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WO2016002665A1 - Film optique et son procédé de fabrication - Google Patents

Film optique et son procédé de fabrication Download PDF

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Publication number
WO2016002665A1
WO2016002665A1 PCT/JP2015/068546 JP2015068546W WO2016002665A1 WO 2016002665 A1 WO2016002665 A1 WO 2016002665A1 JP 2015068546 W JP2015068546 W JP 2015068546W WO 2016002665 A1 WO2016002665 A1 WO 2016002665A1
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WO
WIPO (PCT)
Prior art keywords
resin
layer
film
stretching
optical film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/068546
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English (en)
Japanese (ja)
Inventor
拓 波多野
智一 木平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
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Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to JP2016531336A priority Critical patent/JPWO2016002665A1/ja
Publication of WO2016002665A1 publication Critical patent/WO2016002665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule

Definitions

  • the present invention relates to an optical film and a method for producing the same.
  • Polycarbonate resins containing polycarbonate are widely used as raw materials for optical disks and films because of their high transparency and toughness (Patent Documents 1 and 2). Moreover, when a film is manufactured with a polycarbonate resin, the film can easily exhibit birefringence by stretching, and thus can be used as a retardation film.
  • a melt extrusion method When a film is produced using a polycarbonate resin, a melt extrusion method may be used.
  • optical defects such as fish eyes tend to occur more than when another method such as an injection molding method is used.
  • the fish eye refers to foreign matters that can be generated inside the film.
  • Such an optical defect may occur not only in a single-layer film having only a layer made of polycarbonate resin, but also in a multilayer film having another layer in addition to a layer made of polycarbonate resin.
  • Such optical defects are particularly likely to occur when the thickness of the layer made of polycarbonate resin is as thin as 10 ⁇ m or less.
  • the present invention was devised in view of the above problems, and includes a layer (A) having a thickness of 10 ⁇ m or less made of a resin (a) containing polycarbonate, and suppresses the occurrence of optical defects in the layer (A). It is an object of the present invention to provide an optical film that can be produced, and a method for producing the optical film.
  • the present inventor used the resin (a) containing a polycarbonate having an amount of phenolic hydroxyl group of 0.005 mol or less with respect to 1 mol of the main chain carbonate unit of the polycarbonate.
  • the inventors have found that generation of optical defects in the layer (A) made of the resin (a) can be suppressed, and completed the present invention. That is, the present invention is as follows.
  • a layer (A) comprising a resin (a) containing polycarbonate,
  • the thickness of the layer (A) is 10 ⁇ m or less
  • the optical film whose quantity of the phenolic hydroxyl group contained in the said polycarbonate is 0.005 mol or less with respect to 1 mol of main chain carbonate units of the said polycarbonate.
  • an optical film comprising a layer (A) made of a resin (a) containing polycarbonate and having a thickness of 10 ⁇ m or less and capable of suppressing the occurrence of optical defects in the layer (A); and the optical film Can be provided.
  • FIG. 1 shows the temperature dependence of retardation ⁇ when the pre-stretched film is stretched, and the temperature dependence of retardation ⁇ when the layers (A) and (B) of the pre-stretched film are stretched. It is a figure which shows an example.
  • intrinsic birefringence being positive means that the refractive index in the stretching direction is larger than the refractive index in the direction perpendicular thereto unless otherwise noted.
  • negative intrinsic birefringence means that the refractive index in the stretching direction is smaller than the refractive index in the direction perpendicular to the stretching direction unless otherwise specified.
  • the value of intrinsic birefringence can be calculated from the dielectric constant distribution.
  • retardation is a value represented by “(nx ⁇ ny) ⁇ d” unless otherwise specified.
  • the plane orientation coefficient is a value represented by “(nx + ny) / 2 ⁇ nz” unless otherwise specified.
  • the birefringence is a value represented by “nx ⁇ ny” unless otherwise specified.
  • the Nz coefficient is a value represented by “(nx ⁇ nz) / (nx ⁇ ny)” unless otherwise specified.
  • nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction and giving the maximum refractive index.
  • ny represents the refractive index in the in-plane direction and perpendicular to the nx direction.
  • nz represents the refractive index in the thickness direction.
  • d represents the thickness. Unless otherwise noted, the measurement wavelength of these refractive indices nx, ny and nz is 532 nm.
  • the slow axis of the film or layer represents the in-plane slow axis unless otherwise specified.
  • the “polarizing plate” includes not only a rigid member but also a flexible member such as a resin film.
  • the direction of the component is “parallel”, “vertical” or “orthogonal”, unless otherwise specified, it is within a range not impairing the effect of the present invention, for example, usually ⁇ 5 °, preferably ⁇ 2 °, Preferably, an error within a range of ⁇ 1 ° may be included.
  • the MD direction is the film flow direction in the production line, and usually coincides with the longitudinal direction and the longitudinal direction of the long film.
  • the TD direction is a direction parallel to the film surface and perpendicular to the MD direction, and usually coincides with the width direction and the lateral direction of a long film.
