WO2015033877A1 - 光学フィルム用共重合体 - Google Patents
光学フィルム用共重合体 Download PDFInfo
- Publication number
- WO2015033877A1 WO2015033877A1 PCT/JP2014/072835 JP2014072835W WO2015033877A1 WO 2015033877 A1 WO2015033877 A1 WO 2015033877A1 JP 2014072835 W JP2014072835 W JP 2014072835W WO 2015033877 A1 WO2015033877 A1 WO 2015033877A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- copolymer
- polymerization
- optical
- solution
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/12—Copolymers of styrene with unsaturated nitriles
Definitions
- the present invention relates to a copolymer for optical films. More specifically, the present invention relates to a copolymer for optical films that exhibits negative orientation birefringence and is excellent in transparency, heat resistance, film strength, and optical properties.
- Transparent resin is used in various applications such as home appliance parts, food containers, and miscellaneous goods.
- an optical component such as a retardation film, a polarizing film protective film, an antireflection film, a diffusion plate, and a light guide plate in a thin liquid crystal display element that replaces a cathode ray tube type TV monitor and an electroluminescence element, It is in a situation where it is frequently used in terms of cost.
- stretched films obtained by uniaxially or biaxially stretching a resin film are widely used for optical films of liquid crystal displays.
- a typical optical film there is a retardation film, and a ⁇ / 2 plate that converts the vibration direction of polarized light and a ⁇ / 4 plate that converts circularly polarized light into linearly polarized light or linearly polarized light into circularly polarized light are widely used. ing.
- Patent Document 1 discloses a liquid crystal display device including a laminate of a transparent stretched film having negative orientation birefringence and a transparent stretched film having positive orientation birefringence. Has been.
- a stretched film exhibiting negative orientation birefringence and a stretched film exhibiting positive orientation birefringence are laminated so that the slow axes of the stretched films are parallel to each other.
- a method for widening the viewing angle of a liquid crystal display device by using an optical compensation film having a phase difference (Re) of 60 to 300 nm and an alignment parameter (Nz) within a range of 0.5 ⁇ 0.1 is disclosed.
- the stretched film showing negative intrinsic birefringence is a resin composition of a copolymer composed of an ⁇ -olefin and an N-phenyl-substituted maleimide and an acrylonitrile-styrene copolymer.
- thermoplastic resins exhibiting positive orientation birefringence include polycarbonate and amorphous cyclic polyolefin, which are excellent in heat resistance, transparency, film strength, and retardation development. It is used.
- thermoplastic resin exhibiting negative orientation birefringence there are very few examples of practical use because heat resistance, transparency, film strength, and retardation development are inferior.
- a plurality of stretched films exhibiting positive orientation birefringence are bonded together at an appropriate angle. Therefore, the optical compensation design is complicated and expensive, and the optical compensation performance is insufficient. From the viewpoint of improvement of optical compensation performance, simplification of optical design, and cost reduction, the appearance of a thermoplastic resin exhibiting negative orientation birefringence that can be practically used for an optical film is awaited.
- Patent Document 3 discloses a thermoplastic resin copolymer excellent in transparency, heat resistance, film formability, film strength, and retardation development, and a stretched film exhibiting negative orientation birefringence. Proposed. Certainly, if it is a general film forming process, the film formability is good, but in the case of an optical film, a very beautiful film without foreign matters is necessary. A polymer filter with an extremely small opening is often used for removal, and the thermoplastic resin copolymer of Patent Document 3 has a high melt viscosity, so that it tends to stay in the polymer filter and has a high set temperature for measures against pressure loss. In some cases, foaming and die lines are generated due to thermal decomposition of the resin, which limits the practical range.
- An object of the present invention is to provide a copolymer for an optical film that exhibits negative orientation birefringence and is excellent in transparency, heat resistance, film strength, and optical properties.
- the gist of the present invention is as follows. (1) Consisting of 65 to 90% by weight of aromatic vinyl monomer unit, 5 to 25% by weight of vinyl cyanide monomer unit, and 5 to 20% by weight of unsaturated dicarboxylic acid anhydride monomer unit, weight average molecular weight A copolymer for optical films having a (Mw) of 120,000 to 250,000, and a haze of 2 mm measured by ASTM D1003 is 1% or less. (2) The aromatic vinyl monomer unit is 70 to 80% by mass, the vinyl cyanide monomer unit is 10 to 20% by mass, and the unsaturated dicarboxylic anhydride monomer unit is 10 to 15% by mass. The copolymer for optical films as described.
- Laminating film A obtained by stretching a thermoplastic resin film exhibiting negative orientation birefringence and film B obtained by stretching a thermoplastic resin film exhibiting positive orientation birefringence Any one of (1) to (6), characterized in that it is for an optical film having a refractive index profile of nx>nz> ny and is a thermoplastic resin used for the film A.
- Copolymer for optical film (8) The copolymer for optical films according to (7), wherein the film A is formed by stretching a film produced by melt extrusion. (9) The copolymer for optical films according to (7) or (8), wherein the Nz coefficient is 0.4 to 0.6.
- the present invention is to provide a copolymer for an optical film that exhibits negative orientation birefringence and is excellent in transparency, heat resistance, film strength, and optical properties.
- Aromatic vinyl monomer units include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, p-tert-butyl styrene, ⁇ -methyl styrene, ⁇ Examples thereof include units derived from styrene monomers such as -methyl-p-methylstyrene. Of these, styrene units are preferred. These aromatic vinyl monomer units may be one type or a combination of two or more types.
- vinyl cyanide monomer units examples include units derived from vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Of these, acrylonitrile units are preferred. These vinyl cyanide monomer units may be used alone or in combination of two or more.
- Examples of the unsaturated dicarboxylic acid anhydride monomer unit include units derived from respective anhydride monomers such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride. Among these, maleic anhydride units are preferable.
- the unsaturated dicarboxylic acid anhydride monomer unit may be one type or a combination of two or more types.
- the constitutional unit of the copolymer of the present invention is an aromatic vinyl monomer unit of 65 to 90% by mass, an acrylonitrile monomer unit of 5 to 25% by mass, and an unsaturated dicarboxylic acid anhydride monomer unit of 5 to 20% by mass.
- the aromatic vinyl monomer unit is 70 to 80% by mass
- the acrylonitrile monomer unit is 10 to 20% by mass
- the unsaturated dicarboxylic anhydride monomer unit is 10 to 15% by mass.
- the heat resistance or film strength is improved, and if it is 80% by mass or less, the heat resistance or film strength is further improved.
- the acrylonitrile monomer unit is 25% by mass or less, transparency or optical properties, particularly negative orientation birefringence, is improved, and if it is 20% by mass or less, transparency or optical properties are further improved, which is preferable.
- the unsaturated dicarboxylic acid anhydride monomer unit is 20% by mass or less, the film strength is improved, and if it is 15% by mass or less, the film strength is further improved.
- the aromatic vinyl monomer unit is 65% by mass or more, transparency or optical properties, particularly negative orientation birefringence is improved, and if it is 70% by mass or more, further transparency or optical properties are obtained. Since it improves, it is preferable.
- the acrylonitrile monomer unit is 5% by mass or more, the film strength is improved, and if it is 10% by mass or more, the film strength is further improved.
- the unsaturated dicarboxylic acid anhydride monomer unit is 5% by mass or more, the heat resistance is improved, and if it is 10% by mass or more, the heat resistance is further improved, which is preferable.
- the copolymer of the present invention comprises units of copolymerizable vinyl monomers other than aromatic vinyl monomer units, vinyl cyanide monomer units, and unsaturated dicarboxylic anhydride monomer units. It may be contained in the polymer as long as the effects of the invention are not impaired, and is preferably 5% by mass or less.
