WO2021261435A1 - 円偏光板、有機エレクトロルミネッセンス表示装置 - Google Patents

円偏光板、有機エレクトロルミネッセンス表示装置 Download PDF

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WO2021261435A1
WO2021261435A1 PCT/JP2021/023379 JP2021023379W WO2021261435A1 WO 2021261435 A1 WO2021261435 A1 WO 2021261435A1 JP 2021023379 W JP2021023379 W JP 2021023379W WO 2021261435 A1 WO2021261435 A1 WO 2021261435A1
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Prior art keywords
optically anisotropic
anisotropic layer
liquid crystal
crystal compound
layer
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French (fr)
Japanese (ja)
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慎平 吉田
勇太 高橋
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022531969A priority Critical patent/JP7578692B2/ja
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Priority to US18/068,211 priority patent/US12092847B2/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • 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
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/868—Arrangements for polarized light emission
    • 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

Definitions

  • the present invention relates to a circularly polarizing plate and an organic electroluminescence display device.
  • Patent Document 1 discloses a circularly polarizing plate having an optically anisotropic layer formed by using a liquid crystal compound having a reverse wavelength dispersibility.
  • the present inventors have produced a circularly polarizing plate disclosed in Patent Document 1, attached it to a display element, and evaluated its performance, and found that the above requirements were not sufficiently satisfied.
  • the present invention has a small change in color and a low reflectance when the obtained display device is arranged on a display element and the obtained display device is visually recognized by changing the direction from an oblique direction.
  • An object of the present invention is to provide a circularly polarizing plate. It is also an object of the present invention to provide an organic electroluminescence display device.
  • a circularly polarizing plate having a polarizing element and an optically anisotropic layer is a layer formed by fixing a liquid crystal compound having a reverse wavelength dispersibility twisted and oriented with a spiral axis in the thickness direction.
  • the molecular axis of the liquid crystal compound in the optically anisotropic layer is horizontal with respect to the surface of the optically anisotropic layer.
  • the twist angle is within the range of 64 ⁇ 20 °
  • the polarizing element, the second optically anisotropic layer, and the first optically anisotropic layer are provided in this order.
  • the first optically anisotropic layer is a layer formed by fixing a liquid crystal compound having a reverse wavelength dispersibility twisted and oriented with a spiral axis in the thickness direction.
  • the molecular axis of the liquid crystal compound in the first optically anisotropic layer is horizontal with respect to the surface of the first optically anisotropic layer.
  • the second optically anisotropic layer is a layer formed by immobilizing a homogenically oriented reverse wavelength dispersible liquid crystal compound.
  • the twist angle in the first optically anisotropic layer is within the range of 85 ⁇ 20 °.
  • the polarizing element, the fourth optically anisotropic layer, and the third optically anisotropic layer are provided in this order.
  • the third optically anisotropic layer is a layer formed by fixing a liquid crystal compound having a reverse wavelength dispersibility twisted and oriented with a spiral axis in the thickness direction.
  • the molecular axis of the liquid crystal compound in the third optically anisotropic layer is horizontal with respect to the surface of the third optically anisotropic layer.
  • the fourth optically anisotropic layer is a layer formed by fixing a liquid crystal compound having a reverse wavelength dispersibility twisted and oriented with a spiral axis in the thickness direction.
  • the molecular axis of the liquid crystal compound in the fourth optically anisotropic layer is horizontal with respect to the surface of the fourth optically anisotropic layer.
  • the twisting direction of the liquid crystal compound in the third optically anisotropic layer and the twisting direction of the liquid crystal compound in the fourth optically anisotropic layer are the same.
  • the twist angle of the liquid crystal compound in the fourth optically anisotropic layer is within the range of 26.5 ⁇ 10.0 °.
  • the twist angle of the liquid crystal compound in the third optically anisotropic layer is within the range of 78.6 ⁇ 10.0 °.
  • the circular polarizing plate according to (1) wherein the value of the product ⁇ n4d4 of the rate anisotropy ⁇ n4 and the thickness d4 of the fourth optically anisotropic layer satisfies the formulas (3) and (4) described later, respectively. .. (5)
  • An organic electroluminescence display device having the circularly polarizing plate according to any one of (1) to (5).
  • a circularly polarizing plate having little change in color and low reflectance is provided.
  • an organic electroluminescence display device can also be provided.
  • FIG. It is a schematic diagram. It is sectional drawing of the composition layer for demonstrating step 1.
  • FIG. It is sectional drawing of the composition layer for demonstrating step 2.
  • FIG. In the graph plotting the relationship between the spiral inducing force (HTP: Helical Twisting Power) ( ⁇ m -1 ) ⁇ concentration (mass%) and the light irradiation amount (mJ / cm 2) for each of the chiral agent A and the chiral agent B.
  • HTP Helical Twisting Power
  • ⁇ m -1 concentration
  • mass% the light irradiation amount
  • the in-plane slow phase axis is defined at 550 nm unless otherwise specified.
  • Re ( ⁇ ) and Rth ( ⁇ ) represent in-plane retardation at wavelength ⁇ and retardation in the thickness direction, respectively. Unless otherwise specified, the wavelength ⁇ is 550 nm.
  • the values of the average refractive index of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), And polystyrene (1.59).
  • light means active light or radiation, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excima laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, ultraviolet rays, and the like. It also means an electron beam (EB: Electron Beam) or the like.
  • EUV light Extreme Ultraviolet
  • X-rays extreme ultraviolet rays
  • EB Electron Beam
  • visible light refers to light having a diameter of 380 to 780 nm.
  • the measurement wavelength is 550 nm.
  • the relationship between angles includes a range of errors allowed in the technical field to which the present invention belongs. Specifically, it means that the angle is within a strict angle of ⁇ 10 °, and the error from the strict angle is preferably within a range of ⁇ 5 °, and is within a range of ⁇ 3 ° or less. Is more preferable.
  • the circularly polarizing plate of the present invention has a polarizing element and an optically anisotropic layer, and the optically anisotropic layer is formed by immobilizing a reverse wavelength dispersible liquid crystal compound twist-oriented with a spiral axis in the thickness direction. It is a layer, the molecular axis of the liquid crystal compound in the optically anisotropic layer is horizontal with respect to the surface of the optically anisotropic layer, and the twist angle of the twist-oriented liquid crystal compound is 15 to 360 °.
  • the above-mentioned horizontal means that the inclination angle formed by the average molecular axis of the liquid crystal compound in the optically anisotropic layer with the surface of the optically anisotropic layer is less than 20 °.
  • the inclination angle of the average molecular axis of the liquid crystal compound with the surface of the optically anisotropic layer is measured using an AxoScan (polarimeter) device manufactured by Axometrics and using the device analysis software of the same company.
  • AxoScan polarimeter
  • the present inventors have found that the effect of the present invention can be obtained by immobilizing a liquid crystal compound having a reverse wavelength dispersibility and using an optically anisotropic layer having a twist angle in a predetermined range.
  • FIG. 1 shows a schematic cross-sectional view of the first embodiment of the circularly polarizing plate of the present invention.
  • the circularly polarizing plate 100A has a polarizing element 10 and an optically anisotropic layer 12.
  • the optically anisotropic layer 12 is a layer formed by using the rod-shaped liquid crystal compound LC.
  • the optically anisotropic layer 12 is a layer formed by fixing a rod-shaped liquid crystal compound LC twist-oriented with the thickness direction as a spiral axis, and the molecular axis of the rod-shaped liquid crystal compound LC in the optically anisotropic layer 12 is optically anisotropic.
  • the rod-shaped liquid crystal compound LC shown in the optically anisotropic layer 12 is twist-oriented in the optically anisotropic layer 12.
  • a rod-shaped liquid crystal compound is used for forming the optically anisotropic layer 12, but the liquid crystal compound is not limited to the rod-shaped liquid crystal compound as described later.
  • the optically anisotropic layer 12 is included as the optically anisotropic layer formed by using the liquid crystal compound.
  • the optically anisotropic layer formed by using the liquid crystal compound has a single-layer structure, and only the optically anisotropic layer 12 which is a single layer is optical formed by using the liquid crystal compound. Included as an anisotropic layer.
  • each layer will be described in detail.
  • the polarizing element 10 (linearly polarized light) may be any member as long as it has a function of converting natural light into specific linearly polarized light, and examples thereof include an absorption type polarizing element.
  • the type of the polarizing element 10 is not particularly limited, and a commonly used polarizing element can be used. Examples thereof include an iodine-based polarizing element, a dye-based polarizing element using a dichroic dye, and a polyene-based polarizing element. ..
  • Iodine-based and dye-based polarizing elements are generally produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching it.
