WO2010058723A1 - Resin composition for optical film and optical film thereof - Google Patents

Resin composition for optical film and optical film thereof Download PDF

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Publication number
WO2010058723A1
WO2010058723A1 PCT/JP2009/069183 JP2009069183W WO2010058723A1 WO 2010058723 A1 WO2010058723 A1 WO 2010058723A1 JP 2009069183 W JP2009069183 W JP 2009069183W WO 2010058723 A1 WO2010058723 A1 WO 2010058723A1
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mass
styrene
film
optical film
acrylonitrile
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PCT/JP2009/069183
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French (fr)
Japanese (ja)
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慶太 大橋
幸一 小澤
哲央 野口
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電気化学工業株式会社
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Publication of WO2010058723A1 publication Critical patent/WO2010058723A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride 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
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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

Definitions

  • the present invention relates to a resin composition for an optical film and the optical film.
  • 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.
  • an optical film there is a film called a retardation film that plays a role of compensating the retardation of the liquid crystal of the liquid crystal display or improving the viewing angle.
  • the retardation film for example, polycarbonate or amorphous cyclic polyolefin is used, and these have positive orientation birefringence. It is known that the viewing angle can be further improved by laminating this and an optical film exhibiting negative orientation birefringence.
  • the objective of this invention provides the resin composition for optical films, and its optical film. Further, the present invention provides a film having high strength, few film defects, negative orientation birefringence, and excellent retardation development.
  • the gist of the present invention is as follows. (1) (i) Styrene monomer units 35 to 55% by mass, maleimide monomer units 30 to 60% by mass, unsaturated dicarboxylic acid anhydride monomer units 0 to 15% by mass, acrylonitrile monomers 20 to 40% by mass of a styrene-maleimide copolymer (A) having a body unit of 0 to 15% by mass and having a weight average molecular weight (Mw) of 100,000 to 145,000, (Ii) A styrene-acrylonitrile copolymer comprising 65 to 70% by mass of a styrene monomer unit and 30 to 35% by mass of an acrylonitrile monomer unit and having a weight average molecular weight (Mw) of 150,000 to 250,000.
  • a styrene-acrylonitrile copolymer comprising 65 to 70% by mass of a styrene monomer unit and 30 to 35% by mass of an acrylon
  • a resin composition for an optical film comprising 60 to 80% by mass of the polymer (B), and when formed into an unstretched film having a thickness of 100 ⁇ m, film defects having a length of 50 ⁇ m or more are 5 / m 2.
  • the resin composition for optical films which is less than.
  • the “film defect” refers to a portion that appears to be non-uniform due to the mixing of foreign matters, the occurrence of unmelted spots, and the like.
  • the unmelted material is mainly caused by the styrene-maleimide copolymer (A) that cannot be dispersed due to insufficient melt kneading.
  • Film defects are measured per 1 m 2 of unstretched film using an image processing analyzer after molding the resin composition for optical films according to the present invention into an unstretched film having a thickness of 100 ⁇ m using an extruder. This is done by examining the number of film defects having a length of 50 ⁇ m or more.
  • optical film refers to a film used for optical applications such as a retardation film, an antireflection film, and a polarizer protective film
  • melt extruded film refers to a film formed by melt extrusion
  • the resin composition of the present invention is useful for an optical film for a thin liquid crystal display element because of its good transparency, heat resistance, film moldability, and film strength.
  • a stretched and oriented film is a film. It is useful for retardation films since it has few defects, exhibits negative orientation birefringence, and is excellent in retardation development.
  • styrene-maleimide copolymer (A) The composition ratio of the styrene-maleimide copolymer (A) is as follows: styrene monomer unit 35 to 55% by mass, maleimide monomer unit 30 to 60% by mass, unsaturated dicarboxylic anhydride monomer unit 0 15% by mass and 0-15% by mass of acrylonitrile monomer units. If the styrene monomer unit is 35% by mass or more, or if the maleimide monomer unit is 60% by mass or less, it will be easy to mix with the styrene-acrylonitrile copolymer (B) described later, so it will not melt.
  • the transparency of the film can be sufficiently secured.
  • the unsaturated dicarboxylic acid anhydride monomer unit and the acrylonitrile monomer unit are optional components. In some cases, the transparency of the film can be improved by blending an unsaturated dicarboxylic acid anhydride monomer unit into the styrene-maleimide copolymer (A).
  • strength of a film may be able to be improved by mix
  • the unsaturated dicarboxylic acid anhydride monomer unit is 15% by mass or less, the thermal stability is not impaired and the film is not colored.
  • the acrylonitrile monomer unit is 15% by mass or less, sufficient transparency of the film can be ensured.
  • 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 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.
  • These maleimide monomers may be a mixture of two or more.
  • 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 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 a mixture of two or more.
  • the styrene-maleimide copolymer (A) includes copolymerizable vinyl monomer units such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2 Monomer units such as ethylhexyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate may be blended in the range of less than 10% by mass.
  • vinyl monomer units such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2
  • Monomer units such as ethylhexyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate may be blended in the range of less than 10% by mass
  • styrene-maleimide copolymer (A) As a method for producing the styrene-maleimide copolymer (A), a known method can be adopted, 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 a method of reacting ammonia and / or a primary amine to convert an acid anhydride group into an imide group.
  • the polymerization mode is preferably solution polymerization or bulk polymerization. If a styrene-maleimide copolymer obtained by suspension polymerization or emulsion polymerization is used, the transparency of the film may be low.
  • the weight average molecular weight (Mw) of the styrene-maleimide copolymer (A) is 100,000 to 145,000, more preferably 110,000 to 130,000. If Mw is 145,000 or less, it becomes easy to mix with the styrene-acrylonitrile copolymer (B) described later, and hence generation of unmelted spots can be suppressed, and as a result, film defects can be reduced. Moreover, if Mw is 100,000 or more, sufficient film strength can be obtained.
  • the method for controlling the Mw of the styrene-maleimide copolymer (A) is not particularly limited, but can be controlled by adjusting the types and addition amounts of the polymerization initiator, the chain transfer agent and the solvent, the polymerization temperature, and the like.
  • 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 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 a mixture of two or more.
  • the styrene-acrylonitrile copolymer (B) includes copolymerizable vinyl monomer units such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2 10 masses of monomer units such as ethylhexyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, maleic anhydride, etc. with respect to the styrene-acrylonitrile copolymer (B) You may mix
  • the styrene-acrylonitrile copolymer (B) As a method for producing the styrene-acrylonitrile copolymer (B), a known method can be adopted, for example, a monomer comprising a styrene monomer, an acrylonitrile monomer and a copolymerizable vinyl monomer. The method of copolymerizing a mixture is mentioned.
  • the polymerization mode is preferably bulk polymerization or solution polymerization, and more preferably bulk polymerization. If a styrene-acrylonitrile copolymer obtained by suspension polymerization or emulsion polymerization is used, the transparency of the film may be inferior.
  • the Mw of the styrene-acrylonitrile copolymer (B) is from 150,000 to 250,000, more preferably from 170,000 to 230,000. If Mw is 250,000 or less, the fluidity is sufficient because the film formability is good, and if Mw is 150,000 or more, the film strength is sufficient.
  • the method for controlling Mw of the styrene-acrylonitrile copolymer (B) is not particularly limited, but it can be controlled by adjusting the types and addition amounts of the polymerization initiator, chain transfer agent and solvent, polymerization temperature and the like.
  • the resin composition for an optical film 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. It is composed of 25 to 35% by mass of the blend (A) and 65 to 75% by mass of the styrene-acrylonitrile copolymer (B).
  • the heat resistance is sufficiently excellent.
  • the polymer (A) is 40% by mass or less and the styrene-acrylonitrile copolymer (B) is 60% by mass or more, the film strength is sufficiently excellent.
  • the glass transition temperature of the resin composition for optical films is preferably 110 to 150 ° C, more preferably 115 to 140 ° C. If glass transition temperature is 110 degreeC or more, since heat resistance is high, it is suitable for an optical film. Moreover, if it is 150 degrees C or less, sufficient film moldability can be ensured.
  • the glass transition temperature can be adjusted by the composition ratio of the copolymer constituting the resin composition.
  • the resin composition for optical films has less than 5 film defects having a length of 50 ⁇ m or more per 1 m 2 of unstretched film having a thickness of 100 ⁇ m.
  • An unstretched film refers to a film that has been extruded using an extruder and has not been stretched after being extruded.
  • the film defect can be measured using an image processing analyzer such as LUZEX SE (manufactured by Nireco).
