WO2020166476A1 - Plaque de polarisation circulaire et dispositif d'affichage el organique l'utilisant - Google Patents

Plaque de polarisation circulaire et dispositif d'affichage el organique l'utilisant Download PDF

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Publication number
WO2020166476A1
WO2020166476A1 PCT/JP2020/004517 JP2020004517W WO2020166476A1 WO 2020166476 A1 WO2020166476 A1 WO 2020166476A1 JP 2020004517 W JP2020004517 W JP 2020004517W WO 2020166476 A1 WO2020166476 A1 WO 2020166476A1
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group
liquid crystal
polarizing plate
film
polymerizable liquid
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PCT/JP2020/004517
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English (en)
Japanese (ja)
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伸行 幡中
耕太 村野
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住友化学株式会社
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Priority to CN202080009401.7A priority Critical patent/CN113302528B/zh
Priority to KR1020217025373A priority patent/KR20210127704A/ko
Publication of WO2020166476A1 publication Critical patent/WO2020166476A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements

Definitions

  • the present invention relates to a circularly polarizing plate and an organic EL display device using the circularly polarizing plate.
  • organic EL panel has a problem that clear black display cannot be obtained because external light is reflected by the internal metal electrodes.
  • a circularly polarizing plate on the visible surface, it is possible to suppress the reflection of external light. That is, the stacking order from the viewer is circular polarizing plate ⁇ organic EL display.
  • the circularly polarizing plate can be generally produced by laminating a polarizing plate and a retardation film.
  • polarizing plate generally, a polarizer in which PVA (polyvinyl alcohol) is stretched and dyed with iodine and a transparent protective film is laminated, and as the retardation film, a stretched film or a retardation film in which liquid crystal molecules are aligned ( ⁇ /4 plate) is used.
  • a ⁇ /4 plate having a property of increasing birefringence as the wavelength becomes longer is preferably used.
  • the organic EL layer deteriorates due to oxygen and moisture depending on the use environment and does not emit light
  • both surfaces of the organic EL panel may be protected by a low moisture-permeable base material such as glass. ..
  • the outermost surface of the panel may also be protected from the water resistant surface by a base material having low moisture permeability.
  • color change occurs in a high temperature environment depending on the type of retardation film.
  • a small amount of water contained in the protective film forming the polarizing plate, polyvinyl alcohol, etc. remains in the system, and the water causes hydrolysis of the retardation film, which causes a color change.
  • a polarizing plate in which a polarizing film containing a dichroic dye and a transparent protective film having a thickness of 10 ⁇ m or more and 80 ⁇ m or less are laminated, and a retardation film which is a cured product of a composition containing a polymerizable liquid crystal compound B.
  • a circularly polarizing plate including The retardation film has a thickness of 5 ⁇ m or less,
  • the polymerizable liquid crystal compound B is a compound having an ester bond in the molecular structure,
  • a circularly polarizing plate having an equilibrium water content of 1.5% by mass or less at a temperature of 23° C. and a relative humidity of 50%.
  • Re(450)/Re(550) ⁇ 1 [In the formula, Re(450) and Re(550) represent in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively. ] [9] The circularly polarizing plate according to any one of [1] to [8], wherein an angle formed by the slow axis of the retardation film and the absorption axis of the polarizing film is substantially 45°. [10] The circularly polarizing plate according to any one of [1] to [9], wherein the polymerizable liquid crystal compound B has at least one polymerizable group of an acryloyloxy group and a methacryloyloxy group. [11] The circularly polarizing plate according to any one of [1] to [10], wherein the polymerizable liquid crystal compound B is a compound represented by the following formula (II).
  • Ar represents a divalent aromatic group which may have a substituent.
  • G 1 and G 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group.
  • L 1 and L 2 are each independently a divalent linking group having an ester structure.
  • T 1 and T 2 are each independently a single bond or a divalent linking group.
  • h and i each independently represent an integer of 0 to 3 and satisfy the relation of 1 ⁇ h+i.
  • T 1 and T 2 , and G 1 and G 2 may be the same as or different from each other.
  • E 1 and E 2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom and is contained in the alkanediyl group.
  • —CH 2 — may be substituted with —O—, —S—, and —COO—, and when they have a plurality of —O—, —S—, and —COO—, they are not adjacent to each other.
  • P 1 and P 2 each independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.
  • the circularly polarizing plate of the present invention can prevent color change even in a high temperature environment.
  • the circularly polarizing plate is composed of a polarizing plate and a retardation film.
  • it is necessary to control the equilibrium water content of the polarizing plate at a temperature of 23° C. and a humidity of 50% to 1.5% by mass or less.
  • the equilibrium water content is defined as the water content in a state where the water content in the material reaches equilibrium in the atmosphere in air at a constant temperature and humidity.
  • a polarizing plate (size: width 4 cm, length 10 cm) is kept in a clean room with a temperature of 23° C. and a relative humidity of 50% for 1 day to measure the mass, and then the polarizing plate is dried at 105° C. for 1 hour to measure the mass.
  • the equilibrium water content of the polarizing plate is higher than 1.5% by mass, color change of the circularly polarizing plate is likely to occur at high temperature, which is not preferable.
  • the equilibrium water content of the polarizing plate is preferably 1.0% by mass or less, more preferably 0.5% by mass or less.
  • the lower limit of the equilibrium water content of the polarizing plate may be 0.
  • the equilibrium water content of the polarizing plate is higher than 1.5% by mass, the equilibrium water content can be lowered by drying. Drying is appropriately performed, such as standing in a dry environment, in addition to heating.
  • the circularly polarizing plate of the present invention is a cured product of a polarizing plate in which a polarizing film containing a dichroic dye and a transparent protective film having a thickness of 10 ⁇ m or more and 80 ⁇ m or less are laminated, and a composition containing the polymerizable liquid crystal compound B. Including a phase difference film.
  • the polarizing film is a film having a function of light absorption anisotropy.
  • the polarizing film may be a stretched film having a dichroic dye adsorbed thereon, or may be a cured product of a composition containing a horizontally aligned polymerizable liquid crystal compound and a horizontally aligned dichroic dye.
  • the polarizing film is more preferably a polarizing film made of a polymer of a polymerizable liquid crystal compound.
  • a film containing a stretched film having a dichroic dye adsorbed thereon as a polarizing film is usually a step of uniaxially stretching a polyvinyl alcohol-based resin film, and a dichroic dye is obtained by dyeing the polyvinyl alcohol-based resin film with the dichroic dye. It is manufactured through a step of adsorbing, a step of treating the polyvinyl alcohol-based resin film on which the dichroic dye is adsorbed with an aqueous solution of boric acid, and a step of washing with water after the aqueous solution of boric acid.
  • Polyvinyl alcohol resin is obtained by saponifying polyvinyl acetate resin.
  • polyvinyl acetate-based resin in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used.
  • the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
  • the saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more.
  • the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used.
  • the degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably 1,500 to 5,000.
  • a film produced from such a polyvinyl alcohol resin is used as the original film for the polarizing film.
  • the method for forming a film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method.
  • the film thickness of the polyvinyl alcohol-based original film can be set to, for example, about 10 to 150 ⁇ m.
  • the uniaxial stretching of the polyvinyl alcohol resin film can be performed before dyeing with the dichroic dye, simultaneously with dyeing, or after dyeing.
  • the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. It is also possible to carry out uniaxial stretching in these plural stages.
  • stretching may be uniaxial between rolls having different peripheral speeds, or uniaxial stretching may be performed using hot rolls.
  • the uniaxial stretching may be dry stretching in which stretching is performed in the atmosphere, or wet stretching in which a polyvinyl alcohol-based resin film is swollen in a solvent and stretched.
  • the draw ratio is usually about 3 to 8 times.
  • the dyeing of the polyvinyl alcohol-based resin film with the dichroic dye is performed by, for example, immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.
  • dichroic pigment iodine or a dichroic organic dye is used as the dichroic pigment.
