WO2020195881A1 - 偏光フィルムの製造方法及び偏光フィルム - Google Patents

偏光フィルムの製造方法及び偏光フィルム Download PDF

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Publication number
WO2020195881A1
WO2020195881A1 PCT/JP2020/010747 JP2020010747W WO2020195881A1 WO 2020195881 A1 WO2020195881 A1 WO 2020195881A1 JP 2020010747 W JP2020010747 W JP 2020010747W WO 2020195881 A1 WO2020195881 A1 WO 2020195881A1
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Prior art keywords
film
polarizing film
group
liquid crystal
polarizing
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PCT/JP2020/010747
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English (en)
French (fr)
Japanese (ja)
Inventor
智煕 柳
東輝 金
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住友化学株式会社
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Priority to KR1020217031039A priority Critical patent/KR20210148141A/ko
Publication of WO2020195881A1 publication Critical patent/WO2020195881A1/ja

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    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

Definitions

  • the present invention relates to a method for producing a polarizing film and a polarizing film.
  • Patent Document 1 describes a coating type polarizing film formed by coating a composition containing a polymerizable liquid crystal compound and a dichroic dye. According to the coating type polarizing film, it is easy to achieve thinning.
  • a method for producing a polarizing film including a base material and a polarizing film includes the following inventions.
  • a method for producing a polarizing film including a base material and a polarizing film includes (A) A step of applying an alignment film composition to the substrate to form a first coating film.
  • D A step of forming a polarizing film on the alignment film
  • a method for producing a polarizing film which comprises a step of uniaxially stretching an alignment film laminate containing at least the base material and the alignment film in an atmosphere having a temperature of 60 ° C. to 150 ° C.
  • step (d) A step of applying a polarizing film composition on the alignment film to form a second coating film.
  • D2 A step of drying the second coating film to form a second dry film.
  • step (D3) The method for producing a polarizing film according to [1] or [2], which comprises a step of curing the second dry film to form the polarizing film.
  • the polarizing film contains a dichroic dye and a polymer of a polymerizable liquid crystal compound.
  • the average value S 1ave of the order parameter is a polarizing film satisfying the relationship of the following formula (1a).
  • S 1ave ⁇ 0.998 (1a) [8] The polarizing film according to [7], wherein the order parameter difference ⁇ S 1 satisfies the relationship of the following formula (3a).
  • the present invention is a method for producing a polarizing film including a base material and a polarizing film.
  • E A method for producing a polarizing film, which comprises a step of uniaxially stretching an alignment film laminate containing at least the base material and the alignment film in an atmosphere having a temperature of 60 ° C. to 150 ° C.
  • a polarizing film including a base material, an alignment film, and a polarizing film in this order, and a polarizing film having good optical characteristics can be manufactured.
  • the substrate is preferably long.
  • a long polarizing film can be continuously produced.
  • the length of the base material in the longitudinal direction is usually 10 to 10000 m, preferably 100 to 2000 m.
  • the length of the base material in the lateral direction is usually 0.1 to 5 m, preferably 0.2 to 2 m.
  • the "long" base material refers to "a long base material rolled into a roll” and "a long base material unwound from a long roll-shaped base material”. The same applies to "long” when referring to a long alignment film and a long polarizing film.
  • the base material is not limited to a long length, but is preferably rectangular.
  • the base material is usually a resin base material.
  • the resin base material is usually a transparent resin base material.
  • the transparent resin base material means a base material having translucency capable of transmitting light, particularly visible light, and the translucency means a transmittance of 80% or more for light having a wavelength of 380 nm to 780 nm. Refers to characteristics.
  • the resin constituting the base material examples include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; triacetyl cellulose, diacetyl cellulose, and Cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketone; polyphenylene sulfide; and polyphenylene oxide and the like.
  • Cellulose ester is an esterified product of at least a part of the hydroxyl groups contained in cellulose and can be obtained from the market. Substrates containing cellulose esters are also available on the market. Commercially available substrates containing cellulose esters include Fujitac (registered trademark) film (Fuji Photo Film Co., Ltd.), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC8UY (Konica Minolta Opto Co., Ltd.), and KC4UY (Konica Minolta Opto Co., Ltd.). Examples include Minolta Opto Co., Ltd.
  • the cyclic olefin-based resin includes a polymer of a cyclic olefin such as norbornene or a polycyclic norbornene-based monomer, or a copolymer thereof.
  • the cyclic olefin-based resin may contain a ring-opening structure, or may be a hydrogenated cyclic olefin-based resin containing a ring-opening structure.
  • the cyclic olefin resin may contain structural units derived from the chain olefin and the vinylized aromatic compound as long as the transparency is not significantly impaired and the hygroscopicity is not significantly increased.
  • the cyclic olefin resin may have a polar group introduced into its molecule. Examples of the chain olefin include ethylene and propylene, and examples of the vinylized aromatic compound include styrene, ⁇ -methylstyrene and alkyl-substituted styrene.
  • the cyclic olefin resin is a copolymer of a cyclic olefin and a chain olefin or a vinylized aromatic compound
  • the content of the structural unit derived from the cyclic olefin is based on the total structural unit of the copolymer. , Usually 50 mol% or less, preferably 15-50 mol%.
  • the cyclic olefin resin is a ternary copolymer of a cyclic olefin, a chain olefin, and a vinylized aromatic compound
  • the content of the structural unit derived from the chain olefin is the total structure of the copolymer. It is usually 5 to 80 mol% with respect to the unit, and the content ratio of the structural unit derived from the vinylized aromatic compound is usually 5 to 80 mol% with respect to the total structural unit of the copolymer.
  • Such a ternary copolymer has an advantage that the amount of expensive cyclic olefin used can be relatively reduced.
  • Cyclic olefin resin is available on the market.
  • Commercially available cyclic olefin resins are Topas (registered trademark) (manufactured by Ticona), Arton (registered trademark) (manufactured by JSR Corporation), ZEONOR (registered trademark) and ZEONEX (registered trademark) ( As mentioned above, Zeon Corporation (manufactured by Nippon Zeon Corporation), Appel (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.) and the like can be mentioned.
  • Such a cyclic olefin resin can be used as a base material by forming a film by a known means such as a solvent casting method or a melt extrusion method.
