脂（ｂ）が芳香族ビニル化合物単位を６８～８４質量％、および、環状酸無水物単位を１６～３２質量％含む（ただし、芳香族ビニル化合物単位および環状酸無水物単位の合計が１００質量％を超えることは無い）、＜４＞～＜１０＞のいずれか１つに記載の樹脂組成物。
＜１２＞前記スチレン樹脂（ｂ）がスチレン単位を含む、＜４＞～＜１１＞のいずれか１つに記載の樹脂組成物。
＜１３＞前記スチレン樹脂（ｂ）が無水マレイン酸単位を含む、＜４＞～＜１２＞のいずれか１つに記載の樹脂組成物。
＜１４＞アクリル樹脂（ａ）とスチレン樹脂（ｂ）との含有量の合計１００質量部を基準として、アクリル樹脂（ａ）の含有量は１５～８５質量部であり、スチレン樹脂（ｂ）の含有量は１５～８５質量部である、＜４＞～＜１３＞のいずれか１つに記載の樹脂組成物。
＜１５＞さらに、酸化防止剤および／または離型剤を含む、＜１＞～＜１４＞のいずれか１つに記載の樹脂組成物。
＜１６＞＜１＞～＜１５＞のいずれか１つに記載の樹脂組成物から形成された平板状成形体。
＜１７＞厚みが１０～５,０００μｍである、＜１６＞に記載の平板状成形体。
＜１８＞＜１６＞または＜１７＞に記載の平板状成形体を含む多層体。
＜１９＞＜１６＞または＜１７＞に記載の平板状成形体と、ポリカーボネート樹脂を含む層とを有する多層体。
＜２０＞さらに、ハードコート層を含み、前記ハードコート層は、前記ポリカーボネート樹脂を含む層、前記平板状成形体、前記ハードコート層の順に積層している、＜１９＞に記載の多層体。
＜２１＞さらに、前記多層体の片面または両面に、耐指紋処理、反射防止処理、防眩処理、耐候性処理、帯電防止処理、防汚染処理およびアンチブロッキング処理のいずれか１つ以上が施されている、＜１８＞～＜２０＞のいずれか１つに記載の多層体。
＜２２＞＜１８＞～＜２１＞のいずれか１つに記載の多層体から形成された成形品であって、曲率半径が５０ｍｍＲ以下の部位を有する、成形品。
＜２３＞＜１８＞～＜２１＞のいずれか１つに記載の多層体を１３３～１４３℃で熱曲成形することを含む、成形品の製造方法。 Based on the above problems, a resin containing a (meth) acrylic compound unit and an aromatic vinyl compound unit is used, the initial glass transition temperature of the resin composition is high, the Charpy impact strength is high, and the melt viscosity is low. By doing so, it was found that the above-mentioned problems could be solved.
Specifically, the above problem was solved by the following means.
<1> A resin composition containing a resin containing a (meth) acrylic compound unit and an aromatic vinyl compound unit, wherein the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit in the resin composition is 55. Notch when the resin composition is formed into an ISO test piece having a thickness of 3 mm or more and the initial glass transition temperature (Tig) measured by the differential scanning calorific value measurement of the resin composition is 135 ° C. or more. None Sharpy impact strength is 10.0 kJ / m 2 or more, and the notchless Sharpy impact strength changes the thickness of the ISO test piece from 4 mm to 3 mm in JIS K 711-1, and the others are the same. A resin composition having a melt viscosity of 500 Pa · s or less at a shear rate of 240 ° C. and 1220 seconds -1 .
<2> The resin composition according to <1>, wherein the haze when the resin composition is molded into a test piece having a thickness of 1 mm is 5.0% or less.
<3> The resin composition according to <1> or <2>, wherein the initial glass transition temperature (Tig) measured by differential scanning calorimetry of the resin composition is 140 ° C. or higher.
<4> Any of <1> to <3>, wherein the resin composition contains an acrylic resin (a) containing a (meth) acrylic compound unit and a styrene resin (b) as a resin containing an aromatic vinyl compound unit. The resin composition according to one.
<5> The resin composition according to <4>, wherein the acrylic resin (a) contains at least one of a cyclic acid anhydride unit, an imide unit, and a glutarimide unit.
<6> The resin composition according to <4>, wherein the acrylic resin (a) contains a cyclic acid anhydride unit and / or an N-substituted maleimide unit.
<7> The resin composition according to <5> or <6>, wherein the acrylic resin (a) contains an N-substituted maleimide unit.
<8> The resin composition according to <5> or <6>, wherein the acrylic resin (a) contains an N-phenylmaleimide unit and / or an N-cyclohexylmaleimide unit.
<9> The acrylic resin (a) contains 37 to 96% by mass of the (meth) acrylic compound unit, 1 to 60% by mass of the aromatic vinyl compound unit, and 3 of maleic anhydride and / or N-substituted maleimide units. -74% by mass (however, the total of (meth) acrylic compound unit, aromatic vinyl compound unit, and maleic anhydride and / or N-substituted maleimide unit does not exceed 100% by mass), <4>- The resin composition according to any one of <8>.
<10> The resin composition according to any one of <4> to <9>, wherein the styrene resin (b) contains a cyclic acid anhydride unit.
<11> The styrene resin (b) contains 68 to 84% by mass of an aromatic vinyl compound unit and 16 to 32% by mass of a cyclic acid anhydride unit (however, an aromatic vinyl compound unit and a cyclic acid anhydride unit). The resin composition according to any one of <4> to <10>.
<12> The resin composition according to any one of <4> to <11>, wherein the styrene resin (b) contains a styrene unit.
<13> The resin composition according to any one of <4> to <12>, wherein the styrene resin (b) contains a maleic anhydride unit.
<14> The content of the acrylic resin (a) is 15 to 85 parts by mass based on the total content of 100 parts by mass of the acrylic resin (a) and the styrene resin (b), and the content of the styrene resin (b) is 15 to 85 parts by mass. The resin composition according to any one of <4> to <13>, which has a content of 15 to 85 parts by mass.
<15> The resin composition according to any one of <1> to <14>, further comprising an antioxidant and / or a mold release agent.
<16> A flat plate-shaped molded product formed from the resin composition according to any one of <1> to <15>.
<17> The flat plate-shaped molded product according to <16>, which has a thickness of 10 to 5,000 μm.
<18> A multilayer body including the flat plate-shaped molded body according to <16> or <17>.
<19> A multilayer body having the flat plate-shaped molded body according to <16> or <17> and a layer containing a polycarbonate resin.
<20> The multilayer body according to <19>, further comprising a hard coat layer, wherein the hard coat layer is laminated in the order of a layer containing the polycarbonate resin, the flat plate-shaped molded body, and the hard coat layer.
<21> Further, one or more of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, anti-static treatment, anti-fouling treatment and anti-blocking treatment are applied to one or both sides of the multilayer body. The multilayer body according to any one of <18> to <20>.
<22> A molded product formed from the multilayer body according to any one of <18> to <21>, which has a portion having a radius of curvature of 50 mmR or less.
<23> A method for producing a molded product, which comprises thermally bending the multilayer body according to any one of <23> and <18> to <21> at 133 to 143 ° C.
　本発明により、クラックの発生が抑制でき、かつ、フローマークが発生しにくい多層体を提供可能な樹脂組成物、ならびに、前記樹脂組成物を用いた平板状成形体、多層体および成形品を提供可能になった。特に、１３５℃程度の高温で成形しても、多層体にクラックを発生しにくくすることが可能になった。 INDUSTRIAL APPLICABILITY According to the present invention, a resin composition capable of suppressing the generation of cracks and providing a multilayer body in which flow marks are less likely to occur, and a flat plate-shaped molded body, a multilayer body and a molded product using the resin composition are provided. It became possible. In particular, even when molded at a high temperature of about 135 ° C., it has become possible to make it difficult for cracks to occur in the multilayer body.
図１は、反射防止フィルムの一例の構成を示す模式図である。FIG. 1 is a schematic diagram showing the configuration of an example of an antireflection film.
　以下、本発明を実施するための形態（以下、単に「本実施形態」という）について詳細に説明する。なお、以下の本実施形態は、本発明を説明するための例示であり、本発明は本実施形態のみに限定されない。
　なお、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書において、各種物性値および特性値は、特に述べない限り、２３℃におけるものとする。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。本明細書では、置換および無置換を記していない表記は、無置換の方が好ましい。
　本明細書において、「（メタ）アクリル化合物」は、アクリル化合物およびメタクリル化合物の双方、または、いずれかを表し、メタクリル化合物が好ましい。また、アクリル樹脂は、アクリレートの（共）重合体に加え、メタクリレートの（共）重合体も含む。
　本明細書における平板状成形体および多層体は、それぞれ、フィルムまたはシートの形状をしているものを含む趣旨である。「フィルム」および「シート」とは、それぞれ、長さと幅に対して、厚さが薄く、概ね、平らな成形体をいう。また、本明細書における「フィルム」および「シート」は、単層であっても多層であってもよい。
　なお、本明細書における「質量部」とは成分の相対量を示し、「質量％」とは成分の絶対量を示す。
　本明細書で示す規格が年度によって、測定方法等が異なる場合、特に述べない限り、出願時点における規格に基づくものとする。 Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
In addition, in this specification, "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
In the present specification, various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the notation that does not describe substitution and non-substitution is preferably non-substitution.
In the present specification, the "(meth) acrylic compound" represents both an acrylic compound and / or a methacrylic compound, and a methacrylic compound is preferable. The acrylic resin also contains a methacrylate (co) polymer in addition to the acrylate (co) polymer.
The term "plate-shaped molded article" and "multilayer" in the present specification are intended to include those in the shape of a film or a sheet, respectively. The "film" and the "sheet" refer to a molded product having a thickness thin and generally flat with respect to the length and width, respectively. Further, the "film" and "sheet" in the present specification may be a single layer or a multilayer.
In the present specification, "part by mass" indicates a relative amount of a component, and "mass%" indicates an absolute amount of a component.
If the standards shown in this specification differ from year to year in terms of measurement method, etc., they shall be based on the standards at the time of filing unless otherwise specified.
　本実施形態の樹脂組成物は、（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂を含む樹脂組成物であって、前記樹脂組成物中、前記（メタ）アクリル化合物単位と芳香族ビニル化合物単位の合計が５５質量％以上であり、樹脂組成物の示差走査熱量測定により測定した初期ガラス転移温度（Ｔｉｇ）が１３５℃以上であり、樹脂組成物を３ｍｍ厚さのＩＳＯ試験片に成形したときのノッチ無しシャルピー衝撃強さが１０．０ｋＪ／ｍ２以上であり、前記ノッチ無しシャルピー衝撃強さは、ＪＩＳ　Ｋ　７１１１－１において、ＩＳＯ試験片の厚さを４ｍｍから３ｍｍに変更し、他は同様に行って測定した値であり、樹脂組成物の２４０℃、１２２０秒－１のせん断速度での溶融粘度が５００Ｐａ・ｓ以下であることを特徴とする。このような構成とすることにより、クラックの発生を抑制でき、かつ、フローマークが発生しにくい多層体を提供可能な樹脂組成物が得られる。特に、１３５℃程度の高温で成形しても、クラックを発生しにくくできる。例えば、本実施形態の樹脂組成物から形成される層（本実施形態の平板状成形体）とポリカーボネート樹脂を含む層（以下、「ポリカーボネート樹脂層」ということがある）とを有する多層体は、１２５℃程度でも熱曲げできるが、１３５℃以上であると、熱曲げ時間を効果的に短縮でき、また、樹脂の応力緩和が早くなり、スプリングバックがより発生しにくくなり好ましい。 The resin composition of the present embodiment is a resin composition containing a resin containing a (meth) acrylic compound unit and an aromatic vinyl compound unit, and the (meth) acrylic compound unit and the aromatic vinyl in the resin composition. The total of the compound units is 55% by mass or more, the initial glass transition temperature (Tig) measured by the differential scanning calorimetry of the resin composition is 135 ° C. or more, and the resin composition is molded into an ISO test piece having a thickness of 3 mm. The impact strength of the unnotched Sharpy is 10.0 kJ / m 2 or more, and the thickness of the ISO test piece is changed from 4 mm to 3 mm in JIS K 711-1. Others are values measured in the same manner, and are characterized in that the melt viscosity of the resin composition at a shear rate of 240 ° C. and 1220 seconds -1 is 500 Pa · s or less. With such a configuration, it is possible to obtain a resin composition capable of suppressing the occurrence of cracks and providing a multilayer body in which flow marks are less likely to occur. In particular, even if it is molded at a high temperature of about 135 ° C., cracks can be less likely to occur. For example, a multilayer body having a layer formed from the resin composition of the present embodiment (flat plate-shaped molded product of the present embodiment) and a layer containing a polycarbonate resin (hereinafter, may be referred to as “polycarbonate resin layer”) may be used. Thermal bending can be performed even at about 125 ° C., but when the temperature is 135 ° C. or higher, the thermal bending time can be effectively shortened, stress relaxation of the resin is accelerated, and springback is less likely to occur, which is preferable.
　上記メカニズムは以下の通りであると推定される。すなわち、樹脂組成物のガラス転移温度を高くし、かつ、所定のシャルピー衝撃強さ以上とすることにより、クラックの発生を効果的に抑制できる。また、樹脂組成物の溶融粘度を低くすることにより、フローマークの発生を効果的に抑制できる。すなわち、本実施形態の樹脂組成物と、他の樹脂（例えば、ポリカーボネート樹脂）を多層押出すると、本実施形態の樹脂組成物と他の樹脂成分が合流する地点がある。このとき、樹脂の溶融粘度に違いが大きすぎると、流れ不良を引き起こしやすくなる。本実施形態では、樹脂組成物の溶融粘度を、アクリル樹脂と共押出される樹脂の溶融粘度に近づけることにより、流れ不良を効果的に抑制し、フローマークを抑制できたと推測される。 The above mechanism is presumed to be as follows. That is, by raising the glass transition temperature of the resin composition and making it equal to or higher than a predetermined Charpy impact strength, the occurrence of cracks can be effectively suppressed. Further, by lowering the melt viscosity of the resin composition, the generation of flow marks can be effectively suppressed. That is, when the resin composition of the present embodiment and another resin (for example, a polycarbonate resin) are extruded in multiple layers, there is a point where the resin composition of the present embodiment and the other resin components merge. At this time, if the difference in the melt viscosity of the resin is too large, a flow failure is likely to occur. In the present embodiment, it is presumed that by bringing the melt viscosity of the resin composition close to the melt viscosity of the resin co-extruded with the acrylic resin, flow failure can be effectively suppressed and flow marks can be suppressed.
＜樹脂＞
　本実施形態の樹脂組成物は、（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂を含み、前記樹脂組成物中、前記（メタ）アクリル化合物単位と芳香族ビニル化合物単位の合計が５５質量％以上である。（メタ）アクリル化合物単位を含むことにより、鉛筆硬度および耐衝撃性がより向上する傾向にあり、芳香族ビニル化合物単位を含むことにより、屈折率が向上し、芳香族ポリカーボネート樹脂等の他の樹脂層との多層体とした際の干渉縞を効果的に抑制することができる。また、樹脂組成物中の（メタ）アクリル化合物単位と芳香族ビニル化合物単位の合計を５５質量％以上とすることにより、透明性を維持しつつ、樹脂の鉛筆硬度と高屈折率化が達成される。ここで、（メタ）アクリル化合物単位とは、樹脂中の（メタ）アクリル化合物から構成される構成単位をいい、芳香族ビニル化合物単位とは、樹脂中の芳香族ビニル化合物から構成される構成単位をいう。本実施形態において、（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂は、（メタ）アクリル化合物単位含むアクリル樹脂（ａ）と、芳香族ビニル化合物単位を含むスチレン樹脂（ｂ）のブレンド物であってもよいし、（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む共重合体であってもよい。本実施形態の樹脂組成物は、（メタ）アクリル化合物単位含むアクリル樹脂（ａ）と、芳香族ビニル化合物単位を含むスチレン樹脂（ｂ）の両方を含むことが好ましい。アクリル樹脂（ａ）とスチレン樹脂（ｂ）を用いることにより、得られる樹脂組成物の溶融粘度を効果的に低くしつつ、樹脂組成物の耐熱性を高くすることができる。 <Resin>
The resin composition of the present embodiment contains a resin containing a (meth) acrylic compound unit and an aromatic vinyl compound unit, and the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit in the resin composition is 55. It is mass% or more. Inclusion of (meth) acrylic compound units tends to further improve pencil hardness and impact resistance, and inclusion of aromatic vinyl compound units improves refractive index and other resins such as aromatic polycarbonate resins. It is possible to effectively suppress interference fringes when a multilayer body with a layer is formed. Further, by setting the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit in the resin composition to 55% by mass or more, the pencil hardness and high refractive index of the resin are achieved while maintaining the transparency. To. Here, the (meth) acrylic compound unit means a structural unit composed of the (meth) acrylic compound in the resin, and the aromatic vinyl compound unit is a structural unit composed of the aromatic vinyl compound in the resin. To say. In the present embodiment, the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit is a blend of the acrylic resin (a) containing the (meth) acrylic compound unit and the styrene resin (b) containing the aromatic vinyl compound unit. It may be a product, or it may be a copolymer containing a (meth) acrylic compound unit and an aromatic vinyl compound unit. The resin composition of the present embodiment preferably contains both an acrylic resin (a) containing a (meth) acrylic compound unit and a styrene resin (b) containing an aromatic vinyl compound unit. By using the acrylic resin (a) and the styrene resin (b), it is possible to increase the heat resistance of the resin composition while effectively lowering the melt viscosity of the obtained resin composition.
　まず、（メタ）アクリル化合物について説明する。
　（メタ）アクリル化合物としては、（メタ）アクリル基を含む限り特に定めるものではないが、式（ａ１）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000001
 （式（ａ１）中、Ｒａ１は、水素原子またはメチル基であり、Ｒａ２は、脂肪族基である。）
　上記式（ａ１）において、Ｒａ１は、水素原子またはメチル基であり、メチル基が好ましい。Ｒａ２は、脂肪族基であり、直鎖または分岐の脂肪族基であることが好ましく、直鎖の脂肪族基であることがより好ましい。脂肪族基は、アルキル基（シクロアルキル基を含む）、アルキニル基（シクロアルキニル基を含む）、アルケニル基（シクロアルケニル基を含む）等が例示され、アルキル基が好ましく、直鎖または分岐のアルキル基がより好ましく、直鎖のアルキル基がさらに好ましい。Ｒａ２である脂肪族基の炭素原子数は、１～１０であることが好ましく、１～５であることがより好ましく、１～３であることがさらに好ましく、１または２であることが一層好ましく、１であることがより一層好ましい。
　式（ａ１）で表される（メタ）アクリル化合物は、アルキル（メタ）アクリレート（好ましくはアルキルメタクリレート）であることが好ましく、メチル（メタ）アクリレート（好ましくはメチルメタクリレート）であることがより好ましい。メチルメタクリレートを用いることにより、得られる平板状成形体の衝撃強さと鉛筆硬度が向上する傾向にある。 First, the (meth) acrylic compound will be described.
