WO2021015226A1 - メタクリル系溶融押出成形体 - Google Patents

メタクリル系溶融押出成形体 Download PDF

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WO2021015226A1
WO2021015226A1 PCT/JP2020/028397 JP2020028397W WO2021015226A1 WO 2021015226 A1 WO2021015226 A1 WO 2021015226A1 JP 2020028397 W JP2020028397 W JP 2020028397W WO 2021015226 A1 WO2021015226 A1 WO 2021015226A1
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Prior art keywords
methacrylic
acrylic
mass
melt
block copolymer
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English (en)
French (fr)
Japanese (ja)
Inventor
純平 小寺
侑亮 菊川
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to EP20843315.1A priority Critical patent/EP4006071A4/en
Priority to JP2021534062A priority patent/JP7693541B2/ja
Priority to CN202080045961.8A priority patent/CN114026171B/zh
Publication of WO2021015226A1 publication Critical patent/WO2021015226A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92523—Force; Tension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92942—Moulded article
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such 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
    • C08J2433/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a methacrylic melt extrusion molded article. More specifically, the present invention is a methacrylic melt extrusion molding suitable for decoration applications and building material applications, which is excellent in transparency, surface smoothness, bending whitening resistance, pencil hardness, flexibility, moldability and appearance after molding. Regarding the body.
  • the methacrylic resin molded product has excellent optical properties such as transparency and weather resistance, and the molded product has a beautiful appearance. Therefore, it has been used for decoration applications such as automobile interior / exterior and building materials. It was.
  • Acrylic resin film with excellent weather resistance, transparency, pencil hardness and surface smoothness has been used for the purpose of protecting decorative layers such as printing layers and imparting design such as luxury and depth. It is used as a surface protective film.
  • the application to members molded into a three-dimensional shape is increasing. Problems during three-dimensional molding include stress whitening during molding, increase in surface haze, cracking, etc.
  • the surface protective layer has stress whitening resistance, surface smoothness, flexibility, and bending resistance. Sex is needed.
  • Patent Document 1 A method (Patent Document 1) has been presented in which crosslinked rubber polymer particles having a particle diameter of 0.1 ⁇ m or less are used as a resin molded product having excellent whitening properties during molding. However, it has been difficult to suppress cracking during molding while maintaining high surface hardness only with crosslinked polymer particles having a small particle size or block copolymers.
  • Patent Document 1 As a film having excellent pencil hardness and stress whitening resistance, a method using rubber polymer particles having a particle diameter of 0.07 ⁇ m or less (Patent Document 1) and a method using a block copolymer as rubber particles (Patent Document 2) are available. It is disclosed. However, it has been difficult to suppress cracking during molding while maintaining high surface hardness only with polymer particles having a small particle size.
  • An object of the present invention is to provide a methacrylic melt-extruded molded article having excellent transparency, surface smoothness, bending whitening resistance, pencil hardness, flexibility, moldability and appearance after molding, and suitable for decorative applications. That is.
  • the rubber component layer (b1) contains 50 to 99.99% by mass of an acrylic ester monomer unit, 1 to 44.99% by mass of another monofunctional monomer unit, and 0.
  • the thermoplastic resin component layer (b2) contains a copolymer consisting of 01 to 10% by mass, and the thermoplastic resin component layer (b2) is composed of 40 to 100% by mass of a methacrylate ester monomer unit and 60 to 0% by mass of another monomer unit.
  • the acrylic block copolymer (C) contains at least one methacrylic acid ester polymer block (c1) and at least one acrylic acid ester polymer block (c2), and is contained in the acrylic block copolymer (C). It has 30 to 60% by mass of the methacrylic acid ester polymer block (c1) and 40 to 70% by mass of the acrylic acid ester polymer block (c2), and the acrylic block copolymer in the methacrylic melt-extruded product ( The methacrylic melt-extruded polymer according to [1], wherein the content of C) is 1 to 15% by mass.
  • a method for producing a methacrylic melt-extruded molded product which comprises a step of melt-extruding a methacrylic resin composition using a T-die.
  • the methacrylic resin composition contains a methacrylic resin (A) containing 80% by mass or more of methyl methacrylate units and having a weight average molecular weight of 50,000 or more and 500,000 or less, and at least one rubber component layer (b1) inside.
  • the methacrylic melt-extruded body of the present invention is excellent in transparency, surface smoothness, bending whitening resistance, pencil hardness, and flexibility, and is suitable for decoration applications and building material applications.
  • FIG. 6 is a schematic view of a cross-sectional section of a plane parallel to the extrusion direction of the methacrylic melt-extruded body of the present invention obtained in Examples.
  • the acrylic ester polymer block (c2) of the acrylic block copolymer (C) is spherically dispersed.
  • FIG. 6 is a schematic view of a cross-sectional section of a plane parallel to the extrusion direction of the methacrylic melt-extruded body of the present invention obtained in Examples.
  • the acrylic ester polymer block (c2) of the acrylic block copolymer (C) is dispersed in columns.
  • the methacrylic melt-extruded product of the present invention comprises a methacrylic resin (A) containing 80% by mass or more of methyl methacrylate units and having a weight average molecular weight of 50,000 or more and 500,000 or less.
  • An acrylic multilayer polymer (B) containing an outermost layer composed of a thermoplastic resin component and a rubber component layer covered in contact with at least one outermost layer.
  • an acrylic block copolymer (C) containing a methacrylic acid ester polymer block (c1) and an acrylic acid ester polymer block (c2).
  • the acetone insoluble content of the molded product is 1 to 60% by mass
  • the acrylic acid ester polymer block (c2) forms a spherical or columnar phase in a cross section parallel to the extrusion direction of the molded product.
  • the diameter of the spherical phase or the minor axis of the columnar phase is 1 nm or more and 100 nm or less
  • the major axis of the columnar phase is 10 nm or more and 500 nm or less.
  • the molded product of the present invention is a rubber in which a methacrylic resin (A) forms a matrix and contains an acrylic multilayer polymer (B) and an acrylic block copolymer (C). The state elastic body is dispersed.
  • the acetone-insoluble content of the methacrylic melt-extruded product of the present invention is preferably 1 to 60% by mass, more preferably 1 to 50% by mass, still more preferably 5 to 45% by mass, and particularly preferably 10 to 40% by mass. Most preferably, it is 20 to 40% by mass. It is preferable that the molded product is finely cut and used for measuring the acetone insoluble matter.
  • the acetone-soluble content of the methacrylic melt-extruded product of the present invention is preferably 99 to 40% by mass, more preferably 99 to 50% by mass, still more preferably 95 to 55% by mass, and particularly preferably 90 to 60% by mass. , Most preferably 80 to 60% by mass.
  • Acetone insoluble content is determined by using 25 mL of acetone per 1 g of the molded product, stirring at room temperature for 24 hours, centrifuging to separate the precipitate as acetone insoluble matter, and measuring the mass after drying according to the following formula. Can be done.
  • the methacrylic melt-extruded product contains a methacrylic resin (A), an acrylic multilayer polymer (B), and an acrylic block copolymer (C) in the following proportions: -Content of methacrylic resin (A) preferably 10 to 89.9% by mass, more preferably 20 to 79% by mass. -Content of acrylic multilayer polymer (B) preferably 10 to 89.9% by mass, more preferably 20 to 79% by mass. -The content of the acrylic block copolymer (C) is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass.
  • the methacrylic resin (A) used in the present invention has a structural unit derived from methyl methacrylate in an amount of 80% by mass or more, preferably 90% by mass or more. Further, in the methacrylic resin (A), the proportion of structural units derived from a monomer other than methyl methacrylate is 20% by mass or less, preferably 10% by mass or less.
  • Examples of the monomer other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, and t-butyl acrylate.