  • the “long” means one having a length of 5 times or more with respect to the width, preferably 10 times or more, and specifically wound in a roll shape. It has a length that can be stored or transported.
  • the optical film of the present invention includes a layer (A) made of a resin (a) containing polycarbonate. Moreover, the optical film of this invention may be equipped with layers other than a layer (A). For example, when performing viewing angle compensation of a polarizing plate using the optical film of the present invention, the optical film of the present invention includes a layer (B) made of a resin (b) different from the resin (a). Is preferred.
  • the resin (a) forming the layer (A) contains polycarbonate.
  • Polycarbonate is a polymer having a carbonate unit, and is excellent in retardation development, low temperature stretchability, and adhesion to other layers.
  • the carbonate unit is a structural unit containing a carbonate bond (—O—C ( ⁇ O) —O—), and examples thereof include a structural unit of the following formula (I).
  • R 0 represents a divalent hydrocarbon group.
  • R 1 to R 8 each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
  • the alkyl group, cycloalkyl group, and aryl group may be substituted or unsubstituted.
  • the alkyl group usually has 1 to 10 carbon atoms
  • the cycloalkyl group usually has 1 to 10 carbon atoms
  • the aryl group usually has 1 to 10 carbon atoms.
  • R 1 to R 8 are the same as those in the formula (I).
  • R 9 represents a hydrogen atom, an alkyl group or an aryl group.
  • the number of carbon atoms of the alkyl group is usually 1 to 9
  • the number of carbon atoms of the aryl group is usually 1 to 9.
  • Z is a residue capable of forming a saturated or unsaturated hydrocarbon ring having 4 to 11 carbon atoms together with the carbon atom to which it is bonded.
  • the hydrocarbon ring is preferably a saturated hydrocarbon ring having 6 carbon atoms.
  • R 1 to R 8 are the same as those in the formula (I).
  • carbonate units preferred examples include the following.
  • polycarbonate one containing one type of carbonate unit may be used, or one containing two or more types of carbonate units combined at an arbitrary ratio may be used.
  • the polycarbonate may contain an arbitrary structural unit in addition to the carbonate unit.
  • the proportion of the carbonate unit is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more from the viewpoint of effectively exhibiting the advantages of the polycarbonate.
  • suitable polycarbonates include bisphenol A polycarbonate, branched bisphenol A polycarbonate, o, o, o ′, o′-tetramethylbisphenol A polycarbonate, and the like. Moreover, a polycarbonate may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the amount of the phenolic hydroxyl group contained in the polycarbonate is usually 0.005 mol or less, preferably 0.003 mol or less, more preferably 0.002 mol or less with respect to 1 mol of the main chain carbonate unit of the polycarbonate. Ideally 0 mol.
  • the phenolic hydroxyl group represents a hydroxyl group directly bonded to the benzene ring.
  • the main chain carbonate unit represents a carbonate unit contained in the main chain of the polycarbonate.
  • the thickness of the layer (A) is as thin as 10 ⁇ m or less, the occurrence of optical defects in the layer (A) can be suppressed.
  • the present invention is not limited by the following inference.
  • the resin (a) is formed into a film by a melt extrusion method
  • the resin (a) is in a molten state.
  • the resin (a) is at a high temperature not lower than the glass transition temperature.
  • the melt extrusion method generally takes a longer time for the resin (a) to remain in a molten state at a high temperature than other methods such as an injection molding method.
  • the phenolic hydroxyl groups may react to increase the molecular weight, thereby causing the polycarbonate to gel.
  • the physical properties of the resin (a) change, and the generated gel becomes a fish eye, which may contribute to optical defects.
  • gelation is unlikely to occur, and it is assumed that optical defects caused by this gelation can be prevented.
  • the amount of the phenolic hydroxyl group contained in the polycarbonate relative to 1 mol of the main chain carbonate unit of the polycarbonate can be measured by 1 H-NMR.
  • the resin (a) may contain an optional component other than polycarbonate as long as the effects of the present invention are not significantly impaired.
  • the resin (a) may contain a polymer other than polycarbonate, a compounding agent, and the like.
  • polymers other than polycarbonate that can be contained in the resin (a) include acrylic polymers such as polymethyl methacrylate; olefin polymers such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyphenylene sulfide and the like.
  • the amount of the polymer other than polycarbonate is small in the resin (a) from the viewpoint of effectively utilizing the advantages of the polycarbonate.
  • the amount of the polymer other than polycarbonate is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 3 parts by weight or less with respect to 100 parts by weight of polycarbonate.
  • compounding agents that can be contained in the resin (a) include lubricants; layered crystal compounds; inorganic fine particles; stabilizers such as antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers; Agents, plasticizers, coloring agents such as dyes and pigments, antistatic agents, and the like.
  • a lubricant and an ultraviolet absorber are preferable because they can improve the flexibility and weather resistance of the optical film.
  • a compounding agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the lubricant examples include inorganic particles such as silicon dioxide, titanium dioxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, strontium sulfate; polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, polystyrene, cellulose acetate, cellulose acetate pro Organic particles such as pionate can be mentioned. Among these, organic particles are preferable as the lubricant.