  • the base materials containing a commercially available cyclic olefin resin are Scina (registered trademark), SCA40 (all manufactured by Sekisui Chemical Co., Ltd.), Zeonoa Film (registered trademark) (Optes Co., Ltd.), and Arton Film (registered trademark). ) (JSR Co., Ltd.) and the like.
  • the base material may be surface-treated.
  • the surface treatment of the base material includes, for example, corona or plasma treatment in a vacuum atmosphere to an atmospheric pressure atmosphere, laser treatment, ozone treatment, saponification treatment, flame treatment, coupling agent coating treatment, primer treatment, and reactivity. Examples thereof include treatment by a graft polymerization method in which a monomer or a reactive polymer is attached to the surface of a substrate and then irradiated with radiation, plasma or ultraviolet rays to cause a reaction. Of these, corona or plasma treatment in a vacuum atmosphere to an atmospheric pressure atmosphere is preferable.
  • a method of placing the base material between the opposing electrodes under a pressure near atmospheric pressure and generating corona or plasma to perform the surface treatment of the base material, facing each other a method in which a gas is passed between the electrodes, the gas is turned into plasma between the electrodes, and the plasmaized gas is blown onto the base material, and a method in which glow discharge plasma is generated under low pressure conditions to perform surface treatment on the base material.
  • a method in which a base material is placed between opposing electrodes under a pressure near atmospheric pressure to generate corona or plasma to perform surface treatment of the base material or a method in which gas is passed between the facing electrodes to conduct electrodes.
  • a method in which the gas is turned into plasma between them and the turned gas is blown onto the substrate is preferable.
  • Such surface treatment with corona or plasma is usually performed by a commercially available surface treatment apparatus.
  • the base material may have a protective film on the surface opposite to the surface on which the polarizing film composition is applied.
  • the protective film include films such as polyethylene, polyethylene terephthalate, polycarbonate and polyolefin, and films having an adhesive layer on the film. Of these, polyethylene terephthalate is preferable because it has a small thermal deformation during drying.
  • the thickness of the base material is preferably thin in that it is heavy enough to be handled practically, but if it is too thin, the strength tends to decrease and the workability tends to be inferior.
  • the thickness of the base material is usually 5 to 300 ⁇ m, preferably 20 to 200 ⁇ m.
  • the alignment film is (A) A step of applying an alignment film composition to the substrate to form a first coating film. (B) A step of drying the first coating film to form the first dry film. (C) A step of irradiating the first dry film with polarized light to form an alignment film. Is formed on the substrate through.
  • the alignment film has an orientation regulating force that orients the polymerizable liquid crystal compound contained in the polarizing film composition applied on the alignment film in a certain direction.
  • the polymerizable liquid crystal compound can be oriented so that its molecular major axis direction is parallel to the direction of the orientation regulating force.
  • the direction of the orientation regulating force of the alignment film is usually parallel or perpendicular to the polarization direction of the polarized light to be irradiated.
  • the alignment film preferably has solvent resistance that does not dissolve when the polarizing film composition is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the dichroic dye.
  • the film thickness of the alignment film is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm, more preferably 500 nm or less, and more preferably 10 nm or more. Within the above range, the orientation regulating force is sufficiently exhibited.
  • the alignment film composition contains a polymer or monomer having a photoreactive group and a solvent.
  • a photoreactive group is a group that exhibits an orientation ability when irradiated with light. Specifically, a photoreactive group undergoes a photoreaction that is the origin of orientation ability, such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction by irradiation with light. To do.
  • the photoreactive groups those that cause a dimerization reaction or a photocrosslinking reaction are preferable because they are excellent in orientation.
  • a photoreactive group that undergoes a photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarized light required for photoalignment and excellent thermal stability and temporal stability can be easily obtained.
  • Groups and chalcone groups are preferred.
  • the polymer having a photoreactive group a polymer having a cinnamoyl group such that the terminal portion of the side chain of the polymer has a cinnamon acid structure is particularly preferable.
  • the solvent of the alignment film composition is preferably one that dissolves a polymer and a monomer having a photoreactive group.
  • the solvent is water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve or alcohol such as propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma butyrolactone, propylene glycol methyl.
  • Ester solvents such as ether acetate or ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; non-chlorine aliphatic hydrocarbon solvents such as pentane, hexane or heptane; Non-chlorine aromatic hydrocarbon solvents such as toluene or xylene, nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran or dimethoxyethane; chlorine solvents such as chloroform or chlorobenzene; and the like can be mentioned. These solvents may be used alone or in combination.
  • the content of the polymer or monomer having a photoreactive group in the alignment film composition can be appropriately adjusted depending on the type of the polymer or monomer having a photoreactive group and the thickness of the photoalignment film to be produced, but is at least 0. It is preferably .2% by mass or more, and particularly preferably in the range of 0.3 to 10% by mass. Further, a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer may be contained as long as the characteristics of the alignment film are not significantly impaired.
  • the first coating film is formed by applying the alignment film composition to the substrate.
  • the method for applying the alignment film composition to the substrate include a gravure coating method, a die coating method, an applicator method, a flexographic method and the like. According to these methods, the alignment film composition can be continuously applied to a long base material.
  • the gravure coating method, the die coating method and the flexographic method are preferable.
  • the first dry film is formed by drying the first coating film.
  • a film in which the content of the solvent contained in the first coating film is 50% by mass or less with respect to the total mass of the first coating film is referred to as a first dry film.
  • Examples of the method for drying the first coating film include a natural drying method, a ventilation drying method, a heat drying method, and a vacuum drying method.
  • a method that combines a ventilation drying method and a heat drying method is preferable.
  • the drying temperature is preferably 10 to 250 ° C, more preferably 25 to 200 ° C.
  • the drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. By drying, the solvent contained in the first coating film is removed.
  • the content of the solvent in the first dry film is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • the first dry film is irradiated with polarized light to form an alignment film having an orientation regulating force.
  • the angle formed by the direction of the alignment regulating force of the alignment film and the longitudinal direction of the alignment film is preferably 0 ° ⁇ 15 ° or 90 ° ⁇ 15 °, more preferably. Is 0 ° ⁇ 10 ° or 90 ° ⁇ 10 °, more preferably 0 ° ⁇ 5 ° or 90 ° ⁇ 5 °, and particularly preferably 0 ° ⁇ 1 ° or 90 ° ⁇ 1 °.