  • Olefins conjugated diene such as butadiene, isoprene, milsen; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene; acrylamide, methacrylicamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl Examples thereof include pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride: and the like.
  • the stereoregularity of the methacrylic resin (A) is not particularly limited, and for example, one having stereoregularity such as isotactic, heterotactic, and syndiotactic may be used.
  • the weight average molecular weight of the methacrylic resin (A) (hereinafter referred to as Mw (A)) is preferably 50,000 or more and 500,000 or less, and more preferably 60,000 or more and 200,000 or less. If Mw (A) is too small, the impact resistance and toughness of the obtained molded product tend to decrease. If Mw (A) is too large, the fluidity of the methacrylic resin composition to be subjected to melt extrusion tends to decrease, and the moldability tends to decrease.
  • Ratio of weight average molecular weight Mw (A) and number average molecular weight Mn (A) of methacrylic resin (A), Mw (A) / Mn (A) (hereinafter, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight) / Number average molecular weight) is sometimes referred to as “molecular weight distribution”), preferably 1.03 or more and 2.6 or less, more preferably 1.05 or more and 2.3 or less, and particularly preferably 1.2 or more 2 It is less than or equal to 0.0. If the molecular weight distribution is too small, the molding processability of the methacrylic resin composition tends to decrease. If the molecular weight distribution is too large, the impact resistance of the obtained molded product is lowered and it tends to be brittle.
  • Mw (A) and Mn (A) are standard polystyrene-equivalent values measured by GPC (gel permeation chromatography).
  • the molecular weight and molecular weight distribution of the methacrylic resin can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.
  • the methacrylic resin (A) is obtained by polymerizing a monomer or a monomer mixture containing 80% by mass or more of methyl methacrylate.
  • a commercially available product may be used as the methacrylic resin (A).
  • methacrylic resins include "Parapet H1000B” (MFR: 22 g / 10 minutes (230 ° C., 37.3N)) and "Parapet GF” (MFR: 15 g / 10 minutes (230 ° C., 37.3N)).
  • the acrylic multilayer polymer (B) has at least one rubber component layer (b1) (hereinafter, may be simply abbreviated as "(b1)”) inside, and at least one thermoplastic resin component. It is a particle having a core-shell structure having a layer (b2) (hereinafter, may be simply abbreviated as “(b2)”) and the outermost layer being a thermoplastic resin component layer (b2).
  • the core of the acrylic multilayer polymer (B) is regarded as a "layer".
  • the number of layers of the acrylic multilayer polymer (B) may be two or more, and may be three, four, or more.
  • the layer structure is a two-layer structure of (b1)-(b2) from the center; (b1)-(b1)-(b2), (b1)-(b2)-(b2), or (b2)-( A three-layer structure of b1)-(b2); a four-layer structure of (b1)-(b2)-(b1)-(b2) and the like can be mentioned.
  • the two-layer structure of (b1)-(b2); the three-layer structure of (b1)-(b1)-(b2) or (b2)-(b1)-(b2) is preferable.
  • a three-layer structure of (b2)-(b1)-(b2) is more preferable.
  • the mass ratio ((b1) / (b2)) of the total amount of the rubber component layer (b1) and the total amount of the thermoplastic resin component layer (b2) is 30/70 to 90/10. If the ratio of (b1) is less than the above range, the impact strength of the molded product may be insufficient. If the ratio of (b1) exceeds the above range, it may be difficult to form a particle structure, and the melt fluidity may be lowered, making it difficult to knead with other components and to form a resin composition.
  • the mass ratio ((b1) / (b2)) is preferably 30/70 to 80/20, more preferably 40/60 to 70/30. When the resin composition has two or more rubber component layers (b1), the mass ratio is calculated based on the total amount, and when the resin composition has two or more thermoplastic resin component layers (b2), the total amount is calculated. Calculate the mass ratio by quantity.
  • (B1) is an acrylic acid ester monomer unit of 50 to 99.99% by mass, another monofunctional monomer unit of 44.99 to 1% by mass, and a polyfunctional monomer unit of 0.01 to 10%. It is preferable to contain a copolymer containing% by mass.
  • the content of the acrylic ester monomer unit is more preferably 55 to 89.9% by mass, the content of the monofunctional monomer unit is more preferably 44.9 to 10% by mass, and the polyfunctional monomer.
  • the content of the unit is more preferably 0.1 to 5% by mass.
  • the rubber elasticity of the acrylic multilayer polymer (B) may be insufficient and the impact strength of the molded product may be insufficient. If it exceeds .99% by mass, it may be difficult to form a particle structure. If the content of the other monofunctional monomer unit is less than 1% by mass, the optical performance of the multilayer structure polymer particles may be insufficient, and if it exceeds 44.99% by mass, the acrylic multilayer polymer may be insufficient. The weather resistance of (B) may be insufficient. If the content of the polyfunctional monomer unit exceeds 10% by mass, the rubber elasticity of the acrylic multilayer polymer (B) may be insufficient and the impact strength of the molded product may be insufficient. If it is less than 0.01% by mass, it may be difficult to form a particle structure.
  • acrylic acid esters examples include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate, and hexyl acrylate.
  • MA methyl acrylate
  • BA isobutyl acrylate
  • s-butyl acrylate s-butyl acrylate
  • t-butyl acrylate pentyl acrylate
  • hexyl acrylate examples include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate
  • esters of acrylic acids such as octyl acrylates, 2-ethylhexyl acrylates, dodecyl acrylates, and octadecyl acrylates with saturated aliphatic alcohols (preferably C 1 to C 18 saturated aliphatic alcohols); acrylic acids such as cyclohexyl acrylate and C 5 or esters of cycloaliphatic alcohols C 6; esters of acrylic acid and phenols such as phenyl acrylate, esters of acrylic acid and aromatic alcohols such as benzyl acrylate.
  • Acrylic ester may be used alone or in combination of two or more.
  • MMA methyl methacrylate
  • ethyl methacrylate ethyl methacrylate
  • n-propyl methacrylate isopropyl methacrylate
  • n-butyl methacrylate isobutyl methacrylate
  • pentyl methacrylate hexyl methacrylate
  • octyl methacrylate 2-ethylhexyl methacrylate
  • esters of methacrylic acid such as dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, and behenyl methacrylate with saturated aliphatic alcohols (preferably C 1 to C 22 saturated aliphatic alcohols); methacrylic acid such as cyclohexyl methacrylate and C.
  • esters of cycloaliphatic alcohols C 6 esters of methacrylic acid and phenols phenyl methacrylate, methacrylic acid esters such as esters of methacrylic acid and aromatic alcohols such as benzyl methacrylate; styrene (St), ⁇ -Methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and halogenated Aromatic vinyl-based monomers such as styrene; vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile can be mentioned. Of these, styrene is preferable. Other monofunctional monomers may be used alone or in combination of two or more.
  • the polyfunctional monomer is a monomer having two or more carbon-carbon double bonds in the molecule.
  • an ester of an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, and cinnamic acid and an unsaturated alcohol such as allyl alcohol and metallic alcohol
  • the above-mentioned unsaturated monocarboxylic acid Diesters with glycols such as ethylene glycol, butanediol, and hexanediol
  • diesters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and maleic acid and the unsaturated alcohols mentioned above.
  • One or more polyfunctional monomers can be used.
  • the layer (b2) preferably contains a copolymer composed of 40 to 100% by mass of a methacrylic ester monomer unit and 60 to 0% by mass of another monomer unit.
  • the content of the methacrylic ester monomer unit is more preferably 50 to 99% by mass, further preferably 60 to 99% by mass, particularly preferably 80 to 99% by mass, and the content of other monomer units is more preferable. Is 50 to 1% by mass, more preferably 40 to 1% by mass, still more preferably 20 to 1% by mass. If the content of the methacrylic acid ester monomer unit is less than 50% by mass, the weather resistance of the acrylic multilayer polymer (B) may be insufficient.