  • ultraviolet absorbers examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, acrylonitrile ultraviolet absorbers, triazine compounds, nickel complex compounds. And inorganic powders.
  • UV absorbers include 2,2′-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) ) Phenol, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone and the like. Particularly preferred are 2,2′-methylenebis ( 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol).
  • the amount of the compounding agent can be appropriately determined as long as the effects of the present invention are not significantly impaired.
  • the amount of the compounding agent may be within a range where the total light transmittance in terms of 1 mm thickness of the optical film can be maintained at 80% or more.
  • the glass transition temperature Tg (a) of the resin (a) is usually 147 ° C. or higher, preferably 150 ° C. or higher.
  • the glass transition temperature Tg (a) is usually 147 ° C. or higher, preferably 150 ° C. or higher.
  • the elongation at break of the resin (a) at the glass transition temperature Tg (b) of the resin (b) is preferably 50% or more, and 80% or more. More preferably. Although there is no restriction
  • the elongation at break can be determined by using a test piece of test piece type 1B described in JIS K 7127 at a pulling speed of 100 mm / min.
  • the optical film of the present invention can suppress the occurrence of optical defects in the layer (A). Therefore, the number of optical defects in the layer (A) is small. Specifically, the number of optical defects in the layer (A) per unit area is usually 0.1 / m 2 or less, preferably 0.06 / m 2 or less, more preferably 0.03 / m 2. 2 or less, ideally zero.
  • the thickness of the layer (A) is 10 ⁇ m or less.
  • the thickness of the layer (A) is so thin, conventionally, optical defects such as fish eyes were easily generated in the layer (A). However, in the optical film of the present invention, such optical defects are not generated. Can be suppressed.
  • the lower limit of the thickness of the layer (A) is usually 0.2 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more.
  • the layer (A) can have birefringence.
  • the birefringence value is preferably 0.002 or more, more preferably 0.004 or more.
  • the variation in the slow axis of the layer (A) is small.
  • the variation of the slow axis of the layer (A) is preferably within ⁇ 1 °, more preferably within ⁇ 0.5 °, particularly preferably within ⁇ 0.3 °, ideally Zero.
  • the Nz coefficient of the layer (A) is preferably 10 or less, more preferably 5 or less. By setting the Nz coefficient of the layer (A) within the above range, it is easy to reduce the variation of the slow axis of the layer (A).
  • the lower limit value of the Nz coefficient of the layer (A) can be 1 or more, but is usually 1.5 or more from the viewpoint of industrial production.
  • the plane orientation coefficient of the layer (A) is preferably larger than 0.025, more preferably 0.026 or more, preferably 0.035 or less, more preferably 0.030 or less.
  • the optical film of the present invention may have only one layer (A) or two or more layers.
  • the optical film of the present invention may be a multilayer film having the first layer (A), the layer (B), and the second layer (A) in this order.
  • the layer (A) is preferably on the outermost surface of the optical film of the present invention.
  • an optical defect can be caused by a depression or protrusion on the surface of the layer (A)
  • the depression or protrusion is a layer covering the surface of the layer (A). It may be buried to prevent the appearance of optical defects.
  • the layer (A) is on the outermost surface, the depressions or protrusions are not filled with another layer, so conventionally it has been particularly difficult to prevent the occurrence of optical defects.
  • the generation of the depressions and protrusions can be suppressed, the generation of optical defects can be effectively suppressed even when the layer (A) is on the outermost surface.
  • the resin (b) is preferably a thermoplastic resin.
  • the polymer contained in the resin (b) include a styrene or a homopolymer of a styrene derivative, and a polystyrene polymer including a copolymer of styrene or a styrene derivative and an arbitrary monomer; a polyacrylonitrile polymer.
  • styrene or a styrene derivative acrylonitrile, maleic anhydride, methyl methacrylate, and butadiene are mentioned as a preferable thing, for example.
  • these polymers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • a polymer having at least one of a styrene unit and a methyl methacrylate unit is preferable.
  • the styrene unit is a structural unit having a structure formed by polymerizing styrene.
  • the methyl methacrylate unit is a structural unit having a structure formed by polymerizing methyl methacrylate.
  • a polystyrene polymer is particularly preferable from the viewpoint of high retardation development.
  • the amount of the structural unit having a structure formed by polymerizing maleic anhydride is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, particularly preferably 100 parts by weight of the polystyrene polymer. Is 15 parts by weight or more, preferably 30 parts by weight or less, more preferably 28 parts by weight or less, and particularly preferably 26 parts by weight or less.
  • the resin (b) may contain an optional component other than the polymer as long as the effects of the present invention are not significantly impaired.
  • the resin (b) may contain a compounding agent or the like.
  • Examples of the compounding agent that can be contained in the resin (b) include those in the same range as those described as the compounding agent that the resin (a) can contain. Moreover, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the amount of the compounding agent can be appropriately determined as long as the effects of the present invention are not significantly impaired. For example, the amount of the compounding agent may be within a range where the total light transmittance in terms of 1 mm thickness of the optical film can be maintained at 80% or more.