  • the direction of the orientation regulating force of the alignment film can be adjusted by the polarization direction of the polarized light to be irradiated.
  • the direction of the orientation regulating force can also be changed depending on the type of polymer having a photoreactive group.
  • the polarization direction of the polarization is preferably 0 ° ⁇ 15 °, more preferably 0 ° ⁇ 10 °, still more preferably 0 ° ⁇ 5 °, and particularly preferably 0 ° ⁇ 5 ° with respect to the longitudinal direction of the alignment film. It is 0 ° ⁇ 1 °.
  • the polarization direction of the polarized light is preferably 90 ° ⁇ 15 ° with respect to the longitudinal direction of the alignment film, which is more preferable. Is 90 ° ⁇ 10 °, more preferably 90 ° ⁇ 5 °, and particularly preferably 90 ° ⁇ 1 °.
  • Polarized light may be directly irradiated to the first dry film from the first dry film side, or may be irradiated by transmitting the base material from the base material side.
  • the wavelength of polarized light is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy.
  • ultraviolet rays having a wavelength in the range of 250 to 400 nm are preferable.
  • the polarized light source include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps are preferable. These lamps are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • Polarized light is obtained, for example, by passing light from the light source through a polarizer.
  • a polarizer By adjusting the polarization angle of the polarizer, the direction of polarization can be arbitrarily adjusted.
  • the polarizer include a polarizing filter, a polarizing prism such as a Gran Thomson or a Granter, and a wire grid type polarizer.
  • the polarized light is preferably substantially parallel light.
  • the alignment film can induce the orientation of the liquid crystal material.
  • the orientation regulation direction of the alignment film is parallel to the longitudinal direction of the long substrate, the direction of the absorption axis is parallel to the longitudinal direction of the long substrate, for the production of a long polarizing film. It is useful.
  • the orientation regulation direction of the alignment film is orthogonal to the longitudinal direction of the long substrate, the direction of the absorption axis is orthogonal to the longitudinal direction of the long substrate for manufacturing a long polarizing film. It is useful.
  • Step (d)> The step (d) of forming the polarizing film on the alignment film is (D1) A step of applying a polarizing film composition on the alignment film to form a second coating film. (D2) A step of drying the second coating film to form a second dry film. (D3) The step of curing the second dry film to form the polarizing film is included.
  • the polarizing film composition preferably contains a dichroic dye and a polymerizable liquid crystal compound.
  • the polarizing film containing the polymerizable liquid crystal compound has improved strength and reduced color unevenness.
  • the viscosity of the polarizing film composition is preferably 10 mPa ⁇ s or less, more preferably 0.1 to 7 mPa ⁇ s, because the film thickness of the second coating film is less likely to be uneven.
  • the polarizing film composition may further contain a solvent, a polymerization initiator, a sensitizer, a polymerization inhibitor, a leveling agent, a polymerizable non-liquid crystal compound, and the like.
  • the dichroic dye refers to a dye having a property in which the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different.
  • the dichromatic dye preferably has an absorption maximum wavelength ( ⁇ MAX) in the range of 300 to 700 nm.
  • a dichroic dye examples include an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye and an anthraquinone dye, and among them, the azo dye is preferable.
  • the azo dye examples include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye and a stilbene azo dye, and preferably a bisazo dye and a trisazo dye.
  • the dichroic dyes may be used alone or in combination, but it is preferable to combine three or more kinds. In particular, it is preferable to combine three or more kinds of azo compounds.
  • Examples of the azo dye include a compound represented by the formula (2) (hereinafter, in some cases, referred to as “compound (2)”).
  • a 1 (-N NA 2 )
  • p -N NA 3 (2)
  • a 1 and A 3 are independent of each other, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent.
  • a 2 is a divalent 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent group which may have a substituent.
  • p represents an integer of 1 to 4. If p is an integer of 2 or more, it may be the same or different and the plurality of A 2 independently of one another. ]
  • Examples of the monovalent heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole and benzoxazole.
  • Examples of the divalent heterocyclic group include a group obtained by removing two hydrogen atoms from the heterocyclic compound.
  • the unsubstituted amino group is -NH2). Specific examples of the alkyl group having 1 to 6 carbon atoms are the same as those exemplified by the substituent arbitrarily contained in the phenylene group of the compound (1).
  • the compounds represented by the following formulas (2-1) to (2-6) are preferable.
  • B 1 to B 20 are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, and a substituted or unsubstituted amino group (substituted amino group and The definition of an unsubstituted amino group is as described above), and represents a chlorine atom or a trifluoromethyl group.
  • n1 to n4 represent integers of 0 to 3 independently of each other.
  • n1 is 2 or more, a plurality of B 2 may be the same or different independently of one another, if n2 is 2 or more, plural B 6 may be the same or different independently of each other, If n3 is 2 or more, plural B 9 may be the same or different independently of each other, when n4 is 2 or more, a plurality of B 14 may be the same or different independently of each other.
  • the anthraquinone dye is preferably a compound represented by the formula (2-7).
  • R 1 to R 8 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the oxazone dye is preferably a compound represented by the formula (2-8).
  • R 9 to R 15 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the acridine dye is preferably a compound represented by the formula (2-9).
  • R 16 to R 23 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms represented by R x in the formula (2-7), the formula (2-8) and the formula (2-9) includes a methyl group, an ethyl group, a propyl group and a butyl group.
  • Pentyl group, hexyl group and the like, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xsilyl group and a naphthyl group.
  • the cyanine dye is preferably a compound represented by the formula (2-10) and a compound represented by the formula (2-11).
  • D 1 and D 2 represent groups represented by any of the formulas (2-10a) to (2-10d) independently of each other.
  • n5 represents an integer of 1 to 3.
  • D 3 and D 4 represent groups represented by any of the formulas (2-11a) to (2-11h) independently of each other.
  • n6 represents an integer of 1 to 3.
  • the content of the dichroic dye in the polarizing film composition is 0.1 part by mass or more and 30 parts by mass with respect to 100 parts by mass of the solid content of the polarizing film composition from the viewpoint of improving the orientation of the dichroic dye.
