WO2009151102A1 - Resin composition for optical molded object and optical molded object obtained therefrom - Google Patents

Resin composition for optical molded object and optical molded object obtained therefrom Download PDF

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Publication number
WO2009151102A1
WO2009151102A1 PCT/JP2009/060708 JP2009060708W WO2009151102A1 WO 2009151102 A1 WO2009151102 A1 WO 2009151102A1 JP 2009060708 W JP2009060708 W JP 2009060708W WO 2009151102 A1 WO2009151102 A1 WO 2009151102A1
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mass
styrene
optical molded
film
copolymer
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PCT/JP2009/060708
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French (fr)
Japanese (ja)
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幸一 小澤
哲央 野口
慶太 大橋
英樹 戸谷
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電気化学工業株式会社
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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
    • 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
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers

Definitions

  • the present invention relates to a resin composition for an optical molded body and an optical molded body thereof.
  • Optical molded bodies with controlled optical anisotropy are used for liquid crystal display elements, electroluminescence elements, and the like.
  • optical films there are many types of optical molded bodies, for example, optical films.
  • optical films for example, there is a film called a retardation film.
  • retardation films using resins such as polycarbonate and amorphous cyclic polyolefin have positive orientation birefringence.
  • patent document 1 what is disclosed by patent document 1 is known as an optical film which shows negative orientation birefringence.
  • the gist of the present invention is as follows. (1) A resin composition for an optical molded article comprising 20 to 40% by mass of the following styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B). Then, the resin composition for an optical molded body, in which the haze of an unstretched film having a thickness of 100 ⁇ m, measured based on ASTM D1003, is 1.0% or less.
  • a resin composition for an optical molded article comprising 20 to 40% by mass of the following styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B). Then, the resin composition for an optical molded body, in which the haze of an unstretched film having a thickness of 100 ⁇ m, measured based on ASTM D1003, is 1.0% or less.
  • Mw weight average molecular weight
  • Styrene-acrylonitrile copolymer (B) Styrene monomer Copolymer containing 70 to 82% by mass of unit and 18 to 30% by mass of acrylonitrile monomer unit and having a weight average molecular weight (Mw) of 150,000 to 250,000
  • Styrene-maleimide copolymer (A) is a resin composition for optically molded products according to (1), which is obtained by solution polymerization or bulk polymerization.
  • the optically molded product according to (6) which is a melt-extruded film and is a film that exhibits negative orientation birefringence when stretched and oriented.
  • the optical molded body according to (7) or (8) which is a stretched film.
  • the resin composition for an optical molded body of the present invention is useful for an optical film for a thin liquid crystal display element because of good transparency, heat resistance, film moldability, film strength, and film appearance.
  • the stretched and oriented film exhibits negative orientation birefringence and is excellent in retardation development, and thus is useful as a retardation film.
  • the resin composition for optical molded bodies of the present invention comprises 20 to 40% by mass of a styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B). Details of each of the copolymers (A) and (B) will be described below.
  • the styrene-maleimide copolymer (A) is a styrene monomer unit of 40 to 70% by mass, a maleimide monomer unit of 30 to 60% by mass, and an unsaturated dicarboxylic acid anhydride monomer unit of 0 to 15% by mass. %, And 0 to 15% by mass of acrylonitrile monomer units.
  • the styrene monomer unit is less than 40% by mass or the maleimide monomer unit exceeds 60% by mass, unmelted spots are generated and the film appearance is poor.
  • the styrene monomer unit exceeds 70% by mass or the maleimide monomer unit is less than 30% by mass, the heat resistance is poor.
  • the thermal stability is deteriorated and the film appearance is inferior.
  • the acrylonitrile monomer unit exceeds 15% by mass, the coloring becomes strong and the film appearance is inferior.
  • styrene monomer in the styrene-maleimide copolymer (A) examples include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and chlorostyrene.
  • examples thereof include styrene monomers, and among these, styrene is particularly preferable. These styrenic monomers may be contained in a mixture of two or more.
  • maleimide monomers in the styrene-maleimide copolymer (A) include N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide, and N-phenylmaleimide and N-chlorophenyl.
  • maleimide monomers such as N-arylmaleimides such as maleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-tribromophenylmaleimide and the like, among which N-cyclohexylmaleimide, N-phenyl Maleimide is preferred.
  • two or more of these maleimide monomers may be mixed and contained.
  • Examples of the unsaturated dicarboxylic acid anhydride monomer in the styrene-maleimide copolymer (A) include anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, with maleic anhydride being particularly preferred. These unsaturated dicarboxylic acid anhydride monomers may be contained in a mixture of two or more.
  • acrylonitrile monomer in the styrene-maleimide copolymer (A) examples include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. These acrylonitrile monomers may be contained in a mixture of two or more.
  • the styrene-maleimide copolymer (A) is a copolymerizable vinyl monomer unit such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methacrylic acid.
  • Monomer units such as methyl acrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate may be contained as long as they are less than 10% by mass relative to the styrene-maleimide copolymer (A).
  • styrene-maleimide copolymer (A) can be carried out by a known method.
  • a styrene monomer, a maleimide monomer, an acrylonitrile monomer, and a copolymerizable vinyl monomer A monomer mixture comprising a styrene monomer, an unsaturated dicarboxylic acid anhydride monomer, an acrylonitrile monomer and a copolymerizable vinyl monomer. And the like, and then reacting ammonia and / or a primary amine to convert an acid anhydride group into an imide group.
  • a known polymerization method can be used as a polymerization mode. Among these, solution polymerization or bulk polymerization is preferable.
  • the weight average molecular weight (Mw) of the styrene-maleimide copolymer (A) is preferably 100,000 to 145,000, more preferably 105,000 to 130,000. When the weight average molecular weight (Mw) exceeds 145,000, unmelted spots are generated and the film appearance is inferior. When the weight average molecular weight (Mw) is less than 100,000, the film strength is inferior.
  • Mw in this specification is Mw of polystyrene conversion measured by GPC, and measured on the measurement conditions of the following description.
  • 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: produced using standard polystyrene (PS) (manufactured by PL), and Mw was expressed in terms of polystyrene.
  • composition ratio of the styrene monomer and the acrylonitrile monomer in the styrene-acrylonitrile copolymer (B) is 70 to 82% by mass of the styrene monomer and 18 to 30% by mass of the acrylonitrile monomer, preferably Is 71 to 80% by mass of styrene monomer and 20 to 29% by mass of acrylonitrile monomer.
  • the styrene monomer is less than 70% by mass and the acrylonitrile monomer is more than 30% by mass, the coloring becomes strong and the appearance of the film is poor.
  • the styrene monomer exceeds 82% by mass and the acrylonitrile monomer is less than 18% by mass, the transparency and film strength of the film are inferior.
  • styrene monomer of the styrene-acrylonitrile copolymer (B) examples include styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, t-butyl styrene, and chlorostyrene.
  • examples thereof include styrene monomers, and among these, styrene is particularly preferable. These styrenic monomers may be contained in a mixture of two or more.
  • Examples of the acrylonitrile monomer of the styrene-acrylonitrile copolymer (B) include acrylonitrile and methacrylonitrile. Among these, acrylonitrile is particularly preferable. These acrylonitrile monomers may be contained in a mixture of two or more.
  • the styrene-acrylonitrile copolymer (B) is a copolymerizable vinyl monomer unit such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methacrylic acid. If monomer units such as methyl acid, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, maleic anhydride are less than 10% by mass with respect to the styrene-acrylonitrile copolymer (B) You may contain.
  • the styrene-acrylonitrile copolymer (B) can be produced by a known method, for example, a monomer comprising a styrene monomer, an acrylonitrile monomer, and a copolymerizable vinyl monomer. Examples include copolymerizing the mixture.
  • a known polymerization method can be used as a polymerization mode. Among them, bulk polymerization or solution polymerization is preferable, and bulk polymerization is more preferable.
  • the weight average molecular weight (Mw) of the styrene-acrylonitrile copolymer (B) is preferably 150,000 to 250,000, more preferably 170,000 to 230,000. When the weight average molecular weight (Mw) exceeds 250,000, the film formability is inferior, and when Mw is less than 150,000, the film strength is inferior.
  • the weight average molecular weight (Mw) in this specification is Mw of polystyrene conversion measured by GPC, and was measured on the following measurement conditions.
  • 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: produced using standard polystyrene (PS) (manufactured by PL), and Mw was expressed in terms of polystyrene.
  • the resin composition for optical molded bodies comprises 20 to 40% by mass of a styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B), more preferably a styrene-maleimide copolymer.
  • the blend (A) contains 25 to 35% by mass and the styrene-acrylonitrile copolymer (B) 65 to 75% by mass. Thereby, good physical properties can be obtained.
  • the method for producing a resin composition for an optical molded body is not particularly limited as long as the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer (B) are uniformly dispersed.
  • These kneading techniques can be used.
  • melt kneading can be mentioned using a Banbury mixer, kneader, single screw or twin screw extruder, etc. In order to obtain a particularly beautiful film, it is preferable to melt knead using a twin screw extruder.
  • the extrusion method of the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer (B) is to feed the whole amount at once, or the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer. For example, a part of the copolymer (B) is fed from the root position of the screw, and the remainder of the styrene-acrylonitrile copolymer (B) is side-fed from an intermediate position of the screw.
  • the resin temperature is preferably 260 to 320 ° C, more preferably 270 to 310 ° C.
  • the resin temperature can be adjusted by the cylinder temperature, screw rotation speed, and raw material feed amount.
  • the configuration of the screw is not particularly limited, but a kneading disc light in which a plurality of paddle type discs are shifted to the right and overlapped, a kneading disc left in which a plurality of paddle type discs are shifted to the left and overlapped, and a paddle type disc is 90
  • a combination of a plurality of kneading discs such as a kneading disc neutral, which are shifted and overlapped each other, is preferable.
  • a screen mesh with a mesh opening of 50 ⁇ m or less, a sintered filter, a polymer filter, etc. can be installed in the die part at the tip of the extruder.
  • the glass transition temperature of the resin composition for optical molded bodies is preferably 110 to 150 ° C., more preferably 115 to 140 ° C. If the glass transition temperature is less than 110 ° C., the heat resistance is low and may not be suitable for an optical film. On the other hand, if the glass transition temperature exceeds 150 ° C., the film formability may deteriorate.
  • the glass transition temperature can be adjusted by the composition ratio of the copolymer constituting the composition.
  • the glass transition temperature of the present invention was measured by DSC under the measurement conditions described below. Device name: Robot DSC6200 manufactured by Seiko Instruments Inc. Temperature increase rate: 10 ° C / min
  • the melt mass flow rate (MFR) of the resin composition for optical molded bodies of the present invention measured at a temperature of 200 ° C. and a load of 49 N is preferably 0.1 to 3 (g / 10 minutes). The preferred range is 0.2 to 1.5 (g / 10 min). If the MFR is less than 0.1 (g / 10 minutes) or exceeds 3 (g / 10 minutes), the film formability may deteriorate.
  • MFR was measured using a melt indexer (F-F01) manufactured by Toyo Seiki Seisakusho.
  • heat-resistant stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, sulfur compounds, and light-resistant stabilizers such as hindered amine compounds and benzotriazole compounds.
  • Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oils may be blended. It is preferable that the compounding quantity is less than 1 mass part with respect to 100 mass parts of resin compositions for optical molded objects.
  • the film When the resin composition for optical molded bodies is formed into a film, the film exhibits negative orientation birefringence when stretched and oriented.
  • the resin composition for optical molded bodies can be used as a known molded body such as an injection molded body, a sheet, and a film, and the method for molding the film is not particularly limited, but is preferably melt-extruded using a film extruder.
  • An optical molded body refers to a molded body, a sheet, or a film used for optical applications
  • a melt-extruded film refers to a film formed by melt extrusion.
  • the film refers to a known optical film such as a retardation film, an antireflection film, and a polarizer protective film.
  • the film of the present invention can be stretched and oriented by a known method.
  • the film is made into a film, it is most preferable for use in a retardation film because if the film is further stretched and oriented, negative orientation birefringence occurs.
  • Example A-1 In an autoclave having a volume of about 25 liters equipped with a stirrer, 60 parts by mass of styrene, 0.15 parts by mass of ⁇ -methylstyrene dimer and 100 parts by mass of methyl ethyl ketone were charged, and the inside of the system was replaced with nitrogen gas. The temperature was raised to 0 ° C., and a solution prepared by dissolving 40 parts by mass of maleic anhydride and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate in 200 parts of methyl ethyl ketone was continuously added over 10 hours. . After the addition, it was kept at 100 ° C. for 3 hours.
  • the reaction solution was supplied to a vented twin screw extruder and devolatilized to obtain a styrene-maleimide copolymer A-1. From the C-13 NMR analysis, the styrene-maleimide copolymer A-1 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, and 2% by mass of maleic anhydride units. 000.
  • Example A-2 A styrene-maleimide copolymer A-2 was obtained in the same manner as in Experimental Example A-1, except that 0.05 part by mass of ⁇ -methylstyrene dimer was used. From the C-13 NMR analysis, the styrene-maleimide copolymer A-2 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, and 2% by mass of maleic anhydride units. 000.
  • Example A-3 A styrene-maleimide copolymer A-3 was obtained in the same manner as in Experimental Example A-1, except that 0.3 part by mass of ⁇ -methylstyrene dimer was used. According to C-13 NMR analysis, the styrene-maleimide copolymer A-3 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, 2% by mass of maleic anhydride units, and Mw is 79,000. Met.
  • Example A-4 In an autoclave having a volume of about 15 liters equipped with a stirrer, 150 parts by mass of water and 3 parts by mass of tricalcium phosphate were charged, and the system was replaced with nitrogen gas, and then the temperature was raised to 90 ° C. A mixture of 45 parts by mass of styrene, 55 parts by mass of N-phenylmaleimide and 0.15 parts by mass of ⁇ -methylstyrene dimer and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate for 10 hours Over time. After completion of the addition, 0.1 part by mass of t-butyl peroxyacetate was added and kept at 130 ° C. for 3 hours.
  • the resulting slurry was neutralized with hydrochloric acid, dehydrated and dried, and the resulting beads were extruded with a vented twin screw extruder to obtain a styrene-maleimide copolymer A-4.
  • the styrene-maleimide copolymer A-4 contained 45% by mass of styrene units and 55% by mass of N-phenylmaleimide units, and Mw was 119,000.
  • Example A-5 A styrene-maleimide copolymer A was prepared in the same manner as in Experimental Example A-1, except that 76 parts by mass of styrene, 24 parts by mass of maleic anhydride, 21.6 parts by mass of aniline, and 0.36 parts by mass of triethylamine were used. -5 was obtained. According to C-13 NMR analysis, styrene-maleimide copolymer A-5 contains 65% by mass of styrene units, 34% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride units, and Mw is 112, 000.
  • the reaction solution was supplied to a vented twin screw extruder and devolatilized to obtain a styrene-maleimide copolymer A-6.
  • the styrene-maleimide copolymer A-6 contained 49% by mass of styrene units, 40% by mass of N-phenylmaleimide units, and 11% by mass of acrylonitrile units, and the Mw was 145,000. It was.
  • Example A-7 A styrene-maleimide copolymer A-7 was obtained in the same manner as in Experimental Example A-1, except that 36 parts by mass of aniline was changed to 36 parts by mass of cyclohexylamine. From C-13 NMR analysis, styrene-maleimide copolymer A-7 contains 47% by mass of styrene units, 51% by mass of N-cyclohexylmaleimide units, and 2% by mass of maleic anhydride units, and Mw is 110,000.
  • Example A-8 In an autoclave having a volume of about 25 liters equipped with a stirrer, 37 parts by mass of styrene, 0.15 parts by mass of ⁇ -methylstyrene dimer and 100 parts by mass of methyl ethyl ketone were charged, and the inside of the system was replaced with nitrogen gas. The temperature was raised to 0 ° C., and a solution prepared by dissolving 63 parts by mass of N-phenylmaleimide and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate in 200 parts of methyl ethyl ketone was continuously added over 12 hours. . After the addition, it was kept at 100 ° C. for 4 hours.
  • the reaction solution was supplied to a twin screw extruder with a vent and devolatilized to obtain a styrene-maleimide copolymer A-8.
  • the styrene-maleimide copolymer A-8 contained 37% by mass of styrene units and 63% by mass of N-phenylmaleimide units, and the Mw was 114,000.
  • Example A-9 A styrene-maleimide copolymer A-9 was obtained in the same manner as in Experimental Example A-1, except that 0.20 parts by mass of ⁇ -methylstyrene dimer was used. According to C-13 NMR analysis, styrene-maleimide copolymer A-9 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, and 2% by mass of maleic anhydride units, and Mw is 100 000.
  • Example A-10 A styrene-maleimide copolymer A- was prepared in the same manner as in Experimental Example A-1, except that 85 parts by weight of styrene, 15 parts by weight of maleic anhydride, 13.5 parts by weight of aniline, and 0.23 parts by weight of triethylamine were used. 10 was obtained. From the C-13 NMR analysis, the styrene-maleimide copolymer A-10 contains 77% by mass of styrene units, 22% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride units. 000.
  • Table 1 shows the component compositions and weight average molecular weights (Mw) of the copolymers obtained in Experimental Examples A-1 to A-10.
  • Example B-1 A devolatilization tank equipped with a preheater was connected to a fully mixed reactor having a capacity of about 20 liters equipped with a stirrer.
  • Mercaptan (0.013 parts by mass) was mixed to prepare a raw material solution. This raw material solution was introduced at 5 kg / h into a fully mixed reactor controlled at a temperature of 120 ° C.
  • the stirring number of the complete mixing reactor was 180 rpm.
  • the reaction solution was continuously withdrawn from the complete mixing reactor, and this reaction solution was introduced into a devolatilization tank controlled at a temperature of 235 ° C. and a pressure of 1.0 kPa while being heated by a preheater. Volatile matter such as body was removed.
  • the resin liquid was extracted with a gear pump and extruded and cut into strands to obtain a pellet-shaped polymer B-1. From C-13 NMR analysis, the polymer B-1 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and the Mw was 202,000.
  • Example B-2 A styrene-acrylonitrile copolymer B-2 was obtained in the same manner as in Experimental Example B-1, except that 68.2 parts by mass of styrene, 31.8 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-2 contained 70% by mass of styrene units and 30% by mass of acrylonitrile units, and Mw was 198,000.
  • Example B-3 In an autoclave having a volume of about 15 liters equipped with a stirrer, 150 parts by mass of pure water, 3 parts of tribasic calcium phosphate, 45 parts by mass of styrene, 26 parts by mass of acrylonitrile, 0.05 part by mass of ⁇ -methylstyrene dimer, t-butyl per After charging 0.2 parts by mass of oxyisopropyl monocarbonate and 0.1 part of t-butyl peroxyacetate and replacing the system with nitrogen gas, the temperature was kept at 103 ° C., and 29 parts by mass of styrene was then added at 103 ° C. For 4 hours and at 105 ° C.
  • the temperature was kept at 120 ° C. for 3 hours.
  • the obtained slurry was neutralized with hydrochloric acid, dehydrated and dried, and beads obtained were extruded with a twin screw extruder equipped with a vent to obtain a styrene-acrylonitrile copolymer B-3.
  • the styrene-acrylonitrile copolymer B-3 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and Mw was 153,000.
  • Example B-4 A styrene-acrylonitrile copolymer B-4 was obtained in the same manner as in Experimental Example B-1, except that 76.2 parts by mass of styrene and 23.8 parts by mass of acrylonitrile were used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-4 contained 76% by mass of styrene units and 24% by mass of acrylonitrile units, and Mw was 201,000.
  • Example B-5 A styrene-acrylonitrile copolymer B-5 was obtained in the same manner as in Experimental Example B-1, except that 82.9 parts by mass of styrene, 17.1 parts by mass of acrylonitrile, and 15 parts by mass of ethylbenzene were used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-5 contained 82% by mass of styrene units and 18% by mass of acrylonitrile units, and Mw was 245,000.
  • Example B-6 A styrene-acrylonitrile copolymer B-6 was obtained in the same manner as in Experimental Example B-1, except that 91.8 parts by mass of styrene and 9.2 parts by mass of acrylonitrile were used. From C-13 NMR analysis, the styrene-acrylonitrile copolymer B-6 contained 90% by mass of styrene units and 10% by mass of acrylonitrile units, and Mw was 197,000.
  • Example B-7 A styrene-acrylonitrile copolymer B-7 was obtained in the same manner as in Experimental Example B-1, except that 60.5 parts by mass of styrene, 39.5 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. From C-13 NMR analysis, styrene-acrylonitrile copolymer B-7 contained 65% by mass of styrene units and 35% by mass of acrylonitrile units, and Mw was 210,000.
  • Example B-8 A styrene-acrylonitrile copolymer B-8 was obtained in the same manner as in Experimental Example B-1, except that 0.056 parts by mass of n-dodecyl mercaptan was used. From C-13 NMR analysis, styrene-acrylonitrile copolymer B-8 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and Mw was 134,000.
  • Example B-9 A styrene-acrylonitrile copolymer B-9 was obtained in the same manner as in Experimental Example B-1, except that 15 parts by weight of ethylbenzene and 0.005 parts by weight of n-dodecyl mercaptan were used. From C-13 NMR analysis, the styrene-acrylonitrile copolymer B-9 contained 74% by mass of styrene units, 26% by mass of acrylonitrile units, and Mw was 272,000.
  • Example B-10 A styrene-acrylonitrile copolymer was prepared in the same manner as in Experimental Example B-1, except that 56.1 parts by mass of styrene, 17.5 parts by mass of ⁇ -methylstyrene, 26.4 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. B-10 was obtained. According to C-13 NMR analysis, styrene-acrylonitrile copolymer B-10 contained 60% by mass of styrene units, 14% by mass of ⁇ -methylstyrene units, and 26% by mass of acrylonitrile units, and Mw was 201,000. It was.
  • Example B-11 A styrene-acrylonitrile copolymer B-11 was obtained in the same manner as in Experimental Example B-3, except that 0.02 part by mass of ⁇ -methylstyrene dimer was used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-11 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and Mw was 192,000.
  • Table 2 shows the component compositions and weight average molecular weights (Mw) of the copolymers obtained in Experimental Examples B-1 to B-11.
  • the resin composition for optical molded bodies was extruded into a film having a thickness of 100 ⁇ m at a cylinder temperature of 240 ° C. and a die temperature of 240 ° C. using a film extrusion machine with a T-die, and wound on a roll.
  • the obtained film was uniaxially stretched 1.8 times at Tg + 20 ° C. using a tenter transverse stretching machine to obtain a stretched optical film (referred to as “stretched film”).
  • the measurement results regarding the obtained stretched film are shown in Tables 3 to 4.
  • Measurement conditions Measuring instrument: MIT-D FOLDING ENDURANCE TESTER (Toyo Seiki Co., Ltd.) Load (tension): 500 g weight Bending speed: 175 times / min Bending angle: 45 degrees each left and right Folding device tip radius: 0.38 mm Test width: 15mm Folding direction: Film extrusion direction Strength criteria “excellent”: Bending frequency 100 times or more “Good”: Bending frequency 50 times or more and less than 100 “Bad”: Bending frequency 50 times or less (5) Film appearance Visual appearance of film Judgment was made based on the following criteria, and “good” and “good” were evaluated as acceptable.
  • Examples according to the present invention have good transparency, heat resistance, film moldability, film strength, and film appearance, and from these facts, the obtained film is optimal for optical molded bodies, particularly optical films. I understand that. Moreover, the stretched and oriented centrifugal film is suitable as a retardation film because it exhibits good retardation and exhibits negative orientation birefringence.