The (meth) acrylic compound is not particularly specified as long as it contains a (meth) acrylic group, but a compound represented by the formula (a1) is preferable.
Figure JPOXMLDOC01-appb-C000001
 (In the 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. Ra 2 is an aliphatic group, preferably a linear or branched aliphatic group, and 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), an alkenyl group (including a cycloalkenyl group), and the like, and an alkyl group is preferable, and a linear or branched alkyl is preferable. Groups are more preferred, and straight chain alkyl groups are even more preferred. The number of carbon atoms of the aliphatic group of Ra 2 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and further preferably 1 or 2. It is preferably 1, and even more preferably 1.
The (meth) acrylic compound represented by the formula (a1) is preferably an alkyl (meth) acrylate (preferably alkyl methacrylate), and more preferably a methyl (meth) acrylate (preferably methyl methacrylate). By using methyl methacrylate, the impact strength and pencil hardness of the obtained flat plate-shaped molded product tend to be improved.
　次に、芳香族ビニル化合物について説明する。
　芳香族ビニル化合物は、ビニル基と芳香環基を有する化合物であり、（メタ）アクリル化合物と共重合可能な化合物を広く採用できる。芳香族ビニル化合物は、ＣＨ２＝ＣＨ－Ｌ１－Ａｒ１で表される化合物であることが好ましい。ここで、Ｌ１は単結合または２価の連結基であり、単結合または式量１００～５００の２価の連結基であることが好ましく、単結合または式量１００～３００の２価の連結基であることがより好ましく、単結合であることがさらに好ましい。Ｌ１が２価の連結基の場合、脂肪族炭化水素基または、脂肪族炭化水素基と－Ｏ－との組み合わせからなる基であることが好ましい。ここで、式量とは、芳香族ビニル化合物のＬ１に相当する部分の１モル当たりの質量（ｇ）を意味する。以下、他の「式量」についても同様に考える。Ａｒ１は芳香環基であり、置換または無置換の、ベンゼン環基またはナフタレン環（好ましくはベンゼン環）であることが好ましく、無置換のベンゼン環基であることがさらに好ましい。 Next, the aromatic vinyl compound will be described.
The aromatic vinyl compound is a compound having a vinyl group and an aromatic ring group, and a compound copolymerizable with the (meth) acrylic compound can be widely adopted. The aromatic vinyl compound is preferably a compound represented by CH 2 = CH-L 1 -Ar 1 . Here, L 1 is a single bond or a divalent linking group, preferably a single bond or a divalent linking group having a formula of 100 to 500, and a single bond or a divalent link having a formula of 100 to 300. It is more preferably a group, and even more preferably a single bond. When L 1 is a divalent linking group, it is preferably an aliphatic hydrocarbon group or a group consisting of a combination of an aliphatic hydrocarbon group and —O—. Here, the formula amount means the mass (g) per mole of the portion corresponding to L 1 of the aromatic vinyl compound. Hereinafter, other "formulas" will be considered in the same manner. Ar 1 is an aromatic ring group, preferably a substituted or unsubstituted benzene ring group or a naphthalene ring (preferably a benzene ring), and more preferably an unsubstituted benzene ring group.
　より具体的には、芳香族ビニル化合物は式（ｂ１）で表される芳香族ビニル化合物を含むことが好ましい。
式（ｂ１）
Figure JPOXMLDOC01-appb-C000002
 （式（ｂ１）中、Ｒａ３は、置換基であり、ｎａは、０～６の整数である。） More specifically, the aromatic vinyl compound preferably contains an aromatic vinyl compound represented by the formula (b1).
Equation (b1)
Figure JPOXMLDOC01-appb-C000002
 (In the formula (b1), Ra 3 is a substituent and na is an integer of 0 to 6).
　式（ｂ１）中、Ｒａ３は、置換基であり、ハロゲン原子（好ましくは、塩素原子、フッ素原子または臭素原子）、水酸基、アルキル基（好ましくは炭素原子数１～５のアルキル基）、アリール基（好ましくはフェニル基）、アルケニル基（好ましくは炭素原子数２～５のアルケニル基）、アルコキシ基（好ましくは炭素原子数１～５のアルコキシ基）、アリールオキシ基（好ましくはフェノキシ基）が例示される。ｎａが２以上のとき、複数のＲａ３は、それぞれ同一であってもよいし、異なっていてもよい。
　ｎａは、５以下の整数であることが好ましく、４以下の整数であることがより好ましく、３以下の整数であることがさらに好ましく、２以下の整数であることが一層好ましく、１以下の整数であることがより一層好ましく、０であることがさらに一層好ましい。 In the formula (b1), Ra 3 is a substituent, which is a halogen atom (preferably a chlorine atom, a fluorine atom or a bromine atom), a hydroxyl group, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and an aryl. A group (preferably a phenyl group), an alkenyl group (preferably an alkenyl group having 2 to 5 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and an aryloxy group (preferably a phenoxy group). Illustrated. When na is 2 or more, the plurality of Ra 3s may be the same or different.
na is preferably an integer of 5 or less, more preferably an integer of 4 or less, further preferably an integer of 3 or less, further preferably an integer of 2 or less, and an integer of 1 or less. Is even more preferable, and 0 is even more preferable.
　芳香族ビニル化合物は、分子量１０４～６００の化合物であることが好ましく、分子量１０４～４００の化合物であることがより好ましい。
　芳香族ビニル化合物は、具体的には、スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｐ－メチルスチレン、ビニルキシレン、エチルスチレン、ジメチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、ビニルナフタレン、メトキシスチレン、モノブロモスチレン、ジブロモスチレン、フルオロスチレン、トリブロモスチレン等のスチレン系モノマー（スチレン誘導体）が挙げられ、特にスチレンが好ましい。 The aromatic vinyl compound is preferably a compound having a molecular weight of 104 to 600, and more preferably a compound having a molecular weight of 104 to 400.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene and methoxystyrene. Examples thereof include styrene-based monomers (styrene derivatives) such as monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.
　次に、本実施形態の樹脂組成物に含まれる（メタ）アクリル化合物単位と芳香族ビニル化合物単位の質量比率について述べる。
　本実施形態の樹脂組成物においては、（メタ）アクリル化合物単位と芳香族ビニル化合物単位の質量比率は、（メタ）アクリル化合物単位１００質量部に対し、芳香族ビニル化合物単位が、２５質量部以上であることが好ましく、５０質量部以上であることがより好ましく、６０質量部以上であることがさらに好ましく、７０質量部以上であることが一層好ましく、７５質量部以上であることがより一層好ましい。前記下限値以上とすることにより、屈折率向上により、ポリカーボネート樹脂層と積層した際の干渉縞の発生を効果的に抑制できる。また、前記（メタ）アクリル化合物単位と芳香族ビニル化合物単位の質量比率は、（メタ）アクリル化合物単位１００質量部に対し、芳香族ビニル化合物単位が、２５０質量部以下であることが好ましく、２００質量部以下であることがより好ましく、１９０質量部以下であることがさらに好ましく、１８０質量部以下であることが一層好ましく、１７５質量部以下であることがより一層好ましい。前記上限値以下とすることにより、本実施形態の樹脂組成物から形成される平板状成形体の衝撃強さと耐擦傷性がより向上する傾向にある。
　本実施形態の樹脂組成物において、（メタ）アクリル化合物単位と芳香族ビニル化合物単位は、それぞれ、１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 Next, the mass ratio of the (meth) acrylic compound unit and the aromatic vinyl compound unit contained in the resin composition of the present embodiment will be described.
In the resin composition of the present embodiment, the mass ratio of the (meth) acrylic compound unit to the aromatic vinyl compound unit is 25 parts by mass or more of the aromatic vinyl compound unit with respect to 100 parts by mass of the (meth) acrylic compound unit. It is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 70 parts by mass or more, and further preferably 75 parts by mass or more. .. By setting the value to the lower limit or more, the occurrence of interference fringes when laminated with the polycarbonate resin layer can be effectively suppressed by improving the refractive index. The mass ratio of the (meth) acrylic compound unit to the aromatic vinyl compound unit is preferably 250 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic compound unit. It is more preferably parts by mass or less, more preferably 190 parts by mass or less, further preferably 180 parts by mass or less, and even more preferably 175 parts by mass or less. By setting the value to the upper limit or less, the impact strength and scratch resistance of the flat plate-shaped molded product formed from the resin composition of the present embodiment tend to be further improved.
In the resin composition of the present embodiment, the (meth) acrylic compound unit and the aromatic vinyl compound unit may contain only one kind or two or more kinds, respectively. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　次に、アクリル樹脂（ａ）について説明する。
　本実施形態の樹脂組成物は、（メタ）アクリル化合物単位を含むアクリル樹脂（ａ）を含むことが好ましい。アクリル樹脂（ａ）中の（メタ）アクリル化合物単位の割合は、末端基を除く全構成単位中、５０質量％超であることが好ましく、５５質量％以上であることがより好ましく、６０質量％以上であることがさらに好ましく、６５質量％以上であることが一層好ましく、７０質量％以上であることがより一層好ましい。前記下限値以上とすることにより、耐擦傷性がより向上する傾向にある。前記アクリル樹脂（ａ）中の（メタ）アクリル化合物単位の割合の上限値は、末端基を除く全構成単位中、１００質量％であることが好ましく、９０質量％以下であることが好ましく、８５質量％以下であることがより好ましい。
　アクリル樹脂（ａ）は、（メタ）アクリル化合物単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 Next, the acrylic resin (a) will be described.
The resin composition of the present embodiment preferably contains an acrylic resin (a) containing a (meth) acrylic compound unit. The ratio of the (meth) acrylic compound unit in the acrylic resin (a) is preferably more than 50% by mass, more preferably 55% by mass or more, and more preferably 60% by mass in all the constituent units excluding the terminal group. The above is more preferable, 65% by mass or more is further preferable, and 70% by mass or more is further preferable. By setting the value to the lower limit or more, the scratch resistance tends to be further improved. The upper limit of the ratio of the (meth) acrylic compound unit in the acrylic resin (a) is preferably 100% by mass, preferably 90% by mass or less, and preferably 85% by mass in all the constituent units excluding the terminal group. It is more preferably mass% or less.
The acrylic resin (a) may contain only one type of (meth) acrylic compound unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　アクリル樹脂（ａ）は、（メタ）アクリル化合物単位以外のモノマー単位を含んでいてもよい。他のモノマーとしては、（メタ）アクリル化合物以外のモノマーであって、（メタ）アクリル化合物と共重合可能な化合物が例示される。
　他のモノマー単位としては、具体的には、芳香族ビニル化合物単位、環状酸無水物単位、イミド構造単位、ラクトン環構造単位、および、脂肪族ビニル化合物単位が例示される。
　他のモノマー単位の好ましい一例は、芳香族ビニル化合物単位、環状酸無水物単位、ラクトン環構造単位、および、Ｎ置換マレイミド単位から選択される少なくとも１種である。
　他のモノマー単位の好ましい他の一例は、環状酸無水物単位、イミド単位、グルタルイミド単位、および、ラクトン環構造単位の少なくとも１種である。
　他のモノマー単位の好ましい他の一例は、環状酸無水物単位、および／または、Ｎ置換マレイミド単位を含むことである。
　他のモノマー単位の好ましい他の一例は、芳香族ビニル化合物単位およびＮ置換マレイミド単位を含むことである。
　他のモノマー単位の好ましい他の一例は、芳香族ビニル化合物単位、Ｎ－フェニルマレイミド単位、および、Ｎ－シクロヘキシルマレイミド単位を含むことである。 The acrylic resin (a) may contain a monomer unit other than the (meth) acrylic compound unit. Examples of other monomers include monomers other than the (meth) acrylic compound and which can be copolymerized with the (meth) acrylic compound.
Specific examples of other monomer units include aromatic vinyl compound units, cyclic acid anhydride units, imide structural units, lactone ring structural units, and aliphatic vinyl compound units.
A preferred example of the other monomer unit is at least one selected from an aromatic vinyl compound unit, a cyclic acid anhydride unit, a lactone ring structure unit, and an N-substituted maleimide unit.
Another preferred example of the other monomer unit is at least one of a cyclic acid anhydride unit, an imide unit, a glutarimide unit, and a lactone ring structure unit.
Another preferred example of the other monomer unit is to include a cyclic acid anhydride unit and / or an N-substituted maleimide unit.
Another preferred example of the other monomer unit is to include an aromatic vinyl compound unit and an N-substituted maleimide unit.
Another preferred example of the other monomer unit is to include an aromatic vinyl compound unit, an N-phenylmaleimide unit, and an N-cyclohexylmaleimide unit.
　前記アクリル樹脂（ａ）が芳香族ビニル化合物単位を含む場合、その詳細は、上述の芳香族ビニル化合物単位と同様である。また、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、１質量％以上であることが好ましく、３質量％以上であることがより好ましい。前記下限値以上とすることにより、スチレン樹脂との相溶性が向上する傾向にある。また、前記アクリル樹脂（ａ）が芳香族ビニル化合物単位を含む場合、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、４９質量％以下であることが好ましく、３０質量％以下であることがより好ましく、さらには、２５質量％以下、２０質量％以下、１０質量％以下、７質量％以下であってもよい。前記上限値以下とすることにより、耐擦傷性や耐衝撃性がより向上する傾向にある。前記アクリル樹脂（ａ）は芳香族ビニル化合物単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the acrylic resin (a) contains an aromatic vinyl compound unit, the details thereof are the same as those of the above-mentioned aromatic vinyl compound unit. The content thereof is preferably 1% by mass or more, and more preferably 3% by mass or more, in all the constituent units excluding the terminal group in the acrylic resin (a). By setting the value to the lower limit or higher, the compatibility with the styrene resin tends to be improved. When the acrylic resin (a) contains an aromatic vinyl compound unit, the content thereof is preferably 49% by mass or less in all the constituent units excluding the terminal group in the acrylic resin (a). It is more preferably 25% by mass or less, more preferably 25% by mass or less, 20% by mass or less, 10% by mass or less, and 7% by mass or less. By setting the value to the upper limit or less, the scratch resistance and the impact resistance tend to be further improved. The acrylic resin (a) may contain only one type of aromatic vinyl compound unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　環状酸無水物単位は、無水マレイン酸単位、グルタル酸無水物単位が例示され、無水マレイン酸単位が好ましい。環状酸無水物単位、特に、マレイン酸単位を含むことにより、スチレン樹脂（ｂ）との相溶性の向上効果および耐熱性の向上効果がより効果的に発揮される。
　前記アクリル樹脂（ａ）が環状酸無水物単位を含む場合、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、１質量％以上であることが好ましく、４質量％以上であることがより好ましい。前記下限値以上とすることにより、耐熱性がより向上する傾向にある。また、前記アクリル樹脂（ａ）が環状酸無水物単位を含む場合、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。前記上限値以下とすることにより、スチレン樹脂（ｂ）との相溶性がより向上する傾向にある。前記アクリル樹脂（ａ）は環状酸無水物単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 Examples of the cyclic acid anhydride unit include a maleic anhydride unit and a glutaric anhydride unit, and the maleic anhydride unit is preferable. By containing the cyclic acid anhydride unit, particularly the maleic acid unit, the effect of improving the compatibility with the styrene resin (b) and the effect of improving the heat resistance are more effectively exhibited.
When the acrylic resin (a) contains a cyclic acid anhydride unit, the content thereof is preferably 1% by mass or more, preferably 4% by mass, based on all the constituent units excluding the terminal group in the acrylic resin (a). The above is more preferable. By setting the value to the lower limit or more, the heat resistance tends to be further improved. When the acrylic resin (a) contains a cyclic acid anhydride unit, the content thereof is preferably 40% by mass or less in all the constituent units excluding the terminal group in the acrylic resin (a). It is more preferably mass% or less. By setting the value to the upper limit or less, the compatibility with the styrene resin (b) tends to be further improved. The acrylic resin (a) may contain only one type of cyclic acid anhydride unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　イミド構造単位として、Ｎ置換マレイミド単位やグルタルイミド単位が挙げられる。
　Ｎ置換マレイミド単位は、Ｎ－フェニルマレイミド単位、Ｎ－シクロヘキシルマレイミド単位、Ｎ－ベンジルマレイミド、Ｎ－（４－カルボキシフェニル）マレイミド）が例示され、Ｎ－フェニルマレイミド単位、および／または、Ｎ－シクロヘキシルマレイミド単位が好ましい。また、特開２０１８－００９１４４号公報の段落００３０～００３４の記載を参酌でき、この内容は本明細書に組み込まれる。
　グルタルイミド単位としては、特開２０１８－００９１４４号公報の段落００４０～００４７の記載を参酌でき、この内容は本明細書に組み込まれる。 Examples of the imide structural unit include N-substituted maleimide units and glutarimide units.
Examples of the N-substituted maleimide unit include N-phenylmaleimide unit, N-cyclohexylmaleimide unit, N-benzylmaleimide, and N- (4-carboxyphenyl) maleimide), N-phenylmaleimide unit, and / or N-cyclohexyl. Maleimide units are preferred. Further, the description in paragraphs 0030 to 0034 of JP-A-2018-009144 can be referred to, and the contents thereof are incorporated in the present specification.
As the glutarimide unit, the description in paragraphs 0040 to 0047 of JP-A-2018-009144 can be referred to, and the contents thereof are incorporated in the present specification.
　本実施形態においては、アクリル樹脂（ａ）がＮ置換マレイミド単位、特に、Ｎ－フェニルマレイミド単位、および／または、Ｎ－シクロヘキシルマレイミドを含むことにより、耐熱性、および、スチレン樹脂（ｂ）との相溶性がより効果的に発揮される。
　前記アクリル樹脂（ａ）がＮ置換マレイミド単位やグルタルイミド単位（好ましくはＮ置換マレイミド単位）を含む場合、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、５質量％以上であることが好ましく、１０質量％以上であることがより好ましい。前記下限値以上とすることにより、耐熱性がより向上する傾向にある。また、前記アクリル樹脂（ａ）がＮ置換マレイミド単位やグルタルイミド単位（好ましくはＮ置換マレイミド単位）を含む場合、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、４９質量％以下であることが好ましく、３０質量％以下であることがより好ましく、さらには、２５質量％以下、２０質量％以下、１０質量％以下であってもよい。前記上限値以下とすることにより、耐衝撃性や耐擦傷性がより向上する傾向にある。
　前記アクリル樹脂（ａ）はＮ置換マレイミド単位やグルタルイミド単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 In the present embodiment, the acrylic resin (a) contains an N-substituted maleimide unit, particularly an N-phenylmaleimide unit, and / or an N-cyclohexylmaleimide, so that the acrylic resin (a) has heat resistance and a styrene resin (b). Compatibility is exhibited more effectively.