  • a protective film may be arranged on one side or both sides of the polarizing element 10.
  • the optically anisotropic layer 12 is a layer formed by fixing a liquid crystal compound twisted and oriented with the thickness direction as a spiral axis, and the molecular axis of the liquid crystal compound in the optically anisotropic layer 12 is the surface of the optically anisotropic layer 12. Horizontal to.
  • the liquid crystal compound having a reverse wavelength dispersibility is an in-plane retardation (Re) value at a specific wavelength (visible light range) of an optically anisotropic layer prepared by using only this compound as a liquid crystal compound. When the measurement is performed, the Re value becomes equal or higher as the measurement wavelength increases.
  • the molecular axis is horizontal with respect to the surface of the optically anisotropic layer, as described above, the inclination angle formed by the average molecular axis of the liquid crystal compound with the surface of the optically anisotropic layer is It shall mean that it is less than 20 °.
  • the method for measuring the tilt angle is as described above.
  • the molecular axis means a major axis (molecular major axis) when the liquid crystal compound is a rod-shaped liquid crystal compound, and a disk-shaped liquid crystal compound when the liquid crystal compound is a disk-shaped liquid crystal compound. Means an axis parallel to the normal direction of the disk surface of.
  • the optically anisotropic layer 12 is preferably a layer in which a chiral nematic phase having a so-called spiral structure is fixed. That is, the optically anisotropic layer 12 is preferably a layer formed by fixing a liquid crystal compound whose molecular axis is horizontally oriented and twist-oriented with the thickness direction as a spiral axis.
  • the "fixed" state is a state in which the orientation of the liquid crystal compound is maintained.
  • the layer has no fluidity in the temperature range of 0 to 50 ° C., usually -30 to 70 ° C. under more severe conditions, and the orientation morphology is changed by an external field or an external force. It is preferable that the state is such that the fixed orientation form can be kept stable.
  • the twist angle of the liquid crystal compound (twist angle in the orientation direction of the rod-shaped liquid crystal compound LC) in the optically anisotropic layer 12 is preferably in the range of 64 ⁇ 20 °. That is, the twist angle of the liquid crystal compound is preferably 44 to 84 °.
  • the twist angle of the liquid crystal compound is preferably 44 to 84 °.
  • the twisting orientation of the liquid crystal compound is intended to mean that the liquid crystal compound from one main surface to the other main surface of the optically anisotropic layer 12 is twisted about the thickness direction of the optically anisotropic layer 12. ..
  • the orientation direction (in-plane slow phase axial direction) of the liquid crystal compound differs depending on the position in the thickness direction of the optically anisotropic layer 12.
  • twisting directions There are two types of twisting directions, but either right-handed twisting or left-handing twisting may be used.
  • the right-handed twist is an in-plane delay on the surface of the optically anisotropic layer 12 on the substituent 10 side, which is the reference axis, when observed from the polarizing element 10 toward the optically anisotropic layer 12. This means that the in-plane slow phase axis on the side opposite to the polarizing element 10 side of the optically anisotropic layer 12 is located clockwise with respect to the phase axis.
  • the twist angle is measured by using an AxoScan (polarimeter) device manufactured by Axometrics and using the device analysis software of the same company.
  • the value of the product ⁇ nd of the refractive index anisotropy ⁇ n of the optically anisotropic layer 12 and the thickness d of the optically anisotropic layer 12 measured at a wavelength of 550 nm is 160 to 240 nm in that the effect of the present invention is more excellent. It is preferably 170 to 230 nm, more preferably 180 to 220 nm, and particularly preferably 190 to 210 nm.
  • the above ⁇ nd is measured by using an AxoScan (polarimeter) device manufactured by Axometrics as in the method for measuring the twist angle, and using the device analysis software of the same company.
  • the thickness of the optically anisotropic layer 12 is not particularly limited, and is preferably 10 ⁇ m or less, more preferably 0.5 to 8.0 ⁇ m, still more preferably 0.5 to 6.0 ⁇ m from the viewpoint of thinning.
  • the thickness of the optically anisotropic layer is intended to be the average thickness of the optically anisotropic layer. The average thickness is obtained by measuring the thicknesses of any five or more points of the optically anisotropic layer and arithmetically averaging them.
  • the in-plane slow phase axis on the surface of the optically anisotropic layer 12 on the polarizing element 10 side and the absorption axis of the polarizing element 10 are parallel to each other.
  • the definition of parallelism is as described above. That is, the angle formed by the in-plane slow phase axis on the surface of the optically anisotropic layer 12 on the polarizing element 10 side and the absorption axis of the polarizing element 10 is preferably within 10 ° (0 to 10 °). ..
  • the angle between the in-plane slow phase axis on the surface of the optically anisotropic layer 12 on the polarizing element 10 side and the absorption axis of the polarizing element 10 is less than 5 °. (0 ° or more and less than 5 °) is more preferable.
  • a rod-shaped liquid crystal compound is used for forming the optically anisotropic layer 12, but the present invention is not limited to this embodiment.
  • a liquid crystal compound can be classified into a rod-shaped type (rod-shaped liquid crystal compound) and a disk-shaped type (disk-shaped liquid crystal compound) according to its shape. Further, there are a small molecule type and a high molecular type, respectively.
  • a polymer generally refers to a molecule having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used.
  • rod-shaped liquid crystal compounds two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of disk-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound
  • the rod-shaped liquid crystal compound include the liquid crystal compounds described in claim 1 of JP-A No. 11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980, which are disk-shaped.
  • the liquid crystal compound include the liquid crystal compounds described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038.
  • the optically anisotropic layer 12 can reduce temperature changes or humidity changes, it is formed by using a reverse wavelength dispersible liquid crystal compound having a polymerizable group (hereinafter, also simply referred to as “polymerizable liquid crystal compound”). Is more preferable. That is, the optically anisotropic layer 12 is preferably a layer formed by fixing a liquid crystal compound having a polymerizable group and having a reverse wavelength dispersibility by polymerization or the like.
  • the type of the polymerizable group is not particularly limited, and a functional group capable of an addition polymerization reaction is preferable, a polymerizable ethylenically unsaturated group or a ring-polymerizable group is more preferable, and a (meth) acryloyl group, a vinyl group, a styryl group, etc. Alternatively, an allyl group is more preferred, and a (meth) acryloyl group is particularly preferred.
  • a polymerizable liquid crystal compound represented by the following formula (I) is preferable.
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
  • the plurality of R 1 , the plurality of R 2 , the plurality of R 3 and the plurality of R 4 may be the same or different from each other. good.
  • G 1 and G 2 are independently divalent alicyclic hydrocarbon groups having 5 to 8 carbon atoms, a group formed by linking a plurality of the alicyclic hydrocarbon groups, an aromatic hydrocarbon group, or an aromatic hydrocarbon group.
  • Representing a group formed by linking a plurality of the aromatic hydrocarbon groups, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or NH—. ..
  • the group in which the plurality of alicyclic hydrocarbon groups are linked means a group in which divalent alicyclic hydrocarbon groups having 5 to 8 carbon atoms are linked by a single bond.
  • the group formed by linking the plurality of the aromatic hydrocarbon groups means a group formed by connecting the aromatic hydrocarbon groups with a single bond.
  • L 1 and L 2 each independently represent a monovalent organic group, and at least one selected from the group consisting of L 1 and L 2 represents a monovalent group having a polymerizable group.
  • Ar represents any aromatic ring selected from the group consisting of the groups represented by the formulas (Ar-1) to (Ar-7).
  • Q 1 represents N or CH
  • Q 2 represents -S-, -O-, or -N (R 7 )-
  • R 7 is a hydrogen atom or Representing an alkyl group having 1 to 6 carbon atoms
  • Y 1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent. show.
  • Examples of the alkyl group having 1 to 6 carbon atoms indicated by R 7 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. Groups and n-hexyl groups are mentioned.
  • Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y 1 include a phenyl group, a 2,6-diethylphenyl group, and an aryl group of a naphthyl group.
  • Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y 1 include a thienyl group, a thiazolyl group, a frill group, and a heteroaryl group of a pyridyl group.
  • examples of the substituent that Y 1 may have include an alkyl group, an alkoxy group, and a halogen atom.
  • an alkyl group an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group) is preferable.
  • alkyl groups having 1 to 4 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred.
  • the alkyl group may be linear, branched, or cyclic.
  • an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group) is more preferable.
  • An alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom or a chlorine atom is preferable.
  • Z 1 , Z 2 and Z 3 are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon.
  • a monovalent alicyclic hydrocarbon group having a number of 3 to 20, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR 8 , -NR 9 R 10 , or , -SR 11 and R 8 to R 11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may be bonded to each other to form an aromatic ring. good.