  • thermoplastic resin component layer (b2) the raw material monomer of the thermoplastic resin component layer (b2) will be described.
  • Methacrylic acid esters include methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and dodecyl methacrylate.
  • MMA methyl methacrylate
  • ethyl methacrylate ethyl methacrylate
  • n-propyl methacrylate isopropyl methacrylate
  • n-butyl methacrylate isobutyl methacrylate
  • pentyl methacrylate hexyl methacrylate
  • octyl methacrylate 2-ethylhexyl methacrylate
  • MMA methyl methacrylate
  • monomers include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate, and hexyl.
  • Ester of acrylic acid such as acrylate, octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and octadecyl acrylate with saturated aliphatic alcohol (preferably C 1 to C 18 saturated aliphatic alcohol); acrylic acid such as cyclohexyl acrylate and C.
  • styrene alpha-methyl styrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2- Aromatic vinyl-based monomers such as ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and styrene halide; vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile; maleimide, N-methylmaleimide , N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, and maleimide-based monomers
  • acrylic acid alkyl esters such as methyl acrylate (MA), ethyl acrylate, and n-butyl acrylate (BA) are preferable.
  • the weight average molecular weight (Mw) of the constituent copolymer of the outermost layer (b2) measured by the GPC method is in the range of 20,000 to 100,000. It is preferably in the range of 30,000 to 90,000, more preferably in the range of 40,000 to 80,000. If the Mw is less than 20,000, the rubber elasticity of the acrylic multilayer polymer (B) may be insufficient, making it difficult to mold the resin composition. If Mw exceeds 100,000, the impact strength of the molded product may decrease.
  • the average particle size (de) of the acrylic multilayer polymer (B) rubber component layer (b1) closest to the outermost layer (preferably in contact with the outermost layer) is in the range of 0.05 to 0.15 ⁇ m. If the average particle size (de) is less than 0.05 ⁇ m, the stress concentration on the acrylic multilayer polymer (B) becomes insufficient, and the impact strength of the molded product may decrease. When the average particle size (de) exceeds 0.15 ⁇ m, voids are generated inside the acrylic multilayer polymer (B) and whitening occurs. Further, when the rubber content in the resin composition is constant, the number of particles decreases when the particle size becomes larger than a certain level, so that the distance between the surfaces of the particles tends to increase, and cracks occur in the continuous phase. The probability is high, and the impact strength of the molded product may decrease.
  • the void referred to here is a fracture that occurs only inside the particle, and since the amount of energy absorbed is very small, it does not contribute much to the development of impact resistance.
  • the average particle size (de) is preferably 0.05 to 0.15 ⁇ m, more preferably 0.07 to 0.12 ⁇ m.
  • the average particle size (de) of the rubber component layer (b1) of the acrylic multilayer polymer (B) is determined by a method of measuring a section of a molded product with an electron microscope or a method of measuring latex by a light scattering method. be able to.
  • the method using an electron microscope is performed in the rubber component layer (b2) of the stained acrylic multilayer polymer (B) observed by a transmission electron microscope when a section of a molded product is electronically dyed with ruthenium tetroxide. It is the average value of the major axis diameter and the minor axis diameter of what constitutes the outermost part.
  • the latex polymerized up to the rubber component layer is sampled and measured using a laser diffraction / scattering type particle size distribution measuring device LA-950V2 manufactured by Horiba Seisakusho Co., Ltd. it can.
  • the method for producing the acrylic multilayer polymer (B) is the acrylic multilayer polymer (B) having the rubber component layer (b1) / thermoplastic resin component layer (b2) as described above. ) Is not particularly limited as long as it can be obtained.
  • a preferred method for producing the acrylic multilayer polymer (B) having a three-layer structure (core-intermediate layer-outermost layer) is to emulsion-polymerize a monomer for obtaining a polymer constituting the center core to obtain seed particles (i).
  • the monomer for obtaining the polymer constituting the intermediate layer is seed-emulsified and polymerized in the presence of the seed particles (i) to obtain the seed particles (ii), and in the presence of the seed particles (ii). It includes a step of seed emulsion polymerization of a monomer for obtaining a polymer constituting the outermost layer to obtain seed particles (iii).
  • the acrylic multilayer polymer (B) having a two-layer structure or a four-layer or higher layer structure may be one of ordinary skill in the art with reference to the description of the above-mentioned production method of the acrylic multilayer polymer (B) having a three-layer structure. Can be easily manufactured.
  • the seed particles (i) are single-layer particles composed of the thermoplastic resin component layer (b2, core), and the seed particles (ii) are the thermoplastic resin component layer (b2, core) +.
  • the particles have a two-layer structure of a rubber component layer (b1, intermediate layer), and the seed particles (iii) are a thermoplastic resin component layer (b2, core) + a rubber component layer (b1, intermediate layer) + a thermoplastic resin component layer. It is a particle having a three-layer structure (b2, outermost layer).
  • the polymerization conditions are adjusted so that the Mw of the constituent copolymer of the thermoplastic resin component layer (b2) constituting at least the outermost layer is 20,000 to 100,000.
  • the polymerization conditions are mainly adjusted by the amount of a molecular weight modifier such as alkyl mercaptan.
  • the average particle size up to the outermost thermoplastic resin component layer (b2) in the finally obtained acrylic multilayer polymer (B) is in the range of 0.05 to 0.15 ⁇ m. Adjust the polymerization conditions.
  • the average particle size of the acrylic multilayer polymer particles (B) up to the outermost thermoplastic resin component layer (b2) is determined by sampling the polymerized latex during multilayer structure polymer particle polymerization and using a laser manufactured by Horiba Seisakusho. It can be measured by the light scattering method using a diffraction / scattering type particle size distribution measuring device LA-950V2.
  • the acrylic block copolymer (C) used in the present invention has a methacrylic acid ester polymer block (c1) and an acrylic acid ester polymer block (c2).
  • the acrylic block copolymer (C) may have only one methacrylic acid ester polymer block (c1) or may have a plurality of methacrylic acid ester polymer blocks (c1). Further, the acrylic block copolymer (C) may have only one acrylic ester polymer block (c2) or may have a plurality of acrylic block copolymers (C).
  • the acrylic block copolymer (C) has good compatibility with the methacrylic resin (A) and the acrylic multilayer polymer (B).
  • the acrylic block copolymer (C) includes 10 to 80% by mass of the polymer block (c1) having a methacrylic acid ester monomer unit and mainly an acrylic acid ester monomer unit.
  • a block copolymer containing 90 to 20% by mass of the polymer block (c2) having (however, the total amount of the polymer block (c1) and the polymer block (c2) is 100% by mass) is preferable.
  • the content of the polymer block (c1) is more preferably 20 to 70% by mass, further preferably 30 to 60% by mass, and that of the polymer block (c2).
  • the content is more preferably 80 to 30% by mass, still more preferably 70 to 40% by mass.
  • the number of polymer blocks (c1) in one molecule may be singular or plural.
  • the composition and molecular weight of the structural units of the plurality of polymer blocks (c1) may be the same or non-identical.
  • the number of polymer blocks (c2) in one molecule may be singular or plural.
  • the composition and molecular weight of the structural units of the plurality of polymer blocks (c2) may be the same or non-identical.
  • the polymer block (c1) mainly contains a methacrylic acid ester monomer unit.
  • the content of the methacrylic ester monomer unit in the polymer block (c1) is preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 98% by mass or more. It may be composed of only the methacrylic ester monomer unit.
  • methacrylic ester examples include methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, and n-hexyl.