  • the following is preferable, 0.1 parts by mass or more and 20 parts by mass or less is more preferable, 0.1 parts by mass or more and 10 parts by mass or less is further preferable, and 0.1 parts by mass or more and 5 parts by mass or less is particularly preferable.
  • the solid content means the total amount of the components excluding the solvent from the polarizing film composition.
  • the polymerizable liquid crystal compound is a compound having a polymerizable group and exhibiting liquid crystallinity.
  • the polymerizable group means a group involved in the polymerization reaction, and is preferably a photopolymerizable group.
  • the photopolymerizable group refers to a group that can undergo a polymerization reaction with an active radical, an acid, or the like generated from a photopolymerization initiator described later.
  • Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxylanyl group, an oxetanyl group and the like.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.
  • the liquid crystal compound may be a thermotropic liquid crystal or a riotropic liquid crystal, and may be a nematic liquid crystal or a smectic liquid crystal in the thermotropic liquid crystal.
  • a smectic liquid crystal compound is preferable in that higher polarization characteristics can be obtained, and a higher-order smectic liquid crystal compound is more preferable.
  • higher-order smectic liquid crystal compounds forming smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase or smectic L phase More preferably, a higher-order smectic liquid crystal compound forming a smectic B phase, smectic F phase or smectic I phase is more preferable.
  • a polarizing film having a higher degree of orientation order can be produced.
  • a polarizing film having such a high degree of orientation order can obtain a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement.
  • the Bragg peak is a peak derived from the periodic structure of molecular orientation, and when the liquid crystal phase formed by the polymerizable liquid crystal compound is these higher-order smectic phases, the periodic interval is 3.0 to 6.0 ⁇ .
  • a membrane can be obtained.
  • Specific examples of such a compound include a compound represented by the following formula (B) (hereinafter, may be referred to as compound (B)) and the like.
  • the polymerizable liquid crystal compound may be used alone or in combination.
  • X 1 , X 2 and X 3 represent, independently of each other, a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
  • at least one of X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent. It is, -O - - -CH 2 constituting hexane-1,4-diyl group cycloheteroalkyl, - may be replaced by S- or -NR-.
  • R represents an alkyl group or a phenyl group having 1 to 6 carbon atoms.
  • R a and R b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • U 1 represents a hydrogen atom or a polymerizable group.
  • U 2 represents a polymerizable group.
  • W 1 and W 2 independently represent a single bond, -O-, -S-, -COO- or -OCOO-.
  • V 1 and V 2 represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent independently of each other, and -CH 2- constituting the alkanediyl group is -O-,-. It may be replaced with S- or -NH-.
  • At least one of X 1 , X 2 and X 3 is preferably a 1,4-phenylene group which may have a substituent.
  • the 1,4-phenylene group which may have a substituent is preferably unsubstituted.
  • the cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent, and is a substituent.
  • the trans-cyclohexane-1,4-diyl group which may have is preferably unsubstituted.
  • the substituents arbitrarily contained in the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent are methyl group, ethyl group and butyl. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group, a cyano group and a halogen atom.
  • Y 1 is preferably -CH 2 CH 2- , -COO- or a single bond
  • Y 2 is preferably -CH 2 CH 2- or -CH 2 O-.
  • U 2 is a polymerizable group.
  • U 1 is a hydrogen atom or a polymerizable group, preferably a polymerizable group. Both U 1 and U 2 are preferably polymerizable groups, and both are preferably photopolymerizable groups.
  • a polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under lower temperature conditions.
  • the polymerizable groups represented by U 1 and U 2 may be different from each other independently of each other, but are preferably the same.
  • the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxylanyl group, an oxetanyl group and the like.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.
  • the alkanediyl groups represented by V 1 and V 2 include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-. 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group Examples include groups and icosan-1,20-diyl groups.
  • V 1 and V 2 are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.
  • substituent arbitrarily contained in the alkanediyl group having 1 to 20 carbon atoms which may have a substituent include a cyano group and a halogen atom, and the alkanediyl group may be unsubstituted. It is preferably an unsubstituted and linear alkanediyl group, more preferably.
  • W 1 and W 2 are independent of each other, preferably single bond or —O—.
  • compound (B) examples include compounds represented by the formulas (1-1) to (1-23).
  • the cyclohexane-1,4-diyl group is preferably a trans form.
  • the exemplified compound (B) can be used alone or in combination for a long polarizing film.
  • the liquid crystal property may be temporarily maintained even at a temperature equal to or lower than the liquid crystal-crystal phase transition temperature.
  • the mixing ratio when the two kinds of polymerizable liquid crystal compounds are combined is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50. is there.
  • the compound (B) is, for example, Lub et all. Recl. Trav. Chim. It is produced by a known method described in Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.
  • the content ratio of the polymerizable liquid crystal compound in the polarizing film composition is usually 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polarizing film composition from the viewpoint of increasing the orientation of the polymerizable liquid crystal compound. It is preferably 80 to 99 parts by mass, more preferably 80 to 94 parts by mass, and further preferably 80 to 90 parts by mass.
  • the solvent is preferably one that can completely dissolve the polymerizable liquid crystal compound, and is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound.
  • Solvents are alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone or Ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; toluene and Examples include aromatic hydrocarbon solvents such as xylene, nitrile solvents such as acetonitrile; ether solvents such as tetrahydr
  • the content of the solvent is preferably 50 to 98% by mass with respect to the total amount of the polarizing film composition.
  • the solid content in the polarizing film composition is preferably 2 to 50% by mass.
  • the viscosity of the polarizing film composition is low, so that the thickness of the polarizing film becomes substantially uniform, and the polarizing film tends to be less likely to be uneven. Further, the solid content can be determined in consideration of the thickness of the polarizing film to be produced.
  • the polymerization initiator is a compound such as a polymerizable liquid crystal compound that can initiate a polymerization reaction.
  • the polymerization initiator is preferably a photopolymerization initiator that generates active radicals by the action of light.
  • polymerization initiator examples include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether.
  • Benzophenone compounds include, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl). Examples thereof include benzophenone and 2,4,6-trimethylbenzophenone.
  • Alkylphenone compounds include, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl).
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
  • the triazine compounds include, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl).
  • a commercially available polymerization initiator can be used.
