WO2014168259A1 - 光学異方性フィルムの製造方法 - Google Patents
光学異方性フィルムの製造方法 Download PDFInfo
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- WO2014168259A1 WO2014168259A1 PCT/JP2014/060885 JP2014060885W WO2014168259A1 WO 2014168259 A1 WO2014168259 A1 WO 2014168259A1 JP 2014060885 W JP2014060885 W JP 2014060885W WO 2014168259 A1 WO2014168259 A1 WO 2014168259A1
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- optically anisotropic
- anisotropic film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
- B29D11/00788—Producing optical films
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- 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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- 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
- B32B2551/00—Optical elements
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- 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 an optically anisotropic film.
- a member including an optically anisotropic film such as a polarizing plate or a retardation plate is used.
- an optically anisotropic film an optically anisotropic film produced by applying a composition containing a liquid crystal compound onto a substrate is known.
- Patent Document 1 describes a method for producing an optically anisotropic film in which a composition containing a liquid crystal compound is applied and dried on a substrate subjected to an alignment treatment. The conditions are not described.
- the present invention includes the following inventions.
- a method for producing an optically anisotropic film comprising the following steps (1) to (3): (1) Step of applying optical anisotropic layer forming composition to substrate surface or alignment layer surface formed on substrate surface (2) Drying applied optical anisotropic layer forming composition Step of forming a dry film (3) Step of forming an optically anisotropic film by cooling the dry film at a rate of 6 ° C./sec or more [2] Optical by cooling at a rate of 6 ° C./sec or more The method for producing an optically anisotropic film according to [1], wherein after forming the anisotropic film, the cooling rate is gradually lowered.
- [3] The method for producing an optically anisotropic film according to [1] or [2], further comprising the step of (4) irradiating the optically anisotropic film with light. [4] It takes 2 seconds to 10 minutes for the cooling rate to reach 0.5 ° C / sec after the cooling rate of 6 ° C / sec or higher is started. The method for producing an optically anisotropic film according to any one of [1] to [3]. [5] The method for producing an optically anisotropic film according to any one of [1] to [4], wherein the substrate is a roll-shaped substrate, and the steps (1) to (3) are continuously performed. .
- Step of applying optical anisotropic layer forming composition to substrate surface or alignment layer surface formed on substrate surface (2) Drying applied optical anisotropic layer forming composition Step (3) for forming a dry film (3) Step for forming an optically anisotropic film by cooling the dry film at a rate of 6 ° C./sec or more
- a polarizing plate having the optically anisotropic film according to any one of [8] to [10].
- a display device comprising the optically anisotropic film according to any one of [8] to [10].
- an optically anisotropic film excellent in transparency can be produced.
- the method for producing an optically anisotropic film of the present invention includes the following steps (1) to (3).
- a transparent substrate is usually used as the substrate.
- a transparent substrate means a substrate having translucency capable of transmitting light, particularly visible light, and the translucency is a transmittance with respect to a light beam having a wavelength of 380 to 780 nm of 80% or more.
- the transparent substrate include glass and a translucent resin substrate, and a translucent resin substrate is preferable.
- a film-like substrate is usually used, and among them, a film-roll substrate that can be unwound and wound by a roll-to-roll is particularly preferable in terms of productivity.
- Examples of the resin constituting the translucent resin base material include polyolefins such as polyethylene, polypropylene and norbornene polymers; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; cellulose ester; polyethylene naphthalate; And sulfone; polyether sulfone; polyether ketone; polyphenylene sulfide; and polyphenylene oxide.
- the substrate may be surface treated.
- Surface treatment methods include a method of treating the surface of the substrate with corona or plasma under vacuum or atmospheric pressure, a method of laser treating the surface of the substrate, a method of treating the surface of the substrate with ozone, and a surface of the substrate.
- a method of performing a chemical treatment or a method of flame-treating the surface of a substrate, a method of applying a primer to apply a coupling agent to the surface of the substrate, and attaching a reactive monomer or a reactive polymer to the surface of the substrate examples thereof include a graft polymerization method in which a reaction is performed by irradiation with radiation, plasma or ultraviolet rays. Among them, a method of corona or plasma treatment of the substrate surface under vacuum or atmospheric pressure is preferable.
- a method of performing a surface treatment of a substrate by installing a substrate between opposed electrodes under a pressure near atmospheric pressure and generating corona or plasma, A method of flowing a gas between the electrodes facing each other, converting the gas into a plasma between the electrodes, and spraying the plasmad gas onto the substrate; and There is a method in which glow discharge plasma is generated under low pressure conditions to perform surface treatment of the substrate.
- a substrate is placed between opposed electrodes, and corona or plasma is generated to treat the surface of the substrate, or a gas is flowed between the opposed electrodes.
- a method is preferred in which the gas is converted into plasma and the plasmaized gas is sprayed onto the substrate.
- Such surface treatment with corona or plasma is usually performed by a commercially available surface treatment apparatus.
- An alignment layer is preferably formed on the substrate surface.
- a method for forming an alignment layer on the surface of the substrate a method using an orientation polymer that provides an alignment regulating force only by coating or rubbing the surface, an alignment regulating force is imparted by irradiating polarized light. Examples include a method using a photo-alignable polymer, a method in which silicon oxide is obliquely deposited on the substrate surface, and a method in which a monomolecular film having a long-chain alkyl group is formed using the Langmuir-Blodgett method (LB method). It is done.
- a method using an alignment polymer is preferable from the viewpoints of alignment uniformity and productivity of the liquid crystal compound.
- orientation polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule and hydrolyzates thereof, polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, Examples include polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters. These polymers may be used alone, may be a composition combining a plurality of types of polymers, or may be a copolymer combining a plurality of types of polymers.
- polymers can be easily obtained by subjecting the monomer to polycondensation such as dehydration or dealcoholization, chain polymerization such as radical polymerization, anionic polymerization, and cationic polymerization, coordination polymerization, or ring-opening polymerization.
- orientation polymers include Sanever (registered trademark, manufactured by Nissan Chemical Industries), Optomer (registered trademark, manufactured by JSR), and the like.
- An alignment layer formed from such an alignment polymer facilitates liquid crystal alignment of the liquid crystal compound.
- Various liquid crystal alignments such as horizontal alignment, vertical alignment, hybrid alignment, and tilt alignment can be controlled depending on the type of the alignment polymer and rubbing conditions. In the present invention, the alignment polymer and rubbing for vertically aligning the liquid crystal compound are possible. Conditions apply.
- the rubbing method includes a method in which a rubbing cloth is wound and a rotating rubbing roll is brought into contact with an oriented polymer on a substrate which is carried on a stage.
- Examples of the photo-alignment polymer include a polymer having a photosensitive structure.
- a polymer having a photosensitive structure When a polymer having a photosensitive structure is irradiated with polarized light, the photosensitive structure in the irradiated portion is isomerized or cross-linked so that the photo-alignable polymer is aligned, and an alignment regulating force is imparted to the film made of the photo-alignable polymer.
- the Examples of the photosensitive structure include an azobenzene structure, a maleimide structure, a chalcone structure, a cinnamic acid structure, a 1,2-vinylene structure, a 1,2-acetylene structure, a spiropyran structure, a spirobenzopyran structure, and a fulgide structure.
- the photoalignable polymer forming the alignment layer may be used alone, a plurality of polymers having different structures may be combined, or a copolymer having a plurality of different photosensitive structures may be used.
- a photo-alignment polymer is obtained by subjecting a monomer having a photosensitive structure to polycondensation such as dehydration or dealcoholization, chain polymerization such as radical polymerization, anion polymerization, or cationic polymerization, coordination polymerization, or ring-opening polymerization.
- Examples of the photo-alignment polymer include light described in Japanese Patent No. 4450261, Japanese Patent No. 4011652, Japanese Patent Application Laid-Open No. 2010-49230, Japanese Patent No. 444090, Japanese Patent Application Laid-Open No. 2007-156439, and Japanese Patent Application Laid-Open No. 2007-232934.
- An orientation polymer is mentioned.
- the photo-alignment polymer a polymer that forms a crosslinked structure by irradiation with polarized light is preferable from the viewpoint of durability.