  • MMA methyl methacrylate
  • ethyl methacrylate ethyl methacrylate
  • n-propyl methacrylate isopropyl methacrylate
  • n-butyl methacrylate isobutyl methacrylate
  • s-butyl methacrylate s-butyl methacrylate
  • t-butyl methacrylate amyl methacrylate
  • isoamyl methacrylate isoamyl methacrylate
  • Methacrylate Cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate. (ALMA) and the like.
  • methyl methacrylate (MMA) ethyl methacrylate
  • isopropyl methacrylate n-butyl methacrylate
  • t-butyl methacrylate cyclohexyl methacrylate
  • isobornyl methacrylate and the like are preferable, and methyl methacrylate (Methyl methacrylate) (MMA) is particularly preferred.
  • methacrylic acid esters can be used.
  • the weight average molecular weight (Mw (c1)) of the methacrylic polymer block (c1) has a lower limit of preferably 5,000, more preferably 8,000, still more preferably 12,000, and particularly preferably 15,000. It is preferably 20,000, with an upper limit of preferably 150,000, more preferably 120,000, and particularly preferably 100,000.
  • the weight average molecular weight (Mw (c1)) is the total amount of Mw of the plurality of polymer blocks (c1).
  • the ratio of the weight average molecular weight Mw (A) of the methacrylic resin (A) to Mw (c1) is 0.5 or more and 2.5 or less, preferably 0.6 or more. It is 3 or less, more preferably 0.7 or more and 2.2 or less.
  • Mw (A) / Mw (c1) is out of the above range, the dispersed particle size of the acrylic block copolymer (C) in the methacrylic resin (A) becomes large, and when stress is applied. Whiten.
  • Mw (A) / Mw (c1) is in the above range, the dispersed particle size of the acrylic block copolymer (C) in the methacrylic resin (A) becomes small, so that the stress whitening resistance is excellent.
  • the content of the methacrylic polymer block (c1) in the acrylic block copolymer (C) is the transparency, flexibility, flexibility, bending resistance, impact resistance, and moldability of the molded product of the present invention. From the viewpoint of surface smoothness, it is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.
  • the content of the polymer block (c1) is the total content of the plurality of polymer blocks (c1).
  • the acrylic polymer block (c2) mainly contains an acrylic acid ester monomer unit.
  • the content of the acrylic acid ester monomer unit in the acrylic polymer block (c2) is preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 90% by mass. % Or more.
  • acrylic acid esters examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, amyl acrylate, isoamyl acrylate, and n-hexyl.
  • Acrylic ester may be used alone or in combination of two or more.
  • the acrylic polymer block (c2) includes an acrylic acid alkyl ester monomer unit and a (meth) acrylic acid aromatic hydrocarbon ester single amount.
  • a polymer block (c2-p) containing a body unit is preferable.
  • the content of the acrylic acid alkyl ester monomer unit in the polymer block (c2) is preferably 50 to 90% by mass, more preferably 60 to 80% by mass, and (meth) acrylic acid aromatic carbonation.
  • the content of the hydrogen ester monomer unit is preferably 50 to 10% by mass, more preferably 40 to 20% by mass.
  • the weight average molecular weight Mw (c2) of the acrylic polymer block (c2) satisfies the following formula (Z), more preferably the following formula (Z1). 5,000 ⁇ Mw (c2) ⁇ 120,000 (Z) 40,000 ⁇ Mw (c2) ⁇ 120,000 (Z1)
  • the weight average molecular weight Mw (c2) of the acrylic polymer block (c2) has a lower limit of preferably 5,000, more preferably 15,000, still more preferably 20,000, particularly preferably 30,000, and most preferably. It is 40,000, with an upper limit of preferably 120,000, more preferably 110,000, and particularly preferably 100,000. If Mw (c2) is too small, the impact resistance of the molded product may decrease. On the other hand, if Mw (c2) is excessive, the surface smoothness of the molded product may decrease.
  • the weight average molecular weight Mw (c2) is the total amount of Mw of the plurality of polymer blocks (c2).
  • the content of the acrylic polymer block (c2) in the acrylic block copolymer (C) is the transparency, flexibility, flexibility, bending resistance, impact resistance, moldability, and surface of the molded product. From the viewpoint of smoothness, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass.
  • the content of the polymer block (c2) is the total content of the plurality of acrylic polymer blocks (c2).
  • the dispersed phase of the acrylic polymer block (b2) in the cross section parallel to the extrusion direction in the methacrylic resin (A) in the melt extrusion molded body is preferably a spherical or columnar phase.
  • the dispersed phase becomes a lamellar phase, the extruded body becomes cloudy and whitens when stress is applied.
  • the particle size of the dispersed phase of the acrylic polymer block (b2) is preferably 1 nm or more and 200 nm or less in diameter, and more preferably 10 nm or more and 100 nm or less in the case of a spherical phase. If it is less than 1 nm, the stress concentration around the acrylic polymer block is small and bending resistance is not exhibited, and if it exceeds 200 nm, it whitens when stress is applied.
  • the minor axis of the columnar phase is 1 nm or more and 200 nm or less
  • the major axis of the columnar phase is preferably 1 nm or more and 500 nm or less, and more preferably the major axis is 10 nm or more and 400 nm or less.
  • the major axis is less than 10 nm, the stress concentration around the acrylic polymer block is small and bending resistance is not exhibited, and when it exceeds 500 nm, whitening occurs when stress is applied.
  • the bond form between the methacrylic polymer block (c1) and the acrylic polymer block (c2) in the acrylic block copolymer (C) is not particularly limited.
  • the acrylic block copolymer (C) a diblock copolymer having a (c1)-(c2) structure in which one end of the polymer block (c2) is connected to one end of the polymer block (c1);
  • Examples thereof include linear block copolymers such as triblock copolymers having a structure of (c1)-(c2)-(c1) in which one end of a polymer block (c1) is connected to each end.
  • diblock copolymers and triblock copolymers are preferable, and diblock copolymers having a (c1)-(c2) structure and triblock copolymers having a (c1)-(c2)-(c1) structure are preferable. More preferred.
  • the acrylic block copolymer (C) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, and an amino group in the molecular chain and / or at the terminal of the molecular chain, if necessary.
  • the acrylic block copolymer (C) has a weight average molecular weight (Mw (C)) of 32,000 to 300,000, preferably 40,000 to 250,000, and more preferably 45,000 to 230,000. Particularly preferably, it is 50,000 to 200,000.
  • Mw (C) is within the above range, the amount of unmelted material at the time of melt-kneading of the raw material in the production of the resin composition which causes the generation of lumps in the molded product can be made extremely small.
  • the acrylic block copolymer (C) preferably has a ratio (Mw (C) / Mn (C)) of a weight average molecular weight (Mw (C)) to a number average molecular weight (Mn (C)) of 1.0. It is ⁇ 2.0, more preferably 1.0 to 1.6.
  • Mw (C) / Mn (C) is within the above range, the amount of unmelted material at the time of melt-kneading of the raw material in the production of the resin composition which causes the generation of lumps in the molded product should be extremely small. Can be done.
  • the method for producing the acrylic block copolymer (C) is not particularly limited, and a method of living-polymerizing each polymer block is common.
  • a method of living-polymerizing each polymer block is common.
  • an organic alkali metal compound is used as a polymerization initiator to perform anionic polymerization in the presence of an alkali metal or an alkali earth metal salt or other mineral salt, and an organic alkali metal compound is used as a polymerization initiator to form an organic aluminum.
  • Examples thereof include a method of anion polymerization in the presence of a compound, a method of polymerizing using an organic rare earth metal complex as a polymerization initiator, and a method of radical polymerization in the presence of a copper compound using an ⁇ -halogen ester compound as a polymerization initiator.
  • a method of polymerizing using a multivalent radical polymerization initiator or a multivalent radical chain transfer agent can also be mentioned.