  • an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group, an ethyl group, an isopropyl group, or tert is preferable.
  • -Pentyl group (1,1-dimethylpropyl group), tert-butyl group, or 1,1-dimethyl-3,3-dimethyl-butyl group is more preferable, and methyl group, ethyl group, or tert-butyl group. Is particularly preferable.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, and the like.
  • Monocyclic saturated hydrocarbon groups such as ethylcyclohexyl group; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, And monocyclic unsaturated hydrocarbon groups such as cyclodecadien; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 2,6].
  • Decyl group tricyclo [3.3.1.1 3,7 ] decyl group, tetracyclo [6.2.1.1 3,6 . 0 2,7 ]
  • Dodecyl group polycyclic saturated hydrocarbon group such as adamantyl group; and the like.
  • the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group, and an aryl group having 6 to 12 carbon atoms ( Especially phenyl group) is preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom, a chlorine atom, or a bromine atom is preferable.
  • alkyl group having 1 to 6 carbon atoms indicated by R 8 to R 11 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Examples thereof include an n-pentyl group and an n-hexyl group.
  • a 1 and A 2 are independently derived from -O-, -N (R 12 )-, -S-, and -CO-, respectively.
  • R 12 represents a hydrogen atom or a substituent.
  • Examples of the substituent represented by R 12 include the same substituents that Y 1 in the above formula (Ar-1) may have.
  • X represents a non-metal atom of groups 14 to 16.
  • a hydrogen atom or a substituent may be bonded to the non-metal atom.
  • R represents a substituent.
  • Examples of the substituent include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, and an aryl group (for example, a phenyl group, etc.). And naphthyl group), cyano group, amino group, nitro group, alkylcarbonyl group, sulfo group, and hydroxyl group.
  • R 2a- , -CR 3a CR 4a- , -NR 5a- , or a divalent linking group consisting of a combination of two or more of these, and R 1a to R 5a are independent hydrogen atoms, respectively. It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 1b , R 2b and R 3b independently represent a hydrogen atom, a fluorine atom, or an alkyl
  • SP 1 and SP 2 are independently single-bonded, have a linear or branched alkylene group having 1 to 12 carbon atoms, or have 1 to 12 carbon atoms.
  • One or more of -CH 2- constituting a linear or branched alkylene group was substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. It represents a divalent linking group and Q represents a substituent. Examples of the substituent include the same substituents that Y 1 in the above formula (Ar-1) may have.
  • examples of the linear or branched alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and the like. Petylene groups are preferred.
  • L 3 and L 4 each independently represent a monovalent organic group.
  • the monovalent organic group include an alkyl group, an aryl group, and a heteroaryl group.
  • the alkyl group may be linear, branched or cyclic, but linear is preferred.
  • the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.
  • the aryl group may be monocyclic or polycyclic, but monocyclic is preferable.
  • the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the heteroaryl group may be monocyclic or polycyclic.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
  • the hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom.
  • the heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the alkyl group, the aryl group, and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents that Y 1 in the above formula (Ar-1) may have.
  • Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
  • Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic. Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
  • aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may be bonded to each other to form a ring.
  • Q 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of Patent Document 2 (International Publication No. 2014/010325).
  • D 1, D 2 G 1 relates to compounds described in JP 2012-021068 (A), G 2, L 1 , L 2 , R 4 , R 5 , R 6 , R 7 , X 1 , Y 1 , Q 1 , Q 2 are described as D 1 , D 2 , G 1 , G 2 , L 1 , L 2 , respectively.
  • R 1 , R 2 , R 3 , R 4 , Q 1 , Y 1 , Z 1 , and Z 2 can be referred to, and the compound represented by the general formula (I) described in JP-A-2008-107767 can be referred to.
  • a 1, a 2, and a 1 a description of X respectively
  • a 2, and X can refer for, Ax of the compound represented by the general formula described in WO 2013/018526 (I), Ay, The description regarding Q 1 can be referred to for Ax, Ay, and Q 3, respectively.
  • Z 3 can refer to the description for Q 1 relates to compounds (A) described in JP-A-2012-021068.
  • the organic group represented by L 1 and L 2 is preferably a group represented by * -D 3- G 3- Sp-P 3, respectively. * Represents the bond position.
  • D 3 is synonymous with D 1.
  • G 3 is a single bond, a divalent aromatic ring group or heterocyclic group having 6 to 12 carbon atoms, a group formed by linking a plurality of the above aromatic ring groups or heterocyclic groups, and a divalent group having 5 to 8 carbon atoms.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the group in which the plurality of aromatic ring groups or heterocyclic groups are linked means a divalent aromatic ring group having 6 to 12 carbon atoms or a group in which the heterocyclic groups are linked by a single bond.
  • the group in which the plurality of alicyclic hydrocarbon groups are linked means a group in which divalent alicyclic hydrocarbon groups having 5 to 8 carbon atoms are linked by a single bond.
  • the G 3 preferred group wherein two cyclohexane rings are linked via a single bond.
  • n represents an integer of 2 to 12
  • m represents an integer of 2 to 6
  • R 8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • -CH 2 in the above group - hydrogen atoms may be substituted with a methyl group.
  • P 3 represents a polymerizable group.
  • the polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
  • examples of the radically polymerizable group include known radically polymerizable groups, and an acryloyl group or a methacryloyl group is preferable. It is known that the acryloyl group is generally faster in terms of polymerization rate, and the acryloyl group is preferable from the viewpoint of improving productivity, but the methacryloyl group can also be used as the polymerizable group of the highly birefringent liquid crystal.
  • Examples of the cationically polymerizable group include known cationically polymerizable groups, and examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and a vinyloxy group. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is more preferable. Examples of particularly preferable polymerizable groups include the following.
  • alkyl group may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group.
  • Se-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and Cyclohexyl group can be mentioned.
  • the method for producing the optically anisotropic layer 12 is not particularly limited, but is a composition containing a polymerizable liquid crystal compound (for example, a rod-shaped liquid crystal compound having a polymerizable group and having a reverse wavelength dispersibility) (hereinafter, simply "polymerizable liquid crystal composition”. ”) Is preferred.
  • a polymerizable liquid crystal compound for example, a rod-shaped liquid crystal compound having a polymerizable group and having a reverse wavelength dispersibility
  • polymerizable liquid crystal composition for example, a rod-shaped liquid crystal compound having a polymerizable group and having a reverse wavelength dispersibility
  • the polymerizable liquid crystal composition contains the above-mentioned polymerizable liquid crystal compound.
  • the polymerizable liquid crystal composition may contain components other than the polymerizable liquid crystal compound.
  • Other components include polymerization initiators.
  • the polymerization initiator used is selected according to the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
  • the content of the polymerization initiator in the polymerizable liquid crystal composition is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the composition.
  • the solid content means a component capable of forming an optically anisotropic layer from which the solvent has been removed, and is a solid content even if the property is liquid.
  • the polymerizable liquid crystal compound may contain a polymerizable monomer other than the liquid crystal compound having a polymerizable group.
  • the polymerizable monomer include radically polymerizable or cationically polymerizable compounds, and a polyfunctional radically polymerizable monomer is preferable.
  • the content of the polymerizable monomer in the polymerizable liquid crystal composition is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, based on the total mass of the liquid crystal compound.
  • the polymerizable liquid crystal compound contains surfactants, adhesion improvers, plasticizers, and solvents in addition to the above.
  • the polymerizable liquid crystal composition contains a chiral agent.
  • the chiral agent is added to twist-orient the polymerizable liquid crystal compound.
  • the liquid crystal compound is a compound exhibiting optical activity such as having an asymmetric carbon in the molecule, the chiral agent is added. Not needed. Further, depending on the manufacturing method and the twist angle, it is not necessary to add a chiral agent.
  • the chiral agent is not particularly limited in structure as long as it is compatible with the polymerizable liquid crystal compound used in combination.
  • Use any of the known chiral agents for example, "Liquid Crystal Device Handbook” edited by the Japan Society for the Promotion of Science 142, Chapter 3, 4-3, TN, Chiral Auxiliary for STN, p. 199, 1989). Can be done.
  • the amount of the chiral agent used is not particularly limited and is adjusted so that the above-mentioned twist angle is achieved.
  • the polymerizable liquid crystal composition contains an orientation control agent (vertical alignment agent, horizontal alignment agent).
  • orientation control agent a known compound can be used.
  • a polymerizable liquid crystal composition is applied to form a coating film, the coating film is subjected to an orientation treatment, the polymerizable liquid crystal compound is oriented, and a curing treatment is performed.
  • the method can be mentioned.
  • the target to which the polymerizable liquid crystal composition is applied is not particularly limited, and examples thereof include a support described later and a polarizing element described above.