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Abstract

A resin composition for optical molded objects is provided which has satisfactory transparency, hue, heat resistance, film-forming properties, film strength, film appearance, and phase-difference-inducing properties.  Also provided is a stretched film formed from the composition and having negative orientational birefringence. The resin composition for optical molded objects comprises 20-40 mass% the following styrene/maleimide copolymer (A) and 60-80 mass% the following styrene/acrylonitrile copolymer (B).  The composition gives a 100 µm-thick unstretched film having a haze, as measured in accordance with ASTM D1003, of 1.0% or lower.  (A): a copolymer comprising 40-70 mass% styrene monomer units, 30-60 mass% maleimide monomer units, 0-15 mass% units of an unsaturated dicarboxylic anhydride monomer, and 0-15 mass% acrylonitrile monomer units and having a weight-average molecular weight (Mw) of 100,000-145,000.  (B): a copolymer comprising 70-82 mass% styrene monomer units and 18-30 mass% acrylonitrile monomer units and having a weight-average molecular weight of 150,000-250,000.

Description

光学成形体用樹脂組成物及びその光学成形体Resin composition for optical molded body and optical molded body thereof
　本発明は、光学成形体用樹脂組成物及びその光学成形体に関する。 The present invention relates to a resin composition for an optical molded body and an optical molded body thereof.
　液晶ディスプレー表示素子、エレクトロルミネッセンス素子などに、光学異方性が制御された光学成形体が用いられている。 Optical molded bodies with controlled optical anisotropy are used for liquid crystal display elements, electroluminescence elements, and the like.
　光学成形体には、数多くの種類が存在し、例えば光学フィルムが挙げられる。光学フィルムの中にも、例えば位相差フィルムと呼ばれるフィルムがある。このうち、ポリカーボネートや非晶性の環状ポリオレフィン等の樹脂を用いた位相差フィルムは正の配向複屈折性を有している。一方、負の配向複屈折性を示す光学フィルムとしては、特許文献１に開示されるようなものが知られている。 There are many types of optical molded bodies, for example, optical films. Among optical films, for example, there is a film called a retardation film. Among these, retardation films using resins such as polycarbonate and amorphous cyclic polyolefin have positive orientation birefringence. On the other hand, what is disclosed by patent document 1 is known as an optical film which shows negative orientation birefringence.
特開２００４－３１５７８８号公報JP 2004-315788 A
　本発明の目的は、従来よりも優れた特性を有する光学成形体用樹脂組成物及びその光学成形体を提供することである。また、本発明の別の目的は、負の配向複屈折性を示し、位相差発現性に優れた延伸フィルムを提供することである。 An object of the present invention is to provide a resin composition for an optical molded body having characteristics superior to those of the prior art and the optical molded body. Another object of the present invention is to provide a stretched film that exhibits negative orientation birefringence and is excellent in retardation development.
　本発明は、以下を要旨とするものである。
　（１）下記のスチレン－マレイミド系共重合体（Ａ）２０～４０質量％とスチレン－アクリロニトリル系共重合体（Ｂ）６０～８０質量％を含有してなる光学成形体用樹脂組成物であって、ＡＳＴＭ　Ｄ１００３に基づき測定した、厚み１００μｍの未延伸フィルムのヘーズが１．０％以下である光学成形体用樹脂組成物。
　スチレン－マレイミド系共重合体（Ａ）：スチレン系単量体単位４０～７０質量％、マレイミド系単量体単位３０～６０質量％、不飽和ジカルボン酸無水物単量体単位０～１５質量％、アクリロニトリル系単量体単位０～１５質量％を含み、重量平均分子量（Ｍｗ）が１００，０００～１４５，０００である共重合体
　スチレン－アクリロニトリル系共重合体（Ｂ）：スチレン系単量体単位７０～８２質量％、アクリロニトリル系単量体単位１８～３０質量％を含み、重量平均分子量（Ｍｗ）が１５０，０００～２５０，０００である共重合体
　（２）スチレン－マレイミド系共重合体（Ａ）が溶液重合もしくは塊状重合により得られたものである（１）記載の光学成形体用樹脂組成物。
　（３）スチレン－アクリロニトリル系共重合体（Ｂ）が塊状重合もしくは溶液重合により得られたものである（１）又は（２）記載の光学成形体用樹脂組成物。
　（４）ガラス転移温度が１１０～１５０℃である（１）～（３）のいずれか１項に記載の光学成形体用樹脂組成物。
　（５）ＪＩＳ　Ｋ７２１０に基づき、温度２００℃、荷重４９Ｎで測定した光学成形体用樹脂組成物のメルトマスフローレイト（ＭＦＲ）が０．１～３（ｇ／１０分）である（１）～（４）のいずれか１項に記載の光学成形体用樹脂組成物。
　（６）（１）～（５）のいずれか１項に記載の光学成形体用樹脂組成物からなる光学成形体。
　（７）フィルムであって、延伸して配向させると負の配向複屈折性を示すフィルムである（６）記載の光学成形体。
　（８）溶融押出フィルムであって、延伸して配向させると負の配向複屈折性を示すフィルムである（６）記載の光学成形体。
　（９）延伸フィルムである（７）又は（８）記載の光学成形体。
（１０）位相差フィルムである（９）記載の光学成形体。 The gist of the present invention is as follows.
(1) A resin composition for an optical molded article comprising 20 to 40% by mass of the following styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B). Then, the resin composition for an optical molded body, in which the haze of an unstretched film having a thickness of 100 μm, measured based on ASTM D1003, is 1.0% or less.
Styrene-maleimide copolymer (A): styrene monomer unit 40 to 70% by mass, maleimide monomer unit 30 to 60% by mass, unsaturated dicarboxylic anhydride monomer unit 0 to 15% by mass A copolymer containing 0 to 15% by mass of an acrylonitrile monomer unit and having a weight average molecular weight (Mw) of 100,000 to 145,000. Styrene-acrylonitrile copolymer (B): Styrene monomer Copolymer containing 70 to 82% by mass of unit and 18 to 30% by mass of acrylonitrile monomer unit and having a weight average molecular weight (Mw) of 150,000 to 250,000 (2) Styrene-maleimide copolymer (A) is a resin composition for optically molded products according to (1), which is obtained by solution polymerization or bulk polymerization.
(3) The resin composition for optical molded articles according to (1) or (2), wherein the styrene-acrylonitrile copolymer (B) is obtained by bulk polymerization or solution polymerization.
(4) The resin composition for an optical molded article according to any one of (1) to (3), wherein the glass transition temperature is 110 to 150 ° C.
(5) Based on JIS K7210, the melt mass flow rate (MFR) of the resin composition for optical moldings measured at a temperature of 200 ° C. and a load of 49 N is 0.1 to 3 (g / 10 min). 4) The resin composition for optical molded bodies according to any one of 4).
(6) An optical molded body comprising the resin composition for optical molded bodies according to any one of (1) to (5).
(7) The optically molded article according to (6), which is a film that exhibits negative orientation birefringence when stretched and oriented.
(8) The optically molded product according to (6), which is a melt-extruded film and is a film that exhibits negative orientation birefringence when stretched and oriented.
(9) The optical molded body according to (7) or (8), which is a stretched film.
(10) The optical molded body according to (9), which is a retardation film.
　本発明の光学成形体用樹脂組成物は、透明性、耐熱性、フィルム成形性、フィルム強度およびフィルム外観が良好なことから、薄型液晶表示素子用の光学フィルムに有用である。また、延伸して配向させたフィルムは、負の配向複屈折性を示しかつ位相差発現性に優れることから、位相差フィルムとして有用である。 The resin composition for an optical molded body of the present invention is useful for an optical film for a thin liquid crystal display element because of good transparency, heat resistance, film moldability, film strength, and film appearance. In addition, the stretched and oriented film exhibits negative orientation birefringence and is excellent in retardation development, and thus is useful as a retardation film.
　本発明の光学成形体用樹脂組成物は、スチレン－マレイミド系共重合体（Ａ）２０～４０質量％とスチレン－アクリロニトリル系共重合体（Ｂ）６０～８０質量％を含有してなる。共重合体（Ａ）および（Ｂ）の各々の詳細を以下に説明する。 The resin composition for optical molded bodies of the present invention comprises 20 to 40% by mass of a styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B). Details of each of the copolymers (A) and (B) will be described below.
　スチレン－マレイミド系共重合体（Ａ）は、スチレン系単量体単位４０～７０質量％、マレイミド系単量体単位３０～６０質量％、不飽和ジカルボン酸無水物単量体単位０～１５質量％、およびアクリロニトリル系単量体単位０～１５質量％を含む。 The styrene-maleimide copolymer (A) is a styrene monomer unit of 40 to 70% by mass, a maleimide monomer unit of 30 to 60% by mass, and an unsaturated dicarboxylic acid anhydride monomer unit of 0 to 15% by mass. %, And 0 to 15% by mass of acrylonitrile monomer units.
　スチレン系単量体単位が４０質量％未満、または、マレイミド系単量体単位が６０質量％を超えると、未溶融ブツが発生し、フィルム外観性が劣る。スチレン系単量体単位が７０質量％を超える、または、マレイミド系単量体単位３０質量％未満であると、耐熱性が劣る。 When the styrene monomer unit is less than 40% by mass or the maleimide monomer unit exceeds 60% by mass, unmelted spots are generated and the film appearance is poor. When the styrene monomer unit exceeds 70% by mass or the maleimide monomer unit is less than 30% by mass, the heat resistance is poor.
　不飽和ジカルボン酸無水物単量体単位が１５質量％を超えると、熱安定性が悪くなり、フィルム外観性が劣る。アクリロニトリル系単量体単位が１５質量％を超えると、着色が強くなり、フィルム外観性が劣る。 When the unsaturated dicarboxylic acid anhydride monomer unit exceeds 15% by mass, the thermal stability is deteriorated and the film appearance is inferior. When the acrylonitrile monomer unit exceeds 15% by mass, the coloring becomes strong and the film appearance is inferior.
　スチレン－マレイミド系共重合体（Ａ）におけるスチレン系単量体としては、スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｔ－ブチルスチレン、クロルスチレン等のスチレン系単量体が挙げられ、これらの中でも特にスチレンが好ましい。また、これらのスチレン系単量体は２種以上混合して含有されてもよい。 Examples of the styrene monomer in the styrene-maleimide copolymer (A) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and chlorostyrene. Examples thereof include styrene monomers, and among these, styrene is particularly preferable. These styrenic monomers may be contained in a mixture of two or more.
　スチレン－マレイミド系共重合体（Ａ）におけるマレイミド系単量体としては、Ｎ－メチルマレイミド、Ｎ－ブチルマレイミド、Ｎ－シクロヘキシルマレイミド等のＮ－アルキルマレイミド、及びＮ－フェニルマレイミド、Ｎ－クロルフェニルマレイミド、Ｎ－メチルフェニルマレイミド、Ｎ－メトキシフェニルマレイミド、Ｎ－トリブロモフェニルマレイミド等のＮ－アリールマレイミド等のマレイミド系単量体が挙げられ、これらの中で特にＮ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミドが好ましい。また、これらのマレイミド系単量体は２種以上混合して含有されてもよい。 Examples of maleimide monomers in the styrene-maleimide copolymer (A) include N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide, and N-phenylmaleimide and N-chlorophenyl. And maleimide monomers such as N-arylmaleimides such as maleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-tribromophenylmaleimide and the like, among which N-cyclohexylmaleimide, N-phenyl Maleimide is preferred. Moreover, two or more of these maleimide monomers may be mixed and contained.
