WO2016186121A1 - Composition de résine transparente et son procede de fabrication - Google Patents

Composition de résine transparente et son procede de fabrication 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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English (en)
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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Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to DE112016002240.9T priority Critical patent/DE112016002240T5/de
Priority to KR1020177035721A priority patent/KR20180011140A/ko
Priority to JP2017519375A priority patent/JPWO2016186121A1/ja
Priority to CN201680029252.4A priority patent/CN107614622A/zh
Publication of WO2016186121A1 publication Critical patent/WO2016186121A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Un objectif de la présente invention est de proposer une composition de résine présentant une excellente transparence et une résistance à la chaleur, et qui ne présente pas de défauts visibles de l'extérieur lorsqu'elle est moulée par injection. Cette composition de résine contient : une résine de styrène (A) comprenant un copolymère comprenant un motif monomère anhydride d'acide dicarboxylique insaturé ; et une résine transparente (B) autre que la résine de styrène (A). Lorsqu'elle est mesurée selon la norme ASTM D1003, à une épaisseur de 2 mm, la composition de résine a une transmittance lumineuse totale d'au moins 88 % et une valeur de trouble d'au plus 0,3 %. La résine de styrène (A) est de préférence un copolymère comprenant 45 à 90 % en masse d'un motif monomère styrène, et 10 à 55 % en masse d'un motif monomère anhydride d'acide dicarboxylique insaturé, un motif monomère acide (méth)acrylique, un motif monomère ester d'acide (méth)acrylique, etc. La résine transparente (B) est, de préférence, au moins un élément choisi parmi une résine méthacrylique, un copolymère méthacrylate de méthyle-styrène et un copolymère de styrène-acrylonitrile.
PCT/JP2016/064684 2015-05-20 2016-05-18 Composition de résine transparente et son procede de fabrication WO2016186121A1 (fr)

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DE112016002240.9T DE112016002240T5 (de) 2015-05-20 2016-05-18 Transparente Harzzusammensetzung sowie Herstellungsverfahren dafür
KR1020177035721A KR20180011140A (ko) 2015-05-20 2016-05-18 투명한 수지 조성물 및 그의 제조 방법
JP2017519375A JPWO2016186121A1 (ja) 2015-05-20 2016-05-18 透明な樹脂組成物及びその製造方法
CN201680029252.4A CN107614622A (zh) 2015-05-20 2016-05-18 透明树脂组合物及其制造方法

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49132126A (fr) * 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 (ja) * 1989-07-15 1991-02-28 Matsushita Electric Works Ltd 成形材料の混練方法
JPH0671640A (ja) * 1992-08-27 1994-03-15 Japan Steel Works Ltd:The 混練押し出し方法
JPH0732357A (ja) * 1993-07-23 1995-02-03 Hiroshi Morohashi プラスチック混和物の成形装置及びその装置を用いた成形方法
WO1998028365A1 (fr) * 1996-12-20 1998-07-02 Dsm N.V. Composition polymere
US6040382A (en) * 1994-02-04 2000-03-21 Phillips Petroleum Company Polymer blend clarity
WO2009084382A1 (fr) * 2007-12-28 2009-07-09 Jsr Corporation Corps moulé par injection et composition polymère
JP2009282146A (ja) * 2008-05-20 2009-12-03 Asahi Kasei E-Materials Corp 機械強度に優れた光学フィルム
JP2010070646A (ja) * 2008-09-18 2010-04-02 Asahi Kasei Chemicals Corp 光学材料用樹脂組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014021264A1 (fr) * 2012-07-30 2014-02-06 電気化学工業株式会社 Copolymère destiné à améliorer la résistance à la chaleur d'une résine méthacrylique

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49132126A (fr) * 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 (ja) * 1989-07-15 1991-02-28 Matsushita Electric Works Ltd 成形材料の混練方法
JPH0671640A (ja) * 1992-08-27 1994-03-15 Japan Steel Works Ltd:The 混練押し出し方法
JPH0732357A (ja) * 1993-07-23 1995-02-03 Hiroshi Morohashi プラスチック混和物の成形装置及びその装置を用いた成形方法
US6040382A (en) * 1994-02-04 2000-03-21 Phillips Petroleum Company Polymer blend clarity
WO1998028365A1 (fr) * 1996-12-20 1998-07-02 Dsm N.V. Composition polymere
WO2009084382A1 (fr) * 2007-12-28 2009-07-09 Jsr Corporation Corps moulé par injection et composition polymère
JP2009282146A (ja) * 2008-05-20 2009-12-03 Asahi Kasei E-Materials Corp 機械強度に優れた光学フィルム
JP2010070646A (ja) * 2008-09-18 2010-04-02 Asahi Kasei Chemicals Corp 光学材料用樹脂組成物

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CN107614622A (zh) 2018-01-19

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