  • the object to which the polymerizable liquid crystal composition is applied may be subjected to a rubbing treatment.
  • a support that has been subjected to a rubbing treatment may be used.
  • the coating method of the polymerizable liquid crystal composition includes a curtain coating method, a dip coating method, a spin coating method, a printing coating method, a spray coating method, a slot coating method, a roll coating method, a slide coating method, a blade coating method, and a gravure coating method. , And the wire bar method.
  • the formed coating film is subjected to an orientation treatment to orient the polymerizable liquid crystal compound in the coating film.
  • the alignment treatment can be performed by drying the coating film at room temperature or by heating the coating film.
  • the liquid crystal phase formed by the alignment treatment can generally be transferred by a change in temperature or pressure.
  • a lyotropic liquid crystal compound it can also be transferred by a composition ratio such as the amount of solvent.
  • the conditions for heating the coating film are not particularly limited, but the heating temperature is preferably 50 to 250 ° C, more preferably 50 to 150 ° C, and the heating time is preferably 10 seconds to 10 minutes. Further, after heating the coating film, the coating film may be cooled, if necessary, before the curing treatment (light irradiation treatment) described later.
  • the cooling temperature is preferably 20 to 200 ° C, more preferably 30 to 150 ° C.
  • the coating film on which the polymerizable liquid crystal compound is oriented is subjected to a curing treatment.
  • the method of curing treatment performed on the coating film in which the polymerizable liquid crystal compound is oriented is not particularly limited, and examples thereof include light irradiation treatment and heat treatment. Among them, the light irradiation treatment is preferable, and the ultraviolet irradiation treatment is more preferable from the viewpoint of manufacturing suitability.
  • the irradiation conditions of the light irradiation treatment are not particularly limited, but an irradiation amount of 50 to 1000 mJ / cm 2 is preferable.
  • the atmosphere during the light irradiation treatment is not particularly limited, but a nitrogen atmosphere is preferable.
  • the circularly polarizing plate 100A may have a layer other than the above-mentioned polarizing element 10 and the optically anisotropic layer 12.
  • the circularly polarizing plate 100A may have a support. The support does not correspond to an optically anisotropic layer formed by using a liquid crystal compound.
  • the circularly polarizing plate 100A may have a support between the polarizing element 10 and the optically anisotropic layer 12.
  • the transparent support is intended to be a support having a visible light transmittance of 60% or more, and the transmittance is preferably 80% or more, more preferably 90% or more.
  • the support may be a long support (long support).
  • the length of the long support in the longitudinal direction is not particularly limited, but a support of 10 m or more is preferable, and 100 m or more is preferable from the viewpoint of productivity.
  • the length in the longitudinal direction is not particularly limited, and is often 10,000 m or less.
  • the width of the long support is not particularly limited, but is often 150 to 3000 mm, preferably 300 to 2000 mm.
  • polymer films that can be used as supports include, for example, cellulose acylate films (eg, cellulose triacetate films, cellulose diacetate films, cellulose acetate butyrate films, and cellulose acetate propionate films), polyethylene, polypropylene, and the like.
  • cellulose acylate films eg, cellulose triacetate films, cellulose diacetate films, cellulose acetate butyrate films, and cellulose acetate propionate films
  • polyethylene polypropylene, and the like.
  • Polyethylene film polyester film such as polyethylene terephthalate and polyethylene naphthalate
  • polyacrylic film such as polymethylmethacrylate, polyethersulfone film, polyurethane film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone Film, (meth) acrylic nitrile film
  • polymer film having an alicyclic structure Nonbornen-based resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (Zeonex: trade name, manufactured by Nippon Zeon)
  • the material of the polymer film triacetyl cellulose, polyethylene terephthalate, or a polymer having an alicyclic structure is preferable.
  • the support may contain various additives (eg, optical anisotropy adjuster, wavelength dispersion adjuster, fine particles, plasticizer, UV inhibitor, deterioration inhibitor, and release agent). ..
  • the retardation value (Rth (550)) in the thickness direction at a wavelength of 550 nm of the support is not particularly limited, but is preferably ⁇ 110 to 110 nm, and more preferably ⁇ 80 to 80 nm.
  • the in-plane retardation value (Re (550)) of the support at a wavelength of 550 nm is not particularly limited, but is preferably 0 to 50 nm, more preferably 0 to 30 nm, still more preferably 0 to 10 nm.
  • the thickness of the support is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and even more preferably 20 to 90 ⁇ m.
  • the support may be made of a plurality of laminated sheets.
  • the support is subjected to surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, and flame treatment) on the surface of the support in order to improve the adhesion to the layer provided on the support. May be good.
  • surface treatment eg, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, and flame treatment
  • an adhesive layer undercoat layer
  • the support may be a so-called temporary support.
  • the surface of the support may be directly subjected to the rubbing treatment. That is, a support that has been subjected to a rubbing treatment may be used.
  • the direction of the rubbing treatment is not particularly limited, and the optimum direction is appropriately selected according to the direction in which the liquid crystal compound is desired to be oriented.
  • a processing method widely adopted as a liquid crystal alignment processing step of an LCD (liquid crystal display) can be applied. That is, a method of obtaining orientation by rubbing the surface of the support with paper, gauze, felt, rubber, nylon fiber, polyester fiber, or the like in a certain direction can be used.
  • the circularly polarizing plate 100A may have an alignment film.
  • the alignment film can be a rubbing treatment of an organic compound (preferably a polymer), an oblique deposition of an inorganic compound, the formation of a layer with microgrooves, or an organic compound (eg, ⁇ -tricosan) by the Langmuir-Blojet method (LB film). It can be formed by means such as accumulation of acid (acid, dioctadecylmethylammonium chloride, methyl stearylate). Further, an alignment film in which an alignment function is generated by applying an electric field, applying a magnetic field, or irradiating with light (preferably polarized light) is also known. The alignment film is preferably formed by a polymer rubbing treatment.
  • the circularly polarizing plate 100A may have an adhesive layer.
  • the pressure-sensitive adhesive layer may be provided on the surface of the optically anisotropic layer 12 opposite to the polarizing element 10 side.
  • a known pressure-sensitive adhesive is used as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer.
  • FIG. 2 shows a schematic cross-sectional view of a second embodiment of the circularly polarizing plate of the present invention.
  • the circularly polarizing plate 100B has a polarizing element 10, a second optically anisotropic layer 16, and a first optically anisotropic layer 14 in this order.
  • the first optically anisotropic layer 14 and the second optically anisotropic layer 16 are both layers formed by using the rod-shaped liquid crystal compound LC.
  • the first optically anisotropic layer 14 is a layer formed by fixing a liquid crystal compound having a reverse wavelength dispersibility twisted and oriented with the thickness direction as a spiral axis, and is a rod-shaped liquid crystal compound LC in the first optically anisotropic layer.
  • the molecular axis of is horizontal to the surface of the first optically anisotropic layer. That is, the rod-shaped liquid crystal compound LC shown in the first optically anisotropic layer 14 is twist-oriented in the first optically anisotropic layer 14.
  • the optically anisotropic layer formed by using the liquid crystal compound includes the first optically anisotropic layer 14 and the second optically anisotropic layer 16.
  • the optically anisotropic layer has a multi-layer structure.
  • each layer will be described in detail. Since the polarizing element 10 is the same as the polarizing element 10 described in the first embodiment described above, the description thereof will be omitted.
  • the first optically anisotropic layer 14 is a layer formed by fixing a rod-shaped liquid crystal compound LC twist-oriented with the thickness direction (in the z-axis direction in FIG. 1) as a spiral axis.
  • the molecular axis of the rod-shaped liquid crystal compound LC in the optically anisotropic layer 14 is horizontal to the surface of the first optically anisotropic layer 14.
  • the first optically anisotropic layer 14 is preferably a layer in which a chiral nematic phase having a so-called spiral structure is fixed.
  • the first optically anisotropic layer 14 is preferably a layer formed by fixing a liquid crystal compound whose molecular axis is horizontally oriented and twist-oriented with the thickness direction as a spiral axis.
  • a liquid crystal compound showing a nematic liquid crystal phase and a chiral agent described later.
  • the meaning of the "fixed" state is as described above.
  • the definition that the molecular axis is horizontal with respect to the surface of the optically anisotropic layer is as described in the above-described first embodiment.
  • the twist angle of the rod-shaped liquid crystal compound LC (the twist angle in the orientation direction of the rod-shaped liquid crystal compound LC) is preferably within the range of 85 ⁇ 20 °. That is, the twist angle is preferably 65 to 105 °. Among them, 75 to 95 ° is more preferable, and 80 to 90 ° is even more preferable, because the effect of the present invention is more excellent.