　スチレン－マレイミド系共重合体（Ａ）における不飽和ジカルボン酸無水物単量体としては、マレイン酸、イタコン酸、シトラコン酸、アコニット酸等の無水物が挙げられ、特にマレイン酸無水物が好ましい。また、これらの不飽和ジカルボン酸無水物単量体は２種以上混合して含有されてもよい。 Examples of the unsaturated dicarboxylic acid anhydride monomer in the styrene-maleimide copolymer (A) include anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, with maleic anhydride being particularly preferred. These unsaturated dicarboxylic acid anhydride monomers may be contained in a mixture of two or more.
　スチレン－マレイミド系共重合体（Ａ）におけるアクリロニトリル系単量体としては、アクリロニトリル、メタアクリロニトリル等が挙げられ、特にアクリロニトリルが好ましい。また、これらのアクリロニトリル系単量体は２種以上混合して含有されてもよい。 Examples of the acrylonitrile monomer in the styrene-maleimide copolymer (A) include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. These acrylonitrile monomers may be contained in a mixture of two or more.
　スチレン－マレイミド系共重合体（Ａ）は、共重合可能なビニル系単量体単位、例えばアクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸２エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸２エチルヘキシル等の単量体単位をスチレン－マレイミド系共重合体（Ａ）に対して１０質量％未満であれば含有してもよい。 The styrene-maleimide copolymer (A) is a copolymerizable vinyl monomer unit such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methacrylic acid. Monomer units such as methyl acrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate may be contained as long as they are less than 10% by mass relative to the styrene-maleimide copolymer (A).
　スチレン－マレイミド系共重合体（Ａ）の製造は、公知の手法で行うことができ、例えば、スチレン系単量体、マレイミド系単量体、アクリロニトリル系単量体および共重合可能なビニル単量体からなる単量体混合物を共重合させることや、スチレン系単量体、不飽和ジカルボン酸無水物単量体、アクリロニトリル系単量体及び共重合可能なビニル単量体からなる単量体混合物を共重合させた後、アンモニア及び／または第一級アミンを反応させて酸無水物基をイミド基に変換させること等が挙げられる。また、重合の様式としては、公知の重合方法が利用できる。その中でも溶液重合または塊状重合が好ましい。 Production of the styrene-maleimide copolymer (A) can be carried out by a known method. For example, a styrene monomer, a maleimide monomer, an acrylonitrile monomer, and a copolymerizable vinyl monomer A monomer mixture comprising a styrene monomer, an unsaturated dicarboxylic acid anhydride monomer, an acrylonitrile monomer and a copolymerizable vinyl monomer. And the like, and then reacting ammonia and / or a primary amine to convert an acid anhydride group into an imide group. Moreover, as a polymerization mode, a known polymerization method can be used. Among these, solution polymerization or bulk polymerization is preferable.
　スチレン－マレイミド系共重合体（Ａ）の重量平均分子量（Ｍｗ）は、好ましくは１００，０００～１４５，０００であり、より好ましくは１０５，０００～１３０，０００である。重量平均分子量（Ｍｗ）が１４５，０００を超えると未溶融ブツが発生しフィルム外観性が劣り、重量平均分子量（Ｍｗ）が１００，０００未満であるとフィルム強度が劣る。 The weight average molecular weight (Mw) of the styrene-maleimide copolymer (A) is preferably 100,000 to 145,000, more preferably 105,000 to 130,000. When the weight average molecular weight (Mw) exceeds 145,000, unmelted spots are generated and the film appearance is inferior. When the weight average molecular weight (Mw) is less than 100,000, the film strength is inferior.
　なお、本明細書におけるＭｗは、ＧＰＣにて測定されるポリスチレン換算のＭｗであり、下記記載の測定条件で測定した。
　　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、Ｍｗはポリスチレン換算値で表した。 In addition, Mw in this specification is Mw of polystyrene conversion measured by GPC, and measured on the measurement conditions of the following description.
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: produced using standard polystyrene (PS) (manufactured by PL), and Mw was expressed in terms of polystyrene.
　スチレン－アクリロニトリル系共重合体（Ｂ）におけるスチレン系単量体とアクリロニトリル系単量体の構成割合は、スチレン系単量体７０～８２質量％とアクリロニトリル系単量体１８～３０質量％、好ましくはスチレン系単量体７１～８０質量％とアクリロニトリル系単量体２０～２９質量％である。 The composition ratio of the styrene monomer and the acrylonitrile monomer in the styrene-acrylonitrile copolymer (B) is 70 to 82% by mass of the styrene monomer and 18 to 30% by mass of the acrylonitrile monomer, preferably Is 71 to 80% by mass of styrene monomer and 20 to 29% by mass of acrylonitrile monomer.
　スチレン系単量体が７０質量％未満でアクリロニトリル系単量体が３０質量％を超えると、着色が強くなりフィルムの外観性が劣る。スチレン系単量体が８２質量％を超えアクリロニトリル系単量体が１８質量％未満であると、フィルムの透明性、フィルム強度が劣る。 When the styrene monomer is less than 70% by mass and the acrylonitrile monomer is more than 30% by mass, the coloring becomes strong and the appearance of the film is poor. When the styrene monomer exceeds 82% by mass and the acrylonitrile monomer is less than 18% by mass, the transparency and film strength of the film are inferior.
　スチレン－アクリロニトリル系共重合体（Ｂ）のスチレン系単量体としては、スチレン、α－メチルスチレン、ο－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｔ－ブチルスチレン、クロルスチレン等のスチレン系単量体が挙げられ、これらの中でも特にスチレンが好ましい。また、これらのスチレン系単量体は２種以上混合して含有されてもよい。 Examples of the styrene monomer of the styrene-acrylonitrile copolymer (B) include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, t-butyl styrene, and chlorostyrene. Examples thereof include styrene monomers, and among these, styrene is particularly preferable. These styrenic monomers may be contained in a mixture of two or more.
　スチレン－アクリロニトリル系共重合体（Ｂ）のアクリロニトリル系単量体としては、アクリロニトリル、メタクリロニトリル等が挙げられ、これらの中では特にアクリロニトリルが好ましい。また、これらのアクリロニトリル系単量体は２種以上混合して含有されてもよい。 Examples of the acrylonitrile monomer of the styrene-acrylonitrile copolymer (B) include acrylonitrile and methacrylonitrile. Among these, acrylonitrile is particularly preferable. These acrylonitrile monomers may be contained in a mixture of two or more.
　スチレン－アクリロニトリル系共重合体（Ｂ）は、共重合可能なビニル系単量体単位、例えばアクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸２エチルヘキシル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸２エチルヘキシル、マレイン酸無水物等の単量体単位を、スチレン－アクリロニトリル系共重合体（Ｂ）に対して１０質量％未満であれば含有してもよい。 The styrene-acrylonitrile copolymer (B) is a copolymerizable vinyl monomer unit such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methacrylic acid. If monomer units such as methyl acid, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, maleic anhydride are less than 10% by mass with respect to the styrene-acrylonitrile copolymer (B) You may contain.
　スチレン－アクリロニトリル系共重合体（Ｂ）の製造は、公知の手法で行うことができ、例えば、スチレン系単量体、アクリロニトリル系単量体および共重合可能なビニル単量体からなる単量体混合物を共重合させることが挙げられる。また、重合の様式としては、公知の重合方法が利用できる。その中でも塊状重合または溶液重合が好ましく、塊状重合がさらに好ましい。 The styrene-acrylonitrile copolymer (B) can be produced by a known method, for example, a monomer comprising a styrene monomer, an acrylonitrile monomer, and a copolymerizable vinyl monomer. Examples include copolymerizing the mixture. Moreover, as a polymerization mode, a known polymerization method can be used. Among them, bulk polymerization or solution polymerization is preferable, and bulk polymerization is more preferable.
　スチレン－アクリロニトリル系共重合体（Ｂ）の重量平均分子量（Ｍｗ）は、好ましくは、１５０，０００～２５０，０００であり、より好ましくは１７０，０００～２３０，０００である。重量平均分子量（Ｍｗ）が２５０，０００を超えるとフィルム成形性が劣り、Ｍｗが１５０，０００未満であるとフィルム強度が劣る。 The weight average molecular weight (Mw) of the styrene-acrylonitrile copolymer (B) is preferably 150,000 to 250,000, more preferably 170,000 to 230,000. When the weight average molecular weight (Mw) exceeds 250,000, the film formability is inferior, and when Mw is less than 150,000, the film strength is inferior.
　なお、本明細書における重量平均分子量（Ｍｗ）は、ＧＰＣにて測定されるポリスチレン換算のＭｗであり、下記記載の測定条件で測定した。
　　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、Ｍｗはポリスチレン換算値で表した。 In addition, the weight average molecular weight (Mw) in this specification is Mw of polystyrene conversion measured by GPC, and was measured on the following measurement conditions.
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: produced using standard polystyrene (PS) (manufactured by PL), and Mw was expressed in terms of polystyrene.
　光学成形体用樹脂組成物は、スチレン－マレイミド系共重合体（Ａ）２０～４０質量％とスチレン－アクリロニトリル系共重合体（Ｂ）６０～８０質量％、より好ましくはスチレン－マレイミド系共重合体（Ａ）２５～３５質量％とスチレン－アクリロニトリル系共重合体（Ｂ）６５～７５質量％とを含有してなる。これにより良好な物性が得られる。 The resin composition for optical molded bodies comprises 20 to 40% by mass of a styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B), more preferably a styrene-maleimide copolymer. The blend (A) contains 25 to 35% by mass and the styrene-acrylonitrile copolymer (B) 65 to 75% by mass. Thereby, good physical properties can be obtained.
　光学成形体用樹脂組成物の製造方法においては、スチレン－マレイミド系共重合体（Ａ）とスチレン－アクリロニトリル系共重合体（Ｂ）とが均一に分散する方法であれば特に制限されず、公知の混練技術を用いることができる。例えばバンバリーミキサー、ニーダー、単軸もしくは二軸押出機等を用いて溶融混練することが挙げられるが、特に美麗なフィルムを得るためには、二軸押出機を用いて溶融混練することが好ましい。 The method for producing a resin composition for an optical molded body is not particularly limited as long as the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer (B) are uniformly dispersed. These kneading techniques can be used. For example, melt kneading can be mentioned using a Banbury mixer, kneader, single screw or twin screw extruder, etc. In order to obtain a particularly beautiful film, it is preferable to melt knead using a twin screw extruder.
　スチレン－マレイミド系共重合体（Ａ）とスチレン－アクリロニトリル系共重合体（Ｂ）の押出方法としては、全量を一括フィードすることや、スチレン－マレイミド系共重合体（Ａ）とスチレン－アクリロニトリル系共重合体（Ｂ）との一部をスクリューの根元位置からフィードし、スチレン－アクリロニトリル系共重合体（Ｂ）の残りをスクリューの中間位置からサイドフィードすること等が挙げられる。 The extrusion method of the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer (B) is to feed the whole amount at once, or the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer. For example, a part of the copolymer (B) is fed from the root position of the screw, and the remainder of the styrene-acrylonitrile copolymer (B) is side-fed from an intermediate position of the screw.
　二軸押出機を用いて溶融混練する際の押出条件としては、樹脂温度が２６０～３２０℃であることが好ましく、さらに好ましくは２７０～３１０℃である。樹脂温度は、シリンダー温度、スクリュー回転数、および原料フィード量によって調整することができる。 As extrusion conditions for melt-kneading using a twin screw extruder, the resin temperature is preferably 260 to 320 ° C, more preferably 270 to 310 ° C. The resin temperature can be adjusted by the cylinder temperature, screw rotation speed, and raw material feed amount.
