WO2016186121A1 - Transparent resin composition, and manufacturing method for same - Google Patents

Transparent resin composition, and manufacturing method for same Download PDF

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Publication number
WO2016186121A1
WO2016186121A1 PCT/JP2016/064684 JP2016064684W WO2016186121A1 WO 2016186121 A1 WO2016186121 A1 WO 2016186121A1 JP 2016064684 W JP2016064684 W JP 2016064684W WO 2016186121 A1 WO2016186121 A1 WO 2016186121A1
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Prior art keywords
resin
styrene
resin composition
mass
copolymer
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PCT/JP2016/064684
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French (fr)
Japanese (ja)
Inventor
広平 西野
智輝 小林
裕一 下木場
黒川　欽也
Original Assignee
デンカ株式会社
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Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to KR1020177035721A priority Critical patent/KR20180011140A/en
Priority to CN201680029252.4A priority patent/CN107614622A/en
Priority to DE112016002240.9T priority patent/DE112016002240T5/en
Priority to JP2017519375A priority patent/JPWO2016186121A1/en
Publication of WO2016186121A1 publication Critical patent/WO2016186121A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C08L25/08—Copolymers of styrene
    • 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
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
    • B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • 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
    • C08J2325/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/14—Copolymers of styrene with unsaturated esters
    • 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
    • C08J2333/00—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
    • C08J2333/04—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
    • C08J2333/06—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
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C08J2335/00—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 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; Derivatives of such polymers
    • C08J2335/06—Copolymers with vinyl aromatic monomers
    • 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
    • C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
    • 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
    • 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
    • C08J2435/00—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 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; Derivatives of such polymers
    • C08J2435/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the present invention relates to a transparent resin composition and a method for producing the same.
  • Transparent resins such as methacrylic resin, methyl methacrylate-styrene copolymer and styrene-acrylonitrile copolymer are used in various applications such as home appliance parts, automobile parts, food packaging containers, building materials, sundries, etc. . Further, taking advantage of excellent transparency, it is also used as an optical member for liquid crystal displays such as an optical film, a diffusion plate, and a light guide plate. These transparent resins have good optical properties such as transparency, but have problems such as low heat resistance, and have been used only for limited applications. There are Patent Documents 1 and 2 as techniques for increasing the heat resistance of a transparent resin.
  • An object of the present invention is to provide a novel transparent resin composition and a method for producing the same.
  • a styrene resin (A) comprising a copolymer containing unsaturated dicarboxylic acid anhydride monomer units and a transparent resin (B) other than the styrene resin (A), and based on ASTM D1003 A resin composition having a measured total light transmittance of 2% thickness of 88% or more and a haze of 0.3% or less.
  • the styrene resin (A) contains 45 to 90% by mass of a styrene monomer unit, an unsaturated dicarboxylic acid anhydride monomer unit, a (meth) acrylic acid monomer unit, (meth) It is a copolymer comprising 10 to 55% by mass of at least one monomer unit selected from acrylic ester monomer units and other vinyl monomer units copolymerizable therewith.
  • the transparent resin (B) comprises at least one selected from a methacrylic resin, a methyl methacrylate-styrene copolymer, and a styrene-acrylonitrile copolymer (1) or (2 ).
  • Separate quantitative feeders for the styrene resin (A) comprising a copolymer containing unsaturated dicarboxylic acid anhydride monomer units and the transparent resin (B) other than the styrene resin (A).
  • the manufacturing method of a resin composition provided with the process of using and supplying to an extruder and melt-kneading.
  • Styrenic resin (A) comprises 45 to 90% by mass of styrene monomer units, unsaturated dicarboxylic acid anhydride monomer units, (meth) acrylic acid monomer units, (meth) It is a copolymer comprising 10 to 55% by mass of at least one monomer unit selected from acrylic ester monomer units and other vinyl monomer units copolymerizable therewith.
  • the transparent resin (B) comprises at least one selected from a methacrylic resin, a methyl methacrylate-styrene copolymer, and a styrene-acrylonitrile copolymer (7) or (8 The manufacturing method of the resin composition as described in).
  • the resin composition of the present invention is excellent in transparency, it is useful for parts of home appliances, automobile parts, building materials, optical members, food containers, etc. that are required to have heat resistance and good appearance, particularly at the time of injection molding. A molded article having no appearance defect is obtained.
  • the transparent resin composition of the present invention comprises a styrene resin (A) comprising a copolymer containing unsaturated dicarboxylic acid anhydride monomer units, and a transparent resin (B) other than the styrene resin (A).
  • A styrene resin
  • B transparent resin
  • the total light transmittance of 2 mm thickness measured based on ASTM D1003 is 88% or more, and Haze is 0.3% or less.
  • Such a resin composition is obtained by supplying the styrene resin (A) and the transparent resin (B) to an extruder using separate quantitative feeders and melt-kneading them.
  • Styrenic resin (A) is a copolymer containing a styrene monomer unit and an unsaturated dicarboxylic anhydride monomer unit, a (meth) acrylic acid monomer unit, (meth) It may also contain at least one monomer unit selected from an acrylate ester monomer unit and other vinyl monomers copolymerizable therewith.
  • the styrene resin (A) include a styrene-methyl methacrylate-maleic anhydride copolymer, a styrene-maleic anhydride copolymer, and the like.
  • Styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, pt-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl -P-methylstyrene and the like. Of these, styrene is preferred. Styrenic monomers may be used alone or in combination of two or more.
  • the unsaturated dicarboxylic acid anhydride monomer includes maleic anhydride, itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride, and the like. Of these, maleic anhydride is preferred.
  • the unsaturated dicarboxylic acid anhydride monomer may be used alone or in combination of two or more.
  • (Meth) acrylic acid monomer units are acrylic acid, methacrylic acid and the like, and among these, methacrylic acid is preferable.
  • (Meth) acrylic acid ester monomer units include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, etc.
  • acrylate monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate.
  • a methyl methacrylate unit is preferable.
  • the (meth) acrylic acid ester monomer may be used alone or in combination of two or more.
  • acrylonitrile monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile and fumaronitrile, and N-substituted maleimide monomers such as N-phenylmaleimide may be used. it can.
  • the structural unit of the styrene resin (A) is 45 to 90% by mass of a styrene monomer unit, an unsaturated dicarboxylic acid anhydride monomer unit, a (meth) acrylic acid monomer unit, (meth).
  • the content is preferably 10 to 55% by mass of at least one monomer selected from acrylic acid ester monomer units and other vinyl monomers copolymerizable therewith.
  • the styrene monomer unit is 45 to 85% by mass
  • the unsaturated dicarboxylic acid anhydride monomer unit is 10 to 30% by mass
  • the (meth) acrylic acid ester monomer unit is 5 to 45% by mass.
  • it has an excellent balance between heat resistance and strength.
  • composition analysis of each monomer unit is a value measured by the C-13 NMR method under the measurement conditions described below.
  • the weight average molecular weight (Mw) of the styrenic resin (A) is preferably 50,000 to 300,000, and more preferably 100,000 to 250,000.
  • a weight average molecular weight (Mw) in the range of 50,000 to 300,000 is preferable because of a good balance between strength and moldability.
  • the weight average molecular weight (Mw) can be controlled by the polymerization temperature and polymerization time in the polymerization process, the type and addition amount of the polymerization initiator, the type and addition amount of the chain transfer agent, the type and amount of the solvent used during the polymerization, and the like. it can.
  • the weight average molecular weight (Mw) is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and is a value measured under the measurement conditions described below.
  • Device name SYSTEM-21 Shodex (manufactured by Showa Denko) Column: 3 series PL gel MIXED-B Temperature: 40 ° C Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
  • a known method can be adopted as the polymerization method of the styrene resin (A).
  • the radical polymerization method is preferable because it is a simple process and excellent in productivity.
  • the styrene resin (A) As a method for producing the styrene resin (A), a known method can be employed. For example, it can be produced by solution polymerization, bulk polymerization or the like. Moreover, any of a continuous method and a batch method is applicable. In the copolymerization of styrene monomer and unsaturated dicarboxylic acid anhydride monomer, the alternating copolymerization is high, so the copolymerization can be achieved by polymerizing while adding unsaturated dicarboxylic acid anhydride monomer separately. Solution polymerization is preferred because the polymerization composition can be made uniform.
  • the solvent for the solution polymerization is preferably non-polymerizable from the viewpoint that by-products are difficult to be produced and have few adverse effects.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, 1,4- And ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, 1,4- And ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like.
  • a polymerization initiator and a chain transfer agent can be used, and the polymerization temperature is preferably in the range of 70 to 180 ° C.
  • the polymerization initiator include dibenzoyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxide.
  • Peroxides such as oxy-2-ethylhexanoate, t-butylperoxyacetate, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate, azobisisobutyronitrile, These are azo compounds such as azobiscyclohexanecarbonitrile, azobismethylpropionitrile, azobismethylbutyronitrile, etc., and these may be used alone or in combination. Two or more of these polymerization initiators can be used in combination. Of these, organic peroxides having a 10-hour half-life temperature of 70 to 110 ° C. are preferably used.
  • chain transfer agent examples include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, and terpinolene.
  • a devolatilization method for removing volatile components such as unreacted monomers and a solvent used for solution polymerization from the solution after completion of the polymerization of the styrene-based resin (A) a known method can be adopted.
  • a vacuum devolatilization tank with a preheater or a vented devolatilization extruder can be used.
  • the devolatilized molten styrene resin (A) is transferred to a granulation process, extruded into a strand shape from a porous die, and processed into a pellet shape by a cold cut method, an air hot cut method, or an underwater hot cut method. be able to.
  • the 2 mm-thick total light transmittance measured based on ASTM D1003 of the styrene resin (A) in the present invention is preferably 88% or more, and Haze is preferably 0.5% or less, more preferably.
  • the total light transmittance is 90% or more, and the haze is 0.3% or less.
  • the Vicat softening temperature of the styrenic resin (A) obtained at a load of 50 N and a heating rate of 50 ° C./hour is preferably 115 ° C. or higher, more preferably 125 ° C. or higher.
  • the higher the Vicat softening temperature the higher the effect of improving the heat resistance of the methacrylic resin, which is preferable.
  • the Vicat softening temperature of the styrenic resin (A) can be adjusted by the content of heat-resistant monomers such as unsaturated dicarboxylic acid anhydride monomer units and (meth) acrylic acid monomer units. .
  • the transparent resin (B) is a resin that is transparent and compatible with the styrene resin (A) at the temperature during melt-kneading and molding, such as methacrylic resin, methyl methacrylate-styrene copolymer. And styrene-acrylonitrile copolymers. Among these, a methacrylic resin is preferable because of its excellent optical properties.