  • the twisting orientation of the liquid crystal compound means that the liquid crystal compound from one main surface to the other main surface of the first optically anisotropic layer 14 is twisted about the thickness direction of the first optically anisotropic layer 14. Intended to be.
  • the orientation direction (in-plane slow phase axial direction) of the liquid crystal compound differs depending on the position in the thickness direction of the first optically anisotropic layer 14.
  • twisting directions There are two types of twisting directions, but either right-handed twisting or left-handing twisting may be used.
  • the right-handed twist is the surface of the first optically anisotropic layer 14 on the substituent 10 side, which is the reference axis when observed from the polarizing element 10 toward the first optically anisotropic layer 14. It means that the in-plane slow phase axis on the side opposite to the polarizing element 10 side of the first optically anisotropic layer 14 is located clockwise with respect to the in-plane slow phase axis in the above.
  • the twist angle is measured by using an AxoScan (polarimeter) device manufactured by Axometrics and using the device analysis software of the same company.
  • Equation (1) 150 nm ⁇ ⁇ n1 d1 ⁇ 230 nm Above all, it is more preferable to satisfy the relation of the formula (1A), and it is further preferable to satisfy the relation of the formula (1B).
  • AxoScan polarimeter
  • the second optically anisotropic layer 16 is a layer formed by using the rod-shaped liquid crystal compound LC. More specifically, the second optically anisotropic layer 16 is a layer formed by using a composition containing a rod-shaped liquid crystal compound LC. Unlike the first optically anisotropic layer 14, the second optically anisotropic layer 16 is a layer formed by immobilizing a homogeneously oriented liquid crystal compound. The meaning of the "fixed" state is as described above.
  • the homogenic orientation is a state in which the molecular axes of the liquid crystal compound (for example, the major axis in the case of a rod-shaped liquid crystal compound) are arranged horizontally and in the same direction with respect to the layer surface (for example, the major axis corresponds to the rod-shaped liquid crystal compound).
  • the term "horizontal” does not require that the liquid crystal compound be strictly horizontal, but means that the angle of inclination of the average molecular axis of the liquid crystal compound in the layer with the surface of the layer is less than 20 °. ..
  • the same direction does not require that the directions are exactly the same, and when the directions of the slow phase axes are measured at arbitrary 20 positions in the plane, the slow phase axes at 20 points are measured. It is assumed that the maximum difference between the slow-phase axis directions among the two directions (the difference between the two slow-phase axis directions having the maximum difference among the 20 slow-phase axis directions) is less than 10 °. ..
  • Equation (2A) 180 nm ⁇ ⁇ n 2d2 ⁇ 220 nm
  • Equation (2B) 190 nm ⁇ ⁇ n 2d2 ⁇ 210 nm
  • AxoScan polarimeter
  • the definition of parallelism is as described above. That is, the in-plane slow phase axis on the surface of the first optically anisotropic layer 14 on the side of the second optically anisotropic layer 16 and the side of the first optically anisotropic layer 14 of the second optically anisotropic layer 16.
  • the angle formed by the in-plane slow phase axis on the surface is within 10 ° (0 to 10 °).
  • An alignment film described later may be arranged between the first optically anisotropic layer 14 and the second optically anisotropic layer 16, but as shown in FIG. 2, the first optically anisotropic layer may be arranged. It is preferable that the layer 14 and the second optically anisotropic layer 16 are adjacent to each other and substantially no alignment film is provided between the first optically anisotropic layer 14 and the second optically anisotropic layer 16. .. When there is substantially no alignment film between the first optically anisotropic layer 14 and the second optically anisotropic layer 16, covalent bonds between the compounds contained in the respective optically anisotropic layers can be used. , Excellent in adhesion.
  • the first optically anisotropic layer 14 contains a twist-oriented liquid crystal compound, a circularly polarizing plate can be obtained without performing a rubbing treatment. More specifically, when the first optically anisotropic layer 14 is produced and then the second optically anisotropic layer 16 is formed on the first optically anisotropic layer 14 by using a liquid crystal compound, the first optically anisotropic layer 14 is formed. (2) The direction of the in-plane slow phase axis on the surface 141 on the optically anisotropic layer 16 side and the surface 142 on the side opposite to the second optically anisotropic layer 16 side is different, and the rubbing treatment is intentionally performed. If the liquid crystal compound is applied onto the surface 141, the liquid crystal compound is oriented along the orientation state of the surface 141, and a desired optically anisotropic layer can be obtained.
  • a rod-shaped liquid crystal compound is used for forming the first optically anisotropic layer 14 and the second optically anisotropic layer 16, but the present invention is not limited to this embodiment.
  • the embodiment of the reverse wavelength dispersible liquid crystal compound used for forming the first optically anisotropic layer 14 and the second optically anisotropic layer 16 is as described in the above-described first embodiment.
  • the relationship between the absorption axis of the polarizing element 10 and the in-plane slow phase axis of the first optically anisotropic layer 14 and the second optically anisotropic layer 16 is as follows (Xa) or (Ya). ) Satisfy the requirements.
  • (Xa) The angle formed by the in-plane slow phase axis of the second optically anisotropic layer 16 and the absorption axis of the polarizing element 10 is within the range of 13 ⁇ 10 ° (3 to 23 °) (preferably 13 ⁇ 6 °). It is within the range of, more preferably within the range of 13 ⁇ 3 °.).
  • the angle formed by the in-plane slow phase axis of the second optically anisotropic layer 16 and the absorption axis of the polarizing element 10 is within the range of 103 ⁇ 10 ° (93 to 113 °) (preferably 103 ⁇ 6 °). It is within the range of, more preferably within the range of 103 ⁇ 3 °.).
  • the relationship between the above will be described in more detail with reference to FIG.
  • the arrows in the polarizing element 10 in FIG. 3 represent the absorption axis
  • the arrows in the second optically anisotropic layer 16 and the first optically anisotropic layer 14 represent the in-plane slow-phase axes in the respective layers. Further, in FIG.
  • the absorption axis of the polarizing element 10, the in-plane slow phase axis of the second optically anisotropic layer 16, and the first optical anisotropy when observed from the white arrow in FIG. 3 are shown.
  • the relationship of the angle of the layer 14 with the in-plane slow phase axis is shown.
  • the rotation angle of the in-plane slow-phase axis is a positive value in the counterclockwise direction and a negative value in the clockwise direction with respect to the absorption axis of the polarizing element 10 when observed from the white arrow in FIG. Expressed as a value.
  • the angle ⁇ 1a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis of the second optically anisotropic layer 16 is 13 °. That is, the in-plane slow phase axis of the second optically anisotropic layer 16 is rotated by ⁇ 13 ° (clockwise 13 °) with respect to the absorption axis of the polarizing element 10.
  • FIG. 3 shows an embodiment in which the in-plane slow phase axis of the second optically anisotropic layer 16 is located at a position of -13 °, but the present invention is not limited to this embodiment and may be in the range of -13 ⁇ 10 °. Just do it.
  • the second optically anisotropic layer 16 has the same in-plane slow phase axis at both interfaces. That is, the angle ⁇ 2a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 162 on the first optically anisotropic layer 14 side is substantially the same as the above ⁇ 1a.
  • the in-plane slow phase axis on the surface 162 of the second optically anisotropic layer 16 on the side of the first optically anisotropic layer 14 and the second optically anisotropic layer 14 of the first optically anisotropic layer 14 are shown. It is parallel to the in-plane slow phase axis on the surface 141 on the layer 16 side. That is, the angle ⁇ 3a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 141 of the first optically anisotropic layer 14 on the side of the second optically anisotropic layer 16 is substantially the same as ⁇ 1a. be.
  • the in-plane slow phase axis on the surface 141 of the first optically anisotropic layer 14 on the second optical anisotropic layer 16 side and the second optically anisotropic layer 16 side of the first optically anisotropic layer 14 forms the twist angle described above.
  • a twist angle of 85 ° is described as an example as shown in FIG. 3
  • the in-plane slow phase axis of the optically anisotropic layer 12 rotates by ⁇ 85 ° (clockwise 85 °).
  • the angle ⁇ 4a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 142 of the first optically anisotropic layer 14 is 98 °.
  • the in-plane slow phase axis on the surface 142 of the first optically anisotropic layer 14 is clockwise with respect to the in-plane slow phase axis on the surface 141 of the first optically anisotropic layer 14.
  • the mode of rotation by 85 ° is shown, but the mode is not limited to this mode, and the rotation angle may be in the range of 65 to 105 ° clockwise.