- Examples of the method of irradiating polarized light include a method using an apparatus described in JP-A-2006-323060.
- a patterned alignment film can be formed by repeatedly irradiating polarized light such as linearly polarized ultraviolet light for each region through a photomask corresponding to a desired plurality of regions.
- polarized light such as linearly polarized ultraviolet light
- a photomask usually, a light shielding pattern provided on a film of quartz glass, soda lime glass or polyester is used. The exposed light is blocked in the portion covered with the light shielding pattern, and the exposed light is transmitted in the uncovered portion. Quartz glass is preferable in that the influence of thermal expansion is small.
- the irradiated light is preferably ultraviolet light.
- the alignment polymer and the photo-alignment polymer are usually applied to the substrate surface as a composition for forming an alignment layer dissolved in a solvent.
- a solvent water; alcohol solvent such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene glycol methyl ether acetate, Ester solvents such as ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone, N-methyl-2-pyrrolidone; aliphatic hydrocarbon solvents such as pentane, hexane, heptane; Aromatic hydrocarbon solvents such
- the content of the solvent contained in the composition for forming an alignment layer is usually 10 parts by mass to 100000 parts by mass, preferably 1000 parts by mass to 50000 parts by mass, more preferably 2000 parts per 100 parts by mass of the solid content. Parts by mass to 20000 parts by mass.
- Examples of the method of applying the alignment layer forming composition to the substrate surface include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method.
- coating using coaters such as a dip coater, a bar coater, a spin coater, is also mentioned.
- the solvent is removed by drying.
- Drying methods include natural drying, ventilation drying, heat drying, vacuum drying, and a combination of these.
- the drying temperature is preferably 10 to 250 ° C, more preferably 25 to 200 ° C.
- the drying time is preferably 5 seconds to 60 minutes, more preferably 10 seconds to 30 minutes, depending on the type of solvent.
- the thickness of the alignment layer is usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm. It is preferable that the thickness of the alignment layer be in the above range since the liquid crystal compound can be aligned in a desired direction or angle on the alignment layer.
- composition for forming optically anisotropic layer includes a liquid crystal compound and a solvent.
- the liquid crystal compound is preferably a polymerizable liquid crystal compound.
- the polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group.
- liquid crystal compound examples include a compound containing a group represented by the formula (X) (hereinafter sometimes referred to as “compound (X)”).
- compound (X) a group represented by the formula (X)
- P 11 represents a polymerizable group or a hydrogen atom.
- a 11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group.
- the hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group.
- the hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
- B 11 is —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NR 16 —, —NR 16 —CO—, —CO—, -CS- or a single bond is represented.
- R 16 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- E 11 represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and hydrogen contained in the alkoxy group The atom may be substituted with a halogen atom.
- —CH 2 — constituting the alkanediyl group may be replaced by —O— or —CO—.
- the number of carbon atoms of the aromatic hydrocarbon group and alicyclic hydrocarbon group of A 11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and preferably 5 or 6. Particularly preferred.
- a 11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.
- E 11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms.
- —CH 2 — constituting the alkanediyl group may be replaced by —O—.
- a linear alkanediyl group having 1 to 12 carbon atoms such as: —CH 2 —CH 2 —O—CH 2 —CH 2 —, —CH 2 —CH 2 —
- B 11 is preferably —O—, —S—, —CO—O—, or —O—CO—, and more preferably —CO—O—.
- B 12 and B 13 are each independently —O—, —S—, —C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —, —O.
- —C ( ⁇ O) —O— is preferable, and —O— or —O—C ( ⁇ O) —O— is more preferable.
- P 11 is preferably a polymerizable group.
- the polymerizable group is preferably a radically polymerizable group or a cationically polymerizable group in terms of high polymerization reactivity, particularly photopolymerization reactivity, and is easy to handle and easy to produce a liquid crystal compound.
- the polymerizable group is preferably a group represented by the following formula (P-11) to formula (P-15). [In the formulas (P-11) to (P-15), R 17 to R 21 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. ]
- P 11 is preferably a group represented by formula (P-14) to formula (P-20), more preferably a vinyl group, a p-stilbene group, an epoxy group or an oxetanyl group. More preferably, the group represented by P 11 -B 11- is an acryloyloxy group or a methacryloyloxy group.
- Examples of compound (X) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).
- P 11 -B 11 -E 11 -B 12 -A 11 -B 1 -A 12 -B 14 -A 13 -B 15 -A 14 -B 16 -E 12 -B 17 -P 12 (I) P 11 -B 11 -E 11 -B 12 -A 11 -B 13 -A 12 -B 14 -A 13 -B 15 -A 14 -F 11 (II) P 11 -B 11 -E 11 -B 12 -A 11 -B 13 -A 12 -B 14 -A 13 -B 15 -E 12 -B 17 -P 12 (III) P 11 -B 11 -E 11 -B 12 -A 11 -B 13 -A 12 -B 14 -A 13 -F 11 (IV) P 11 -B 11 -E 11
- F 11 is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxy group, a methylol group, a formyl group, a sulfo group.
- liquid crystal compounds include “3.8.6 Network (completely cross-linked type)”, “6.5” of Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). .1 Liquid Crystal Material b. Polymerizable Nematic Liquid Crystal Material ”, JP 2010-31223 A, JP 2010-270108 A, JP 2011-6360 A, and JP 2011-207765 A The liquid crystal compound is mentioned.
- the compound (X) include the following formula (I-1) to formula (I-4), formula (II-1) to formula (II-4), formula (III-1) to formula (III- 26), compounds represented by formula (IV-1) to formula (IV-26), formula (V-1) to formula (V-2) and formula (VI-1) to formula (VI-6). It is done.
- k1 and k2 each independently represents an integer of 2 to 12.
- solvent an organic solvent that dissolves the solid content of the composition for forming an optically anisotropic layer such as a liquid crystal compound is preferable, and when the composition for forming an optically anisotropic layer contains a polymerizable liquid crystal compound, An organic solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is more preferable.
- alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, phenol; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, Ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane, and heptane Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile;
- the optical anisotropic layer forming composition may contain a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, a chiral agent, a reactive additive, and the like.
- Polymerization initiator As the polymerization initiator, a photopolymerization initiator is preferable, and a photopolymerization initiator that generates radicals by light irradiation is more preferable.
- the polymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, triazine compounds, iodonium salts, and sulfonium salts.
- Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all are made by Ciba Japan Co., Ltd.), Sake All BZ, Sake All Z, Sake All BEE (all are all Seiko) Chemical Co., Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), kayakure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152, Adekaoptomer SP-170 (all above, ADEKA Corporation Product), TAZ-A, TAZ-PP (manufactured by Nippon Siebel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).
- ⁇ -acetophenone compounds are preferable, and examples of ⁇ -acetophenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholino Phenyl) -2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one and the like, more preferably 2- And methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one.
- Examples of commercially available products of ⁇ -acetophenone compounds include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Ltd.), Sequol BEE (manufactured by Seiko Chemical Co., Ltd.), and the like.
- the content of the polymerization initiator 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 liquid crystal compound. If it is in the said range, since it is hard to disturb the orientation of a liquid crystal compound, it is preferable.
- Polymerization inhibitors include hydroquinones having substituents such as hydroquinone and alkyl ethers; catechols having substituents such as alkyl ethers such as butylcatechol; pyrogallols, 2,2,6,6-tetramethyl-1- Radical scavengers such as piperidinyloxy radicals; thiophenols; ⁇ -naphthylamines and ⁇ -naphthols.
- the content of the polymerization inhibitor in the composition for forming an optically anisotropic layer 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 liquid crystal compound. It is. If it is in the said range, since it is hard to disturb the alignment of a liquid crystal compound, it is preferable.
- Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracene having a substituent such as anthracene and alkyl ether; phenothiazine; and rubrene.
- xanthones such as xanthone and thioxanthone
- anthracene having a substituent such as anthracene and alkyl ether
- phenothiazine phenothiazine
- rubrene a photosensitizer
- the content of the photosensitizer 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 liquid crystal compound.