　二軸押出機のスクリュー長さ／シリンダー径（＝Ｌ／Ｄ）は２１～４８の範囲である。スクリューの構成は特に制限されないが、複数のパドル型円盤が右方向にずれて重なったニーディングディスクライト、複数のパドル型円盤が左方向にずれて重なったニーディングディスクレフト、パドル型円盤が９０度ずつずれて重なったニーディングディスクニュートラル等のニーディングディスクを複数個組み合わせたものが好ましい。 The screw length / cylinder diameter (= L / D) of the twin screw extruder is in the range of 21 to 48. The configuration of the screw is not particularly limited, but a kneading disc light in which a plurality of paddle type discs are shifted to the right and overlapped, a kneading disc left in which a plurality of paddle type discs are shifted to the left and overlapped, and a paddle type disc is 90 A combination of a plurality of kneading discs such as a kneading disc neutral, which are shifted and overlapped each other, is preferable.
　異物除去のため、目開きが５０μｍ以下のスクリーンメッシュや焼結フィルター、ポリマーフィルター等を押出機先端のダイス部に設置することができる。 To remove foreign matter, a screen mesh with a mesh opening of 50 μm or less, a sintered filter, a polymer filter, etc. can be installed in the die part at the tip of the extruder.
　光学成形体用樹脂組成物のガラス転移温度は好ましくは１１０～１５０℃であり、より好ましくは１１５～１４０℃である。ガラス転移温度が１１０℃未満であると、耐熱性が低く光学フィルムに適さない場合がある。またガラス転移温度が１５０℃を超えると、フィルム成形性が低下する場合がある。ガラス転移温度は、組成物を構成する共重合体の組成比等により調整できる。なお、本発明のガラス転移温度はＤＳＣにて、下記記載の測定条件で測定した。
　　装置名：セイコーインスツルメンツ（株）社製　Ｒｏｂｏｔ　ＤＳＣ６２００
　　昇温速度：１０℃／分 The glass transition temperature of the resin composition for optical molded bodies is preferably 110 to 150 ° C., more preferably 115 to 140 ° C. If the glass transition temperature is less than 110 ° C., the heat resistance is low and may not be suitable for an optical film. On the other hand, if the glass transition temperature exceeds 150 ° C., the film formability may deteriorate. The glass transition temperature can be adjusted by the composition ratio of the copolymer constituting the composition. The glass transition temperature of the present invention was measured by DSC under the measurement conditions described below.
Device name: Robot DSC6200 manufactured by Seiko Instruments Inc.
Temperature increase rate: 10 ° C / min
　ＪＩＳ　Ｋ７２１０に基づき、温度２００℃、荷重４９Ｎで測定した本発明の光学成形体用樹脂組成物のメルトマスフローレイト（ＭＦＲ）は、好ましくは０．１～３（ｇ／１０分）であり、さらに好ましくは０．２～１．５（ｇ／１０分）である。ＭＦＲが０．１（ｇ／１０分）未満や３（ｇ／１０分）を超える場合には、フィルム成形性が低下する場合がある。なお、本発明では、ＭＦＲを東洋精機製作所社製メルトインデックサ（Ｆ－Ｆ０１）を使用して測定した。 Based on JIS K7210, the melt mass flow rate (MFR) of the resin composition for optical molded bodies of the present invention measured at a temperature of 200 ° C. and a load of 49 N is preferably 0.1 to 3 (g / 10 minutes). The preferred range is 0.2 to 1.5 (g / 10 min). If the MFR is less than 0.1 (g / 10 minutes) or exceeds 3 (g / 10 minutes), the film formability may deteriorate. In the present invention, MFR was measured using a melt indexer (F-F01) manufactured by Toyo Seiki Seisakusho.
　光学成形体用樹脂組成物には、必要に応じてヒンダードフェノール系化合物、ラクトン系化合物、リン系化合物、イオウ系化合物などの耐熱安定剤、ヒンダードアミン系化合物、ベンゾトリアゾール系化合物等の耐光安定剤、滑剤や可塑剤、着色剤、帯電防止剤、鉱油等の添加剤が配合されてもよい。その配合量は光学成形体用樹脂組成物１００質量部に対して１質量部未満であることが好ましい。 In the resin composition for optical molded articles, if necessary, heat-resistant stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, sulfur compounds, and light-resistant stabilizers such as hindered amine compounds and benzotriazole compounds. Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oils may be blended. It is preferable that the compounding quantity is less than 1 mass part with respect to 100 mass parts of resin compositions for optical molded objects.
　光学成形体用樹脂組成物は、フィルムにされたとき、延伸して配向させるとフィルムが負の配向複屈折性を示すものである。 When the resin composition for optical molded bodies is formed into a film, the film exhibits negative orientation birefringence when stretched and oriented.
　光学成形体用樹脂組成物は、射出成形体、シート、フィルム等公知の成形体として使用でき、フィルムを成形する方法は特に制限はないが、フィルム押出機を用いて溶融押出することが好ましい。 The resin composition for optical molded bodies can be used as a known molded body such as an injection molded body, a sheet, and a film, and the method for molding the film is not particularly limited, but is preferably melt-extruded using a film extruder.
　光学成形体とは、光学用途に使用される成形体、シート、フィルムをいい、溶融押出フィルムとは、溶融押出により形成されたフィルムをいう。フィルムは、位相差フィルム、反射防止フィルム、偏光子保護フィルム等、公知の光学フィルムをいう。 An optical molded body refers to a molded body, a sheet, or a film used for optical applications, and a melt-extruded film refers to a film formed by melt extrusion. The film refers to a known optical film such as a retardation film, an antireflection film, and a polarizer protective film.
　本発明のフィルムは、公知の手法で延伸して配向させることができる。フィルムにした時、さらに延伸して配向させるとフィルムが負の配向複屈折性が発生するため、位相差フィルム用途に最も好ましい。 The film of the present invention can be stretched and oriented by a known method. When the film is made into a film, it is most preferable for use in a retardation film because if the film is further stretched and oriented, negative orientation birefringence occurs.
　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.
［実験例Ａ－１］
　撹拌機を備えた容積約２５リットルのオートクレーブ中にスチレン６０質量部、α－メチルスチレンダイマー０．１５質量部、およびメチルエチルケトン１００質量部を仕込み、系内を窒素ガスで置換した後、温度を９０℃に昇温し、マレイン酸無水物４０質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１４質量部とをメチルエチルケトン２００部に溶解した溶液を１０時間かけて連続的に添加した。添加後、１００℃にて３時間保った。粘稠な反応液にアニリン３６質量部、およびトリエチルアミン０．６質量部を加え１４０℃で７時間反応させた。反応液をベント付き二軸押出機に供給し、脱揮してスチレン－マレイミド系共重合体Ａ－１を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－１はスチレン単位４７質量％、Ｎ－フェニルマレイミド単位５１質量％、およびマレイン酸無水物単位２質量％を含んでおり、Ｍｗは１１１，０００であった。 [Experiment A-1]
In an autoclave having a volume of about 25 liters equipped with a stirrer, 60 parts by mass of styrene, 0.15 parts by mass of α-methylstyrene dimer and 100 parts by mass of methyl ethyl ketone were charged, and the inside of the system was replaced with nitrogen gas. The temperature was raised to 0 ° C., and a solution prepared by dissolving 40 parts by mass of maleic anhydride and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate in 200 parts of methyl ethyl ketone was continuously added over 10 hours. . After the addition, it was kept at 100 ° C. for 3 hours. 36 parts by mass of aniline and 0.6 parts by mass of triethylamine were added to the viscous reaction liquid and reacted at 140 ° C. for 7 hours. The reaction solution was supplied to a vented twin screw extruder and devolatilized to obtain a styrene-maleimide copolymer A-1. From the C-13 NMR analysis, the styrene-maleimide copolymer A-1 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, and 2% by mass of maleic anhydride units. 000.
［実験例Ａ－２］
　α－メチルスチレンダイマー０．０５質量部とした以外は、実験例Ａ－１と同様に行い、スチレン－マレイミド系共重合体Ａ－２を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－２はスチレン単位４７質量％、Ｎ－フェニルマレイミド単位５１質量％、およびマレイン酸無水物単位２質量％を含んでおり、Ｍｗは１５０，０００であった。 [Experiment A-2]
A styrene-maleimide copolymer A-2 was obtained in the same manner as in Experimental Example A-1, except that 0.05 part by mass of α-methylstyrene dimer was used. From the C-13 NMR analysis, the styrene-maleimide copolymer A-2 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, and 2% by mass of maleic anhydride units. 000.
［実験例Ａ－３］
　α－メチルスチレンダイマー０．３質量部とした以外は、実験例Ａ－１と同様に行い、スチレン－マレイミド系共重合体Ａ－３を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－３はスチレン単位４７質量％、Ｎ－フェニルマレイミド単位５１質量％、マレイン酸無水物単位２質量％を含んであり、Ｍｗは７９，０００であった。 [Experiment A-3]
A styrene-maleimide copolymer A-3 was obtained in the same manner as in Experimental Example A-1, except that 0.3 part by mass of α-methylstyrene dimer was used. According to C-13 NMR analysis, the styrene-maleimide copolymer A-3 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, 2% by mass of maleic anhydride units, and Mw is 79,000. Met.
［実験例Ａ－４］
　撹拌機を備えた容積約１５リットルのオートクレーブ中に水１５０質量部、第三リン酸カルシウム３質量部を仕込み、系内を窒素ガスで置換した後、温度を９０℃に昇温した。スチレン４５質量部、Ｎ－フェニルマレイミド５５質量部、およびα－メチルスチレンダイマー０．１５質量部の混合液と、ｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１４質量部とを１０時間かけて連続的に添加した。添加終了後、ｔ－ブチルパーオキシアセテート０．１質量部を加え、１３０℃にて３時間保った。得られたスラリーを塩酸で中和し、脱水、乾燥して得られたビーズをベント付き二軸押出機にて押し出し、スチレン－マレイミド系共重合体Ａ－４を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－４はスチレン単位４５質量％、およびＮ－フェニルマレイミド単位５５質量％を含んでおり、Ｍｗは１１９，０００であった。 [Experiment A-4]
In an autoclave having a volume of about 15 liters equipped with a stirrer, 150 parts by mass of water and 3 parts by mass of tricalcium phosphate were charged, and the system was replaced with nitrogen gas, and then the temperature was raised to 90 ° C. A mixture of 45 parts by mass of styrene, 55 parts by mass of N-phenylmaleimide and 0.15 parts by mass of α-methylstyrene dimer and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate for 10 hours Over time. After completion of the addition, 0.1 part by mass of t-butyl peroxyacetate was added and kept at 130 ° C. for 3 hours. The resulting slurry was neutralized with hydrochloric acid, dehydrated and dried, and the resulting beads were extruded with a vented twin screw extruder to obtain a styrene-maleimide copolymer A-4. According to C-13 NMR analysis, the styrene-maleimide copolymer A-4 contained 45% by mass of styrene units and 55% by mass of N-phenylmaleimide units, and Mw was 119,000.
［実験例Ａ－５］
　スチレン７６質量部、マレイン酸無水物２４質量部、アニリン２１．６質量部、およびトリエチルアミン０．３６質量部とした以外は、実験例Ａ－１と同様に行い、スチレン－マレイミド系共重合体Ａ－５を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－５は、スチレン単位６５質量％、Ｎ－フェニルマレイミド３４質量％、およびマレイン酸無水物単位１質量％を含んでおり、Ｍｗは１１２，０００であった。 [Experimental example A-5]
A styrene-maleimide copolymer A was prepared in the same manner as in Experimental Example A-1, except that 76 parts by mass of styrene, 24 parts by mass of maleic anhydride, 21.6 parts by mass of aniline, and 0.36 parts by mass of triethylamine were used. -5 was obtained. According to C-13 NMR analysis, styrene-maleimide copolymer A-5 contains 65% by mass of styrene units, 34% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride units, and Mw is 112, 000.
［実験例Ａ－６］
　撹拌機を備えた容積約２５リットルのオートクレーブ中にスチレン４９質量部、アクリロニトリル１１質量部、α－メチルスチレンダイマー０．０５質量部、およびメチルエチルケトン１００質量部を仕込み、系内を窒素ガスで置換した後、温度を９０℃に昇温し、Ｎ－フェニルマレイミド４０質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１４質量部をメチルエチルケトン２００部に溶解した溶液を１２時間かけて連続的に添加した。添加後、１００℃にて４時間保った。反応液をベント付き二軸押出機に供給し、脱揮してスチレン－マレイミド系共重合体Ａ－６を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－６は、スチレン単位４９質量％、Ｎ－フェニルマレイミド単位４０質量％、およびアクリロニトリル単位１１質量を含んでおり、Ｍｗは１４５，０００であった。 [Experiment A-6]