  • dichroic organic dye examples include C.I. I.
  • the polyvinyl alcohol-based resin film is preferably immersed in water before dyeing.
  • iodine When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide and dyeing is usually employed.
  • the content of iodine in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water.
  • the content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water.
  • the temperature of the aqueous solution used for dyeing is usually about 20 to 40°C.
  • the immersion time (dyeing time) in this aqueous solution is usually about 20 to 1800 seconds.
  • a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually employed.
  • the content of the dichroic organic dye in this aqueous solution is usually about 1 ⁇ 10 ⁇ 4 to 10 parts by mass, preferably 1 ⁇ 10 ⁇ 3 to 1 part by mass, and more preferably 100 parts by mass of water. Is 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 2 parts by mass.
  • This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid.
  • the temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C.
  • the immersion time (dyeing time) in this aqueous solution is usually about 10 to 1800 seconds.
  • the boric acid treatment after dyeing with the dichroic dye can usually be performed by a method of immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution.
  • the content of boric acid in this aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water.
  • the aqueous boric acid solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually 0.1 to 100 parts by mass of water.
  • the amount is about 15 parts by mass, preferably 5 to 12 parts by mass.
  • the immersion time in the aqueous boric acid solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds.
  • the temperature of boric acid treatment is usually 50° C. or higher, preferably 50 to 85° C., more preferably 60 to 80° C.
  • the polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water.
  • the water washing treatment can be performed by, for example, a method of immersing the polyvinyl alcohol-based resin film treated with boric acid in water.
  • the temperature of water in the washing treatment is usually about 5 to 40°C.
  • the immersion time is usually about 1 to 120 seconds.
  • a drying process is applied to obtain a polarizing film.
  • the drying treatment can be performed using, for example, a hot air dryer or a far infrared heater.
  • the temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C.
  • the drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds.
  • the water content of the polarizer is reduced to a practical level.
  • the water content thereof is usually about 5 to 20% by mass, preferably 8 to 15% by mass.
  • the water content is less than 5% by mass, the flexibility of the polarizing film is lost, and the polarizing film may be damaged or broken after being dried. Further, if the water content exceeds 20 mass %, the thermal stability of the polarizing film may deteriorate.
  • the thickness of the polarizing film obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing it with a dichroic dye, treating with boric acid, washing with water and drying is preferably 5 to 40 ⁇ m.
  • the polarizing film is a cured product of a composition containing a horizontally aligned polymerizable liquid crystal compound and a horizontally aligned dichroic dye (hereinafter sometimes referred to as the polymerizable liquid crystal composition (A)).
  • the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but when mixed with a dichroic dye, the thermotropic liquid crystal is preferable.
  • it may be a thermotropic liquid crystal compound showing a nematic liquid crystal phase or a thermotropic liquid crystal compound showing a smectic liquid crystal phase.
  • the liquid crystal state of the polymerizable liquid crystal compound is preferably a smectic phase. Specific examples of such compounds will be described later.
  • the polymerizable liquid crystal composition (A) is a liquid crystal compound having at least one polymerizable group, and preferably has a smectic liquid crystallinity (hereinafter, also referred to as “polymerizable liquid crystal compound (A)”). Comprises. By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a polarizing film having a high degree of alignment order can be formed.
  • the liquid crystal state of the polymerizable liquid crystal compound (A) is preferably a smectic phase (smectic liquid crystal state), and is a higher-order smectic phase (higher-order smectic liquid crystal state) from the viewpoint that a higher degree of alignment order can be realized.
  • the higher order smectic phase means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase and a smectic L phase.
  • the smectic B phase, the smectic F phase and the smectic I phase are more preferable.
  • the liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferable in that precise film thickness control is possible.
  • the polymerizable liquid crystal compound may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.
  • the polymerizable liquid crystal compound (A) is a liquid crystal compound having at least one polymerizable group.
  • the polymerizable group refers to a group that can participate in the polymerization reaction by an active radical or an acid generated from the polymerization initiator.
  • Examples of the polymerizable group contained in the polymerizable liquid crystal compound (A) include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, Examples include an oxetanyl group.
  • a radical polymerizable group is preferable, an acryloyloxy group, a methacryloyloxy group, a vinyl group and a vinyloxy group are more preferable, and an acryloyloxy group and a methacryloyloxy group are further preferable.
  • the polymerizable liquid crystal compound (A) is not particularly limited as long as it is a liquid crystal compound having at least one polymerizable group, and a known polymerizable liquid crystal compound can be used, for example, represented by the following formula (A1).
  • X 1 and X 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or the divalent alicyclic hydrocarbon group is used.
  • the hydrogen atom contained in the group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group.
  • the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom.
  • at least one of X 1 and X 2 is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. ..
  • Y 1 is a single bond or a divalent linking group.
  • n is 1 to 3, and when n is 2 or more, a plurality of X 1's may be the same as or different from each other.
  • X 2 may be the same as or different from any or all of the plurality of X 1 .
  • n is preferably 2 or more.
  • U 1 represents a hydrogen atom or a (meth)acryloyloxy group.
  • U 2 represents a (meth)acryloyloxy group.
  • W 1 and W 2 are, independently of each other, a single bond or a divalent linking group.
  • V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group is —O—, It may be replaced with —CO—, —S— or NH—.
  • X 1 and X 2 are independently of each other, preferably a 1,4-phenylene group which may have a substituent, or a substituent which may have a substituent.
  • the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent may have a methyl group or an ethyl group.
  • examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group and a butyl group, a cyano group, and a halogen atom such as a chlorine atom and a fluorine atom. It is preferably unsubstituted.
  • the polymerizable liquid crystal compound (A1) has the formula (A1-1): -(X 1 -Y 1 -) n -X 2 -(A1-1) [In the formula, X 1 , Y 1 , X 2 and n each have the same meaning as described above. ]
  • a portion represented by [hereinafter referred to as a partial structure (A1-1). ] Is preferably an asymmetric structure from the viewpoint of easily exhibiting smectic liquid crystallinity.
  • the polymerizable liquid crystal compound (A1) in which the partial structure (A1-1) is an asymmetric structure is, for example, a polymerizable liquid crystal compound (A1) in which n is 1 and one X 1 and X 2 are different from each other.
  • n 2 and two Y 1 have the same structure as each other, two X 1 have the same structure as each other, and one X 2 has a structure different from these two X 1.
  • the polymerizable liquid crystal compound (A1), X 1 to bind to W 1 of the two X 1 is a structure that is different from the other of X 1 and X 2, the other of X 1 and X 2 and are mutually the same structure
  • the polymerizable liquid crystal compound (A1) is also included.
  • R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Y 1 is, -CH 2 CH 2 -, - more preferably COO- or a single bond, when a plurality of Y 1 are present, Y 1 which binds to X 2 is, -CH 2 CH 2 - or - More preferably CH 2 O—.
  • X 1 and X 2 all have the same structure, it is preferable that there are two or more Y 1 which are bonding methods different from each other.
  • the structure becomes asymmetric, so that smectic liquid crystallinity tends to be exhibited.
  • U 2 is a (meth)acryloyloxy group.
  • U 1 is a hydrogen atom or a (meth)acryloyloxy group, preferably a (meth)acryloyloxy group. From the viewpoint of improving the adhesion between layers of the polarizing film and improving the heat resistance, it is preferable that both U 1 and U 2 are (meth)acryloyloxy groups.
  • the (meth)acryloyloxy group may be in a polymerized state or an unpolymerized state, but is preferably an unpolymerized state.
  • Examples of the alkanediyl group 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, 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 Group and icosane-1,20-diyl group and the like.
  • V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.
  • Examples of the substituent optionally possessed by the alkanediyl group include a cyano group and a halogen atom.
  • the alkanediyl group is preferably unsubstituted, and is an unsubstituted linear alkanediyl group. Is more preferable.