  • Commercially available polymerization initiators are Irgacure (registered trademark) 907, 184, 651, 819, 250 and 369 (manufactured by BASF Japan Ltd.); Sakeol (registered trademark) BZ, Z and BEE (Seiko Kagaku).
  • the polymerization initiator is preferably contained in the polarizing film composition.
  • the content of the polymerization initiator in the polarizing film composition is 100, from the viewpoint that the orientation of the polymerizable liquid crystal compound is not easily disturbed. It is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass with respect to the parts by mass.
  • the sensitizer is preferably a photosensitizer.
  • the sensitizer is, for example, a xanthone compound such as xanthone and thioxanthone (eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); an anthracene compound such as anthracene and an alkoxy group-containing anthracene (eg, dibutoxyanthracene, etc.); Examples include phenothiazine and rubrene.
  • the sensitizer is preferably contained in the polarizing film composition.
  • the content of the sensitizer in the polarizing film composition is usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the content of the polymerizable liquid crystal compound. It is preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass.
  • the polymerization inhibitor is a radical scavenger such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (for example, butylcatechol, etc.), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxyradical. Thiophenols; ⁇ -naphthylamines, ⁇ -naphthols and the like.
  • the polymerization inhibitor is preferably contained in the polarizing film composition when the polarizing film composition contains a polymerizable liquid crystal compound.
  • the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled by the polymerization inhibitor.
  • the content of the sensitizer in the polarizing film composition is usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the content of the polymerizable liquid crystal compound. It is preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass.
  • the leveling agent has a function of adjusting the fluidity of the polarizing film composition and flattening the coating film of the polarizing film composition, and examples thereof include a surfactant.
  • Preferred leveling agents include a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component.
  • leveling agent containing a polyacrylate compound as a main component examples include "BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380, BYK-381 and , BYK-392 (manufactured by BYK Chemie) and the like.
  • leveling agent containing a fluorine atom-containing compound as a main component examples include Megafuck (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, and F-.
  • the leveling agent is preferably contained in the polarizing film composition when the polarizing film composition contains a polymerizable liquid crystal compound.
  • the content of the leveling agent in the polarizing film composition is usually 0.3 parts by mass or more and 5 parts by mass or less, preferably 0.5 parts by mass or more and 3 parts by mass with respect to 100 parts by mass of the content of the polymerizable liquid crystal compound. It is less than a part.
  • the content of the leveling agent is within the above range, it is easy to horizontally orient the polymerizable liquid crystal compound, and the obtained long polarizing film tends to be smoother, which is preferable. If the content of the leveling agent with respect to the polymerizable liquid crystal compound exceeds the above range, the obtained polarizing film tends to be uneven, which is not preferable.
  • the polarizing film composition may contain two or more kinds of leveling agents.
  • the polarizing film composition may contain a polymerizable non-liquid crystal compound.
  • the crosslink density of the polymerization-reactive site can be increased and the strength of the polarizing film can be improved.
  • the polymerizable non-liquid crystal compound preferably has at least one polymerizable group in the group consisting of an acryloyl group, a methacryloyl group, and an isocyanate group. It is more preferable to have 2 or more and 10 or less polymerizable groups, and further preferably 3 or more and 8 or less polymerizable groups.
  • the content of the polymerizable non-liquid crystal compound in the polarizing film composition is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the solid content of the polarizing film composition. is there.
  • the second coating film is formed by applying the polarizing film composition on the alignment film.
  • Examples of the method of applying the polarizing film composition to the alignment film include the same method as the method of applying the alignment film composition.
  • the dichroic dye has a lyotropic liquid crystal property
  • the dichroic dye can be oriented by applying a shearing force.
  • the second coating film is dried to form the second dry film.
  • a film having a solvent content of 50% by mass or less in the second coating film with respect to the total mass of the second coating film is referred to as a second dry film.
  • the content of the solvent is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • Examples of the method for drying the second coating film include the same method as the method for drying the first coating film.
  • the dichroic dye and the polymerizable liquid crystal compound are usually oriented by heating and drying the second coating film to transfer the dichroic dye and the polymerizable liquid crystal compound to the liquid crystal phase.
  • the liquid crystal phase is formed by heating the second dry film to a temperature at which these show the liquid crystal phase. Can be formed.
  • a liquid crystal phase may be formed.
  • the drying and heating for forming the liquid crystal phase may be performed by the same heating step.
  • the second dry film may be used as it is as a polarizing film, but when the second dry film contains a polymerizable liquid crystal compound, it is preferably cured by the step (d3).
  • Curing means that the polymerizable liquid crystal compound contained in the second dry film is polymerized, and examples of the polymerization method include heating and light irradiation, preferably light irradiation. By this curing, the dichroic dye contained in the second dry film can be fixed in an oriented state.
  • Curing is preferably performed in a state where a liquid crystal phase is formed on a polymerizable liquid crystal compound, and may be cured by irradiating light at a temperature indicating the liquid crystal phase.
  • Examples of light in light irradiation include visible light and ultraviolet light. Ultraviolet light is preferable because it is easy to handle.
  • the light may be directly irradiated to the second dry film, or may be irradiated through a long base material.
  • Examples of the light source for light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps. preferable. These lamps are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • the thickness of the polarizing film is usually 5 ⁇ m or less, preferably 0.5 ⁇ m or more and 3 ⁇ m or less, and more preferably 1 ⁇ m or more and 3 ⁇ m or less.
  • the thickness of the long polarizing film can be measured with an interference film thickness meter, a laser microscope, or a stylus type film thickness meter.
  • the long polarizing film preferably shows a Bragg peak in the X-ray diffraction measurement.
  • the production method of the present invention includes a step (e) of uniaxially stretching an alignment film laminate containing at least the base material and the alignment film in an atmosphere having a temperature of 60 ° C. to 150 ° C.
  • the timing of the step (e) is not limited as long as it is after the step (c) of forming the alignment film, and may be after the step (c) and before the step (d). , Simultaneously with step (d) or after step (d).
  • the angle formed by the direction of uniaxial stretching with the direction of the orientation regulating force of the alignment film is preferably within the range of 0 ° ⁇ 15 ° or 90 ° ⁇ 15 °, and more preferably 0 ° ⁇ . It is 10 ° or 90 ° ⁇ 10 °, more preferably 0 ° ⁇ 5 ° or 90 ° ⁇ 5 °, and particularly preferably 0 ° ⁇ 1 ° or 90 ° ⁇ 1 °.