In an autoclave having a volume of about 25 liters equipped with a stirrer, 49 parts by mass of styrene, 11 parts by mass of acrylonitrile, 0.05 part by mass of α-methylstyrene dimer, and 100 parts by mass of methyl ethyl ketone were charged, and the system was replaced with nitrogen gas. Thereafter, the temperature was raised to 90 ° C., and a solution obtained by dissolving 40 parts by mass of N-phenylmaleimide and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate in 200 parts of methyl ethyl ketone was continuously added over 12 hours. Was added. After the addition, it was kept at 100 ° C. for 4 hours. The reaction solution was supplied to a vented twin screw extruder and devolatilized to obtain a styrene-maleimide copolymer A-6. From the C-13 NMR analysis, the styrene-maleimide copolymer A-6 contained 49% by mass of styrene units, 40% by mass of N-phenylmaleimide units, and 11% by mass of acrylonitrile units, and the Mw was 145,000. It was.
［実験例Ａ－７］
　アニリン３６質量部をシクロヘキシルアミン３６質量部とした以外は、実験例Ａ－１と同様に行い、スチレン－マレイミド系共重合体Ａ－７を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－７は、スチレン単位４７質量％、Ｎ－シクロヘキシルマレイミド単位５１質量％、およびマレイン酸無水物単位２質量％を含有しており、Ｍｗは１１０，０００であった。 [Experiment A-7]
A styrene-maleimide copolymer A-7 was obtained in the same manner as in Experimental Example A-1, except that 36 parts by mass of aniline was changed to 36 parts by mass of cyclohexylamine. From C-13 NMR analysis, styrene-maleimide copolymer A-7 contains 47% by mass of styrene units, 51% by mass of N-cyclohexylmaleimide units, and 2% by mass of maleic anhydride units, and Mw is 110,000.
［実験例Ａ－８］
　撹拌機を備えた容積約２５リットルのオートクレーブ中にスチレン３７質量部、α－メチルスチレンダイマー０．１５質量部、およびメチルエチルケトン１００質量部を仕込み、系内を窒素ガスで置換した後、温度を９０℃に昇温し、Ｎ－フェニルマレイミド６３質量部とｔ－ブチルパーオキシ－２－エチルヘキサノエート０．１４質量部とをメチルエチルケトン２００部に溶解した溶液を１２時間かけて連続的に添加した。添加後、１００℃にて４時間保った。反応液をベント付き二軸押出機に供給し、脱揮してスチレン－マレイミド系共重合体Ａ－８を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－８は、スチレン単位３７質量％、およびＮ－フェニルマレイミド単位６３質量％を含んでおり、Ｍｗは１１４，０００であった。 [Experiment A-8]
In an autoclave having a volume of about 25 liters equipped with a stirrer, 37 parts by mass of styrene, 0.15 parts by mass of α-methylstyrene dimer and 100 parts by mass of methyl ethyl ketone were charged, and the inside of the system was replaced with nitrogen gas. The temperature was raised to 0 ° C., and a solution prepared by dissolving 63 parts by mass of N-phenylmaleimide and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate in 200 parts of methyl ethyl ketone was continuously added over 12 hours. . After the addition, it was kept at 100 ° C. for 4 hours. The reaction solution was supplied to a twin screw extruder with a vent and devolatilized to obtain a styrene-maleimide copolymer A-8. According to C-13 NMR analysis, the styrene-maleimide copolymer A-8 contained 37% by mass of styrene units and 63% by mass of N-phenylmaleimide units, and the Mw was 114,000.
［実験例Ａ－９］
　α－メチルスチレンダイマー０．２０質量部とした以外は、実験例Ａ－１と同様に行い、スチレン－マレイミド系共重合体Ａ－９を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－９は、スチレン単位４７質量％、Ｎ－フェニルマレイミド単位５１質量％、およびマレイン酸無水物単位２質量％を含んでおり、Ｍｗは１００，０００であった。 [Experiment A-9]
A styrene-maleimide copolymer A-9 was obtained in the same manner as in Experimental Example A-1, except that 0.20 parts by mass of α-methylstyrene dimer was used. According to C-13 NMR analysis, styrene-maleimide copolymer A-9 contains 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, and 2% by mass of maleic anhydride units, and Mw is 100 000.
［実験例Ａ－１０］
　スチレン８５質量部、マレイン酸無水物１５質量部、アニリン１３．５質量部、トリエチルアミン０．２３質量部とした以外は、実験例Ａ－１と同様に行い、スチレン－マレイミド系共重合体Ａ－１０を得た。Ｃ－１３ＮＭＲ分析より、スチレン－マレイミド系共重合体Ａ－１０は、スチレン単位７７質量％、Ｎ－フェニルマレイミド２２質量％、およびマレイン酸無水物単位１質量％を含んでおり、Ｍｗは１１７，０００であった。 [Experiment A-10]
A styrene-maleimide copolymer A- was prepared in the same manner as in Experimental Example A-1, except that 85 parts by weight of styrene, 15 parts by weight of maleic anhydride, 13.5 parts by weight of aniline, and 0.23 parts by weight of triethylamine were used. 10 was obtained. From the C-13 NMR analysis, the styrene-maleimide copolymer A-10 contains 77% by mass of styrene units, 22% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride units. 000.
　上記実験例Ａ－１～Ａ－１０で得られた共重合体の成分組成と重量平均分子量（Ｍｗ）を表１に示す。
Figure JPOXMLDOC01-appb-T000001
 Table 1 shows the component compositions and weight average molecular weights (Mw) of the copolymers obtained in Experimental Examples A-1 to A-10.
Figure JPOXMLDOC01-appb-T000001
［実験例Ｂ－１］
　撹拌機を付した容積約２０リットルの完全混合型反応器に、予熱器を付した脱揮槽を接続した。スチレン７３．６質量部、アクリロニトリル２６．４質量部、およびエチルベンゼン２０質量部で構成される単量体混合液を調製し、さらにｔ－ブチルパーオキシイソプロピルモノカーボネート０．０１５質量部とｎ－ドデシルメルカプタン０．０１３質量部を混合し、原料溶液とした。この原料溶液を毎時５ｋｇで、温度１２０℃に制御した完全混合型反応器に導入した。なお、完全混合型反応器の撹拌数は１８０ｒｐｍとした。次いで、完全混合型反応器より反応液を連続的に抜き出し、この反応液を予熱器で加温しながら、温度２３５℃で圧力１．０ｋＰａに制御した脱揮槽に導入し、未反応単量体等の揮発分を除去した。樹脂液をギアポンプで抜き出し、ストランド状に押出し切断することにより、ペレット形状の重合体Ｂ－１を得た。Ｃ－１３ＮＭＲ分析より、重合体Ｂ－１はスチレン単位７４質量％、およびアクリロニトリル単位２６質量％を含んでおり、Ｍｗは２０２，０００であった。 [Experiment B-1]
A devolatilization tank equipped with a preheater was connected to a fully mixed reactor having a capacity of about 20 liters equipped with a stirrer. A monomer mixture composed of 73.6 parts by mass of styrene, 26.4 parts by mass of acrylonitrile, and 20 parts by mass of ethylbenzene was prepared, and 0.015 parts by mass of t-butylperoxyisopropyl monocarbonate and n-dodecyl were further prepared. Mercaptan (0.013 parts by mass) was mixed to prepare a raw material solution. This raw material solution was introduced at 5 kg / h into a fully mixed reactor controlled at a temperature of 120 ° C. The stirring number of the complete mixing reactor was 180 rpm. Next, the reaction solution was continuously withdrawn from the complete mixing reactor, and this reaction solution was introduced into a devolatilization tank controlled at a temperature of 235 ° C. and a pressure of 1.0 kPa while being heated by a preheater. Volatile matter such as body was removed. The resin liquid was extracted with a gear pump and extruded and cut into strands to obtain a pellet-shaped polymer B-1. From C-13 NMR analysis, the polymer B-1 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and the Mw was 202,000.
［実験例Ｂ－２］
　スチレン６８．２質量部、アクリロニトリル３１．８質量部、およびエチルベンゼン１８質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－２を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－２はスチレン単位７０質量％、およびアクリロニトリル単位３０質量％を含んでおり、Ｍｗは１９８，０００であった。 [Experiment B-2]
A styrene-acrylonitrile copolymer B-2 was obtained in the same manner as in Experimental Example B-1, except that 68.2 parts by mass of styrene, 31.8 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-2 contained 70% by mass of styrene units and 30% by mass of acrylonitrile units, and Mw was 198,000.
［実験例Ｂ－３］
　撹拌機を備えた容積約１５リットルのオートクレーブ中に純水１５０質量部、第三リン酸カルシウム３部、スチレン４５質量部、アクリロニトリル２６質量部、α－メチルスチレンダイマー０．０５質量部、ｔ－ブチルパーオキシイソプロピルモノカーボネート０．２質量部、およびｔ－ブチルパーオシキアセテート０．１部を仕込み、系内を窒素ガスで置換した後、温度を１０３℃℃に保ち、その後スチレン２９質量部を１０３℃で４時間、１０５℃で２時間の計６時間かけて連続添加した。添加終了後、１２０℃で３時間保った。得られたスラリーを塩酸で中和し、脱水、乾燥して得られたビーズをベント付き二軸押出機にて押し出し、スチレン－アクリロニトリル系共重合体Ｂ－３を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－３はスチレン単位７４質量％、およびアクリロニトリル単位２６質量％を含んでおり、Ｍｗは１５３，０００であった。 [Experiment B-3]
In an autoclave having a volume of about 15 liters equipped with a stirrer, 150 parts by mass of pure water, 3 parts of tribasic calcium phosphate, 45 parts by mass of styrene, 26 parts by mass of acrylonitrile, 0.05 part by mass of α-methylstyrene dimer, t-butyl per After charging 0.2 parts by mass of oxyisopropyl monocarbonate and 0.1 part of t-butyl peroxyacetate and replacing the system with nitrogen gas, the temperature was kept at 103 ° C., and 29 parts by mass of styrene was then added at 103 ° C. For 4 hours and at 105 ° C. for 2 hours, continuously added over 6 hours. After completion of the addition, the temperature was kept at 120 ° C. for 3 hours. The obtained slurry was neutralized with hydrochloric acid, dehydrated and dried, and beads obtained were extruded with a twin screw extruder equipped with a vent to obtain a styrene-acrylonitrile copolymer B-3. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-3 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and Mw was 153,000.
［実験例Ｂ－４］
　スチレン７６．２質量部、アクリロニトリル２３．８質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－４を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－４はスチレン単位７６質量％、およびアクリロニトリル単位２４質量％を含んでおり、Ｍｗは２０１，０００であった。 [Experiment B-4]
A styrene-acrylonitrile copolymer B-4 was obtained in the same manner as in Experimental Example B-1, except that 76.2 parts by mass of styrene and 23.8 parts by mass of acrylonitrile were used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-4 contained 76% by mass of styrene units and 24% by mass of acrylonitrile units, and Mw was 201,000.
［実験例Ｂ－５］
　スチレン８２．９質量部、アクリロニトリル１７．１質量部、エチルベンゼン１５質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－５を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－５はスチレン単位８２質量％、およびアクリロニトリル単位１８質量％を含んでおり、Ｍｗは２４５，０００であった。 [Experiment B-5]
A styrene-acrylonitrile copolymer B-5 was obtained in the same manner as in Experimental Example B-1, except that 82.9 parts by mass of styrene, 17.1 parts by mass of acrylonitrile, and 15 parts by mass of ethylbenzene were used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-5 contained 82% by mass of styrene units and 18% by mass of acrylonitrile units, and Mw was 245,000.
［実験例Ｂ－６］
　スチレン９１．８質量部、アクリロニトリル９．２質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－６を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－６はスチレン単位９０質量％、およびアクリロニトリル単位１０質量％を含んでおり、Ｍｗは１９７，０００であった。 [Experiment B-6]