- Leveling agent examples include organic modified silicone oil-based, polyacrylate-based and perfluoroalkyl-based leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all are manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all, Momentive Performance Materials Japan GK) Manufactured), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (above, Manufactured by Sumitomo 3M Co
- a smoother optically anisotropic film can be obtained by the leveling agent. Moreover, in the production process of the optically anisotropic film, the fluidity of the composition for forming an optically anisotropic layer can be controlled, and the crosslinking density of the optically anisotropic film can be adjusted.
- the content of the leveling agent is usually 0.1 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal compound.
- chiral agent examples include known chiral agents (for example, liquid crystal device handbook, Chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 142nd Committee, 1989). It is done.
- the chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used as the chiral agent.
- the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
- PALIOCOLOR (registered trademark) LC756 manufactured by BASF Japan Ltd. are preferable.
- the content of the chiral agent is usually 0.1 to 30 parts by mass, preferably 1.0 to 25 parts by mass with respect to 100 parts by mass of the liquid crystal compound. If it is in the said range, since it is hard to disturb alignment of a liquid crystal compound, it is preferable.
- the reactive additive is preferably one having a carbon-carbon unsaturated bond and an active hydrogen reactive group in the molecule.
- the “active hydrogen reactive group” as used herein is a group reactive to a group having active hydrogen such as a carboxyl group (—COOH), a hydroxyl group (—OH), an amino group (—NH 2 ), and the like. Typical examples include glycidyl group, oxazoline group, carbodiimide group, aziridine group, imide group, isocyanato group, thioisocyanato group, maleic anhydride group and the like.
- the reactive additive it is preferable that at least two active hydrogen reactive groups are present. In this case, a plurality of active hydrogen reactive groups may be the same or different.
- the carbon-carbon unsaturated bond of the reactive additive may be a carbon-carbon double bond, a carbon-carbon triple bond, or a combination thereof, but is preferably a carbon-carbon double bond.
- the reactive additive preferably contains a carbon-carbon unsaturated bond as a vinyl group and / or a (meth) acryl group.
- the active hydrogen reactive group is preferably at least one selected from the group consisting of an epoxy group, a glycidyl group and an isocyanato group, and a reactive additive having an acrylic group and an isocyanato group is particularly preferable.
- reactive additives include compounds having (meth) acrylic groups and epoxy groups, such as methacryloxyglycidyl ether and acryloxyglycidyl ether; (meth) acrylic groups and oxetane, such as oxetane acrylate and oxetane methacrylate.
- a compound having a group a compound having a (meth) acryl group and a lactone group, such as lactone acrylate and lactone methacrylate; a compound having a vinyl group and an oxazoline group, such as vinyl oxazoline and isopropenyl oxazoline; isocyanatomethyl acrylate , Oligomers of compounds having (meth) acrylic groups and isocyanato groups, such as isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate and 20 isocyanatoethyl methacrylate And the like. Moreover, the compound etc.
- methacryloxyglycidyl ether methacryloxyglycidyl ether, acryloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyl oxazoline, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate and the above oligomers are preferred, isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate and the aforementioned oligomers are particularly preferred.
- This preferable reactive additive is represented by the following formula (Y), for example.
- n represents an integer of 1 to 10
- R 1 ′ is a divalent aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 5 to 20 carbon atoms.
- Two R 2 ′ s in each repeating unit are groups represented by one of —NH— and the other of N—C ( ⁇ O) —R 3 ′.
- R 3 ′ represents a group having a hydroxyl group or a carbon-carbon unsaturated bond.
- at least one R 3 ′ is a group having a carbon-carbon unsaturated bond.
- a compound represented by the following formula (YY) (hereinafter, sometimes referred to as “compound (YY)”) is particularly preferable (n Is as defined above.
- compound (YY) a commercially available product can be used as it is or after purification as necessary. Examples of commercially available products include Laromer (registered trademark) LR-9000 (manufactured by BASF).
- the content of the reactive additive is usually 0.1 to 30 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal compound.
- Examples of the method for applying the optically anisotropic layer forming composition to the substrate surface or the alignment layer surface formed on the substrate surface include the same method as the method for applying the alignment layer forming composition.
- the CAP coating method, the inkjet method, the dip coating method, the slit coating method, the die coating method, and the coating method using a bar coater are capable of continuously applying the composition for forming an optical anisotropic layer on the surface of the alignment layer in the RolltoRoll format. Is preferred.
- the composition for forming an alignment layer is applied to the surface of the substrate, an alignment layer is formed on the surface of the substrate, and the composition for forming an optical anisotropic layer is further formed on the surface of the obtained alignment layer. It can also be applied continuously.
- Examples of the method for drying the applied optical anisotropic layer forming composition include a heating method, a heating and ventilation method, a heating and decompression method, and a combination of these methods. Among them, a method of heating in the staying gas layer is preferable.
- the drying temperature is usually in the range of 40 ° C. to 150 ° C., preferably in the range of 80 ° C. to 140 ° C., and more preferably in the range of 90 ° C. to 130 ° C.
- the drying temperature is preferably a temperature at which the solvent can be removed if the liquid crystal compound has a solid-liquid crystal phase transition temperature at a temperature lower than the temperature at which the solvent can be removed, and the liquid crystal compound can be removed by the solvent. As long as it has a solid-liquid crystal phase transition temperature at a temperature higher than the temperature, a temperature equal to or higher than the solid-liquid crystal phase transition temperature of the liquid crystal compound is preferable.
- the air layer during heating is usually composed of air, but may be composed of an inert gas such as nitrogen and carbon dioxide.
- the drying time is usually 10 seconds to 60 minutes, preferably 30 seconds to 30 minutes.
- the liquid crystal alignment state of the liquid crystal compound includes horizontal alignment, vertical alignment, hybrid alignment, tilted alignment, and the like, and is preferably vertical alignment.
- Expressions such as horizontal and vertical represent the alignment direction of the major axis of the liquid crystal compound with respect to the substrate surface.
- the vertical alignment is to have the long axis of the liquid crystal compound in a direction perpendicular to the substrate surface.
- the state of liquid crystal alignment varies depending on the properties of the alignment layer and the liquid crystal compound, and the combination can be arbitrarily selected.
- the alignment layer is a material that expresses horizontal alignment as an alignment regulating force
- the liquid crystal compound can form horizontal alignment or hybrid alignment
- the alignment layer is a material that expresses vertical alignment
- the liquid crystal compound can be aligned vertically or A tilted orientation can be formed.
- the alignment regulating force can be arbitrarily adjusted depending on the surface state and rubbing conditions when the alignment film is formed of an alignment polymer, and polarized irradiation conditions when it is formed of a photo-alignment polymer. It is possible to adjust arbitrarily by such as.
- the liquid crystal alignment can also be controlled by selecting the physical properties of the liquid crystal compound such as surface tension and liquid crystallinity.
- the surface of the substrate opposite to the surface on which the alignment layer is formed is brought into contact with the air layer for cooling.
- Method a method of bringing the surface of the substrate opposite to the surface on which the alignment layer is formed into contact with or close to the cooling plate, and a surface of the substrate on which the dry film is formed in contact with the gas layer for cooling And the like.
- a method in which the surface on the side opposite to the surface on which the alignment layer on the substrate side is formed and the surface on the side on which the dry film is formed is brought into contact with the gas layer for cooling.
- the cooling rate is preferably 6 to 40 ° C./sec.
- the temperature of the dried film before cooling at a rate of 6 ° C./sec or more is the above-described drying temperature (usually in the range of 40 ° C. to 150 ° C., preferably in the range of 80 ° C. to 140 ° C., more preferably 90 ° C. C. to 130 ° C.).
- the temperature of the dried film after cooling at a rate of 6 ° C./sec or more is preferably 0 ° C. to 30 ° C.
- the air layer nitrogen or air can be used, and preferably air.
- the temperature of the gas layer is usually 0 ° C. to 30 ° C., preferably 23 ° C. to 25 ° C.
- the gas in the gas layer may stay or circulate, but staying is preferable because temperature unevenness during cooling is less likely to occur.
- the temperature of the cooling plate is usually 0 ° C. to 30 ° C., and it is preferable that condensation does not occur due to cooling.
- the cooled dried film When the cooled dried film exhibits a liquid crystal phase such as a nematic phase, it exhibits birefringence due to monodomain alignment. Moreover, by cooling at a rate of 6 ° C./sec or more, the monodomain orientation is stabilized and an optically anisotropic film with little unevenness is obtained.