  • Unmelted spots that cause film defects are the composition ratio of maleimide monomer units in the styrene-maleimide copolymer (A), Mw, and the styrene-maleimide copolymer (A) and styrene-acrylonitrile system. It can be reduced by adjusting the conditions of melt kneading with the copolymer (B).
  • the method for producing a resin composition for an optical film is not particularly limited as long as the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer (B) are uniformly dispersed.
  • a melt kneading method using a twin screw extruder can be mentioned.
  • a method of feeding the whole amount or a styrene-maleimide copolymer (A) and a styrene-acrylonitrile are used. Examples thereof include a method of feeding a part of the copolymer (B) from the root position of the screw and side-feeding the remainder of the styrene-acrylonitrile copolymer (B) from the middle 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 adjusting the cylinder temperature, screw rotation speed, and raw material feed amount.
  • a combination of a plurality of kneading discs such as a kneading disc neutral that is shifted by 90 degrees and overlapped is preferable.
  • a method of installing a screen mesh, a sintered filter, a polymer filter or the like having a mesh opening of 50 ⁇ m or less in a die portion at the tip of the extruder is preferable for removing foreign substances.
  • the resin composition for an optical film is a heat resistant stabilizer such as a hindered phenol compound, a lactone compound, a phosphorus compound, or a sulfur compound, a light resistant stabilizer such as a hindered amine compound or a benzotriazole compound, Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oil may be added. The addition amount is preferably less than 1 part by mass with respect to 100 parts by mass of the resin composition.
  • the resin composition for an optical film according to the present embodiment exhibits negative orientation birefringence when stretched and oriented.
  • the optical film according to this embodiment can be stretched and oriented by a known method. Since negative orientation birefringence is generated by stretching orientation, it is most preferable for retardation film applications.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • 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. According to C-13 NMR analysis, it was 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, 2% by mass of maleic anhydride units, and Mw was 144,000.
  • Example A-3 A styrene-maleimide copolymer A-3 was obtained in the same manner as in Experimental Example A-1, except that 0.15 parts by mass of ⁇ -methylstyrene dimer was used. C-13 NMR analysis showed that the styrene unit was 47% by mass, the N-phenylmaleimide unit was 51% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 106,000.
  • Example A-4 A styrene-maleimide copolymer A-4 was obtained in the same manner as in Experimental Example A-1, except that 0.25 part by mass of ⁇ -methylstyrene dimer was used. C-13 NMR analysis showed that the styrene unit was 47% by mass, the N-phenylmaleimide unit was 51% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 92,000.
  • Example A-5 A styrene-maleimide copolymer A-5 was obtained in the same manner as in Experimental Example A-1, except that 0.03 part by mass of ⁇ -methylstyrene dimer was used. According to C-13 NMR analysis, it was 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, 2% by mass of maleic anhydride units, and Mw was 160,000.
  • Example A-6 A styrene-maleimide copolymer A-6 was prepared in the same manner as in Experimental Example A-1, except that 54 parts by mass of styrene, 46 parts by mass of maleic anhydride, 41 parts by mass of aniline, and 0.7 parts by mass of triethylamine were used. Obtained. According to C-13 NMR analysis, the styrene unit was 41% by mass, the N-phenylmaleimide was 57% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 123,000.
  • Example A-7 A styrene-maleimide copolymer A-7 was prepared in the same manner as in Experimental Example A-1, except that 70 parts by weight of styrene, 30 parts by weight of maleic anhydride, 27 parts by weight of aniline, and 0.5 parts by weight of triethylamine were used. Obtained. According to C-13 NMR analysis, the styrene unit was 58% by mass, the N-phenylmaleimide was 41% by mass, the maleic anhydride unit was 1% by mass, and the Mw was 122,000.
  • Example A-8 In an autoclave having a volume of about 25 liters equipped with a stirrer, 37 parts by mass of styrene, 0.1 part 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, 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 unit was 37% by mass
  • the N-phenylmaleimide unit was 63% by mass
  • the Mw was 124,000.
  • 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-maleimide copolymer A-9.
  • C-13 NMR analysis showed that the styrene unit was 45% by mass, the N-phenylmaleimide unit was 55% by mass, and the Mw was 129,000.
  • Example A-11 A styrene-maleimide copolymer A-11 was obtained in the same manner as in Experimental Example A-10 except that 49 parts by mass of styrene, 11 parts by mass of acrylonitrile, and 40 parts by mass of N-phenylmaleimide were used. According to C-13 NMR analysis, the styrene unit was 49% by mass, the N-phenylmaleimide unit was 40% by mass, the acrylonitrile unit was 11% by mass, and the Mw was 125,000.
  • Example A-12 A styrene-maleimide copolymer A-12 was obtained in the same manner as in Experimental Example A-10 except that 37 parts by mass of styrene, 11 parts by mass of acrylonitrile, and 52 parts by mass of N-phenylmaleimide were used. According to C-13 NMR analysis, it was 37% by mass of styrene units, 52% by mass of N-phenylmaleimide units, 11% by mass of acrylonitrile units, and Mw was 126,000.
  • Example A-13 A styrene-maleimide copolymer A-13 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. C-13 NMR analysis revealed that the styrene unit was 47% by mass, the N-cyclohexylmaleimide unit was 51% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 120,000.
  • Example A-14 A styrene-maleimide copolymer A-14 was obtained in the same manner as in Experimental Example A-1, except that 30 parts by weight of aniline was used. C-13 NMR analysis showed that the styrene unit was 48% by mass, the N-phenylmaleimide unit was 46% by mass, the maleic anhydride unit was 6% by mass, and the Mw was 120,000. Table 1 shows the component compositions and Mw of Experimental Examples A-1 to A-14.
  • Example B-1 A complete mixing type reactor having a volume of about 20 liters equipped with a stirrer and a devolatilizing tank equipped with a preheater were connected.
  • the stirring rate of the complete mixing reactor was 180 rpm.
  • the reaction solution was continuously withdrawn from the complete mixing reactor, and the 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. And other volatiles were removed.
  • the resin liquid was extracted with a gear pump and extruded into a strand shape to obtain a pellet-shaped polymer B-1. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 198,000.
  • Example B-2 A styrene-acrylonitrile copolymer B-2 was obtained in the same manner as in Experimental Example B-1, except that 60.5 parts by mass of styrene and 39.5 parts by mass of acrylonitrile were used. According to C-13 NMR analysis, the styrene unit was 65% by mass, the acrylonitrile unit was 35% by mass, and the Mw was 210,000.
  • Example B-3 A styrene-acrylonitrile copolymer B-3 was obtained in the same manner as in Experimental Example B-1, except that 73.6 parts by mass of styrene, 26.4 parts by mass of acrylonitrile, and 20 parts by mass of ethylbenzene were used. According to C-13 NMR analysis, the styrene unit was 74% by mass, the acrylonitrile unit was 26% by mass, and the Mw was 202,000.
  • Example B-4 A styrene-acrylonitrile copolymer B-4 was obtained in the same manner as in Experimental Example B-1, except that 55.8 parts by mass of styrene and 44.2 parts by mass of acrylonitrile were used. According to C-13 NMR analysis, the styrene unit was 62% by mass, the acrylonitrile unit was 38% by mass, and the Mw was 201,000.
  • Example B-5 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, 31 parts by mass of acrylonitrile, 0.05 part by mass of ⁇ -methylstyrene dimer, t-butylperoxy After charging 0.2 parts by weight of isopropyl monocarbonate and 0.1 part of t-butyl peroxyacetate and replacing the system with nitrogen gas, the temperature was kept at 103 ° C., and then 24 parts by weight of styrene was kept at 103 ° C. for 4 hours. And continuously added at 105 ° C. for 2 hours over 6 hours.
  • Example B-6 A styrene-acrylonitrile copolymer B-6 was obtained in the same manner as in Experimental Example B-5, except that 0.02 part by mass of ⁇ -methylstyrene dimer was used. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 192,000.
  • Example B-7 A styrene-acrylonitrile copolymer B-7 was obtained in the same manner as in Experimental Example B-1, except that 15 parts by mass of ethylbenzene was used. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 245,000.
  • 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. C-13 NMR analysis showed that the styrene unit was 69% by mass, the acrylonitrile unit was 31% by mass, and the 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. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 272,000.
  • Example B-10 A styrene-acrylonitrile copolymer was obtained in the same manner as in Experimental Example B-1, except that 51.1 parts by mass of styrene, 17.5 parts by mass of ⁇ -methylstyrene, 31.4 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. B-10 was obtained. According to C-13 NMR analysis, the styrene unit was 55% by mass, the ⁇ -methylstyrene unit was 14% by mass, the acrylonitrile unit was 31% by mass, and the Mw was 201,000. Table 2 shows the component compositions and Mw of Experimental Examples B-1 to B-10.