  • the glass transition temperature Tg (b) of the resin (b) is usually 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. Since the glass transition temperature Tg (b) is thus high, the relaxation of the orientation of the resin (b) can be reduced. Moreover, although there is no restriction
  • the glass transition temperature Tg (b) of the resin (b) is equal to the glass transition temperature Tg (a) of the resin (a). Even if the difference Tg (a) ⁇ Tg (b) from the glass transition temperature Tg (b) of the resin (b) is set to satisfy the relationship of “Tg (a) ⁇ Tg (b)> 20 ° C.” Good. More specifically, Tg (a) -Tg (b) may be preferably greater than 20 ° C, more preferably greater than 22 ° C. Thereby, when it is desired to develop retardation in the optical film of the present invention by stretching, the temperature dependency of the development of retardation can be increased during stretching.
  • the molecular chains contained in the layer (A) and the layer (B) can be largely oriented by stretching. Therefore, the thickness of the optical film after stretching can be reduced.
  • the upper limit of the temperature difference Tg (a) ⁇ Tg (b) is preferably 50 ° C. or less, more preferably 40 ° C. or less, and particularly preferably 30 ° C. or less. Thereby, it is easy to improve the flatness of the optical film.
  • the breaking elongation of the resin (b) at the glass transition temperature Tg (a) of the resin (a) is preferably 50% or more, and more preferably 80% or more. Although there is no restriction
  • the thickness of the layer (B) is usually 10 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and usually 100 ⁇ m or less, preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less.
  • the layer (B) can have birefringence.
  • the birefringence value is preferably 0.004 or more, more preferably 0.005 or more, preferably 0.010 or less, more preferably 0.008 or less. is there.
  • the birefringence of the layer (B) is not less than the lower limit of the above range, the thickness of the optical film is reduced when the optical film satisfies the relationship of 0.92 ⁇ R 40 /Re ⁇ 1.08. Is possible.
  • the Nz coefficient of the layer (B) is preferably ⁇ 0.30 or more, more preferably ⁇ 0.25 or more. By setting the Nz coefficient of the layer (B) in the above range, when the optical film satisfies the relationship of 0.92 ⁇ R 40 /Re ⁇ 1.08, it is possible to reduce the thickness of the optical film. .
  • the upper limit may be 0 or less, but is usually ⁇ 0.10 or less from the viewpoint of industrial production.
  • the plane orientation coefficient of the layer (B) is preferably ⁇ 0.002 or less, more preferably ⁇ 0.003 or less.
  • the optical film of the present invention may have only one layer (B) or two or more layers.
  • the optical film of the present invention may further include an arbitrary layer in addition to the layer (A) and the layer (B).
  • the optional layer include a mat layer capable of improving the slipperiness of the film, a hard coat layer such as an impact-resistant polymethacrylate resin layer, an antireflection layer, and an antifouling layer.
  • optical film of the present invention can have desired optical properties depending on the application.
  • the optical film may be an optically isotropic film having substantially no retardation.
  • the optical film may be a film having optical anisotropy having a retardation of a desired size.
  • the optical film of the present invention when used as a viewing angle compensation film in an image display device, the optical film preferably satisfies 0.92 ⁇ R 40 /Re ⁇ 1.08.
  • Re represents retardation at an incident angle of 0 ° of the optical film.
  • R 40 represents retardation at an incident angle of 40 ° of the optical film.
  • the total light transmittance of the optical film of the present invention is preferably 85% or more.
  • the light transmittance can be measured using a spectrophotometer (manufactured by JASCO Corporation, ultraviolet-visible near-infrared spectrophotometer “V-570”) in accordance with JIS K0115.
  • the haze of the optical film of the present invention is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
  • the clarity of the display image of the display device including the optical film can be improved.
  • the haze can be measured at five locations using “turbidity meter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997, and the average value obtained therefrom can be adopted.
  • ⁇ YI is preferably 5 or less, and more preferably 3 or less. When this ⁇ YI is in the above range, there is no coloring and the visibility is good.
  • the lower limit is ideally zero.
  • ⁇ YI can be measured using “Spectral Color Difference Meter SE2000” manufactured by Nippon Denshoku Industries Co., Ltd. according to ASTM E313. The same measurement is performed five times, and the arithmetic average value is obtained.
  • the optical film of the present invention preferably has a JIS pencil hardness of H or higher.
  • This JIS pencil hardness can be adjusted by the type of resin and the thickness of the resin layer.
  • the JIS pencil hardness is determined by tilting a pencil of various hardnesses by 45 °, applying a load of 500 g weight from above, scratching the film surface, and starting scratching. That's it.
  • the optical film of the present invention may shrink in the longitudinal direction and the transverse direction by heat treatment at a temperature of 60 ° C., a humidity of 90% RH, and 100 hours.
  • the shrinkage rate is preferably 0.5% or less, more preferably 0.3% or less.
  • the dimension in the width direction of the optical film of the present invention is preferably 500 mm or more, more preferably 1000 mm or more, and preferably 2000 mm or less.
  • the optical film of the present invention can be produced by a melt extrusion method.