- the copolymerizable vinyl monomer unit include methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate, and methyl acrylate.
- Acrylate monomers such as ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, vinyl carboxylic acid monomers such as acrylic acid, methacrylic acid, N-methylmaleimide, N-alkylmaleimide monomers such as N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorf
- a unit derived from the monomers such as N- arylmaleimide monomers such as sulfonyl maleimides and the like. Two or more types of copolymerizable vinyl monomer units may be used.
- the copolymer of the present invention has a weight average molecular weight (Mw) of 120,000 to 250,000, preferably 130,000 to 230,000, more preferably 140,000 to 200,000.
- the weight average molecular weight (Mw) is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and is a value measured under the measurement conditions described below.
- Device name SYSTEM-21 Shodex (manufactured by Showa Denko) Column: 3 series PL gel MIXED-B Temperature: 40 ° C Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
- the film strength is excellent, and the film breakage during stretching is also improved.
- the weight average molecular weight (Mw) is 250,000 or less, a film having good film moldability and excellent transparency can be obtained.
- the copolymer of the present invention has a 2 mm thickness haze measured according to ASTM D1003 of 1% or less, preferably 0.8% or less, and more preferably 0.6% or less. If the haze of 2 mm thickness is 1% or less, a copolymer composition distribution is small and the film strength is excellent, and a film having excellent transparency can be obtained even when film forming or stretching is performed.
- the haze level is obtained by using an injection molding machine (IS-50EPN manufactured by TOSHIBA MACHINERY CO., LTD.) With a mirror plate of 90 mm in length, 55 mm in width and 2 mm in thickness formed under the molding conditions of cylinder temperature 230 ° C. and mold temperature 40 ° C. The measured value was measured using a haze meter (NDH-1001DP type manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with ASTM D1003.
- the copolymer of the present invention has excellent transparency that does not impair the image quality of the liquid crystal device, heat resistance that does not change orientation birefringence even in a high temperature environment, film strength that can withstand film processing such as stretching and cutting, and punching, and Since it has negative orientation birefringence, it is preferably used for an optical film.
- optical films such as a polarizing film protective film, a retardation film, and an antireflection film.
- the method of processing the copolymer of the present invention into an optical film is not particularly limited, and can be processed using a known technique such as a melt extrusion method or a casting method.
- the optical anisotropy is preferably small, and the in-plane retardation (Re) calculated by the following (Formula 1) is 20 nm or less, preferably 10 nm or less, more preferably
- the thickness direction retardation (Rth) calculated by the following (Formula 2) is 50 nm or less, preferably 20 nm or less, more preferably 5 nm or less. If the in-plane retardation (Re) is 20 nm or less and the thickness direction retardation is 50 nm or less, when the polarizing film protective film is used for a polarizing plate of a liquid crystal display device, problems such as a decrease in contrast of the liquid crystal display device occur. This is preferable.
- nx, ny, and nz are when the direction in which the in-plane refractive index is maximized is the X axis, the direction perpendicular to the X axis is the Y axis, and the thickness direction of the film is the Z axis. Is the refractive index in the axial direction, and d is the film thickness.
- An example of reducing the optical anisotropy is a method using a flexible roll that can be elastically deformed, but any molding method can be used as long as it can reduce the optical anisotropy.
- an unstretched film having a small optical anisotropy can be used as a polarizing film protective film as it is, but a stretched film stretched within a range where the optical anisotropy is allowed to increase the film strength is used as a polarizing film protective film. It can also be used.
- optical anisotropy examples include a method of blending a polymer having positive intrinsic birefringence such as polycarbonate, polyethylene terephthalate, polyphenylene ether, a method of adding acicular inorganic crystal fine particles, etc. Any method can be used as long as it can reduce anisotropy.
- a stretched film that is stretched by adjusting stretching conditions so as to have a desired in-plane retardation (Re) and thickness direction retardation (Rth) is suitably used.
- the stretched film is usually laminated with another stretched film so that a ⁇ / 2 plate that changes the vibration direction of polarized light, circularly polarized light becomes linearly polarized light, or It is often used as a ⁇ / 4 plate that converts linearly polarized light into circularly polarized light. Therefore, it only needs to have an appropriate retardation, and both the other stretched films to be laminated are adjusted so that the in-plane retardation (Re) and the thickness direction retardation (Rth) become a desired retardation. Used.
- Stretched film A which consists of the copolymer of this invention
- Stretched film B which consists of a thermoplastic resin which shows positive orientation birefringence
- the Nz coefficient is particularly preferably 0.4 to 0.6.
- nx is the refractive index in the slow axis direction in the film plane
- ny is the refractive index in the fast axis direction in the film plane
- nz is the refractive index in the direction perpendicular to the film plane, that is, in the thickness direction.
- the slow axis is the direction in which the refractive index in the film plane is maximized
- the fast axis is the direction perpendicular to the slow axis in the film plane.
- the optical film formed with the refractive index distribution of nx> nz> ny is a thermoplastic resin having negative orientation birefringence.
- a stretched film A, a method of laminating a film B was stretched thermoplastic resin having positive orientation birefringence is valid, the copolymer of the present invention is very suitable as a film for A.
- the stretched film A made of the copolymer of the present invention and the stretched film B made of a thermoplastic resin exhibiting positive orientation birefringence are so arranged that their slow axes are orthogonal to each other.
- the in-plane retardations Re (450), Re (590) and Re (750) at wavelengths of 450 nm, 590 nm and 750 nm satisfy the relationship of Re (450) ⁇ Re (590) ⁇ Re (750). Things.
- the wavelength light is ⁇ / 2 or ⁇ / 4.
- Re (450) 225 nm
- Re (590) 295 nm
- Re (750) 375 nm.
- a thermoplastic resin has a characteristic that the in-plane retardation Re increases as the wavelength becomes shorter.
- This characteristic is called the normal wavelength dispersion characteristic, and the opposite characteristic, that is, the characteristic that the in-plane retardation Re becomes smaller as the wavelength becomes shorter is called the reverse wavelength dispersion characteristic.
- the stretched film A and the stretched film B having the positive wavelength dispersion characteristics are laminated so that the slow axis is perpendicular, and the reverse wavelength dispersion characteristics, that is, the relationship of Re (450) ⁇ Re (590) ⁇ Re (750) is satisfied.
- the stretched film A has a larger wavelength dependency of the in-plane retardation Re than the stretched film B
- the stretched film A has a smaller in-plane retardation Re than the stretched film B.
- the film which has a reverse wavelength dispersion characteristic can be obtained by producing a stretched film and laminating
- the method for producing the copolymer of the present invention will be described.
- the polymerization mode is not particularly limited and can be produced by a known method such as solution polymerization or bulk polymerization, but solution polymerization is more preferable.
- the solvent used in the solution polymerization is preferably non-polymerizable from the viewpoint that a by-product is difficult to produce and that there are few adverse effects.
- the type of the solvent is not particularly limited.
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, ethers such as tetrahydrofuran, 1,4-dioxane, toluene, ethylbenzene, xylene, chlorobenzene Aromatic hydrocarbons, etc. are mentioned, but methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of the solubility of the monomer and copolymer and the ease of solvent recovery.
- the amount of the solvent added is preferably 10 to 100 parts by mass, and more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the copolymer obtained. If it is 10 parts by mass or more, it is suitable for controlling the reaction rate and the polymerization solution viscosity, and if it is 100 parts by mass or less, it is suitable for obtaining the target weight average molecular weight (Mw).
- the polymerization process may be any of a batch polymerization method, a semi-batch polymerization method, and a continuous polymerization method, but the batch polymerization method is preferable for obtaining a desired weight average molecular weight (Mw) and transparency. It is.
