WO2022131014A1 - Composition de résine, corps moulé de forme plate, stratifié, produit moulé, et procédé de production d'un produit moulé - Google Patents

Composition de résine, corps moulé de forme plate, stratifié, produit moulé, et procédé de production d'un produit moulé Download PDF

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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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resin composition
resin
unit
mass
acrylic
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PCT/JP2021/044412
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English (en)
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/zh
Priority to JP2022569857A priority patent/JPWO2022131014A1/ja
Priority to KR1020237022905A priority patent/KR20230119165A/ko
Publication of WO2022131014A1 publication Critical patent/WO2022131014A1/fr

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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. ..

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
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Abstract

Composition de résine permettant de fournir un stratifié dans lequel l'apparition de craquelures est supprimée et dans lequel des marques d'écoulement ne sont pas susceptibles de se produire ; un corps moulé de forme plate, un stratifié et un produit moulé qui utilisent la composition de résine. Cette composition de résine contient une résine qui contient des motifs de composé (méth)acrylique et des motifs de composé de vinyle aromatique ; dans la composition de résine, le total des motifs de composé (méth)acrylique et des motifs de composé de vinyle aromatique est supérieur ou égal à 55 % en masse, la température de transition vitreuse initiale (Tig) de la composition de résine mesurée par calorimétrie différentielle à compensation de puissance est supérieure ou égale à 135 °C, la résistance aux chocs de Charpy sans entaille lors de la formation de la composition de résine dans une éprouvette de test ISO d'une épaisseur de 3 mm est supérieure ou égale à 10,0 kJ/m2, la résistance aux chocs de Charpy sans entaille est la valeur obtenue en changeant l'épaisseur de l'éprouvette de test ISO de 4 mm à 3 mm et en mesurant par ailleurs de la même manière que selon la norme JIS K 7111-1 ; la viscosité à l'état fondu de la composition de résine à 240 °C et sous une vitesse de cisaillement de 1 220 s-1 est inférieure ou égale à 500 Pa*s.
PCT/JP2021/044412 2020-12-18 2021-12-03 Composition de résine, corps moulé de forme plate, stratifié, produit moulé, et procédé de production d'un produit moulé WO2022131014A1 (fr)

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JP2022569857A JPWO2022131014A1 (fr) 2020-12-18 2021-12-03
KR1020237022905A KR20230119165A (ko) 2020-12-18 2021-12-03 수지 조성물, 평판상 성형체, 다층체, 성형품 및 성형품의제조 방법

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WO2024057985A1 (fr) * 2022-09-13 2024-03-21 三菱瓦斯化学株式会社 Stratifié antireflet et son procédé de fabrication

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JP2011116928A (ja) * 2009-10-29 2011-06-16 Sanyo Chem Ind Ltd 低複屈折性透明樹脂組成物
WO2017141787A1 (fr) * 2016-02-15 2017-08-24 三菱瓦斯化学株式会社 Stratifié de résine transparent
JP2018156081A (ja) * 2017-03-17 2018-10-04 旭化成株式会社 ヘッドマウントディスプレイ用部材
WO2019049704A1 (fr) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 Feuille de résine de moulage de haute dureté et article moulé l'utilisant
WO2021100661A1 (fr) * 2019-11-18 2021-05-27 三菱瓦斯化学株式会社 Composition de résine, corps moulé plat, corps multicouche et corps moulé antireflet
WO2021215515A1 (fr) * 2020-04-24 2021-10-28 株式会社クラレ Plaque de protection d'afficheur à cristaux liquides, plaque de protection d'afficheur à cristaux liquides incurvée attachée à la surface, et son procédé de fabrication

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Publication number Priority date Publication date Assignee Title
JP2008050536A (ja) 2006-08-28 2008-03-06 Denki Kagaku Kogyo Kk 樹脂組成物と光学成形体

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2011116928A (ja) * 2009-10-29 2011-06-16 Sanyo Chem Ind Ltd 低複屈折性透明樹脂組成物
WO2017141787A1 (fr) * 2016-02-15 2017-08-24 三菱瓦斯化学株式会社 Stratifié de résine transparent
JP2018156081A (ja) * 2017-03-17 2018-10-04 旭化成株式会社 ヘッドマウントディスプレイ用部材
WO2019049704A1 (fr) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 Feuille de résine de moulage de haute dureté et article moulé l'utilisant
WO2021100661A1 (fr) * 2019-11-18 2021-05-27 三菱瓦斯化学株式会社 Composition de résine, corps moulé plat, corps multicouche et corps moulé antireflet
WO2021215515A1 (fr) * 2020-04-24 2021-10-28 株式会社クラレ Plaque de protection d'afficheur à cristaux liquides, plaque de protection d'afficheur à cristaux liquides incurvée attachée à la surface, et son procédé de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024057985A1 (fr) * 2022-09-13 2024-03-21 三菱瓦斯化学株式会社 Stratifié antireflet et son procédé de fabrication

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