  • Examples of the method of continuously uniaxially stretching the long alignment film laminate include a method of using a nip roll and a method of clipping both ends of the alignment film laminate and stretching in the width direction of the alignment film laminate.
  • the alignment film laminate is sandwiched between the pair of rolls of the nip roll composed of a pair of rolls, and the rotation speed of the pair of rolls is relatively changed, so that the alignment film laminate is uniaxial in the transport direction. Stretch.
  • the ambient temperature can be adjusted by uniaxially stretching the alignment film laminate in a heating furnace.
  • the ambient temperature is 60 ° C. to 150 ° C., preferably 65 ° C. to 100 ° C.
  • the temperature of the base material of the alignment film laminate during uniaxial stretching is preferably 60 ° C. to 150 ° C., more preferably 65 ° C. to 100 ° C.
  • the draw ratio of uniaxial stretching is preferably 1.01 to 1.5 times, more preferably 1.05 to 1.5 times, and 1.1 to 1.3 times. Is even more preferable.
  • the manufacturing method of the present invention can improve the order parameter (S 1 ) of the polarizing film, can improve the value of the luminosity factor correction polarization degree (Py), and can improve the surface. It is possible to easily obtain a uniform color within.
  • a polarizing film including a base material, an alignment film, and a polarizing film in this order can be produced, and a polarizing film having good optical characteristics can be produced.
  • a circular polarizing plate can be obtained by further adhering a 1 / 4 ⁇ wave plate to the polarizing film of the present invention.
  • a single-wafer-shaped polarizing film can be obtained by cutting it into a single-wafer shape.
  • the single-wafer shape excludes a film having a significantly different balance between the longitudinal direction and the lateral direction, and in the present specification, if the length in the longitudinal direction is 5 times or less the length in the lateral direction. It is called a single leaf.
  • the cutting can be performed by any method.
  • a preferred form of the polarizing film of the present invention includes a base material and a polarizing film, and the polarizing film contains a dichroic dye and a polymer of a polymerizable liquid crystal compound.
  • the average value (S 1ave ) of the order parameter (S 1 ) of the polarizing film of the present invention preferably satisfies the relationship of the following formula (1a), and more preferably satisfies the relationship of the following formula (1b).
  • the average value (S 1ave ) of the order parameter (S 1 ) of the polarizing film may be less than 1. S 1ave ⁇ 0.998 (1a) S 1ave ⁇ 0.999 (1b)
  • the order parameter (S 1 ) of the arbitrary region divides the arbitrary region of the polarizing film into a plurality of minute regions, the axis angle of the absorption axis of each minute region is ⁇ 1 , and the standard deviation of the axis angle ⁇ 1 of the minute region is ⁇ . Is the value defined by the equation (2).
  • the order parameter (S 1 ) and the average value (S 1ave ) of the order parameters are values obtained by the method described below.
  • the order parameter difference ( ⁇ S 1 ) of the polarizing film of the present invention in the direction orthogonal to the stretching direction (for example, the absorption axis direction) preferably satisfies the relationship of the following formula (3a), and more preferably of the following formula (3b). Meet the relationship. ⁇ S 1 ⁇ 0.0015 (3a) ⁇ S 1 ⁇ 0.0010 (3b)
  • the order parameter (S 1 ), the average value of the order parameters (S 1ave ), and the order parameter difference ( ⁇ S 1 ) can be measured as follows.
  • the polarizing film to be measured may be long or single-wafered. First, 20 measurement regions having an absorption axis direction of 1.7 mm and a transmission axis direction of 1.4 mm are set at equal intervals over the entire width of the polarizing film in the absorption axis direction. Each measurement region is further divided into 168 in the absorption axis direction and 128 in the transmission axis direction to set 21504 minute regions.
  • the absorption axis angle is measured using an absorption axis angle measuring meter (AXOMETRICS, AXoStep_Imaging Polarimeter). Then, the order parameter (S 1 ) is calculated for each measurement region according to the above equation (2).
  • the average value of 20 order parameters be the average value of order parameters (S 1ave) .
  • the order parameter difference ( ⁇ S 1 ) is calculated from the difference between the largest order parameter (S 1max ) and the smallest order parameter (S 1min ) among the order parameters calculated at 20 locations.
  • the luminosity factor correction polarization degree (Py) of the polarizing film of the present invention preferably satisfies the relationship of the following formula (6a), and more preferably satisfies the relationship of the following formula (6b).
  • the luminosity factor correction polarization degree (Py) of the polarizing film of the present invention may satisfy the relationship of the following formula (6c).
  • the luminosity factor correction transmittance (Ty) of the polarizing film of the present invention is usually 35% or more, preferably 40% or more, and more preferably 42% or more.
  • Ty is 35% or more, white brightness is improved, which is preferable.
  • the transmittance here includes the interfacial reflection loss due to the difference in refractive index between the base film and the air interface and the loss due to absorption of the base film itself. Further, when the polarizing film is provided with antiglare performance by anti-glare treatment or the like, it is a value measured by an integrating sphere including scattered light.
  • the first roll 210 in which the long base material is wound around the first winding core 210A is easily available from the market, for example.
  • Examples of the long base material available on the market in the form of such a roll include a film made of a cellulose ester, a cyclic olefin resin, a polyethylene terephthalate, or a polymethacrylic acid ester, among the base materials already exemplified.
  • the long base material is unwound from the first roll 210.
  • the method of unwinding the long base material is performed by installing an appropriate rotating means on the winding core 210A of the first roll 210 and rotating the first roll 210 by the rotating means.
  • an appropriate auxiliary roll 300 may be installed in the direction of transporting the long base material from the first roll 210, and the long base material may be unwound by the rotating means of the auxiliary roll 300.
  • the long base material may be unwound while applying an appropriate tension to the long base material.
  • the alignment film composition is coated on the surface of the long base material by the coating device 211A (step (a)).
  • the coating device 211A for continuously applying the alignment film composition in this way preferably has a gravure coating method, a die coating method, or a flexographic method.
  • the long base material on which the first coating film is formed has passed through the coating device 211A and is conveyed to the drying furnace 212A, and the first coating film is dried by the drying furnace 212A to form the first drying film (step). (B)).