  • W 1 and W 2 are preferably a single bond, —O—, —S—, —COO— or —OCOO—, and more preferably a single bond or —O—.
  • the polymerizable liquid crystal compound (A) is specifically a polymerizable liquid crystal compound having a structure represented by the formulas (Aa) to (Ai) and showing a smectic liquid crystallinity. Is more preferable. From the viewpoint of easily exhibiting high-order smectic liquid crystallinity, it is more preferable to have a structure represented by formula (Aa), formula (Ab) or formula (Ac). In formulas (Aa) to (Ai), * represents a bond (single bond).
  • polymerizable liquid crystal compound (A1) examples include compounds represented by formula (A-1) to formula (A-25).
  • the cyclohexane-1,4-diyl group is preferably a trans isomer.
  • the polymerizable liquid crystal compound (A1) one type may be used alone, or two or more types may be used in combination.
  • the polymerizable liquid crystal compound (A1) is described in, for example, Lub et al., Recl. Trav. Chim. It can be produced by a known method described in Pays-Bas, 115, 321-328 (1996), Japanese Patent No. 4719156 or the like.
  • the polymerizable liquid crystal composition (A) may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (A) as long as the effect of the present invention is not impaired, but a polarizing film having a high degree of alignment order is required.
  • the ratio of the polymerizable liquid crystal compound (A) to the total mass of all the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition (A) is preferably 51% by mass or more, and more preferably 70% by mass. It is above, and more preferably 90% by mass or more.
  • the polymerizable liquid crystal composition (A) contains two or more kinds of polymerizable liquid crystal compounds (A), at least one of them may be the polymerizable liquid crystal compound (A1), all of which are polymerizable. It may be a liquid crystal compound (A1). By combining a plurality of polymerizable liquid crystal compounds, it may be possible to temporarily maintain the liquid crystallinity even at a temperature below the liquid crystal-crystal phase transition temperature.
  • the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition (A) is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, based on the solid content of the polymerizable liquid crystal composition. And more preferably 70 to 99% by mass.
  • solid content means the total amount of the components excluding the solvent from the polymerizable liquid crystal composition.
  • the polymerizable liquid crystal composition (A) comprises a dichroic dye.
  • the dichroic dye means a dye having a property in which the absorbance in the major axis direction of the molecule and the absorbance in the minor axis direction are different.
  • the dichroic dye is a dye that aligns with the liquid crystal compound and exhibits dichroism, and the dichroic dye itself may have polymerizability or may have liquid crystallinity.
  • the dichroic dye that can be used in the present invention is not particularly limited as long as it has the above properties, and may be a dye or a pigment. Further, two or more kinds of dyes or pigments may be used in combination, or a dye and a pigment may be used in combination.
  • the dichroic dye preferably has a maximum absorption wavelength ( ⁇ MAX ) in the range of 300 to 700 nm.
  • ⁇ MAX maximum absorption wavelength
  • dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes.
  • the azo dye examples include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye and a stilbeneazo dye, and a bisazo dye and a trisazo dye are preferable.
  • a compound represented by the formula (I) (hereinafter, referred to as “compound (I)” is also mentioned.
  • K 1 and K 3 independently of each other may have a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a substituent which may have a substituent. It represents a good monovalent heterocyclic group.
  • K 2 is a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic ring which may have a substituent.
  • p represents an integer of 1 to 4.
  • a plurality of K 2 may be the same as or different from each other.
  • Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole.
  • Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from the above heterocyclic compound.
  • the unsubstituted amino group is —NH 2. ) and the like.
  • B 1 to B 30 are each independently 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, a substituted or unsubstituted amino group (substituted amino group). And the definition of the unsubstituted amino group are as described above), chlorine atom or trifluoromethyl group.
  • n1 to n4 each independently represent an integer of 0 to 3.
  • n1 is 2 or more
  • a plurality of B 2 may be the same or different from each other
  • n2 is 2 or more
  • a plurality of B 6 may be the same or different from each other
  • n3 is 2 or more
  • plural B 9 may be the same or different from each other
  • n4 is 2 or more
  • a plurality of B 14 may be the same as or different from each other.
  • the anthraquinone dye is preferably a compound represented by the formula (I-9).
  • R 1 to R 8 each 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.
  • oxazone dye a compound represented by the formula (I-10) is preferable.
  • R 9 to R 15 each 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.
  • acridine dye a compound represented by the formula (I-11) is preferable.
  • R 16 to R 23 each 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 6 carbon atoms of R x is a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group.
  • the aryl group having 6 to 12 carbon atoms include phenyl group, toluyl group, xylyl group and naphthyl group.
  • cyanine dye a compound represented by the formula (I-12) and a compound represented by the formula (I-13) are preferable.
  • D 1 and D 2 each independently represent a group represented by any one of formulas (I-12a) to (I-12d).
  • n5 represents an integer of 1 to 3.
  • D 3 and D 4 each independently represent a group represented by any one of formulas (I-13a) to (1-13h).
  • n6 represents an integer of 1 to 3.
  • the content of the dichroic dye in the polymerizable liquid crystal composition (A) can be appropriately determined according to the type of the dichroic dye to be used, etc., but is preferably 0.
  • the amount is 1 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and further preferably 0.1 to 12 parts by mass.
  • the content of the dichroic dye is within the above range, it is difficult to disturb the alignment of the polymerizable liquid crystal compound, and a polarizing film having a high degree of alignment order can be obtained.
  • the polymerizable liquid crystal composition (A) may further contain a polymerization initiator.
  • the polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound, and is preferably a photopolymerization initiator because it can initiate the polymerization reaction under lower temperature conditions. Specific examples include photopolymerization initiators capable of generating active radicals or acids by the action of light, and among them, photopolymerization initiators capable of generating radicals by the action of light are preferable.
  • the polymerization initiators may be used alone or in combination of two or more.
  • 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 compound examples include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone. And 2,4,6-trimethylbenzophenone and the like.
  • alkylphenone compound examples include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane.
  • 1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[ 4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one Oligomer etc. are mentioned.
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.
  • triazine compound examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl).
  • a commercially available initiator can be used as the polymerization initiator.
  • examples of commercially available polymerization initiators include “Irgacure (registered trademark) 907”, “Irgacure (registered trademark) 184”, “Irgacure (registered trademark) 651”, “Irgacure (registered trademark) 819”, and “Irgacure (registered trademark) 819”.
  • the content may be appropriately determined according to the type and amount of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition (A).
  • the content of the polymerizable initiator is within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the alignment.
  • the polymerizable liquid crystal composition (A) may further contain a photosensitizer.
  • a photosensitizer By using the photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound can be further promoted.
  • photosensitizers include xanthone compounds such as xanthone and thioxanthone (eg, 2,4-diethylthioxanthone and 2-isopropylthioxanthone); anthracene compounds such as anthracene and alkoxy group-containing anthracene (eg dibutoxyanthracene); Examples include phenothiazine and rubrene.
  • the photosensitizers may be used alone or in combination of two or more.
  • the content of the photosensitizer in the polymerizable liquid crystal composition (A) may be appropriately determined depending on the types and the amounts of the photopolymerization initiator and the polymerizable liquid crystal compound, but the content of the polymerizable liquid crystal compound is 100 parts by mass. On the other hand, 0.1 to 30 parts by mass is preferable, 0.5 to 10 parts by mass is more preferable, and 0.5 to 8 parts by mass is further preferable.
  • the polymerizable liquid crystal composition (A) may further contain a leveling agent.
  • the leveling agent has the function of adjusting the fluidity of the polymerizable liquid crystal composition (A) and making the coating film obtained by applying the polymerizable liquid crystal composition (A) even more flat.
  • surfactants As the leveling agent, at least one selected from the group consisting of 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 is preferable.
  • the leveling agents can be used alone or in combination of two or more kinds.
  • 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” (BYK Chemie).