- the polymerization method is not particularly limited, but is preferably a radical polymerization method from the viewpoint that it can be produced with high productivity by a simple process.
- the polymerization initiator is not particularly limited.
- Known organic peroxides such as-(t-butylperoxy) butyrate and known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, azobis
- the copolymer of the present invention has a weight average molecular weight (Mw) of 120,000 to 250,000, and a 2 mm thick haze measured based on ASTM D1003 is 1% or less. If a copolymer satisfying these conditions is obtained, the polymerization procedure is not particularly limited, but in order to obtain a copolymer having transparency with a haze of 1% or less, the copolymer composition distribution becomes small. Must be polymerized as follows. Since the aromatic vinyl monomer and the unsaturated dicarboxylic acid anhydride monomer have strong alternating copolymerization properties, they are not suitable for the polymerization rate of the aromatic vinyl monomer and the vinyl cyanide monomer.
- a method of continuously adding a saturated dicarboxylic acid anhydride monomer is preferred.
- the control of the polymerization rate can be adjusted by the polymerization temperature, the polymerization time, and the addition amount of the polymerization initiator. It is preferable to continuously add a polymerization initiator because the polymerization rate can be more easily controlled.
- a method for obtaining a copolymer having a weight average molecular weight (Mw) of 120,000 to 250,000 in addition to adjustment of polymerization temperature, polymerization time, and polymerization initiator addition amount, solvent addition amount and chain transfer agent It can be obtained by adjusting the addition amount.
- the chain transfer agent is not particularly limited.
- a known chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene is used. Can do.
- the polymerization solution is optionally provided with a heat resistant stabilizer such as a hindered phenol compound, a lactone compound, a phosphorus compound, or a sulfur compound, a light stabilizer such as a hindered amine compound or a benzotriazole compound, Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oils may be added. The addition amount is preferably less than 0.2 parts by mass with respect to 100 parts by mass of all monomer units. These additives may be used alone or in combination of two or more.
- a heat resistant stabilizer such as a hindered phenol compound, a lactone compound, a phosphorus compound, or a sulfur compound
- a light stabilizer such as a hindered amine compound or a benzotriazole compound
- Additives such as lubricants, plasticizers, colorants, antistatic agents and mineral oils may be added. The addition amount is preferably less than 0.2 parts by mass with respect to 100 parts by mass of all mono
- the method for recovering the copolymer of the present invention from the polymerization solution is not particularly limited, and a known devolatilization technique can be used.
- a method of continuously feeding the polymerization liquid to a twin-screw devolatilizing extruder using a gear pump and devolatilizing a polymerization solvent, an unreacted monomer and the like can be mentioned.
- the devolatilizing component including the polymerization solvent, unreacted monomer, etc. is condensed and recovered using a condenser, etc., and the polymerization solvent can be reused by purifying the condensate in a distillation tower. .
- a 120-liter autoclave equipped with a stirrer is charged with 2.0 kg of a 20% maleic anhydride solution, 30 kg of styrene, 6 kg of acrylonitrile, 30 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone, and the gas phase is replaced with nitrogen gas. Then, the temperature was raised to 85 ° C. over 40 minutes with stirring. While maintaining the temperature at 85 ° C. after the temperature rise, a 20% maleic anhydride solution was added at a rate of 1.38 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 429 g / hour, respectively.
- Example 2 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120 liter autoclave equipped with a stirrer was charged with 3.0 kg of a 20% maleic anhydride solution, 30 kg of styrene, 4 kg of acrylonitrile, and 40 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas, followed by stirring. The temperature was raised to 85 ° C. over 40 minutes. While maintaining the temperature at 85 ° C.
- Example 3 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120 liter autoclave equipped with a stirrer is charged with 2.0 kg of a 20% maleic anhydride solution, 28 kg of styrene, 8.0 kg of acrylonitrile, 30 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone, and the gas phase portion is filled with nitrogen gas.
- the temperature was raised to 88 ° C. over 40 minutes with stirring. While maintaining the temperature at 88 ° C.
- a 20% maleic anhydride solution was added at 1.5 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 285.7 g / hour. Each continuously for 7 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 20 g of t-butylperoxyisopropyl monocarbonate was added. The temperature was raised to 125 ° C. over 5 hours at a temperature increase rate of 7.4 ° C./hour while maintaining a 20 kg maleic anhydride solution 1.5 kg / hour. The addition of the 20% maleic anhydride solution was stopped when the total reached 18 kg.
- the polymerization was terminated by maintaining 125 ° C. for 1 hour. After completion of the polymerization, a small amount of the polymerization solution was sampled, and the polymerization rate of each monomer was measured.
- the polymerization liquid was continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a trace amount of unreacted monomer were devolatilized to obtain a copolymer A-3.
- the polymerization rate, composition analysis, molecular weight, and haze of the monomers were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
- Example 4 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120 liter autoclave equipped with a stirrer was charged with 2 kg of a 20% maleic anhydride solution, 32 kg of styrene, 4 kg of acrylonitrile, 30 g of t-dodecyl mercaptan and 2 kg of methyl isobutyl ketone, and the gas phase was replaced with nitrogen gas. The temperature was raised to 95 ° C. over 40 minutes with stirring.
- the 20% maleic anhydride solution was added at 1.125 kg / hour and the 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 200 g / hour. The addition continued continuously over 10 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 60 g of t-butylperoxyisopropyl monocarbonate was added.
- the 20% maleic anhydride solution was heated to 120 ° C. over 6 hours at a temperature increase rate of 4.17 ° C./hour while maintaining the addition rate of 1.125 kg / hour.
- Example 5 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120 liter autoclave equipped with a stirrer was charged with 3.0 kg of a 20% maleic anhydride solution, 32 kg of styrene, 1.2 kg of acrylonitrile, and 30 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 90 ° C. over 40 minutes with stirring. While maintaining 90 ° C.
- the polymerization solution was continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer were devolatilized to obtain a copolymer A-5.
- the polymerization rate, composition analysis, molecular weight, and haze of each monomer were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
- Example 6 10% maleic anhydride solution dissolved in methyl isobutyl ketone so that maleic anhydride has a concentration of 10% by mass and methyl so that t-butylperoxy-2-ethylhexanoate becomes 2% by mass A 2% t-butyl peroxy-2-ethylhexanoate solution diluted in isobutyl ketone was prepared in advance and used for the polymerization.
- a 120 liter autoclave equipped with a stirrer was charged with 2 kg of 10% maleic anhydride solution, 28 kg of styrene, 10 kg of acrylonitrile, 48 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone, and the gas phase was replaced with nitrogen gas.
- the temperature was raised to 90 ° C. over 40 minutes with stirring. While maintaining 90 ° C. after the temperature rise, a 10% maleic anhydride solution was added at a rate of 1.64 kg / hour, and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 286 g / hour, respectively. The addition continued for 7 hours continuously.
- the polymerization solution was continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer were devolatilized to obtain a copolymer A-6.
- the polymerization rate, composition analysis, molecular weight, and haze of each monomer were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
- Example 7 25% maleic anhydride solution dissolved in methyl isobutyl ketone so that maleic anhydride has a concentration of 25% by mass and methyl so that t-butylperoxy-2-ethylhexanoate becomes 2% by mass
- a 2% t-butyl peroxy-2-ethylhexanoate solution diluted in isobutyl ketone was prepared in advance and used for the polymerization.
- a 120 liter autoclave equipped with a stirrer was charged with 2.88 kg of a 25% maleic anhydride solution, 26.8 kg of styrene, 6 kg of acrylonitrile, and 30 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas.
- the temperature was raised to 85 ° C. over 40 minutes with stirring. While maintaining the temperature at 85 ° C., the 25% maleic anhydride solution was 2.16 kg / hour and the 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 286 g / hour. The addition continued for 7 hours continuously.