When the acrylic resin (a) contains an N-substituted maleimide unit or a glutarimide unit (preferably an N-substituted maleimide unit), the content thereof is 5 mass in all the constituent units excluding the terminal group in the acrylic resin (a). % Or more, more preferably 10% by mass or more. By setting the value to the lower limit or more, the heat resistance tends to be further improved. When the acrylic resin (a) contains an N-substituted maleimide unit or a glutarimide unit (preferably an N-substituted maleimide unit), the content thereof is the content of all the constituent units excluding the terminal group in the acrylic resin (a). It is preferably 49% by mass or less, more preferably 30% by mass or less, and further, 25% by mass or less, 20% by mass or less, and 10% by mass or less. By setting the value to the upper limit or less, the impact resistance and the scratch resistance tend to be further improved.
The acrylic resin (a) may contain only one type of N-substituted maleimide unit or glutarimide unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　ラクトン環構造としては、特開２０１８－００９１４４号公報の段落００４８～００５０の記載を参酌でき、この内容は本明細書に組み込まれる。
　前記アクリル樹脂（ａ）がラクトン環単位を含む場合、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、１質量％以上であることが好ましく、４質量％以上であることがより好ましい。前記下限値以上とすることにより、耐熱性がより向上する傾向にある。また、前記アクリル樹脂（ａ）がラクトン環構造単位を含む場合、その含有量は、アクリル樹脂（ａ）中の末端基を除く全構成単位中、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。前記上限値以下とすることにより、スチレン樹脂（ｂ）との相溶性がより向上する傾向にある。
　前記アクリル樹脂（ａ）はラクトン環単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 As the lactone ring structure, the description in paragraphs 0048 to 0050 of JP-A-2018-009144 can be referred to, and the contents thereof are incorporated in the present specification.
When the acrylic resin (a) contains a lactone ring unit, the content thereof is preferably 1% by mass or more, preferably 4% by mass or more, in all the constituent units excluding the terminal group in the acrylic resin (a). It is more preferable to have. By setting the value to the lower limit or more, the heat resistance tends to be further improved. When the acrylic resin (a) contains a lactone ring structural unit, the content thereof is preferably 40% by mass or less, preferably 30% by mass, based on all the structural units excluding the terminal group in the acrylic resin (a). % Or less is more preferable. By setting the value to the upper limit or less, the compatibility with the styrene resin (b) tends to be further improved.
The acrylic resin (a) may contain only one type of lactone ring unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　前記アクリル樹脂（ａ）の第一の実施形態は、（メタ）アクリル化合物単位（好ましくは、メチルメタクリレート単位）を３７～９６質量％、芳香族ビニル化合物単位（好ましくはスチレン）を１～６０質量％、ならびに、環状酸無水物単位、イミド単位、および、ラクトン環構造単位の１種以上からなる単位（好ましくは、無水マレイン酸および／またはＮ置換マレイミド単位、より好ましくはＮ置換マレイミド単位）を３～７４質量％含むことが好ましく、（メタ）アクリル化合物単位を４８～９３質量％、芳香族ビニル化合物単位を２～４５質量％、ならびに、環状酸無水物単位、イミド単位、および、ラクトン環構造単位の１種以上からなる単位（好ましくは、無水マレイン酸および／またはＮ置換マレイミド単位）を７～５０質量％含むことがより好ましい。ただし、（メタ）アクリル化合物単位、芳香族ビニル化合物単位、ならびに、環状酸無水物単位、イミド単位、および、ラクトン環構造単位の１種以上からなる単位（好ましくは、無水マレイン酸および／またはＮ置換マレイミド単位）の合計が１００質量％を超えることは無い。第一の実施形態において、（メタ）アクリル化合物単位、芳香族ビニル化合物単位、ならびに、環状酸無水物単位、イミド単位、および、ラクトン環構造単位の１種以上からなる単位（好ましくは、無水マレイン酸および／またはＮ置換マレイミド単位）の合計が、アクリル樹脂（ａ）の末端基を除く全構成単位の９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることがさらに好ましい。 In the first embodiment of the acrylic resin (a), the (meth) acrylic compound unit (preferably methylmethacrylate unit) is 37 to 96% by mass, and the aromatic vinyl compound unit (preferably styrene) is 1 to 60% by mass. %, And a unit consisting of one or more of a cyclic acid anhydride unit, an imide unit, and a lactone ring structure unit (preferably maleic anhydride and / or an N-substituted maleimide unit, more preferably an N-substituted maleimide unit). It preferably contains 3 to 74% by mass, a (meth) acrylic compound unit of 48 to 93% by mass, an aromatic vinyl compound unit of 2 to 45% by mass, and a cyclic acid anhydride unit, an imide unit, and a lactone ring. It is more preferable to contain 7 to 50% by mass of a unit consisting of one or more structural units (preferably maleic anhydride and / or N-substituted maleimide unit). However, a unit consisting of one or more of a (meth) acrylic compound unit, an aromatic vinyl compound unit, and a cyclic acid anhydride unit, an imide unit, and a lactone ring structure unit (preferably maleic anhydride and / or N). The total of substituted maleimide units) does not exceed 100% by mass. In the first embodiment, a unit consisting of a (meth) acrylic compound unit, an aromatic vinyl compound unit, and one or more of a cyclic acid anhydride unit, an imide unit, and a lactone ring structure unit (preferably maleic anhydride). The total of the acid and / or N-substituted maleimide units) is preferably 90% by mass or more, more preferably 95% by mass or more, and 99% by mass of all the constituent units excluding the terminal group of the acrylic resin (a). % Or more is more preferable.
　前記アクリル樹脂（ａ）の第二の実施形態は、前記第一の実施形態のアクリル樹脂と、（メタ）アクリル化合物単位を９０質量％以上含むアクリル樹脂（ａｘ）のブレンド物である。このような構成とすることにより、クラックの発生が抑制でき、かつ、フローマークが発生しにくいことに加え、高温高湿後の反りが発生しにくい多層体とすることができる。
　前記第一の実施形態のアクリル樹脂と（メタ）アクリル化合物単位を９０質量％以上含むアクリル樹脂（ａｘ）のブレンド比率（質量比率）は、１～１０：１であることが好ましく、２～９：１であることがより好ましく、３～８：１であることがさらに好ましく、３～７：１であることが一層好ましく、４～６：１であることがより一層好ましい。 The second embodiment of the acrylic resin (a) is a blend of the acrylic resin of the first embodiment and an acrylic resin (ax) containing 90% by mass or more of a (meth) acrylic compound unit. With such a configuration, it is possible to obtain a multilayer body in which the generation of cracks can be suppressed, the flow marks are less likely to occur, and the warp is less likely to occur after high temperature and high humidity.
The blend ratio (mass ratio) of the acrylic resin of the first embodiment and the acrylic resin (ax) containing 90% by mass or more of the (meth) acrylic compound unit is preferably 1 to 10: 1, preferably 2 to 9. It is more preferably 1: 1, further preferably 3 to 8: 1, further preferably 3 to 7: 1, and even more preferably 4 to 6: 1.
　前記アクリル樹脂（ａ）の初期ガラス転移温度（Ｔｉｇ）は、１２０℃以上であることが好ましく、１２５℃以上であることがより好ましく、１３０℃以上であることがさらに好ましく、１３３℃以上であってもよい。前記下限値以上とすることにより、熱曲げ成形時のクラック発生防止効果がより向上する傾向にある。また、前記アクリル樹脂（ａ）の初期ガラス転移温度（Ｔｉｇ）は、１７０℃以下であることが好ましく、１６０℃以下であることがより好ましく、１５０℃以下であることがさらに好ましく、１４０℃以下であってもよい。前記上限値以下とすることにより、熱曲げ成形時のスプリングバックの抑制効果がより向上する傾向にある。
　本実施形態の樹脂組成物がアクリル樹脂（ａ）を２種以上含む場合、アクリル樹脂（ａ）の初期ガラス転移温度（Ｔｉｇ）とは、混合物のＴｉｇとする。また、ガラス転移温度の測定方法は後述する実施例に記載の方法に従う（以下、重量平均分子量、鉛筆硬度、ならびに、スチレン樹脂（ｂ）のガラス転移温度、重量平均分子量、鉛筆硬度についても同じ）。 The initial glass transition temperature (Tig) of the acrylic resin (a) is preferably 120 ° C. or higher, more preferably 125 ° C. or higher, further preferably 130 ° C. or higher, and 133 ° C. or higher. You may. By setting the value to the lower limit or more, the effect of preventing crack generation during thermal bending molding tends to be further improved. The initial glass transition temperature (Tig) of the acrylic resin (a) is preferably 170 ° C. or lower, more preferably 160 ° C. or lower, further preferably 150 ° C. or lower, and 140 ° C. or lower. May be. By setting the value to the upper limit or less, the effect of suppressing springback during hot bending tends to be further improved.
When the resin composition of the present embodiment contains two or more kinds of acrylic resin (a), the initial glass transition temperature (Tig) of the acrylic resin (a) is Tig of the mixture. The method for measuring the glass transition temperature follows the method described in Examples described later (hereinafter, the same applies to the weight average molecular weight, pencil hardness, and the glass transition temperature, weight average molecular weight, and pencil hardness of the styrene resin (b)). ..
　前記アクリル樹脂（ａ）の重量平均分子量は、５０，０００以上であることが好ましく、７０，０００以上であることがより好ましく、１００，０００以上であることがさらに好ましく、１２０，０００以上であることが一層好ましく、１５０，０００以上であることがより一層好ましい。前記下限値以上とすることにより、得られる平板状成形体の衝撃強さをより向上させることができる。前記アクリル樹脂（ａ）の重量平均分子量は、３００，０００以下であることが好ましく、２５０，０００以下であることがより好ましく、２２５，０００以下であることがさらに好ましく、２１０，０００以下であることが一層好ましく、２００，０００以下であることがより一層好ましい。前記上限値以下とすることにより、樹脂組成物の溶融粘度を効果的に低くすることができる。 The weight average molecular weight of the acrylic resin (a) is preferably 50,000 or more, more preferably 70,000 or more, further preferably 100,000 or more, and 120,000 or more. It is more preferably 150,000 or more, and even more preferably 150,000 or more. By setting the value to the lower limit or more, the impact strength of the obtained flat plate-shaped molded product can be further improved. The weight average molecular weight of the acrylic resin (a) is preferably 300,000 or less, more preferably 250,000 or less, further preferably 225,000 or less, and 210,000 or less. It is more preferably 200,000 or less, and even more preferably 200,000 or less. By setting the value to the upper limit or less, the melt viscosity of the resin composition can be effectively lowered.
　前記アクリル樹脂（ａ）の鉛筆硬度は、ＨＢ以上であることが好ましく、Ｈ以上であることがより好ましい。前記下限値以上とすることにより、得られる平板状成形体の表面硬度をより高くすることができる。また、前記アクリル樹脂（ａ）の鉛筆硬度は、２Ｈ以下であることが好ましく、Ｈ以下であることがより好ましい。 The pencil hardness of the acrylic resin (a) is preferably HB or higher, and more preferably H or higher. By setting the value to the lower limit or more, the surface hardness of the obtained flat plate-shaped molded product can be further increased. Further, the pencil hardness of the acrylic resin (a) is preferably 2H or less, and more preferably H or less.
　次に、スチレン樹脂（ｂ）について説明する。
　本実施形態の樹脂組成物は、芳香族ビニル化合物単位を含む樹脂としてスチレン樹脂（ｂ）を含むことが好ましい。スチレン樹脂（ｂ）とは、芳香族ビニル化合物単位として、スチレン単位、α－メチルスチレン単位、ｏ－メチルスチレン単位、ｐ－メチルスチレン単位等のスチレン系モノマー単位の少なくとも１種を含む樹脂であり、スチレン単位を含むことが好ましい。スチレン樹脂（ｂ）中の芳香族ビニル化合物単位（好ましくはスチレン系モノマー単位）の割合は、末端基を除く全構成単位中、５０質量％超であることが好ましく、５５質量％以上であることがより好ましく、６０質量％以上であることがさらに好ましく、６５質量％以上であることが一層好ましく、７０質量％以上であることがより一層好ましい。前記下限値以上とすることにより、屈折率向上により、ポリカーボネート樹脂層と積層した際の干渉縞を効果的に抑制できる傾向にある。前記スチレン樹脂（ｂ）中の芳香族ビニル化合物単位の割合の上限値は、末端基を除く全構成単位中、１００質量％である。
　スチレン樹脂（ｂ）は、芳香族ビニル化合物単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 Next, the styrene resin (b) will be described.
The resin composition of the present embodiment preferably contains a styrene resin (b) as a resin containing an aromatic vinyl compound unit. The styrene resin (b) is a resin containing at least one styrene-based monomer unit such as a styrene unit, an α-methylstyrene unit, an o-methylstyrene unit, and a p-methylstyrene unit as an aromatic vinyl compound unit. , Styrene units are preferably included. The ratio of the aromatic vinyl compound unit (preferably the styrene-based monomer unit) in the styrene resin (b) is preferably more than 50% by mass and 55% by mass or more in all the constituent units excluding the terminal group. Is more preferably 60% by mass or more, further preferably 65% by mass or more, and even more preferably 70% by mass or more. By setting the value to the lower limit or more, the refractive index is improved, and the interference fringes when laminated with the polycarbonate resin layer tend to be effectively suppressed. The upper limit of the ratio of the aromatic vinyl compound unit in the styrene resin (b) is 100% by mass in all the constituent units excluding the terminal group.
The styrene resin (b) may contain only one aromatic vinyl compound unit, or may contain two or more aromatic vinyl compound units. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　スチレン樹脂（ｂ）は、芳香族ビニル化合物単位以外のモノマー単位、および、スチレン系モノマー単位以外の芳香族ビニル化合物単位を含んでいてもよい。他のモノマーとしては、芳香族ビニル化合物以外のモノマーであって、芳香族ビニル化合物と共重合可能な化合物が例示される。
　他のモノマー単位としては、具体的には、環状酸無水物単位、Ｎ置換マレイミド単位、シアン化アルケニル単位が例示され、環状酸無水物単位が好ましい。 The styrene resin (b) may contain a monomer unit other than the aromatic vinyl compound unit and an aromatic vinyl compound unit other than the styrene-based monomer unit. Examples of the other monomer include monomers other than the aromatic vinyl compound and which can be copolymerized with the aromatic vinyl compound.
Specific examples of the other monomer unit include a cyclic acid anhydride unit, an N-substituted maleimide unit, and a cyanide alkenyl unit, and a cyclic acid anhydride unit is preferable.
　環状酸無水物単位は、無水マレイン酸単位、グルタル酸無水物が例示され、無水マレイン酸単位が好ましい。環状酸無水物単位、特に、マレイン酸単位を含むことにより、得られるスチレン樹脂（ｂ）のガラス転移温度を高くできる。
　前記スチレン樹脂（ｂ）が環状酸無水物単位を含む場合、その含有量は、スチレン樹脂（ｂ）中の末端基を除く全構成単位中、１６質量％以上であることが好ましく、２０質量％以上であることがより好ましい。また、前記スチレン樹脂（ｂ）が環状酸無水物単位を含む場合、その含有量は、スチレン樹脂（ｂ）中の末端基を除く全構成単位中、３２質量％以下であることが好ましく、２６質量％以下であることがより好ましい。前記下限値以上、また、上限値以下とすることにより、アクリル樹脂との相溶性がより向上する傾向にある。また前記下限値以上にすることで、樹脂組成物全体の耐熱性を向上することができる。前記スチレン樹脂（ｂ）は環状酸無水物単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 Examples of the cyclic acid anhydride unit include maleic anhydride unit and glutaric anhydride, and maleic anhydride unit is preferable. By containing the cyclic acid anhydride unit, particularly the maleic acid unit, the glass transition temperature of the obtained styrene resin (b) can be increased.
When the styrene resin (b) contains a cyclic acid anhydride unit, the content thereof is preferably 16% by mass or more, preferably 20% by mass, based on all the constituent units excluding the terminal group in the styrene resin (b). The above is more preferable. When the styrene resin (b) contains a cyclic acid anhydride unit, the content thereof is preferably 32% by mass or less in all the constituent units excluding the terminal group in the styrene resin (b). It is more preferably mass% or less. By setting the value to be equal to or higher than the lower limit and not higher than the upper limit, the compatibility with the acrylic resin tends to be further improved. Further, by setting the value to the lower limit or more, the heat resistance of the entire resin composition can be improved. The styrene resin (b) may contain only one type of cyclic acid anhydride unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
　前記スチレン樹脂（ｂ）は、芳香族ビニル化合物単位（好ましくはスチレン単位）を６８～８４質量％、および、環状酸無水物単位（好ましくは無水マレイン酸単位）を１６～３２質量％含むことが好ましく、芳香族ビニル化合物単位を７０～８３質量％、環状酸無水物単位を１７～３０質量％含むことがより好ましい。ただし、芳香族ビニル化合物単位および環状酸無水物単位の合計が１００質量％を超えることは無い。芳香族ビニル化合物単位および環状酸無水物単位の合計は、スチレン樹脂（ｂ）の末端基を除く全構成単位の９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることがさらに好ましい。 The styrene resin (b) may contain 68 to 84% by mass of an aromatic vinyl compound unit (preferably styrene unit) and 16 to 32% by mass of a cyclic acid anhydride unit (preferably maleic anhydride unit). It is more preferable to contain 70 to 83% by mass of the aromatic vinyl compound unit and 17 to 30% by mass of the cyclic acid anhydride unit. However, the total of the aromatic vinyl compound unit and the cyclic acid anhydride unit does not exceed 100% by mass. The total of the aromatic vinyl compound unit and the cyclic acid anhydride unit is preferably 90% by mass or more, more preferably 95% by mass or more of all the constituent units excluding the terminal group of the styrene resin (b). It is more preferably 99% by mass or more.