  • leveling agent containing a fluorine atom-containing compound as a main component examples include, for example, “Megafuck (registered trademark) R-08”, “R-30”, “R-90”, “F-410”, and “F-410”.
  • F-411 same “F-443”, same “F-445”, same “F-470”, same "F-471", same “F-477”, same “F-479”, same “ F-482” and “F-483” (DIC Corporation);
  • E1830 "E5844” (Daikin Fine Chemical Research Institute, Inc.) "F-top EF301", “F-top EF303”, “F-top EF351” and “F-top EF352” (Mitsubishi Materials Electronic Chemicals).
  • the content of the leveling agent in the polymerizable liquid crystal composition (A) is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound.
  • the content of the leveling agent is within the above range, the polymerizable liquid crystal compound is likely to be horizontally aligned, unevenness is unlikely to occur, and a smoother polarizing film tends to be obtained.
  • the polymerizable liquid crystal composition (A) may further contain other additives besides the polymerization initiator, the photosensitizer and the leveling agent.
  • Other additives include, for example, release agents, stabilizers, coloring agents such as bluing agents, flame retardants and lubricants.
  • the content of the other additives is more than 0% and 20% by mass with respect to the solid content of the polymerizable liquid crystal composition (A). It is preferably the following or less, more preferably more than 0% and 10% by mass or less.
  • the polymerizable liquid crystal composition (A) may further contain a solvent.
  • a solvent in general, a compound exhibiting a smectic liquid crystallinity has a high viscosity, and therefore it is easy to apply it by adding a solvent to the polymerizable liquid crystal composition, and as a result, a polarizing film is often formed easily.
  • the solvent can be appropriately selected depending on the solubility of the polymerizable liquid crystal compound and the dichroic dye, and specifically, for example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve.
  • Alcohol solvent such as propylene glycol monomethyl ether, ester solvent such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene glycol methyl ether acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl Amyl ketone, ketone solvent such as methyl isobutyl ketone, pentane, hexane, aliphatic hydrocarbon solvent such as heptane, toluene, aromatic hydrocarbon solvent such as xylene, nitrile solvent such as acetonitrile, tetrahydrofuran, ether solvent such as dimethoxyethane, And chlorinated hydrocarbon solvents such as chloroform and chlorobenzene.
  • ester solvent such as ethyl acetate, butyl acetate,
  • the content of the solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 900 parts by mass, and further preferably 180 to 600 with respect to 100 parts by mass of the solid component constituting the polymerizable liquid crystal composition. It is a mass part.
  • the polymerizable liquid crystal composition (A) can be produced by a conventionally known method for preparing a polymerizable liquid crystal composition, and usually the polymerizable liquid crystal compound and the dichroic dye, and if necessary, the above-mentioned additives and It can be prepared by mixing and stirring a solvent and the like.
  • the polymerizable liquid crystal composition (A) contains a polymerizable liquid crystal compound that exhibits a smectic liquid crystal phase and cures in a horizontal alignment state
  • the polymerizable liquid crystal composition (A) has an excellent effect of suppressing the photodegradation of the dichroic dye, and the polarization performance of the composition is improved with time. It is possible to obtain a polarizing film that is less likely to deteriorate from the polymerizable liquid crystal composition (A).
  • a polarizing film is formed from the polymerizable liquid crystal composition (A) containing a polymerizable liquid crystal compound that exhibits a smectic liquid crystal phase and is cured in a horizontally aligned state, a polarizing film having a high degree of alignment order can be obtained.
  • a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase can be obtained by X-ray diffraction measurement.
  • the Bragg peak means a peak derived from the plane periodic structure of molecular orientation. Therefore, in the polarizing film formed from the polymerizable liquid crystal composition of the present invention, it is preferable that the polymerizable liquid crystal compound or a polymer thereof is oriented so that the polarizing film exhibits a Bragg peak in X-ray diffraction measurement.
  • the “horizontal alignment” in which the molecules of the polymerizable liquid crystal compound are aligned in the direction of absorbing light is more preferable.
  • a polarizing film having a molecular orientation plane periodicity of 3.0 to 6.0 ⁇ is preferable.
  • a high degree of orientational order showing a Bragg peak can be realized by controlling the type of polymerizable liquid crystal compound used, the type and amount of dichroic dye, and the like.
  • the polarizing film in the present invention is, for example, to form a coating film of the polymerizable liquid crystal composition (A), Removing solvent from the coating, Increasing the temperature of the polymerizable liquid crystal compound (A) to a temperature at which the liquid phase transitions to a liquid phase or higher, and then decreasing the temperature to cause the polymerizable liquid crystal compound to undergo a phase transition to a smectic phase (smectic liquid crystal state); It can be produced by a method including polymerizing a polymerizable liquid crystal compound while maintaining the smectic phase (smectic liquid crystal state).
  • the coating film of the polymerizable liquid crystal composition (A) is formed, for example, by the polymerizable liquid crystal composition (A) on a substrate or an alignment film described later, particularly a polymerizable liquid crystal in which a solvent is added to adjust the viscosity. It can be performed by applying the composition (A) (hereinafter, also referred to as “polarizing film forming composition”). Further, the composition for forming a polarizing film may be directly applied onto the retardation film or other layers constituting the polarizing plate of the present invention.
  • Examples of the method for applying the composition for forming a polarizing film to a substrate include spin coating method, extrusion method, gravure coating method, die coating method, bar coating method, coating method such as applicator method, and flexo printing method.
  • a known method such as a method can be used.
  • the solvent is removed by drying or the like under the condition that the polymerizable liquid crystal compound (A) contained in the coating film obtained from the composition for forming a polarizing film is not polymerized to form a dry coating film.
  • the drying method include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method.
  • the temperature is raised to a temperature at which the polymerizable liquid crystal compound undergoes a phase transition to a liquid phase or higher, and then the temperature is lowered to allow the polymerizable liquid crystal compound to undergo a smectic phase (smectic liquid crystal State).
  • phase transition may be performed after removing the solvent in the coating film, or may be performed simultaneously with the removal of the solvent.
  • the light to be applied to the dry coating film includes the type of the photopolymerization initiator contained in the dry coating film and the type of the polymerizable liquid crystal compound (A) (in particular, the polymerization of the polymerizable liquid crystal compound (A)). It is appropriately selected depending on the type of the functional group) and the amount thereof.
  • ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction, and that widely used in the art as a photopolymerization device can be used, and by ultraviolet light, as photopolymerizable, It is preferable to select the type of the polymerizable liquid crystal compound or photopolymerization initiator contained in the polymerizable liquid crystal composition.
  • the polymerization temperature can be controlled by irradiating with light while cooling the dried coating film by an appropriate cooling means.
  • the polarizing film can be appropriately formed even if the substrate has relatively low heat resistance. It is also possible to obtain a patterned polarizing film by performing masking or development during photopolymerization.
  • the ultraviolet irradiation intensity is usually 10 to 3,000 mW/cm 2 .
  • the ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of the photopolymerization initiator.
  • the irradiation time with light is usually 0.1 second to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and further preferably 10 seconds to 1 minute.
  • the integrated light amount thereof is 10 to 3,000 mJ/cm 2 , preferably 50 to 2,000 mJ/cm 2 , and more preferably 100 to 1,000 mJ/cm 2. It is 2 .
  • the polarizing film is accompanied by the action of the dichroic dye, so that the conventional host guest type polarizing film (that is, nematic) is used. It has an advantage that the polarization performance is high as compared with a polarizing film having a liquid crystal state of a phase). Further, it has an advantage that it is superior in strength as compared with the case where only the dichroic dye or the lyotropic liquid crystal is applied.
  • the thickness of the polarizing film can be appropriately selected according to the applied display device, and is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 4 ⁇ m, and further preferably 0.5 to 3 ⁇ m.
  • the polarizing film is preferably formed on the alignment film.
  • the alignment film has an alignment regulating force for aligning the polymerizable liquid crystal compound (A) in a desired direction.