  • the constituent units of the methyl methacrylate-styrene copolymer system copolymer are preferably 70 to 97% by mass of methyl methacrylate units and 3 to 30% by mass of styrene.
  • the structural unit of the styrene-acrylonitrile copolymer is preferably 70 to 85% by mass of styrene and 15 to 30% by mass of acrylonitrile.
  • methacrylic resin methyl methacrylate-styrene copolymer, and styrene-acrylonitrile copolymer, commercially available general ones can be used.
  • the shape may be pellets or beads, but it is preferable that the particle size distribution is uniform.
  • the total light transmittance of 2 mm thickness measured based on ASTM D1003 of the transparent resin (B) in the present invention is preferably 88% or more, and Haze is preferably 0.5% or less, more preferably, The total light transmittance is 90% or more and Haze is 0.3% or less.
  • the styrene resin (A) and the transparent resin (B) need to be quantitatively supplied to the extruder using separate quantitative feeders.
  • the raw material charging port of the extruder may be provided in one place, or a plurality may be provided depending on the number of metering feeders.
  • the hopper is fed to the extruder provided at one place of the raw material charging port, or the extruder is provided with only one quantitative feeder.
  • the method of supplying the blended resin in a lump when the obtained resin composition is injection-molded, fluctuation occurs inside the molded body, resulting in poor appearance.
  • This fluctuation is due to non-uniformity of the refractive index, and occurs when the blending ratio of the styrene resin (A) and the transparent resin (B) varies in the resin composition.
  • the molten resin that flows in from the gate fills the mold while spreading like a balloon in the flow direction. Observed. When the fluctuation becomes noticeable, it may appear streaks. This fluctuation is sometimes called striae.
  • segregation occurs due to the difference in shape and density between the styrene resin (A) and the transparent resin (B), and the blending ratio fluctuates. End up.
  • styrene resin (A) or transparent resin (B) Two or more types can be used as long as they are compatible with each other, but it is necessary to use different feeders for each.
  • the supply ratio of the styrene resin (A) and the transparent resin (B) may be arbitrarily determined within a range in which both are compatible.
  • a feeder is a device that supplies pellet or bead-shaped raw material resin to an extruder, and a known material can be used. However, since quantitative raw material supply is essential, a quantitative feeder must be used. . Examples of the quantitative feeder include loss-in-weight feeders, positive displacement feeders, and heavy-weight belt feeders. Loss-in-weight feeders are particularly preferable, and supply accuracy is preferably within ⁇ 1%. . It is preferable to control each feeder in conjunction with each other, and it is preferable to perform control so that the supply amount of other feeders is a constant ratio with respect to the supply amount of the main feeder.
  • the raw material resin supplied to the extruder is melted and kneaded continuously in the extruder, extruded into a strand form from a perforated die, a pellet-shaped resin composition by a cold cut method, an air hot cut method, or an underwater hot cut method. Is obtained.
  • a well-known apparatus can be used for an extruder, for example, a twin screw extruder, a single screw extruder, a multi screw extruder, a continuous kneader with a twin screw rotor, etc. are mentioned.
  • additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a lubricant, a dye, and a flame retardant may be blended as long as transparency is not impaired.
  • the contents of the styrene resin (A) and the transparent resin (B) in the resin composition are preferably 5 to 50% by mass and 95 to 50% by mass, respectively, more preferably 15 to 50% by mass and 85%, respectively. To 50% by mass, more preferably 15 to 35% by mass and 85 to 65% by mass, respectively.
  • the total light transmittance with a thickness of 2 mm measured based on ASTM D1003 of the resin composition in the present invention is 88% or more, and Haze is 0.3% or less.
  • the total light transmittance is preferably 90% or more.
  • the haze is preferably 0.2% or less.
  • the Vicat softening temperature of the resin composition determined at a load of 50 N and a heating rate of 50 ° C./hour is preferably 110 ° C. or higher, more preferably 113 ° C. or higher, and even more preferably 115 ° C. That's it.
  • the molding method of the resin composition a known method can be adopted.
  • injection molding, press molding, sheet molding and the like can be mentioned.
  • injection molding is preferable because no fluctuating molding defects occur inside the molded body. Fluctuation-like molding defects are particularly noticeable with injection molded articles having a large thickness, but the resin composition of the present invention does not cause poor appearance even with an injection molded article having a large thickness.
  • a 120 liter autoclave equipped with a stirrer was charged with 3.6 kg of a 20% maleic anhydride solution, 24 kg of styrene, 8.8 kg of methyl methacrylate, and 20 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. Then, the temperature was raised to 88 ° C. over 40 minutes with stirring. After maintaining the temperature at 88 ° C., a 20% maleic anhydride solution was added at a rate of 2.7 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 375 g / hour. The addition continued continuously over 8 hours.
  • the polymerization liquid is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and styrene in the form of pellets is formed by devolatilizing methyl isobutyl ketone and a small amount of unreacted monomer, and extruding and cutting into strands.
  • a resin (A-1) was obtained.
  • the resulting A-1 was subjected to composition analysis by C-13 NMR method. Furthermore, molecular weight measurement was performed with a GPC apparatus. As a result of composition analysis, the structural unit of A-1 was 60% by mass of a styrene monomer unit, 22% of a methyl methacrylate monomer unit, and 18% by mass of a maleic anhydride monomer unit.
  • the weight average molecular weight (Mw) was 160,000, and Mw / Mn which is a ratio with the number average molecular weight (Mn) was 2.4.
  • the 2 mmt specular plate molded by injection molding had a total light transmittance of 91% and a haze of 0.2%.
  • the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 133 ° C.
  • a 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as A-1.
  • a 120 liter autoclave equipped with a stirrer was charged with 2.8 kg of a 20% maleic anhydride solution, 25.6 kg of styrene, 8.8 kg of methyl methacrylate, and 20 g of t-dodecyl mercaptan. The temperature was raised to 88 ° C. over 40 minutes with stirring. While maintaining the temperature at 88 ° C.
  • the 20% maleic anhydride solution was added at a rate of 2.1 kg / hour and the 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 500 g / hour, respectively. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C. over 4 hours at a temperature rising rate of 8 ° C./hour while maintaining the addition rate of 2.1 kg / hour as it was.
  • the addition of the 20% maleic anhydride solution was stopped when the amount of addition reached 25.2 kg.
  • the polymerization liquid which has been held at 120 ° C. for 1 hour to finish the polymerization is continuously fed to a twin-screw devolatilizing extruder using a gear pump to remove methyl isobutyl ketone and a small amount of unreacted monomer.
  • the styrene resin (A-2) in the form of pellets was obtained by volatilization treatment and extrusion cutting into strands.
  • the composition analysis, molecular weight, and total light transmittance were measured in the same manner as in A-1.
  • the constituent unit of A-2 was 64% by mass of a styrene monomer unit, 22% of a methyl methacrylate monomer unit, and 14% by mass of a maleic anhydride monomer unit.
  • the weight average molecular weight (Mw) was 170,000 and Mw / Mn which is a ratio with the number average molecular weight (Mn) was 2.6.
  • the 2 mmt specular plate molded by injection molding had a total light transmittance of 91% and a haze of 0.2%.
  • the Vicat softening temperature obtained at a load of 50 N and a heating rate of 50 ° C./hour was 126 ° C.
  • the temperature was raised to 92 ° C. over 40 minutes with stirring. While maintaining the temperature at 92 ° C. after the temperature rise, a 25% maleic acid-free aqueous solution and a 2% t-butylperoxy-2-ethylhexanoate solution were successively added.
  • the 25% maleic anhydride solution was 3.96 kg / hour from the 4th hour to the start of the addition, 3.17 kg / hour from the 4th to the 7th hour, and 1.58 kg from the 7th to the 10th hour. / Hour, the addition speed was changed stepwise so that the addition speed was 0.54 kg / hour from the 10th hour to the 13th hour, and a total of 31.71 kg was added.
  • the 2% t-butylperoxy-2-ethylhexanoate solution has a rate of addition of 0.24 kg / hour from the start of the addition to 7 hours and 0.39 kg / hour from the 7th to 13th hours.
  • the addition speed was changed stepwise so that a total of 4.02 kg was added.
  • the polymerization temperature is maintained at 92 ° C. until 7 hours from the start of the addition, and then heated to 116 ° C. over 6 hours at a rate of 4 ° C./hour, and further maintained at 116 ° C. for 1 hour for polymerization. Was terminated.
  • the polymerization liquid is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and styrene in the form of pellets is formed by devolatilizing methyl isobutyl ketone and a small amount of unreacted monomer, and extruding and cutting into strands.
  • a resin (A-3) was obtained.
  • the composition analysis, molecular weight, and total light transmittance were measured in the same manner as in A-1.
  • the constitutional unit of A-3 was 60% by mass of a styrene monomer unit, 18% of a methyl methacrylate monomer unit, and 22% by mass of a maleic anhydride monomer unit.
  • the weight average molecular weight (Mw) was 160,000, and Mw / Mn which is a ratio with the number average molecular weight (Mn) was 2.4.
  • the 2 mmt specular plate molded by injection molding had a total light transmittance of 90% and a haze of 0.2%.
  • the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 142 ° C.
  • the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 108 ° C.
  • Transparent resin (B-2) As the transparent resin (B-2), a methyl methacrylate-styrene copolymer having 80% by mass of methyl methacrylate units and 20% by mass of styrene units was used. In accordance with JIS K7206, the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 104 ° C.
  • Example 1 to 6 Comparative Examples 1 to 6> Styrenic resin (A) and transparent resin (B) were blended as shown in Table 1 and melt kneaded using an extruder to obtain a resin composition.
  • the styrenic resin (A) and the transparent resin (B) were supplied to the extruder using separate quantitative feeders.
  • the supply amount of the transparent resin (B) was set to 15 kg / hr in Examples 1 to 3, 19 kg / hr in Example 4, 10 kg / hr in Example 5, 15 kg / hr in Example 6, and styrene resin (
  • the supply amount of A) was controlled so as to be the mixing ratio shown in Table 1 (total supply amount was 20 kg / hr).
  • a loss-in-weight feeder (CE-W-1 manufactured by Kubota Corporation) was used.
  • pellets of the styrene resin (A) and the transparent resin (B) were dry blended at the blending ratio shown in Table 1, and then supplied to the extruder using the same feeder.
  • the supply amount of the dry blended pellets was set to 20 kg / hr.
  • a twin screw extruder (TEM-26SX manufactured by Toshiba Machine Co., Ltd.) was used, the cylinder temperature was set to 240 ° C., and the screw rotation speed was set to 250 rpm.
  • the Vicat softening point was measured according to JIS K7206: 1999 using 50 specimens (load 50 N, temperature rising rate 50 ° C./hour) with a test piece of 10 mm ⁇ 10 mm and a thickness of 4 mm.