  • the acrylic block copolymer (C) can be obtained with high purity, the composition and molecular weight of each block can be easily controlled, and it is economical. Therefore, an organoalkali metal compound is used as a polymerization initiator and organoaluminum.
  • a method of anionic polymerization in the presence of a compound is particularly preferred.
  • the refractive index of the acrylic block copolymer (C) is not particularly limited, and is preferably 1.485 to 1.495, more preferably 1.487 to 1.493. When the refractive index is within the above range, the transparency is high.
  • the "refractive index” means a value measured at a wavelength of 587.6 nm (D line).
  • Methodacrylic resin composition By adding the acrylic multilayer polymer (B) according to the present invention to the mixing step with the methacrylic resin (A) and the acrylic block copolymer (C) and kneading the mixture, transparency, surface smoothness, and bending resistance are obtained. It is possible to obtain a methacrylic resin composition for producing a methacrylic melt-extruded product having excellent whitening property, pencil hardness, and flexibility.
  • a kneading method a known method such as a batch type kneader such as a Banbury mixer, a pressure kneader, or a lavender plast graph, or a continuous kneader such as a single-screw, twin-screw, or multi-screw extruder is used. It can be carried out. Alternatively, a method may be used in which a high-concentration master pellet is once produced by the above method, and then the diluted product is melt-kneaded. From the viewpoint of productivity, the single-screw method or the double-screw method is preferable. In particular, a single-screw extruder is preferable because the shear energy given to the resin composition is small.
  • the total amount of the rubber component layer (b1) of the acrylic multilayer polymer (B) and the acrylic polymer block (c2) of the acrylic block copolymer (C) is 5 to 60% by mass. , It is preferably 6 to 50% by mass, and more preferably 7 to 30% by mass. If the total amount of the rubber component layer (b1) and the acrylic polymer block (c2) is less than 5% by mass, the impact strength deteriorates, and if it exceeds 60% by mass, the rigidity deteriorates.
  • the acrylic polymer block (c2) content ratio to the total rubber content of (b1) and (c2) is in the range of 5 to 90% by mass and in the range of 10 to 85% by mass. Is preferable, and the range is more preferably 15 to 80% by mass.
  • the acrylic polymer block (c2) content ratio to the rubber content is in the range of 5 to 90% by mass, the synergistic effect of the multilayer structure polymer particles and the block copolymer works, and the impact strength is excellent. ..
  • Optional ingredient In addition to the methacrylic resin (A), the acrylic multilayer polymer (B), and the acrylic block copolymer (C), other polymers are contained as necessary, as long as the effects of the present invention are not impaired. You may.
  • Other polymers include olefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionomers; polystyrene, styrene-maleic anhydride copolymers, high impact.
  • Sterylene resins such as polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; methyl methacrylate-styrene copolymer; ester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, Amid resins such as nylon 66 and polyamide elastomers; polyphenylene sulfide, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene- Other thermoplastic resins such as vinyl alcohol copolymers, polyacetals, and phenoxy resins; thermocurable resins such as phenolic resins, melamine resins, silicone resins, and epoxy resins; polyurethanes; modified polyphenylene ethers; silicones.
  • Modified resins acrylic rubbers, silicone rubbers; styrene-based thermoplastic polymers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM.
  • Other polymers may be used alone or in combination of two or more.
  • the methacrylic melt-extruded molded product of the present invention may contain various additives, if necessary.
  • Additives include antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, matting agents, and anti-sticking agents. Examples include agents, impact resistant modifiers, phosphors and the like.
  • the content of these additives can be appropriately set within a range that does not impair the effects of the present invention, and for example, the content of the antioxidant is 0.01 with respect to 100 parts by mass of the thermoplastic resin composition to be subjected to melt extrusion molding.
  • UV absorber content is 0.01 ⁇ 3 parts by mass
  • light stabilizer content is 0.01 ⁇ 3 parts by mass
  • lubricant content is 0.01 ⁇ 3 parts by mass
  • dye The content of the pigment is preferably 0.01 to 3 parts by mass
  • the content of the matting agent is preferably 0.1 to 20 parts by mass
  • the content of the anti-adhesion agent is 0.001 to 1 part by mass.
  • Other additives can also be added in the range of 0.01 to 3 parts by mass.
  • the antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen.
  • phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like can be mentioned.
  • phosphorus-based antioxidants and phenol-based antioxidants are preferable from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, and the phenol-based antioxidants are used alone or the phosphorus-based antioxidants and phenol-based antioxidants are used. The combined use is more preferable.
  • a phosphorus-based antioxidant and a phenol-based antioxidant are used in combination, it is preferable to use the phosphorus-based antioxidant / phenol-based antioxidant in a mass ratio of 0.2 / 1 to 2/1. It is more preferable to use it at 5/1 to 1/1.
  • phosphorus-based antioxidants 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite ("ADEKA STAB HP-10" manufactured by ADEKA Corporation), Tris (2,4-di-t) -Butylphenyl) phosphite (“IRGAFOS168” manufactured by BASF Japan Corporation), and 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa- 3,9-Diphosphaspiro [5.5] undecane (“ADEKA STAB PEP-36” manufactured by ADEKA Corporation) and the like are preferable.
  • Phenolic antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF Japan Co., Ltd. "IRGANOX1010”) and octadecyl-3-3. (3,5-Di-t-Butyl-4-hydroxyphenyl) propionate (“IRGANOX1076” manufactured by BASF Japan Ltd.) and the like are preferable.
  • sulfur-based antioxidant dilauryl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate) and the like are preferable.
  • amine-based antioxidant octylated diphenylamine and the like are preferable.
  • the heat deterioration of the resin can be prevented by supplementing the polymer radicals generated when exposed to a high temperature under substantially oxygen-free conditions.
  • the heat deterioration inhibitor include 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenyl acrylate ("Sumilyzer GM” manufactured by Sumitomo Chemical Co., Ltd.) and 2,4-di-t-amyl-6- (3', 5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl) phenylacrylate ("Sumilyzer GS" manufactured by Sumitomo Chemical Co., Ltd.), etc. preferable.
  • the ultraviolet absorber is a compound that has an ultraviolet absorbing ability and is said to have a function of mainly converting light energy into heat energy.
  • Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, and formamidines. Of these, benzotriazoles and triazines are preferable.
  • One kind or two or more kinds of ultraviolet absorbers can be used.
  • Benzotriazoles are highly effective in suppressing deterioration of optical properties such as coloring due to exposure to ultraviolet rays, and are therefore suitable for application in optical applications.
  • benzotriazoles include 4-methyl-2- (2H-benzotriazole-2-yl) phenol (“trade name JF-77” manufactured by Johoku Chemical Industry Co., Ltd.) and 2- (2H-benzotriazole-2-yl).
  • TINUVIN329 manufactured by BASF Japan KK
  • TINUVIN234 manufactured by BASF Japan Ltd.
  • 2,2′-methylenebis [6- (2H-benzotriazole-2-yl) -4-t-octylphenol] (“Adecastab LA-31” manufactured by ADEKA Co., Ltd.) and the like are preferable.
  • a triazine-type ultraviolet absorber is preferably used.
  • examples of such an ultraviolet absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (“Adecastab LA-F70” manufactured by ADEKA Co., Ltd.). ”), And its analogs, hydroxyphenyltriazine-based ultraviolet absorbers (“TINUVIN 477” and “TINUVIN 460” manufactured by BASF Japan Ltd.) and the like.
  • the light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light.
  • Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-1 tetraalkylpiperidine skeleton.
  • hindered amines such as compounds having a 2,2,6,6-1 tetraalkylpiperidine skeleton.
  • bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (“ADEKA STAB LA-77Y” manufactured by ADEKA Corporation) and the like can be mentioned.