　前記スチレン樹脂（ｂ）の初期ガラス転移温度（Ｔｉｇ）は、１３０℃以上であることが好ましく、１３５℃以上であることがより好ましく、１４０℃以上であることがさらに好ましく、１４３℃以上であることがさらに好ましい。前記下限値以上とすることにより、熱曲げ成形時のクラックの発生を効果的に抑制することができる。また、前記スチレン樹脂（ｂ）の初期ガラス転移温度（Ｔｉｇ）は、１８０℃以下であることが好ましく、１６０℃以下であることがより好ましく、１５５℃以下であることがさらに好ましい。前記上限値以下とすることにより、熱曲げ時におけるスプリングバックの抑制効果がより向上する傾向にある。 The initial glass transition temperature (Tig) of the styrene resin (b) is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, further preferably 140 ° C. or higher, and 143 ° C. or higher. Is even more preferable. By setting the value to the lower limit or more, it is possible to effectively suppress the occurrence of cracks during thermal bending molding. The initial glass transition temperature (Tig) of the styrene resin (b) is preferably 180 ° C. or lower, more preferably 160 ° C. or lower, and even more preferably 155 ° C. or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
　前記スチレン樹脂（ｂ）の重量平均分子量は、２０，０００以上であることが好ましく、２５，０００以上であることがより好ましく、３０，０００以上であることがさらに好ましく、４０，０００以上であることが一層好ましく、６０，０００以上であることがより一層好ましい。前記下限値以上とすることにより、得られる平板状成形体の衝撃強さをより向上させることができる。また、前記スチレン樹脂（ｂ）の重量平均分子量は、１５０，０００以下であることが好ましく、１３０，０００以下であることがより好ましく、１２０，０００以下であることがさらに好ましく、１００，０００以下であることが一層好ましく、８０，０００以下であることがより一層好ましく、７０，０００以下であってもよい。前記上限値以下とすることにより、樹脂組成物の溶融粘度を効果的に低くすることができる。 The weight average molecular weight of the styrene resin (b) is preferably 20,000 or more, more preferably 25,000 or more, still more preferably 30,000 or more, and 40,000 or more. It is more preferably 60,000 or more, and even more preferably 60,000 or more. By setting the value to the lower limit or more, the impact strength of the obtained flat plate-shaped molded product can be further improved. The weight average molecular weight of the styrene resin (b) is preferably 150,000 or less, more preferably 130,000 or less, still more preferably 120,000 or less, and 100,000 or less. It is more preferably 80,000 or less, and it may be 70,000 or less. By setting the value to the upper limit or less, the melt viscosity of the resin composition can be effectively lowered.
　前記スチレン樹脂（ｂ）の鉛筆硬度は、Ｂ以上であることが好ましく、ＨＢ以上であることがより好ましい。前記下限値以上とすることにより、得られる平板状成形体の表面硬度をより高くすることができる。また、前記スチレン樹脂（ｂ）の鉛筆硬度は、Ｈ以下であることが好ましく、ＨＢ以下であることがより好ましい。 The pencil hardness of the styrene resin (b) is preferably B or higher, and more preferably HB or higher. By setting the value to the lower limit or more, the surface hardness of the obtained flat plate-shaped molded product can be further increased. Further, the pencil hardness of the styrene resin (b) is preferably H or less, and more preferably HB or less.
　次に、本実施形態の樹脂組成物における、アクリル樹脂（ａ）とスチレン樹脂（ｂ）のブレンド形態について述べる。本実施形態においては、アクリル樹脂（ａ）とスチレン樹脂（ｂ）との含有量の合計１００質量部を基準として、アクリル樹脂（ａ）の含有量は１５～８５質量部であり、スチレン樹脂（ｂ）の含有量は１５～８５質量部であることが好ましく、アクリル樹脂（ａ）の含有量は２０～８０質量部であり、スチレン樹脂（ｂ）の含有量は８０～２０質量部であることがより好ましく、アクリル樹脂（ａ）の含有量は３０～７０質量部であり、スチレン樹脂（ｂ）の含有量は７０～３０質量部であることがさらに好ましい。このような構成とすることにより、耐擦傷性と耐衝撃性、耐熱性が両立し、熱曲げ成形時にクラックの発生を効果的に防止することができる。 Next, the blended form of the acrylic resin (a) and the styrene resin (b) in the resin composition of the present embodiment will be described. In the present embodiment, the content of the acrylic resin (a) is 15 to 85 parts by mass based on the total content of 100 parts by mass of the acrylic resin (a) and the styrene resin (b), and the styrene resin ( The content of b) is preferably 15 to 85 parts by mass, the content of the acrylic resin (a) is 20 to 80 parts by mass, and the content of the styrene resin (b) is 80 to 20 parts by mass. It is more preferable that the content of the acrylic resin (a) is 30 to 70 parts by mass, and the content of the styrene resin (b) is 70 to 30 parts by mass. With such a configuration, scratch resistance, impact resistance, and heat resistance are compatible, and the occurrence of cracks during thermal bending molding can be effectively prevented.
　本実施形態の樹脂組成物においては、前記樹脂組成物中、前記（メタ）アクリル化合物単位と芳香族ビニル化合物単位の合計が５５質量％以上であり、６０質量％以上であることが好ましく、６５質量％以上であることがより好ましく、７０質量％以上であることがさらに好ましく、７３質量％以上であることが一層好ましい。前記下限値以上とすることにより、高鉛筆硬度や高屈折率がより効果的に発揮される傾向にある。また、前記樹脂組成物中、前記（メタ）アクリル化合物単位と芳香族ビニル化合物単位の合計は、９５質量％以下であることが好ましく、９０質量％以下であることがより好ましく、８５質量％以下であることがさらに好ましく、８０質量％以下であることが一層好ましい。前記上限値以下とすることにより、他の単位による樹脂組成物全体の耐熱性や剛性が向上する傾向にある。
　本実施形態では、上記（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂（好ましくは、アクリル樹脂（ａ）およびスチレン樹脂（ｂ））が樹脂組成物の９０質量％以上を占めることが好ましく、９４質量％以上を占めることがより好ましく、９７質量％以上を占めることがさらに好ましい。上限値としては、樹脂組成物の９９．９質量％であってもよい。
　また、（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂以外の他の樹脂成分としては、ポリカーボネート樹脂、ポリアリレート樹脂などが例示される。 In the resin composition of the present embodiment, the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit in the resin composition is 55% by mass or more, preferably 60% by mass or more, preferably 65. It is more preferably 7% by mass or more, further preferably 70% by mass or more, and further preferably 73% by mass or more. By setting the value to the lower limit or higher, high pencil hardness and high refractive index tend to be exhibited more effectively. Further, in the resin composition, the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less. Is more preferable, and 80% by mass or less is further preferable. By setting the value to the upper limit or less, the heat resistance and rigidity of the entire resin composition due to other units tend to be improved.
In the present embodiment, the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit (preferably acrylic resin (a) and styrene resin (b)) occupies 90% by mass or more of the resin composition. It is more preferable to occupy 94% by mass or more, and even more preferably 97% by mass or more. The upper limit value may be 99.9% by mass of the resin composition.
Further, examples of the resin component other than the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit include a polycarbonate resin and a polyarylate resin.
＜酸化防止剤＞
　本実施形態の樹脂組成物は、酸化防止剤を含有することが好ましい。
　酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、チオエーテル系酸化防止剤などが挙げられる。中でも本実施形態においては、リン系酸化防止剤およびフェノール系酸化防止剤（より好ましくはヒンダードフェノール系酸化防止剤）が好ましい。リン系酸化防止剤は、成形品の色相に優れることから特に好ましい。 <Antioxidant>
The resin composition of the present embodiment preferably contains an antioxidant.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant. Above all, in this embodiment, a phosphorus-based antioxidant and a phenol-based antioxidant (more preferably, a hindered phenol-based antioxidant) are preferable. Phosphorus-based antioxidants are particularly preferable because they are excellent in hue of molded products.
　リン系酸化防止剤は、ホスファイト系酸化防止剤が好ましく、以下の式（１）または（２）で表されるホスファイト化合物が好ましい。
Figure JPOXMLDOC01-appb-C000003
 （式（１）中、Ｒ１１およびＲ１２はそれぞれ独立に、炭素原子数１～３０のアルキル基または炭素原子数６～３０のアリール基を表す。）
Figure JPOXMLDOC01-appb-C000004
 （式（２）中、Ｒ１３～Ｒ１７は、それぞれ独立に、水素原子、炭素原子数６～２０のアリール基または炭素原子数１～２０のアルキル基を表す。） As the phosphorus-based antioxidant, a phosphite-based antioxidant is preferable, and a phosphite compound represented by the following formula (1) or (2) is preferable.
Figure JPOXMLDOC01-appb-C000003
 (In the formula (1), R 11 and R 12 independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.)
Figure JPOXMLDOC01-appb-C000004
 (In the formula (2), R 13 to R 17 independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.)
　上記式（１）中、Ｒ１１、Ｒ１２で表されるアルキル基は、それぞれ独立に、炭素原子数１～１０の直鎖または分岐のアルキル基であることが好ましい。Ｒ１１、Ｒ１２がアリール基である場合、以下の式（１－ａ）、（１－ｂ）、または（１－ｃ）のいずれかで表されるアリール基が好ましい。式中の＊は結合位置を表す。 In the above formula (1), the alkyl groups represented by R 11 and R 12 are preferably linear or branched alkyl groups having 1 to 10 carbon atoms, respectively. When R 11 and R 12 are aryl groups, an aryl group represented by any of the following formulas (1-a), (1-b), or (1-c) is preferable. * In the formula represents the bond position.
Figure JPOXMLDOC01-appb-C000005
 （式（１－ａ）中、ＲＡは、それぞれ独立に、炭素原子数１～１０のアルキル基を表す。式（１－ｂ）中、ＲＢは、それぞれ独立に、炭素原子数１～１０のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000005
 (In formula (1-a), RA independently represents an alkyl group having 1 to 10 carbon atoms. In formula (1- b ), RB independently represent 1 to 10 carbon atoms. Represents an alkyl group of 10.)
　ヒンダードフェノール系酸化防止剤としては、特開２０１８－０９０６７７号公報の段落００６３、特開２０１８－１８８４９６号公報の段落００７６の記載を参照でき、この内容は本明細書に組み込まれる。 As the hindered phenolic antioxidant, the description in paragraph 0063 of JP-A-2018-090677 and paragraph 0076 of JP-A-2018-188496 can be referred to, and the contents thereof are incorporated in the present specification.
　酸化防止剤は、上記の他、特開２０１７－０３１３１３号公報の段落００５７～００６１の記載を参酌でき、この内容は本明細書に組み込まれる。 In addition to the above, the antioxidant can be referred to in paragraphs 0057 to 0061 of JP-A-2017-031313, the contents of which are incorporated in the present specification.
　酸化防止剤の含有量は、樹脂組成物１００質量部に対して、０．００１質量部以上であることが好ましく、０．００８質量部以上であることがより好ましい。また、酸化防止剤の含有量の上限値としては、樹脂組成物１００質量部に対して、０．５質量部以下が好ましく、０．３質量部以下がより好ましく、０．２質量部以下がさらに好ましく、０．１５質量部以下であることが一層好ましく、０．１０質量部以下であることがさらに一層好ましく、０．０８質量部以下であることが特に一層好ましい。 The content of the antioxidant is preferably 0.001 part by mass or more, and more preferably 0.008 part by mass or more with respect to 100 parts by mass of the resin composition. The upper limit of the content of the antioxidant is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and 0.2 parts by mass or less with respect to 100 parts by mass of the resin composition. It is even more preferably 0.15 parts by mass or less, further preferably 0.10 parts by mass or less, and even more preferably 0.08 parts by mass or less.
　酸化防止剤の含有量を上記下限値以上とすることにより、色相、耐熱変色性がより良好な成形品を得ることができる。また、酸化防止剤の含有量を上記上限値以下とすることにより、耐熱変色性を悪化させることなく、湿熱安定性が良好な平板状成形体を得ることができる。
　酸化防止剤は、１種のみ用いても、２種以上用いてもよい。２種以上用いる場合は合計量が上記範囲となることが好ましい。 By setting the content of the antioxidant to the above lower limit value or more, a molded product having better hue and heat-resistant discoloration can be obtained. Further, by setting the content of the antioxidant to be equal to or less than the above upper limit value, it is possible to obtain a flat plate-shaped molded product having good moist heat stability without deteriorating the heat discoloration property.
Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.
＜離型剤＞
　本実施形態の樹脂組成物は、離型剤を含むことが好ましい。
　離型剤を含むことにより、平板状成形体の成形性を向上させることができる。
　離型剤の種類は特に定めるものではないが、例えば、脂肪族カルボン酸、脂肪族カルボン酸とアルコールとのエステル、数平均分子量２００～１５，０００の脂肪族炭化水素化合物、数平均分子量１００～５，０００のポリエーテル、ポリシロキサン系シリコーンオイル等が挙げられる。 <Release agent>
The resin composition of the present embodiment preferably contains a mold release agent.
By including a mold release agent, the moldability of the flat plate-shaped molded product can be improved.
The type of the release agent is not particularly specified, but for example, an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a number average molecular weight of 100 to 100. Examples thereof include 5,000 polyethers and polysiloxane-based silicone oils.
　離型剤の詳細は、国際公開第２０１５／１９０１６２号の段落００３５～００３９の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The details of the release agent can be referred to in paragraphs 0035 to 0039 of International Publication No. 2015/190162, and these contents are incorporated in the present specification.
　離型剤の含有量は、樹脂組成物１００質量部に対して、０．００１質量部以上であることが好ましく、０．００５質量部以上であることがより好ましく、０．０１質量部以上であることがさらに好ましい。上限値としては、０．５質量部以下であることが好ましく、０．３質量部以下であることがより好ましく、０．２質量部以下であることがさらに好ましい。
　離型剤は、１種のみ用いてもよく、２種以上用いてもよい。２種以上用いる場合、合計量が上記範囲となることが好ましい。 The content of the release agent is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and 0.01 part by mass or more with respect to 100 parts by mass of the resin composition. It is more preferable to have. The upper limit value is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and further preferably 0.2 parts by mass or less.
Only one type of release agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.
＜その他の成分＞
　本実施形態の樹脂組成物は、上記成分の他、上記以外の熱可塑性樹脂、紫外線吸収剤、熱安定剤、難燃剤、難燃助剤、着色剤、帯電防止剤、蛍光増白剤、防曇剤、流動性改良剤、可塑剤、分散剤、抗菌剤、アンチブロッキング剤、衝撃改良剤、摺動改良剤、色相改良剤、酸トラップ剤等を含んでいてもよい。これらの成分は、１種を用いてもよいし、２種以上を併用してもよい。
　上記成分の含有量は、含有する場合、合計で樹脂組成物の０．１～５質量％であることが好ましい。 <Other ingredients>
In addition to the above components, the resin composition of the present embodiment includes a thermoplastic resin other than the above, an ultraviolet absorber, a heat stabilizer, a flame retardant, a flame retardant aid, a colorant, an antistatic agent, a fluorescent whitening agent, and a protective agent. It may contain a fogging agent, a fluidity improving agent, a plasticizer, a dispersant, an antibacterial agent, an anti-blocking agent, an impact improving agent, a sliding improving agent, a hue improving agent, an acid trapping agent and the like. One of these components may be used, or two or more thereof may be used in combination.
When contained, the content of the above components is preferably 0.1 to 5% by mass in total of the resin composition.
＜樹脂組成物の物性＞
　本実施形態の樹脂組成物は、示差走査熱量測定による初期ガラス転移温度（Ｔｉｇ）が１３５℃以上であり、１３６℃以上であることが好ましく、１３７℃以上であることがより好ましく、１３８℃以上であることがさらに好ましく、１３９以上であることが一層好ましく、１４０℃以上であることがより一層好ましい。前記下限値以上とすることにより、クラックの発生を効果的に抑制することができる。さらに、湿熱試験、高温試験などの耐環境試験の耐久性がより向上する傾向にある。前記初期ガラス転移温度（Ｔｉｇ）の上限値は、特に定めるものではないが、１４５℃以下が実際的であり、１４４℃以下、さらには、１４３℃以下であってもよい。前記上限値以下とすることにより、熱曲げ時におけるスプリングバックの抑制効果がより向上する傾向にある。
　本実施形態の樹脂組成物は、示差走査熱量測定による中間ガラス転移温度（Ｔｍｇ）が１３９℃以上であることが好ましく、１４０℃以上であることがより好ましく、１４１℃以上であることがさらに好ましく、１４２℃以上であることが一層好ましく、１４３℃以上であることがより一層好ましい。前記下限値以上とすることにより、クラックの発生を効果的に抑制することができる。さらに、湿熱試験、高温試験などの耐環境試験の耐久性がより向上する傾向にある。前記中間ガラス転移温度（Ｔｍｇ）の上限値は、特に定めるものではないが、１４９℃以下が実際的であり、１４８℃以下、さらには、１４７℃以下であってもよい。前記上限値以下とすることにより、熱曲げ時におけるスプリングバックの抑制効果がより向上する傾向にある。
　ガラス転移温度（Ｔｉｇ、Ｔｍｇ）は、後述する実施例に記載の方法に従って測定される。
　初期ガラス転移温度（Ｔｉｇ）を高くするには、樹脂の原料モノマーを調整することが例示される。また、樹脂の分子量を高くすることも挙げられる。樹脂のガラス転移温度は一般的に原料モノマーと分子量によって決まり、当業者が適宜選択できる。 <Physical characteristics of resin composition>
The resin composition of the present embodiment has an initial glass transition temperature (Tig) of 135 ° C. or higher, preferably 136 ° C. or higher, more preferably 137 ° C. or higher, and more preferably 138 ° C. or higher by differential scanning calorimetry. It is more preferably 139 or more, and even more preferably 140 ° C. or higher. By setting the value to the lower limit or higher, the occurrence of cracks can be effectively suppressed. Further, the durability of environmental resistance tests such as wet heat test and high temperature test tends to be further improved. The upper limit of the initial glass transition temperature (Tig) is not particularly determined, but is practically 145 ° C or lower, and may be 144 ° C or lower, further may be 143 ° C or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
In the resin composition of the present embodiment, the intermediate glass transition temperature (Tmg) measured by differential scanning calorimetry is preferably 139 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 141 ° C. or higher. , 142 ° C. or higher is more preferable, and 143 ° C. or higher is even more preferable. By setting the value to the lower limit or higher, the occurrence of cracks can be effectively suppressed. Further, the durability of environmental resistance tests such as wet heat test and high temperature test tends to be further improved. The upper limit of the intermediate glass transition temperature (Tmg) is not particularly determined, but is practically 149 ° C. or lower, and may be 148 ° C. or lower, and further may be 147 ° C. or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
The glass transition temperature (Tig, Tmg) is measured according to the method described in Examples described later.