- the polymerization solution was continuously fed to a twin-screw devolatilizing extruder using a gear pump, and methyl isobutyl ketone and a small amount of unreacted monomer were devolatilized to obtain a copolymer A-7.
- the polymerization rate, composition analysis, molecular weight, and haze of each monomer were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
- Example 8 A 10% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 6.
- a 120 liter autoclave equipped with a stirrer was charged with 2.8 kg of a 10% maleic anhydride solution, 34.4 kg of styrene, 1.8 kg of acrylonitrile, and 10 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. Then, it heated up to 90 degreeC over 40 minutes, stirring. While maintaining 90 ° C.
- Example 1 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120-liter autoclave equipped with a stirrer is charged with 2.0 kg of a 20% maleic anhydride solution, 30 kg of styrene, 6 kg of acrylonitrile, 60 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone, and the gas phase is replaced with nitrogen gas. Then, the temperature was raised to 95 ° C. over 40 minutes with stirring.
- the 20% maleic anhydride solution was added at 1.38 kg / hour and the 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 375 g / hour. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 20 g of t-butylperoxyisopropyl monocarbonate was added.
- the 20% maleic anhydride solution was heated to 125 ° C. over 5 hours at a temperature rising rate of 6.0 ° C./hour while maintaining the addition rate of 1.38 kg / hour.
- Example 2 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120 liter autoclave equipped with a stirrer was charged with 10 kg of a 20% maleic anhydride solution, 30 kg of styrene, 6 kg of acrylonitrile, 30 g of t-dodecyl mercaptan, and 2 kg of methyl isobutyl ketone, and the gas phase was replaced with nitrogen gas.
- the temperature was raised to 85 ° C. over 40 minutes with stirring. While maintaining the temperature at 85 ° C.
- the 20% maleic anhydride solution was continuously added at a rate of 769 g / hour, and the 2% t-butylperoxy-2-ethylhexanoate solution was continuously added at a rate of 375 g / hour. The addition was continued over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 20 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated up to 120 ° C. over 5 hours at a temperature increase rate of 7 ° C./hour while maintaining the addition rate of 769 g / hour.
- Example 3 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120 liter autoclave equipped with a stirrer was charged with 3 kg of a 20% maleic anhydride solution, 30 kg of styrene, 4 kg of acrylonitrile, and 4 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 86 ° C over a period of minutes. While maintaining the temperature at 86 ° C.
- a 20% maleic anhydride solution was added at a rate of 1.17 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 100 g / hour. The addition continued continuously over 15 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 60 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated to 115 ° C. over 8 hours at a rate of 3.63 ° C./hour while maintaining the addition rate of 1.17 kg / hour.
- Example 4 A 20% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 1.
- a 120 liter autoclave equipped with a stirrer was charged with 2 kg of a 20% maleic anhydride solution, 22 kg of styrene, 14 kg of acrylonitrile, 30 g of t-dodecyl mercaptan and 4 kg of methyl isobutyl ketone, and the gas phase was replaced with nitrogen gas.
- the temperature was raised to 85 ° C. over 40 minutes with stirring. While maintaining the temperature at 85 ° C.
- a 20% maleic anhydride solution was added at a rate of 2 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 83.3 g / hour, respectively. The addition continued continuously over 6 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 10 g of t-butylperoxyisopropyl monocarbonate was added. The 20% maleic anhydride solution was heated up to 120 ° C. over 3 hours at a temperature increase rate of 11.67 ° C./hour while maintaining the addition rate of 2 kg / hour.
- Example 5 A 25% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 7.
- a 120-liter autoclave equipped with a stirrer was charged with 4 kg of a 25% maleic anhydride solution, 26 kg of styrene, 4 kg of acrylonitrile, and 30 g of t-dodecyl mercaptan, and the gas phase was replaced with nitrogen gas. The temperature was raised to 85 ° C over a period of minutes.
- the 25% maleic anhydride solution was added at a rate of 2.77 kg / hour and the 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 375 g / hour. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 20 g of t-butylperoxyisopropyl monocarbonate was added. The 25% maleic anhydride solution was heated to 125 ° C. over 5 hours at a temperature rising rate of 8 ° C./hour while maintaining the addition rate of 2.77 kg / hour.
- Example 6 A 10% maleic anhydride solution and a 2% t-butylperoxy-2-ethylhexanoate solution were prepared as in Example 6.
- a 120 liter autoclave equipped with a stirrer 2.8 kg of 10% maleic anhydride solution, 37.2 kg of styrene, 30 g of t-dodecyl mercaptan, the gas phase was replaced with nitrogen gas, and then stirred for 40 minutes. The temperature was raised to 95 ° C.
- a 10% maleic anhydride solution was added at a rate of 1.48 kg / hour and a 2% t-butylperoxy-2-ethylhexanoate solution was added at a rate of 500 g / hour. The addition continued continuously over 8 hours. Thereafter, the addition of the 2% t-butylperoxy-2-ethylhexanoate solution was stopped, and 60 g of t-butylperoxyisopropyl monocarbonate was added. The 10% maleic anhydride solution was heated to 120 ° C. over 9 hours at a heating rate of 2.77 ° C./hour while maintaining the addition rate of 1.48 kg / hour.
- each monomer polymerization rate was calculated
- Styrene monomer polymerization rate and acrylonitrile monomer polymerization rate About each polymerization liquid sample, the unreacted styrene monomer and acrylonitrile monomer were measured using the following apparatuses.
- Apparatus name Gas chromatograph (6890 series, manufactured by Agilent) Column: Capillary column (DB-1 (polysiloxane), manufactured by Agilent)
- DB-1 polysiloxane
- films were prepared as follows. In a clean booth that is in a clean environment of class 1000 or less in a stationary state, a gear pump, a polymer filter “Dena filter, aperture 5 ⁇ m” (manufactured by Nagase Sangyo Co., Ltd.), 300 mm width, single layer T die, A film having a width of 250 mm and a thickness of 100 ⁇ 5 ⁇ m was formed using a film-forming machine equipped with a take-up winder “touch roll flexible type” (manufactured by Plastics Engineering Laboratory).
- Test piece 20 unstretched films of length 50 mm ⁇ width 50 mm ⁇ film thickness 100 ⁇ 5 ⁇ m
- Weight iron ball 11 mm in diameter and 5.45 g in weight Fixed state; The 50% fracture height was measured at 1 cm intervals in accordance with JIS K7211, and the 50% fracture energy was calculated.
- ⁇ 3 (mJ) all which fractured
- Examples relating to the copolymer for optical films of the present invention were all excellent in film strength, film transparency, optical properties, negative retardation development, and heat resistance, but did not meet the conditions of the present invention.
- the comparative example of the copolymer was inferior in any of physical properties among film strength, film transparency, optical properties, negative retardation development, and heat resistance.
- Example 9 Using the copolymer A-1 obtained in Example 1, an unstretched film having a thickness of 0.25 mm was produced using the film casting machine described in Example 1. The obtained unstretched film was cut into a square with a side of 120 mm, and 2. A longitudinal direction was performed at a temperature of 125 ° C. and a stretching speed of 25 mm / min by a biaxial stretching test apparatus (EX10-B, manufactured by Toyo Seiki Seisakusho). A film A1 having a thickness of 0.10 mm was obtained, which was stretched 5 times and uniaxially stretched 1.0 times in the lateral direction.
- EX10-B biaxial stretching test apparatus
- an unstretched film having a thickness of 0.16 mm is similarly produced, and the obtained unstretched film is cut into a square of 120 mm each.