- the temperature of the optically anisotropic film and the liquid crystal compound contained in the optically anisotropic film is preferably 0 to 30 ° C., more preferably 23 to 25 ° C. By cooling to this temperature range, an optically anisotropic film having few alignment defects of the liquid crystal compound and excellent in transparency can be obtained.
- the cooling rate After forming the optically anisotropic film by cooling at a rate of 6 ° C./sec or more, it is preferable to gradually lower the cooling rate.
- a method for gradually decreasing the cooling rate the same method as described above may be used.
- the time from when the cooling at a rate of 6 ° C./sec or more is started to when the cooling rate is gradually lowered and the cooling rate reaches 0.5 ° C./sec is preferably 2 seconds to 10 minutes.
- the cooling rate reaches 0.5 ° C./sec, it means that the temperature of the dry film has reached a substantially constant temperature by cooling.
- cooling rate examples include a method of bringing a thermocouple into contact, a method of observing with an infrared thermography, a method of performing detection with an infrared sensor, and the like.
- the time is preferably 2 seconds to 5 minutes, more preferably 2 seconds to 1 minute, and further preferably 2 seconds to 30 seconds. If it is in the said range, the optically anisotropic film excellent in transparency with few orientation defects can be obtained.
- the thickness of the optically anisotropic film may be appropriately adjusted depending on the application or the retardation value of the laminated display device, but is usually 0.1 ⁇ m to 10 ⁇ m, preferably in terms of reducing photoelasticity. It is 0.2 ⁇ m to 5 ⁇ m.
- the optically anisotropic film is preferably irradiated with light.
- the polymerizable liquid crystal compound is polymerized to obtain an immobilized optically anisotropic film.
- a fixed optically anisotropic film is preferable because the orientation of the liquid crystal compound is fixed and is not easily affected by the change in birefringence due to heat.
- the polymerization can be carried out at a low temperature, which is preferable because the selection range of the substrate to be used is widened in terms of heat resistance.
- the polymerization is usually performed by irradiating visible light, ultraviolet light or laser light, but is preferably performed by irradiating ultraviolet light.
- the time from the start of cooling at a rate of 6 ° C./sec or higher to the light irradiation is preferably 2 seconds to 10 minutes. More preferably, it is 2 seconds to 5 minutes, more preferably 2 seconds to 1 minute, and further preferably 2 seconds to 30 seconds. If it is in the said range, an optically anisotropic film with few orientation defects can be formed.
- the step (3) is preferably performed with light shielding. That is, the period from the cooling to the light irradiation is preferably performed while shielding light. More preferably, the step (2) is also performed with light shielding. That is, it is more preferably performed while shielding the light from the drying of the applied optically anisotropic layer forming composition to light irradiation.
- the light shielding method include a method of covering a film transport zone from drying to obtaining an optically anisotropic film with a light shielding film, or covering with a member that completely blocks light.
- the composition for forming an optically anisotropic layer contains a photopolymerization initiator, it is preferable to block light corresponding to the photosensitive wavelength of the photopolymerization initiator. For example, light having a short wavelength of 500 nm or less is not directly applied to the film. More preferably.
- the production method of the present invention is preferably carried out continuously on a roll-shaped substrate.
- the production method for continuously producing in a roll form preferably includes the following steps (1) to (6): (1) a step of forming an alignment layer on the substrate unwound from the roll; (2) The process of apply
- the roll-like optically anisotropic film obtained by the above production method has little fluctuation in the liquid crystal alignment of the liquid crystal compound and is excellent in transparency.
- the optically anisotropic film manufactured by the manufacturing method of the present invention (hereinafter sometimes referred to as the present optically anisotropic film) is excellent in transparency in the visible light region and can be used as various display device members.
- liquid crystal compounds that are vertically aligned have a phase difference, so that linearly polarized light as seen from the oblique angle on the light exit side is converted to circularly polarized light or elliptically polarized light, or circularly polarized light or elliptically polarized light is linearly polarized light. It is useful as a retardation film that is used to convert the light into a linearly polarized light or to change the polarization direction of linearly polarized light.
- the optically anisotropic film may be used separately from the substrate or the substrate and the alignment layer.
- the optical anisotropic film having no base material or the base material and the alignment layer is usually combined with other members such as a polarizing film via an adhesive.
- a method of combining with other members via an adhesive a method of bonding the optically anisotropic film having no base material or a base material and an alignment film to other members using an adhesive, And after sticking this optical anisotropic film formed in the alignment layer surface formed in the base-material surface to other members using an adhesive agent, the method of removing a base material or a base material, and an alignment film Etc.
- the adhesive may be applied to the optically anisotropic film or may be applied to other members.
- This optically anisotropic film may be laminated in plural or in combination with other films. Laminating a plurality of the present optical anisotropic films having different alignment states of the liquid crystal compound, or combining the present optical anisotropic film and another film, a viewing angle compensation film, a viewing angle widening film, an antireflection film, It can be used as a polarizing plate, a circularly polarizing plate, an elliptically polarizing plate or a brightness enhancement film.
- the optically anisotropic film can change the optical properties depending on the alignment state of the liquid crystal compound, and includes a VA (vertical alignment) mode, an IPS (in-plane switching) mode, an OCB (optically compensated bend) mode, and a TN (twisted). nematic) mode, STN (super twisted nematic) mode and the like, and can be used as a retardation film for various liquid crystal display devices. Among them, it is preferable as a retardation film for an IPS (in-plane switching) liquid crystal display device.
- This optically anisotropic film the refractive index of the refractive index n y, in the thickness direction of the slow axis direction of the refractive indices n x in the plane, the direction perpendicular to the slow axis in the plane (fast axis direction) the case of a n z, can be classified as follows.
- This optically anisotropic film is particularly preferably used for a positive C plate.
- the front retardation value Re (549) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm.
- the value R th is generally in the range of -10 ⁇ -300 nm, preferably may be adjusted in the range of -20 ⁇ -200 nm.
- the front phase difference value Re (549) is preferably selected as appropriate in accordance with the characteristics of the liquid crystal cell.
- the thickness direction retardation value R th which means the refractive index anisotropy in the thickness direction of the optically anisotropic film is a retardation value R 50 measured by inclining 50 degrees with the in-plane fast axis as the tilt axis. And the in-plane retardation value R 0 .
- the retardation value R th in the thickness direction is the in-plane retardation value R 0
- the film thickness d the average of the film
- n 0 , n x , ny and nz can be obtained by the following formulas (9) to (11), and can be calculated by substituting these into formula (8).
- Rth [( nx + ny ) / 2- nz ] * d (8)
- R 0 (n x -n y ) ⁇ d (9)
- ny ′ ny ⁇ nz / [ ny 2 ⁇ sin 2 ( ⁇ ) + nz 2 ⁇ cos 2 ( ⁇ )] 1/2
- the optically anisotropic film is useful as a member constituting a polarizing plate.
- the polarizing plate of the present invention includes at least one of the present optically anisotropic film and may be included as a retardation film.
- Specific examples of the polarizing plate include polarizing plates shown in FIGS. 1 (a) to 1 (e).
- a polarizing plate 4a shown in FIG. 1 (a) is a polarizing plate in which a retardation film 1 and a polarizing film 2 are directly laminated, and a polarizing plate 4b shown in FIG. 1 (b) is a retardation film. 1 and the polarizing film 2 are the polarizing plates bonded together through adhesive layer 3 '.
- a polarizing plate 4d shown in FIG. 1 (d) is obtained by laminating a retardation film 1 and a retardation film 1 ′ via an adhesive layer 3, and further laminating a polarizing film 2 on the retardation film 1 ′. It is the made polarizing plate.
- a polarizing plate 4e shown in FIG. 1 (e) is obtained by bonding a retardation film 1 and a retardation film 1 ′ through an adhesive layer 3, and further bonding the retardation film 1 ′ and the polarizing film 2 together. It is a polarizing plate bonded through an agent layer 3 ′.
- Adhesive means a general term for an adhesive and / or an adhesive.
- the polarizing film 2 may be a film having a polarizing function.