  • the in-plane slow-phase axis of the second optically anisotropic layer 16 is located at a position of 13 ° clockwise with respect to the absorption axis of the polarizing element 10, and the first optical difference is obtained.
  • the twisting direction of the liquid crystal compound in the anisotropic layer 14 indicates a clockwise direction (right twist). The twisting direction is observed from the white arrow in FIG. 3, and is it twisted to the right with respect to the in-plane slow phase axis on the surface (surface 141) on the polarizing element 10 side in the first optically anisotropic layer 14. , Judge whether it is a left twist.
  • FIG. 3 the in-plane slow-phase axis of the second optically anisotropic layer 16 is located at a position of 13 ° clockwise with respect to the absorption axis of the polarizing element 10, and the first optical difference is obtained.
  • the twisting direction of the liquid crystal compound in the anisotropic layer 14 indicates a clockwise direction (right twist). The twist
  • the in-plane slow phase axis of the second optically anisotropic layer 16 and the twisting direction of the liquid crystal compound in the first optically anisotropic layer 14 are described in detail in a clockwise direction, but at a predetermined angle.
  • the counterclockwise aspect may be used as long as the above relationship is satisfied. More specifically, the in-plane slow-phase axis of the second optically anisotropic layer 16 is located at a position of 13 ° counterclockwise with respect to the absorption axis of the polarizing element 10, and the first optically anisotropic layer 14 is located.
  • the twisting direction of the liquid crystal compound inside may be counterclockwise (left twist).
  • the absorption axis of the substituent 10 is used as a reference (0 °) as a reference (0 °).
  • the in-plane slow axis of the optically anisotropic layer 16 is in the range of 13 ⁇ 10 °, and the twisting direction of the first optically anisotropic layer 14 is counterclockwise, or the second optical anisotropic.
  • the in-plane slow axis of the sex layer 16 may be in the range of ⁇ 13 ⁇ 10 °, and the twisting direction of the first optically anisotropic layer 14 may be clockwise.
  • the relationship with the phase axis will be described in more detail with reference to FIG.
  • the arrows in the polarizing element 10 in FIG. 5 represent the absorption axis
  • the arrows in the second optically anisotropic layer 16 and the first optically anisotropic layer 14 represent the in-plane slow-phase axes in the respective layers.
  • the absorption axis of the polarizing element 10, the in-plane slow phase axis of the second optically anisotropic layer 16, and the first optical anisotropy when observed from the white arrow in FIG. 5 are shown.
  • the relationship of the angle of the layer 14 with the in-plane slow phase axis is shown.
  • the rotation angle of the in-plane slow-phase axis is a positive value in the counterclockwise direction and a negative value in the clockwise direction with respect to the absorption axis of the polarizing element 10 when observed from the white arrow in FIG. Expressed as a value.
  • the embodiment shown in FIG. 5 has the same configuration as the embodiment shown in FIG. 3, except that the absorption axis of the polarizing element 10 differs from the absorption axis of the polarizing element 10 in FIG. 5 by 90 °.
  • the angle ⁇ 1a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis of the second optically anisotropic layer 16 is 103 °. That is, the in-plane slow phase axis of the second optically anisotropic layer 16 is rotated by ⁇ 103 ° (clockwise 103 °) with respect to the absorption axis of the polarizing element 10. Note that FIG.
  • the present invention is not limited to this embodiment and may be in the range of ⁇ 103 ⁇ 10 °. Just do it.
  • the second optically anisotropic layer 16 has the same in-plane slow phase axis at both interfaces. That is, the angle ⁇ 2a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 162 on the optically anisotropic layer 12 side is substantially the same as ⁇ 1a.
  • the in-plane slow phase axis on the surface 162 of the second optically anisotropic layer 16 on the side of the first optically anisotropic layer 14 and the first optically anisotropic layer 14 are shown. It is parallel to the in-plane slow phase axis on the surface 141 on the second optically anisotropic layer 16 side. That is, the angle ⁇ 3a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 141 of the first optically anisotropic layer 14 on the side of the second optically anisotropic layer 16 is substantially the same as ⁇ 1a. be.
  • the in-plane slow phase axis on the surface 141 of the first optically anisotropic layer 14 on the side of the second optically anisotropic layer 16 and the first optically anisotropic layer 14 are shown.
  • the in-plane slow phase axis on the surface 142 opposite to the second optically anisotropic layer 16 side has the above-mentioned twist angle.
  • a twist angle of 85 ° is described as an example as shown in FIG. 3
  • the in-plane slow phase axis of the optically anisotropic layer 12 rotates by ⁇ 85 ° (clockwise 85 °). Therefore, the angle ⁇ 4a formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 142 of the first optically anisotropic layer 14 is 188 °.
  • the in-plane slow phase axis of the second optically anisotropic layer 16 is located at ⁇ 103 ° with respect to the absorption axis of the polarizing element 10, and the first optically anisotropic layer 16 is located at ⁇ 103 °.
  • the twisting direction of the liquid crystal compound in the layer 14 indicates clockwise (right twist). The twisting direction is observed from the white arrow in FIG. 5, and is it twisted to the right with respect to the in-plane slow phase axis on the surface (surface 141) on the polarizing element 10 side in the first optically anisotropic layer 14. , Judge whether it is a left twist. In FIG.
  • the in-plane slow phase axis of the second optically anisotropic layer 16 and the twisting direction of the liquid crystal compound in the first optically anisotropic layer 14 are described in detail in a clockwise direction, but at a predetermined angle.
  • the counterclockwise aspect may be used as long as the above relationship is satisfied.
  • the liquid crystal compound in the first optically anisotropic layer 14 has the in-plane slow phase axis of the second optically anisotropic layer 16 at a position of 103 ° with respect to the absorption axis of the polarizing element 10.
  • the twisting direction may be counterclockwise (left twist).
  • the absorption axis of the substituent 10 is used as a reference (0 °) as a reference (0 °).
  • the in-plane slow axis of the optically anisotropic layer 16 is in the range of 103 ⁇ 10 °, and the twisting direction of the first optically anisotropic layer 14 is counterclockwise, or the second optical anisotropic.
  • the in-plane slow axis of the sex layer 16 may be in the range of ⁇ 103 ⁇ 10 °, and the twisting direction of the first optically anisotropic layer 14 may be clockwise.
  • the circularly polarizing plate 100B may have a layer other than the polarizing element 10, the second optically anisotropic layer 16, and the first optically anisotropic layer 14.
  • the circularly polarizing plate 100B may have a support. The embodiment of the support is as described in the first embodiment described above.
  • the circularly polarizing plate 100B may have a support between the polarizing element 10 and the second optically anisotropic layer 16.
  • the circularly polarizing plate 100B may have an alignment film. The aspect of the alignment film is as described in the first embodiment described above.
  • the circularly polarizing plate 100B may have an adhesive layer.
  • the pressure-sensitive adhesive layer may be provided on the surface of the first optically anisotropic layer 14 opposite to the polarizing element 10 side.
  • a known pressure-sensitive adhesive is used as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer.
  • the method for producing the circularly polarizing plate is not particularly limited, and known methods can be mentioned.
  • the circularly polarizing plate may be continuously manufactured by roll-to-roll.
  • a first optically anisotropic layer and a second optically anisotropic layer exhibiting predetermined optical characteristics are respectively produced, and the optically anisotropic layer and the polarizing element are attached to an adhesive layer (for example, an adhesive layer or an adhesive layer).
  • the circularly polarizing plate can be manufactured by laminating them in a predetermined order.
  • a first optically anisotropic layer and a second optically anisotropic layer are sequentially produced on the support using the polymerizable liquid crystal composition to produce an optical film, and the obtained optical film is produced.
  • a circularly polarizing plate may be manufactured by bonding with a polarizing element.
  • the polymerizable liquid crystal composition is applied onto the support to form the second optically anisotropic layer, and then the polymerizable liquid crystal composition is applied onto the second optically anisotropic layer to form the first optical.
  • An anisotropic layer may be formed.
  • the embodiment of the polymerizable liquid crystal composition and the procedure of the method for producing the optically anisotropic layer using the polymerizable liquid crystal composition are as described in the first embodiment.
  • the following steps 1 to 5 may be carried out.
  • a laminate of the first optically anisotropic layer and the second optically anisotropic layer can be produced in one coating step.
  • Step 1 A chiral agent containing at least a photosensitive chiral agent whose spiral inducing force is changed by light irradiation, and a reverse wavelength dispersible liquid crystal compound having a polymerizable group (hereinafter, in the description of steps 1 to 5, simply A step of applying a polymerizable liquid crystal composition containing a "liquid crystal compound") onto a support to form a composition layer
  • Step 2 The composition layer is heat-treated to obtain a liquid crystal in the composition layer.