  • the measuring machine used the Toyo Seiki Seisakusho Co., Ltd. HDT & VSPT test apparatus.
  • Total light transmittance, Haze The total light transmittance and Haze were 90 mm in length, 55 mm in width, and 2 mm in thickness formed using an injection molding machine (IS-50EPN, manufactured by Toshiba Machine Co., Ltd.) under molding conditions of a cylinder temperature of 240 ° C. and a mold temperature of 70 ° C.
  • the specular plate was measured using a haze meter (NDH-1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) according to ASTM D1003.
  • the resin composition of the present invention is transparent, excellent in appearance, and excellent in heat resistance, it is useful for home appliance parts, automobile parts, building materials, optical members, food containers and the like. In particular, there is no appearance defect in injection molding, and it can be suitably used.

Abstract

An objective of the present invention is to provide a resin composition exhibiting excellent transparency and heat resistance, and which has no externally visible defects when injection molded. This resin composition contains: a styrene resin (A) comprising a copolymer including an unsaturated dicarboxylic acid anhydride monomer unit; and a transparent resin (B) other than the styrene resin (A). When measured according to ASTM D1003 at a thickness of 2mm, the resin composition has a total luminous transmittance of at least 88% and a haze value of at most 0.3%. The styrene resin (A) is preferably a copolymer comprising 45-90 mass% of a styrene monomer unit, and 10-55 mass% of an unsaturated dicarboxylic acid anhydride monomer unit, a (meth)acrylic acid monomer unit, a (meth)acrylic acid ester monomer unit, etc. The transparent resin (B) is preferably at least one selected from a methacrylic resin, a methyl methacrylate-styrene copolymer, and a styrene-acrylonitrile copolymer.

Description

透明な樹脂組成物及びその製造方法Transparent resin composition and method for producing the same
　本発明は、透明な樹脂組成物及びその製造方法に関するものである。 The present invention relates to a transparent resin composition and a method for producing the same.
　メタクリル樹脂、メチルメタクリレート－スチレン系共重合体やスチレン－アクリロニトリル系共重合体等の透明樹脂は、家電製品の部品や自動車部品、食品包装容器、建材、雑貨等の様々な用途に用いられている。また、優れた透明性を活かして、光学フィルムや拡散板、導光板等の液晶ディスプレイ用の光学部材としても使用されている。これらの透明樹脂は透明性等の光学特性が良好な反面、耐熱性が低い等の課題があり、限定された用途にしか使用されていなかった。透明樹脂の耐熱性を高める技術としては特許文献１～２がある。 Transparent resins such as methacrylic resin, methyl methacrylate-styrene copolymer and styrene-acrylonitrile copolymer are used in various applications such as home appliance parts, automobile parts, food packaging containers, building materials, sundries, etc. . Further, taking advantage of excellent transparency, it is also used as an optical member for liquid crystal displays such as an optical film, a diffusion plate, and a light guide plate. These transparent resins have good optical properties such as transparency, but have problems such as low heat resistance, and have been used only for limited applications. There are Patent Documents 1 and 2 as techniques for increasing the heat resistance of a transparent resin.
ＷＯ２０１４／０２１２６４号公報WO2014 / 021264 ＷＯ２０１４／０６５１２９号公報WO2014 / 065129
　本発明は、新規な透明な樹脂組成物及びその製造方法を提供することを課題とする。 An object of the present invention is to provide a novel transparent resin composition and a method for producing the same.
（１）不飽和ジカルボン酸無水物系単量体単位を含む共重合体からなるスチレン系樹脂（Ａ）と、前記スチレン系樹脂（Ａ）以外の透明樹脂（Ｂ）を含み、ＡＳＴＭ　Ｄ１００３に基づき測定した２ｍｍ厚みの全光線透過率が８８％以上、Ｈａｚｅが０．３％以下である樹脂組成物。
（２）スチレン系樹脂（Ａ）が、スチレン系単量体単位４５～９０質量％と、不飽和ジカルボン酸無水物系単量体単位、（メタ）アクリル酸系単量体単位、（メタ）アクリル酸エステル系単量体単位及びこれらと共重合可能な他のビニル系単量体単位から選ばれた少なくとも１種の単量体単位１０～５５質量％からなる共重合体であることを特徴とする（１）に記載の樹脂組成物。
（３）透明樹脂（Ｂ）が、メタクリル樹脂、メチルメタクリレート－スチレン系共重合体、及びスチレン－アクリロニトリル系共重合体から選択される少なくとも１種からなることを特徴とする（１）又は（２）に記載の樹脂組成物。
（４）スチレン系樹脂（Ａ）の含有量が５～５０質量％、透明樹脂（Ｂ）の含有量が９５～５０質量％であることを特徴とする（１）～（３）のいずれかに記載の樹脂組成物。
（５）ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたスチレン系樹脂（Ａ）のビカット軟化温度が１１０℃以上であることを特徴とする（１）～（４）のいずれかに記載の樹脂組成物。
（６）（１）～（５）のいずれかに記載の樹脂組成物を射出成形して得られる成形体。
（７）不飽和ジカルボン酸無水物系単量体単位を含む共重合体からなるスチレン系樹脂（Ａ）と、前記スチレン系樹脂（Ａ）以外の透明樹脂（Ｂ）をそれぞれ別の定量フィーダを用いて押出機に供給し、溶融混錬する工程を備える、樹脂組成物の製造方法。
（８）スチレン系樹脂（Ａ）が、スチレン系単量体単位４５～９０質量％と、不飽和ジカルボン酸無水物系単量体単位、（メタ）アクリル酸系単量体単位、（メタ）アクリル酸エステル系単量体単位及びこれらと共重合可能な他のビニル系単量体単位から選ばれた少なくとも１種の単量体単位１０～５５質量％からなる共重合体であることを特徴とする（７）に記載の樹脂組成物の製造方法。
（９）透明樹脂（Ｂ）が、メタクリル樹脂、メチルメタクリレート－スチレン系共重合体、及びスチレン－アクリロニトリル系共重合体から選択される少なくとも１種からなることを特徴とする（７）又は（８）に記載の樹脂組成物の製造方法。
（１０）スチレン系樹脂（Ａ）の含有量が５～５０質量％、透明樹脂（Ｂ）の含有量が９５～５０質量％であることを特徴とする（７）～（９）のいずれかに記載の樹脂組成物の製造方法。
（１１）ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたスチレン系樹脂（Ａ）のビカット軟化温度が１１０℃以上であることを特徴とする（７）～（１０）のいずれかに記載の樹脂組成物の製造方法。 (1) A styrene resin (A) comprising a copolymer containing unsaturated dicarboxylic acid anhydride monomer units and a transparent resin (B) other than the styrene resin (A), and based on ASTM D1003 A resin composition having a measured total light transmittance of 2% thickness of 88% or more and a haze of 0.3% or less.
(2) The styrene resin (A) contains 45 to 90% by mass of a styrene monomer unit, an unsaturated dicarboxylic acid anhydride monomer unit, a (meth) acrylic acid monomer unit, (meth) It is a copolymer comprising 10 to 55% by mass of at least one monomer unit selected from acrylic ester monomer units and other vinyl monomer units copolymerizable therewith. The resin composition according to (1).
(3) The transparent resin (B) comprises at least one selected from a methacrylic resin, a methyl methacrylate-styrene copolymer, and a styrene-acrylonitrile copolymer (1) or (2 ).
(4) Any of (1) to (3), wherein the content of the styrene resin (A) is 5 to 50% by mass and the content of the transparent resin (B) is 95 to 50% by mass The resin composition described in 1.
(5) According to JIS K7206, the Vicat softening temperature of the styrene-based resin (A) obtained at a load of 50 N and a heating rate of 50 ° C./hour is 110 ° C. or higher (1) to (4) The resin composition in any one of.
(6) A molded product obtained by injection molding the resin composition according to any one of (1) to (5).
(7) Separate quantitative feeders for the styrene resin (A) comprising a copolymer containing unsaturated dicarboxylic acid anhydride monomer units and the transparent resin (B) other than the styrene resin (A). The manufacturing method of a resin composition provided with the process of using and supplying to an extruder and melt-kneading.
(8) Styrenic resin (A) comprises 45 to 90% by mass of styrene monomer units, unsaturated dicarboxylic acid anhydride monomer units, (meth) acrylic acid monomer units, (meth) It is a copolymer comprising 10 to 55% by mass of at least one monomer unit selected from acrylic ester monomer units and other vinyl monomer units copolymerizable therewith. The manufacturing method of the resin composition as described in (7).
(9) The transparent resin (B) comprises at least one selected from a methacrylic resin, a methyl methacrylate-styrene copolymer, and a styrene-acrylonitrile copolymer (7) or (8 The manufacturing method of the resin composition as described in).
(10) Any one of (7) to (9), wherein the content of the styrenic resin (A) is 5 to 50% by mass and the content of the transparent resin (B) is 95 to 50% by mass A method for producing the resin composition according to 1.
(11) According to JIS K7206, the Vicat softening temperature of the styrene-based resin (A) obtained at a load of 50 N and a heating rate of 50 ° C./hour is 110 ° C. or more (7) to (10) The manufacturing method of the resin composition in any one of.
　本発明の樹脂組成物は透明性に優れることから、耐熱性と良外観を求められる家電製品の部品や自動車部品、建材、光学部材、食品容器等に有用であり、特に、射出成形の際に外観不良の無い成形体が得られる。 Since the resin composition of the present invention is excellent in transparency, it is useful for parts of home appliances, automobile parts, building materials, optical members, food containers, etc. that are required to have heat resistance and good appearance, particularly at the time of injection molding. A molded article having no appearance defect is obtained.
＜用語の説明＞
　本願明細書において、例えば、「Ａ～Ｂ」なる記載は、Ａ以上でありＢ以下であることを意味する。 <Explanation of terms>
In the present specification, for example, the description “A to B” means not less than A but not more than B.
　以下、本発明の実施形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本発明の透明な樹脂組成物は、不飽和ジカルボン酸無水物系単量体単位を含む共重合体からなるスチレン系樹脂（Ａ）と、前記スチレン系樹脂（Ａ）以外の透明樹脂（Ｂ）を含み、ＡＳＴＭ　Ｄ１００３に基づき測定した２ｍｍ厚みの全光線透過率が８８％以上、Ｈａｚｅが０．３％以下である。このような樹脂組成物は、スチレン系樹脂（Ａ）と透明樹脂（Ｂ）をそれぞれ別の定量フィーダを用いて押出機に供給し、溶融混錬することで得られる。 The transparent resin composition of the present invention comprises a styrene resin (A) comprising a copolymer containing unsaturated dicarboxylic acid anhydride monomer units, and a transparent resin (B) other than the styrene resin (A). The total light transmittance of 2 mm thickness measured based on ASTM D1003 is 88% or more, and Haze is 0.3% or less. Such a resin composition is obtained by supplying the styrene resin (A) and the transparent resin (B) to an extruder using separate quantitative feeders and melt-kneading them.