  • An unstretched film having a thickness of 100 ⁇ m was extruded from the resin composition at a cylinder temperature of 260 ° C. and a die temperature of 260 ° C. using a film extruder equipped with a T die, and wound around a roll.
  • the obtained unstretched film was uniaxially stretched 1.8 times at Tg + 20 ° C. using a tenter transverse stretching machine to obtain a stretched optical film.
  • the evaluation results of the obtained film are shown in Tables 3 to 4.
  • the glass transition temperature was measured by differential scanning calorimetry (DSC) under the following measurement conditions.
  • Device name Robot DSC6200 manufactured by Seiko Instruments Inc. Rate of temperature increase: 10 ° C./min A glass transition temperature of 110 ° C. or higher was regarded as acceptable for heat resistance.
  • Measurement conditions Measuring instrument: MIT-D FOLDING ENDURANCE TESTER (Toyo Seiki Co., Ltd.) Load (tension): 500 g Heavy folding speed: 175 times / min Folding angle: Left and right 45 degree folding device Tip radius: 0.38 mm Test width: 15mm Bending direction: Film extrusion direction strength criteria “excellent”: folding number 150 times or more “good”: folding number 100 times or more and less than 150 “bad”: folding number 100 times or less (5) Film defect For unstretched film, image Observation was made using a processing analyzer (manufactured by Nireco: LUZEX SE), and the quality was judged according to the following criteria. “Excellent” and “Good” were accepted.
  • the resin compositions of Examples 1 to 16 are excellent in transparency, heat resistance, film moldability, and film strength, and have optimal properties particularly for optical films. . Moreover, since there are few film defects, the phase difference development property by extending
  • the resin compositions of Comparative Examples 1 to 10 are excellent as optical films in any of transparency, heat resistance, film moldability, film strength, film defects, and retardation development. The value was not shown.

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Abstract

Disclosed is a resin composition for an optical film having excellent transparency, heat-resistance, film formability, film strength, and phase difference expression; further disclosed is an optical film with few film defects and a negative orientation birefringence. Said composition contains: 20-40 mass% of a styrene-maleimide copolymer (A) with a weight-average molecular weight (Mw) of 100,000-145,000, comprised of 35-55 mass% of a styrene monomer unit, 30-60 mass% of a maleimide monomer unit, 0-15 mass% of an unsaturated dicarboxylic anhydride monomer unit, and 0-15 mass% of an acrylonitrile monomer unit; and 60-80 mass% of a styrene-acrylonitrile copolymer (B) with an Mw of 150,000-250,000, comprised of 65-70 mass% of a styrene monomer unit and 30-35 mass% of an acrylonitrile monomer unit.

Description

光学フィルム用樹脂組成物及びその光学フィルムOptical film resin composition and optical film
本発明は、光学フィルム用樹脂組成物及びその光学フィルムに関するものである。 The present invention relates to a resin composition for an optical film and the optical film.
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、光学異方性を制御し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ある。例えば、光学フィルムがある。光学フィルムの１つとして、液晶ディスプレーの液晶の位相差を補償したり、視野角を向上させたりする役割を担う位相差フィルムと呼ばれるフィルムがある。位相差フィルムとしては例えばポリカーボネートや非晶性の環状ポリオレフィンが用いられていて、これらは正の配向複屈折性を有している。これと負の配向複屈折性を示す光学フィルムとを貼りあわせることで、更に視野角を向上させることができることが知られている。
一方、負の配向複屈折性を示す光学フィルムは実用化にはいたってはいないが、特許文献１、２に記載されているように、ポリスチレン、スチレン－アクリロニトリル共重合体や、スチレン－無水マレイン酸共重合体などが知られている。しかし、これらは、耐熱性やフィルム強度の面で不十分である。これに対し、耐熱性とフィルム強度とを向上させた光学フィルムとしては特許文献３に記載されているものが知られている。 There are many types of optical molded bodies. For example, there is an optical film. As one of the optical films, there is a film called a retardation film that plays a role of compensating the retardation of the liquid crystal of the liquid crystal display or improving the viewing angle. As the retardation film, for example, polycarbonate or amorphous cyclic polyolefin is used, and these have positive orientation birefringence. It is known that the viewing angle can be further improved by laminating this and an optical film exhibiting negative orientation birefringence.
On the other hand, an optical film exhibiting negative orientation birefringence has not been put into practical use, but as described in Patent Documents 1 and 2, polystyrene, styrene-acrylonitrile copolymer, styrene-maleic anhydride Copolymers are known. However, these are insufficient in terms of heat resistance and film strength. On the other hand, what was described in patent document 3 is known as an optical film which improved heat resistance and film strength.
特開２００２－０４０２５８号公報Japanese Patent Laid-Open No. 2002-040258 特開２００５－２９２３１１号公報JP 2005-29211 A 特開２００８－０９４９１２号公報JP 2008-094912 A
しかしながら、現在、更にフィルム強度が高く、しかも異物の混入や未溶融ブツの発生等によって生じるフィルム欠陥の少ない光学フィルムが求められており、特許文献３の方法では必ずしもこの課題を解決することはできない。
本発明の目的は、光学フィルム用樹脂組成物及びその光学フィルムを提供するものである。また、強度が高く、フィルム欠陥が少なく、負の配向複屈折性を示し、位相差発現性に優れたフィルムを提供するものである。 However, at present, there is a demand for an optical film having a higher film strength and less film defects caused by foreign matters, unmelted spots, etc., and the method of Patent Document 3 cannot always solve this problem. .
The objective of this invention provides the resin composition for optical films, and its optical film. Further, the present invention provides a film having high strength, few film defects, negative orientation birefringence, and excellent retardation development.
本発明は、以下を要旨とするものである。
（１）（ｉ）スチレン系単量体単位３５～５５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％からなり、重量平均分子量（Ｍｗ）が１００，０００～１４５，０００であるスチレン－マレイミド系共重合体（Ａ）２０～４０質量％と、
（ｉｉ）スチレン系単量体単位６５～７０質量％、アクリロニトリル系単量体単位３０～３５質量％からなり、重量平均分子量（Ｍｗ）が１５０，０００～２５０，０００であるスチレン－アクリロニトリル系共重合体（Ｂ）６０～８０質量％と
を含有してなる光学フィルム用樹脂組成物であって、厚み１００μｍの未延伸フィルムに成形した場合に長さ５０μｍ以上のフィルム欠陥が５個／ｍ２未満である光学フィルム用樹脂組成物。
（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ることを特徴とする（１）記載の光学フィルム用樹脂組成物。
（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ることを特徴とする（１）又は（２）記載の光学フィルム用樹脂組成物。
（４）ガラス転移温度が１１０～１５０℃である（１）～（３）のいずれかに記載の光学フィルム用樹脂組成物。
（５）（１）～（４）のいずれかに記載の光学フィルム用樹脂組成物からなる光学フィルム。
（６）延伸して配向させると負の配向複屈折性を示す（５）に記載の光学フィルム。
（７）溶融押出フィルムであって、さらに延伸して配向させると負の配向複屈折性を示す（５）に記載の光学フィルム。
（８）延伸フィルムであることを特徴とする（６）又は（７）に記載の光学フィルム。
（９）位相差フィルムであることを特徴とする（８）に記載の光学フィルム。
　ここで「フィルム欠陥」とは、異物の混入や未溶融ブツの発生等により、周囲とは不均一となって見える部分を指す。未溶融ブツは、主として、溶融混練が不十分なために分散しきらなかったスチレン－マレイミド系共重合体（Ａ）に起因する。フィルム欠陥の測定は、本発明に係る光学フィルム用樹脂組成物を押出成形機を用いて厚み１００μｍの未延伸フィルムに成形した後、画像処理解析装置を用いて、未延伸フィルム１ｍ２あたりに存在する長さ５０μｍ以上のフィルム欠陥の数を調べることによって行われる。
また「光学フィルム」とは、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の光学用途に使用されるフィルムをいい、「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。 The gist of the present invention is as follows.
(1) (i) Styrene monomer units 35 to 55% by mass, maleimide monomer units 30 to 60% by mass, unsaturated dicarboxylic acid anhydride monomer units 0 to 15% by mass, acrylonitrile monomers 20 to 40% by mass of a styrene-maleimide copolymer (A) having a body unit of 0 to 15% by mass and having a weight average molecular weight (Mw) of 100,000 to 145,000,
(Ii) A styrene-acrylonitrile copolymer comprising 65 to 70% by mass of a styrene monomer unit and 30 to 35% by mass of an acrylonitrile monomer unit and having a weight average molecular weight (Mw) of 150,000 to 250,000. A resin composition for an optical film comprising 60 to 80% by mass of the polymer (B), and when formed into an unstretched film having a thickness of 100 μm, film defects having a length of 50 μm or more are 5 / m 2. The resin composition for optical films which is less than.