- the film include a stretched film on which a dye having absorption anisotropy is adsorbed and a film coated with a dye having absorption anisotropy.
- the dye having absorption anisotropy include dichroic dyes such as iodine and azo compounds.
- a film coated with a dye having absorption anisotropy a film obtained by applying a composition containing a dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal compound, etc. Is mentioned.
- the film having a polarizing function preferably has a protective film on one side or both sides thereof.
- Examples of the protective film include the same ones as described above.
- stretched film on which the dye having absorption anisotropy is adsorbed include the polarizing plates described in Japanese Patent No. 3708062, Japanese Patent No. 4432487, and the like.
- film coated with the pigment having absorption anisotropy include polarizing films described in JP 2012-33249 A and the like.
- the adhesive forming the adhesive layer 3 and the adhesive layer 3 ′ is preferably an adhesive having high transparency and excellent heat resistance.
- adhesives include acrylic adhesives, epoxy adhesives, and urethane adhesives.
- This optically anisotropic film is useful as a member constituting a display device.
- a liquid crystal display device including a liquid crystal panel in which the optically anisotropic film and a liquid crystal panel are bonded together, and an organic electroluminescence (hereinafter, referred to as “optically anisotropic film” and a light emitting layer).
- an organic EL display device including a panel.
- a liquid crystal display device will be described as an embodiment of a display device provided with the optically anisotropic film.
- Examples of the liquid crystal display device include liquid crystal display devices 10a and 10b shown in FIGS. 2 (a) and 2 (b).
- the polarizing plate 4 and the liquid crystal panel 6 of the present invention are bonded together via an adhesive layer 5.
- the polarizing plate 4 of the present invention is on one surface of the liquid crystal panel 6, the polarizing plate 4 'of the present invention is on the other surface of the liquid crystal panel 6, and the adhesive layer 5 and It has a structure in which the adhesive layers 5 'are bonded to each other.
- an electrode not shown
- Table 1 shows the composition of the composition for forming an alignment layer. N-methyl-2-pyrrolidone, 2-butoxyethanol and ethylcyclohexane were added to a commercially available orientation polymer, Sunever SE-610 (manufactured by Nissan Chemical Industries, Ltd.) to obtain an alignment layer forming composition (1). .
- Table 1 represents the content ratio of each component with respect to the total amount of the prepared composition.
- SE-610 the solid content was converted from the concentration described in the delivery specification.
- optical anisotropic layer forming composition The composition of the optical anisotropic layer forming composition is shown in Table 2. After mixing each component and stirring the obtained solution at 60 degreeC for 1 hour, it cooled to room temperature and obtained the composition (1) for optically anisotropic layer formation.
- LR9000 in Table 2 is Laromer (registered trademark) LR-9000 manufactured by BASF Japan
- Irg907 is Irgacure 907 manufactured by BASF Japan
- BYK361N is a leveling agent manufactured by BYK Japan
- LC242 is the following formula PGMEGA represents propylene glycol 1-monomethyl ether 2-acetate.
- an atmospheric pressure plasma surface treatment apparatus (roll direct head type AP-T04S-R890, manufactured by Sekisui Chemical Co., Ltd.).
- plasma was generated under conditions of 1.3 k
- composition for optically anisotropic layer formation (1) was applied using a die coater, transported to a drying furnace at 80 ° C. and dried for 1 minute, and then removed from the drying furnace at a rate of 10 ° C./sec.
- the cooling rate was gradually decreased from the start of cooling, and reached 10 ° C after 10 seconds, and the temperature of the dried film became 23 ° C after 50 seconds from the start of cooling.
- a high-pressure mercury lamp manufactured by GS Yuasa Co., Ltd.
- a high-pressure mercury lamp manufactured by GS Yuasa Co., Ltd.
- a roll-like optically anisotropic film (1) was obtained.
- the temperature change of the dry film is shown in FIG.