  • the melt extrusion method is an excellent production method from the viewpoints of production efficiency and that a volatile component such as a solvent does not remain in the film.
  • a coextrusion method can be used in the melt extrusion method.
  • the coextrusion method include a coextrusion T-die method, a coextrusion inflation method, and a coextrusion lamination method.
  • the coextrusion T-die method is preferable.
  • the coextrusion T-die method includes a feed block method and a multi-manifold method, and the multi-manifold method is particularly preferable in that variation in thickness can be reduced.
  • the method for producing an optical film of the present invention includes a step of heating and melting the resin (a), and a step of extruding the molten resin (a) from a die into a film. Furthermore, when manufacturing an optical film provided with a layer (B), the manufacturing method of an optical film includes the process of heating and fuse
  • the melting temperature of the resin (a) is preferably Tg (a) + 80 ° C. or higher, more preferably Tg (a) + 100 ° C. or higher, preferably Tg (a) + 180 ° C.
  • it is more preferably Tg (a) + 150 ° C. or less.
  • the residence time from when the resin (a) is melted until it is discharged from the die is preferably 5 hours or less, more preferably 3 hours or less, and particularly preferably 2 hours or less.
  • a film-like molten resin extruded from an opening of a die is usually brought into close contact with a cooling roll (including a cooling drum).
  • a cooling roll including a cooling drum
  • the method for bringing the resin into close contact with the cooling roll include an air knife method, a vacuum box method, and an electrostatic contact method.
  • the number of cooling rolls is not particularly limited, but is usually 2 or more.
  • examples of the arrangement method of the cooling roll include, but are not particularly limited to, a linear type, a Z type, and an L type.
  • the way of passing the resin extruded from the opening of the die through the cooling roll is not particularly limited.
  • the degree of adhesion of the extruded film-like resin to the cooling roll varies depending on the temperature of the cooling roll. Increasing the temperature of the cooling roll tends to improve adhesion. Moreover, by not making the temperature of a cooling roll too high, peeling from the cooling roll of film-form resin can be made easy, and the winding of resin to a cooling roll can be prevented. From this point of view, the temperature of the cooling roll is preferably (Tg ′ + 30 ° C.) or less, more preferably (Tg ′ ⁇ ), where Tg ′ is the glass transition temperature of the resin extruded from the die and contacting the drum. 5 ° C.) to (Tg′ ⁇ 45 ° C.). Thereby, malfunctions, such as a slip and a crack, can be prevented.
  • the residual solvent contained in the resin as a raw material is reduced; (2) before the film is formed
  • the resin may be pre-dried.
  • the preliminary drying is performed using, for example, a hot air dryer or the like in the form of pellets or the like.
  • the drying temperature is preferably 100 ° C. or more, and the drying time is preferably 2 hours or more.
  • the optical film of the present invention is obtained by the melt extrusion method.
  • the optical film obtained in this way does not develop a large retardation. Therefore, for example, in order to express a desired retardation, the obtained optical film may be stretched. Therefore, in the following, an example of producing an optical film having the layer (A) and the layer (B) and satisfying 0.92 ⁇ R 40 /Re ⁇ 1.08 will be described.
  • stretching process in a manufacturing method is demonstrated.
  • an optical film before being subjected to stretching treatment may be appropriately referred to as “film before stretching” and an optical film that has been subjected to stretching treatment as “stretched film”.
  • the film before stretching in the example shown here is a film including a layer (A) made of the resin (a) and a layer (B) made of the resin (b).
  • This pre-stretched film satisfies the following requirement P in order to obtain a film satisfying 0.92 ⁇ R 40 /Re ⁇ 1.08 as a stretched film.
  • Requirement P When the uniaxial stretching direction is the X axis, the direction perpendicular to the uniaxial stretching direction in the film plane is the Y axis, and the film thickness direction is the Z axis, the phase of the XZ polarized light with respect to the YZ polarized light is Delayed when uniaxially stretched in the X-axis direction at temperature T1, The process proceeds when uniaxial stretching is performed in the X-axis direction at a temperature T2 different from the temperature T1.
  • XZ polarized light refers to linearly polarized light that is incident perpendicularly to the film surface and has an electric vector vibration plane in the XZ plane.
  • YZ polarized light refers to linearly polarized light that is incident perpendicularly to the film surface and the vibration plane of the electric vector is on the YZ plane.
  • the pre-stretch film is an isotropic (that is, has no anisotropy) raw film, so if one of the in-plane directions is taken as the X-axis, any other direction can be satisfied.
  • the requirement P can also be satisfied when is the X axis.
  • the phase of XZ polarized light is usually delayed from that of YZ polarized light.
  • the phase of XZ polarized light usually proceeds with respect to that of YZ polarized light.
  • the pre-stretch film satisfying the above requirement P is a film using these properties, and the slow axis or fast axis appears depending on the stretch temperature.
  • the temperature dependence of the expression of such retardation can be adjusted, for example, by adjusting the relationship such as the photoelastic coefficient of the resin contained in the pre-stretched film and the thickness ratio of each layer.