  • the alignment film has solvent resistance that does not dissolve by coating the polymerizable liquid crystal compound composition (A) and the like, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound (A). Those having are preferable.
  • Examples of such an alignment film include an alignment film containing an alignment polymer, a photo-alignment film and a glub alignment film having a concavo-convex pattern and a plurality of grooves on the surface, a stretched film stretched in the alignment direction, and the like. And from the viewpoint of quality, a photo-alignment film is preferable.
  • the oriented polymer for example, polyamides or gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, poly Examples include oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable.
  • the oriented polymer may be used alone or in combination of two or more kinds.
  • the orientation film containing the orientation polymer is usually obtained by applying a composition in which the orientation polymer is dissolved in a solvent (hereinafter, sometimes referred to as “orientation polymer composition”) to a substrate and removing the solvent, or It is obtained by applying the oriented polymer composition to a substrate, removing the solvent, and rubbing (rubbing method).
  • a solvent hereinafter, sometimes referred to as “orientation polymer composition”
  • the solvent include the same solvents as those exemplified above as the solvent that can be used when forming the polarizing film.
  • the concentration of the orienting polymer in the orienting polymer composition may be within a range in which the orienting polymer material can be completely dissolved in a solvent, but is preferably 0.1 to 20% in terms of solid content in the solution, and 0 It is more preferably about 1 to 10%.
  • a commercially available alignment film material may be used as it is as the alignment polymer composition.
  • Examples of commercially available alignment film materials include Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), and the like.
  • Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method, and a reduced pressure drying method.
  • Rubbing treatment can be performed as necessary to give the alignment control force to the alignment film (rubbing method).
  • a rubbing cloth is wrapped around a rubbing roll that is rotated, and the orientational polymer composition is applied to the substrate and annealed to form the substrate surface.
  • a method of bringing a film of an oriented polymer into contact can be mentioned.
  • the photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as "composition for forming photo-alignment film") to a substrate and polarizing (preferably, It is obtained by irradiating polarized UV).
  • composition for forming photo-alignment film a composition containing a polymer or monomer having a photoreactive group and a solvent
  • the photo-alignment film is more preferable in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
  • Photoreactive group refers to a group that produces a liquid crystal alignment ability when irradiated with light. Specific examples thereof include a group involved in a photoreaction which is a source of liquid crystal alignment ability such as orientation induction or isomerization reaction of molecules generated by light irradiation, dimerization reaction, photocrosslinking reaction or photodecomposition reaction. Among them, a group involved in the dimerization reaction or the photocrosslinking reaction is preferable because of excellent orientation.
  • a photoreactive group involved in the photodimerization reaction is preferable, and the amount of polarized light irradiation required for photoalignment is relatively small, and in that a photoalignment film excellent in thermal stability and stability over time is easily obtained, Cinnamoyl and chalcone groups are preferred.
  • the polymer having a photoreactive group a polymer having a cinnamoyl group such that the end portion of the polymer side chain has a cinnamic acid structure is particularly preferable.
  • the photo-alignment inducing layer can be formed on the base material by applying the photo-alignment film forming composition onto the base material.
  • the solvent contained in the composition include the same solvents as those exemplified above as the solvent that can be used when forming the polarizing film, and are appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group. You can choose.
  • the content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the kind of the polymer or the monomer and the thickness of the desired photo-alignment film. It is preferably at least 0.2% by mass, and more preferably in the range of 0.3 to 10% by mass.
  • the composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer as long as the characteristics of the photo-alignment film are not significantly impaired.
  • the same method as the method of applying the alignment composition to the base material can be mentioned.
  • the method for removing the solvent from the applied composition for forming a photo-alignment film include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method.
  • polarized light is irradiated from the base material side and the polarized light is transmitted.
  • the irradiation may be performed.
  • the polarized light is substantially parallel light.
  • the wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet) having a wavelength of 250 to 400 nm is particularly preferable.
  • Examples of the light source used for the irradiation of polarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an ultraviolet laser such as KrF and ArF, and the like.
  • a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp are preferable because they have high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer.
  • a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Teller, or a wire grid type polarizer can be used.
  • masking can be performed to form a plurality of regions (patterns) having different liquid crystal alignment directions.
  • the groove alignment film is a film having an uneven pattern or a plurality of grooves (grooves) on the film surface.
  • a polymerizable liquid crystal compound is applied to a film having a plurality of linear globbings arranged at equal intervals, liquid crystal molecules are aligned in the direction along the groove.
  • a method for obtaining the glube alignment film after exposure through an exposure mask having a patterned slit on the photosensitive polyimide film surface, a method of developing and rinsing to form an uneven pattern, a plate having grooves on the surface
  • a method of developing and rinsing to form an uneven pattern, a plate having grooves on the surface To form a layer of UV-curable resin before curing on a sheet-shaped master, and transfer the formed resin layer to a substrate and then cure, and to a film of the UV-curable resin before curing formed on the substrate, Examples include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.
  • the thickness of the alignment film is usually in the range of 10 to 10000 nm, preferably 10 to 1000 nm, more preferably 500 nm or less, and further preferably The range is 10 to 200 nm, and particularly preferably 50 to 150 nm.
  • the polarizing plate of the present invention can be obtained by laminating a transparent protective film having a thickness of 10 ⁇ m or more and 80 ⁇ m or less on at least one surface of the polarizing film via an adhesive composition.
  • the adhesive composition is not particularly limited, and a known adhesive may be used.
  • the polarizing plate in the invention preferably has a transparent protective film laminated only on one surface of the polarizing film.
  • the transparent protective film means a base material having a transparency capable of transmitting light, particularly visible light, and the transparency means a characteristic that the transmittance for a light ray having a wavelength of 380 to 780 nm is 80% or more.
  • Specific transparent protective films include polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; triacetyl cellulose, diacetyl cellulose, cellulose.
  • Cellulose ester such as acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyphenylene sulfide and polyphenylene oxide.
  • polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin resin or polycarbonate is preferable.
  • the cellulose ester is one in which some or all of the hydroxyl groups contained in cellulose have been esterified, and can be easily obtained from the market. Further, the cellulose ester base material can be easily obtained from the market.
  • cellulose ester base materials examples include “Fujituck Film” (Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (Konica Minolta Opto Co., Ltd.). Of these, from the viewpoint of equilibrium water content, cyclic olefin resins, polyethylene terephthalate and polycarbonate are preferable, and cyclic olefin resins are more preferable.
  • the characteristics required of the transparent protective film differ depending on the configuration of the polarizing plate, but normally, a film with the smallest possible retardation is preferable.
  • the film having the smallest retardation include zero-tack (Konica Minolta Opto Co., Ltd.), Z-tack (Fuji Film Co., Ltd.) and other cellulose ester films having no retardation.
  • An unstretched cyclic olefin resin film is also preferable.
  • the surface of the transparent protective film on which the polarizing film is not laminated may be subjected to hard coat treatment, antireflection treatment, antistatic treatment, or the like.
  • the thickness of the transparent protective film is usually 10 to 80 ⁇ m, preferably 20 to 60 ⁇ m, and more preferably 20 to 40 ⁇ m, because if it is too thin, the strength tends to decrease and the workability tends to be poor.
  • the retardation film has the following formula (1): 100 ⁇ Re(550) ⁇ 180 (1) [In the formula, Re(550) represents an in-plane retardation value at a wavelength of 550 nm] It is preferable to satisfy.
  • the retardation film has the in-plane retardation value represented by the above (1), it functions as a so-called ⁇ /4 plate.
  • the formula (1) is preferably 100 nm ⁇ Re(550) ⁇ 180 nm, more preferably 120 nm ⁇ Re(550) ⁇ 160 nm.
  • Re(550) can be measured by the method described in the examples.
  • the retardation film has the following formula (2): Re(450)/Re(550) ⁇ 1 (2) [In the formula, Re(450) and Re(550) represent in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively] It is preferable to satisfy.
  • the retardation film satisfying the above formula (2) has so-called reverse wavelength dispersion and exhibits excellent polarization performance.