  • Step 3 Orienting the compound Step 3: After step 2, the composition layer is irradiated with light under the condition of an oxygen concentration of 1% by volume or more.
  • Step 4 After step 3, the composition layer is heat-treated.
  • Step 5 After step 4, the composition layer is subjected to a curing treatment to fix the orientation state of the liquid crystal compound, and to form a first optically anisotropic layer and a second optically anisotropic layer. Steps The procedure of each of the above steps will be described in detail below.
  • Step 1 supports a polymerizable liquid crystal composition containing at least a photosensitive chiral agent whose spiral inducing force is changed by light irradiation, a reverse wavelength dispersible liquid crystal compound having a polymerizable group, and an orientation control agent. This is a step of applying on the body to form a composition layer. By carrying out this step, a composition layer to be subjected to a light irradiation treatment described later is formed.
  • the various components contained in the polymerizable liquid crystal composition are as described above, and the photosensitive chiral agent not described above will be described in detail below.
  • the spiral-inducing force (HTP) of the chiral agent is a factor indicating the spiral orientation ability represented by the following formula (X).
  • Formula (X) HTP 1 / (length of spiral pitch (unit: ⁇ m) ⁇ concentration of chiral auxiliary to liquid crystal compound (mass%)) [ ⁇ m -1 ]
  • the photosensitive chiral agent whose spiral-inducing force changes by light irradiation may be liquid crystal or non-liquid crystal.
  • the chiral agent A generally contains an asymmetric carbon atom in many cases.
  • the chiral agent A may be an axial asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom.
  • the chiral agent A may have a polymerizable group.
  • the chiral agent A may be a chiral agent whose spiral-inducing force is increased by light irradiation, or may be a chiral agent whose spiral-inducing force is decreased. Of these, a chiral agent whose spiral-inducing force is reduced by light irradiation is preferable.
  • "increase and decrease of spiral-inducing force” means increase / decrease when the initial spiral direction (before light irradiation) of chiral agent A is "positive".
  • Examples of the chiral agent A include so-called photoreactive chiral agents.
  • the photoreactive chiral agent is a compound having a chiral portion and a photoreactive portion whose structure is changed by light irradiation, and for example, a compound that greatly changes the torsional force of the liquid crystal compound according to the irradiation amount.
  • the chiral agent A is preferably a compound having at least a photoisomerization site, and more preferably the photoisomerization site has a photoisomerizable double bond.
  • the photoisomerization site having a double bond capable of photoisomerization is a stilbene site, a chalcone site, an azobenzene site or a stilbene site in that photoisomerization is likely to occur and the difference in spiral induced force before and after light irradiation is large.
  • a stilbene moiety is preferred, and a cinnamoyle moiety, a chalcone moiety or a stilbene moiety is more preferred in that the absorption of visible light is small.
  • the photoisomerization site corresponds to the photoreaction site whose structure is changed by the above-mentioned light irradiation.
  • step 1 at least the above-mentioned chiral agent A is used.
  • the step 1 may be an embodiment in which two or more kinds of chiral agents A are used, or a chiral agent whose spiral inducing force does not change by irradiation with at least one kind of chiral agent A and at least one kind of light (hereinafter, simply "chiral agent”). B ”) may be used.
  • the chiral agent B may be liquid crystal or non-liquid crystal.
  • the chiral agent B generally contains an asymmetric carbon atom in many cases.
  • the chiral agent B may be an axial asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom.
  • the chiral agent B may have a polymerizable group.
  • the chiral agent B a known chiral agent can be used.
  • the chiral agent B is preferably a chiral agent that induces a spiral in the opposite direction to the above-mentioned chiral agent A. That is, for example, when the spiral induced by the chiral agent A is in the right direction, the helix induced by the chiral agent B is in the left direction.
  • the content of the chiral agent A in the composition layer is not particularly limited, but is preferably 5.0% by mass or less, preferably 3.0% by mass or less, based on the total mass of the liquid crystal compound in that the liquid crystal compound can be easily oriented uniformly. It is more preferably 0% by mass or less, further preferably 2.0% by mass or less, particularly preferably less than 1.0% by mass, particularly preferably 0.8% by mass or less, and most preferably 0.5% by mass or less.
  • the lower limit is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more.
  • the chiral auxiliary A may be used alone or in combination of two or more. When two or more kinds of the above chiral agents A are used in combination, the total content is preferably within the above range.
  • the content of the chiral agent B in the composition layer is not particularly limited, but is preferably 5.0% by mass or less, preferably 3.0% by mass or less, based on the total mass of the liquid crystal compound in that the liquid crystal compound can be easily oriented uniformly. It is more preferably 0% by mass or less, further preferably 2.0% by mass or less, particularly preferably less than 1.0% by mass, particularly preferably 0.8% by mass or less, and most preferably 0.5% by mass or less.
  • the lower limit is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more.
  • the chiral auxiliary B may be used alone or in combination of two or more. When two or more kinds of the above chiral agents B are used in combination, the total content is preferably within the above range.
  • the total content of the chiral agents (total content of all chiral agents) in the composition layer is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, based on the total mass of the liquid crystal compound. , 2.0% by mass or less is more preferable, and 1.0% by mass or less is particularly preferable.
  • the lower limit is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more.
  • the method of applying the polymerizable liquid crystal composition to form the composition layer is not particularly limited, and examples thereof include the method of applying the above-mentioned polymerizable liquid crystal composition.
  • the film thickness of the composition layer is not particularly limited, but is preferably 0.1 to 20 ⁇ m, more preferably 0.2 to 15 ⁇ m, and even more preferably 0.5 to 10 ⁇ m.
  • Step 2 is a step of heat-treating the composition layer to orient the liquid crystal compound in the composition layer.
  • the liquid crystal compound in the composition layer is in a predetermined orientation state.
  • the heat treatment conditions the optimum conditions are selected according to the liquid crystal compound used. Among them, the heating temperature is often 10 to 250 ° C, more often 40 to 150 ° C, and even more often 50 to 130 ° C.
  • the heating time is often 0.1 to 60 minutes, and more often 0.2 to 5 minutes.
  • the absolute value of the weighted average helical twisting power of the chiral agent in the composition layer formed in the step 1 is preferably 0.0 ⁇ 1.9 .mu.m -1, is 0.0 ⁇ 1.5 [mu] m -1 It is more preferably 0.0 to 1.0 ⁇ m -1 , particularly preferably 0.0 to 0.5 ⁇ m -1 , and most preferably zero.
  • the weighted average chiral-inducing force of the chiral agent is the spiral-inducing force of each chiral agent and the composition of each chiral agent when two or more kinds of chiral agents are contained in the composition layer. It represents the total value of the product of the concentration (% by mass) in the material layer divided by the total concentration (% by mass) of the chiral auxiliary in the composition layer. For example, when two kinds of chiral agents (chiral agent X and chiral agent Y) are used in combination, it is represented by the following formula (Y).
  • the spiral-inducing force is a positive value.
  • the spiral-inducing force is a negative value. That is, for example, if helical twisting power of the chiral agent of 10 [mu] m -1, when the spiral direction of the spiral, which is induced by the chiral agent is a right-handed represents a helical twisting power as 10 [mu] m -1. On the other hand, when the spiral direction of the spiral induced by the chiral agent is left-handed, the spiral induced force is expressed as -10 ⁇ m -1.
  • FIG. 7 is a schematic cross-sectional view of the support 18 and the composition layer 20.
  • the chiral agent A and the chiral agent B are present at the same concentration, the spiral direction induced by the chiral agent A is left-handed, and the spiral direction induced by the chiral agent B is. Is right-handed.
  • the absolute value of the spiral-inducing force of the chiral agent A and the absolute value of the spiral-inducing force of the chiral agent B are assumed to be the same.
  • Step 3 is a step of irradiating the composition layer with light in the presence of oxygen after the step 2.
  • the mechanism of this process will be described with reference to the drawings.
  • the support 18 is viewed from the direction opposite to the composition layer 20 side (the direction of the white arrow in FIG. 8). Irradiate with light. Although the light irradiation is carried out from the support 18 side in FIG. 8, it may be carried out from the composition layer 20 side.
  • the surface of the second region 20B is on the air side.
  • the oxygen concentration in the second region 20B is high, and the oxygen concentration in the first region 20A is low. Therefore, when the composition layer 20 is irradiated with light, the polymerization of the liquid crystal compound easily proceeds in the first region 20A, and the orientation state of the liquid crystal compound is fixed.
  • the chiral agent A is also present in the first region 20A, and the chiral agent A is also exposed to light, and the spiral inducing force changes.
  • the orientation state of the liquid crystal compound remains. No change occurs.