- the in-plane retardation Re (590), Nz coefficient, and three-dimensional refractive index of the film A1 and the film B1 were measured using a birefringence measuring apparatus “KOBRA-WR manufactured by Oji Scientific Instruments”. The results are shown in Table 5. Further, regarding the laminated film obtained by laminating the film A1 and the film B1 so that the slow axis is perpendicular, the in-plane retardations Re (450), Re (590), and Re (750) at wavelengths of 450 nm, 590 nm, and 750 nm, respectively. ) And the Nz coefficient were measured using a birefringence measuring apparatus (KOBRA-WR, manufactured by Oji Scientific Instruments). The results are shown in Table 5.
- the characteristics of the retardation film that improves the viewing angle of the liquid crystal device that is, the in-plane retardation (Re) is 60 to 300 nm, and the Nz coefficient is 0.4 to 0.6. It is possible to produce an optical film that satisfies the above relationship. Furthermore, it is possible to produce an optical film satisfying an ideal inverse wavelength dispersion characteristic from the viewpoint of color compensation, that is, a relationship of Re (450) ⁇ Re (590) ⁇ Re (750).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
(1)芳香族ビニル単量体単位65~90質量%、シアン化ビニル単量体単位5~25質量%、不飽和ジカルボン酸無水物単量体単位5~20質量%からなり、重量平均分子量(Mw)が12万~25万であり、ASTM D1003に基づき測定した2mm厚みの曇り度が1%以下である光学フィルム用共重合体。
(2)芳香族ビニル単量体単位70~80質量%、シアン化ビニル単量体単位10~20質量%、不飽和ジカルボン酸無水物単量体単位10~15質量%である(1)に記載の光学フィルム用共重合体。
(3)芳香族ビニル単量体単位がスチレン単位である(1)または(2)に記載の光学フィルム用共重合体。
(4)シアン化ビニル単量体単位がアクリロニトリル単位である(1)~(3)のいずれか1項に記載の光学フィルム用共重合体。
(5)不飽和ジカルボン酸無水物単量体単位がマレイン酸無水物単位である(1)~(4)のいずれか1項に記載の光学フィルム用共重合体。
(6)偏光膜保護フィルム、位相差フィルム、または反射防止フィルムに使用されることを特徴とする(1)~(5)のいずれか1項に記載の光学フィルム用共重合体。
(7)負の配向複屈折性を示す熱可塑性樹脂フィルムを延伸して得られるフィルムAと正の配向複屈折性を示す熱可塑性樹脂フィルムを延伸して得られるフィルムBとを積層させて、nx>nz>nyの屈折率分布を形成している光学フィルム用であり、フィルムAに使用される熱可塑性樹脂であることを特徴とする(1)~(6)のいずれか1項に記載の光学フィルム用共重合体。
(8)フィルムAが溶融押出により製造されたフィルムを延伸してなることを特徴とする(7)に記載の光学フィルム用共重合体。
(9)Nz係数が、0.4~0.6であることを特徴とする(7)または(8)に記載の光学フィルム用共重合体。
(10)フィルムAとフィルムBを遅相軸が直交するように積層させることで波長450nm、590nmおよび750nmにおける面内位相差Re(450)、Re(590)およびRe(750)がRe(450)<Re(590)<Re(750)の関係を満たすことを特徴とする(7)~(9)のいずれか1項に記載の光学フィルム用共重合体。
本願明細書において、「~」という記号は「以上」及び「以下」を意味し、例えば、「A~B」なる記載は、A以上でありB以下であることを意味する。
装置名:SYSTEM-21 Shodex(昭和電工社製)
カラム:PL gel MIXED-Bを3本直列
温度:40℃
検出:示差屈折率
溶媒:テトラヒドロフラン
濃度:2質量%
検量線:標準ポリスチレン(PS)(PL社製)を用いて作製した。
Rth={(nx+ny)÷2-nz}×d・・・(式2)
なお、上記式中において、nx、ny、およびnzは、それぞれ面内屈折率が最大となる方向をX軸、X軸に垂直な方向をY軸、フィルムの厚さ方向をZ軸としたときのそれぞれの軸方向の屈折率であり、dはフィルム厚さである。
Nz=(nx-nz)/(nx-ny) (1)
重合様式においては特に限定はなく、溶液重合、塊状重合等公知の方法で製造できるが、溶液重合がより好ましい。溶液重合で用いる溶剤は、副生成物が出来難く、悪影響が少ないという観点から非重合性であることが好ましい。溶剤の種類としては、特に限定されるものではないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン等のケトン類、テトラヒドロフラン、1、4-ジオキサン等のエーテル類、トルエン、エチルベンゼン、キシレン、クロロベンゼン等の芳香族炭化水素などが挙げられるが、単量体や共重合体の溶解度、溶剤回収のし易さの観点から、メチルエチルケトン、メチルイソブチルケトンが好ましい。溶剤の添加量は、得られる共重合体量100質量部に対して、10~100質量部が好ましく、さらに好ましくは30~80質量部である。10質量部以上であれば、反応速度および重合液粘度を制御する上で好適であり、100質量部以下であれば、目的の重量平均分子量(Mw)を得る上で好適である。
[実施例1]
マレイン酸無水物が20質量%濃度となるようにメチルイソブチルケトンに溶解させた20%マレイン酸無水物溶液と、t-ブチルパーオキシ-2-エチルヘキサノエートが2質量%となるようにメチルイソブチルケトンに希釈した2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液とを事前に調製し、重合に使用した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液2.0kg、スチレン30kg、アクリロニトリル6kg、t-ドデシルメルカプタン30g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて85℃まで昇温した。昇温後85℃を保持しながら、20%マレイン酸無水物溶液を1.38kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を429g/時の分添速度で各々連続的に7時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを25g添加した。20%マレイン酸無水物溶液は、そのまま1.38kg/時の分添速度を維持しながら、6.7℃/時の昇温速度で6時間かけて125℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で18kgになった時点で停止した。昇温後、1時間125℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-1を得た。得られた共重合体A-1をC-13NMR法により組成分析を行った。さらにGPC装置にて分子量測定を行った。また、射出成形機にて2mm厚みの鏡面プレートを成形し、ヘーズメーターにて曇り度を測定した。各々単量体の重合率、組成分析結果、分子量測定結果、および曇り度測定結果を表1に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液3.0kg、スチレン30kg、アクリロニトリル4kg、t-ドデシルメルカプタン40gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて85℃まで昇温した。昇温後85℃を保持しながら、20%マレイン酸無水物溶液を1.8kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を375g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを40g添加した。20%マレイン酸無水物溶液はそのまま1.8kg/時の分添速度を維持しながら、5.71℃/時の昇温速度で7時間かけて125℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で27kgになった時点で停止した。昇温後、1時間125℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-2を得た。得られた共重合体A-2について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表1に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液2.0kg、スチレン28kg、アクリロニトリル8.0kg、t-ドデシルメルカプタン30g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて88℃まで昇温した。昇温後88℃を保持しながら、20%マレイン酸無水物溶液を1.5kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を285.7g/時の分添速度で各々連続的に7時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを20g添加した。20%マレイン酸無水物溶液1.5kg/時の分添速度を維持しながら、7.4℃/時の昇温速度で5時間かけて125℃まで昇温した。20%マレイン酸無水物溶液の分添は積算で18kgになった時点で各々の分添を停止した。昇温後、1時間125℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-3を得た。得られた共重合体A-3について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表1に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液2kg、スチレン32kg、アクリロニトリル4kg、t-ドデシルメルカプタン30g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて95℃まで昇温した。