  • the value of Re(450)/Re(550) is preferably 0.93 or less, more preferably 0.88 or less, further preferably 0.86 or less, preferably 0.80 or more, more preferably 0. 82 or more.
  • the retardation film is generally obtained by polymerizing a polymerizable liquid crystal compound in an aligned state.
  • the polymerizable liquid crystal compound forming the retardation film (hereinafter, also referred to as “polymerizable liquid crystal compound B”) means a liquid crystal compound having a polymerizable group, particularly a photopolymerizable group.
  • the photopolymerizable group refers to a group that can participate in a polymerization reaction by an active radical generated from a photopolymerization initiator or an acid.
  • Examples of the photopolymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferable, an acryloyloxy group and a methacryloyloxy group are more preferable, and an acryloyloxy group is still more preferable.
  • the liquid crystal property may be thermotropic liquid crystal or lyotropic liquid crystal, and the phase ordered structure may be nematic liquid crystal or smectic liquid crystal.
  • the polymerizable liquid crystal compound B only one kind may be used, or two or more kinds may be used in combination.
  • Examples of the polymerizable liquid crystal compound B include compounds satisfying all of the following (a) to (d) from the viewpoint of providing ease of film formation and the characteristics represented by the formula (Y).
  • a compound having thermotropic liquid crystallinity (A) Having ⁇ electrons in the major axis direction (a) of the polymerizable liquid crystal compound. (C) ⁇ electrons are present in the direction [intersection direction (b)] that intersects with the major axis direction (a). (D) A polymerizable liquid crystal compound defined by the following formula (i), where N( ⁇ a) is the total of ⁇ electrons existing in the major axis direction (a) and N(Aa) is the total of molecular weights present in the major axis direction.
  • ⁇ electron density in the major axis direction (a) of: D( ⁇ a) N( ⁇ a)/N(Aa) (i) And a total of ⁇ electrons existing in the cross direction (b) is N( ⁇ b) and a total of molecular weights existing in the cross direction (b) is N(Ab), and the polymerizable liquid crystal compound is defined by the following formula (ii).
  • ⁇ electron density in the cross direction (b) of: D( ⁇ b) N( ⁇ b)/N(Ab) (ii) And 0 ⁇ [D( ⁇ a)/D( ⁇ b)] ⁇ 1 (Ie, the ⁇ electron density in the cross direction (b) is higher than the ⁇ electron density in the major axis direction (a)).
  • the polymerizable liquid crystal compound B satisfying all of the above (a) to (d) can form a nematic phase by applying it on the alignment film formed by the rubbing treatment and heating it above the phase transition temperature.
  • the polymerizable liquid crystal compounds are usually aligned so that the major axis directions thereof are parallel to each other, and the major axis direction is the alignment direction of the nematic phase. ..
  • the polymerizable liquid crystal compound B having the above properties generally exhibits reverse wavelength dispersion.
  • Specific examples of the compound satisfying the above characteristics (a) to (d) include compounds represented by the following formula (II):
  • the compounds represented may be mentioned.
  • the compounds represented by the above formula (II) can be used alone or in combination of two or more kinds.
  • Ar represents a divalent aromatic group which may have a substituent.
  • the aromatic group as used herein means a group having a planar cyclic structure, and the cyclic structure has a number of ⁇ electrons of [4n+2] according to Huckel's rule.
  • n represents an integer.
  • the divalent aromatic group preferably contains at least one of nitrogen atom, oxygen atom and sulfur atom.
  • G 1 and G 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group.
  • the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a carbon atom.
  • the carbon atom which may be substituted with an alkoxy group, a cyano group or a nitro group of the formulas 1 to 4 and which constitutes the divalent aromatic group or the divalent alicyclic hydrocarbon group is an oxygen atom or a sulfur atom. Alternatively, it may be substituted with a nitrogen atom.
  • L 1 and L 2 are each independently a divalent linking group having an ester structure.
  • T 1 and T 2 are each independently a single bond or a divalent linking group.
  • h and i each independently represent an integer of 0 to 3 and satisfy the relationship of 1 ⁇ h+i.
  • T 1 and T 2 and G 1 and G 2 may be the same or different from each other.
  • E 1 and E 2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom.
  • the contained —CH 2 — may be substituted with —O—, —S—, —Si—, and —COO—.
  • P 1 and P 2 independently of each other represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.
  • G 1 and G 2 are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms.
  • a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group.
  • a substituted 1,4-trans-cyclohexanediyl group is a substituted 1,4-trans-cyclohexanediyl group.
  • at least one of a plurality of G 1 and G 2 present is preferably a divalent alicyclic hydrocarbon group, and at least 1 of G 1 and G 2 bonded to L 1 or L 2 More preferably, it is a divalent alicyclic hydrocarbon group.
  • L 1 and L 2 are each independently preferably —R a1 COOR a2 — (R a1 and R a2 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms), and more preferably — COOR a2-1 - a (R a2-1 is a single bond, -CH 2 -, - - CH 2 CH 2 of representing any), more preferably -COO- or -COOCH 2 CH 2 - is.
  • T 1 and T 2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R a9 OR a10 —, —R a11 COOR a12 —, or —R a13.
  • R a9 to R a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms.
  • T 1 and T 2 are each independently more preferably a single bond, —OR a10-1 —, —CH 2 —, —CH 2 CH 2 —, —COOR a12-1 —, or OCOR a14-1 —. ..
  • R a10-1 , R a12-1 , and R a14-1 each independently represents a single bond, —CH 2 —, or —CH 2 CH 2 —.
  • T 1 and T 2 are each independently more preferably a single bond, —O—, —CH 2 CH 2 —, —COO—, —COOCH 2 CH 2 —, —OCO—, or OCOCH 2 CH 2 —. ..
  • E 1 and E 2 are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.
  • Examples of the polymerizable group represented by P 1 or P 2 include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group and an oxiranyl group. , And an oxetanyl group.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.
  • Ar preferably has at least one selected from an aromatic hydrocarbon ring that may have a substituent, an aromatic heterocycle that may have a substituent, and an electron-withdrawing group.
  • aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable.
  • the aromatic heterocycle includes a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring and a pyrazole ring.
  • a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazole group is more preferable.
  • Ar contains a nitrogen atom, the nitrogen atom preferably has ⁇ electrons.
  • the total number N ⁇ of ⁇ electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, further preferably 14 or more, and particularly It is preferably 16 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.
  • Examples of the aromatic group represented by Ar include groups represented by the following formulas (Ar-1) to (Ar-23).
  • Z 0 , Z 1 and Z 2 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms.
  • Q 1 and Q 2 each independently, -CR 2 'R 3' - , - S -, - NH -, - NR 2 '-, - CO- or O- to represent, R 2' and R 3 '
  • J 1 and J 2 each independently represent a carbon atom or a nitrogen atom.
  • Y 1 , Y 2 and Y 3 each independently represent an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.
  • W 1 and W 2 each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
  • Examples of the aromatic hydrocarbon group for Y 1 , Y 2 and Y 3 include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group.
  • a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aromatic heterocyclic group includes a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, a benzothiazolyl group and the like, a nitrogen atom, an oxygen atom, a sulfur atom and the like, which has at least one hetero atom and has 4 to 20 carbon atoms.
  • Examples of the aromatic heterocyclic group include furyl group, thienyl group, pyridinyl group, thiazolyl group and benzothiazolyl group.
  • Y 1 and Y 2 may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group.
  • the polycyclic aromatic hydrocarbon group means a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly.
  • the polycyclic aromatic heterocyclic group means a fused polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
  • Z 0 , Z 1 and Z 2 are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group or an alkoxy group having 1 to 12 carbon atoms
  • Z 0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyano group
  • Z 1 and Z 2 are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a cyano group.
  • Q 1 and Q 2 are preferably —NH—, —S—, —NR 2′ — and —O—, and R 2′ is preferably a hydrogen atom.