　スチレン系樹脂（Ａ）とは、スチレン系単量体単位と、不飽和ジカルボン酸無水物系単量体単位を含む共重合体であり、（メタ）アクリル酸系単量体単位、（メタ）アクリル酸エステル系単量体単位及びこれらと共重合可能な他のビニル系単量体から選ばれた少なくとも１種の単量体単位を含んでもよい。スチレン系樹脂（Ａ）としては、例えば、スチレン－メチルメタクリレート－無水マレイン酸共重合体、スチレン－無水マレイン酸共重合体などが挙げられる。 Styrenic resin (A) is a copolymer containing a styrene monomer unit and an unsaturated dicarboxylic anhydride monomer unit, a (meth) acrylic acid monomer unit, (meth) It may also contain at least one monomer unit selected from an acrylate ester monomer unit and other vinyl monomers copolymerizable therewith. Examples of the styrene resin (A) include a styrene-methyl methacrylate-maleic anhydride copolymer, a styrene-maleic anhydride copolymer, and the like.
　スチレン系単量体とは、スチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、２，４－ジメチルスチレン、エチルスチレン、ｐ－ｔ－ブチルスチレン、α－メチルスチレン、α－メチル－ｐ－メチルスチレン等である。これらの中でもスチレンが好ましい。スチレン系単量体は、単独でも良いが２種類以上を併用してもよい。 Styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, pt-butylstyrene, α-methylstyrene, α-methyl -P-methylstyrene and the like. Of these, styrene is preferred. Styrenic monomers may be used alone or in combination of two or more.
　不飽和ジカルボン酸無水物系単量体とは、無水マレイン酸、イタコン酸無水物、シトラコン酸無水物、アコニット酸無水物等である。これらの中でも無水マレイン酸が好ましい。不飽和ジカルボン酸無水物系単量体は、単独でも良いが２種類以上を併用してもよい。 The unsaturated dicarboxylic acid anhydride monomer includes maleic anhydride, itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride, and the like. Of these, maleic anhydride is preferred. The unsaturated dicarboxylic acid anhydride monomer may be used alone or in combination of two or more.
　（メタ）アクリル酸系単量体単位とは、アクリル酸、メタクリル酸等であり、これらの中でもメタクリル酸が好ましい。 (Meth) acrylic acid monomer units are acrylic acid, methacrylic acid and the like, and among these, methacrylic acid is preferable.
　（メタ）アクリル酸エステル系単量体単位とは、例えば、メチルメタクリレート、エチルメタクリレート、ｎ－ブチルメタクリレート、２－エチルヘキシルメタクリレート、ジシクロペンタニルメタクリレート、イソボルニルメタクリレートなどの各メタクリル酸エステル単量体、およびメチルアクリレート、エチルアクリレート、ｎ－ブチルアクリレート、２－メチルヘキシルアクリレート、２－エチルヘキシルアクリレート、デシルアクリレート等の各アクリル酸エステル単量体である。これらの中でもはメチルメタクリレート単位が好ましい。（メタ）アクリル酸エステル単量体は、単独でも良いが２種類以上を併用してもよい。 (Meth) acrylic acid ester monomer units include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, etc. And acrylate monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate. Among these, a methyl methacrylate unit is preferable. The (meth) acrylic acid ester monomer may be used alone or in combination of two or more.
　共重合可能な他のビニル系単量体として、アクリロニトリル、メタクリロニトリル、エタクリロニトリル、フマロニトリル等のアクリロニトリル系単量体、Ｎ－フェニルマレイミド等のＮ－置換マレイミド系単量体を用いることができる。 As other copolymerizable vinyl monomers, acrylonitrile monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile and fumaronitrile, and N-substituted maleimide monomers such as N-phenylmaleimide may be used. it can.
　スチレン系樹脂（Ａ）の構成単位は、スチレン系単量体単位４５～９０質量％と、不飽和ジカルボン酸無水物系単量体単位、（メタ）アクリル酸系単量体単位、（メタ）アクリル酸エステル系単量体単位及びこれらと共重合可能な他のビニル系単量体から選ばれた少なくとも１種の単量体１０～５５質量％であることが好ましい。スチレン系単量体単位４５～８５質量％、不飽和ジカルボン酸無水物系単量体単位１０～３０質量％、（メタ）アクリル酸エステル系単量体単位５～４５質量％であることがより好ましく、耐熱性と強度のバランスに優れる。各単量体単位の組成分析は、Ｃ－１３ＮＭＲ法にて下記記載の測定条件で測定された値である。
　　装置名：ＦＴ－ＮＭＲ　ＡＶＡＮＣＥ３００（ＢＲＵＫＥＲ社製）
　　溶媒：重水素化クロロホルム
　　濃度：１４質量％
　　温度：２７℃
　　積算回数：８０００回 The structural unit of the styrene resin (A) is 45 to 90% by mass of a styrene monomer unit, an unsaturated dicarboxylic acid anhydride monomer unit, a (meth) acrylic acid monomer unit, (meth). The content is preferably 10 to 55% by mass of at least one monomer selected from acrylic acid ester monomer units and other vinyl monomers copolymerizable therewith. The styrene monomer unit is 45 to 85% by mass, the unsaturated dicarboxylic acid anhydride monomer unit is 10 to 30% by mass, and the (meth) acrylic acid ester monomer unit is 5 to 45% by mass. Preferably, it has an excellent balance between heat resistance and strength. The composition analysis of each monomer unit is a value measured by the C-13 NMR method under the measurement conditions described below.
Device name: FT-NMR AVANCE300 (manufactured by BRUKER)
Solvent: Deuterated chloroform Concentration: 14% by mass
Temperature: 27 ° C
Integration count: 8000 times
　スチレン系樹脂（Ａ）の重量平均分子量（Ｍｗ）は５万～３０万であることが好ましく、１０万～２５万であることがより好ましい。重量平均分子量（Ｍｗ）が５万～３０万の範囲であれば、強度と成形性のバランスに優れることから好ましい。重量平均分子量（Ｍｗ）は重合工程での重合温度及び重合時間、重合開始剤の種類及び添加量、連鎖移動剤の種類及び添加量、重合時に使用する溶媒の種類及び量等によって制御することができる。なお、重量平均分子量（Ｍｗ）とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定されるポリスチレン換算の値であり、下記記載の測定条件における測定値である。
　　装置名：ＳＹＳＴＥＭ－２１　Ｓｈｏｄｅｘ（昭和電工社製）
　　カラム：ＰＬ　ｇｅｌ　ＭＩＸＥＤ－Ｂを３本直列
　　温度：４０℃
　　検出：示差屈折率
　　溶媒：テトラヒドロフラン
　　濃度：２質量％
　　検量線：標準ポリスチレン（ＰＳ）（ＰＬ社製）を用いて作製した。 The weight average molecular weight (Mw) of the styrenic resin (A) is preferably 50,000 to 300,000, and more preferably 100,000 to 250,000. A weight average molecular weight (Mw) in the range of 50,000 to 300,000 is preferable because of a good balance between strength and moldability. The weight average molecular weight (Mw) can be controlled by the polymerization temperature and polymerization time in the polymerization process, the type and addition amount of the polymerization initiator, the type and addition amount of the chain transfer agent, the type and amount of the solvent used during the polymerization, and the like. it can. The weight average molecular weight (Mw) is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and is a value measured under the measurement conditions described below.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko)
Column: 3 series PL gel MIXED-B Temperature: 40 ° C
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
　スチレン系樹脂（Ａ）の重合方法は、公知の方法が採用できる。簡潔なプロセスで生産性に優れることから、ラジカル重合法が好ましい。 A known method can be adopted as the polymerization method of the styrene resin (A). The radical polymerization method is preferable because it is a simple process and excellent in productivity.
　スチレン系樹脂（Ａ）の製造方法としては、公知の方法が採用できる。例えば、溶液重合、塊状重合等により製造することができる。また、連続法、バッチ法のいずれも適用できる。スチレン系単量体と不飽和ジカルボン酸無水物系単量体との共重合では、交互共重合性が高いため、不飽和ジカルボン酸無水物系単量体を分割添加しながら重合することで共重合組成が均一にすることができることから、溶液重合が好ましい。溶液重合の溶媒は、副生成物が出来難く、悪影響が少ないという観点から非重合性であることが好ましく、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン等のケトン類、テトラヒドロフラン、１，４－ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン、クロロベンゼン等の芳香族炭化水素、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチル－２－ピロリドン等である。 As a method for producing the styrene resin (A), a known method can be employed. For example, it can be produced by solution polymerization, bulk polymerization or the like. Moreover, any of a continuous method and a batch method is applicable. In the copolymerization of styrene monomer and unsaturated dicarboxylic acid anhydride monomer, the alternating copolymerization is high, so the copolymerization can be achieved by polymerizing while adding unsaturated dicarboxylic acid anhydride monomer separately. Solution polymerization is preferred because the polymerization composition can be made uniform. The solvent for the solution polymerization is preferably non-polymerizable from the viewpoint that by-products are difficult to be produced and have few adverse effects. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, 1,4- And ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like.
　スチレン系樹脂（Ａ）の溶液重合或いは塊状重合では、重合開始剤、連鎖移動剤を用いることができ、重合温度は７０～１８０℃の範囲であることが好ましい。重合開始剤は、例えば、ジベンゾイルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、１，１－ビス（ｔ－ブチルパーオキシ）－２－メチルシクロヘキサン、ｔ－ブチルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシアセテート、ジクミルパーオキサイド、エチル－３，３－ジ－（ｔ－ブチルパーオキシ）ブチレート等のパーオキサイド類やアゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビスメチルプロピオニトリル、アゾビスメチルブチロニトリル等のアゾ化合物であり、これらの１種あるいは２種以上を組み合わせて使用してもよい。これらの重合開始剤は２種以上を併用することも出来る。これらの中でも１０時間半減期温度が、７０～１１０℃である有機過酸化物を用いるのが好ましい。連鎖移動剤は、例えば、ｎ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、α－メチルスチレンダイマー、チオグリコール酸エチル、リモネン、ターピノーレン等がある。 In solution polymerization or bulk polymerization of the styrene resin (A), a polymerization initiator and a chain transfer agent can be used, and the polymerization temperature is preferably in the range of 70 to 180 ° C. Examples of the polymerization initiator include dibenzoyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxide. Peroxides such as oxy-2-ethylhexanoate, t-butylperoxyacetate, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate, azobisisobutyronitrile, These are azo compounds such as azobiscyclohexanecarbonitrile, azobismethylpropionitrile, azobismethylbutyronitrile, etc., and these may be used alone or in combination. Two or more of these polymerization initiators can be used in combination. Of these, organic peroxides having a 10-hour half-life temperature of 70 to 110 ° C. are preferably used. Examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, and terpinolene.