  • Lubricants are compounds that are said to have the effect of improving mold releasability, processability, etc. by adjusting the slip between the resin and the metal surface and preventing adhesion or adhesion.
  • higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, fatty acid esters and the like can be mentioned.
  • aliphatic monohydric alcohols having 12 to 18 carbon atoms and aliphatic amides are preferable, and aliphatic amides are more preferable, from the viewpoint of compatibility with the methacrylic resin composition.
  • Aliphatic amides are classified into saturated aliphatic amides and unsaturated aliphatic amides, and unsaturated aliphatic amides are more preferable because a slip effect due to anti-adhesion is expected.
  • unsaturated aliphatic amides N, N'-ethylenebisoleic acid amide ("Slipax O” manufactured by Nihon Kasei Corporation) and N, N'-diorail adipic acid amide (“Slipax ZOA" manufactured by Nihon Kasei Corporation) ") And the like.
  • the release agent examples include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
  • higher alcohols and glycerin fatty acid monoester in combination as a release agent.
  • the ratio is not particularly limited, but the amount of the higher alcohols used: the amount of the glycerin fatty acid monoester used is 2.5: 1 to 3. 5: 1 is preferable, and 2.8: 1 to 3.2: 1 is more preferable.
  • the polymer processing aid is a compound that exerts an effect on thickness accuracy and thinning when molding a methacrylic resin composition.
  • the polymer processing aid is a polymer particle having a particle size of 0.05 to 0.5 ⁇ m, which can be usually produced by an emulsion polymerization method.
  • Antistatic agents include sodium heptyl sulfonate, sodium octyl sulfonate, sodium nonyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium cetyl sulfonate, sodium octadecyl sulfonate, sodium diheptyl sulfonate, heptyl sulfonic acid.
  • potassium octyl sulfonate potassium nonyl sulfonate, potassium decyl sulfonate, potassium dodecyl sulfonate, potassium cetyl sulfonate, potassium octadecyl sulfonate, potassium diheptyl sulfonate, lithium heptyl sulfonate, lithium octyl sulfonate, nonyl sulfonate
  • alkyl sulfonates such as lithium silicate, lithium decyl sulfonate, lithium dodecyl sulfonate, lithium cetyl sulfonate, lithium octadecyl sulfonate, and lithium diheptyl sulfonate.
  • Examples of the flame retardant include metal hydrates having a hydroxyl group or crystalline water such as magnesium hydroxide, aluminum hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, and hydrotalcite, and phosphoric acid such as polyphosphate amine and phosphoric acid ester.
  • Examples include compounds and silicon compounds, including trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and dimethyl ethyl.
  • Phosphate-based flame retardants such as phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, and hydroxyphenyldiphenyl phosphate are preferred.
  • Dyes / pigments include red organic pigments such as parared, fire red, pyrazolone red, thioindico red, and perylene red, blue organic pigments such as cyanine blue and indanslen blue, and green organic pigments such as cyanine green and naphthol green. Pigments are mentioned, and one or more of these can be used.
  • matting agent examples include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, mica, talc, calcium carbonate, barium sulfate, and the like.
  • Anti-sticking agents include fatty acids such as stearic acid and palmitic acid; fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate and sodium palmitate; polyethylene wax, polypropylene wax, montanic acid wax and the like. Waxes; low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene; acrylic resin powders; polyorganosiloxanes such as dimethylpolysiloxane; amide resins such as octadecylamine, alkyl phosphate, fatty acid esters, and ethylenebisstearylamide. Examples thereof include powder, fluororesin powder such as ethylene tetrafluoride resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, and silica.
  • fatty acids such as stearic acid and palmitic acid
  • fatty acid metal salts such as calcium stearate,
  • the impact resistance modifier examples include a core-shell type modifier containing diene-based rubber as a core layer component; and a modifier containing a plurality of rubber particles.
  • fluorescent substance examples include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, and fluorescent bleaching agents.
  • the methacrylic resin (A) and / or the acrylic multilayer polymer (B) and / or the acrylic block copolymer (C) may be added at the time of polymerization, may be added at the time of mixing with the methacrylic resin (A) and / or the acrylic multilayer polymer (B) and / or the acrylic block copolymer (C), or may be added at the time of mixing.
  • the based resin (A) and / or the acrylic multilayer polymer (B) and / or the acrylic block copolymer (C) may be added after mixing.
  • the molded product of the present invention is molded by a melt extrusion method in order to control the dispersed phase of the acrylic block polymer (C).
  • the molded product is also useful as a film, and is satisfactorily processed by, for example, an inflation method, a T-die extrusion method, a calendar method, a solution casting method, or the like, which are ordinary melt extrusion methods.
  • a film having better surface properties can be obtained by simultaneously contacting both sides of the film with a roll or a metal belt, particularly by simultaneously contacting a roll or a metal belt heated to a temperature equal to or higher than the glass transition temperature. It is also possible to obtain.
  • the thickness of the film is preferably 20 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
  • the ratio of the lip opening (Dr) of the die to the thickness (Dt) of the molded product is in the range of 1 ⁇ Dr / Dt ⁇ 20 in the T-die extrusion method. Is preferable, and the range of 3 ⁇ Dr / Dt ⁇ 10 is more preferable.
  • Dr / Dt is less than 1, the acrylic block polymer becomes a spherical phase having a large dispersed particle size and whitens when stress is applied.
  • Dr / Dt exceeds 20, a columnar phase having a large major axis is formed, whitening occurs when stress is applied, and anisotropy increases.
  • the shear rate applied during die discharge is preferably in the range of 200 to 650 / s, more preferably in the range of 300 to 550 / s.
  • the shear rate is less than 200 / s, the shear applied to the block copolymer is small, the dispersed particle size is large, and whitening occurs.
  • the shear rate exceeds 650 / s, the block copolymer is strongly sheared, the dispersed particle size becomes 1 nm or less, and the flexibility of the molded product is not exhibited.
  • the methacrylic melt-extruded molded product of the present invention can be used by laminating it on a metal, plastic or the like.
  • the laminating method include wet laminating, dry laminating, extraction laminating, hot melt laminating, and the like, in which an adhesive is applied to a metal plate such as a steel plate, and then a film is placed on the metal plate and dried and bonded.
  • the film As a method of laminating a film on a plastic part, the film is placed in a mold, and a resin is filled by injection molding. Film insert molding, laminate injection press molding, or preforming the film and then in the mold. Examples include film-in-mold molding in which the resin is placed and filled with resin by injection molding.
  • the methacrylic melt-extruded film of the present invention can be further laminated with a functional layer or a thermoplastic resin film to form a laminated film.
  • the methacrylic melt-extruded film and the functional layer can be laminated to form a laminated film.
  • the functional layer can be formed on one side or both sides of the film. Examples of the functional layer include a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, and the like, and at least one of these layers can be included.
  • the thickness of the functional layer is preferably 0.1 to 20 ⁇ m, more preferably 1 to 10 ⁇ m, and the thickness of the laminated film is preferably 0.1 to 20 ⁇ m.
  • the thickness is preferably 20 to 220 ⁇ m, more preferably 30 to 110 ⁇ m.
  • the methacrylic melt-extruded film and the thermoplastic resin film can be laminated to form a laminated film.
  • the thermoplastic resin film can be formed on one side or both sides of the methacrylic melt-extruded film.
  • the thermoplastic resin of the thermoplastic resin film include various thermoplastic resins such as polyolefin (polyethylene, polypropylene, polymethylpentene, etc.), polystyrene, polycarbonate, polyvinyl chloride, methacrylic resin, nylon, polyethylene terephthalate, and the like. Examples thereof include a copolymer having a plurality of types of monomer units constituting a thermoplastic resin. In the thermoplastic resin film, only one type of thermoplastic resin may be contained, or two or more types of thermoplastic resin may be contained.