In order to increase the initial glass transition temperature (Tig), it is exemplified to adjust the raw material monomer of the resin. Another example is to increase the molecular weight of the resin. The glass transition temperature of the resin is generally determined by the raw material monomer and the molecular weight, and can be appropriately selected by those skilled in the art.
　本実施形態の樹脂組成物は、２４０℃、１２２０秒－１のせん断速度での溶融粘度が５００Ｐａ・ｓ以下である。前記溶融粘度は、４９５Ｐａ・ｓ以下であることが好ましく、４９０Ｐａ・ｓ以下であることがより好ましく、４８５Ｐａ・ｓ以下であることがさらに好ましく、４８０Ｐａ・ｓ以下であることが一層好ましい。前記溶融粘度の下限値は、２５０Ｐａ・ｓ以上であることが好ましく、３００Ｐａ・ｓ以上であることがより好ましく、３５０Ｐａ・ｓ以上であることがさらに好ましく、３７５Ｐａ・ｓ以上であることが一層好ましく、４００Ｐａ・ｓ以上であることがより一層好ましい。上記範囲とすることにより、フローマークの発生を効果的に抑制することができる。
　溶融粘度は後述する実施例の記載に従って測定される。
　溶融粘度を上記範囲とする手段としては、樹脂の分子量を調整することや、樹脂に悪影響を及ぼさない低分子量化合物を加えることが挙げられる。 The resin composition of the present embodiment has a melt viscosity of 500 Pa · s or less at a shear rate of 240 ° C. and 1220 seconds -1 . The melt viscosity is preferably 495 Pa · s or less, more preferably 490 Pa · s or less, further preferably 485 Pa · s or less, and even more preferably 480 Pa · s or less. The lower limit of the melt viscosity is preferably 250 Pa · s or more, more preferably 300 Pa · s or more, further preferably 350 Pa · s or more, and further preferably 375 Pa · s or more. , 400 Pa · s or more is even more preferable. By setting the above range, the generation of flow marks can be effectively suppressed.
The melt viscosity is measured according to the description of Examples described later.
As means for setting the melt viscosity within the above range, adjustment of the molecular weight of the resin and addition of a low molecular weight compound that does not adversely affect the resin can be mentioned.
　本実施形態の樹脂組成物は、透明性に優れていることが好ましい。具体的には、本実施形態の樹脂組成物を１ｍｍの厚さに成形したときのヘイズが５．０％以下であることが好ましく、２．０％以下であることがより好ましく、１．０％以下であることがさらに好ましく、０．４％以下であることが一層好ましく、０．２％以下であることがより一層好ましい。下限値は、０％が理想であるが、０．０１％以上が実際的である。
　ヘイズは後述する実施例の記載に従って測定される。 The resin composition of the present embodiment is preferably excellent in transparency. Specifically, the haze when the resin composition of the present embodiment is molded to a thickness of 1 mm is preferably 5.0% or less, more preferably 2.0% or less, and 1.0. % Or less, more preferably 0.4% or less, and even more preferably 0.2% or less. The lower limit is ideally 0%, but 0.01% or more is practical.
Haze is measured according to the description of Examples described later.
　本実施形態の樹脂組成物は、鉛筆硬度が高い（硬い）ことが好ましい。具体的には、本実施形態の樹脂組成物を１ｍｍの厚さに成形し、ＪＩＳ　Ｋ５６００－５－４：１９９９に準拠し、鉛筆硬度試験機を用いて、７５０ｇ荷重にて測定した鉛筆硬度が、Ｆ以上であることが好ましく、Ｈ以上であることがより好ましい。前記鉛筆硬度をＦ以上とすることにより、多層体全体の硬度を高めることができ、耐擦傷性を向上させることができる。上限は特に定めるものではないが、３Ｈ以下が実際的である。
　鉛筆硬度は後述する実施例の記載に従って測定される。 The resin composition of the present embodiment preferably has a high pencil hardness (hardness). Specifically, the resin composition of the present embodiment is molded to a thickness of 1 mm, and the pencil hardness measured with a pencil hardness tester at a load of 750 g according to JIS K5600-5-4: 1999 is obtained. , F or more is preferable, and H or more is more preferable. By setting the pencil hardness to F or higher, the hardness of the entire multilayer body can be increased, and the scratch resistance can be improved. The upper limit is not particularly set, but 3H or less is practical.
Pencil hardness is measured according to the description of Examples described later.
　本実施形態の樹脂組成物は、衝撃強さに優れていることが好ましい。具体的には、ＪＩＳ　Ｋ　７１１１－１において、ＩＳＯ試験片の厚さを４ｍｍから３ｍｍに変更し、他は同様に行って測定したノッチ無しシャルピー衝撃強さが、１０．０ｋＪ／ｍ２以上であり、１０．２ｋＪ／ｍ２以上であることが好ましく、１０．５ｋＪ／ｍ２以上であることがより好ましい。前記下限値以上とすることにより、クラックの発生を抑制できる。前記シャルピー衝撃強さの上限値は、特に定めるものではないが、２０．０ｋＪ／ｍ２以下が実際的であり、１３．０ｋＪ／ｍ２以下であっても十分に要求性能を満たす。
　シャルピー衝撃強さを高くする方法としては、ポリメチルメタクリレートなど公知の耐衝撃性が高い樹脂を配合する、分子量が高い樹脂を採用する、ゴムなどの耐衝撃改質剤を配合することなどが例示される。 The resin composition of the present embodiment is preferably excellent in impact strength. Specifically, in JIS K 711-1, the thickness of the ISO test piece was changed from 4 mm to 3 mm, and the other was measured in the same manner. The impact strength without notch was 10.0 kJ / m 2 or more. Yes, 10.2 kJ / m 2 or more is preferable, and 10.5 kJ / m 2 or more is more preferable. By setting the value to the lower limit or higher, the occurrence of cracks can be suppressed. The upper limit of the Charpy impact strength is not particularly determined, but it is practically 20.0 kJ / m 2 or less, and even if it is 13.0 kJ / m 2 or less, the required performance is sufficiently satisfied.
Examples of methods for increasing the Charpy impact strength include blending a known high impact resistant resin such as polymethylmethacrylate, adopting a resin having a high molecular weight, and blending a shock resistant modifier such as rubber. Will be done.
＜平板状成形体＞
　本実施形態の樹脂組成物は、平板状成形体に加工して用いることが好ましい。すなわち、本実施形態の平板状成形体は、本実施形態の樹脂組成物から形成される。本実施形態の平板状成形体は、耐湿熱性に優れる。
　平板状成形体としては、プレート、フィルム、シート等が例示される。また、平板状成形体は、詳細を後述するとおり、他の基材等に積層された多層体に含まれていてもよい。また、本実施形態の平板状成形体は、多層体の一部に組み込まれた後に、曲げ加工などが施されていてもよい。
　平板状成形体の厚さは、下限値が、例えば、１μｍ以上であり、１０μｍ以上であることが好ましく、２０μｍ以上であることがより好ましく、５０μｍ以上であることがさらに好ましく、８０μｍ以上であることが一層好ましく、１００μｍ以上であってもよい。前記下限値以上とすることにより、成形がより容易となるとともに、硬度が向上する傾向にある。また、平板状成形体の厚さの上限に特に制限は無いが、５，０００μｍ以下であることが好ましく、２，０００μｍ以下であることがより好ましく、１，０００μｍ以下であることがさらに好ましく、５００μｍ以下であることが一層好ましく、３００μｍ以下であることがより一層好ましい。特に、詳細を後述する通り、平板状成形体とポリカーボネート樹脂層の厚さの合計に対し、平板状成形体が薄い方が好ましい。このような構成とすることにより、多層体を加熱成形しても、クラックの発生が効果的に抑制され、かつ、スプリングバックの発生が効果的に抑制される。
　本実施形態の平板状成形体は、射出成形やＴダイによる押出成形などにより成形される。 <Plate-shaped molded body>
The resin composition of the present embodiment is preferably processed into a flat plate-shaped molded product and used. That is, the flat plate-shaped molded product of the present embodiment is formed from the resin composition of the present embodiment. The flat plate-shaped molded product of the present embodiment has excellent moisture and heat resistance.
Examples of the flat plate-shaped molded body include a plate, a film, and a sheet. Further, the flat plate-shaped molded body may be included in a multilayer body laminated on another base material or the like, as described in detail later. Further, the flat plate-shaped molded body of the present embodiment may be subjected to bending or the like after being incorporated into a part of the multilayer body.
The lower limit of the thickness of the flat plate-shaped molded product is, for example, 1 μm or more, preferably 10 μm or more, more preferably 20 μm or more, further preferably 50 μm or more, and further preferably 80 μm or more. It is more preferable, and it may be 100 μm or more. By setting the value to the lower limit or more, molding tends to be easier and the hardness tends to be improved. The upper limit of the thickness of the flat plate-shaped molded product is not particularly limited, but is preferably 5,000 μm or less, more preferably 2,000 μm or less, and further preferably 1,000 μm or less. It is more preferably 500 μm or less, and even more preferably 300 μm or less. In particular, as will be described in detail later, it is preferable that the flat plate-shaped molded product is thinner than the total thickness of the flat plate-shaped molded product and the polycarbonate resin layer. With such a configuration, even if the multilayer body is heat-molded, the generation of cracks is effectively suppressed and the generation of springback is effectively suppressed.
The flat plate-shaped molded body of the present embodiment is molded by injection molding, extrusion molding with a T-die, or the like.
　本実施形態の平板状成形体は、ＪＩＳ　Ｋ５６００－５－４：１９９９に準拠し、鉛筆硬度試験機を用いて、７５０ｇ荷重にて測定した鉛筆硬度が、Ｆ以上であることが好ましく、Ｈ以上であることがより好ましい。前記鉛筆硬度をＦ以上とすることにより、多層体全体の硬度を高めることができ、耐擦傷性を向上させることができる。上限は特に定めるものではないが、３Ｈ以下が実際的である。
　鉛筆硬度は、後述する実施例の記載に従って測定される。 The flat plate-shaped molded body of the present embodiment conforms to JIS K5600-5-4: 1999, and the pencil hardness measured with a pencil hardness tester at a load of 750 g is preferably F or more, preferably H or more. Is more preferable. By setting the pencil hardness to F or higher, the hardness of the entire multilayer body can be increased, and the scratch resistance can be improved. The upper limit is not particularly set, but 3H or less is practical.
Pencil hardness is measured according to the description of Examples described later.
＜多層体＞
　本実施形態の多層体は、本実施形態の平板状成形体を含む。このような多層体は表面硬度に優れたものとなる。さらに、本実施形態の多層体は、本実施形態の平板状成形体と、ポリカーボネート樹脂を含む層（ポリカーボネート樹脂層）とを有する多層体であることが好ましい。ポリカーボネート樹脂層は、通常、多層体の基材の役割を果たす。
　本実施形態の多層体は、さらに、ハードコート層を含むことが好ましい。前記ハードコート層は、前記ポリカーボネート樹脂を含む層、前記平板状成形体、前記ハードコート層の順に積層していることが好ましい。また、ハードコート層は、ポリカーボネート樹脂層側にも設けられていてもよい。なお、ポリカーボネート樹脂層と平板状成形体の間、および、平板状成形体とハードコート層の間には、本実施形態の趣旨を逸脱しない範囲で、他の層を有していてもよい。
　さらに、本実施形態の多層体は、前記ハードコート層上であって、基材（前記ポリカーボネート樹脂層）とは反対側の面に、低屈折率層を有することも好ましい。すなわち、上記多層体は、反射防止フィルムとして用いることができる。
　図１は、反射防止フィルムの一例を示す模式図であって、１は基材（ポリカーボネート樹脂層）を、２は平板状成形体を、３はハードコート層を、４は反射防止層を示している。図１では、基材１、平板状成形体２、ハードコート層３および反射防止層４が、前記順に積層しているが、本実施形態の趣旨を逸脱しない範囲で、他の層を有していてもよい。多層体が他の層を有している場合の態様としては、前記多層体の片面または両面に、耐指紋処理、反射防止処理、防眩処理、耐候性処理、帯電防止処理、防汚染処理およびアンチブロッキング処理のいずれか１つ以上が施されていることが好ましい。このときの多層体の最表面の一例として、ハードコート層が挙げられる。また、アンチブロッキング処理とは、フィルム同士が密着しても容易に剥離できるようにする処理をいい、アンチブロッキング剤を添加すること、多層体の表面に凹凸を設けることなどが例示される。さらに、本実施形態の多層体には、上記の他、他の層を有していてもよい。具体的には、接着層、粘着層、防汚層等が例示される。 <Multilayer>
The multilayer body of the present embodiment includes the flat plate-shaped molded body of the present embodiment. Such a multilayer body has excellent surface hardness. Further, the multilayer body of the present embodiment is preferably a multilayer body having the flat plate-shaped molded body of the present embodiment and a layer containing a polycarbonate resin (polycarbonate resin layer). The polycarbonate resin layer usually serves as a substrate for the multilayer body.
The multilayer body of the present embodiment further preferably includes a hard coat layer. It is preferable that the hard coat layer is laminated in the order of the layer containing the polycarbonate resin, the flat plate-shaped molded product, and the hard coat layer. Further, the hard coat layer may be provided on the polycarbonate resin layer side as well. It should be noted that another layer may be provided between the polycarbonate resin layer and the flat plate-shaped molded body and between the flat plate-shaped molded body and the hard coat layer as long as the gist of the present embodiment is not deviated.
Further, it is also preferable that the multilayer body of the present embodiment has a low refractive index layer on the surface of the hard coat layer opposite to the base material (the polycarbonate resin layer). That is, the multilayer body can be used as an antireflection film.
FIG. 1 is a schematic view showing an example of an antireflection film, in which 1 is a substrate (polycarbonate resin layer), 2 is a flat plate-shaped molded product, 3 is a hard coat layer, and 4 is an antireflection layer. ing. In FIG. 1, the base material 1, the flat plate-shaped molded body 2, the hard coat layer 3, and the antireflection layer 4 are laminated in the above-mentioned order, but have other layers as long as the gist of the present embodiment is not deviated. May be. When the multilayer body has another layer, one side or both sides of the multilayer body are subjected to fingerprint resistance treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment, antifouling treatment and the like. It is preferable that any one or more of the anti-blocking treatments are applied. An example of the outermost surface of the multilayer body at this time is a hard coat layer. Further, the anti-blocking treatment refers to a treatment that enables the films to be easily peeled off even if they are in close contact with each other, and examples thereof include adding an anti-blocking agent and providing irregularities on the surface of the multilayer body. Further, the multilayer body of the present embodiment may have other layers in addition to the above. Specifically, an adhesive layer, an adhesive layer, an antifouling layer and the like are exemplified.
　次に、基材１について説明する。
　基材１は、その種類について特に定めるものではなく、本実施形態の多層体に求められる性能を満たす限り、公知の基材を採用できる。具体的には、樹脂基材が好ましく、ポリオレフィン樹脂、ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリスチレン樹脂がより好ましく、ポリカーボネート樹脂を含むことがさらに好ましい。これらは、１種単独でも、２種以上による複合基材を構成していてもよい。本実施形態の多層体において、基材１は、上述の通り、ポリカーボネート樹脂を含む層（ポリカーボネート樹脂層）が好ましい。ポリカーボネート樹脂層におけるポリカーボネート樹脂の割合は８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。 Next, the base material 1 will be described.
The type of the base material 1 is not particularly specified, and a known base material can be used as long as it satisfies the performance required for the multilayer body of the present embodiment. Specifically, a resin base material is preferable, a polyolefin resin, a polyester resin, a polycarbonate resin, an acrylic resin, and a polystyrene resin are more preferable, and it is further preferable to contain a polycarbonate resin. These may form a composite base material of one kind alone or two or more kinds. In the multilayer body of the present embodiment, as described above, the base material 1 is preferably a layer containing a polycarbonate resin (polycarbonate resin layer). The proportion of the polycarbonate resin in the polycarbonate resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
　ポリカーボネート樹脂としては、芳香族ポリカーボネート樹脂であることが好ましく、ビスフェノールＡ型ポリカーボネート樹脂であることがより好ましい。ビスフェノールＡ型ポリカーボネート樹脂とは、ビスフェノールＡおよびその誘導体由来のカーボネート構成単位を有する樹脂をいい、下記式（Ｂ－１）で表される構成単位を有していることが好ましい。式中の＊は結合位置を表す。
Figure JPOXMLDOC01-appb-C000006
 　式（Ｂ－１）中、Ｘ１は下記構造を表す。
Figure JPOXMLDOC01-appb-C000007
 　Ｒ５およびＲ６は、アルキル基または水素原子であり、少なくとも一方がメチル基であることが好ましく、両方がメチル基であることがより好ましい。
　式（Ｂ－１）は下記式（Ｂ－２）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000008
 The polycarbonate resin is preferably an aromatic polycarbonate resin, and more preferably a bisphenol A type polycarbonate resin. The bisphenol A type polycarbonate resin refers to a resin having a carbonate constituent unit derived from bisphenol A and its derivative, and preferably has a constituent unit represented by the following formula (B-1). * In the formula represents the bond position.
Figure JPOXMLDOC01-appb-C000006
 In formula (B-1), X 1 represents the following structure.
Figure JPOXMLDOC01-appb-C000007
 R 5 and R 6 are alkyl groups or hydrogen atoms, preferably at least one of which is a methyl group and more preferably both of which are methyl groups.
The formula (B-1) is preferably represented by the following formula (B-2).
Figure JPOXMLDOC01-appb-C000008
　ビスフェノールＡ型ポリカーボネート樹脂における、式（Ｂ－１）で表される構成単位の含有量は、両末端を除く全構成単位中、７０モル％以上であることが好ましく、８０モル％以上であることがより好ましく、９０モル％以上であることがさらに好ましい。上限値は特に限定されず、１００モル％が式（Ｂ－１）で表される構成単位であってもよい。ビスフェノールＡ型ポリカーボネートとして特に好ましくは実質的に両末端を除く全構成単位が式（Ｂ－１）の構成単位で構成された樹脂が挙げられる。ここでの実質的に両末端を除く全構成単位とは、両末端を除く全構成単位の９９．０モル％以上であることを意味し、９９．５モル％以上が好ましく、９９．９モル％以上がより好ましい。
　ビスフェノールＡ型ポリカーボネート樹脂は、ビスフェノールＡおよびその誘導体由来のカーボネート構成単位以外の他の構成単位を有していてもよい。このような他の構成単位を構成するジヒドロキシ化合物としては、例えば、特開２０１８－１５４８１９号公報の段落００１４に記載の芳香族ジヒドロキシ化合物を挙げることができ、これらの内容は本明細書に組み込まれる。 The content of the structural unit represented by the formula (B-1) in the bisphenol A type polycarbonate resin is preferably 70 mol% or more, preferably 80 mol% or more, in all the structural units excluding both ends. Is more preferable, and 90 mol% or more is further preferable. The upper limit is not particularly limited, and 100 mol% may be a structural unit represented by the formula (B-1). As the bisphenol A type polycarbonate, a resin in which substantially all the constituent units excluding both ends are composed of the constituent units of the formula (B-1) can be mentioned. Here, substantially all the constituent units excluding both ends mean that it is 99.0 mol% or more of all the constituent units excluding both ends, and 99.5 mol% or more is preferable, and 99.9 mol. % Or more is more preferable.