  • the drying furnace 212A for example, a hot air drying furnace that combines a ventilation drying method and a heating drying method is used.
  • the set temperature of the drying furnace 212A is determined according to the type of solvent contained in the photoalignment film composition and the like.
  • the drying furnace 212A may consist of a plurality of zones having different set temperatures, or may have a plurality of drying furnaces having different set temperatures installed in series.
  • a long alignment film is obtained by irradiating the obtained first dry film with polarized light by the polarizing irradiation device 213A (step (c)). At that time, the polarized light is irradiated so that the direction of the orientation regulating force of the alignment film is the longitudinal direction of the long base material.
  • the long base material on which the long alignment film is formed is conveyed to the heating furnace 214, and the alignment film laminate composed of the long base material and the long alignment film is heated by the heating furnace.
  • the alignment film laminate is conveyed between the pair of nip rolls 215 and uniaxially stretched in the semimajor direction (step (e)).
  • the temperature of the heating furnace 214 is preferably 60 ° C. to 150 ° C., more preferably 65 ° C. to 100 ° C.
  • the draw ratio of uniaxial stretching by the nip roll 215 is preferably 1.01 to 1.5 times, more preferably 1.05 to 1.5 times, and further preferably 1.1 to 1.3 times. It is double.
  • the long base material on which the long alignment film is formed passes through the coating device 211B.
  • the polarizing film composition (containing the polymerizable liquid crystal compound) is coated on the long alignment film by the coating device 211B to form a second coating film (step d1).
  • a second drying film is formed (step d2).
  • the drying furnace 212B may consist of a plurality of zones having different set temperatures, or may have a plurality of drying furnaces having different set temperatures installed in series. ..
  • the polymerizable liquid crystal compound contained in the polarizing film composition forms a liquid crystal phase, and the dichroic dye is oriented.
  • the polymerizable liquid crystal compound contained in the second dry film forms a liquid crystal phase and is irradiated with light by the light irradiation device 213B, the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal phase and is long.
  • a polarizing film is formed (step d3).
  • the long polarizing film thus obtained is wound around the second winding core 220A, and the form of the second roll 220 is obtained.
  • the winding may be performed using an appropriate spacer.
  • the long base material is in the order of the coating device 211A, the drying furnace 212A, the polarizing irradiation device 213A, the heating furnace 214, the nip roll 215, the coating device 211B, the drying furnace 212B, and the light irradiation device 213B from the first roll 210.
  • a long polarizing film can be continuously produced in the Roll to Roll format.
  • a method of continuously manufacturing from a long base material to a long polarizing film is shown, but it can also be manufactured by another method.
  • the long base material is unwound from the first roll 210, passed through the coating device 211A, the drying furnace 212A, the polarizing irradiation device 213A, the heating furnace 214, and the nip roll 215 in this order, and wound around the winding core.
  • a roll-shaped elongated alignment film is continuously produced, and then the obtained roll-shaped elongated alignment film is unwound and passed through the coating device 211B, the drying furnace 212B and the light irradiation device 213B in this order.
  • a long polarizing film may be manufactured.
  • a circular polarizing plate may be manufactured by laminating, but a long circular polarizing plate is continuously manufactured by preparing a third roll in which a long retardation film is wound around a winding core. You can also do it.
  • the long polarizing film of the present invention is continuously unwound from the second roll 220, and the long position is continuously wound from the third roll 230 in which the long retardation film is wound.
  • the step of unwinding the retardation film, the step of continuously laminating a long polarizing film and a long retardation film to obtain a long circular polarizing plate, and the obtained long circular polarizing film. Is wound around a fourth winding core 240A to obtain a fourth roll 240. This method is so-called Roll to Roll bonding.
  • the long polarizing film and the long retardation film can be bonded together using an appropriate adhesive.
  • the long polarizing film obtained as described above can be cut as needed and used for various display devices.
  • the long polarizing film and the polarizing film cut out from the long polarizing film are usually attached to the display device via an adhesive or a pressure-sensitive adhesive.
  • the elongated polarizing film is continuously attached to the display device, and more preferably continuously attached to a plurality of display devices.
  • the display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source.
  • the display device including the long polarizing film of the present invention or the polarizing film cut out from the long polarizing film of the present invention is, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, or an inorganic electroluminescence (EL) display.
  • EL organic electroluminescence
  • EL inorganic electroluminescence
  • electron emission display devices for example, electric field emission display device (FED), surface electric field emission display device (SED)), electronic paper (display device using electronic ink or electrophoresis element, plasma display device, projection type display device ( Examples thereof include a grating light valve (GLV) display device, a display device having a digital micromirror device (DMD)) and a piezoelectric ceramic display.
  • the liquid crystal display device includes a transmissive liquid crystal display device, a transflective liquid crystal display device, and a reflective one. It includes any of a type liquid crystal display device, a direct-view type liquid crystal display device, a projection type liquid crystal display device, and the like.
  • These display devices may be a display device for displaying a two-dimensional image or a three-dimensional image. It may be a three-dimensional display device.
  • the long polarizing film of the present invention and the polarizing film cut out from the long polarizing film of the present invention are particularly the organic electroluminescence (EL) display device and the inorganic electroluminescence (EL). ) Effectively used for display devices such as display devices and display devices including touch panels.
  • Example 1 ⁇ Preparation of alignment film composition> The following components were mixed, and the obtained mixture was stirred at 80 ° C. for 1 hour to obtain an alignment film composition.
  • the following photo-oriented materials were synthesized by the method described in JP2013-33248. Photo-oriented material (2 parts): Solvent (98 parts): o-xylene
  • polarizing film composition ⁇ Preparation of polarizing film composition> The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a polarizing film composition.
  • dichroic dye the azo dye described in Examples of JP2013-101328A was used.
  • a long roll-shaped triacetyl cellulose film with a width of 640 mm (KC4UY-TAC thickness 40 ⁇ m manufactured by Konica Minolta Co., Ltd.) is continuously unwound at a speed of 8 m / min, and after plasma treatment is applied to the film surface, Slot Daiko
  • the alignment film composition was discharged at a flow rate of 16 ml / min using a tar to form a first coating film in a width of 400 mm at the center of the film (step (a)). Further, the solvent was removed by transporting the mixture in a ventilation drying oven set at 100 ° C. for 2 minutes to form a first drying film (step (b)).