  • the thickness of the thermoplastic resin film is preferably 20 to 200 ⁇ m, more preferably 30 to 100 ⁇ m, and the thickness of the methacrylic melt-extruded film is , It is preferably 5 to 100 ⁇ m, and more preferably 10 to 15 ⁇ m.
  • the methacrylic melt-extruded molded product of the present invention can be used as a member for various purposes.
  • Specific applications include, for example, signboard parts such as advertising towers, stand signs, sleeve signs, column signboards, roof signs, and marking films; display parts such as showcases, dividers, and store displays; fluorescent lamp covers, mood lighting.
  • Lighting parts such as covers, lamp shades, light ceilings, light walls, chandeliers; interior parts such as furniture, pendants, mirrors; doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, roofs of leisure buildings, etc.
  • Transport equipment related parts such as; nameplates for audiovisual images, stereo covers, TV protective masks, vending machines, mobile phones, personal computers and other electronic equipment parts; incubators, roentgen parts and other medical equipment parts; machine covers, instrument covers, etc.
  • Equipment-related parts such as experimental equipment, rulers, dials, observation windows; optical parts such as liquid crystal protective plates, light guide plates, light guide films, frennel lenses, lenticular lenses, front plates of various displays, diffusers, etc .; road signs, Traffic-related parts such as information boards, curved mirrors, soundproof walls; other greenhouses, large water tanks, box water tanks, bathroom parts, clock panels, bathtubs, sanitary, desk mats, game parts, toys, face protection masks during welding, Examples include backsheets for solar cells, front seats for flexible solar cells; surface materials used for personal computers, mobile phones, furniture, vending machines, bathroom members, and the like.
  • the methacrylic melt-extruded molded product of the present invention particularly the laminated laminated product of the film, includes automobile interior / exterior materials, daily necessities, wallpaper, coating alternative applications, housings for furniture and electrical equipment, and OA equipment such as facsimiles. It can be used for housings, flooring materials, electrical or electronic equipment parts, bathroom equipment, etc.
  • the methacrylic melt-extruded product of the present invention contains a methacrylic resin (A), an acrylic multilayer polymer (B), and an acrylic block copolymer (C), and is an acrylic block polymer.
  • A methacrylic resin
  • B acrylic multilayer polymer
  • C acrylic block copolymer
  • the methacrylic melt-extruded molded product which is a film, was evaluated by the following method.
  • a resin film (thickness 75 ⁇ m) was cut into 50 mm ⁇ 50 mm pieces to obtain test pieces, and haze was measured at 23 ° C. according to JIS K7105 and evaluated according to the following criteria. ⁇ : 0.5% or less ⁇ : 0.5% to 1.0% ⁇ : 1.0% or more [ ⁇ haze before and after heating]
  • a resin film (thickness 75 ⁇ m) was cut into 100 mm ⁇ 100 mm pieces to obtain test pieces, which were heated in an oven set at 100 ° C. for 30 minutes. The haze was measured for the sample immediately after heating, and the difference from the haze value before heating was calculated as ⁇ haze and evaluated according to the following criteria. ⁇ : 0.5% or less ⁇ : More than 0.5% and less than 1.0% ⁇ : 1.0% or more
  • MIT flexibility A test piece was taken from the center of a film having a thickness of 75 ⁇ m, and the number of times it was bent in a direction perpendicular to the film flow method was measured by a method conforming to ISO 5626 (JIS P8115 (2001)) and evaluated according to the following criteria. .. ⁇ : 60 times or more ⁇ : 30 times or more ⁇ : Less than 30 times
  • Block copolymer (C-1) Block copolymer (C-1): Consists of [methyl methacrylate (MMA) polymer block (c1)]-[n-butyl acrylate (BA) / benzyl acrylate (BzA) copolymer block (c2)].
  • the weight average molecular weight (Mw) is 120,000
  • the mass ratio of the polymer blocks (c1): (c2) is 50:50
  • the mass ratio of each monomer (MMA: BA) (50:50).
  • a diblock copolymer was produced according to a conventional method.
  • Block Copolymer (C-2) Block copolymer (C-2): [Methyl methacrylate (MMA) polymer block (c1)]-[n-butyl acrylate (BA) polymer block (c2)]-[Methyl methacrylate (MMA) polymer block (MMA) c1)], the weight average molecular weight (Mw) is 70,000, and the mass ratio (b1) :( b2) :( b1) of the polymer block is 14.3: 50.0: 35.7, respectively.
  • a triblock copolymer having a monomer mass ratio (MMA: BA) (50:50).
  • Block Copolymer (C-3) Block copolymer (C-3): [Methyl methacrylate (MMA) polymer block (c1)]-[n-butyl acrylate (BA) polymer block (c2)]-[Methyl methacrylate (MMA) polymer block (MMA) c1)], the weight average molecular weight (Mw) is 65,000, the mass ratio of the polymer blocks (c1) :( c2) :( c1) is 15:70:15, and the mass ratio of each monomer.
  • a triblock copolymer in which (MMA: BA) (30:70).
  • Block copolymer (C-4) [Methyl methacrylate (MMA) polymer block (c1)]-[n-butyl acrylate (BA) polymer block (c2)]-[Methyl methacrylate (MMA) polymer block (MMA) c1)], the weight average molecular weight (Mw) is 120,000, and the mass ratio (c1) :( c2) :( c1) of the polymer block is 8.5: 83: 8.5, each unit amount.
  • a triblock copolymer having a body mass ratio (MMA: BA) (17:83).
  • Example 1 47 parts of acrylic multilayer polymer (B-1) pellets, 50 parts of methacrylic resin (A-1) (MMA-derived structural unit 100%, weight average molecular weight 80,000), acrylic block copolymer (C) Three parts of the pellets of -1) were kneaded using a twin-screw extruder and pelletized using a pelletizer to obtain a thermoplastic resin (R1).
  • A-1 methacrylic resin
  • R1 thermoplastic resin
  • thermoplastic resin (R1) is melt-extruded at a discharge rate of 40 kg / h and a resin temperature of 260 ° C. using a single-screw vent extruder having a screw diameter of 50 mm and a T-die having a width of 500 mm and a lip opening of 0.5 mm. To obtain a film-like melt. The shear rate was 480 / s. Next, the melt was sandwiched at a linear pressure of 30 kg / cm by a first nip roll having a spacing of 50 ⁇ m composed of a mirror-finished metal elastic roll whose temperature was adjusted to 85 ° C. and a mirror-finished metal rigid body roll whose temperature was adjusted to 90 ° C.
  • a second nip roll consisting of a mirror-finished metal rigid body roll whose temperature has been adjusted to 90 ° C. and a mirror-finished metal rigid body roll whose temperature has been adjusted to 85 ° C.
  • a single-layer resin film (1) (acetone insoluble content 28%) having a temperature of 75 ⁇ m was obtained.
  • the resin film (1) was excellent in transparency, surface hardness, stress whitening resistance, and flexibility.
  • Example 2 A resin film (2) (acetone insoluble content 28%) was obtained by the same method as in Example 1 except that C-2 was used as the acrylic block copolymer.
  • C-2 was used as the acrylic block copolymer.
  • the morphology of the block copolymer of the obtained resin film (2) was confirmed by the above-mentioned measuring method, it was found to be columnar dispersed in a minor axis of 20 nm and a major axis of 100 nm.
  • the evaluation results are shown in Table 1.
  • the resin film (2) was excellent in transparency, surface hardness, stress whitening resistance, and flexibility.
  • Example 3 Resin film (3) (acetone insoluble content 29%) in the same manner as in Example 1 except that the acrylic multilayer polymer (B-1) was changed to 49 parts and C-3 was changed to 1 part as an acrylic block copolymer. ) was obtained.