昇温後95℃を保持しながら、20%マレイン酸無水物溶液を1.125kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を200g/時の分添速度で各々連続的に10時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを60g添加した。20%マレイン酸無水物溶液はそのまま1.125kg/時の分添速度を維持しながら、4.17℃/時の昇温速度で6時間かけて120℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で18kgになった時点で停止した。昇温後、1時間120℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-4を得た。得られた共重合体A-4について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表1に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液3.0kg、スチレン32kg、アクリロニトリル1.2kg、t-ドデシルメルカプタン30gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて90℃まで昇温した。昇温後90℃を保持しながら、20%マレイン酸無水物溶液を1.8kg/時、アクリロニトリルを53.3g/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を375g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを80g添加した。20%マレイン酸無水物溶液1.8kg/時、アクリロニトリルを53.3g/時の分添速度を維持しながら、5℃/時の昇温速度で7時間かけて125℃まで昇温した。20%マレイン酸無水物溶液の分添は積算で27kg、アクリロニトリルの分添は積算で800gになった時点で分添を停止した。昇温後、1時間125℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-5を得た。得られた共重合体A-5について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表1に示す。
マレイン酸無水物が10質量%濃度となるようにメチルイソブチルケトンに溶解させた10%マレイン酸無水物溶液と、t-ブチルパーオキシ-2-エチルヘキサノエートが2質量%となるようにメチルイソブチルケトンに希釈した2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液とを事前に調製し、重合に使用した。
撹拌機を備えた120リットルのオートクレーブ中に、10%マレイン酸無水物溶液2kg、スチレン28kg、アクリロニトリル10kg、t-ドデシルメルカプタン48g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて90℃まで昇温した。昇温後90℃を保持しながら、10%マレイン酸無水物溶液を1.64kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を286g/時の分添速度で各々連続的に7時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを30g添加した。10%マレイン酸無水物溶液1.64kg/時の分添速度を維持しながら、7.5℃/時の昇温速度で4時間かけて120℃まで昇温した。10%マレイン酸無水物溶液の分添は積算で18kgになった時点で各々の分添を停止した。昇温後、1時間120℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-6を得た。得られた共重合体A-6について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表1に示す。
マレイン酸無水物が25質量%濃度となるようにメチルイソブチルケトンに溶解させた25%マレイン酸無水物溶液と、t-ブチルパーオキシ-2-エチルヘキサノエートが2質量%となるようにメチルイソブチルケトンに希釈した2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液とを事前に調製し、重合に使用した。
撹拌機を備えた120リットルのオートクレーブ中に、25%マレイン酸無水物溶液2.88kg、スチレン26.8kg、アクリロニトリル6kg、t-ドデシルメルカプタン30gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて85℃まで昇温した。昇温後85℃を保持しながら、25%マレイン酸無水物溶液を2.16kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を286g/時の分添速度で各々連続的に7時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを40g添加した。25%マレイン酸無水物溶液はそのまま2.88kg/時の分添速度を維持しながら、7℃/時の昇温速度で5時間かけて120℃まで昇温した。25%マレイン酸無水物溶液の分添は、分添量が積算で25.9kgになった時点で停止した。昇温後、1時間120℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-7を得た。得られた共重合体A-7について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表1に示す。
10%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例6と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、10%マレイン酸無水物溶液2.8kg、スチレン34.4kg、アクリロニトリル1.8kg、t-ドデシルメルカプタン10gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて90℃まで昇温した。昇温後90℃を保持しながら、10%マレイン酸無水物溶液を1.2kg/時、アクリロニトリルを47.6g/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を181g/時の分添速度で各々連続的に11時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを80g添加した。10%マレイン酸無水物溶液は1.2kg/時、アクリロニトリルは47.6g/時の分添速度を維持しながら、3,5℃/時の昇温速度で10時間かけて125℃まで昇温した。10%マレイン酸無水物溶液の分添は分添量が積算で25.2kg、アクリロニトリルは1kgになった時点で停止した。昇温後、1時間125℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-8を得た。得られた共重合体A-8について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表1に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液2.0kg、スチレン30kg、アクリロニトリル6kg、t-ドデシルメルカプタン60g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて95℃まで昇温した。昇温後95℃を保持しながら、20%マレイン酸無水物溶液を1.38kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を375g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを20g添加した。20%マレイン酸無水物溶液は、そのまま1.38kg/時の分添速度を維持しながら、6.0℃/時の昇温速度で5時間かけて125℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で18kgになった時点で停止した。昇温後、1時間125℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-9を得た。得られた共重合体A-9について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表2に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液10kg、スチレン30kg、アクリロニトリル6kg、t-ドデシルメルカプタン30g、メチルイソブチルケトン2kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて85℃まで昇温した。昇温後85℃を保持しながら、20%マレイン酸無水物溶液を769g/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を375g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを20g添加した。20%マレイン酸無水物溶液は、そのまま769g/時の分添速度を維持しながら、7℃/時の昇温速度で5時間かけて120℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で10kgになった時点で停止した。昇温後、1時間120℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-10を得た。得られた共重合体A-10について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表2に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液3kg、スチレン30kg、アクリロニトリル4kg、t-ドデシルメルカプタン4gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて86℃まで昇温した。昇温後86℃を保持しながら、20%マレイン酸無水物溶液を1.17kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を100g/時の分添速度で各々連続的に15時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを60g添加した。20%マレイン酸無水物溶液はそのまま1.17kg/時の分添速度を維持しながら、3.63℃/時の昇温速度で8時間かけて115℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で27kgになった時点で停止した。昇温後、1時間115℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-11を得た。得られた共重合体A-11について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表2に示す。