A styrene-acrylonitrile copolymer B-6 was obtained in the same manner as in Experimental Example B-1, except that 91.8 parts by mass of styrene and 9.2 parts by mass of acrylonitrile were used. From C-13 NMR analysis, the styrene-acrylonitrile copolymer B-6 contained 90% by mass of styrene units and 10% by mass of acrylonitrile units, and Mw was 197,000.
［実験例Ｂ－７］
　スチレン６０．５質量部、アクリロニトリル３９．５質量部、エチルベンゼン１８質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－７を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－７はスチレン単位６５質量％、およびアクリロニトリル単位３５質量％を含んでおり、Ｍｗは２１０，０００であった。 [Experiment B-7]
A styrene-acrylonitrile copolymer B-7 was obtained in the same manner as in Experimental Example B-1, except that 60.5 parts by mass of styrene, 39.5 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. From C-13 NMR analysis, styrene-acrylonitrile copolymer B-7 contained 65% by mass of styrene units and 35% by mass of acrylonitrile units, and Mw was 210,000.
［実験例Ｂ－８］
　ｎ－ドデシルメルカプタン０．０５６質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－８を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－８はスチレン単位７４質量％、およびアクリロニトリル単位２６質量％を含んでおり、Ｍｗは１３４，０００であった。 [Experiment B-8]
A styrene-acrylonitrile copolymer B-8 was obtained in the same manner as in Experimental Example B-1, except that 0.056 parts by mass of n-dodecyl mercaptan was used. From C-13 NMR analysis, styrene-acrylonitrile copolymer B-8 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and Mw was 134,000.
［実験例Ｂ－９］
　エチルベンゼン１５質量部、ｎ－ドデシルメルカプタン０．００５質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－９を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－９はスチレン単位７４質量％、アクリロニトリル単位２６質量％を含んでおり、Ｍｗは２７２，０００であった。 [Experiment B-9]
A styrene-acrylonitrile copolymer B-9 was obtained in the same manner as in Experimental Example B-1, except that 15 parts by weight of ethylbenzene and 0.005 parts by weight of n-dodecyl mercaptan were used. From C-13 NMR analysis, the styrene-acrylonitrile copolymer B-9 contained 74% by mass of styrene units, 26% by mass of acrylonitrile units, and Mw was 272,000.
［実験例Ｂ－１０］
　スチレン５６．１質量部、α－メチルスチレン１７．５質量部、アクリロニトリル２６．４質量部、エチルベンゼン１８質量部とした以外は、実験例Ｂ－１と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－１０を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－１０はスチレン単位６０質量％、α－メチルスチレン単位１４質量％、およびアクリロニトリル単位２６質量％を含んでおり、Ｍｗは２０１，０００であった。 [Experiment B-10]
A styrene-acrylonitrile copolymer was prepared in the same manner as in Experimental Example B-1, except that 56.1 parts by mass of styrene, 17.5 parts by mass of α-methylstyrene, 26.4 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. B-10 was obtained. According to C-13 NMR analysis, styrene-acrylonitrile copolymer B-10 contained 60% by mass of styrene units, 14% by mass of α-methylstyrene units, and 26% by mass of acrylonitrile units, and Mw was 201,000. It was.
［実験例Ｂ－１１］
　α－メチルスチレンダイマー０．０２質量部とした以外は、実験例Ｂ－３と同様に行い、スチレン－アクリロニトリル系共重合体Ｂ－１１を得た。Ｃ－１３ＮＭＲ分析より、スチレン－アクリロニトリル系共重合体Ｂ－１１は、スチレン単位７４質量％、およびアクリロニトリル単位２６質量％を含んでおり、Ｍｗは１９２，０００であった。 [Experiment B-11]
A styrene-acrylonitrile copolymer B-11 was obtained in the same manner as in Experimental Example B-3, except that 0.02 part by mass of α-methylstyrene dimer was used. From the C-13 NMR analysis, the styrene-acrylonitrile copolymer B-11 contained 74% by mass of styrene units and 26% by mass of acrylonitrile units, and Mw was 192,000.
　上記実験例Ｂ－１～Ｂ－１１で得られた共重合体の成分組成と重量平均分子量（Ｍｗ）を表２に示す。
Figure JPOXMLDOC01-appb-T000002
 Table 2 shows the component compositions and weight average molecular weights (Mw) of the copolymers obtained in Experimental Examples B-1 to B-11.
Figure JPOXMLDOC01-appb-T000002
［実施例１～１３及び比較例１～１０］
　各実験例で製造したスチレン－マレイミド系共重合体（Ａ）とスチレン－アクリロニトリル系共重合体（Ｂ）を、表３～表４で示した割合（質量％）でヘンシェルミキサーを用いて混合した後、二軸押出機（東芝機械（株）社製　ＴＥＭ－３５Ｂ、Ｌ／Ｄ＝３２）を用い、シリンダー温度２６０℃、フィード量２０ｋｇ／時、スクリュー回転数２５０ｒｐｍの条件にて溶融混練してペレット化し、光学成形体用樹脂組成物を得た。なお、樹脂温度はいずれも２７０～３１０℃の範囲であった。 [Examples 1 to 13 and Comparative Examples 1 to 10]
The styrene-maleimide copolymer (A) and styrene-acrylonitrile copolymer (B) produced in each experimental example were mixed using a Henschel mixer in the proportions (mass%) shown in Tables 3 to 4. Then, using a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd., L / D = 32), the mixture was melt-kneaded at a cylinder temperature of 260 ° C., a feed rate of 20 kg / hour, and a screw rotation speed of 250 rpm. The resin composition for optical molded bodies was obtained by pelletizing. The resin temperature was in the range of 270 to 310 ° C.
　光学成形体用樹脂組成物を、Ｔダイを付したフィルム押出成形機を用い、シリンダー温度２４０℃、ダイ温度２４０℃で、厚さ１００μｍのフィルムへと押し出し、ロールに巻き取った。 The resin composition for optical molded bodies was extruded into a film having a thickness of 100 μm at a cylinder temperature of 240 ° C. and a die temperature of 240 ° C. using a film extrusion machine with a T-die, and wound on a roll.
　得られたフィルムを、テンター横延伸機を用い、Ｔｇ＋２０℃で１．８倍に一軸延伸し、延伸された光学フィルム（「延伸フィルム」という。）を得た。得られた延伸フィルムに関する測定結果を表３～表４に示した。 The obtained film was uniaxially stretched 1.8 times at Tg + 20 ° C. using a tenter transverse stretching machine to obtain a stretched optical film (referred to as “stretched film”). The measurement results regarding the obtained stretched film are shown in Tables 3 to 4.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　評価は下記の方法にて行った。
　（１）耐熱性
　ＤＳＣ（セイコーインスツルメンツ（株）社製　Ｒｏｂｏｔ　ＤＳＣ６２００）を用いて測定した（昇温速度：１０℃／分、単位：℃）ガラス転移温度が１１０℃以上である場合、合格と評価した。
　（２）未延伸フィルムの透明性
　ＡＳＴＭ　Ｄ１００３に基づき、ヘーズメーター（日本電色工業社製ＮＤＨ－１００１ＤＰ型）を用いて厚み１００μｍの未延伸フィルムのヘーズ（単位：％）を測定した。ヘーズが１．０％以下である場合、合格と評価した。
　（３）フィルム成形性
　フィルムの押出成形性を下記基準にて判断し、「優」および「良」である場合、合格と評価した。
「優」：押出に問題なく、異常なくロールに巻き取れたもの
「良」：ロールに巻き取れたが、厚み制御ができず、スリットで端部に割れ発生等があるもの
「不良」：ドローダウン、切断等でロールに巻き取れなかったもの
　（４）フィルム強度
　フィルム強度を耐折強度の測定を以下の条件にて行い、下記基準にて判断し、「優」および「良」である場合、合格と評価した。
　　測定条件
　　　測定器：ＭＩＴ－Ｄ　ＦＯＬＯＤＩＮＧ　ＥＮＤＵＲＡＮＣＥ　ＴＥＳＴＥＲ（東洋精機社製）
　　　荷重（張力）：５００ｇ重
　　　折り曲げ速度：１７５回／分
　　　折り曲げ角度：左右各４５度
　　　折り曲げ装置先端半径：０．３８ｍｍ
　　　試験幅：１５ｍｍ
　　　折り曲げ方向：フィルム押出方向
　　強度判断基準
「優」：折り曲げ回数１００回以上
「良」：折り曲げ回数５０回以上１００回未満
「不良」：折り曲げ回数５０回未満
　（５）フィルム外観
　フィルムの外観を目視にて下記基準にて判断し、「優」および「良」である場合、合格と評価した。
「優」：異常なし
「良」：ポリマーゲル、未溶融ブツが１～５個／ｍ２未満
「不良」：ポリマーゲル、未溶融ブツが５個／ｍ２以上あるもの、またはフィルム表面が荒れ透明性のムラがあるもの、または著しい着色があるもの
　（６）延伸フィルムの透明性
　ＡＳＴＭ　Ｄ１００３に基づき、ヘーズメーター（日本電色工業社製ＮＤＨ－１００１ＤＰ型）を用いて延伸フィルムのヘーズ（単位：％）を測定した。ヘーズが１．０％以下である場合、合格と評価した。
　（７）位相差発現性
　位相差測定装置（王子計測社製ＫＯＢＲＡ－ＷＲ）を用いて延伸フィルムのリタデーション（以下「Ｒｅ」，単位：μｍ）を測定し、Ｒｅが３００ｎｍ以上である場合、合格と評価した。また、位相差顕微鏡で観察することで、配向複屈折の符号は、実施例と比較例中の全てのサンプルが負であることを確認した。 Evaluation was performed by the following method.
(1) Heat resistance Measured using DSC (Robot DSC6200 manufactured by Seiko Instruments Inc.) (temperature increase rate: 10 ° C./min, unit: ° C.) When the glass transition temperature is 110 ° C. or higher, it is evaluated as acceptable. did.
(2) Transparency of unstretched film Based on ASTM D1003, the haze (unit:%) of an unstretched film having a thickness of 100 μm was measured using a haze meter (NDH-1001DP type manufactured by Nippon Denshoku Industries Co., Ltd.). When the haze was 1.0% or less, it was evaluated as acceptable.
(3) Film moldability The extrusion moldability of the film was judged according to the following criteria.
“Excellent”: Unrolled without any problems with extrusion, good wound: “Good”: Rolled around the roll, but the thickness could not be controlled, and there was a crack at the end due to the slit, etc. “Bad”: Draw (4) Film strength When the film strength is measured under the following conditions, the film strength is determined according to the following criteria, and “excellent” and “good” , Passed and evaluated.
Measurement conditions Measuring instrument: MIT-D FOLDING ENDURANCE TESTER (Toyo Seiki Co., Ltd.)
Load (tension): 500 g weight Bending speed: 175 times / min Bending angle: 45 degrees each left and right Folding device tip radius: 0.38 mm
Test width: 15mm
Folding direction: Film extrusion direction Strength criteria “excellent”: Bending frequency 100 times or more “Good”: Bending frequency 50 times or more and less than 100 “Bad”: Bending frequency 50 times or less (5) Film appearance Visual appearance of film Judgment was made based on the following criteria, and “good” and “good” were evaluated as acceptable.
“Excellent”: No abnormality “Good”: Polymer gel, unmelted but less than 1 to 5 / m 2 “Poor”: Polymer gel, unmelted but not less than 5 / m 2 , or rough film surface (6) Transparency of stretched film Based on ASTM D1003, the haze of the stretched film (unit: NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.) :%). When the haze was 1.0% or less, it was evaluated as acceptable.
(7) Retardation expression The retardation of the stretched film (hereinafter “Re”, unit: μm) is measured using a phase difference measuring device (KOBRA-WR manufactured by Oji Scientific Co., Ltd.). It was evaluated. Moreover, by observing with a phase-contrast microscope, it confirmed that the sign of orientation birefringence was negative for all the samples in the examples and comparative examples.
　本発明に係る実施例は、透明性、耐熱性、フィルム成形性、フィルム強度、フィルム外観性が良好であり、これらのことから、得られたフィルムが光学成形体、特に光学フィルムに最適であることが分かる。また、延伸して配向させた遠心フィルムは、位相差発現性が良好で且つ負の配向複屈折性を示すため、位相差フィルムとして最適である。 Examples according to the present invention have good transparency, heat resistance, film moldability, film strength, and film appearance, and from these facts, the obtained film is optimal for optical molded bodies, particularly optical films. I understand that. Moreover, the stretched and oriented centrifugal film is suitable as a retardation film because it exhibits good retardation and exhibits negative orientation birefringence.