  • the retardation ⁇ that can be expressed in the entire pre-stretched film when the pre-stretched film is stretched is synthesized from the retardation ⁇ that is expressed in each resin layer included in the pre-stretched film.
  • Temperature T1 of the requirements P is a temperature either temperature T H or T L
  • the temperature T2 is the other of the temperature of different temperatures T H or T L is the temperature T1.
  • the temperature satisfying the requirement P is preferably (Tg 1 ⁇ 10 ° C.) to (Tg h + 10 ° C.) because the birefringence can be easily adjusted. That is, the temperatures T1 and T2 are preferably included in the temperature range of (Tg 1 ⁇ 10 ° C.) to (Tg h + 10 ° C.).
  • the temperature Tg l in the resin contained in the film before stretching, most glass transition temperature means a glass transition temperature of the resin having low.
  • the temperature Tg h and, among the resin contained in the film before stretching, most glass transition temperature means a glass transition temperature of the high resin.
  • FIG. 1 shows the temperature dependence of retardation ⁇ when the pre-stretched film is stretched, and the temperature dependence of retardation ⁇ when the layers (A) and (B) of the pre-stretched film are stretched. It is a figure which shows an example. In the example shown in FIG. 1, the glass transition temperature of the resin (a) is high, and the glass transition temperature of the resin (b) is low.
  • the negative retardation ⁇ expressed in the layer (B) is larger than the positive retardation ⁇ expressed in the layer (A). Overall, a negative retardation ⁇ is developed.
  • the negative retardation ⁇ expressed in the layer (B) is smaller than the positive retardation ⁇ expressed in the layer (A), so that the positive retardation ⁇ is expressed as a whole. To do. Therefore, by combining such stretching at different temperatures Ta and Tb, a retardation ⁇ generated by stretching at each temperature is synthesized, and a stretched film having a desired retardation ⁇ and thus exhibiting desired optical properties. Can be realized stably.
  • the resin contained in the pre-stretch film is a resin that can cause a difference between the refractive index in the X-axis direction and the refractive index in the Y-axis direction in each layer by stretching in one direction (that is, uniaxial stretching).
  • a pre-stretched film satisfying the above requirement P can be obtained.
  • a resin having a large degree of orientation developed by stretching is used, a large retardation ⁇ can be expressed even if the layer thickness is reduced.
  • the specific thickness of the layer constituting the pre-stretched film can be set according to the optical properties of the stretched film to be manufactured so as to satisfy the requirement P described above.
  • the ratio TA / TB of the total thickness TA of the layer (A) and the total thickness TB of the layer (B) is preferably 1/20 or more, more preferably 1/15 or more, preferably 1/4 or less, more preferably 1/5 or less.
  • a stretching process for stretching the pre-stretching film is performed.
  • each layer included in the pre-stretching film is also stretched, and the stretched layers exhibit predetermined optical characteristics.
  • the film before stretching is subjected to a uniaxial stretching process in one direction at one of the temperatures T1 and T2, and a direction orthogonal to the direction in which the uniaxial stretching process is performed in the first stretching process, And a second stretching step in which a uniaxial stretching process is performed at the other temperature of T1 and T2.
  • the film before stretching is uniaxially stretched in one direction at one of the temperatures T1 and T2.
  • the phase of the XZ polarized light with respect to the YZ polarized light is delayed in the pre-stretched film that satisfies the requirement P.
  • the uniaxial stretching is performed at the temperature T2
  • the phase of the XZ polarized light with respect to the YZ polarized light advances.
  • the temperature T1 is preferably higher than Tg (b), more preferably higher than Tg (b) + 5 ° C, preferably lower than Tg (a) + 40 ° C, and lower than Tg (a) + 20 ° C. Is more preferable.
  • the optical characteristics of the layer (B) can be stably kept within a desired range.
  • the optical characteristic of a layer (A) can be stably stored in a desired range.
  • the stretching ratio in the first stretching step is preferably 2 times or more, more preferably 3 times or more, preferably 4 times or less, more preferably 3.5 times or less.
  • the uniaxial stretching process can be performed by a known method.
  • a method of uniaxially stretching in the MD direction using a difference in peripheral speed between rolls; a method of uniaxially stretching in the TD direction using a tenter, and the like can be mentioned.
  • Examples of the method of uniaxially stretching in the MD direction include an IR heating method between rolls, a float method, and the like. Of these, the float method is preferable because a stretched film having high optical uniformity can be obtained.
  • a tenter method can be mentioned as a method of uniaxially stretching in the TD direction.
  • a temperature difference may be created in the TD direction of the film in the stretching zone.
  • a method of adjusting the opening degree of the hot air nozzle in the TD direction or controlling the heating by arranging the IR heaters in the TD direction can be used.
  • a 2nd extending process is performed.
  • the film subjected to the uniaxial stretching process in one direction in the first stretching process is subjected to a uniaxial stretching process in a direction orthogonal to the direction in which the uniaxial stretching process is performed in the first stretching process.