The bisphenol A type polycarbonate resin may have a structural unit other than the carbonate structural unit derived from bisphenol A and its derivative. Examples of the dihydroxy compound constituting such another structural unit include aromatic dihydroxy compounds described in paragraph 0014 of JP-A-2018-154819, the contents of which are incorporated in the present specification. ..
　ビスフェノールＡ型ポリカーボネート樹脂の末端構造としては、アルキル基置換フェノキシ基およびアルコキシカルボニルフェノキシ基などが挙げられる。
　前記アルキル基置換フェノキシ基が有するアルキル基の炭素原子数は１～１０であることが好ましく、１～８であることがより好ましく、２～５であることがさらに好ましい。アルキル基置換フェノキシ基としては、ｍ－メチルフェノキシ基、ｐ－メチルフェノキシ基、ｍ－プロピルフェノキシ基、ｐ－プロピルフェノキシ基、ｐ－ｔｅｒｔ－ブチルフェノキシ基が例示される。
　前記アルコキシカルボニルフェノキシ基が有するアルコキシ基の炭素原子数は１～２０であることが好ましい。アルコキシカルボニルフェノキシ基としては、耐熱性の観点からは、炭素原子数１～１０のアルコキシカルボニルフェノキシ基が好ましく、ｐ－ｔｅｒｔ－ブチルフェノキシ基がより好ましい。
　ポリカーボネート樹脂の初期ガラス転移温度は、１４０～１５５℃であることが好ましい。 Examples of the terminal structure of the bisphenol A type polycarbonate resin include an alkyl group-substituted phenoxy group and an alkoxycarbonyl phenoxy group.
The number of carbon atoms of the alkyl group of the alkyl group substituted phenoxy group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 5. Examples of the alkyl group-substituted phenoxy group include m-methylphenoxy group, p-methylphenoxy group, m-propylphenoxy group, p-propylphenoxy group and p-tert-butylphenoxy group.
The alkoxy group of the alkoxycarbonylphenoxy group preferably has 1 to 20 carbon atoms. As the alkoxycarbonylphenoxy group, an alkoxycarbonylphenoxy group having 1 to 10 carbon atoms is preferable, and a p-tert-butylphenoxy group is more preferable, from the viewpoint of heat resistance.
The initial glass transition temperature of the polycarbonate resin is preferably 140 to 155 ° C.
　ビスフェノールＡ型ポリカーボネート樹脂の製造方法は、特に限定されるものではなく、任意の方法を採用できる。その例を挙げると、界面重合法、溶融エステル交換法、ピリジン法、環状カーボネート化合物の開環重合法、プレポリマーの固相エステル交換法などを挙げることができる。
　その他、ポリカーボネート樹脂の詳細は、特開２０１９－０３５００１号公報の段落００４０～００７３の記載、特開２０１８－１０３５１８号公報の段落００１６～００４３の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The method for producing the bisphenol A type polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
In addition, for details of the polycarbonate resin, the description of paragraphs 0040 to 0073 of JP-A-2019-035001 and the description of paragraphs 0016 to 0043 of JP-A-2018-103518 can be referred to, and these contents are incorporated in the present specification. Is done.
　基材１には、所望の諸物性を著しく損なわない限り、必要に応じて、各種樹脂添加剤を含有していてもよい。樹脂添加剤としては、例えば、酸化防止剤、離型剤、難燃剤、滴下防止剤、染料および顔料（カーボンブラックを含む）、帯電防止剤、防曇剤、アンチブロッキング剤、流動性改良剤、可塑剤、分散剤、抗菌剤などが挙げられる。なお、樹脂添加剤は１種が含有されていてもよく、２種以上が任意の組み合わせおよび比率で含有されていてもよい。 The base material 1 may contain various resin additives, if necessary, as long as the desired physical properties are not significantly impaired. Examples of the resin additive include antioxidants, mold release agents, flame retardants, anti-dripping agents, dyes and pigments (including carbon black), antistatic agents, anti-fog agents, anti-blocking agents, and fluidity improvers. Examples include plasticizers, dispersants, antibacterial agents and the like. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.
　また、基材１は単層であってもよいが、多層であってもよい。
　基材１（好ましくはポリカーボネート樹脂層）の厚みは、特に制限はないが、例えば、１μｍ以上であり、３０μｍ以上であることが好ましく、３５μｍ以上であることがより好ましく、４０μｍ以上であることがさらに好ましく、５０μｍ以上であることが一層好ましく、１００μｍ以上であることがより一層好ましく、３００μｍ以上であることがさらに一層好ましく、５００μｍ以上であることが特に一層好ましく、７００μｍ以上であってもよい。また、基材１の厚みは、１０，０００μｍ以下であることが好ましく、５，０００μｍ以下であることがより好ましく、３，０００μｍ以下であってもよく、２，５００μｍ以下であってもよい。 Further, the base material 1 may be a single layer or a multilayer.
The thickness of the base material 1 (preferably the polycarbonate resin layer) is not particularly limited, but is, for example, 1 μm or more, preferably 30 μm or more, more preferably 35 μm or more, and more preferably 40 μm or more. Further, it is more preferably 50 μm or more, further preferably 100 μm or more, further preferably 300 μm or more, particularly preferably 500 μm or more, and may be 700 μm or more. The thickness of the base material 1 is preferably 10,000 μm or less, more preferably 5,000 μm or less, 3,000 μm or less, or 2,500 μm or less.
　本実施形態の多層体は、上述の通り、平板状成形体および基材を含むことが好ましいが、この時、平板状成形体と基材（好ましくは、ポリカーボネート樹脂層）の厚みの関係性は、平板状成形体の厚み／[平板状成形体と基材の合計厚み]＜１／５を満たすことが好ましい。この関係を満たすことで、平板状成形体が多層体全体として薄いものとなるため、多層体を加熱成形しても、クラックの発生がより効果的に抑制され、かつ、スプリングバックの発生がより効果的に抑制される。より具体的には、スプリングバックを抑制するには、多層体を折り曲げた際に、多層体全体に残っている曲げに対する残留応力を緩和することがより効果的である。かかる観点から、基材だけでなく、平板状成形体についても残留応力を緩和することがより好ましい。平板状成形体と基材が上記関係を満たすようにすることにより、平板状成形体に由来する残留応力が緩和されやすくなり、スプリングバックをより効果的に抑制することができる。本実施形態においては、平板状成形体の厚み／[平板状成形体と基材の合計厚み]＜１／６がより好ましく、平板状成形体の厚み／[平板状成形体と基材の合計厚み]＜１／８がさらに好ましい。また、１／３５＜平板状成形体の厚み／[平板状成形体と基材の合計厚み]であることが好ましく、１／２５＜平板状成形体の厚み／[平板状成形体と基材の合計厚み]であることがより好ましい。特に、本実施形態では、平板状成形体と基材が上述した所定の厚みの好ましい範囲を、また、多層体が後述する厚みの好ましい範囲を満たしつつ、上記関係を満たすことがより好ましい。このような構成とすることにより、本発明の効果がより効果的に達成される。
　特に、本実施形態では、平板状成形体の初期ガラス転移温度（Ｔｉｇ）と基材（好ましくは、ポリカーボネート樹脂層）の初期ガラス転移温度（Ｔｉｇ）と熱曲げ成形温度（℃）が以下の関係を満たすことが好ましい。
平板状成形体のＴｉｇ≧熱曲げ成形温度（℃）＞[基材の初期ガラス転移温度（Ｔｉｇ）－１５℃]
より好ましくは
平板状成形体のＴｉｇ＞熱曲げ成形温度（℃）＞[基材の初期ガラス転移温度（Ｔｉｇ）－１５℃]
さらに好ましくは、
平板状成形体のＴｉｇ＞熱曲げ成形温度（℃）＞[基材の初期ガラス転移温度（Ｔｉｇ）－１０℃]
とすることにより、スプリングバックの抑制とクラックの発生抑制がより向上する傾向にある。 As described above, the multilayer body of the present embodiment preferably includes the flat plate-shaped molded body and the base material, but at this time, the relationship between the thickness of the flat plate-shaped molded body and the base material (preferably the polycarbonate resin layer) is , It is preferable that the thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material] <1/5 is satisfied. By satisfying this relationship, the flat plate-shaped molded body becomes thin as a whole multilayer body, so that even if the multilayer body is heat-molded, the generation of cracks is more effectively suppressed and the generation of springback is more likely to occur. Effectively suppressed. More specifically, in order to suppress the springback, it is more effective to relax the residual stress due to the bending remaining in the entire multilayer body when the multilayer body is bent. From this point of view, it is more preferable to relax the residual stress not only in the base material but also in the flat plate-shaped molded product. By making the flat plate-shaped molded body and the base material satisfy the above relationship, the residual stress derived from the flat plate-shaped molded body can be easily relaxed, and springback can be suppressed more effectively. In the present embodiment, the thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material] <1/6 is more preferable, and the thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material]. Thickness] <1/8 is more preferable. Further, 1/35 <thickness of the flat plate-shaped molded body / [total thickness of the flat plate-shaped molded body and the base material] is preferable, and 1/25 <thickness of the flat plate-shaped molded body / [flat plate-shaped molded body and the base material]. Total thickness] is more preferable. In particular, in the present embodiment, it is more preferable that the flat plate-shaped molded body and the base material satisfy the above-mentioned preferable range of the predetermined thickness, and the multilayer body satisfies the above-mentioned relationship while satisfying the preferable range of the thickness described later. With such a configuration, the effect of the present invention is more effectively achieved.
In particular, in the present embodiment, the initial glass transition temperature (Tig) of the flat plate-shaped molded body, the initial glass transition temperature (Tig) of the base material (preferably the polycarbonate resin layer), and the thermal bending molding temperature (° C.) have the following relationship. It is preferable to satisfy.
Tig of flat plate-shaped molded product ≧ Thermal bending temperature (° C)> [Initial glass transition temperature of substrate (Tig) -15 ° C]
More preferably, Tig of the flat plate-shaped molded body> thermal bending molding temperature (° C)> [initial glass transition temperature (Tig) of the substrate -15 ° C]
More preferably
Tig of flat plate-shaped molded product> Thermal bending temperature (° C)> [Initial glass transition temperature of substrate (Tig) -10 ° C]
By doing so, the suppression of springback and the suppression of crack generation tend to be further improved.
　本実施形態において、前記平板状成形体（アクリル樹脂層）と、ポリカーボネート樹脂層とからなる多層体の高湿熱処理前後の反り変化量は、７００μｍ未満であることが好ましく、２００μｍ未満であることがより好ましい。前記反り変化量の下限は０μｍが理想であるが、１μｍ以上が実際的である。
　反り変化量は、後述する実施例の記載に従って測定される。 In the present embodiment, the amount of change in warpage of the multilayer body composed of the flat plate-shaped molded body (acrylic resin layer) and the polycarbonate resin layer before and after the high-humidity heat treatment is preferably less than 700 μm, and preferably less than 200 μm. More preferred. Ideally, the lower limit of the amount of change in warpage is 0 μm, but 1 μm or more is practical.
The amount of change in warpage is measured according to the description of Examples described later.
　次に、ハードコート層の詳細について説明する。本実施形態の多層体に含まれていてもよいハードコート層は、基材（例えば、ポリカーボネート樹脂層）よりも、表面硬度が高い層である。このようなハードコート層を含むことにより、多層体ないし成形品の表面硬度を高めることができる。
　ハードコート層の厚さは、０．５μｍ以上であることが好ましく、１μｍ以上であることがより好ましく、２μｍ以上であることがさらに好ましく、４μｍ以上であることが一層好ましく、５μｍ以上であることがより一層好ましい。前記下限値以上とすることにより、ハードコート層による多層体全体の鉛筆硬度がより向上する傾向にある。ハードコート層の厚さの上限は、２０μｍ以下であることが好ましく、１５μｍ以下であることがより好ましく、１２μｍ以下であることがさらに好ましく、１０μｍ以下であることが一層好ましく、８μｍ以下であることがより一層好ましい。前記上限値以下とすることにより、熱曲げ時の加工性がより向上する傾向にある。 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 base material (for example, a polycarbonate resin layer). By including such a hard coat layer, the surface hardness of the multilayer body or the molded product can be increased.
The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, further preferably 4 μm or more, and further preferably 5 μm or more. Is even more preferable. By setting the value to the lower limit or more, the pencil hardness of the entire multilayer body due to the hard coat layer tends to be further improved. The upper limit of the thickness of the hard coat layer is preferably 20 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, further preferably 10 μm or less, and further preferably 8 μm or less. Is even more preferable. By setting the value to the upper limit or less, the workability at the time of thermal bending tends to be further improved.
　ハードコート層は、熱硬化または活性エネルギー線による硬化が可能なハードコート材料を塗布後、硬化させて得られるものが好ましい。
　活性エネルギー線を用いて硬化させる塗料の一例としては、１官能あるいは多官能（好ましくは２～１０官能）の（メタ）アクリレートモノマーあるいはオリゴマーなどの単独あるいは複数からなる樹脂組成物が挙げられ、好ましくは、１官能あるいは多官能（好ましくは２～１０官能）ウレタン（メタ）アクリレートオリゴマーを含む樹脂組成物等が挙げられる。これらの樹脂組成物には、硬化触媒として光重合開始剤が加えられることが好ましい。
　また、熱硬化型樹脂塗料としてはポリオルガノシロキサン系、架橋型アクリル系などのものが挙げられる。この様な樹脂組成物は、アクリル樹脂またはポリカーボネート樹脂フィルムまたはシート用ハードコート剤として市販されているものもあり、塗装ラインとの適正を加味し、適宜選択すればよい。
　ハードコート層としては、特開２０１３－０２０１３０号公報の段落００４５～００５５の記載、特開２０１８－１０３５１８号公報の段落００７３～００７６の記載、特開２０１７－２１３７７１号公報の段落００６２～００８２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The hard coat layer is preferably obtained by applying a hard coat material that can be heat-cured or cured by an active energy ray and then curing it.
Examples of the coating material to be cured using the active energy ray include a resin composition composed of one or more monofunctional or polyfunctional (preferably 2 to 10 functional) (meth) acrylate monomers or oligomers, which is preferable. Examples thereof include a resin composition containing a monofunctional or polyfunctional (preferably 2 to 10 functional) urethane (meth) acrylate oligomer. It is preferable to add a photopolymerization initiator as a curing catalyst to these resin compositions.
Examples of the thermosetting resin paint include polyorganosiloxane-based paints and cross-linked acrylic-based paints. Some of such resin compositions are commercially available as acrylic resins, polycarbonate resin films, or hard coat agents for sheets, and may be appropriately selected in consideration of suitability with the coating line.
As the hard coat layer, the description of paragraphs 0045 to 0055 of JP2013-020130, the description of paragraphs 0073 to 0076 of JP-A-2018-103518, and the description of paragraphs 0062-0087 of JP-A-2017-21771. These contents are incorporated herein by reference.
　本実施形態の多層体の総厚みは、特に制限はないが、１０μｍ以上であることが好ましく、２０μｍ以上であることがより好ましく、１００μｍ以上であることがさらに好ましい。層厚みが厚いほうが、多層体としての剛性が向上する傾向がある。また、多層体の総厚みは、１０，０００μｍ以下であることが好ましく、５,０００μｍ以下であることがより好ましく、２,０００μｍ以下であってもよい。このような層厚みにすることで、多層体成形時において、ロール間で多層シートを圧着させ、樹脂を冷却する際に、多層体内部まで樹脂が冷却されるため、多層体の成形性を向上させることができる。 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, and further preferably 100 μm or more. The thicker the layer, the higher the rigidity of the multilayer body tends to be. Further, the total thickness of the multilayer body is preferably 10,000 μm or less, more preferably 5,000 μm or less, and may be 2,000 μm or less. By setting such a layer thickness, the multilayer sheet is crimped between the rolls at the time of forming the multilayer body, and when the resin is cooled, the resin is cooled to the inside of the multilayer body, so that the moldability of the multilayer body is improved. Can be made to.
　本実施形態の多層体は、ポリカーボネート樹脂を含む樹脂組成物を押出するメイン押出機と、本実施形態の樹脂組成物を押出するサブ押出機とを用い、各々用いる樹脂の条件にて樹脂を溶融し押し出しダイに導き、ダイ内部で積層しシート状に成形する、もしくはシート状に成形した後に積層することで多層体を形成することができる。 The multilayer body of the present embodiment uses a main extruder for extruding a resin composition containing a polycarbonate resin and a sub extruder for extruding the resin composition of the present embodiment, and melts the resin under the conditions of the resin to be used. A multilayer body can be formed by guiding the resin to an extrusion die and laminating it inside the die to form a sheet, or by forming the sheet and then laminating.
＜成形品および成形品の製造方法＞
　次に、本実施形態の多層体を用いた成形品および成形品の製造方法について説明する。
　本実施形態の成形品は、本実施形態の多層体から形成された成形品である。
　本実施形態の多層体は、また、熱曲げ耐性に優れているため、屈曲部を有する用途にも適している。例えば、曲率半径が５０ｍｍＲ以下（好ましくは曲率半径が４０～５０ｍｍＲ）の部位を有する成形品にも好ましく用いられる。
　本実施形態の成形品は、好ましくは、本実施形態の多層体を１３０～１５０℃（好ましくは１３３～１４３℃）で熱曲成形することにより得られる。本実施形態の多層体は、熱曲げ耐性に優れているため、曲率半径が５０ｍｍＲ以下の部位を有する成形品としたときに、特に有益である。さらに、スプリングバックやクラックの発生の観点から１３３℃以上であることが好ましい。前記下限値以上とすることにより、熱曲げ時間を短縮でき、また、樹脂の応力緩和が早くなり、スプリングバックが発生しにくくなり好ましい。また、前記熱曲げ温度は、１４７℃以下であることが好ましく、１４４℃以下であることがより好ましく、１４３℃以下であることがさらに好ましい。 <Molded products and manufacturing methods for molded products>
Next, a molded product and a method for manufacturing the molded product using the multilayer body of the present embodiment will be described.