  • R 2′ is preferably a hydrogen atom.
  • —S—, —O—, and —NH— are particularly preferable.
  • formulas (Ar-1) to (Ar-23), formula (Ar-6) and formula (Ar-7) are preferable from the viewpoint of molecular stability.
  • Y 1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0 .
  • the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring which Ar may have, and examples thereof include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and an indole. Ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. This aromatic heterocyclic group may have a substituent.
  • Y 1 may be the above-mentioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0 .
  • examples thereof include a benzofuran ring, a benzothiazole ring and a benzoxazole ring.
  • the compound represented by the formula (II) can be produced, for example, according to the method described in JP 2010-31223A.
  • the content of the polymerizable liquid crystal compound B in the polymerizable liquid crystal composition (B) constituting the retardation film is, for example, 70 to 99.5 with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition (B). It is a mass part, preferably 80 to 99 mass parts, more preferably 90 to 98 mass parts. When the content is within the above range, the orientation of the retardation film tends to be high.
  • the solid content refers to the total amount of components excluding volatile components such as a solvent from the polymerizable liquid crystal composition (B).
  • the polymerizable liquid crystal composition (B) may contain a polymerization initiator for initiating the polymerization reaction of the polymerizable liquid crystal compound B.
  • a polymerization initiator for initiating the polymerization reaction of the polymerizable liquid crystal compound B.
  • the polymerization initiator include the same as those exemplified above as the polymerization initiator that can be used in the polymerizable liquid crystal composition (A).
  • the polymerizable liquid crystal composition (B) contains, as necessary, a photosensitizer, a leveling agent, and the additives exemplified as the additives contained in the polymerizable liquid crystal composition (A). Good.
  • the photosensitizer and the leveling agent include the same as those exemplified above as those usable in the polymerizable liquid crystal composition (A).
  • the retardation film is a composition prepared by adding a solvent to the polymerizable liquid crystal composition (B) containing the polymerizable liquid crystal compound B, and optionally a polymerization initiator, an additive and the like, and mixing and stirring the mixture (
  • composition for forming a retardation film is applied onto a substrate or an alignment film, the solvent is removed by drying, and the polymerizable liquid crystal compound B in the obtained coating film is heated and/or It can be obtained by curing with active energy rays.
  • the base material and/or the alignment film used for producing the retardation film the same ones as those exemplified above as those usable for producing the above-mentioned polarizing film can be mentioned.
  • the solvent used for the composition for forming a retardation film, the coating method of the composition for forming a retardation film, the curing conditions by active energy rays, etc. are all the same as those that can be adopted in the method for producing the above-mentioned polarizing film. Is mentioned.
  • the thickness of the retardation film can be appropriately selected according to the applied display device, but from the viewpoint of thinning and flexibility, it is preferably 0.1 to 10 ⁇ m, more preferably 1 to 5 ⁇ m. More preferably, it is 1 to 3 ⁇ m.
  • the circularly polarizing plate of the present invention comprises the above-mentioned polarizing plate and a retardation film, and the above-mentioned polarizing plate is preferably formed by laminating a transparent protective film, an alignment film (particularly a photo-alignment film) and a polarization film in this order. It becomes.
  • the polarizing plate of the present invention preferably has a transparent protective film laminated on only one side of the polarizing film, and further preferably has the polarizing film and the retardation film laminated.
  • the circularly polarizing plate of the present invention may further include layers other than the polarizing plate and the retardation film (protective layer, adhesive layer, etc.).
  • the above-mentioned polarizing film and retardation film may be bonded via an adhesive layer or a pressure-sensitive adhesive layer, and the retardation film forming composition is directly attached to the above-mentioned polarizing film.
  • the retardation film may be directly formed on the polarizing film of the present invention by coating.
  • the angle formed by the slow axis of the retardation film and the absorption axis of the polarizing film is preferably substantially 45°.
  • substantially 45° means 45° ⁇ 5°.
  • the thickness of the circularly polarizing plate of the present invention is preferably 10 to 300 ⁇ m, more preferably 20 to 200 ⁇ m, and further preferably 25 to 100 ⁇ m from the viewpoint of flexibility and visibility of the display device.
  • the present invention includes a display device including the circularly polarizing plate of the present invention.
  • the display device of the present invention can be obtained, for example, by laminating the polarizing film or the polarizing plate of the present invention on the surface of the display device via an adhesive layer.
  • the effect of the circularly polarizing plate of the present invention is more exerted when the circularly polarizing plate has a hydrophobic base material on both sides.
  • the hydrophobic substrate means, for example, a substrate having a water vapor transmission rate of 10 g/m 2 ⁇ d (40° C./90% RH) (JISK 7129) or less.
  • the type of hydrophobic substrate is not particularly limited, but examples thereof include glass.
  • a display device is a device having a display mechanism and includes a light-emitting element or a light-emitting device as a light-emitting source.
  • a liquid crystal display device an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (field emission display device (FED, etc.), surface field emission display device). (SED)), electronic paper (display device using electronic ink or electrophoretic element), plasma display device, projection display device (grating light valve (GLV) display device, display device having digital micromirror device (DMD)) Etc.) and piezoelectric ceramic displays.
  • EL organic electroluminescence
  • EL inorganic electroluminescence
  • FED field emission display device
  • SED surface field emission display device
  • electronic paper display device using electronic ink or electrophoretic element
  • plasma display device projection display device (grating light valve (GLV) display device, display device having digital micromirror device (DM
  • the liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images.
  • an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.
  • Example 1 ⁇ Production of polarizing plate> [Polarizing plate: production of polarizing plate including a polarizing film formed from a stretched film] A polyvinyl alcohol film having a thickness of 30 ⁇ m (average degree of polymerization: about 2400, saponification degree: 99.9 mol% or more) was uniaxially stretched about 5 times by dry stretching, and while maintaining a tension state, pure water at 40° C. For 40 seconds. Then, the dyeing treatment was carried out by immersing in a dyeing aqueous solution having a iodine/potassium iodide/water mass ratio of 0.044/5.7/100 at 28° C. for 30 seconds.
  • a water-based adhesive was injected between the obtained polarizer and the cycloolefin film (ZF14 manufactured by Zeon Corporation), and they were pasted with a nip roll. While maintaining the tension of the obtained bonded product at 430 N/m, it was dried at 60° C. for 2 minutes to obtain a polarizing plate I having a cycloolefin film as a transparent protective film on one surface.
  • the above water-based adhesive is 100 parts of water, 3 parts of a carboxyl group-modified polyvinyl alcohol (Kuraray Poval KL318; made by Kuraray Co., Ltd.), and a water-soluble polyamide epoxy resin (Sumiraz resin 650; made by Sumika Chemtex Co., Ltd., 1.5 parts of an aqueous solution having a solid content of 30%) was added.
  • a carboxyl group-modified polyvinyl alcohol Kuraray Poval KL318; made by Kuraray Co., Ltd.
  • a water-soluble polyamide epoxy resin Sudiraz resin 650; made by Sumika Chemtex Co., Ltd., 1.5 parts of an aqueous solution having a solid content of 30%
  • composition for forming photo-alignment film was prepared by mixing 5 parts of the following photo-alignment material (number average molecular weight of 28,000) and 95 parts of cyclopentanone (solvent) and stirring the resulting mixture at 80° C. for 1 hour. Obtained.
  • Polymerizable liquid crystal compound B1 (86.0 parts) having the following structure, polymerizable liquid crystal compound A1 (14.0 parts), polyacrylate compound (leveling agent) (BYK-361N; manufactured by BYK-Chemie) (0. 12 parts) and a photopolymerization initiator 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; Ciba Specialty Chemicals) (3.0 parts) are mixed. Then, a polymerizable liquid crystal composition (B1) containing the polymerizable liquid crystal compound B1 and the polymerizable liquid crystal compound A1 was obtained.