　スチレン系樹脂（Ａ）の重合終了後の溶液から、未反応の単量体や溶液重合に用いた溶媒などの揮発成分を取り除く脱揮方法は、公知の手法が採用できる。例えば、予熱器付きの真空脱揮槽やベント付き脱揮押出機を用いることができる。脱揮された溶融状態のスチレン系樹脂（Ａ）は、造粒工程に移送され、多孔ダイよりストランド状に押出し、コールドカット方式や空中ホットカット方式、水中ホットカット方式にてペレット形状に加工することができる。 As a devolatilization method for removing volatile components such as unreacted monomers and a solvent used for solution polymerization from the solution after completion of the polymerization of the styrene-based resin (A), a known method can be adopted. For example, a vacuum devolatilization tank with a preheater or a vented devolatilization extruder can be used. The devolatilized molten styrene resin (A) is transferred to a granulation process, extruded into a strand shape from a porous die, and processed into a pellet shape by a cold cut method, an air hot cut method, or an underwater hot cut method. be able to.
　透明性の観点から、本発明におけるスチレン系樹脂（Ａ）のＡＳＴＭ　Ｄ１００３に基づき測定した２ｍｍ厚みの全光線透過率は８８％以上、Ｈａｚｅは０．５％以下であることが好ましく、より好ましくは、全光線透過率は９０％以上、Ｈａｚｅは０．３％以下である。共重合体組成分布が小さくなるように重合することで、透明性に優れたスチレン系樹脂（Ａ）が得られる。 From the viewpoint of transparency, the 2 mm-thick total light transmittance measured based on ASTM D1003 of the styrene resin (A) in the present invention is preferably 88% or more, and Haze is preferably 0.5% or less, more preferably. The total light transmittance is 90% or more, and the haze is 0.3% or less. By polymerizing the copolymer composition distribution to be small, a styrene resin (A) excellent in transparency can be obtained.
　ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたスチレン系樹脂（Ａ）のビカット軟化温度は１１５℃以上であることが好ましく、より好ましくは１２５℃以上である。ビカット軟化温度が高いほど、メタクリル樹脂の耐熱性を改善する効果が高く、好ましい。スチレン系樹脂（Ａ）のビカット軟化温度は、不飽和ジカルボン酸無水物系単量体単位や（メタ）アクリル酸系単量体単位などの耐熱性単量体の含有量によって調整することができる。 According to JIS K7206, the Vicat softening temperature of the styrenic resin (A) obtained at a load of 50 N and a heating rate of 50 ° C./hour is preferably 115 ° C. or higher, more preferably 125 ° C. or higher. The higher the Vicat softening temperature, the higher the effect of improving the heat resistance of the methacrylic resin, which is preferable. The Vicat softening temperature of the styrenic resin (A) can be adjusted by the content of heat-resistant monomers such as unsaturated dicarboxylic acid anhydride monomer units and (meth) acrylic acid monomer units. .
　透明樹脂（Ｂ）とは、透明で、かつ、スチレン系樹脂（Ａ）と溶融混錬および成形加工時の温度において相溶する樹脂であり、例えば、メタクリル樹脂、メチルメタクリレート－スチレン系共重合体、スチレン－アクリロニトリル系共重合体などである。これらの中でもメタクリル樹脂は光学特性に優れることから好ましい。メチルメタクリレート－スチレン系共重合体系共重合体の構成単位は、メチルメタクリレート単位７０～９７質量％、スチレン３～３０質量％であることが好ましい。スチレン－アクリロニトリル系共重合体の構成単位は、スチレン７０～８５質量％、アクリロニトリル１５～３０質量％であることが好ましい。メタクリル樹脂、メチルメタクリレート－スチレン系共重合体、スチレン－アクリロニトリル系共重合体は、市販されている一般的なものを使用することができる。形状はペレットでもビーズでもよいが、粒度分布は整っている方が好ましい。 The transparent resin (B) is a resin that is transparent and compatible with the styrene resin (A) at the temperature during melt-kneading and molding, such as methacrylic resin, methyl methacrylate-styrene copolymer. And styrene-acrylonitrile copolymers. Among these, a methacrylic resin is preferable because of its excellent optical properties. The constituent units of the methyl methacrylate-styrene copolymer system copolymer are preferably 70 to 97% by mass of methyl methacrylate units and 3 to 30% by mass of styrene. The structural unit of the styrene-acrylonitrile copolymer is preferably 70 to 85% by mass of styrene and 15 to 30% by mass of acrylonitrile. As the methacrylic resin, methyl methacrylate-styrene copolymer, and styrene-acrylonitrile copolymer, commercially available general ones can be used. The shape may be pellets or beads, but it is preferable that the particle size distribution is uniform.
　透明性の観点から、本発明における透明樹脂（Ｂ）のＡＳＴＭ　Ｄ１００３に基づき測定した２ｍｍ厚みの全光線透過率は８８％以上、Ｈａｚｅは０．５％以下であることが好ましく、より好ましくは、全光線透過率は９０％以上、Ｈａｚｅは０．３％以下である。 From the viewpoint of transparency, the total light transmittance of 2 mm thickness measured based on ASTM D1003 of the transparent resin (B) in the present invention is preferably 88% or more, and Haze is preferably 0.5% or less, more preferably, The total light transmittance is 90% or more and Haze is 0.3% or less.
　スチレン系樹脂（Ａ）と透明樹脂（Ｂ）は、それぞれ別の定量フィーダを用いて、押出機に定量的に供給する事が必要である。押出機の原料投入口は、樹脂毎にそれぞれ別の定量フィーダを用いる限りは１箇所でも良く、あるいは定量フィーダの数に応じて複数設けても良い。スチレン系樹脂（Ａ）と透明樹脂（Ｂ）をドライブレンドした後、ホッパーを原料投入口１箇所に設けた押出機へ一括で供給する方法や、定量フィーダを１台のみ設けた押出機へドライブレンドした樹脂を一括で供給する方法では、得られた樹脂組成物を射出成形した場合に、成形体の内部にゆらぎが発生し外観不良となる。このゆらぎは、屈折率の不均一性によるもので、樹脂組成物中にスチレン系樹脂（Ａ）と透明樹脂（Ｂ）の配合比率に変動があると生じる。射出成形では、ゲートから流入した溶融樹脂は、流動方向に風船のように広がりながら金型内に充填されるので、配合比率に変動があると、層状に屈折率の異なる部分が生じ、ゆらぎとして観察される。ゆらぎが顕著になると筋状に見えることもある。また、このゆらぎは脈理（みゃくり）と呼ばれることもある。ドライブレンドした後に一括で押出機に供給する方法では、スチレン系樹脂（Ａ）と透明樹脂（Ｂ）との間の形状の差や密度差等によって、偏析が発生し、配合比率に変動が生じてしまう。 The styrene resin (A) and the transparent resin (B) need to be quantitatively supplied to the extruder using separate quantitative feeders. As long as separate metering feeders are used for each resin, the raw material charging port of the extruder may be provided in one place, or a plurality may be provided depending on the number of metering feeders. After dry blending the styrene resin (A) and the transparent resin (B), the hopper is fed to the extruder provided at one place of the raw material charging port, or the extruder is provided with only one quantitative feeder. In the method of supplying the blended resin in a lump, when the obtained resin composition is injection-molded, fluctuation occurs inside the molded body, resulting in poor appearance. This fluctuation is due to non-uniformity of the refractive index, and occurs when the blending ratio of the styrene resin (A) and the transparent resin (B) varies in the resin composition. In injection molding, the molten resin that flows in from the gate fills the mold while spreading like a balloon in the flow direction. Observed. When the fluctuation becomes noticeable, it may appear streaks. This fluctuation is sometimes called striae. In the method of supplying to the extruder in a lump after dry blending, segregation occurs due to the difference in shape and density between the styrene resin (A) and the transparent resin (B), and the blending ratio fluctuates. End up.
　スチレン系樹脂（Ａ）または透明樹脂（Ｂ）は、相溶する範囲で２種類以上使用することが可能であるが、それぞれ別のフィーダを用いる必要がある。スチレン系樹脂（Ａ）と透明樹脂（Ｂ）との供給比率は、両者が相溶する範囲で任意に定めれば良い。 Two or more types of styrene resin (A) or transparent resin (B) can be used as long as they are compatible with each other, but it is necessary to use different feeders for each. The supply ratio of the styrene resin (A) and the transparent resin (B) may be arbitrarily determined within a range in which both are compatible.
　フィーダとは、ペレットやビーズ形状の原料樹脂を押出機に供給する装置であり、公知のものを使用することができるが、定量的な原料供給が必須である為、定量フィーダを用いる必要がある。定量フィーダとしては、ロス・イン・ウェイト式フィーダ、容積式フィーダ、重量式ベルトフィーダ等が例示できるが、特にロス・イン・ウェイト式フィーダが好ましく、供給精度は±１％以内であることが好ましい。それぞれのフィーダは連動して制御することが好ましく、メインのフィーダの供給量に対して、他のフィーダの供給量が一定の比率となるよう制御する方法が好ましい。 A feeder is a device that supplies pellet or bead-shaped raw material resin to an extruder, and a known material can be used. However, since quantitative raw material supply is essential, a quantitative feeder must be used. . Examples of the quantitative feeder include loss-in-weight feeders, positive displacement feeders, and heavy-weight belt feeders. Loss-in-weight feeders are particularly preferable, and supply accuracy is preferably within ± 1%. . It is preferable to control each feeder in conjunction with each other, and it is preferable to perform control so that the supply amount of other feeders is a constant ratio with respect to the supply amount of the main feeder.
　押出機に供給された原料樹脂は、押出機内で連続的に溶融混錬され、多孔ダイからストランド状に押出、コールドカット方式や空中ホットカット方式、水中ホットカット方式にてペレット形状の樹脂組成物が得られる。押出機は公知の装置を使用することができ、例えば、二軸スクリュー押出機、単軸スクリュー押出機、多軸スクリュー押出機、二軸ロータ付きの連続混錬機などが挙げられる。 The raw material resin supplied to the extruder is melted and kneaded continuously in the extruder, extruded into a strand form from a perforated die, a pellet-shaped resin composition by a cold cut method, an air hot cut method, or an underwater hot cut method. Is obtained. A well-known apparatus can be used for an extruder, for example, a twin screw extruder, a single screw extruder, a multi screw extruder, a continuous kneader with a twin screw rotor, etc. are mentioned.