- the vertical axis represents the temperature (° C.) of the dried film, and the horizontal axis represents time (seconds).
- Comparative Example 1 The optically anisotropic film (2) was carried out under the same conditions as in Example 1 except that the cooling was performed while contacting a heated metal plate on the back surface of the substrate, so that the cooling rate was 2 ° C./sec. Got.
- optically anisotropic film produced in the examples was excellent in transparency.
- an optically anisotropic film excellent in transparency can be produced.
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Abstract
Description
[1] 以下の(1)~(3)の工程を含む光学異方性フィルムの製造方法。
(1)基材表面、又は、基材表面に形成された配向層表面に光学異方層形成用組成物を塗布する工程
(2)塗布された光学異方層形成用組成物を乾燥して乾燥被膜を形成する工程
(3)前記乾燥被膜を6℃/sec以上の速度で冷却することにより光学異方性フィルムを形成する工程
[2] 6℃/sec以上の速度で冷却することにより光学異方性フィルムを形成した後、冷却速度を緩やかに低くする、[1]に記載の光学異方性フィルムの製造方法。
[3] さらに、(4)光学異方性フィルムに光照射する工程を有する[1]又は[2]に記載の光学異方性フィルムの製造方法。
[4] 6℃/sec以上の速度の冷却を開始した時点から、冷却速度を緩やが低くして、冷却速度が0.5℃/secに達するまでの時間が、2秒~10分である[1]~[3]のいずれかに記載の光学異方性フィルムの製造方法。
[5] 基材がロール状の基材であり、(1)~(3)の工程を連続して実施する[1]~[4]のいずれかに記載の光学異方性フィルムの製造方法。
[6] (2)及び(3)の工程を、遮光して行う[1]~[5]のいずれかに記載の光学異方性フィルムの製造方法。
[7] 基材の配向層が形成された面とは反対側の面を気層及びガイドロールのみに接触して冷却し、乾燥被膜の表面を気層のみに接触して冷却する[5]又は[6]のに記載の光学異方性フィルムの製造方法。
[8] 以下の(1)~(3)の工程を行うことにより得られる光学異方性フィルム。
(1)基材表面、又は、基材表面に形成された配向層表面に光学異方層形成用組成物を塗布する工程
(2)塗布された光学異方層形成用組成物を乾燥して乾燥被膜を形成する工程
(3)前記乾燥被膜を6℃/sec以上の速度で冷却することにより光学異方性フィルムを形成する工程
[9] 位相差性を有する[8]に記載の光学異方性フィルム。
[10] IPS(in−plane switching)液晶表示装置用の[8]又は[9]に記載の光学異方性フィルム。
[11] [8]~[10]のいずれかに記載の光学異方性フィルムを有する偏光板。
[12] [8]~[10]のいずれかに記載の光学異方性フィルムを備えた表示装置。
(1)基材表面、又は、基材表面に形成された配向層表面に光学異方層形成用組成物を塗布する工程
(2)塗布された光学異方層形成用組成物を乾燥して乾燥被膜を形成する工程
(3)前記乾燥被膜を6℃/sec以上の速度で冷却することにより光学異方性フィルムを形成する工程
さらに(4)前記光学異方性フィルムに光照射する工程を含んでもよい。
基材には、通常透明基材が用いられる。透明基材とは、光、特に可視光を透過し得る透光性を有する基材を意味し、透光性とは、波長380~780nmにわたる光線に対しての透過率が80%以上となる特性をいう。具体的な透明基材としては、ガラスおよび透光性樹脂基材が挙げられ、透光性樹脂基材が好ましい。基材は、通常フィルム状のものが用いられ、中でも、ロールtoロールによる巻出・巻取が可能であるフィルムロール状の基材が、生産性の点において特に好ましい。
大気圧近傍の圧力下で、対向した電極間に基材を設置し、コロナまたはプラズマを発生させて、基材の表面処理を行う方法、
対向した電極間にガスを流し、電極間でガスをプラズマ化し、プラズマ化したガスを基材に吹付ける方法、および、
低圧条件下で、グロー放電プラズマを発生させて、基材の表面処理を行う方法が挙げられる。
市販の配向性ポリマーとしては、サンエバー(登録商標、日産化学社製)、オプトマー(登録商標、JSR製)等が挙げられる。
このような配向性ポリマーから形成される配向層は、液晶化合物の液晶配向を容易にする。配向性ポリマーの種類やラビング条件によって、水平配向、垂直配向、ハイブリッド配向、傾斜配向等の様々な液晶配向の制御が可能であるが、本発明では、液晶化合物を垂直配向させる配向性ポリマー及びラビング条件が適用される。
溶剤としては、水;メタノール、エタノール、エチレングリコール、イソプロピルアルコール、プロピレングリコール、メチルセロソルブ、ブチルセロソルブ等のアルコール溶媒;酢酸エチル、酢酸ブチル、エチレングリコールメチルエーテルアセテート、γ−ブチロラクトン、プロピレングリコールメチルエーテルアセテート、乳酸エチル等のエステル溶媒;アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、メチルアミルケトン、メチルイソブチルケトン、N−メチル−2−ピロリドン等のケトン溶媒;ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素溶媒;トルエン、キシレン、クロロベンゼン等の芳香族炭化水素溶媒;アセトニトリル等のニトリル溶媒;プロピレングリコールモノメチルエーテル、テトラヒドロフラン、ジメトキシエタン等のエーテル溶媒;クロロホルム等のハロゲン化炭化水素溶媒等が挙げられる。これら有機溶媒は、単独でもよいし、組み合わせてもよい。
光学異方層形成用組成物は、液晶化合物及び溶剤を含む。液晶化合物は好ましくは重合性液晶化合物である。重合性液晶化合物とは重合性基を有する液晶化合物のことである。
液晶化合物としては、例えば、式(X)で表される基を含む化合物(以下「化合物(X)」という場合がある)が挙げられる。
P11−B11−E11−B12−A11−B13− (X)
[式(X)中、P11は、重合性基又は水素原子を表わす。
A11は、2価の脂環式炭化水素基または2価の芳香族炭化水素基を表わす。該2価の脂環式炭化水素基および2価の芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6アルコキシ基、シアノ基またはニトロ基で置換されていてもよく、該炭素数1~6のアルキル基および該炭素数1~6アルコキシ基に含まれる水素原子は、フッ素原子で置換されていてもよい。
B11は、−O−、−S−、−CO−O−、−O−CO−、−O−CO−O−、−CO−NR16−、−NR16−CO−、−CO−、−CS−または単結合を表わす。R16は、水素原子または炭素数1~6のアルキル基を表わす。
B12およびB13は、それぞれ独立に、−C≡C−、−CH=CH−、−CH2−CH2−、−O−、−S−、−C(=O)−、−C(=O)−O−、−O−C(=O)−、−O−C(=O)−O−、−CH=N−、−N=CH−、−N=N−、−C(=O)−NR16−、−NR16−C(=O)−、−OCH2−、−OCF2−、−CH2O−、−CF2O−、−CH=CH−C(=O)−O−、−O−C(=O)−CH=CH−または単結合を表わす。
E11は、炭素数1~12のアルカンジイル基を表わし、該アルカンジイル基に含まれる水素原子は、炭素数1~5のアルコキシ基で置換されていてもよく、該アルコキシ基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。また、該アルカンジイル基を構成する−CH2−は、−O−または−CO−に置き換わっていてもよい。]
具体的には、メチレン基、エチレン基、プロパン−1,3−ジイル基、ブタン−1,4−ジイル基、ペンタン−1,5−ジイル基、ヘキサン−1,6−ジイル基、ヘプタン−1,7−ジイル基、オクタン−1,8−ジイル基、ノナン−1,9−ジイル基、デカン−1,10−ジイル基、ウンデカン−1,11−ジイル基およびドデカン−1,12−ジイル基等の炭素数1~12の直鎖状アルカンジイル基;−CH2−CH2−O−CH2−CH2−、−CH2−CH2−O−CH2−CH2−O−CH2−CH2−および−CH2−CH2−O−CH2−CH2−O−CH2−CH2−O−CH2−CH2−等が挙げられる。B11としては、−O−、−S−、−CO−O−、−O−CO−が好ましく、中でも、−CO−O−がより好ましい。
B12およびB13としては、それぞれ独立に、−O−、−S−、−C(=O)−、−C(=O)−O−、−O−C(=O)−、−O−C(=O)−O−が好ましく、中でも、−O−または−O−C(=O)−O−がより好ましい。
[式(P−11)~(P−15)中、
R17~R21はそれぞれ独立に、炭素数1~6のアルキル基または水素原子を表わす。]
P11−B11−で表わされる基が、アクリロイルオキシ基またはメタアクリロイルオキシ基であることがさらに好ましい。
P11−B11−E11−B12−A11−B1−A12−B14−A13−B15−A14−B16−E12−B17−P12 (I)