Claims (10)

  1. 　下記のスチレン－マレイミド系共重合体（Ａ）２０～４０質量％とスチレン－アクリロニトリル系共重合体（Ｂ）６０～８０質量％を含有してなる光学成形体用樹脂組成物であって、ＡＳＴＭ　Ｄ１００３に基づき測定した、厚み１００μｍの未延伸フィルムのヘーズが１．０％以下である光学成形体用樹脂組成物。
    　スチレン－マレイミド系共重合体（Ａ）：スチレン系単量体単位４０～７０質量％、マレイミド系単量体単位３０～６０質量％、不飽和ジカルボン酸無水物単量体単位０～１５質量％、及びアクリロニトリル系単量体単位０～１５質量％を含み、重量平均分子量（Ｍｗ）が１００，０００～１４５，０００である共重合体。
    　スチレン－アクリロニトリル系共重合体（Ｂ）：スチレン系単量体単位７０～８２質量％、及びアクリロニトリル系単量体単位１８～３０質量％を含み、重量平均分子量（Ｍｗ）が１５０，０００～２５０，０００である共重合体。     A resin composition for an optical molded article comprising 20 to 40% by mass of the following styrene-maleimide copolymer (A) and 60 to 80% by mass of a styrene-acrylonitrile copolymer (B), which is ASTM A resin composition for optical molded bodies, wherein the haze of an unstretched film having a thickness of 100 μm, measured based on D1003, is 1.0% or less.
    Styrene-maleimide copolymer (A): styrene monomer unit 40 to 70% by mass, maleimide monomer unit 30 to 60% by mass, unsaturated dicarboxylic anhydride monomer unit 0 to 15% by mass And a copolymer containing 0 to 15% by mass of an acrylonitrile monomer unit and having a weight average molecular weight (Mw) of 100,000 to 145,000.
    Styrene-acrylonitrile copolymer (B): containing 70 to 82% by mass of styrene monomer units and 18 to 30% by mass of acrylonitrile monomer units, and having a weight average molecular weight (Mw) of 150,000 to 250 A copolymer that is 1,000.
  2. 　スチレン－マレイミド系共重合体（Ａ）が溶液重合もしくは塊状重合により得られたものである請求項１記載の光学成形体用樹脂組成物。 The resin composition for optical molded bodies according to claim 1, wherein the styrene-maleimide copolymer (A) is obtained by solution polymerization or bulk polymerization.
  3. 　スチレン－アクリロニトリル系共重合体（Ｂ）が塊状重合もしくは溶液重合により得られたものである請求項１又は２記載の光学成形体用樹脂組成物。 The resin composition for an optical molded article according to claim 1 or 2, wherein the styrene-acrylonitrile copolymer (B) is obtained by bulk polymerization or solution polymerization.
  4. 　ガラス転移温度が１１０～１５０℃である請求項１～３のいずれか１項に記載の光学成形体用樹脂組成物。 The resin composition for optical molded bodies according to any one of claims 1 to 3, wherein the glass transition temperature is 110 to 150 ° C.
  5. 　ＪＩＳ　Ｋ７２１０に基づき、温度２００℃、荷重４９Ｎで測定した光学成形体用樹脂組成物のメルトマスフローレイト（ＭＦＲ）が０．１～３（ｇ／１０分）である請求項１～４のいずれか１項に記載の光学成形体用樹脂組成物。 The melt mass flow rate (MFR) of the resin composition for optical molded bodies measured at a temperature of 200 ° C. and a load of 49 N based on JIS K7210 is 0.1 to 3 (g / 10 min). 2. The resin composition for optical molded bodies according to item 1.
  6. 　請求項１～５のいずれか１項に記載の光学成形体用樹脂組成物からなる光学成形体。 An optical molded body comprising the resin composition for an optical molded body according to any one of claims 1 to 5.
  7. 　フィルムであって、延伸して配向させると負の配向複屈折性を示すフィルムである請求項６記載の光学成形体。 The optical molded body according to claim 6, wherein the optical molded body is a film that exhibits negative orientation birefringence when stretched and oriented.
  8. 　溶融押出フィルムであって、延伸して配向させると負の配向複屈折性を示すフィルムである請求項６記載の光学成形体。 The optical molded body according to claim 6, which is a melt-extruded film, which is a film exhibiting negative orientation birefringence when oriented by stretching.
  9. 　延伸フィルムである請求項７又は８記載の光学成形体。 The optical molded body according to claim 7 or 8, which is a stretched film.
  10. 　位相差フィルムである請求項９記載の光学成形体。 The optical molded body according to claim 9, which is a retardation film.
PCT/JP2009/060708 2008-06-12 2009-06-11 Resin composition for optical molded object and optical molded object obtained therefrom WO2009151102A1 (en)

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WO2010058723A1 (en) * 2008-11-21 2010-05-27 電気化学工業株式会社 Resin composition for optical film and optical film thereof

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JP2013107933A (en) * 2011-11-17 2013-06-06 Denki Kagaku Kogyo Kk Resin composition for optical molded article, method for producing the same and optical molded article

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JP2008094912A (en) * 2006-10-10 2008-04-24 Denki Kagaku Kogyo Kk Resin composition and optical molded article

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JP2008094912A (en) * 2006-10-10 2008-04-24 Denki Kagaku Kogyo Kk Resin composition and optical molded article

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010058723A1 (en) * 2008-11-21 2010-05-27 電気化学工業株式会社 Resin composition for optical film and optical film thereof

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