(2) The resin composition for an optical film as described in (1), wherein the styrene-maleimide copolymer (A) is obtained by solution polymerization or bulk polymerization.
(3) The resin composition for optical films according to (1) or (2), wherein the styrene-acrylonitrile copolymer (B) is obtained by bulk polymerization or solution polymerization.
(4) The resin composition for optical films according to any one of (1) to (3), wherein the glass transition temperature is 110 to 150 ° C.
(5) An optical film comprising the optical film resin composition according to any one of (1) to (4).
(6) The optical film according to (5), which exhibits negative orientation birefringence when stretched and oriented.
(7) The optical film according to (5), which is a melt-extruded film and exhibits negative orientation birefringence when further stretched and oriented.
(8) The optical film as described in (6) or (7), which is a stretched film.
(9) The optical film as described in (8), which is a retardation film.
Here, the “film defect” refers to a portion that appears to be non-uniform due to the mixing of foreign matters, the occurrence of unmelted spots, and the like. The unmelted material is mainly caused by the styrene-maleimide copolymer (A) that cannot be dispersed due to insufficient melt kneading. Film defects are measured per 1 m 2 of unstretched film using an image processing analyzer after molding the resin composition for optical films according to the present invention into an unstretched film having a thickness of 100 μm using an extruder. This is done by examining the number of film defects having a length of 50 μm or more.
The “optical film” refers to a film used for optical applications such as a retardation film, an antireflection film, and a polarizer protective film, and the “melt extruded film” refers to a film formed by melt extrusion.
本発明の樹脂組成物は、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り、特に、延伸して配向させたフィルムはフィルム欠陥が少なく、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に有用である。 The resin composition of the present invention is useful for an optical film for a thin liquid crystal display element because of its good transparency, heat resistance, film moldability, and film strength. In particular, a stretched and oriented film is a film. It is useful for retardation films since it has few defects, exhibits negative orientation birefringence, and is excellent in retardation development.
＜スチレン－マレイミド系共重合体（Ａ）＞
スチレン－マレイミド系共重合体（Ａ）の構成比率は、スチレン系単量体単位３５～５５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％である。
スチレン系単量体単位が３５質量％以上、または、マレイミド系単量体単位が６０質量％以下であれば、後述するスチレン－アクリロニトリル系共重合体（Ｂ）と混合しやすくなるため、未溶融ブツの発生を抑制することができ、その結果、フィルム欠陥の発生を低減することができる。スチレン系単量体単位が５５質量％以下、または、マレイミド系単量体単位が３０質量％以上であれば、フィルムの透明性を十分に確保することができる。
不飽和ジカルボン酸無水物単量体単位およびアクリロニトリル系単量体単位は、任意配合成分である。スチレン－マレイミド系共重合体（Ａ）中に不飽和ジカルボン酸無水物単量体単位を配合することにより、フィルムの透明性を向上できる場合がある。また、アクリロニトリル系単量体単位を配合することにより、フィルムの強度を向上できる場合がある。一方、不飽和ジカルボン酸無水物単量体単位が１５質量％以下であれば、熱安定性が損なわれずフィルムに着色を生じることがない。また、アクリロニトリル系単量体単位が１５質量％以下であれば、フィルムの十分な透明性を確保することができる。 <Styrene-maleimide copolymer (A)>
The composition ratio of the styrene-maleimide copolymer (A) is as follows: styrene monomer unit 35 to 55% by mass, maleimide monomer unit 30 to 60% by mass, unsaturated dicarboxylic anhydride monomer unit 0 15% by mass and 0-15% by mass of acrylonitrile monomer units.
If the styrene monomer unit is 35% by mass or more, or if the maleimide monomer unit is 60% by mass or less, it will be easy to mix with the styrene-acrylonitrile copolymer (B) described later, so it will not melt. Generation | occurrence | production of a shading can be suppressed and the generation | occurrence | production of a film defect can be reduced as a result. When the styrene monomer unit is 55% by mass or less or the maleimide monomer unit is 30% by mass or more, the transparency of the film can be sufficiently secured.
The unsaturated dicarboxylic acid anhydride monomer unit and the acrylonitrile monomer unit are optional components. In some cases, the transparency of the film can be improved by blending an unsaturated dicarboxylic acid anhydride monomer unit into the styrene-maleimide copolymer (A). Moreover, the intensity | strength of a film may be able to be improved by mix | blending an acrylonitrile-type monomer unit. On the other hand, if the unsaturated dicarboxylic acid anhydride monomer unit is 15% by mass or less, the thermal stability is not impaired and the film is not colored. Moreover, if the acrylonitrile monomer unit is 15% by mass or less, sufficient transparency of the film can be ensured.
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種以上の混合であってもよい。 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 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種以上の混合であってもよい。 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. These maleimide monomers may be 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種以上の混合であってもよい。 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 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種以上の混合であってもよい。 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 a mixture of two or more.
スチレン－マレイミド系共重合体（Ａ）には、以上に加えて、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１０質量％未満の範囲で配合してもよい。 In addition to the above, the styrene-maleimide copolymer (A) includes copolymerizable vinyl monomer units such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2 Monomer units such as ethylhexyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate may be blended in the range of less than 10% by mass.
スチレン－マレイミド系共重合体（Ａ）の製造法としては、公知の手法が採用でき、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方法や、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方法等が挙げられる。また、重合の様式は、溶液重合または塊状重合であることが好ましい。懸濁重合や乳化重合で得られたスチレン―マレイミド系共重合体を用いると、フィルムの透明性が低いものとなる場合がある。 As a method for producing the styrene-maleimide copolymer (A), a known method can be adopted, 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 a method of reacting ammonia and / or a primary amine to convert an acid anhydride group into an imide group. The polymerization mode is preferably solution polymerization or bulk polymerization. If a styrene-maleimide copolymer obtained by suspension polymerization or emulsion polymerization is used, the transparency of the film may be low.
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、１００，０００～１４５，０００であり、より好ましくは１１０，０００～１３０，０００である。Ｍｗが１４５，０００以下であれば、後述するスチレン－アクリロニトリル系共重合体（Ｂ）と混合しやすくなるため未溶融ブツの発生を抑えることができ、その結果フィルム欠陥を低減できる。また、Ｍｗが１００，０００以上であれば、十分なフィルム強度を得ることができる。
スチレン－マレイミド系共重合体（Ａ）のＭｗの制御方法については、特に制限はないが、重合開始剤、連鎖移動剤及び溶剤の種類及び添加量、重合温度等を調節することで制御できる。 The weight average molecular weight (Mw) of the styrene-maleimide copolymer (A) is 100,000 to 145,000, more preferably 110,000 to 130,000. If Mw is 145,000 or less, it becomes easy to mix with the styrene-acrylonitrile copolymer (B) described later, and hence generation of unmelted spots can be suppressed, and as a result, film defects can be reduced. Moreover, if Mw is 100,000 or more, sufficient film strength can be obtained.
The method for controlling the Mw of the styrene-maleimide copolymer (A) is not particularly limited, but can be controlled by adjusting the types and addition amounts of the polymerization initiator, the chain transfer agent and the solvent, the polymerization temperature, and the like.
＜スチレン－アクリロニトリル系共重合体（Ｂ）＞
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アクリロニトリル系単量体の比率は、スチレン系単量体６５～７０質量％とアクリロニトリル系単量体３０～３５質量％である。
スチレン系単量体が６５質量％以上でアクリロニトリル系単量体が３５質量％以下であれば、フィルムの透明性を十分に確保することができる。スチレン系単量体が７０質量％以下でアクリロニトリル系単量体が３０質量％以上であれば、フィルム強度を十分に確保することができる。 <Styrene-acrylonitrile copolymer (B)>
The ratio of the styrene monomer to the acrylonitrile monomer in the styrene-acrylonitrile copolymer (B) is 65 to 70% by mass of the styrene monomer and 30 to 35% by mass of the acrylonitrile monomer.
If the styrene monomer is 65% by mass or more and the acrylonitrile monomer is 35% by mass or less, the transparency of the film can be sufficiently secured. If the styrene monomer is 70% by mass or less and the acrylonitrile monomer is 30% by mass or more, the film strength can be sufficiently secured.
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種以上の混合であってもよい。 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 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種以上の混合であってもよい。 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 a mixture of two or more.