　樹脂組成物には、透明性を損なわない範囲で、酸化防止剤、紫外線吸収剤、光安定剤、可塑剤、滑剤、染料、難燃剤等の添加剤を配合してもよい。 In the resin composition, additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a lubricant, a dye, and a flame retardant may be blended as long as transparency is not impaired.
　樹脂組成物中のスチレン系樹脂（Ａ）、透明樹脂（Ｂ）の含有量はそれぞれ５～５０質量％、９５～５０質量％であることが好ましく、より好ましくはそれぞれ１５～５０質量％、８５～５０質量％、更に好ましくはそれぞれ１５～３５質量％、８５～６５質量％である。スチレン系樹脂（Ａ）、透明樹脂（Ｂ）の含有量をそれぞれ５～５０質量％、９５～５０質量％とすることで、耐熱性と表面硬度のバランスに優れた透明な樹脂組成物が得られる。 The contents of the styrene resin (A) and the transparent resin (B) in the resin composition are preferably 5 to 50% by mass and 95 to 50% by mass, respectively, more preferably 15 to 50% by mass and 85%, respectively. To 50% by mass, more preferably 15 to 35% by mass and 85 to 65% by mass, respectively. By setting the content of the styrene resin (A) and the transparent resin (B) to 5 to 50% by mass and 95 to 50% by mass, respectively, a transparent resin composition having an excellent balance between heat resistance and surface hardness can be obtained. It is done.
　透明性の観点から、本発明における樹脂組成物のＡＳＴＭ　Ｄ１００３に基づき測定した２ｍｍ厚みの全光線透過率は８８％以上、Ｈａｚｅは０．３％以下である。全光線透過率は、好ましくは、９０％以上である。Ｈａｚｅは、好ましくは、０．２％以下である。スチレン系樹脂（Ａ）と透明樹脂（Ｂ）が互いに相溶で、本発明の方法によって製造することにより、透明性に優れた樹脂組成物が得られる。 From the viewpoint of transparency, the total light transmittance with a thickness of 2 mm measured based on ASTM D1003 of the resin composition in the present invention is 88% or more, and Haze is 0.3% or less. The total light transmittance is preferably 90% or more. The haze is preferably 0.2% or less. When the styrene resin (A) and the transparent resin (B) are compatible with each other and are produced by the method of the present invention, a resin composition having excellent transparency can be obtained.
　ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めた樹脂組成物のビカット軟化温度は１１０℃以上であることが好ましく、より好ましくは１１３℃以上であり、さらに好ましくは１１５℃以上である。ビカット軟化温度が高いほど、適用できる部材が増える。 In accordance with JIS K7206, the Vicat softening temperature of the resin composition determined at a load of 50 N and a heating rate of 50 ° C./hour is preferably 110 ° C. or higher, more preferably 113 ° C. or higher, and even more preferably 115 ° C. That's it. The higher the Vicat softening temperature, the more members that can be applied.
　樹脂組成物の成形方法は、公知の方法が採用できる。例えば、射出成形、プレス成形、シート成形等が挙げられる。特に射出成形では、成形体の内部にゆらぎ状の成形不良が発生しないことから、好適である。ゆらぎ状の成形不良は、特に厚みの大きい射出成形体で目立ちやすいが、本発明の樹脂組成物は厚みの大きい射出成形体でも外観不良が発生しない。 As the molding method of the resin composition, a known method can be adopted. For example, injection molding, press molding, sheet molding and the like can be mentioned. In particular, injection molding is preferable because no fluctuating molding defects occur inside the molded body. Fluctuation-like molding defects are particularly noticeable with injection molded articles having a large thickness, but the resin composition of the present invention does not cause poor appearance even with an injection molded article having a large thickness.
　以下、詳細な内容について実施例を用いて説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the detailed contents will be described using examples, but the present invention is not limited to the following examples.
＜スチレン系樹脂（Ａ）＞
＜スチレン系樹脂（Ａ－１）の製造例＞
　マレイン酸無水物が２０質量％濃度となるようにメチルイソブチルケトンに溶解させた２０％マレイン酸無水物溶液と、ｔ－ブチルパーオキシ－２－エチルヘキサノエートが２質量％となるようにメチルイソブチルケトンに希釈した２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液とを事前に調製し、重合に使用した。撹拌機を備えた１２０リットルのオートクレーブ中に、２０％マレイン酸無水物溶液３．６ｋｇ、スチレン２４ｋｇ、メチルメタクレリレート８．８ｋｇ、ｔ－ドデシルメルカプタン２０ｇを仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて８８℃まで昇温した。昇温後８８℃を保持しながら、２０％マレイン酸無水物溶液を２．７ｋｇ／時、および２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液を３７５ｇ／時の分添速度で各々連続的に８時間かけて添加し続けた。その後、２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液の分添を停止し、ｔ－ブチルパーオキシイソプロピルモノカーボネートを４０ｇ添加した。２０％マレイン酸無水物溶液はそのまま２．７ｋｇ／時の分添速度を維持しながら、８℃／時の昇温速度で４時間かけて１２０℃まで昇温した。２０％マレイン酸無水物溶液の分添は、分添量が積算で３２．４ｋｇになった時点で停止した。昇温後、１時間１２０℃を保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系樹脂（Ａ－１）を得た。得られたＡ－１をＣ－１３ＮＭＲ法により組成分析を行った。さらにＧＰＣ装置にて分子量測定を行った。組成分析を実施したところ、Ａ－１の構成単位は、スチレン単量体単位６０質量％、メチルメタクリレート単量体単位２２％、無水マレイン酸単量体単位１８質量％であった。また、重量平均分子量（Ｍｗ）は１６万で、数平均分子量（Ｍｎ）との比であるＭｗ／Ｍｎは２．４であった。射出成形にて成形した２ｍｍｔの鏡面プレートの全光線透過率は９１％、Ｈａｚｅは０．２％であった。ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたビカット軟化温度は１３３℃であった。 <Styrene resin (A)>
<Production example of styrene resin (A-1)>
20% maleic anhydride solution dissolved in methyl isobutyl ketone so that maleic anhydride has a concentration of 20% by mass and methyl so that t-butylperoxy-2-ethylhexanoate becomes 2% by mass. A 2% t-butyl peroxy-2-ethylhexanoate solution diluted in isobutyl ketone was prepared in advance and used for the polymerization. A 120 liter autoclave equipped with a stirrer was charged with 3.6 kg of a 20% maleic anhydride solution, 24 kg of styrene, 8.8 kg of methyl methacrylate, and 20 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. Then, the temperature was raised to 88 ° C. over 40 minutes with stirring. After maintaining the temperature at 88 ° C., a 20% maleic anhydride solution was added at a rate of 2.7 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 375 g / hour. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C. over 4 hours at a heating rate of 8 ° C./hour while maintaining the addition rate of 2.7 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the amount of addition reached 32.4 kg. After the temperature increase, the polymerization was terminated by maintaining 120 ° C. for 1 hour. The polymerization liquid is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and styrene in the form of pellets is formed by devolatilizing methyl isobutyl ketone and a small amount of unreacted monomer, and extruding and cutting into strands. A resin (A-1) was obtained. The resulting A-1 was subjected to composition analysis by C-13 NMR method. Furthermore, molecular weight measurement was performed with a GPC apparatus. As a result of composition analysis, the structural unit of A-1 was 60% by mass of a styrene monomer unit, 22% of a methyl methacrylate monomer unit, and 18% by mass of a maleic anhydride monomer unit. Moreover, the weight average molecular weight (Mw) was 160,000, and Mw / Mn which is a ratio with the number average molecular weight (Mn) was 2.4. The 2 mmt specular plate molded by injection molding had a total light transmittance of 91% and a haze of 0.2%. In accordance with JIS K7206, the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 133 ° C.
＜スチレン系樹脂（Ａ－２）の製造例＞
　２０％マレイン酸無水物溶液と２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液は、Ａ－１と同様に調製した。撹拌機を備えた１２０リットルのオートクレーブ中に、２０％マレイン酸無水物溶液２．８ｋｇ、スチレン２５．６ｋｇ、メチルメタクレリレート８．８ｋｇ、ｔ－ドデシルメルカプタン２０ｇを仕込み、気相部を窒素ガスで置換した後、撹拌しながら４０分かけて８８℃まで昇温した。昇温後８８℃を保持しながら、２０％マレイン酸無水物溶液を２．１ｋｇ／時、および２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液を５００ｇ／時の分添速度で各々連続的に８時間かけて添加し続けた。その後、２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液の分添を停止し、ｔ－ブチルパーオキシイソプロピルモノカーボネートを４０ｇ添加した。２０％マレイン酸無水物溶液はそのまま２．１ｋｇ／時の分添速度を維持しながら、８℃／時の昇温速度で４時間かけて１２０℃まで昇温した。２０％マレイン酸無水物溶液の分添は、分添量が積算で２５．２ｋｇになった時点で停止した。昇温後、１時間１２０℃を保持して重合を終了させた重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系樹脂（Ａ－２）を得た。得られたＡ－２について、Ａ－１と同様に組成分析、分子量、および全光線透過率を測定した。組成分析を実施したところ、Ａ－２の構成単位は、スチレン単量体単位６４質量％、メチルメタクリレート単量体単位２２％、無水マレイン酸単量体単位１４質量％であった。また、重量平均分子量（Ｍｗ）は１７万で、数平均分子量（Ｍｎ）との比であるＭｗ／Ｍｎは２．６であった。射出成形にて成形した２ｍｍｔの鏡面プレートの全光線透過率は９１％、Ｈａｚｅは０．２％であった。ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたビカット軟化温度は１２６℃であった。 <Production example of styrene resin (A-2)>
A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared in the same manner as A-1. A 120 liter autoclave equipped with a stirrer was charged with 2.8 kg of a 20% maleic anhydride solution, 25.6 kg of styrene, 8.8 kg of methyl methacrylate, and 20 g of t-dodecyl mercaptan. The temperature was raised to 88 ° C. over 40 minutes with stirring. While maintaining the temperature at 88 ° C. after heating, the 20% maleic anhydride solution was added at a rate of 2.1 kg / hour and the 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 500 g / hour, respectively. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 40 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 120 ° C. over 4 hours at a temperature rising rate of 8 ° C./hour while maintaining the addition rate of 2.1 kg / hour as it was. The addition of the 20% maleic anhydride solution was stopped when the amount of addition reached 25.2 kg. After the temperature rise, the polymerization liquid which has been held at 120 ° C. for 1 hour to finish the polymerization is continuously fed to a twin-screw devolatilizing extruder using a gear pump to remove methyl isobutyl ketone and a small amount of unreacted monomer. The styrene resin (A-2) in the form of pellets was obtained by volatilization treatment and extrusion cutting into strands. For the obtained A-2, the composition analysis, molecular weight, and total light transmittance were measured in the same manner as in A-1. As a result of composition analysis, the constituent unit of A-2 was 64% by mass of a styrene monomer unit, 22% of a methyl methacrylate monomer unit, and 14% by mass of a maleic anhydride monomer unit. Moreover, the weight average molecular weight (Mw) was 170,000 and Mw / Mn which is a ratio with the number average molecular weight (Mn) was 2.6. The 2 mmt specular plate molded by injection molding had a total light transmittance of 91% and a haze of 0.2%. In accordance with JIS K7206, the Vicat softening temperature obtained at a load of 50 N and a heating rate of 50 ° C./hour was 126 ° C.