  • the uniaxial stretching process in the second stretching step is performed at a temperature different from the stretching temperature in the first stretching step among the temperatures T1 and T2. In the second stretching step, it is preferable to perform a uniaxial stretching process at a temperature T2.
  • the temperature T2 is usually a temperature lower than the temperature T1.
  • the specific temperature T2 is preferably higher than Tg (b) ⁇ 20 ° C., more preferably higher than Tg (b) ⁇ 10 ° C., preferably lower than Tg (b) + 5 ° C., and Tg (b b) is preferably lower.
  • Tg (b b) is preferably lower.
  • the difference between the temperature T1 and the temperature T2 is usually 10 ° C. or higher, preferably 20 ° C. or higher.
  • desired optical characteristics can be stably expressed in the stretched film.
  • 100 degrees C or less is preferable from a viewpoint of industrial productivity.
  • the stretching ratio in the second stretching step is preferably smaller than the stretching ratio in the first stretching step.
  • the state of molecular orientation in the stretched film obtained tends to be more strongly influenced in the second stretching step than in the first stretching step. Therefore, adjustment of the optical characteristic of a stretched film is easy, so that the draw ratio of a 2nd extending process is small.
  • the stretching ratio in the specific second stretching step is preferably 1.1 times or more, preferably 2 times or less, more preferably 1.5 times or less, and particularly preferably 1.3 times or less.
  • the stretching ratio is high in both the first stretching step and the second stretching step.
  • the product of the draw ratio in the first draw step and the draw ratio in the second draw step is preferably 3.6 or more, more preferably 3.8 or more, and even more preferably 4.0 or more. is there.
  • the upper limit of the product of the draw ratio in the first draw step and the draw ratio in the second draw step is preferably 6.0 or less from the viewpoint of facilitating adjustment of optical properties in the draw step.
  • the same method as that which can be adopted in the uniaxial stretching process in the first stretching process can be applied to the uniaxial stretching process in the second stretching process.
  • the combination of the stretching directions in the first stretching process and the second stretching process is arbitrary.
  • the film may be stretched in the MD direction in the first stretching process and stretched in the TD direction in the second stretching process.
  • the film may be stretched in the TD direction in the first stretching process and stretched in the MD direction in the second stretching process.
  • the film may be stretched in an oblique direction in the first stretching process, and may be stretched in an oblique direction orthogonal to the second stretching process.
  • the oblique direction represents a direction that is neither parallel nor perpendicular to the width direction of the film.
  • the method for producing an optical film of the present invention may include a step of heat-treating the film at a predetermined temperature after the first stretching step or after the second stretching step.
  • the temperature of the heat treatment is preferably Tg (b) -30 ° C. or more, more preferably Tg (b) -20 ° C. or more, preferably Tg (b) or less, more preferably Tg (b) ⁇ 5 ° C. or less. is there.
  • the method for producing an optical film of the present invention may include a step (preheating step) of preheating the pre-stretching film before the stretching step.
  • the heating means include an oven-type heating device, a radiation heating device, or immersion in a liquid. Of these, an oven-type heating device is preferable.
  • the heating temperature in this step is preferably a stretching temperature of ⁇ 40 ° C. or more, more preferably a stretching temperature of ⁇ 30 ° C. or more, preferably a stretching temperature of + 20 ° C. or less, more preferably a stretching temperature of + 15 ° C. or less.
  • the stretching temperature means a set temperature of the heating device.
  • the method for producing an optical film of the present invention may further include a step of further providing an arbitrary layer on the surface of the film obtained as described above.
  • optical film of the present invention is arbitrary.
  • the optical film of the present invention can be used for, for example, a viewing angle compensation film, a polarizing plate protective film, and the like.
  • Example 1 [Example 1] [1. Production and evaluation of stretched film) A polycarbonate resin (“Iupilon S3000” manufactured by Mitsubishi Engineering Plastics, glass transition temperature 149 ° C.) was prepared as the resin (a). The amount of the phenolic hydroxyl group of the polycarbonate contained in this polycarbonate resin is 0.0016 mol with respect to 1 mol of the main chain carbonate unit of the polycarbonate. Further, a styrene / maleic anhydride copolymer resin (“Dialark D332” manufactured by Nova Chemicals, glass transition temperature 128 ° C) was prepared as the resin (b).
  • a polycarbonate resin (“Iupilon S3000” manufactured by Mitsubishi Engineering Plastics, glass transition temperature 149 ° C.) was prepared as the resin (a). The amount of the phenolic hydroxyl group of the polycarbonate contained in this polycarbonate resin is 0.0016 mol with respect to 1 mol of the main chain carbonate unit of the polycarbonate. Further, a st
  • a film forming apparatus for coextrusion molding of two types and two layers (layer (A) / layer (B)) was prepared. This film forming apparatus is provided with a single screw extruder for each of the layer (A) and the layer (B).
  • the resin (a) was supplied to a single screw extruder for the layer (A) of the film forming apparatus and melted at 270 ° C.
  • the molten resin (a) was supplied to the manifold for the layer (A) of the multi-manifold die through 20 4.4 inch leaf disk filters having a filtration accuracy of 5 ⁇ m.