スチレン－アクリロニトリル系共重合体（Ｂ）には、以上に加えて、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％未満の範囲で配合してもよい。 In addition to the above, the styrene-acrylonitrile copolymer (B) includes copolymerizable vinyl monomer units such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2 10 masses of monomer units such as ethylhexyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, maleic anhydride, etc. with respect to the styrene-acrylonitrile copolymer (B) You may mix | blend in less than% range.
スチレン－アクリロニトリル系共重合体（Ｂ）の製造法としては、公知の手法が採用でき、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方法が挙げられる。また、重合の様式は、塊状重合または溶液重合であることが好ましく、さらに好ましくは塊状重合である。懸濁重合や乳化重合で得られたスチレン－アクリロニトリル系共重合体を用いると、フィルムの透明性が劣るものとなる場合がある。 As a method for producing the styrene-acrylonitrile copolymer (B), a known method can be adopted, for example, a monomer comprising a styrene monomer, an acrylonitrile monomer and a copolymerizable vinyl monomer. The method of copolymerizing a mixture is mentioned. The polymerization mode is preferably bulk polymerization or solution polymerization, and more preferably bulk polymerization. If a styrene-acrylonitrile copolymer obtained by suspension polymerization or emulsion polymerization is used, the transparency of the film may be inferior.
スチレン－アクリロニトリル系共重合体（Ｂ）のＭｗは、１５０，０００～２５０，０００であり、より好ましくは１７０，０００～２３０，０００である。Ｍｗが２５０，０００以下であれば流動性が十分であるためフィルム成形性が良好であり、Ｍｗが１５０，０００以上であればフィルム強度が十分となる。
スチレン－アクリロニトリル系共重合体（Ｂ）のＭｗの制御方法については、特に制限はないが、重合開始剤、連鎖移動剤及び溶剤の種類及び添加量、重合温度等を調節することで制御できる。 The Mw of the styrene-acrylonitrile copolymer (B) is from 150,000 to 250,000, more preferably from 170,000 to 230,000. If Mw is 250,000 or less, the fluidity is sufficient because the film formability is good, and if Mw is 150,000 or more, the film strength is sufficient.
The method for controlling Mw of the styrene-acrylonitrile copolymer (B) is not particularly limited, but it can be controlled by adjusting the types and addition amounts of the polymerization initiator, chain transfer agent and solvent, polymerization temperature and the like.
＜光学フィルム用樹脂組成物＞
光学フィルム用の樹脂組成物は、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％とからなる。
スチレン－マレイミド系共重合体（Ａ）が２０質量％以上でスチレン－アクリロニトリル系共重合体（Ｂ）が８０質量％以下であれば、耐熱性が十分に優れたものとなり、スチレン－マレイミド系共重合体（Ａ）が４０質量％以下でスチレン－アクリロニトリル系共重合体（Ｂ）が６０質量％以上であれば、フィルム強度が十分に優れたものとなる。 <Resin composition for optical film>
The resin composition for an optical film 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. It is composed of 25 to 35% by mass of the blend (A) and 65 to 75% by mass of the styrene-acrylonitrile copolymer (B).
When the styrene-maleimide copolymer (A) is 20% by mass or more and the styrene-acrylonitrile copolymer (B) is 80% by mass or less, the heat resistance is sufficiently excellent. When the polymer (A) is 40% by mass or less and the styrene-acrylonitrile copolymer (B) is 60% by mass or more, the film strength is sufficiently excellent.
光学フィルム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℃以上であれば、耐熱性が高いため光学フィルムに好適である。また１５０℃以下であれば、十分なフィルム成形性を確保することができる。ガラス転移温度は、樹脂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。 The glass transition temperature of the resin composition for optical films is preferably 110 to 150 ° C, more preferably 115 to 140 ° C. If glass transition temperature is 110 degreeC or more, since heat resistance is high, it is suitable for an optical film. Moreover, if it is 150 degrees C or less, sufficient film moldability can be ensured. The glass transition temperature can be adjusted by the composition ratio of the copolymer constituting the resin composition.
光学フィルム用樹脂組成物は、厚み１００μｍの未延伸フィルム１ｍ２あたり、長さ５０μｍ以上のフィルム欠陥の個数が５個未満である。未延伸フィルムとは、押出成形機を用いて押し出したフィルムであって、押し出した後に延伸処理を施していないフィルムのことを指す。フィルム欠陥は、例えば、ＬＵＺＥＸ　ＳＥ（ニレコ社製）等の画像処理解析装置を用いて測定することができる。
フィルム欠陥の原因となる未溶融ブツは、スチレン－マレイミド系共重合体（Ａ）のマレイミド系単量体単位の構成比率、Ｍｗ、及びスチレン－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）との溶融混練の条件の調節等によって減らすことができる。 The resin composition for optical films has less than 5 film defects having a length of 50 μm or more per 1 m 2 of unstretched film having a thickness of 100 μm. An unstretched film refers to a film that has been extruded using an extruder and has not been stretched after being extruded. The film defect can be measured using an image processing analyzer such as LUZEX SE (manufactured by Nireco).
Unmelted spots that cause film defects are the composition ratio of maleimide monomer units in the styrene-maleimide copolymer (A), Mw, and the styrene-maleimide copolymer (A) and styrene-acrylonitrile system. It can be reduced by adjusting the conditions of melt kneading with the copolymer (B).
光学フィルム用樹脂組成物の製造方法としては、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）とが均一に分散される方法であれば特に制限はなく、公知の混練方法を用いることができるが、例えば二軸押出機を用いて以下のように溶融混練する方法が挙げられる。 The method for producing a resin composition for an optical film is not particularly limited as long as the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer (B) are uniformly dispersed. However, for example, a melt kneading method using a twin screw extruder can be mentioned.
まずスチレン－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）との押出方法としては、全量一括フィードする方法や、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）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方法等が挙げられる。 First, as a method for extruding the styrene-maleimide copolymer (A) and the styrene-acrylonitrile copolymer (B), a method of feeding the whole amount or a styrene-maleimide copolymer (A) and a styrene-acrylonitrile are used. Examples thereof include a method of feeding a part of the copolymer (B) from the root position of the screw and side-feeding the remainder of the styrene-acrylonitrile copolymer (B) from the middle position of the screw.
次いで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。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を調整することで樹脂温度は調整することができる。 Next, 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 adjusting 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であることが好ましく、さらに好ましくは２７～４２である。スクリュー構成については特に制限はないが、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 preferably 21 to 48, more preferably 27 to 42. There are no particular restrictions on the screw configuration, but there are kneading disc lights in which multiple paddle type discs are displaced in the right direction and overlapping, kneading disc lefts in which multiple paddle type discs are displaced in the left direction, and paddle type discs. A combination of a plurality of kneading discs such as a kneading disc neutral that is shifted by 90 degrees and overlapped is preferable.
さらに、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のフィルターを、押出機先端のダイス部に設置する方法が好適である。 Further, a method of installing a screen mesh, a sintered filter, a polymer filter or the like having a mesh opening of 50 μm or less in a die portion at the tip of the extruder is preferable for removing foreign substances.
光学フィルム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、鉱油等の添加剤を添加しても差し支えない。その添加量は樹脂組成物１００質量部に対して１質量部未満であることが好ましい。 If necessary, the resin composition for an optical film is a heat resistant stabilizer such as a hindered phenol compound, a lactone compound, a phosphorus compound, or a sulfur compound, a light resistant stabilizer such as a hindered amine compound or a benzotriazole compound, Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oil may be added. The addition amount is preferably less than 1 part by mass with respect to 100 parts by mass of the resin composition.
本実施形態に係る光学フィルム用樹脂組成物は、延伸して配向させると負の配向複屈折性を示すものである。 The resin composition for an optical film according to the present embodiment exhibits negative orientation birefringence when stretched and oriented.
光学フィルム用樹脂組成物の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方法が好ましい。 Although there is no restriction | limiting in particular in the method to shape | mold the film of the resin composition for optical films, The method of melt-extruding using a film extruder is preferable.
本実施形態に係る光学フィルムは、公知の手法で延伸して配向させることができる。延伸配向により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 optical film according to this embodiment can be stretched and oriented by a known method. Since negative orientation birefringence is generated by stretching orientation, it is most preferable for retardation film applications.
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。
以下において、重量平均分子量（Ｍｗ）は、ゲル浸透クロマトグラフィー（ＧＰＣ）にて測定されるポリスチレン換算のＭｗであり、下記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。 Hereinafter, although detailed content is demonstrated using an Example, this invention is not limited to a following example.
Below, a weight average molecular weight (Mw) is Mw of polystyrene conversion measured by gel permeation chromatography (GPC), and was measured on the following measurement conditions.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko)
Column: 3 PL gel MIXED-B in series 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.