  • the first dry film is irradiated with polarized UV light so as to be parallel to the transport direction of the film so as to have an intensity of 20 mJ / cm 2 (313 nm standard) to impart an orientation regulating force.
  • a long alignment film was formed (step (c)). The direction of the orientation regulating force of the long alignment film was orthogonal to the transport direction.
  • the obtained alignment film laminate of the long base material and the long alignment film was conveyed in a heating furnace set at 80 ° C. and having a pair of nip rolls inside over 0.5 minutes, and when passing through the nip rolls, 1 1. Uniaxial stretching was performed in the transport direction at a stretching ratio of 1 (step (e)). The nip roll was placed in a position to reach 0.3 minutes after being introduced into the heating furnace.
  • the polarizing film composition was discharged on the long alignment film of the alignment film laminate at a flow rate of 24 ml / min using a slot die coater, and a second coating film was formed in a width range of 400 mm at the center of the film (.
  • Step (d1) the solvent was removed by transporting the mixture in a ventilation drying oven set at 110 ° C. over 2 minutes to form a second drying film (step (d2)).
  • a long polarizing film was formed by irradiating UV light at 1000 mJ / cm 2 (365 nm standard) to cure the polymerizable liquid crystal compound contained in the second dry film (step (d3)).
  • it was continuously wound into a roll to obtain a long polarizing film of Example 1 having an absorption axis in a direction perpendicular to the transport direction.
  • the length of the long polarizing film in the longitudinal direction was 200 m.
  • the order parameter (S 1 ) was calculated for each measurement region according to the above equation (2).
  • the average value of the 20 order parameters was taken as the average value of the order parameters (S 1ave) .
  • the order parameter difference ( ⁇ S 1 ) was calculated from the difference between the largest order parameter (S 1max ) and the smallest order parameter (S 1min ) among the order parameters calculated at 20 locations.
  • Table 1 shows the average value (S 1ave ) of the order parameters calculated as described above and the order parameter difference ( ⁇ S 1 ).
  • the polarization degree and transmittance of the sample were measured as follows. Double beam for the transmittance (T1) in the transmission axis direction and the transmittance (T2) in the absorption axis direction using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with a folder with a polarizer set. It was measured in the wavelength range of 2 nm step 380 to 680 nm by the method. From the measured values of the transmittance (T1) in the transmission axis direction and the transmittance (T2) in the absorption axis direction of each wavelength, the single transmittance and the degree of polarization can be determined using the following equations (7) and (8).
  • the obtained long polarizing film was arranged so that the absorption axis was orthogonal to the iodine-PVA polarizing plate (SRW842A; manufactured by Sumitomo Chemical Co., Ltd.), and 40 cm ⁇ 40 cm on the direct backlight.
  • the color of the polarizing film was evaluated according to the following criteria by visually observing the inside of an arbitrary region of the above.
  • B Although there is partial unevenness, the unevenness is thin.
  • C There is partial unevenness, and the unevenness is clear.
  • D The unevenness is clear overall.
  • Example 2 The long polarizing film of Example 2 was manufactured by the same method as that of the long polarizing film of Example 1 except that the draw ratio of the uniaxial stretching in the step (e) was 1.2 times. The obtained long polarizing film was evaluated by the same method as in Example 1.
  • Example 3 In the first embodiment, the step (e) was performed at the timing after the step (c) and before the step (d1), whereas in the third embodiment, the step (e) was performed after the step (d3). Except for the points, the long polarizing film of Example 3 was manufactured by the same method as that of the long polarizing film of Example 1. The obtained long polarizing film was evaluated by the same method as in Example 1.
  • Example 4 In the second embodiment, the step (e) was performed at the timing after the step (c) and before the step (d1), whereas in the fourth embodiment, the step (e) was performed after the step (d3). Except for the points, the long polarizing film of Example 4 was manufactured by the same method as the method for manufacturing the long polarizing film of Example 2. The obtained long polarizing film was evaluated by the same method as in Example 1.
  • Comparative Example 1 The long polarizing film of Comparative Example 1 was manufactured by the same method as that of the long polarizing film of Example 1 except that the step (e) was not performed. The obtained long polarizing film was evaluated by the same method as in Example 1.

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PCT/JP2020/010747 2019-03-28 2020-03-12 偏光フィルムの製造方法及び偏光フィルム WO2020195881A1 (ja)

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JP2009294521A (ja) * 2008-06-06 2009-12-17 Nippon Oil Corp 位相差フィルム、位相差フィルムの製造方法、偏光板および液晶表示装置
JP2013228706A (ja) * 2012-03-30 2013-11-07 Sumitomo Chemical Co Ltd 円偏光板及びその製造方法
JP2015165302A (ja) * 2014-02-07 2015-09-17 住友化学株式会社 長尺偏光フィルムの製造方法
WO2017094253A1 (ja) * 2015-11-30 2017-06-08 富士フイルム株式会社 位相差フィルムおよびその製造方法、位相差フィルムを備えた偏光板および液晶表示装置
US20180355181A1 (en) * 2017-06-12 2018-12-13 Samsung Display Co. Ltd. Dye compound, polarizer using the dye compound, and display device using the dye compound

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DE602004031142D1 (de) 2003-11-06 2011-03-03 Sumitomo Chemical Co Dichroitischer guest-host-polarisierer mit einem orientierten polymerfilm

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JP2002528758A (ja) * 1998-10-28 2002-09-03 オプティヴァ インコーポレイテッド 二色性偏光子及びその製造方法
JP2009288440A (ja) * 2008-05-28 2009-12-10 Nippon Oil Corp 位相差フィルム、位相差フィルムの製造方法、偏光板および液晶表示装置
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JP2013228706A (ja) * 2012-03-30 2013-11-07 Sumitomo Chemical Co Ltd 円偏光板及びその製造方法
JP2015165302A (ja) * 2014-02-07 2015-09-17 住友化学株式会社 長尺偏光フィルムの製造方法
WO2017094253A1 (ja) * 2015-11-30 2017-06-08 富士フイルム株式会社 位相差フィルムおよびその製造方法、位相差フィルムを備えた偏光板および液晶表示装置
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