  • the resin (b) was supplied to a uniaxial stretching machine for the layer (B) of the film forming apparatus and melted at 260 ° C.
  • the molten resin (b) was supplied to the manifold for the layer (B) of the multi-manifold die through 50 12 inch leaf disk filters having a filtration accuracy of 5 ⁇ m.
  • the resin (a) and the resin (b) were simultaneously extruded from the multi-manifold die and formed into a film shape. At this time, the extrusion rate of the resin (a) was 20 kg / hour, and the extrusion rate of the resin (b) was 200 kg / hour. This obtained the elongate multilayer film provided with the layer (A) which consists of resin (a) with a thickness of 20 micrometers, and the layer (B) which consists of resin (b) with a thickness of 200 micrometers.
  • the above multilayer film was stretched in the width direction at a stretching temperature of 160 ° C. and a stretching ratio of 3.0 times using a transverse stretching machine to obtain an intermediate film. Thereafter, this intermediate film was stretched in the longitudinal direction using a longitudinal stretching machine at a stretching temperature of 125 ° C. and a stretching ratio of 1.3 times to obtain a stretched film.
  • the layer (A) of the obtained stretched film had a thickness of 7 ⁇ m, and the layer (B) had a thickness of 67 ⁇ m.
  • the surface of the stretched film thus obtained was washed with pure water. Thereafter, the stretched film was sandwiched between two polarizing plates to produce a sample sheet having a polarizing plate / stretched film / polarizing plate in this order. At this time, the polarizing plates were arranged in crossed Nicols so that the polarization transmission axes of the polarizing plates were perpendicular to each other.
  • the sample sheet was illuminated with a backlight, and the side opposite to the backlight of the data sheet was observed to count the number of bright spots. Since the bright spots are caused by optical defects, a stretched film having a smaller number of bright spots is used as a high-quality optical film with fewer optical defects.
  • a coloring resin was prepared by adding 1% by weight of a pigment (“Kayaset Red ECG” manufactured by Nippon Kayaku Co., Ltd.) to the polycarbonate resin prepared as the resin (a). This colored resin was filled from the single screw extruder for the layer (A) of the film forming apparatus to the multi-manifold die. Thereafter, the polycarbonate resin containing no dye was put into a single screw extruder for the layer (A) and extruded at an extrusion speed of 20 kg / hour. The time from the start of extrusion until the dye concentration of the resin discharged from the multi-manifold die became 1 ppm or less was measured, and this was defined as the longest residence time.
  • a pigment Korean ECG manufactured by Nippon Kayaku Co., Ltd.
  • Example 2 The kind of polycarbonate resin used as the resin (a) was changed to “Taflon A1900” (glass transition temperature 149 ° C.) manufactured by Idemitsu Kosan Co., Ltd.
  • the amount of the phenolic hydroxyl group of the polycarbonate contained in the polycarbonate resin used in Example 2 is 0.0029 mol with respect to 1 mol of the main chain carbonate unit of the polycarbonate. Except for the above, the production and evaluation of a stretched film and the measurement of the longest residence time of the polycarbonate resin were performed in the same manner as in Example 1.

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Abstract

　La présente invention concerne un film optique pourvu d'une couche (A) comprenant une résine (a) incluant du polycarbonate, l'épaisseur de la couche (A) étant inférieure ou égale à 10 µm, et la quantité de groupes hydroxyle phénoliques inclus dans le polycarbonate étant inférieure ou égale à 0,005 mole pour 1 mole d'unités carbonate à chaîne principale du polycarbonate.
PCT/JP2015/068546 2014-06-30 2015-06-26 Film optique et son procédé de fabrication Ceased WO2016002665A1 (fr)

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WO2018135433A1 (fr) * 2017-01-20 2018-07-26 住友化学株式会社 Film optique et procédé de fabrication de film optique
JP2018119133A (ja) * 2017-01-20 2018-08-02 住友化学株式会社 光学フィルムおよび光学フィルムの製造方法

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JP2002059472A (ja) * 2000-08-22 2002-02-26 Sumitomo Bakelite Co Ltd 高分子シート及び高分子シートの製造方法並びに液晶表示装置
JP2005060628A (ja) * 2003-08-20 2005-03-10 Teijin Chem Ltd リフロー耐性に優れたポリカーボネート樹脂
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WO2018135433A1 (fr) * 2017-01-20 2018-07-26 住友化学株式会社 Film optique et procédé de fabrication de film optique
JP2018119133A (ja) * 2017-01-20 2018-08-02 住友化学株式会社 光学フィルムおよび光学フィルムの製造方法
KR20190109453A (ko) * 2017-01-20 2019-09-25 스미또모 가가꾸 가부시키가이샤 광학 필름 및 광학 필름의 제조 방법
KR102461806B1 (ko) 2017-01-20 2022-11-01 스미또모 가가꾸 가부시키가이샤 광학 필름 및 광학 필름의 제조 방법
JP7249732B2 (ja) 2017-01-20 2023-03-31 住友化学株式会社 光学フィルムおよび光学フィルムの製造方法

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