［実験例Ａ－１］
攪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０．１質量部、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、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％であり、Ｍｗは１２１，０００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, 0.1 part 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, and a solution prepared by dissolving 40 parts by weight of maleic anhydride and 0.14 parts by weight 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. According to C-13 NMR analysis, it was 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, 2% by mass of maleic anhydride units, and Mw was 121,000.
［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％であり、Ｍｗは１４４，０００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. According to C-13 NMR analysis, it was 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, 2% by mass of maleic anhydride units, and Mw was 144,000.
［実験例Ａ－３］
α－メチルスチレンダイマー０．１５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％であり、Ｍｗは１０６，０００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 0.15 parts by mass of α-methylstyrene dimer was used. C-13 NMR analysis showed that the styrene unit was 47% by mass, the N-phenylmaleimide unit was 51% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 106,000.
［実験例Ａ－４］
α－メチルスチレンダイマー０．２５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－４を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位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％であり、Ｍｗは９２，０００であった。 [Experiment A-4]
A styrene-maleimide copolymer A-4 was obtained in the same manner as in Experimental Example A-1, except that 0.25 part by mass of α-methylstyrene dimer was used. C-13 NMR analysis showed that the styrene unit was 47% by mass, the N-phenylmaleimide unit was 51% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 92,000.
［実験例Ａ－５］
α－メチルスチレンダイマー０．０３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％であり、Ｍｗは１６０，０００であった。 [Experimental example A-5]
A styrene-maleimide copolymer A-5 was obtained in the same manner as in Experimental Example A-1, except that 0.03 part by mass of α-methylstyrene dimer was used. According to C-13 NMR analysis, it was 47% by mass of styrene units, 51% by mass of N-phenylmaleimide units, 2% by mass of maleic anhydride units, and Mw was 160,000.
［実験例Ａ－６］
スチレン５４質量部、マレイン酸無水物４６質量部、アニリン４１質量部、トリエチルアミン０．７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－６を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位４１質量％、Ｎ－フェニルマレイミド５７質量％、マレイン酸無水物単位２質量％であり、Ｍｗは１２３，０００であった。 [Experiment A-6]
A styrene-maleimide copolymer A-6 was prepared in the same manner as in Experimental Example A-1, except that 54 parts by mass of styrene, 46 parts by mass of maleic anhydride, 41 parts by mass of aniline, and 0.7 parts by mass of triethylamine were used. Obtained. According to C-13 NMR analysis, the styrene unit was 41% by mass, the N-phenylmaleimide was 57% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 123,000.
［実験例Ａ－７］
スチレン７０質量部、マレイン酸無水物３０質量部、アニリン２７質量部、トリエチルアミン０．５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分析よりスチレン単位５８質量％、Ｎ－フェニルマレイミド４１質量％、マレイン酸無水物単位１質量％であり、Ｍｗは１２２，０００であった。 [Experiment A-7]
A styrene-maleimide copolymer A-7 was prepared in the same manner as in Experimental Example A-1, except that 70 parts by weight of styrene, 30 parts by weight of maleic anhydride, 27 parts by weight of aniline, and 0.5 parts by weight of triethylamine were used. Obtained. According to C-13 NMR analysis, the styrene unit was 58% by mass, the N-phenylmaleimide was 41% by mass, the maleic anhydride unit was 1% by mass, and the Mw was 122,000.
［実験例Ａ－８］
攪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０．１質量部、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分析よりスチレン単位３７質量％、Ｎ－フェニルマレイミド単位６３質量％であり、Ｍｗは１２４，０００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, 0.1 part 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, 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 unit was 37% by mass, the N-phenylmaleimide unit was 63% by mass, and the Mw was 124,000.
［実験例Ａ－９］
攪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、α－メチルスチレンダイマー０．１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－９を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位４５質量％、Ｎ－フェニルマレイミド単位５５質量％であり、Ｍｗは１２９，０００であった。 [Experiment A-9]
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 0.1 part by mass of α-methylstyrene dimer and 0.14 parts by mass of t-butylperoxy-2-ethylhexanoate was added over 10 hours. Added continuously. 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 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-maleimide copolymer A-9. C-13 NMR analysis showed that the styrene unit was 45% by mass, the N-phenylmaleimide unit was 55% by mass, and the Mw was 129,000.
［実験例Ａ－１０］
攪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５４質量部、アクリロニトリル１３質量部、α－メチルスチレンダイマー０．１質量部、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３３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－１０を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位５４質量％、Ｎ－フェニルマレイミド単位３３質量％、アクリロニトリル単位１３質量％であり、Ｍｗは１２８，０００であった。 [Experiment A-10]
An autoclave having a volume of about 25 liters equipped with a stirrer was charged with 54 parts by mass of styrene, 13 parts by mass of acrylonitrile, 0.1 part by mass of α-methylstyrene dimer, and 100 parts by mass of methyl ethyl ketone, and the inside of the system was replaced with nitrogen gas. The temperature was raised to 90 ° C., and a solution prepared by dissolving 33 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. 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-10. C-13 NMR analysis showed that the styrene unit was 54% by mass, the N-phenylmaleimide unit was 33% by mass, the acrylonitrile unit was 13% by mass, and the Mw was 128,000.
［実験例Ａ－１１］
スチレン４９質量部、アクリロニトリル１１質量部、Ｎ－フェニルマレイミド４０質量部とした以外は実験例Ａ－１０と同様に行い、スチレン－マレイミド系共重合体Ａ－１１を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位４９質量％、Ｎ－フェニルマレイミド単位４０質量％、アクリロニトリル単位１１質量％であり、Ｍｗは１２５，０００であった。 [Experiment A-11]
A styrene-maleimide copolymer A-11 was obtained in the same manner as in Experimental Example A-10 except that 49 parts by mass of styrene, 11 parts by mass of acrylonitrile, and 40 parts by mass of N-phenylmaleimide were used. According to C-13 NMR analysis, the styrene unit was 49% by mass, the N-phenylmaleimide unit was 40% by mass, the acrylonitrile unit was 11% by mass, and the Mw was 125,000.
［実験例Ａ－１２］
スチレン３７質量部、アクリロニトリル１１質量部、Ｎ－フェニルマレイミド５２質量部とした以外は実験例Ａ－１０と同様に行い、スチレン－マレイミド系共重合体Ａ－１２を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位３７質量％、Ｎ－フェニルマレイミド単位５２質量％、アクリロニトリル単位１１質量％であり、Ｍｗは１２６，０００であった。 [Experiment A-12]
A styrene-maleimide copolymer A-12 was obtained in the same manner as in Experimental Example A-10 except that 37 parts by mass of styrene, 11 parts by mass of acrylonitrile, and 52 parts by mass of N-phenylmaleimide were used. According to C-13 NMR analysis, it was 37% by mass of styrene units, 52% by mass of N-phenylmaleimide units, 11% by mass of acrylonitrile units, and Mw was 126,000.
［実験例Ａ－１３］
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－１３を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位４７質量％、Ｎ－シクロヘキシルマレイミド単位５１質量％、マレイン酸無水物単位２質量％であり、Ｍｗは１２０，０００であった。 [Experiment A-13]
A styrene-maleimide copolymer A-13 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. C-13 NMR analysis revealed that the styrene unit was 47% by mass, the N-cyclohexylmaleimide unit was 51% by mass, the maleic anhydride unit was 2% by mass, and the Mw was 120,000.
［実験例Ａ－１４］
アニリン３０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－１４を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位４８質量％、Ｎ－フェニルマレイミド単位４６質量％、マレイン酸無水物単位６質量％であり、Ｍｗは１２０，０００であった。
上記実験例Ａ－１～Ａ－１４の成分組成とＭｗを表１に示す。 [Experiment A-14]
A styrene-maleimide copolymer A-14 was obtained in the same manner as in Experimental Example A-1, except that 30 parts by weight of aniline was used. C-13 NMR analysis showed that the styrene unit was 48% by mass, the N-phenylmaleimide unit was 46% by mass, the maleic anhydride unit was 6% by mass, and the Mw was 120,000.
Table 1 shows the component compositions and Mw of Experimental Examples A-1 to A-14.