＜スチレン系樹脂（Ａ－３〉の製造例＞
　マレイン酸無水物が２５質量％濃度となるようにメチルイソブチルケトンに溶解させた２５％マレイン酸無水物溶液を事前に調製し、重合に使用した。２％ｔ－ブチルパーオキシ－２－エチルヘキサノネート溶液は（Ａ－１）の製造例と同様に調整し、重合に使用した。攪拌機を備えた１２０リットルのオートクレーブ中に、２５％マレイン酸無水物溶液３．５２ｋｇ、スチレン２４ｋｇ、メチルメタクリレート７．２ｋｇ、ｔ－ドデシルメルカプタン２０ｇを仕込み、気相部を窒素ガスで置換した後、攪拌しながら４０分かけて９２℃まで昇温した。昇温後９２℃を保持しながら、２５％マレイン酸無水溶液と、２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液とを各々連続的に分添開始した。２５％マレイン酸無水物溶液は、分添開始４時間目までが３．９６ｋｇ／時、４時間目から７時間目までが３．１７ｋｇ／時、７時間目から１０時間目までが１．５８ｋｇ／時、１０時間目から１３時間目までが０．５４ｋｇ／時の分添速度となるように段階的に分添速度を変え、合計で３１．７１ｋｇ添加した。２％ｔ－ブチルパーオキシ－２－エチルヘキサノエート溶液は、分添開始から７時間目までが０．２４ｋｇ／時、７時間目から１３時間目までが０．３９ｋｇ／時の分添速度となるように段階的に分添速度を変え、合計で４．０２ｋｇ添加した。重合温度は、分添開始から７時間目までは９２℃を保持し、その後４℃／時の昇温速度で６時間かけて１１６℃まで昇温し、さらに１１６℃を１時間保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン系樹脂（Ａ－３）を得た。得られたＡ－３について、Ａ－１と同様に組成分析、分子量、および全光線透過率を測定した。組成分析を実施したところ、Ａ－３の構成単位は、スチレン単量体単位６０質量％、メチルメタクリレート単量体単位１８％、無水マレイン酸単量体単位２２質量％であった。また、重量平均分子量（Ｍｗ）は１６万で、数平均分子量（Ｍｎ）との比であるＭｗ／Ｍｎは２．４であった。射出成形にて成形した２ｍｍｔの鏡面プレートの全光線透過率は９０％、Ｈａｚｅは０．２％であった。ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたビカット軟化温度は１４２℃であった。 <Production Example of Styrenic Resin (A-3)>
A 25% maleic anhydride solution dissolved in methyl isobutyl ketone so that the concentration of maleic anhydride was 25% by mass was prepared in advance and used for polymerization. A 2% t-butylperoxy-2-ethylhexanoate solution was prepared in the same manner as in the preparation example of (A-1) and used for polymerization. A 120 liter autoclave equipped with a stirrer was charged with 3.52 kg of a 25% maleic anhydride solution, 24 kg of styrene, 7.2 kg of methyl methacrylate, and 20 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 92 ° C. over 40 minutes with stirring. While maintaining the temperature at 92 ° C. after the temperature rise, a 25% maleic acid-free aqueous solution and a 2% t-butylperoxy-2-ethylhexanoate solution were successively added. The 25% maleic anhydride solution was 3.96 kg / hour from the 4th hour to the start of the addition, 3.17 kg / hour from the 4th to the 7th hour, and 1.58 kg from the 7th to the 10th hour. / Hour, the addition speed was changed stepwise so that the addition speed was 0.54 kg / hour from the 10th hour to the 13th hour, and a total of 31.71 kg was added. The 2% t-butylperoxy-2-ethylhexanoate solution has a rate of addition of 0.24 kg / hour from the start of the addition to 7 hours and 0.39 kg / hour from the 7th to 13th hours. The addition speed was changed stepwise so that a total of 4.02 kg was added. The polymerization temperature is maintained at 92 ° C. until 7 hours from the start of the addition, and then heated to 116 ° C. over 6 hours at a rate of 4 ° C./hour, and further maintained at 116 ° C. for 1 hour for polymerization. Was terminated. The polymerization liquid is continuously fed to a twin-screw devolatilizing extruder using a gear pump, and styrene in the form of pellets is formed by devolatilizing methyl isobutyl ketone and a small amount of unreacted monomer, and extruding and cutting into strands. A resin (A-3) was obtained. For the obtained A-3, the composition analysis, molecular weight, and total light transmittance were measured in the same manner as in A-1. As a result of composition analysis, the constitutional unit of A-3 was 60% by mass of a styrene monomer unit, 18% of a methyl methacrylate monomer unit, and 22% by mass of a maleic anhydride monomer unit. Moreover, the weight average molecular weight (Mw) was 160,000, and Mw / Mn which is a ratio with the number average molecular weight (Mn) was 2.4. The 2 mmt specular plate molded by injection molding had a total light transmittance of 90% and a haze of 0.2%. In accordance with JIS K7206, the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 142 ° C.
＜透明樹脂（Ｂ）＞
＜透明樹脂（Ｂ－１）＞
　透明樹脂（Ｂ－１）として、メタクリル樹脂（三菱レイヨン株式会社製　アクリペットＶＨ）を使用した。ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたビカット軟化温度は１０８℃であった。 <Transparent resin (B)>
<Transparent resin (B-1)>
A methacrylic resin (Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.) was used as the transparent resin (B-1). In accordance with JIS K7206, the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 108 ° C.
＜透明樹脂（Ｂ－２）＞
　透明樹脂（Ｂ－２）として、メチルメタクリレート単位８０質量％、スチレン単位２０質量％であるメチルメタクリレート－スチレン系共重合体を使用した。ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたビカット軟化温度は１０４℃であった。 <Transparent resin (B-2)>
As the transparent resin (B-2), a methyl methacrylate-styrene copolymer having 80% by mass of methyl methacrylate units and 20% by mass of styrene units was used. In accordance with JIS K7206, the Vicat softening temperature determined at a load of 50 N and a heating rate of 50 ° C./hour was 104 ° C.
＜実施例１～６、比較例１～６＞
　スチレン系樹脂（Ａ）と透明樹脂（Ｂ）を表１に示す配合で、押出機を用いて溶融混錬し、樹脂組成物を得た。実施例１～６では、スチレン系樹脂（Ａ）と透明樹脂（Ｂ）をそれぞれ別の定量フィーダを用いて押出機に供給した。透明樹脂（Ｂ）の供給量は実施例１～３では１５ｋｇ／ｈｒ、実施例４では１９ｋｇ／ｈｒ、実施例５では１０ｋｇ／ｈｒ、実施例６では１５ｋｇ／ｈｒに設定し、スチレン系樹脂（Ａ）の供給量は表１の配合比率となるよう制御した（合計の供給量は２０ｋｇ／ｈｒ）。定量フィーダは、ロス・イン・ウェイト式フィーダ（株式会社クボタ製　ＣＥ－Ｗ－１）を使用した。比較例１～６では、スチレン系樹脂（Ａ）と透明樹脂（Ｂ）のペレットを表１の配合比率でドライブレンドした後、同一のフィーダを用いて押出機に供給した。ドライブレンドしたペレットの供給量は２０ｋｇ／ｈｒに設定した。押出機は二軸スクリュー押出機（東芝機械株式会社製　ＴＥＭ－２６ＳＸ）を使用し、シリンダー温度は２４０℃、スクリュー回転数は２５０ｒｐｍに設定した。押出機で溶融混錬後、多孔ダイからストランド状に押出、コールドカット方式にてペレット形状の樹脂組成物を得た。得られた樹脂組成物について以下の評価を行った。評価結果を表１に示す。 <Examples 1 to 6, Comparative Examples 1 to 6>
Styrenic resin (A) and transparent resin (B) were blended as shown in Table 1 and melt kneaded using an extruder to obtain a resin composition. In Examples 1 to 6, the styrenic resin (A) and the transparent resin (B) were supplied to the extruder using separate quantitative feeders. The supply amount of the transparent resin (B) was set to 15 kg / hr in Examples 1 to 3, 19 kg / hr in Example 4, 10 kg / hr in Example 5, 15 kg / hr in Example 6, and styrene resin ( The supply amount of A) was controlled so as to be the mixing ratio shown in Table 1 (total supply amount was 20 kg / hr). As the quantitative feeder, a loss-in-weight feeder (CE-W-1 manufactured by Kubota Corporation) was used. In Comparative Examples 1 to 6, pellets of the styrene resin (A) and the transparent resin (B) were dry blended at the blending ratio shown in Table 1, and then supplied to the extruder using the same feeder. The supply amount of the dry blended pellets was set to 20 kg / hr. As the extruder, a twin screw extruder (TEM-26SX manufactured by Toshiba Machine Co., Ltd.) was used, the cylinder temperature was set to 240 ° C., and the screw rotation speed was set to 250 rpm. After melt-kneading with an extruder, a pellet-shaped resin composition was obtained by extrusion from a perforated die into a strand and a cold cut method. The following evaluation was performed about the obtained resin composition. The evaluation results are shown in Table 1.
（ビカット軟化点）
　ビカット軟化点は、ＪＩＳ　Ｋ７２０６：１９９９に基づき、５０法（荷重５０Ｎ、昇温速度５０℃／時間）で試験片は１０ｍｍ×１０ｍｍ、厚さ４ｍｍのものを用いて測定した。なお、測定機は株式会社東洋精機製作所製　ＨＤＴ＆ＶＳＰＴ試験装置を使用した。 (Vicat softening point)
The Vicat softening point was measured according to JIS K7206: 1999 using 50 specimens (load 50 N, temperature rising rate 50 ° C./hour) with a test piece of 10 mm × 10 mm and a thickness of 4 mm. In addition, the measuring machine used the Toyo Seiki Seisakusho Co., Ltd. HDT & VSPT test apparatus.