P11−B11−E11−B12−A11−B13−A12−B14−A13−B15−A14−F11 (II)
P11−B11−E11−B12−A11−B13−A12−B14−A13−B15−E12−B17−P12 (III)
P11−B11−E11−B12−A11−B13−A12−B14−A13−F11 (IV)
P11−B11−E11−B12−A11−B13−A12−B14−E12−B17−P12 (V)
P11−B11−E11−B12−A11−B13−A12−F11 (VI)
(式中、
A12~A14はそれぞれ独立に、A11と同義であり、B14~B16はそれぞれ独立に、B12と同義であり、B17は、B11と同義であり、E12は、E11と同義である。
F11は、水素原子、炭素数1~13のアルキル基、炭素数1~13のアルコキシ基、シアノ基、ニトロ基、トリフルオロメチル基、ジメチルアミノ基、ヒドロキシ基、メチロール基、ホルミル基、スルホ基(−SO3H)、カルボキシ基、炭素数1~10のアルコキシカルボニル基またはハロゲン原子を表わし、該アルキル基およびアルコキシ基を構成する−CH2−は、−O−に置き換っていてもよい。)
溶剤としては、液晶化合物等の光学異方層形成用組成物の固形分を溶解する有機溶剤が好ましく、また、光学異方層形成用組成物が重合性液晶化合物を含む場合には、さらに、重合性液晶化合物の重合反応に不活性な有機溶剤がより好ましい。具体的には、メタノール、エタノール、エチレングリコール、イソプロピルアルコール、プロピレングリコール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、フェノール等のアルコール溶剤;酢酸エチル、酢酸ブチル、エチレングリコールメチルエーテルアセテート、γ−ブチロラクトン、プロピレングリコールメチルエーテルアセテート、乳酸エチル等のエステル溶剤;アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、メチルアミルケトン、メチルイソブチルケトン等のケトン溶剤;ペンタン、ヘキサン、ヘプタン等の非塩素化脂肪族炭化水素溶剤;トルエン、キシレン等の非塩素化芳香族炭化水素溶剤;アセトニトリル等のニトリル溶剤;テトラヒドロフラン、ジメトキシエタン等のエーテル溶剤;およびクロロホルム、クロロベンゼン等の塩素化炭化水素溶剤;等が挙げられる。二種以上の有機溶剤を組み合わせて用いてもよい。中でも、アルコール溶剤、エステル溶剤、ケトン溶剤、非塩素化脂肪族炭化水素溶剤および非塩素化芳香族炭化水素溶剤が好ましい。
重合開始剤としては、光重合開始剤が好ましく、光照射によりラジカルを発生する光重合開始剤がより好ましい。
重合開始剤としては、ベンゾイン化合物、ベンゾフェノン化合物、ベンジルケタール化合物、α−ヒドロキシケトン化合物、α−アミノケトン化合物、トリアジン化合物、ヨードニウム塩およびスルホニウム塩が挙げられる。具体的には、イルガキュア(Irgacure)907、イルガキュア184、イルガキュア651、イルガキュア819、イルガキュア250、イルガキュア369(以上、全てチバ・ジャパン株式会社製)、セイクオールBZ、セイクオールZ、セイクオールBEE(以上、全て精工化学株式会社製)、カヤキュアー(kayacure)BP100(日本化薬株式会社製)、カヤキュアーUVI−6992(ダウ社製)、アデカオプトマーSP−152、アデカオプトマーSP−170(以上、全て株式会社ADEKA製)、TAZ−A、TAZ−PP(以上、日本シイベルヘグナー社製)およびTAZ−104(三和ケミカル社製)が挙げられる。中でも、α−アセトフェノン化合物が好ましく、α−アセトフェノン化合物としては、2−メチル−2−モルホリノ−1−(4−メチルスルファニルフェニル)プロパン−1−オン、2−ジメチルアミノ−1−(4−モルホリノフェニル)−2−ベンジルブタン−1−オン及び2−ジメチルアミノ−1−(4−モルホリノフェニル)−2−(4−メチルフェニルメチル)ブタン−1−オン等が挙げられ、より好ましくは2−メチル−2−モルホリノ−1−(4−メチルスルファニルフェニル)プロパン−1−オン及び2−ジメチルアミノ−1−(4−モルホリノフェニル)−2−ベンジルブタン−1−オンが挙げられる。α−アセトフェノン化合物の市販品としては、イルガキュア369、379EG、907(以上、BASFジャパン(株)製)及びセイクオールBEE(精工化学社製)等が挙げられる。
重合禁止剤としては、ハイドロキノンおよびアルキルエーテル等の置換基を有するハイドロキノン類;ブチルカテコール等のアルキルエーテル等の置換基を有するカテコール類;ピロガロール類、2,2,6,6−テトラメチル−1−ピペリジニルオキシラジカル等のラジカル補足剤;チオフェノール類;β−ナフチルアミン類およびβ−ナフトール類が挙げられる。
光学異方層形成用組成物における重合禁止剤の含有量は、液晶化合物100質量部に対して、通常0.1質量部~30質量部であり、好ましくは0.5質量部~10質量部である。上記範囲内であれば、液晶化合物の配向を乱し難くいため好ましい。
光増感剤としては、キサントン、チオキサントン等のキサントン類;アントラセンおよびアルキルエーテル等の置換基を有するアントラセン類;フェノチアジン;ルブレンが挙げられる。
光増感剤を用いることにより、光重合開始剤の反応を高感度化することができる。光増感剤の含有量は、液晶化合物100質量部に対して、通常0.1質量部~30質量部であり、好ましくは0.5質量部~10質量部である。
レベリング剤としては、有機変性シリコーンオイル系、ポリアクリレート系およびパーフルオロアルキル系のレベリング剤が挙げられる。具体的には、DC3PA、SH7PA、DC11PA、SH28PA、SH29PA、SH30PA、ST80PA、ST86PA、SH8400、SH8700、FZ2123(以上、全て東レ・ダウコーニング(株)製)、KP321、KP323、KP324、KP326、KP340、KP341、X22−161A、KF6001(以上、全て信越化学工業(株)製)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF−4446、TSF4452、TSF4460(以上、全てモメンティブ パフォーマンス マテリアルズ ジャパン合同会社製)、フロリナート(fluorinert)(登録商標)FC−72、同FC−40、同FC−43、同FC−3283(以上、全て住友スリーエム(株)製)、メガファック(登録商標)R−08、同R−30、同R−90、同F−410、同F−411、同F−443、同F−445、同F−470、同F−477、同F−479、同F−482、同F−483(以上、いずれもDIC(株)製)、エフトップ(商品名)EF301、同EF303、同EF351、同EF352(以上、全て三菱マテリアル電子化成(株)製)、サーフロン(登録商標)S−381、同S−382、同S−383、同S−393、同SC−101、同SC−105、KH−40、SA−100(以上、全てAGCセイミケミカル(株)製)、商品名E1830、同E5844((株)ダイキンファインケミカル研究所製)、BM−1000、BM−1100、BYK−352、BYK−353及びBYK−361N(いずれも商品名:BM Chemie社製)が挙げられる。2種以上のレベリング剤を組み合わせて用いてもよい。
カイラル剤としては、公知のカイラル剤(例えば、液晶デバイスハンドブック、第3章4−3項、TN、STN用カイラル剤、199頁、日本学術振興会第142委員会編、1989に記載)が挙げられる。
カイラル剤は、一般に不斉炭素原子を含むが、不斉炭素原子を含まない軸性不斉化合物あるいは面性不斉化合物もカイラル剤として用いることができる。軸性不斉化合物または面性不斉化合物としては、ビナフチル、ヘリセン、パラシクロファンおよびこれらの誘導体が挙げられる。
具体的には、特開2007−269640号公報、特開2007−269639号公報、特開2007−176870号公報、特開2003−137887号公報、特表2000−515496号公報、特開2007−169178号公報および特表平9−506088号公報に記載されているような化合物が挙げられ、好ましくはBASFジャパン(株)製のpaliocolor(登録商標) LC756である。
カイラル剤の含有量は、液晶化合物100質量部に対して、通常0.1質量部~30質量部であり、好ましくは1.0質量部~25質量部である。上記範囲内であれば、液晶化合物の配向を乱し難いため好ましい。
反応性添加剤としては、その分子内に炭素−炭素不飽和結合と活性水素反応性基とを有するものが好ましい。なお、ここでいう「活性水素反応性基」とは、カルボキシル基(−COOH)、水酸基(−OH)、アミノ基(−NH2)等の活性水素を有する基に対して反応性を有する基を意味し、グリシジル基、オキサゾリン基、カルボジイミド基、アジリジン基、イミド基、イソシアナト基、チオイソシアナト基、無水マレイン酸基等がその代表例である。
[式(Y)中、
nは1~10までの整数を表わし、R1’は、炭素数2~20の2価の脂肪族又は脂環式炭化水素基、或いは炭素数5~20の2価の芳香族炭化水素基を表わす。各繰り返し単位にある2つのR2’は、一方が−NH−であり、他方がN−C(=O)−R3’で示される基である。R3’は、水酸基又は炭素−炭素不飽和結合を有する基を表す。
式(Y)中のR3’のうち、少なくとも1つのR3’は炭素−炭素不飽和結合を有する基である。]
化合物(YY)には、市販品をそのまま又は必要に応じて精製して用いることができる。市販品としては、Laromer(登録商標)LR−9000(BASF社製)等が挙げられる。
配向規制力は、配向膜が配向性ポリマーから形成されている場合は、表面状態やラビング条件によって任意に調整することが可能であり、光配向性ポリマーから形成されている場合は、偏光照射条件等によって任意に調整することが可能である。また、液晶化合物の、表面張力や液晶性等の物性を選択することにより、液晶配向を制御することもできる。