  • a cycloolefin polymer film (COP; ZF-14; manufactured by Nippon Zeon Co., Ltd.) was used with a corona treatment device (AGF-B10; manufactured by Kasuga Denki KK) at an output of 0.3 kW and a treatment speed of 3 m/min. Processed twice.
  • the composition for forming a photo-alignment film was applied on a surface subjected to corona treatment by a bar coater and dried at 80° C. for 1 minute, and then a polarized UV irradiation device (SPOT CURE SP-7 with a polarizer unit; manufactured by USHIO INC.) was used.
  • the polymerizable liquid crystal composition B1 was applied onto the alignment film at a speed of 50 mm/sec with a wire of a bar coater set to #30, and dried at 120° C. for 1 minute. Then, using a high pressure mercury lamp (Unicure VB-15201BY-A; manufactured by Ushio Inc.), ultraviolet rays were irradiated from the surface side coated with the polymerizable liquid crystal composition B1 (in a nitrogen atmosphere, a cumulative light amount at a wavelength of 313 nm: 500 mJ. /Cm 2 ) to form a laminate of the retardation film A and the cycloolefin polymer film. When the thickness of the obtained retardation film A was measured with a laser microscope (LEXT; manufactured by Olympus Corporation), it was 2.3 ⁇ m.
  • LXT laser microscope
  • the polyvinyl alcohol side of the polarizing plate I produced as described above and the retardation film A side of the layered product of the retardation film A and the cycloolefin polymer film are compared with the absorption axis of the polarizing plate I and the retardation phase of the retardation film A. After sticking using an acrylic pressure-sensitive adhesive (colorless transparent, non-oriented) so that the angle ( ⁇ ) formed by the axis becomes 45°, the cycloolefin polymer film of the retardation film was peeled off, and the circularly polarizing plate was formed. It was made.
  • composition for forming polarizing layer (Production of composition for forming polarizing layer) The following components were mixed and stirred at 80° C. for 1 hour to obtain a composition for forming a polarizing layer.
  • a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.) was used to irradiate the coating layer for the alignment layer with polarized UV at an integrated light amount of 50 mJ/cm 2 (313 nm standard) to form an alignment layer. Formed.
  • the composition for forming a polarizing layer was applied onto the obtained alignment layer using a bar coater, and then dried in a drying oven set at 110° C. for 1 minute.
  • Example 3 A polarizing plate and a circle were used in the same manner as in Example 2 except that a cycloolefin polymer film (COP; ZF-14; manufactured by Nippon Zeon Co., Ltd.) was used as the base material (transparent protective film) layer instead of the triacetyl cellulose film.
  • COP cycloolefin polymer film
  • ZF-14 cycloolefin polymer film
  • a polarizing plate was prepared and evaluated. The results are shown in Table 1.
  • Example 4 Regarding the retardation film, a polarizing plate and a circularly polarizing plate were produced in the same manner as in Example 2 except that the following polymerizable compound B2 described in JP-A-2016-81035 was used instead of the polymerizable liquid crystal compound B1. Then, the evaluation was carried out. The results are shown in Table 1. Polymerizable compound B2 described in JP-A-2016-81035 was used instead of the polymerizable liquid crystal compound B1. Then, the evaluation was carried out. The results are shown in Table 1. Polymerizable compound B2 described in JP-A-2016-81035 was used instead of the polymerizable liquid crystal compound B1. Then, the evaluation was carried out. The results are shown in Table 1. Polymerizable compound B2 described in JP-A-2016-81035 was used instead of the polymerizable liquid crystal compound B1. Then, the evaluation was carried out. The results are shown in Table 1. Polymerizable compound B2 described in JP-A-2016-81035 was used instead of the poly
  • Example 5 Regarding the retardation film, a polarizing plate and a circularly polarizing plate were prepared and evaluated in the same manner as in Example 2 except that the following polymerizable compound B3 was used instead of the polymerizable liquid crystal compound B1. The results are shown in Table 1. Polymerizable compound B3
  • Example 1 A polarizing plate and a circularly polarizing plate were produced in the same manner as in Example 1 except that a triacetyl cellulose film (TAC; KC2UA; manufactured by Konica Minolta Co., Ltd.) was used as a transparent protective film on both sides of the polarizer as a polarizing plate. , Evaluation was carried out. The results are shown in Table 1.
  • TAC triacetyl cellulose film
  • a triacetyl cellulose film (TAC; KC2UA; manufactured by Konica Minolta Co., Ltd.) is used on one side as a protective film for the polarizing plate, and a cycloolefin polymer film (COP; ZF-14; manufactured by Nippon Zeon Co., Ltd.) is used on the other side of the polarizing plate.
  • a polarizing plate and a circularly polarizing plate were prepared and evaluated in the same manner as in Example 1 except that the retardation layer was attached to the triacetyl cellulose film side. The results are shown in Table 1.
  • Comparative Example 3 A polarizing plate and a circularly polarizing plate were prepared and evaluated in the same manner as in Comparative Example 2 except that the same polymerizable liquid crystal compound as in Example 4 was used as the polymerizable liquid crystal compound in the retardation film. The results are shown in Table 1.
  • Comparative Example 4 A polarizing plate and a circularly polarizing plate were prepared and evaluated in the same manner as in Comparative Example 2 except that the same polymerizable liquid crystal compound as in Example 5 was used as the polymerizable liquid crystal compound in the retardation film.

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Abstract

La présente invention concerne une plaque de polarisation circulaire comprenant : une plaque de polarisation dans laquelle un film protecteur transparent ayant une épaisseur de 10 µm à 80 µm, et un film de polarisation contenant un colorant dichroïque ont été stratifiés ; et un film de contraste de phase qui est un produit durci d'une composition contenant un composé de cristaux liquides polymérisable B. Dans la plaque de polarisation circulaire, le film de contraste de phase a une épaisseur de 5 µm ou moins, le composé de cristaux liquides polymérisable B est un composé ayant une liaison ester à l'intérieur de la structure moléculaire, et la plaque de polarisation a une teneur en humidité d'équilibre à 50 % d'humidité et une température de 23 °C de 1,5 % en masse ou moins.
PCT/JP2020/004517 2019-02-12 2020-02-06 Plaque de polarisation circulaire et dispositif d'affichage el organique l'utilisant WO2020166476A1 (fr)

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JP2022077101A (ja) * 2020-11-11 2022-05-23 日東電工株式会社 位相差層付偏光板の製造方法
TW202234099A (zh) 2020-12-24 2022-09-01 日商住友化學股份有限公司 圓偏光板、光學積層體及圖像顯示裝置
KR20240071393A (ko) 2021-10-01 2024-05-22 스미또모 가가꾸 가부시키가이샤 광학 적층체 및 화상 표시 장치
CN118043708A (zh) 2021-10-01 2024-05-14 住友化学株式会社 层叠膜、光学层叠体以及图像显示装置

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JP2014063143A (ja) * 2012-08-31 2014-04-10 Sumitomo Chemical Co Ltd 円偏光板および表示装置
JP2015143754A (ja) * 2014-01-31 2015-08-06 富士フイルム株式会社 透明フィルム及びその製造方法、透明導電フィルム、タッチパネル、反射防止フィルム、偏光板および表示装置
WO2016194999A1 (fr) * 2015-06-03 2016-12-08 富士フイルム株式会社 Film optique, plaque de polarisation et dispositif d'affichage d'image
WO2017090644A1 (fr) * 2015-11-26 2017-06-01 富士フイルム株式会社 Film optique, plaque polarisante, dispositif d'affichage d'image, procédé de production de composé polymérisable et d'ester monoaryle d'acide 1,4-cyclohexanedicarboxylique
JP2017111264A (ja) * 2015-12-16 2017-06-22 コニカミノルタ株式会社 偏光板保護フィルムの製造方法及び偏光板の製造方法
JP2018022152A (ja) * 2016-07-21 2018-02-08 住友化学株式会社 楕円偏光板

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CN113302528B (zh) 2023-09-22

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