20%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例1と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、20%マレイン酸無水物溶液2kg、スチレン22kg、アクリロニトリル14kg、t-ドデシルメルカプタン30g、メチルイソブチルケトン4kgを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて85℃まで昇温した。昇温後85℃を保持しながら、20%マレイン酸無水物溶液を2kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を83.3g/時の分添速度で各々連続的に6時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを10g添加した。20%マレイン酸無水物溶液はそのまま2kg/時の分添速度を維持しながら、11.67℃/時の昇温速度で3時間かけて120℃まで昇温した。20%マレイン酸無水物溶液の分添は、分添量が積算で18.0kgになった時点で停止した。昇温後、1時間120℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-12を得た。得られた共重合体A-12について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表2に示す。
25%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例7と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、25%マレイン酸無水物溶液4kg、スチレン26kg、アクリロニトリル4kg、t-ドデシルメルカプタン30gを仕込み、気相部を窒素ガスで置換した後、撹拌しながら40分かけて85℃まで昇温した。昇温後85℃を保持しながら、25%マレイン酸無水物溶液を2.77kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を375g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを20g添加した。25%マレイン酸無水物溶液はそのまま2.77kg/時の分添速度を維持しながら、8℃/時の昇温速度で5時間かけて125℃まで昇温した。25%マレイン酸無水物溶液の分添は、分添量が積算で36kgになった時点で停止した。昇温後、1時間125℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-13を得た。得られた共重合体A-13について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表2に示す。
10%マレイン酸無水物溶液と2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液は、実施例6と同様に調製した。
撹拌機を備えた120リットルのオートクレーブ中に、10%マレイン酸無水物溶液2.8kg、スチレン37.2kg、t-ドデシルメルカプタン30g、気相部を窒素ガスで置換した後、撹拌しながら40分かけて95℃まで昇温した。昇温後95℃を保持しながら、10%マレイン酸無水物溶液を1.48kg/時、および2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液を500g/時の分添速度で各々連続的に8時間かけて添加し続けた。その後、2%t-ブチルパーオキシ-2-エチルヘキサノエート溶液の分添を停止し、t-ブチルパーオキシイソプロピルモノカーボネートを60g添加した。10%マレイン酸無水物溶液はそのまま1.48kg/時の分添速度を維持しながら、2.77℃/時の昇温速度で9時間かけて120℃まで昇温した。10%マレイン酸無水物溶液の分添は、分添量が積算で25.2kgになった時点で停止した。昇温後、1時間120℃を保持して重合を終了させた。重合終了後、重合液を少量サンプリングし、各々の単量体の重合率を測定した。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して共重合体A-14を得た。得られた共重合体A-14について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表2に示す。
スチレン-アクリロニトリル共重合体(グレード名「AS-C-800」、電気化学工業株式会社製)について、実施例1と同様に各々単量体の重合率、組成分析、分子量、および曇り度を測定した。測定結果を表2に示す。
(1)スチレン単量体重合率およびアクリロニトリル単量体重合率
各々の重合液サンプルについて、未反応のスチレン単量体およびアクリロニトリル単量体を以下の装置を用いて測定した。
装置名:ガスクロマトグラフ(6890シリーズ、Agilent社製)
カラム:キャピラリーカラム(DB-1(ポリシロキサン)、Agilent社製)
カラム初期温度60℃にて昇温分析を行った。
(昇温条件) 60℃:ホールド16分
60~200℃:20℃/分で昇温
200℃:ホールド8分
測定して得られた分析値より、以下の式にて重合率を算出した。
未反応のスチレン単量体量=a(ppm)
未反応のアクリロニトリル単量体量=b(ppm)
スチレン単量体仕込み総量=d(質量部)
アクリロニトリル単量体仕込み総量=e(質量部)
マレイン酸無水物単量体仕込み総量=f(質量部)
重合溶剤仕込み総量=g(質量部)
・スチレン単量体重合率(%)=100-a×(d+e+f+g)/100d
・アクリロニトリル単量体重合率(%)=100-b×(d+e+f+g)/100e
各々の重合液サンプルについて、マレイン酸無水物単量体を以下の装置を用いて測定した。
装置名:液体クロマトグラフ(LC-10、島津製作所社製)
検出器及び分析波長:UV 230nm
カラム:逆相系カラム(YMC-PACK ODS-A A-312(150mm×6mm 5μm)、YMC社製)
移動相:H2O/CH3OH 50/50(体積比) (pH3.3 H3PO4)
流量 :1ml/分
注入量:20μl
手順 :試料約0.2gを50ml三角フラスコに秤量し、1,2-ジクロロエタン5mlを添加して溶解する。次にn-ヘキサン5mlを加えて振とう器で10~15分間振とうし、ポリマーを析出させ、上澄み液を0.45μmメンブレンフィルターでろ過する。10mlのメス試験管に上澄み液と純水をそれぞれ3mlずつ添加して1時間振とうし、30分間放置後下層液を上記装置にて測定する。なお、定量方法はマレイン酸無水物標準液より絶対検量線法によって算出する。
測定して得られた分析値より、以下の式にて重合率を算出した。
未反応のマレイン酸無水物単量体量=c(ppm)
スチレン単量体仕込み総量=d(質量部)
アクリロニトリル単量体仕込み総量=e(質量部)
マレイン酸無水物単量体仕込み総量=f(質量部)
重合溶剤仕込み総量=g(質量部)
・マレイン酸無水物単量体重合率(%)=100-c×(d+e+f+g)/100f
[実施例1~8、比較例1~7]
共重合体A-1~A-14、AS-C-800について各々、以下の様にしてフィルムを調製した。
静置状態でクラス1000以下のクリーン環境となるクリーンブース内で、40mmΦ単軸押出機にギヤーポンプ、ポリマーフィルター「デナフィルター、目開き5μm」(長瀬産業社製)、300mm幅.単層Tダイ、および引取巻取装置「タッチロールフレキシブルタイプ」(プラスチック工学研究所製)を備えたフィルム製膜機にて幅250mm、厚さ100±5μmのフィルムを成形した。さらに、得られたフィルムにてフィルム物性測定を行った。測定結果を表3、表4に示す。なお使用した共重合体のペレットは予め90℃で2時間乾燥してから上記押出機に供給した他、上記Tダイ温度は260℃とした。
未延伸フィルムより試験片を切り出し、以下の条件により落球衝撃試験を行い、50%破壊エネルギーを測定した。
試験片 ;縦50mm×横50mm×膜厚100±5μmの未延伸フィルム20枚
重錘 ;直径11mm、重さ5.45gの鉄球
固定状態 ;内径34mmのリングでフィルムを挟み込み、上下左右4箇所をクリップで固定
JIS K7211に準拠して1cm間隔で50%破壊高さを測定し、50%破壊エネルギーを算出した。なお、5cm未満は測定時治具が対応出来ないため、5cmで破断したものについては全て「<3(mJ)」と表記した。50%破壊エネルギーが5(mJ)以上のものを合格とした。
未延伸フィルムの曇り度を、ASTM D1003に準拠して測定し、2.0%以下を合格とした。
未延伸フィルムを用いて、ガラス転移温度をDSC装置(Robot DSC6200、セイコーインスツルメンツ社製)にて測定し、以下の条件にて延伸を行った。
装置名:二軸延伸試験装置(EX10-B、東洋精機製作所社製)
試験片 ;未延伸フィルムから90mm×90mm×膜厚100±5μmを切り出し
延伸温度;ガラス転移温度+5℃
延伸速度;25mm/分
延伸方法;自由幅一軸延伸2.0倍延伸
未延伸フィルムおよび自由幅一軸延伸したフィルムを以下の装置を用いて、面内位相差Re(590)および厚み位相差Rthを測定した。延伸フィルムに関しては面内位相差Re(590)が300nm以上、厚み位相差Rthが0nm未満(負)のものを合格とした。但し、フィルム強度不足で延伸時に破断したものについては、測定不可能であることから不合格とした。
装置名 :複屈折測定装置(KOBRA-WR、王子計測機器社製)
測定波長:590nm
(3)で延伸したフィルムを恒温槽中に24時間置いた後、面内位相差Re(590)を測定し、10%以上低下し始める温度をRe(590)低下開始温度とした。Re(590)低下開始温度が110℃以上のものを合格とした。なお、恒温槽の設定温度は5℃間隔で行った。また、(3)で破断したフィルムについては、測定していないため「×」と記載した。
[実施例9]
実施例1で得られた共重合体A-1を用いて、実施例1記載のフィルム製膜機にて厚さ0.25mmの未延伸フィルムを作製した。得られた未延伸フィルムを一辺120mmの正方形に裁断し、二軸延伸試験装置(EX10-B、東洋精機製作所社製)により温度125℃、延伸速度25mm/分の条件にて縦方向に2.5倍延伸、横方向に1.0倍の固定端一軸延伸した厚さ0.10mmのフィルムA1を得た。
次に、ノルボルネン系樹脂(ZEONEX 690R、日本ゼオン社製)を用いて、同様に厚さ0.16mmの未延伸フィルムを作製し、得られた未延伸フィルムを一片120mmの正方形に裁断し、二軸延伸試験装置(EX10-B、東洋精機製作所社製)により温度136℃、延伸速度25mm/分の条件にて縦方向に2.0倍の自由端一軸延伸した厚さ0.10mmのフィルムB1を得た。
フィルムA1およびフィルムB1の面内位相差Re(590)、Nz係数、3次元屈折率を、複屈折測定装置「王子計測社製 KOBRA-WR」を用いて測定した。結果を表5に示す。
さらに、フィルムA1とフィルムB1とを遅相軸が直行するように積層させた積層フィルムについて、波長450nm、590nm、750nmにおける各々の面内位相差Re(450)、Re(590)、Re(750)と、Nz係数を複屈折測定装置(KOBRA-WR、王子計測機器社製)を用いて測定した。結果を表5に示す。