6℃/sec以上の速度で冷却する前の乾燥被膜の温度は、前述した乾燥温度(通常40℃~150℃の範囲であり、好ましくは80℃~140℃の範囲であり、より好ましくは90℃~130℃の範囲)である。また、6℃/sec以上の速度で冷却した後の乾燥被膜の温度は好ましくは0℃~30℃である。
光学異方性フィルムおよび光学異方性フィルムに含まれる液晶化合物の温度は、好ましくは0~30℃であり、より好ましくは23℃~25℃である。該温度範囲に冷却することで、液晶化合物の配向欠陥が少ない、透明性に優れた光学異方性フィルムを得ることができる。
6℃/sec以上の速度の冷却を開始した時点から、冷却速度を緩やか低くして、冷却速度が0.5℃/secに達するまでの時間は、2秒~10分であることが好ましい。冷却速度が0.5℃/secに達するとは、乾燥被膜の温度が冷却によってほぼ一定温度に到達したことを意味する。冷却速度は、例えば熱伝対を接触させる方法、赤外線サーモグラフィで観測する方法、又は赤外線センサーによる検知を行う方法等が挙げられる。前記時間は、好ましくは2秒~5分であり、より好ましくは2秒~1分であり、さらに好ましくは2秒~30秒である。上記範囲内であれば、配向欠陥が少ない透明性に優れた光学異方性フィルムを得ることができる。
(1)ロールから巻き出された基材に、配向層を形成する工程;
(2)得られた配向層の表面に、光学異方層形成用組成物を塗布する工程;
(3)塗布された光学異方層形成用組成物を乾燥して乾燥被膜を形成する工程;
(4)基材側の面がフィルム搬送に使用するガイドロールと気層以外に接触することなく、また、光学異方層形成用組成物側の面が気層以外に接触することなく、得られた乾燥被膜を6℃/sec以上の速度で冷却して光学異方性フィルムを形成する工程;
(5)得られた光学異方性フィルムに光照射する工程;
(6)表面に光学異方性フィルムが形成された基材をロール状に巻き取る工程。
中でも、液晶化合物が垂直配向したものは、位相差性を有するため、光射出側の斜角から確認した場合の直線偏光を円偏光や楕円偏光に変換したり、円偏光または楕円偏光を直線偏光に変換したり、直線偏光の偏光方向を変換したりするために用いられる位相差フィルムとして有用である。
基材、又は、基材及び配向層を有さない本光学異方性フィルムは、通常、接着剤を介して偏光フィルム等のその他の部材と組み合わされる。
接着剤を介してその他の部材と組み合わせる方法としては、基材、又は、基材及び配向膜を有さない本光学異方性フィルムを、接着剤を用いてその他の部材へ貼合する方法、及び、基材表面に形成された配向層表面に形成された本光学異方性フィルムを、接着剤を用いてその他の部材へ貼合した後に基材、又は、基材及び配向膜を取り除く方法等が挙げられる。この際、接着剤は、本光学異方性フィルムに塗布されてもよく、その他の部材に塗布されてもよい。
nx>ny≒nzのポジティブAプレート、
nx≒ny>nzのネガティブCプレート、
nx≒ny<nzのポジティブCプレート、
nx≠ny≠nzのポジティブOプレートおよびネガティブOプレート
R0 =(nx−ny)×d (9)
R50=(nx−ny’)×d/cos(φ) (10)
(nx+ny+nz)/3=n0 (11)
ここで、
φ=sin−1 〔sin(50°)/n0〕
ny’=ny×nz/〔ny 2×sin2(φ)+nz 2×cos2(φ)〕1/2
偏光板の具体例としては、図1(a)~図1(e)で示される偏光板が挙げられる。図1(a)で示される偏光板4aは、位相差フィルム1と、偏光フィルム2とが、直接積層された偏光板であり、図1(b)で示される偏光板4bは、位相差フィルム1と偏光フィルム2とが、接着剤層3’を介して貼り合わされた偏光板である。図1(c)で示される偏光板4cは、位相差フィルム1と、位相差フィルム1’とを積層させ、さらに、位相差フィルム1’と偏光フィルム2とを積層させた偏光板であり、図1(d)で示される偏光板4dは、位相差フィルム1と、位相差フィルム1’とを接着剤層3を介して貼り合わせ、さらに、位相差フィルム1’上に偏光フィルム2を積層させた偏光板である。図1(e)で示される偏光板4eは、位相差フィルム1と、位相差フィルム1’とを接着剤層3を介して貼り合わせ、さらに、位相差フィルム1’と偏光フィルム2とを接着剤層3’を介して貼り合せた偏光板である。”接着剤”とは、接着剤および/または粘着剤の総称を意味する。
前記吸収異方性を有する色素を塗布したフィルムとしては、具体的には、特開2012−33249号公報等に記載の偏光フィルムが挙げられる。
配向層形成用組成物の組成を、表1に示す。市販の配向性ポリマーであるサンエバーSE−610(日産化学工業株式会社製)にN−メチル−2−ピロリドン、2−ブトキシエタノールおよびエチルシクロヘキサンを加えて配向層形成用組成物(1)を得た。
SE−610については、固形分量を納品仕様書に記載の濃度から換算した。
光学異方層形成用組成物の組成を表2に示す。各成分を混合し、得られた溶液を60℃で1時間攪拌した後、室温まで冷却し、光学異方層形成用組成物(1)を得た。
表2におけるLR9000は、BASFジャパン社製のLaromer(登録商標)LR−9000を、Irg907は、BASFジャパン社製のイルガキュア907を、BYK361Nは、ビックケミージャパン製のレベリング剤を、LC242は、下記式で示されるBASF社製の重合性液晶化合物を、PGMEGAは、プロピレングリコール1−モノメチルエーテル2−アセタートを表す。
ロール状のシクロオレフィンポリマーフィルム(ZF−14、日本ゼオン株式会社製)の表面を、常圧プラズマ表面処理装置((ロールダイレクトヘッド型 AP−T04S−R890、積水化学工業株式会社製)を用いて、窒素と酸素とを含む雰囲気(体積比 窒素:酸素=99.9:0.1)下で、1.3kV下の条件でプラズマを発生させ、100m処理した。プラズマ処理を施したシクロオレフィンポリマーフィルム表面に、配向層形成用組成物(1)を、ダイコーターを用いて塗布し、90℃の乾燥炉に搬送して1分間乾燥することにより配向層を形成した。得られた配向層表面に光学異方層形成用組成物(1)を、ダイコーターを用いて塗布し、80℃の乾燥炉に搬送して1分間乾燥した。乾燥炉から出して10℃/secの速さで冷却した。冷却開始から緩やかに冷却速度を低くし、10秒経過した時点で冷却速度が0.5℃/secまで達した。冷却開始から50秒後に、乾燥被膜の温度は23℃になった。冷却開始から50秒後に、高圧水銀ランプ(GSユアサ株式会社製)を用いて、紫外線を、波長365nmにおいて160W/cmの照度で照射することにより重合を行い、ロール状の光学異方性フィルム(1)を得た。
乾燥被膜の温度変化を図3に示す。縦軸は乾燥被膜の温度(℃)を、横軸は時間(秒)を表す。
冷却を、基材の裏面に加熱した金属プレートを接しながら行うことで、冷却速度を2℃/secとした以外は、実施例1と同様の条件で実施し、光学異方性フィルム(2)を得た。
スガ試験機株式会社製 ヘイズメーター(型式HZ−2)を用いて、ダブルビーム法で、光学異方性フィルム(1)及び(2)のヘイズ値を測定した。結果を表3に示す。
上記で作製した光学異方性フィルム(1)及び(2)の位相差値を測定機(KOBRA−WR、王子計測機器社製)により測定した。サンプルへの光の入射角を変えて測定し、重合性液晶化合物の配向方向を確認した。結果を表3に示す。
2、2’:偏光フィルム
3、3’:接着剤層
4a、4b、4c、4d、4e、4、4’:偏光板
5、5’:接着層
6:液晶パネル
10a、10b:液晶表示装置
Claims (12)
- 以下の(1)~(3)の工程を含む光学異方性フィルムの製造方法。
(1)基材表面、又は、基材表面に形成された配向層表面に光学異方層形成用組成物を塗布する工程
(2)塗布された光学異方層形成用組成物を乾燥して乾燥被膜を形成する工程
(3)前記乾燥被膜を6℃/sec以上の速度で冷却することにより光学異方性フィルムを形成する工程 - 6℃/sec以上の速度で冷却することにより光学異方性フィルムを形成した後、冷却速度を緩やか低くする、請求項1に記載の光学異方性フィルムの製造方法。
- さらに、(4)光学異方性フィルムに光照射する工程を有する請求項1又は請求項2に記載の光学異方性フィルムの製造方法。
- 6℃/sec以上の速度の冷却を開始した時点から、冷却速度を緩やか低くして、冷却速度が0.5℃/secに達するまでの時間が、2秒~10分である請求項1~3のいずれかに記載の光学異方性フィルムの製造方法。
- 基材がロール状の基材であり、(1)~(3)の工程を連続して実施する請求項1~4のいずれかに記載の光学異方性フィルムの製造方法。
- (2)及び(3)の工程を、遮光して行う請求項1~5のいずれかに記載の光学異方性フィルムの製造方法。
- 基材の配向層が形成された面とは反対側の面を気層及びガイドロールのみに接触して冷却し、乾燥被膜の表面を気層のみに接触して冷却する請求項5又は請求項6に記載の光学異方性フィルムの製造方法。
- 以下の(1)~(3)の工程を行うことにより得られる光学異方性フィルム。
(1)基材表面、又は、基材表面に形成された配向層表面に光学異方層形成用組成物を塗布する工程
(2)塗布された光学異方層形成用組成物を乾燥して乾燥被膜を形成する工程
(3)前記乾燥被膜を6℃/sec以上の速度で冷却することにより光学異方性フィルムを形成する工程 - 位相差性を有する請求項8に記載の光学異方性フィルム。
- IPS(in−plane switching)液晶表示装置用の請求項8又は請求項9に記載の光学異方性フィルム。
- 請求項8~10のいずれかに記載の光学異方性フィルムを有する偏光板。
- 請求項8~10のいずれかに記載の光学異方性フィルムを備えた表示装置。
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