The molded product of the present embodiment is a molded product formed from the multilayer body of the present embodiment.
Since the multilayer body of the present embodiment is also excellent in thermal bending resistance, it is also suitable for applications having a bent portion. For example, it is also preferably used for a molded product having a portion having a radius of curvature of 50 mmR or less (preferably a radius of curvature of 40 to 50 mmR).
The molded product of the present embodiment is preferably obtained by thermally bending the multilayer body of the present embodiment at 130 to 150 ° C. (preferably 133 to 143 ° C.). Since the multilayer body of the present embodiment is excellent in thermal bending resistance, it is particularly useful when a molded product having a portion having a radius of curvature of 50 mmR or less is formed. Further, from the viewpoint of springback and generation of cracks, the temperature is preferably 133 ° C. or higher. By setting the value to the lower limit or more, the thermal bending time can be shortened, the stress relaxation of the resin is accelerated, and springback is less likely to occur, which is preferable. The thermal bending temperature is preferably 147 ° C. or lower, more preferably 144 ° C. or lower, and even more preferably 143 ° C. or lower.
＜用途＞
　本実施形態の平板状成形体、多層体および成形品は、光学部品や意匠製品、反射防止成形品などに好適に用いることができる。
　本実施形態の平板状成形体、多層体および成形品は、表示装置、電気電子機器、ＯＡ機器、携帯情報端末、機械部品、家電製品、車輌部品、各種容器、照明機器等の部品等に好適に用いられる。これらの中でも、特に、各種ディスプレイ、電気電子機器、ＯＡ機器、携帯情報端末および家電製品の筐体、照明機器および車輌部品（特に、車輌内装部品）、スマートフォンやタッチパネル等の表層フィルム、光学材料、光学ディスクに好適に用いられる。特に、本実施形態の成形品は、タッチパネルのセンサー用フィルムや各種ディスプレイの反射防止成形品として好ましく用いられる。 <Use>
The flat plate-shaped molded product, the multilayer body, and the molded product of the present embodiment can be suitably used for optical parts, design products, antireflection molded products, and the like.
The flat plate-shaped molded body, multilayer body, and molded product of the present embodiment are suitable for parts such as display devices, electrical and electronic devices, OA devices, personal digital assistants, mechanical parts, home appliances, vehicle parts, various containers, lighting equipment, and the like. Used for. Among these, in particular, various displays, electrical and electronic equipment, OA equipment, personal digital assistants and housings of home appliances, lighting equipment and vehicle parts (particularly vehicle interior parts), surface film such as smartphones and touch panels, optical materials, etc. Suitable for optical discs. In particular, the molded product of this embodiment is preferably used as an antireflection molded product for a touch panel sensor film or various displays.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。
　実施例で用いた測定機器等が廃番等により入手困難な場合、他の同等の性能を有する機器を用いて測定することができる。 Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
If the measuring device or the like used in the examples is difficult to obtain due to a discontinued number or the like, measurement can be performed using another device having equivalent performance.
＜原料＞
アクリル樹脂（ＭＭＡ系樹脂）
（Ａ１）日本触媒製、ＰＭＬ２０３、スチレン：Ｎ－フェニルマレイミド：Ｎ－シクロへキシルマレイミド：ＭＭＡ（メタクリル酸メチル）の質量比＝６質量％：１９質量％：４質量％：７１質量％、Ｔｉｇ：１３５℃、重量平均分子量：１８９,０００、鉛筆硬度Ｈ
（Ａ２）アルケマ社製、ＡＬＴＵＧＬＡＳ（登録商標）Ｖ０２０、ＭＭＡ：アクリル酸メチル＝９７質量％：３質量％、Ｔｉｇ：１０９℃、重量平均分子量：１２７，０００、鉛筆硬度：３Ｈ
（Ａ３）ダイセル・エボニック製、ＰＬＥＸＩＭＩＤＥ　ＴＴ５０、ＭＭＡと、グルタルイミド構造単位を含んだ樹脂組成物（ＭＭＡ：グルタルイミド＝２４質量％：６７質量％）、初期ガラス転移温度（Ｔｉｇ）：１５２℃、重量平均分子量：９０，２００、鉛筆硬度Ｈ <Raw materials>
Acrylic resin (MMA resin)
(A1) Made by Nippon Catalyst, PML203, styrene: N-phenylmaleimide: N-cyclohexylmaleimide: MMA (methyl methacrylate) mass ratio = 6% by mass: 19% by mass: 4% by mass: 71% by mass, Tig : 135 ° C, weight average molecular weight: 189,000, pencil hardness H
(A2) Arkema, ALTUGLAS (registered trademark) V020, MMA: Methyl acrylate = 97% by mass: 3% by mass, Tig: 109 ° C., weight average molecular weight: 127,000, pencil hardness: 3H
(A3) Resin composition containing PLEXIMIDE TT50, MMA manufactured by Daicel Evonik and glutarimide structural unit (MMA: glutarimide = 24% by mass: 67% by mass), initial glass transition temperature (Tig): 152 ° C., Weight average molecular weight: 90,200, pencil hardness H
スチレン樹脂（Ｓｔ－ＭＡＨ共重合体（スチレン-無水マレイン酸共重合体））
（Ｂ１）Ｐｏｌｙｓｃｏｐｅ社製、ＸＩＲＡＮＳＯ２３１１０、スチレン：無水マレイン酸＝７７質量％：２３質量％、初期ガラス転移温度（Ｔｉｇ）：１４５℃、重量平均分子量：７４,３００、鉛筆硬度：ＨＢ
（Ｂ２）Ｐｏｌｙｓｃｏｐｅ社製、ＸＩＲＡＮＳＯ２６０８０、スチレン：無水マレイン酸＝７４質量％：２６質量％、初期ガラス転移温度（Ｔｉｇ）：１５０℃、重量平均分子量：４７,６００、鉛筆硬度：ＨＢ Styrene resin (St-MAH copolymer (styrene-maleic anhydride copolymer))
(B1) Made by Polyscope, XIRANSO 23110, Styrene: Maleic anhydride = 77% by mass: 23% by mass, Initial glass transition temperature (Tig): 145 ° C., Weight average molecular weight: 74,300, Pencil hardness: HB
(B2) Made by Polyscope, XIRANSO26080, Styrene: Maleic anhydride = 74% by mass: 26% by mass, Initial glass transition temperature (Tig): 150 ° C., Weight average molecular weight: 47,600, Pencil hardness: HB
Ｓｔ－ＭＭＡ－ＭＡＨ共重合体
（Ｃ）デンカ株式会社製、Ｒ－２００、スチレン：無水マレイン酸：メタクリル酸メチル＝５５質量％：１９質量％：２６質量％、重量平均分子量：１２３，０００、Ｔｉｇ：１２４℃ St-MMA-MAH copolymer (C) manufactured by Denka Co., Ltd., R-200, styrene: maleic anhydride: methyl methacrylate = 55% by mass: 19% by mass: 26% by mass, weight average molecular weight: 123,000, Tig: 124 ° C
（Ｄ）酸化防止剤：アデカスタブＰＥＰ－３６、下記化合物、ｔＢｕは、ｔ－ブチル基を示す。
Figure JPOXMLDOC01-appb-C000009
 (D) Antioxidant: Adecasterb PEP-36, the following compound, tBu represents a t-butyl group.
Figure JPOXMLDOC01-appb-C000009
（Ｅ）離型剤：グリセリンモノステアレート、理研ビタミン株式会社製、リケマールＳ－１００Ａ (E) Release agent: Glycerin monostearate, manufactured by RIKEN Vitamin Co., Ltd., Rikemar S-100A
・ポリカーボネート樹脂層
（Ｆ）末端基がｐ-ｔ-ブチルフェノキシ基であるビスフェノールＡ型ポリカーボネート樹脂、三菱エンジニアリングプラスチックス株式会社製、Ｅ－２０００Ｆ、重量平均分子量：５３，０００、初期ガラス転移温度（Ｔｉｇ）：１４９℃ -Polycarbonate resin layer (F) Bisphenol A type polycarbonate resin whose terminal group is pt-butylphenoxy group, manufactured by Mitsubishi Engineering Plastics Co., Ltd., E-2000F, weight average molecular weight: 53,000, initial glass transition temperature ( Tig): 149 ° C
＜ガラス転移温度の測定＞
　各種樹脂および樹脂組成物のガラス転移温度は、下記の示差走査熱量測定（ＤＳＣ測定）条件のとおりに、昇温、降温を２サイクル行い、２サイクル目の昇温時のガラス転移温度を測定した。
　低温側のベースラインを高温側に延長した直線と、変曲点の接線の交点を開始ガラス転移温度（Ｔｉｇ）とし、高温側のベースラインを低温側に延長した直線と、変曲点の接線の交点を終了ガラス転移温度とし、開始ガラス転移温度と終了ガラス転移温度の中間地点を中間ガラス転移温度（Ｔｍｇ）とした。測定開始温度：３０℃、昇温速度：１０℃／分、到達温度：２５０℃、降温速度：２０℃／分とした。単位は、℃で示した。
　測定装置は、示差走査熱量計（ＤＳＣ、日立ハイテクサイエンス社製、「ＤＳＣ７０２０」）を使用した。 <Measurement of glass transition temperature>
The glass transition temperature of various resins and resin compositions was increased and decreased in two cycles according to the following differential scanning calorimetry (DSC measurement) conditions, and the glass transition temperature at the time of the second cycle of temperature increase was measured. ..
The intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line of the turning point is the starting glass transition temperature (Tig), and the straight line extending the baseline on the high temperature side to the low temperature side and the tangent line of the turning point. The intersection of the above was defined as the end glass transition temperature, and the intermediate point between the start glass transition temperature and the end glass transition temperature was defined as the intermediate glass transition temperature (Tmg). The measurement start temperature was 30 ° C., the temperature rise rate was 10 ° C./min, the ultimate temperature was 250 ° C., and the temperature decrease rate was 20 ° C./min. The unit is shown in ° C.
As a measuring device, a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation, "DSC7020") was used.
＜重量平均分子量の測定方法＞
　各種樹脂および樹脂組成物の重量平均分子量（Ｍｗ）は、ゲル浸透クロマトグラフィーによって測定した。
　具体的には、ゲル浸透クロマトグラフィー装置には、ＬＣ－２０ＡＤ　ｓｙｓｔｅｍ（島津製作所社製）を用い、カラムとして、ＬＦ－８０４（Ｓｈｏｄｅｘ社製）を接続して用いた。カラム温度は４０℃とした。検出器はＲＩＤ－１０Ａ（島津製作所社製）のＲＩ検出器を用いた。溶離液として、クロロホルムを用い、検量線は、東ソー社製の標準ポリスチレンを使用して作成した。
　上記ゲル浸透クロマトグラフィー装置、カラム、検出器が入手困難な場合、同等の性能を有する他の装置等を用いて測定する。 <Measurement method of weight average molecular weight>
The weight average molecular weight (Mw) of various resins and resin compositions was measured by gel permeation chromatography.
Specifically, an LC-20AD system (manufactured by Shimadzu Corporation) was used as a gel permeation chromatography apparatus, and an LF-804 (manufactured by Shodex) was connected and used as a column. The column temperature was 40 ° C. The detector used was an RI detector of RID-10A (manufactured by Shimadzu Corporation). Chloroform was used as the eluent, and the calibration curve was prepared using standard polystyrene manufactured by Tosoh Corporation.
If the gel permeation chromatography device, column, or detector is difficult to obtain, measurement is performed using another device having equivalent performance.
＜鉛筆硬度＞
　各種樹脂および樹脂組成物の鉛筆硬度については、上記で作製した平板状成形体について、ＪＩＳ　Ｋ５６００－５－４：１９９９に準拠し、鉛筆硬度試験機を用いて、７５０ｇ荷重にて測定した鉛筆硬度を求めた。評価は、５人の専門家が行い、多数決で判断した。 <Pencil hardness>
The pencil hardness of various resins and resin compositions is based on JIS K5600-5-4: 1999 for the flat plate-shaped molded body produced above, and the pencil hardness measured with a pencil hardness tester at a load of 750 g. Asked. The evaluation was conducted by five experts and judged by majority vote.
実施例１～５、比較例１～９
＜樹脂組成物（ペレット）の製造＞
　上記に記載した各成分を、表１～３に記載の添加量（表１～３の各成分は質量部表記である）となるように計量した。その後、タンブラーにて１５分間混合した後、スクリュー径３２ｍｍのベント付二軸押出機（日本製鋼所社製「ＴＥＸ３０α」）により、シリンダー温度２６０℃で溶融混練し、ストランドカットによりペレットを得た。 Examples 1-5, Comparative Examples 1-9
<Manufacturing of resin composition (pellet)>
Each component described above was weighed so as to have an addition amount shown in Tables 1 to 3 (each component in Tables 1 to 3 is expressed in parts by mass). Then, after mixing with a tumbler for 15 minutes, the mixture was melt-kneaded at a cylinder temperature of 260 ° C. by a twin-screw extruder with a vent having a screw diameter of 32 mm (“TEX30α” manufactured by Japan Steel Works, Ltd.), and pellets were obtained by strand cutting.
＜溶融粘度の測定＞
　上記樹脂組成物を用いて、溶融粘度を測定した。
　具体的にはペレットを８０℃で３時間予備乾燥させた後、キャピログラフを用いて、溶融粘度測定を行った。測定は、温度２４０℃、キャピラリー長１０ｍｍ、キャピラリー径１ｍｍ、炉体径９．５５ｍｍ、せん断速度１２２０秒－１の条件で行った。単位は、Ｐａ・ｓで示した。
　キャピログラフは、東洋精機製作所社製、キャピログラフ１Ｄ　ＰＭＤ-Ｃを用いた。 <Measurement of melt viscosity>
The melt viscosity was measured using the above resin composition.
Specifically, the pellet was pre-dried at 80 ° C. for 3 hours, and then the melt viscosity was measured using a capillograph. The measurement was performed under the conditions of a temperature of 240 ° C., a capillary length of 10 mm, a capillary diameter of 1 mm, a furnace body diameter of 9.55 mm, and a shear rate of 1220 seconds -1 . The unit is Pa · s.
As the capillograph, Capillograph 1D PMD-C manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
＜１ｍｍ厚の平板状成形体の製造＞
　得られた樹脂組成物（ペレット）をベント付二軸射出成形機（Ｓｏｄｉｃｋ社製「ＰＥ－１００」、二軸スクリュー径２９ｍｍの噛合型同方向回転式、プランジャー直径２８ｍｍ）により、シリンダー温度２６０℃で溶融混練し、金型温度８０℃の条件にて平板状成形体（１００×１００×１ｍｍ）を成形した。 <Manufacturing of 1 mm thick flat plate molded body>
The obtained resin composition (pellet) is subjected to a biaxial injection molding machine with a vent (“PE-100” manufactured by Sodick Co., Ltd., a meshing type co-rotating type with a biaxial screw diameter of 29 mm, a plunger diameter of 28 mm), and a cylinder temperature of 260. It was melt-kneaded at ° C. to form a flat plate-shaped molded product (100 × 100 × 1 mm) under the condition of a mold temperature of 80 ° C.
＜ヘイズの測定＞
　ヘイズメーターを用いて、Ｄ６５光源１０°視野の条件にて、上記で得られた平板状成形体のヘイズを測定した。ヘイズメーターは、村上色彩技術研究所社製「ＨＭ－１５０」を用いた。単位は、％で示した。 <Measurement of haze>
Using a haze meter, the haze of the flat plate-shaped molded product obtained above was measured under the condition of a D65 light source with a field of view of 10 °. As the haze meter, "HM-150" manufactured by Murakami Color Technology Research Institute was used. The unit is shown in%.
＜シャルピー衝撃強さの測定＞
　シャルピー衝撃強さは、ＪＩＳ　Ｋ　７１１１－１において、ＩＳＯ試験片の厚さを４ｍｍから３ｍｍに変更し、他は同様に行って測定した。
　具体的には、得られた樹脂組成物（ペレット）をベント付二軸射出成形機（Ｓｏｄｉｃｋ社製「ＰＥ－１００」、二軸スクリュー径２９ｍｍの噛合型同方向回転式、プランジャー直径２８ｍｍ）により、シリンダー温度２６０℃で溶融混練し、金型温度７０℃の条件にて長さ８０ｍｍ×幅１０ｍｍ×厚さ３ｍｍの成形体（試験片）を作製した。その後、厚み以外はＪＩＳ Ｋ７１１１－１に準拠し、ノッチ無しのシャルピー衝撃試験を行い、シャルピー衝撃強さを測定した。単位は、ｋＪ／ｍ２で示した。 <Measurement of Charpy impact strength>
The Charpy impact strength was measured in JIS K7111-1 by changing the thickness of the ISO test piece from 4 mm to 3 mm and performing the same procedure for the others.
Specifically, the obtained resin composition (pellet) is subjected to a biaxial injection molding machine with a vent (“PE-100” manufactured by Sodick Co., Ltd., a meshing type co-rotating type with a biaxial screw diameter of 29 mm, and a plunger diameter of 28 mm). A molded product (test piece) having a length of 80 mm, a width of 10 mm, and a thickness of 3 mm was produced by melt-kneading at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C. After that, a Charpy impact test without a notch was performed in accordance with JIS K7111-1 except for the thickness, and the Charpy impact strength was measured. The unit is kJ / m 2 .
＜ハードコートなしの多層体の製造＞
　軸径３２ｍｍの単軸押出機と、軸径６５ｍｍの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結された６５０ｍｍ幅のＴダイとを有する多層押出機に各押出機と連結したマルチマニホールドダイとを有する多層押出装置を用いて多層体を成形した。軸径３２ｍｍの単軸押出機に、表１～３に示す実施例または比較例の樹脂組成物を導入し、シリンダー温度２５０℃、吐出量を３．６ｋｇ／ｈの条件で押し出した。また、軸径６５ｍｍの単軸押出機に上記ポリカーボネート樹脂（Ｆ）を連続的に導入し、シリンダー温度２８０℃、吐出量を３２．４ｋｇ／ｈで押し出した。全押出機に連結されたフィードブロックは２種２層の分配ピンを備え、温度２７０℃にして、押し出して積層した。その先に連結された温度２７０℃のＴダイでシート状に押し出し、上流側から温度１３０℃、１４０℃、１８０℃とした３本の鏡面仕上げロールで鏡面を転写しながら冷却し、各多層体を得た。得られた多層体の中央部の全体厚みは１０００μｍ、アクリル樹脂層の厚みは１００μｍであった。 <Manufacturing of multilayer bodies without hard coat>
Each is a multi-layer extruder having a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block. Multilayers were molded using a multi-layer extruder with a multi-manifold die coupled to the extruder. The resin compositions of Examples or Comparative Examples shown in Tables 1 to 3 were introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 250 ° C. and a discharge rate of 3.6 kg / h. Further, the polycarbonate resin (F) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm, and the cylinder temperature was 280 ° C. and the discharge amount was 32.4 kg / h. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and was extruded and laminated at a temperature of 270 ° C. A T-die with a temperature of 270 ° C connected to the tip extrudes it into a sheet, and three mirror-finishing rolls with temperatures of 130 ° C, 140 ° C, and 180 ° C are used to cool the mirror while transferring the mirror surface. Got The total thickness of the central portion of the obtained multilayer body was 1000 μm, and the thickness of the acrylic resin layer was 100 μm.