Figure JPOXMLDOC01-appb-T000001
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、予熱器を付した脱揮槽を接続して構成した。スチレン６９．１質量部、アクリロニトリル３０．９質量部、エチルベンゼン１８質量部で構成される単量体混合液を調整し、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で実施した。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。この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分析よりスチレン単位６９質量％、アクリロニトリル単位３１質量％であり、Ｍｗは１９８，０００であった。 [Experiment B-1]
A complete mixing type reactor having a volume of about 20 liters equipped with a stirrer and a devolatilizing tank equipped with a preheater were connected. A monomer mixed solution composed of 69.1 parts by mass of styrene, 30.9 parts by mass of acrylonitrile and 18 parts by mass of ethylbenzene was prepared, and 0.015 part by mass of t-butylperoxyisopropyl monocarbonate and n-dodecyl mercaptan were further prepared. 0.013 mass part was mixed and it was set as the raw material solution. This raw material solution was introduced into a fully mixed reactor controlled at a temperature of 120 ° C. at 5 kg per hour. The stirring rate of the complete mixing reactor was 180 rpm. Next, the reaction solution was continuously withdrawn from the complete mixing reactor, and the 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. And other volatiles were removed. The resin liquid was extracted with a gear pump and extruded into a strand shape to obtain a pellet-shaped polymer B-1. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 198,000.
［実験例Ｂ－２］
スチレン６０．５質量部、アクリロニトリル３９．５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分析よりスチレン単位６５質量％、アクリロニトリル単位３５質量％であり、Ｍｗは２１０，０００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 60.5 parts by mass of styrene and 39.5 parts by mass of acrylonitrile were used. According to C-13 NMR analysis, the styrene unit was 65% by mass, the acrylonitrile unit was 35% by mass, and the Mw was 210,000.
［実験例Ｂ－３］
スチレン７３．６質量部、アクリロニトリル２６．４質量部、エチルベンゼン２０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－３を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位７４質量％、アクリロニトリル単位２６質量％であり、Ｍｗは２０２，０００であった。 [Experiment B-3]
A styrene-acrylonitrile copolymer B-3 was obtained in the same manner as in Experimental Example B-1, except that 73.6 parts by mass of styrene, 26.4 parts by mass of acrylonitrile, and 20 parts by mass of ethylbenzene were used. According to C-13 NMR analysis, the styrene unit was 74% by mass, the acrylonitrile unit was 26% by mass, and the Mw was 202,000.
［実験例Ｂ－４］
スチレン５５．８質量部、アクリロニトリル４４．２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－４を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位６２質量％、アクリロニトリル単位３８質量％であり、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 55.8 parts by mass of styrene and 44.2 parts by mass of acrylonitrile were used. According to C-13 NMR analysis, the styrene unit was 62% by mass, the acrylonitrile unit was 38% by mass, and the Mw was 201,000.
［実験例Ｂ－５］
攪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３１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、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２４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－５を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位６９質量％、アクリロニトリル単位３１質量％であり、Ｍｗは１５３，０００であった。 [Experiment B-5]
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, 31 parts by mass of acrylonitrile, 0.05 part by mass of α-methylstyrene dimer, t-butylperoxy After charging 0.2 parts by weight of isopropyl monocarbonate and 0.1 part of t-butyl peroxyacetate and replacing the system with nitrogen gas, the temperature was kept at 103 ° C., and then 24 parts by weight of styrene was kept at 103 ° C. for 4 hours. And continuously added at 105 ° C. for 2 hours over 6 hours. After completion of the addition, the temperature was kept at 120 ° C. for 3 hours. The resulting slurry was neutralized with hydrochloric acid, dehydrated and dried, and the beads obtained were extruded with a twin screw extruder equipped with a vent to obtain a styrene-acrylonitrile copolymer B-5. C-13 NMR analysis showed that the styrene unit was 69% by mass, the acrylonitrile unit was 31% by mass, and the Mw was 153,000.
［実験例Ｂ－６］
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－５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分析よりスチレン単位６９質量％、アクリロニトリル単位３１質量％であり、Ｍｗは１９２，０００であった。 [Experiment B-6]
A styrene-acrylonitrile copolymer B-6 was obtained in the same manner as in Experimental Example B-5, except that 0.02 part by mass of α-methylstyrene dimer was used. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 192,000.
［実験例Ｂ－７］
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－７を得た。Ｃ－１３ＮＭＲ分析よりスチレン単位６９質量％、アクリロニトリル単位３１質量％であり、Ｍｗは２４５，０００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 15 parts by mass of ethylbenzene was used. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 245,000.
［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分析よりスチレン単位６９質量％、アクリロニトリル単位３１質量％であり、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. C-13 NMR analysis showed that the styrene unit was 69% by mass, the acrylonitrile unit was 31% by mass, and the 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分析よりスチレン単位６９質量％、アクリロニトリル単位３１質量％であり、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. According to C-13 NMR analysis, the content was 69% by mass of styrene units, 31% by mass of acrylonitrile units, and Mw was 272,000.
［実験例Ｂ－１０］
スチレン５１．１質量部、α－メチルスチレン１７．５質量部、アクリロニトリル３１．４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分析よりスチレン単位５５質量％、α－メチルスチレン単位１４質量％、アクリロニトリル単位３１質量％であり、Ｍｗは２０１，０００であった。
上記実験例Ｂ－１～Ｂ－１０の成分組成とＭｗを表２に示す。 [Experiment B-10]
A styrene-acrylonitrile copolymer was obtained in the same manner as in Experimental Example B-1, except that 51.1 parts by mass of styrene, 17.5 parts by mass of α-methylstyrene, 31.4 parts by mass of acrylonitrile, and 18 parts by mass of ethylbenzene were used. B-10 was obtained. According to C-13 NMR analysis, the styrene unit was 55% by mass, the α-methylstyrene unit was 14% by mass, the acrylonitrile unit was 31% by mass, and the Mw was 201,000.
Table 2 shows the component compositions and Mw of Experimental Examples B-1 to B-10.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
[実施例１～１６及び比較例１～１０]
上記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２７０℃、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、樹脂組成物を得た。なお、溶融混練する際の樹脂温度はどれも２８０～３２０℃の範囲であった。 [Examples 1 to 16 and Comparative Examples 1 to 10]
The styrene-maleimide copolymer (A) and styrene-acrylonitrile copolymer (B) produced in the above 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 under the conditions of a cylinder temperature of 270 ° C., a feed rate of 20 kg / hour, and a screw rotation speed of 250 rpm. Pelletized to obtain a resin composition. The resin temperature during melt kneading was in the range of 280 to 320 ° C.
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２６０℃、ダイ温度２６０℃で、厚さ１００μｍの未延伸フィルムを押し出し、ロールに巻き取った。
得られた未延伸フィルムを、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を得た。得られたフィルムの評価結果を表３～表４に示した。 An unstretched film having a thickness of 100 μm was extruded from the resin composition at a cylinder temperature of 260 ° C. and a die temperature of 260 ° C. using a film extruder equipped with a T die, and wound around a roll.
The obtained unstretched film was uniaxially stretched 1.8 times at Tg + 20 ° C. using a tenter transverse stretching machine to obtain a stretched optical film. The evaluation results of the obtained film are shown in Tables 3 to 4.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-I000006
評価は下記の方法にて行った。
（１）ガラス転移温度
ガラス転移温度は、下記の測定条件で示差走査熱量測定（ＤＳＣ）にて測定した。
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
ガラス転移温度が１１０℃以上であるものを耐熱性について合格とした。
（２）ヘーズ
　ＡＳＴＭ　Ｄ１００３に基づき、ヘーズメーター（日本電色工業社製ＮＤＨ－１００１ＤＰ型）を用いて未延伸フィルムのヘーズ（単位：％）を測定した。
ヘーズの値が１．２％以下であるものを未延伸フィルムの透明性について合格とした。
（３）フィルム成形性
　一貫してフィルムを押出成形できたものを「良」、流動性が不足して一貫しては押出成形できなかったものを「不良」とし、「良」を合格とした。
（４）フィルム強度
　未延伸フィルムについて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た。「優」、「良」を合格とした。
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１５０回以上
「良」：折り曲げ回数１００回以上１５０回未満
「不良」：折り曲げ回数１００回未満
（５）フィルム欠陥
　未延伸フィルムについて、画像処理解析装置（ニレコ社製：ＬＵＺＥＸ　ＳＥ）を用いて観測し、下記基準にて良否を判断した。「優」、「良」を合格とした。
「優」：長さ５０μｍ以上のフィルム欠陥が０個／ｍ２
「良」：長さ５０μｍ以上のフィルム欠陥が１～４個／ｍ２
「不良」：長さ５０μｍ以上のフィルム欠陥が５個／ｍ２以上
（６）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、３００ｎｍ以上を合格とした。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) Glass transition temperature The glass transition temperature was measured by differential scanning calorimetry (DSC) under the following measurement conditions.
Device name: Robot DSC6200 manufactured by Seiko Instruments Inc.
Rate of temperature increase: 10 ° C./min A glass transition temperature of 110 ° C. or higher was regarded as acceptable for heat resistance.