（全光線透過率、Ｈａｚｅ）
　全光線透過率およびＨａｚｅは、射出成形機（東芝機械株式会社製　ＩＳ－５０ＥＰＮ）を用いて、シリンダー温度２４０℃、金型温度７０℃の成形条件で成形された縦９０ｍｍ、横５５ｍｍ、厚み２ｍｍの鏡面プレートをＡＳＴＭ　Ｄ１００３に準拠しヘーズメータ（日本電色工業株式会社製　ＮＤＨ－１００１ＤＰ型）を用いて測定した。 (Total light transmittance, Haze)
The total light transmittance and Haze were 90 mm in length, 55 mm in width, and 2 mm in thickness formed using an injection molding machine (IS-50EPN, manufactured by Toshiba Machine Co., Ltd.) under molding conditions of a cylinder temperature of 240 ° C. and a mold temperature of 70 ° C. The specular plate was measured using a haze meter (NDH-1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) according to ASTM D1003.
（外観不良の有無）
　射出成形機（株式会社日本製鋼所製　Ｊ１４０ＡＤ－１８０Ｈ）を用いて、シリンダー温度２５０℃、金型温度７０℃の成形条件で縦１２７ｍｍ、横１２７ｍｍ、厚み６ｍｍの鏡面プレートを成形し、ゆらぎ状の外観不良の有無を確認した。 (Existence of appearance defects)
Using an injection molding machine (J140AD-180H, manufactured by Nippon Steel Co., Ltd.), a mirror surface plate having a length of 127 mm, a width of 127 mm, and a thickness of 6 mm was formed under the molding conditions of a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. The presence or absence of appearance defects was confirmed.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　スチレン系樹脂（Ａ）と透明樹脂（Ｂ）を別フィードした実施例では、ゆらぎ状の外観不良が無く、外観、透明性及び耐熱性に優れる。一方、ドライブレンドにて一括フィードした比較例ではゆらぎ状の外観不良が発生する。 In the example in which the styrene resin (A) and the transparent resin (B) are separately fed, there is no fluctuation-like appearance defect and the appearance, transparency and heat resistance are excellent. On the other hand, a fluctuation-like appearance defect occurs in the comparative example that is batch fed by dry blending.
　本発明の樹脂組成物は透明で外観に優れ、耐熱性に優れることから、家電製品の部品や自動車部品、建材、光学部材、食品容器等に有用である。特に、射出成形での外観不良が無く、好適に用いることができる。 Since the resin composition of the present invention is transparent, excellent in appearance, and excellent in heat resistance, it is useful for home appliance parts, automobile parts, building materials, optical members, food containers and the like. In particular, there is no appearance defect in injection molding, and it can be suitably used.

Claims (11)

  1. 不飽和ジカルボン酸無水物系単量体単位を含む共重合体からなるスチレン系樹脂（Ａ）と、前記スチレン系樹脂（Ａ）以外の透明樹脂（Ｂ）を含み、ＡＳＴＭ　Ｄ１００３に基づき測定した２ｍｍ厚みの全光線透過率が８８％以上、Ｈａｚｅが０．３％以下である、樹脂組成物。 2 mm measured based on ASTM D1003, including a styrene resin (A) composed of a copolymer containing unsaturated dicarboxylic acid anhydride monomer units and a transparent resin (B) other than the styrene resin (A). A resin composition having a total light transmittance of thickness of 88% or more and a haze of 0.3% or less.
  2. スチレン系樹脂（Ａ）が、スチレン系単量体単位４５～９０質量％と、不飽和ジカルボン酸無水物系単量体単位、（メタ）アクリル酸系単量体単位、（メタ）アクリル酸エステル系単量体単位及びこれらと共重合可能な他のビニル系単量体単位から選ばれた少なくとも１種の単量体単位１０～５５質量％からなる共重合体であることを特徴とする請求項１に記載の樹脂組成物。 Styrenic resin (A) contains 45 to 90% by mass of styrene monomer units, unsaturated dicarboxylic acid anhydride monomer units, (meth) acrylic acid monomer units, and (meth) acrylic acid esters. A copolymer comprising 10 to 55% by mass of at least one monomer unit selected from a monomer unit and other vinyl monomer units copolymerizable therewith. Item 2. The resin composition according to Item 1.
  3. 透明樹脂（Ｂ）が、メタクリル樹脂、メチルメタクリレート－スチレン系共重合体、及びスチレン－アクリロニトリル系共重合体から選択される少なくとも１種からなることを特徴とする請求項１又は請求項２に記載の樹脂組成物。 The transparent resin (B) is composed of at least one selected from a methacrylic resin, a methyl methacrylate-styrene copolymer, and a styrene-acrylonitrile copolymer. Resin composition.
  4. スチレン系樹脂（Ａ）の含有量が５～５０質量％、透明樹脂（Ｂ）の含有量が９５～５０質量％であることを特徴とする請求項１～請求項３のいずれか１項に記載の樹脂組成物。 The content of the styrene-based resin (A) is 5 to 50% by mass, and the content of the transparent resin (B) is 95 to 50% by mass, according to any one of claims 1 to 3. The resin composition as described.
  5. ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたスチレン系樹脂（Ａ）のビカット軟化温度が１１０℃以上であることを特徴とする請求項１～請求項４のいずれか１項に記載の樹脂組成物。 5. The Vicat softening temperature of the styrenic resin (A) obtained at a load of 50 N and a heating rate of 50 ° C./hour in accordance with JIS K7206 is 110 ° C. or higher, or any one of claims 1 to 4 2. The resin composition according to item 1.
  6. 請求項１～請求項５のいずれか１項に記載の樹脂組成物を射出成形して得られる成形体。 A molded article obtained by injection molding the resin composition according to any one of claims 1 to 5.
  7. 不飽和ジカルボン酸無水物系単量体単位を含む共重合体からなるスチレン系樹脂（Ａ）と、前記スチレン系樹脂（Ａ）以外の透明樹脂（Ｂ）をそれぞれ別の定量フィーダを用いて押出機に供給し、溶融混錬する工程を備える、樹脂組成物の製造方法。 Extrude a styrene resin (A) composed of a copolymer containing unsaturated dicarboxylic acid anhydride monomer units and a transparent resin (B) other than the styrene resin (A) using separate quantitative feeders. The manufacturing method of a resin composition provided with the process of supplying to a machine and melt-kneading.
  8. スチレン系樹脂（Ａ）が、スチレン系単量体単位４５～９０質量％と、不飽和ジカルボン酸無水物系単量体単位、（メタ）アクリル酸系単量体単位、（メタ）アクリル酸エステル系単量体単位及びこれらと共重合可能な他のビニル系単量体単位から選ばれた少なくとも１種の単量体単位１０～５５質量％からなる共重合体であることを特徴とする請求項７に記載の樹脂組成物の製造方法。 Styrenic resin (A) contains 45 to 90% by mass of styrene monomer units, unsaturated dicarboxylic acid anhydride monomer units, (meth) acrylic acid monomer units, and (meth) acrylic acid esters. A copolymer comprising 10 to 55% by mass of at least one monomer unit selected from a monomer unit and other vinyl monomer units copolymerizable therewith. Item 8. A method for producing a resin composition according to Item 7.
  9. 透明樹脂（Ｂ）が、メタクリル樹脂、メチルメタクリレート－スチレン系共重合体、及びスチレン－アクリロニトリル系共重合体から選択される少なくとも１種からなることを特徴とする請求項７又は請求項８に記載の樹脂組成物の製造方法。 9. The transparent resin (B) comprises at least one selected from a methacrylic resin, a methyl methacrylate-styrene copolymer, and a styrene-acrylonitrile copolymer. A method for producing the resin composition.
  10. スチレン系樹脂（Ａ）の含有量が５～５０質量％、透明樹脂（Ｂ）の含有量が９５～５０質量％であることを特徴とする請求項７～請求項９のいずれか１項に記載の樹脂組成物の製造方法。 The content of the styrene resin (A) is 5 to 50% by mass, and the content of the transparent resin (B) is 95 to 50% by mass, according to any one of claims 7 to 9. The manufacturing method of the resin composition of description.
  11. ＪＩＳ　Ｋ７２０６に準拠し、荷重５０Ｎ、昇温速度５０℃／時間で求めたスチレン系樹脂（Ａ）のビカット軟化温度が１１０℃以上であることを特徴とする請求項７～請求項１０のいずれか１項に記載の樹脂組成物の製造方法。 11. The Vicat softening temperature of the styrene-based resin (A) obtained at a load of 50 N and a heating rate of 50 ° C./hour according to JIS K7206 is 110 ° C. or higher, or any one of claims 7 to 10 2. A method for producing a resin composition according to item 1.
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JPH0347709A (en) * 1989-07-15 1991-02-28 Matsushita Electric Works Ltd Kneading method of molding material
JPH0671640A (en) * 1992-08-27 1994-03-15 Japan Steel Works Ltd:The Kneading extrusion method
JPH0732357A (en) * 1993-07-23 1995-02-03 Hiroshi Morohashi Molding equipment for mixture of plastic and molding method using the equipment
WO1998028365A1 (en) * 1996-12-20 1998-07-02 Dsm N.V. Polymer composition
US6040382A (en) * 1994-02-04 2000-03-21 Phillips Petroleum Company Polymer blend clarity
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JP2009282146A (en) * 2008-05-20 2009-12-03 Asahi Kasei E-Materials Corp Optical film excellent in mechanical strength
JP2010070646A (en) * 2008-09-18 2010-04-02 Asahi Kasei Chemicals Corp Resin composition for use as optical material

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JPS49132126A (en) * 1973-04-02 1974-12-18
US4647620A (en) * 1984-08-24 1987-03-03 Doak Kenneth W Polyblends of a copolymer of a vinyl aromatic monomer and an unsaturated dicarboxylic acid anhydride with a methyl methacrylate homopolymer or copolymer
JPH0347709A (en) * 1989-07-15 1991-02-28 Matsushita Electric Works Ltd Kneading method of molding material
JPH0671640A (en) * 1992-08-27 1994-03-15 Japan Steel Works Ltd:The Kneading extrusion method
JPH0732357A (en) * 1993-07-23 1995-02-03 Hiroshi Morohashi Molding equipment for mixture of plastic and molding method using the equipment
US6040382A (en) * 1994-02-04 2000-03-21 Phillips Petroleum Company Polymer blend clarity
WO1998028365A1 (en) * 1996-12-20 1998-07-02 Dsm N.V. Polymer composition
WO2009084382A1 (en) * 2007-12-28 2009-07-09 Jsr Corporation Injection molded body and polymer composition
JP2009282146A (en) * 2008-05-20 2009-12-03 Asahi Kasei E-Materials Corp Optical film excellent in mechanical strength
JP2010070646A (en) * 2008-09-18 2010-04-02 Asahi Kasei Chemicals Corp Resin composition for use as optical material

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JPWO2016186121A1 (en) 2018-03-15
TW201708362A (en) 2017-03-01

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