＜高温高湿環境下の反り評価＞
　上記で得られたハードコートなしの多層体の中央付近から縦１０ｃｍ、横６ｃｍの試験片を切り出した。試験片を２点支持型のホルダーにセットして温度２３℃、相対湿度５０％に設定した環境試験機に２４時間以上投入して状態調整した後、反りを測定した。このときの値を処理前反り量の値とした。次に試験片をホルダーにセットして温度８５℃、相対湿度８５％に設定した環境試験機の中に投入し、その状態で１２０時間保持した。さらに温度２３℃、相対湿度５０％に設定した環境試験機の中にホルダーごと移動し、その状態で４時間保持後に再度反りを測定した。このときの値を処理後反り量の値とした。反りの測定には、電動ステージ具備の３次元形状測定機を使用し、取り出した試験片を上に凸の状態で水平に静置し、１ｍｍ間隔でスキャンし、中央部の盛り上がりを反りとして計測した。処理前後の反り量の差、すなわち、（処理後反り量）－（処理前反り量）を反り変化量として評価した。その際、平板状成形体（アクリル樹脂層）側が凸の場合は「－」符号を付して示した。
Ａ：反り変化量の絶対値が２００μｍ未満であった。
Ｂ：反り変化量の絶対値が２００μｍ以上７００μ未満であった。
Ｃ：反り変化量の絶対値が７００μｍ以上であった。 <Evaluation of warpage in a high temperature and high humidity environment>
A test piece having a length of 10 cm and a width of 6 cm was cut out from the vicinity of the center of the multilayer body without a hard coat obtained above. The test piece was set in a two-point support type holder and placed in an environmental tester set at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more to adjust the state, and then the warp was measured. The value at this time was taken as the value of the amount of warpage before processing. Next, the test piece was set in a holder and placed in an environmental tester set at a temperature of 85 ° C. and a relative humidity of 85%, and held in that state for 120 hours. Further, the holder was moved into an environmental tester set at a temperature of 23 ° C. and a relative humidity of 50%, and the warp was measured again after holding for 4 hours in that state. The value at this time was taken as the value of the amount of warpage after processing. To measure the warp, a three-dimensional shape measuring machine equipped with an electric stage is used, and the taken-out test piece is placed horizontally in a convex state and scanned at 1 mm intervals, and the swelling in the center is measured as the warp. did. The difference in the amount of warpage before and after the treatment, that is, (the amount of warpage after treatment)-(the amount of warpage before treatment) was evaluated as the amount of change in warpage. At that time, when the flat plate-shaped molded body (acrylic resin layer) side is convex, it is indicated by a “-” sign.
A: The absolute value of the amount of change in warpage was less than 200 μm.
B: The absolute value of the amount of change in warpage was 200 μm or more and less than 700 μm.
C: The absolute value of the amount of change in warpage was 700 μm or more.
＜ハードコート付き多層体の製造＞
　６官能ウレタンアクリレートオリゴマー（製品名：Ｕ６ＨＡ、新中村化学工業株式会社製）６０質量部、ＰＥＧ２００＃ジアクリレート（製品名：４ＥＧ－Ａ、共栄社化学株式会社製）３５質量部、および含フッ素基・親水性基・親油性基・ＵＶ反応性基含有オリゴマー（製品名：ＲＳ－９０、ＤＩＣ株式会社製）５質量部の合計１００質量部に対して、光重合開始剤（製品名：Ｉ－１８４〔化合物名：１－ヒドロキシ－シクロヘキシルフェニルケトン〕ＢＡＳＦ株式会社製）を１質量％加えた塗料を、上記で作製したハードコートなしの多層体のアクリル樹脂層の表面にバーコーターにて塗布し、メタルハライドランプ（２０ｍＷ／ｃｍ２）を５秒間当ててハードコートを硬化させた。ハードコート層の膜厚は６μｍであった。 <Manufacturing of multilayer body with hard coat>
6-functional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 60 parts by mass, PEG200 # diacrylate (product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) 35 parts by mass, and fluorine-containing group. Photopolymerization initiator (product name: I-184) for a total of 100 parts by mass of 5 parts by weight of hydrophilic group, lipophilic group, UV reactive group-containing oligomer (product name: RS-90, manufactured by DIC Co., Ltd.) [Compound name: 1-hydroxy-cyclohexylphenylketone] manufactured by BASF Co., Ltd.) was applied in an amount of 1% by mass on the surface of the multilayer acrylic resin layer without a hard coat prepared above with a bar coater. A metal halide lamp (20 mW / cm 2 ) was applied for 5 seconds to cure the hard coat. The film thickness of the hard coat layer was 6 μm.
＜熱プレス成形加工性１（１３５℃、７分熱曲げ）＞
　上記で得られたハードコート付き多層体について、曲率半径が５０ｍｍＲとなる凸型（オス型）と凹型（メス型）の金型を作製した。ハードコート層を塗装した多層体は成形前に９０℃で１分間予備加熱し、ハードコート層を塗装した側の表面が凸側になるように、金型に置き、金型温度１３５℃で７分間プレスを行い、自然冷却することにより、熱プレス成形品を作製した。
　上記熱プレス成形品の曲げ部分のクラックを目視で評価した。評価は、５人の専門家が行い、多数決で判断した。
Ａ：熱プレス成形品の曲げ部分にクラックが確認されなかった。
Ｂ：熱プレス成形品の曲げ部分にクラックが確認された。 <Hot press formability 1 (135 ° C, 7 minutes heat bending)>
For the hard-coated multilayer body obtained above, convex (male) and concave (female) molds having a radius of curvature of 50 mmR were produced. The multilayer body coated with the hard coat layer is preheated at 90 ° C. for 1 minute before molding, placed in a mold so that the surface on the side coated with the hard coat layer is on the convex side, and the mold temperature is 135 ° C. 7 A hot press molded product was produced by pressing for a minute and allowing it to cool naturally.
The cracks in the bent portion of the hot press molded product were visually evaluated. The evaluation was conducted by five experts and judged by majority vote.
A: No cracks were found in the bent part of the hot press molded product.
B: Cracks were confirmed in the bent portion of the hot press molded product.
＜熱プレス成形加工性２（１４０℃、３分熱曲げ）＞
　上記で得られたハードコート付き多層体について、曲率半径が５０ｍｍＲとなる凸型（オス型）と凹型（メス型）の金型を作製した。ハードコート層を塗装した多層体は成形前に９０℃で１分間予備加熱し、ハードコート層を塗装した側の表面が凸側になるように、金型に置き、金型温度１４０℃で３分間プレスを行い、自然冷却することにより、熱プレス成形品を作製した。
　上記熱プレス成形品の曲げ部分のクラックを目視で評価した。評価は、５人の専門家が行い、多数決で判断した。
Ａ：熱プレス成形品の曲げ部分にクラックが確認されなかった。
Ｂ：熱プレス成形品の曲げ部分にクラックが確認された。 <Hot press formability 2 (140 ° C, 3 minutes heat bending)>
For the hard-coated multilayer body obtained above, convex (male) and concave (female) molds having a radius of curvature of 50 mmR were produced. The multilayer body coated with the hard coat layer is preheated at 90 ° C. for 1 minute before molding, placed in a mold so that the surface on the side coated with the hard coat layer is on the convex side, and the mold temperature is 140 ° C. 3 A hot press molded product was produced by pressing for a minute and allowing it to cool naturally.
The cracks in the bent portion of the hot press molded product were visually evaluated. The evaluation was conducted by five experts and judged by majority vote.
A: No cracks were found in the bent part of the hot press molded product.
B: Cracks were confirmed in the bent portion of the hot press molded product.
＜外観フローマーク＞
　上記＜多層体の製造＞において目視でフローマークの有無を確認した。評価は、５人の専門家が行い、多数決で判断した。
Ａ：フローマークが認められなかった。
Ｂ：フローマークが認められた。 <Appearance flow mark>
In the above <Manufacturing of multilayer body>, the presence or absence of the flow mark was visually confirmed. The evaluation was conducted by five experts and judged by majority vote.
A: No flow mark was found.
B: A flow mark was recognized.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　上記表におけるＴｉｇ、Ｔｍｇ、溶融粘度、ヘイズ、鉛筆硬度およびノッチ無しシャルピー衝撃強さは、（メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂を含む樹脂組成物の測定値を示している。 The Tig, Tmg, melt viscosity, haze, pencil hardness and Charpy impact strength without notch in the above table show the measured values of the resin composition containing the resin containing the (meth) acrylic compound unit and the aromatic vinyl compound unit. ..
１　　基材
２　　平板状成形体
３　　ハードコート層
４　　反射防止層 1 Base material 2 Flat plate 3 Hard coat layer 4 Anti-reflection layer

Claims (23)

  1. （メタ）アクリル化合物単位と芳香族ビニル化合物単位を含む樹脂を含む樹脂組成物であって、
    前記樹脂組成物中、前記（メタ）アクリル化合物単位と芳香族ビニル化合物単位の合計が５５質量％以上であり、
    前記樹脂組成物の示差走査熱量測定により測定した初期ガラス転移温度（Ｔｉｇ）が１３５℃以上であり、
    前記樹脂組成物を３ｍｍ厚さのＩＳＯ試験片に成形したときのノッチ無しシャルピー衝撃強さが１０．０ｋＪ／ｍ２以上であり、前記ノッチ無しシャルピー衝撃強さは、ＪＩＳ　Ｋ　７１１１－１において、ＩＳＯ試験片の厚さを４ｍｍから３ｍｍに変更し、他は同様に行って測定した値であり、
    前記樹脂組成物の２４０℃、１２２０秒－１のせん断速度での溶融粘度が５００Ｐａ・ｓ以下である樹脂組成物。     A resin composition containing a resin containing a (meth) acrylic compound unit and an aromatic vinyl compound unit.
    In the resin composition, the total of the (meth) acrylic compound unit and the aromatic vinyl compound unit is 55% by mass or more.
    The initial glass transition temperature (Tig) measured by differential scanning calorimetry of the resin composition is 135 ° C. or higher.
    The notchless Charpy impact strength when the resin composition was molded into an ISO test piece having a thickness of 3 mm was 10.0 kJ / m 2 or more, and the notchless Charpy impact strength was determined by JIS K 711-1. The thickness of the ISO test piece was changed from 4 mm to 3 mm, and the others were measured in the same manner.
    A resin composition having a melt viscosity of 500 Pa · s or less at a shear rate of 240 ° C. and 1220 seconds -1 of the resin composition.
  2. 前記樹脂組成物を厚さ１ｍｍの試験片に成形したときのヘイズが５．０％以下である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the haze when the resin composition is molded into a test piece having a thickness of 1 mm is 5.0% or less.
  3. 前記樹脂組成物の示差走査熱量測定により測定した初期ガラス転移温度（Ｔｉｇ）が１４０℃以上である、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the initial glass transition temperature (Tig) measured by differential scanning calorimetry of the resin composition is 140 ° C. or higher.
  4. 前記樹脂組成物が、（メタ）アクリル化合物単位を含むアクリル樹脂（ａ）と芳香族ビニル化合物単位を含む樹脂としてスチレン樹脂（ｂ）を含む、請求項１～３のいずれか１項に記載の樹脂組成物。 The one according to any one of claims 1 to 3, wherein the resin composition contains an acrylic resin (a) containing a (meth) acrylic compound unit and a styrene resin (b) as a resin containing an aromatic vinyl compound unit. Resin composition.
  5. 前記アクリル樹脂（ａ）が、環状酸無水物単位、イミド単位、および、グルタルイミド単位の少なくとも１種を含む、請求項４に記載の樹脂組成物。 The resin composition according to claim 4, wherein the acrylic resin (a) contains at least one of a cyclic acid anhydride unit, an imide unit, and a glutarimide unit.
  6. 前記アクリル樹脂（ａ）が、環状酸無水物単位、および／または、Ｎ置換マレイミド単位を含む、請求項４に記載の樹脂組成物。 The resin composition according to claim 4, wherein the acrylic resin (a) contains a cyclic acid anhydride unit and / or an N-substituted maleimide unit.
  7. 前記アクリル樹脂（ａ）が、Ｎ置換マレイミド単位を含む、請求項５または６に記載の樹脂組成物。 The resin composition according to claim 5 or 6, wherein the acrylic resin (a) contains an N-substituted maleimide unit.
  8. 前記アクリル樹脂（ａ）が、Ｎ－フェニルマレイミド単位、および／または、Ｎ－シクロヘキシルマレイミド単位を含む、請求項５または６に記載の樹脂組成物。 The resin composition according to claim 5 or 6, wherein the acrylic resin (a) contains an N-phenylmaleimide unit and / or an N-cyclohexylmaleimide unit.
  9. 前記アクリル樹脂（ａ）が、（メタ）アクリル化合物単位を３７～９６質量％、芳香族ビニル化合物単位を１～６０質量％、ならびに、無水マレイン酸および／またはＮ置換マレイミド単位を３～７４質量％含む（ただし、（メタ）アクリル化合物単位、芳香族ビニル化合物単位、ならびに、無水マレイン酸および／またはＮ置換マレイミド単位の合計が１００質量％を超えることは無い）、請求項４～８のいずれか１項に記載の樹脂組成物。 The acrylic resin (a) contains 37 to 96% by mass of the (meth) acrylic compound unit, 1 to 60% by mass of the aromatic vinyl compound unit, and 3 to 74% by mass of maleic anhydride and / or N-substituted maleimide units. % (However, the total of (meth) acrylic compound unit, aromatic vinyl compound unit, and maleic anhydride and / or N-substituted maleimide unit does not exceed 100% by mass), any of claims 4 to 8. The resin composition according to item 1.
  10. 前記スチレン樹脂（ｂ）が環状酸無水物単位を含む、請求項４～９のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 4 to 9, wherein the styrene resin (b) contains a cyclic acid anhydride unit.
  11. 前記スチレン樹脂（ｂ）が芳香族ビニル化合物単位を６８～８４質量％、および、環状酸無水物単位を１６～３２質量％含む（ただし、芳香族ビニル化合物単位および環状酸無水物単位の合計が１００質量％を超えることは無い）、請求項４～１０のいずれか１項に記載の樹脂組成物。 The styrene resin (b) contains 68 to 84% by mass of an aromatic vinyl compound unit and 16 to 32% by mass of a cyclic acid anhydride unit (however, the total of the aromatic vinyl compound unit and the cyclic acid anhydride unit is The resin composition according to any one of claims 4 to 10 (which does not exceed 100% by mass).
  12. 前記スチレン樹脂（ｂ）がスチレン単位を含む、請求項４～１１のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 4 to 11, wherein the styrene resin (b) contains a styrene unit.
  13. 前記スチレン樹脂（ｂ）が無水マレイン酸単位を含む、請求項４～１２のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 4 to 12, wherein the styrene resin (b) contains a maleic anhydride unit.
  14. アクリル樹脂（ａ）とスチレン樹脂（ｂ）との含有量の合計１００質量部を基準として、アクリル樹脂（ａ）の含有量は１５～８５質量部であり、スチレン樹脂（ｂ）の含有量は１５～８５質量部である、請求項４～１３のいずれか１項に記載の樹脂組成物。 Based on the total content of 100 parts by mass of the acrylic resin (a) and the styrene resin (b), the content of the acrylic resin (a) is 15 to 85 parts by mass, and the content of the styrene resin (b) is. The resin composition according to any one of claims 4 to 13, which is 15 to 85 parts by mass.
  15. さらに、酸化防止剤および／または離型剤を含む、請求項１～１４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 14, further comprising an antioxidant and / or a mold release agent.
  16. 請求項１～１５のいずれか１項に記載の樹脂組成物から形成された平板状成形体。 A flat plate-shaped molded product formed from the resin composition according to any one of claims 1 to 15.
  17. 厚みが１０～５,０００μｍである、請求項１６に記載の平板状成形体。 The flat plate-shaped molded product according to claim 16, which has a thickness of 10 to 5,000 μm.
  18. 請求項１６または１７に記載の平板状成形体を含む多層体。 A multilayer body including the flat plate-shaped molded body according to claim 16 or 17.
  19. 請求項１６または１７に記載の平板状成形体と、ポリカーボネート樹脂を含む層とを有する多層体。 A multilayer body having the flat plate-shaped molded body according to claim 16 or 17, and a layer containing a polycarbonate resin.
  20. さらに、ハードコート層を含み、前記ハードコート層は、前記ポリカーボネート樹脂を含む層、前記平板状成形体、前記ハードコート層の順に積層している、請求項１９に記載の多層体。 The multilayer body according to claim 19, further comprising a hard coat layer, wherein the hard coat layer is laminated in the order of a layer containing the polycarbonate resin, the flat plate-shaped molded body, and the hard coat layer.
  21. さらに、前記多層体の片面または両面に、耐指紋処理、反射防止処理、防眩処理、耐候性処理、帯電防止処理、防汚染処理およびアンチブロッキング処理のいずれか１つ以上が施されている、請求項１８～２０のいずれか１項に記載の多層体。 Further, one or more of the fingerprint resistant treatment, the antireflection treatment, the antiglare treatment, the weather resistance treatment, the antistatic treatment, the antifouling treatment and the antiblocking treatment are applied to one or both sides of the multilayer body. The multilayer body according to any one of claims 18 to 20.
  22. 請求項１８～２１のいずれか１項に記載の多層体から形成された成形品であって、曲率半径が５０ｍｍＲ以下の部位を有する、成形品。 A molded product formed from the multilayer body according to any one of claims 18 to 21, which has a portion having a radius of curvature of 50 mmR or less.
  23. 請求項１８～２１のいずれか１項に記載の多層体を１３３～１４３℃で熱曲成形することを含む、成形品の製造方法。 A method for producing a molded product, which comprises hot-curving the multilayer body according to any one of claims 18 to 21 at 133 to 143 ° C.
PCT/JP2021/044412 2020-12-18 2021-12-03 Resin composition, plate-shape molded body, laminate, molded product, and molded product production method WO2022131014A1 (en)

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