(2) Haze Based on ASTM D1003, the haze (unit:%) of the unstretched film was measured using a haze meter (NDH-1001DP type manufactured by Nippon Denshoku Industries Co., Ltd.).
A film having a haze value of 1.2% or less was regarded as acceptable for the transparency of the unstretched film.
(3) Film moldability The film that was able to extrude the film consistently was judged as “good”, the one that could not be extruded consistently due to lack of fluidity was judged as “bad”, and “good” was accepted. .
(4) Film strength Folding strength of the unstretched film was measured under the following conditions and judged according to the following criteria. “Excellent” and “Good” were accepted.
Measurement conditions Measuring instrument: MIT-D FOLDING ENDURANCE TESTER (Toyo Seiki Co., Ltd.)
Load (tension): 500 g Heavy folding speed: 175 times / min Folding angle: Left and right 45 degree folding device Tip radius: 0.38 mm
Test width: 15mm
Bending direction: Film extrusion direction strength criteria “excellent”: folding number 150 times or more “good”: folding number 100 times or more and less than 150 “bad”: folding number 100 times or less (5) Film defect For unstretched film, image Observation was made using a processing analyzer (manufactured by Nireco: LUZEX SE), and the quality was judged according to the following criteria. “Excellent” and “Good” were accepted.
“Excellent”: 0 film defects with a length of 50 μm or more / m 2
“Good”: 1 to 4 film defects with a length of 50 μm or more / m 2
“Bad”: Film defects with a length of 50 μm or more are 5 pieces / m 2 or more (6) Retardation expression Retardation of stretched film (hereinafter “Re”) using a phase difference measuring device (manufactured by Oji Scientific Co., Ltd .: KOBRA-WR). “, Unit: μm), and 300 nm or more was regarded as acceptable. Moreover, by observing with a phase-contrast microscope, it confirmed that the sign of orientation birefringence was negative in all the samples in an Example and a comparative example.
上記表３に示されるとおり、実施例１～１６の樹脂組成物は、透明性、耐熱性、フィルム成形性、フィルム強度にすぐれており、特に光学フィルムに最適な特性を備えていることがわかる。また、フィルム欠陥が少なく、延伸配向による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、位相差フィルムに最適な特性を備えていることがわかる。
　一方、上記表４に示されるとおり、比較例１～１０の樹脂組成物は、透明性、耐熱性、フィルム成形性、フィルム強度、フィルム欠陥、位相差発現性のいずれかにおいて、光学フィルムとして良好な値を示さなかった。 As shown in Table 3 above, it can be seen that the resin compositions of Examples 1 to 16 are excellent in transparency, heat resistance, film moldability, and film strength, and have optimal properties particularly for optical films. . Moreover, since there are few film defects, the phase difference development property by extending | stretching orientation is favorable, and since negative orientation birefringence is shown, it turns out that the retardation film is equipped with the optimal characteristic.
On the other hand, as shown in Table 4 above, the resin compositions of Comparative Examples 1 to 10 are excellent as optical films in any of transparency, heat resistance, film moldability, film strength, film defects, and retardation development. The value was not shown.
　以上、本発明を実施例に基づいて説明した。この実施例はあくまで例示であり、種々の変形例が可能なこと、またそうした変形例も本発明の範囲にあることは当業者に理解されるところである。 In the above, this invention was demonstrated based on the Example. It is to be understood by those skilled in the art that this embodiment is merely an example, and that various modifications are possible and that such modifications are within the scope of the present invention.

Claims (9)

  1. （ｉ）スチレン系単量体単位３５～５５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％からなり、重量平均分子量（Ｍｗ）が１００，０００～１４５，０００であるスチレン－マレイミド系共重合体（Ａ）２０～４０質量％と、
    （ｉｉ）スチレン系単量体単位６５～７０質量％、アクリロニトリル系単量体単位３０～３５質量％からなり、重量平均分子量（Ｍｗ）が１５０，０００～２５０，０００であるスチレン－アクリロニトリル系共重合体（Ｂ）６０～８０質量％と
    を含有してなる光学フィルム用樹脂組成物であって、厚み１００μｍの未延伸フィルムに成形した場合に長さ５０μｍ以上のフィルム欠陥が５個／ｍ２未満である光学フィルム用樹脂組成物。     (I) Styrene monomer units 35 to 55% by mass, maleimide monomer units 30 to 60% by mass, unsaturated dicarboxylic acid anhydride monomer units 0 to 15% by mass, acrylonitrile monomer units 0 20 to 40% by mass of a styrene-maleimide copolymer (A) having a weight average molecular weight (Mw) of 100,000 to 145,000,
    (Ii) A styrene-acrylonitrile copolymer comprising 65 to 70% by mass of a styrene monomer unit and 30 to 35% by mass of an acrylonitrile monomer unit and having a weight average molecular weight (Mw) of 150,000 to 250,000. A resin composition for an optical film comprising 60 to 80% by mass of the polymer (B), and when formed into an unstretched film having a thickness of 100 μm, film defects having a length of 50 μm or more are 5 / m 2. The resin composition for optical films which is less than.
  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ることを特徴とする請求項１記載の光学フィルム用樹脂組成物。 The resin composition for an optical film 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ることを特徴とする請求項１又は２記載の光学フィルム用樹脂組成物。 3. The resin composition for an optical film according to claim 1, 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項に記載の光学フィルム用樹脂組成物。 The resin composition for an optical film according to any one of claims 1 to 3, having a glass transition temperature of 110 to 150 ° C.
  5. 請求項１～４のいずれか１項に記載の光学フィルム用樹脂組成物からなる光学フィルム。 An optical film comprising the resin composition for an optical film according to any one of claims 1 to 4.
  6. 延伸して配向させると負の配向複屈折性を示す請求項５記載の光学フィルム。 The optical film according to claim 5, which exhibits negative orientation birefringence when stretched and oriented.
  7. 溶融押出フィルムであって、さらに延伸して配向させると負の配向複屈折性を示す請求項５記載の光学フィルム。 6. The optical film according to claim 5, which is a melt-extruded film and exhibits negative orientation birefringence when further stretched and oriented.
  8. 延伸フィルムであることを特徴とする請求項６又は７記載の光学フィルム。 The optical film according to claim 6, wherein the optical film is a stretched film.
  9. 位相差フィルムであることを特徴とする請求項８記載の光学フィルム。 The optical film according to claim 8, which is a retardation film.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101418755B1 (en) 2011-10-05 2014-07-11 주식회사 엘지화학 Resin Compositions For Optical Film And Optical Compensation Films Formed By Using The Same
EP2910580B1 (en) * 2012-10-22 2017-06-28 Denka Company Limited Aromatic vinyl-vinyl cyanide resin composition with improved heat resistance
KR102148213B1 (en) * 2013-09-03 2020-08-26 덴카 주식회사 Optical film copolymer
WO2015033556A1 (en) * 2013-09-04 2015-03-12 コニカミノルタ株式会社 Polarizing plate protective film, production method therefor, polarizing plate, and liquid crystal display device
TWI642688B (en) * 2014-09-02 2018-12-01 日商電化股份有限公司 Copolymer for optical film

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004107371A (en) * 2002-09-13 2004-04-08 Kanegafuchi Chem Ind Co Ltd Resin composition and optical film
JP2006259622A (en) * 2005-03-18 2006-09-28 Sekisui Chem Co Ltd Polarizer protective film and polarizing plate
JP2007046059A (en) * 2006-10-06 2007-02-22 Tosoh Corp Highly tough film
JP2008094912A (en) * 2006-10-10 2008-04-24 Denki Kagaku Kogyo Kk Resin composition and optical molded article
JP2009276420A (en) * 2008-05-13 2009-11-26 Asahi Kasei Chemicals Corp Optical film and retardation film
WO2009151102A1 (en) * 2008-06-12 2009-12-17 電気化学工業株式会社 Resin composition for optical molded object and optical molded object obtained therefrom

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004107371A (en) * 2002-09-13 2004-04-08 Kanegafuchi Chem Ind Co Ltd Resin composition and optical film
JP2006259622A (en) * 2005-03-18 2006-09-28 Sekisui Chem Co Ltd Polarizer protective film and polarizing plate
JP2007046059A (en) * 2006-10-06 2007-02-22 Tosoh Corp Highly tough film
JP2008094912A (en) * 2006-10-10 2008-04-24 Denki Kagaku Kogyo Kk Resin composition and optical molded article
JP2009276420A (en) * 2008-05-13 2009-11-26 Asahi Kasei Chemicals Corp Optical film and retardation film
WO2009151102A1 (en) * 2008-06-12 2009-12-17 電気化学工業株式会社 Resin composition for optical molded object and optical molded object obtained therefrom

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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