  • the morphology of the block copolymer of the obtained resin film (3) was confirmed by the above-mentioned measuring method, it was found to be columnar dispersed in a minor axis of 20 nm and a major axis of 100 nm.
  • the evaluation results are shown in Table 1.
  • the resin film (3) was excellent in transparency, surface hardness, stress whitening resistance, and flexibility.
  • Example 4 Same as Example 1 except that the acrylic multilayer polymer (B-1) was changed to 65 parts, the methacrylic resin (A-1) was changed to 30 parts, and the acrylic block copolymer (C-2) was changed to 5 parts.
  • a resin film (4) (acetone insoluble content 39%) was obtained by the method.
  • the morphology of the block copolymer of the obtained resin film (4) was confirmed by the above-mentioned measuring method, it was found to be columnar dispersed in a minor axis of 20 nm and a major axis of 200 nm.
  • the evaluation results are shown in Table 1.
  • the resin film (4) was excellent in transparency, surface hardness, stress whitening resistance, and particularly flexibility.
  • Example 5 Same as Example 1 except that the acrylic multilayer polymer (B-1) was changed to 60 parts, the methacrylic resin (A-1) was changed to 30 parts, and the acrylic block copolymer (C-1) was changed to 10 parts.
  • a resin film (5) (acetone insoluble content 36%) was obtained by the method.
  • the morphology of the block copolymer of the obtained resin film (5) was confirmed by the above-mentioned measuring method, it was found to be columnar dispersed in a minor axis of 20 nm and a major axis of 300 nm.
  • the evaluation results are shown in Table 1.
  • the resin film (5) was excellent in transparency, surface hardness, stress whitening resistance, and particularly flexibility.
  • Example 6 Resin film (6) (acetone insoluble content 28%) in the same manner as in Example 1 except that the methacrylic resin (A-2) was changed to 50 parts and the acrylic block copolymer (C-2) was changed to 3 parts.
  • the morphology of the block copolymer of the obtained resin film (6) was confirmed by the above-mentioned measuring method, it was found to be columnar dispersed at a minor axis of 20 nm and a major axis of 200 nm.
  • the evaluation results are shown in Table 1.
  • the resin film (6) was excellent in transparency, surface hardness, stress whitening resistance, and particularly flexibility.
  • Example 7 Example 1 except that the acrylic multilayer polymer (B-1) was changed to 40 parts, the acrylic multilayer polymer (B-2) was changed to 5 parts, and the acrylic block copolymer (C-2) was changed to 5 parts.
  • a resin film (7) (acetone insoluble content 27%) was obtained in the same manner as above.
  • the morphology of the block copolymer of the obtained resin film (7) was confirmed by the above-mentioned measuring method, it was found to be columnar dispersed at a minor axis of 20 nm and a major axis of 200 nm.
  • the evaluation results are shown in Table 1. Although the resin film (7) was slightly inferior in transparency, it was excellent in pencil hardness, stress whitening resistance, and particularly flexibility.
  • Example 3 The resin film was formed in the same manner as in Example 1 except that the acrylic multilayer polymer (B-1) was changed to 40 parts and the acrylic multilayer polymer (B-2) was changed to 10 parts instead of the acrylic block copolymer. (10) (acetone insoluble content 37%) was obtained. The evaluation results are shown in Table 1. The transparency of the resin film (10) deteriorated due to the addition of the multilayer polymer having a large particle size.
  • Example 4 A resin film (11) (acetone insoluble content: 30%) was obtained in the same manner as in Example 1 except that the acrylic multilayer polymer (B-1) was changed to 50 parts and the acrylic block copolymer was changed to 0 parts. .. The evaluation results are shown in Table 1. Since the resin film (11) does not contain a block copolymer, it is predicted that the resin film (11) is inferior in flexibility and easily cracked during processing.
  • Example 6 A resin film (13) (acetone insoluble content 36%) having a thickness of 75 ⁇ m was obtained by the same method as in Example 5 except that the lip opening degree was changed to 1.5 mm.
  • the morphology of the block copolymer of the obtained resin film (13) was confirmed by the above-mentioned measuring method, it was found to be spherically dispersed at a diameter of 200 nm.
  • the evaluation results are shown in Table 1.
  • the resin film (13) had a large dispersed particle size of the block copolymer, and whitening occurred when it was bent.
  • Example 8 Example 1 except that the pellets were changed to 48 parts of the multilayer structure polymer particles (B-1), 50 parts of the methacrylic resin (A-1) pellets, and 2 parts of the block copolymer (C-2) pellets.
  • a resin film (14) (acetone insoluble content 28.8% by mass) was obtained in the same manner. The evaluation results are shown in Table 1.
  • the resin film (14) was excellent in transparency, surface hardness, moldability, and vapor deposition property.
  • Example 9 Example 1 except that the pellets were changed to 66 parts of the multilayer structure polymer particles (B-1), 30 parts of the methacrylic resin (A-2) pellets, and 4 parts of the block copolymer (C-2) pellets.
  • a resin film (15) (acetone insoluble content 39.6% by mass) was obtained in the same manner. The evaluation results are shown in Table 1.
  • the resin film (15) was excellent in transparency, surface hardness, moldability, and vapor deposition property.
  • Example 10 Examples except that the pellets were changed to 45 parts of the multilayer structure polymer particles (B-1), 52 parts of the methacrylic resin (A-2) pellets, and 3 parts of the acrylic block copolymer (C-3) pellets.
  • a resin film (16) (acetone insoluble content 27.0% by mass) was obtained in the same manner as in 1. The evaluation results are shown in Table 1.
  • the resin film (16) was excellent in transparency, surface hardness, moldability, and vapor deposition property.
  • Example 11 Example 1 except that the pellets were changed to 30 parts of the multilayer structure polymer particles (B-1), 66 parts of the methacrylic resin (A-1) pellets, and 4 parts of the block copolymer (C-2) pellets.
  • a resin film (17) (acetone insoluble content 16.8% by mass) was obtained in the same manner. The evaluation results are shown in Table 1.
  • the resin film (17) was excellent in transparency, surface hardness, moldability, and vapor deposition property.
  • Example 12 Examples except that the pellets were changed to 45 parts of the multilayer structure polymer particles (B-1), 51 parts of the methacrylic resin (A-2) pellets, and 4 parts of the acrylic block copolymer (C-4) pellets.
  • a resin film (18) (acetone insoluble content 27.0% by mass) was obtained in the same manner as in 1. The evaluation results are shown in Table 1.
  • the resin film (18) was excellent in surface hardness, moldability, and vapor deposition property, although the haze was slightly inferior.
  • Example 7 Example 1 except that the pellets were changed to 36 parts of the multilayer structure polymer particles (B-2), 59 parts of the methacrylic resin (A-2) pellets, and 5 parts of the block copolymer (C-2) pellets.
  • a resin film (19) (acetone insoluble content 23.8% by volume) was obtained in the same manner. The evaluation results are shown in Table 1. In the resin film (19), an increase in haze was observed after heating, and cloudiness was observed in the appearance after vapor deposition and molding.
  • Example 10 Comparative Example 10 except that the pellets were changed to 30 parts of the multilayer structure polymer particles (B-1), 20 parts of the methacrylic resin (A-1) pellets, and 50 parts of the block copolymer (C-2) pellets.
  • a resin film (22) (acetone insoluble content 18.0% by mass) was obtained in the same manner. The evaluation results are shown in Table 1. The pencil hardness of the resin film (22) was reduced.
  • the film of the present invention is excellent in transparency, surface smoothness, bending whitening resistance, pencil hardness, flexibility, moldability and appearance after molding, and is suitable for decorative applications. ing.

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PCT/JP2020/028397 2019-07-25 2020-07-22 メタクリル系溶融押出成形体 Ceased WO2021015226A1 (ja)

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