Claims (10)
- 芳香族ビニル単量体単位65~90質量%、シアン化ビニル単量体単位5~25質量%、不飽和ジカルボン酸無水物単量体単位5~20質量%からなり、重量平均分子量(Mw)が12万~25万であり、ASTM D1003に基づき測定した2mm厚みの曇り度が1%以下である光学フィルム用共重合体。
- 芳香族ビニル単量体単位70~80質量%、シアン化ビニル単量体単位10~20質量%、不飽和ジカルボン酸無水物単量体単位10~15質量%である請求項1に記載の光学フィルム用共重合体。
- 芳香族ビニル単量体単位がスチレン単位である請求項1または2に記載の光学フィルム用共重合体。
- シアン化ビニル単量体単位がアクリロニトリル単位である請求項1~3のいずれか1項に記載の光学フィルム用共重合体。
- 不飽和ジカルボン酸無水物単量体単位がマレイン酸無水物単位である請求項1~4のいずれか1項に記載の光学フィルム用共重合体。
- 偏光膜保護フィルム、位相差フィルム、または反射防止フィルムに使用されることを特徴とする請求項1~5のいずれか1項に記載の光学フィルム用共重合体。
- 負の配向複屈折性を示す熱可塑性樹脂フィルムを延伸して得られるフィルムAと正の配向複屈折性を示す熱可塑性樹脂フィルムを延伸して得られるフィルムBとを積層させて、nx>nz>nyの屈折率分布を形成している光学フィルム用であり、フィルムAに使用される熱可塑性樹脂であることを特徴とする請求項1~6のいずれか1項に記載の光学フィルム用共重合体。
- フィルムAが溶融押出により製造されたフィルムを延伸してなることを特徴とする請求項7に記載の光学フィルム用共重合体。
- Nz係数が、0.4~0.6であることを特徴とする請求項7または8に記載の光学フィルム用共重合体。
- フィルムAとフィルムBを遅相軸が直交するように積層させることで波長450nm、590nmおよび750nmにおける面内位相差Re(450)、Re(590)およびRe(750)がRe(450)<Re(590)<Re(750)の関係を満たすことを特徴とする請求項7~9のいずれか1項に記載の光学フィルム用共重合体。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167008140A KR102148213B1 (ko) | 2013-09-03 | 2014-08-29 | 광학 필름용 공중합체 |
CN201480060075.7A CN105705971A (zh) | 2013-09-03 | 2014-08-29 | 光学薄膜用共聚物 |
JP2015535452A JP6646445B2 (ja) | 2013-09-03 | 2014-08-29 | 光学フィルム用共重合体 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013182606 | 2013-09-03 | ||
JP2013-182606 | 2013-09-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015033877A1 true WO2015033877A1 (ja) | 2015-03-12 |
Family
ID=52628351
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/072835 WO2015033877A1 (ja) | 2013-09-03 | 2014-08-29 | 光学フィルム用共重合体 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6646445B2 (ja) |
KR (1) | KR102148213B1 (ja) |
CN (1) | CN105705971A (ja) |
WO (1) | WO2015033877A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190025932A (ko) | 2016-06-30 | 2019-03-12 | 덴카 주식회사 | 광시야각 고 콘트라스트 광학 보상 필름 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6376020B2 (ja) * | 2015-03-30 | 2018-08-22 | 東レ株式会社 | 熱可塑性樹脂組成物およびその成形品 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008094912A (ja) * | 2006-10-10 | 2008-04-24 | Denki Kagaku Kogyo Kk | 樹脂組成物と光学成形体 |
JP2009179731A (ja) * | 2008-01-31 | 2009-08-13 | Konica Minolta Opto Inc | アクリル樹脂含有フィルム、それを用いた偏光板及び表示装置 |
JP2009300918A (ja) * | 2008-06-17 | 2009-12-24 | Konica Minolta Opto Inc | 位相差フィルム、位相差フィルムの製造方法、偏光板及び液晶表示装置 |
JP2012025786A (ja) * | 2008-11-21 | 2012-02-09 | Denki Kagaku Kogyo Kk | 光学フィルム用樹脂組成物及びその光学フィルム |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2857889B2 (ja) | 1988-11-04 | 1999-02-17 | 富士写真フイルム株式会社 | 液晶表示装置 |
JP2004317714A (ja) * | 2003-04-15 | 2004-11-11 | Sharp Corp | 液晶表示装置および積層位相差板 |
JP2007024940A (ja) * | 2005-07-12 | 2007-02-01 | Tosoh Corp | 広視野角補償フィルムおよびそれを用いてなる液晶表示装置 |
JP4774856B2 (ja) * | 2005-08-09 | 2011-09-14 | 東ソー株式会社 | 位相差フィルム |
JP5191667B2 (ja) * | 2007-01-29 | 2013-05-08 | 旭化成イーマテリアルズ株式会社 | スチレン系樹脂異方性フィルム |
CN101796086A (zh) * | 2007-09-04 | 2010-08-04 | 电气化学工业株式会社 | 热塑性共聚树脂及其光学成形体 |
JP5104374B2 (ja) * | 2008-02-14 | 2012-12-19 | 日本ゼオン株式会社 | 位相差板の製造方法 |
-
2014
- 2014-08-29 KR KR1020167008140A patent/KR102148213B1/ko active IP Right Grant
- 2014-08-29 CN CN201480060075.7A patent/CN105705971A/zh active Pending
- 2014-08-29 WO PCT/JP2014/072835 patent/WO2015033877A1/ja active Application Filing
- 2014-08-29 JP JP2015535452A patent/JP6646445B2/ja active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008094912A (ja) * | 2006-10-10 | 2008-04-24 | Denki Kagaku Kogyo Kk | 樹脂組成物と光学成形体 |
JP2009179731A (ja) * | 2008-01-31 | 2009-08-13 | Konica Minolta Opto Inc | アクリル樹脂含有フィルム、それを用いた偏光板及び表示装置 |
JP2009300918A (ja) * | 2008-06-17 | 2009-12-24 | Konica Minolta Opto Inc | 位相差フィルム、位相差フィルムの製造方法、偏光板及び液晶表示装置 |
JP2012025786A (ja) * | 2008-11-21 | 2012-02-09 | Denki Kagaku Kogyo Kk | 光学フィルム用樹脂組成物及びその光学フィルム |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190025932A (ko) | 2016-06-30 | 2019-03-12 | 덴카 주식회사 | 광시야각 고 콘트라스트 광학 보상 필름 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2015033877A1 (ja) | 2017-03-02 |
KR102148213B1 (ko) | 2020-08-26 |
CN105705971A (zh) | 2016-06-22 |
KR20160051820A (ko) | 2016-05-11 |
JP6646445B2 (ja) | 2020-02-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6568687B2 (ja) | 光学補償フィルム用共重合体 | |
US9873787B2 (en) | Copolymer for improving methacrylic resin heat resistance | |
US8822614B2 (en) | Acrylic thermoplastic resin and molded object thereof | |
JPWO2009031544A1 (ja) | 熱可塑性共重合樹脂及びその光学成形体 | |
JP6587620B2 (ja) | メタクリル樹脂の耐熱性向上に適した共重合体 | |
JP6646445B2 (ja) | 光学フィルム用共重合体 | |
JP2009275069A (ja) | 光学用延伸フィルムとそれを備える画像表示装置 | |
JP6711914B2 (ja) | 広視野角高コントラスト光学補償フィルム | |
JP5919611B2 (ja) | 低い光弾性係数を有する位相差板 | |
JP6890126B2 (ja) | 樹脂組成物、及びその樹脂組成物からなるフィルム | |
JP2009276554A (ja) | 光学用成形体 | |
TWI642688B (zh) | Copolymer for optical film | |
JP2019049583A (ja) | 位相差フィルム及び画像表示装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14841702 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015535452 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20167008140 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14841702 Country of ref document: EP Kind code of ref document: A1 |