  • the oxygen concentration is high in the second region 20B, even if light irradiation is performed, the polymerization of the liquid crystal compound is inhibited by the oxygen, and the polymerization is difficult to proceed.
  • the chiral agent A is also present in the second region 20B, the chiral agent A is exposed to light and the spiral inducing force changes. Therefore, when step 4 (heat treatment) described later is carried out, the orientation state of the liquid crystal compound changes along the changed spiral-inducing force.
  • step 3 the fixation of the orientation state of the liquid crystal compound is likely to proceed in the region on the substrate side of the composition layer. Further, in the region opposite to the substrate side of the composition layer, the fixation of the orientation state of the liquid crystal compound is difficult to proceed, and the spiral inducing force changes according to the exposed chiral agent A.
  • Step 3 is carried out under the condition that the oxygen concentration is 1% by volume or more.
  • the oxygen concentration is preferably 2% by volume or more, more preferably 5% by volume or more, in that regions having different orientation states of the liquid crystal compounds are likely to be formed in the optically anisotropic layer.
  • the upper limit is not particularly limited, but 100% by volume can be mentioned.
  • the irradiation intensity of the light irradiation in the step 3 is not particularly limited and can be appropriately determined based on the spiral-inducing force of the chiral agent A.
  • the irradiation amount of the light irradiation in the step 3 is not particularly limited, but is preferably 300 mJ / cm 2 or less, and more preferably 200 mJ / cm 2 or less in that a predetermined optically anisotropic layer is easily formed.
  • the lower limit, in terms of easy predetermined optical anisotropic layer is formed is preferably 5 mJ / cm 2 or more, 10 mJ / cm 2 or more is more preferable.
  • the light irradiation in step 3 is preferably carried out at 15 to 70 ° C. (preferably 15 to 50 ° C.).
  • the light used for light irradiation may be any light that is exposed to the chiral agent A. That is, the light used for light irradiation is not particularly limited as long as it is an active ray or radiation that changes the spiral-inducing force of the chiral agent A. Examples include ultraviolet rays, X-rays, ultraviolet rays, and electron beams. Of these, ultraviolet rays are preferable.
  • Step 4 is a step of heat-treating the composition layer after the step 3.
  • the orientation state of the liquid crystal compound changes in the region where the spiral-inducing force of the chiral agent A in the composition layer irradiated with light changes.
  • the orientation state of the liquid crystal compound is fixed in the first region 20A, whereas the liquid crystal compound in the second region 20B.
  • the polymerization of the liquid crystal compound is difficult to proceed, and the orientation state of the liquid crystal compound is not fixed.
  • the spiral-inducing force of the chiral agent A changes.
  • the force for twisting the liquid crystal compound changes in the second region 20B as compared with the state before light irradiation. This point will be described in more detail.
  • the chiral agent A and the chiral agent B are present in the composition layer 20 shown in FIG.
  • the spiral direction induced by the chiral agent A is left-handed, and the chiral agent B causes the composition layer 20.
  • the induced spiral direction is right-handed.
  • the absolute value of the spiral-inducing force of the chiral agent A and the absolute value of the spiral-inducing force of the chiral agent B are the same. Therefore, the weighted average spiral inducing force of the chiral agent in the composition layer before light irradiation is 0.
  • the vertical axis represents “the spiral-inducing force of the chiral agent ( ⁇ m -1 ) ⁇ the concentration of the chiral agent (mass%)”, and the farther the value is from zero, the larger the spiral-inducing force.
  • the horizontal axis represents "light irradiation amount (mJ / cm 2 )”.
  • the weighted average spiral-inducing force of the chiral agent in the above increases, and the right-handed spiral-inducing force becomes stronger. That is, as for the spiral-inducing force that induces the spiral of the liquid crystal compound, the larger the irradiation dose, the larger the spiral-inducing force in the direction (+) of the spiral induced by the chiral agent B. Therefore, when the composition layer 20 after the step 3 in which such a change in the weighted average spiral inducing force is generated is heat-treated to promote the reorientation of the liquid crystal compound, as shown in FIG. In the two regions 20B, the liquid crystal compound LC is twisted and oriented along a spiral axis extending along the thickness direction of the composition layer 20.
  • the polymerization of the liquid crystal compound proceeds during step 3 and the orientation state of the liquid crystal compound is fixed, so that the reorientation of the liquid crystal compound is not possible. Does not progress.
  • a plurality of regions having different orientation states of the liquid crystal compounds are formed along the thickness direction of the composition layer.
  • the degree of twist of the liquid crystal compound LC can be appropriately adjusted depending on the type of chiral agent A used, the exposure amount in step 3, and the like, and a predetermined twist angle can be realized.
  • a chiral agent whose spiral-inducing force is reduced by light irradiation is used as the chiral agent A
  • the present invention is not limited to this embodiment.
  • a chiral agent whose spiral-inducing force is increased by light irradiation may be used as the chiral agent A.
  • the spiral-inducing force induced by the chiral agent A increases due to light irradiation, and the liquid crystal compound is twisted or oriented in the turning direction induced by the chiral agent A.
  • the mode in which the chiral agent A and the chiral agent B are used in combination has been described, but the mode is not limited to this mode.
  • the chiral agent A1 that induces left-handed winding and the chiral agent A2 that induces right-handed winding may be used in combination.
  • the chiral agents A1 and A2 may be chiral agents whose spiral-inducing force increases or may be chiral agents whose spiral-inducing force decreases, respectively.
  • a chiral agent that induces left-handed winding and whose spiral-inducing force increases by light irradiation and a chiral agent that induces right-handed winding and whose spiral-inducing force decreases by light irradiation are used in combination. You may.
  • the optimum conditions are selected according to the liquid crystal compound used.
  • the heating temperature is preferably a temperature for heating from the state of step 3, in many cases of 35 to 250 ° C, more often in the case of 50 to 150 ° C, and in the case of more than 50 ° C and 150 ° C or less. Even more, especially at 60-130 ° C.
  • the heating time is often 0.01 to 60 minutes, and more often 0.03 to 5 minutes.
  • the absolute value of the weighted average spiral-inducing force of the chiral agent in the composition layer after light irradiation is not particularly limited, but the weighted average spiral-inducing force of the chiral agent in the composition layer after light irradiation and before light irradiation.
  • the absolute value of the difference between the weighted average helical twisting power preferably 0.05 .mu.m -1 or more, more preferably 0.05 ⁇ 10.0 [mu] m -1, more preferably 0.1 ⁇ 10.0 [mu] m -1.
  • Step 5 is a step of performing a curing treatment on the composition layer after the step 4 to fix the orientation state of the liquid crystal compound and to form the first optically anisotropic layer and the second optically anisotropic layer. be.
  • the orientation state of the liquid crystal compound in the composition layer is fixed, and as a result, a predetermined optically anisotropic layer is formed. That is, a laminated film of an optically anisotropic layer formed by fixing a liquid crystal compound in a twisted orientation and an optically anisotropic layer formed by fixing a liquid crystal compound not twisted or oriented can be applied in a single coating process. Can be formed.
  • the method of the curing treatment is not particularly limited, and examples thereof include a photo-curing treatment and a thermosetting treatment. Among them, the light irradiation treatment is preferable, and the ultraviolet irradiation treatment is more preferable.
  • a light source such as an ultraviolet lamp is used for ultraviolet irradiation.
  • the irradiation amount of light (for example, ultraviolet rays) is not particularly limited, but is generally preferably about 100 to 800 mJ / cm 2.
  • FIG. 12 shows a schematic cross-sectional view of a third embodiment of the optical film of the present invention.
  • the circularly polarizing plate 100C has a polarizing element 10, a fourth optically anisotropic layer 24, and a third optically anisotropic layer 22 in this order.
  • the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 are both layers in which a rod-shaped liquid crystal compound LC twisted and oriented with the thickness direction as a spiral axis is fixed.
  • the molecular axis of the rod-shaped liquid crystal compound LC in the third optically anisotropic layer 22 is horizontal with respect to the surface of the third optically anisotropic layer 22, and the rod-shaped liquid crystal compound in the fourth optically anisotropic layer 24.
  • the molecular axis of the LC is horizontal to the surface of the fourth optically anisotropic layer 24.
  • the optically anisotropic layer 22 formed by using the liquid crystal compound includes the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24. That is, in the circularly polarizing plate 100C, the optically anisotropic layer has a multi-layer structure.
  • the polarizing element 10 is the same as the polarizing element 10 described in the first embodiment described above, the description thereof will be omitted.
  • each layer will be described in detail.
  • the third optically anisotropic layer 22 is a layer formed by fixing a rod-shaped liquid crystal compound LC twist-oriented with the thickness direction (in the z-axis direction in FIG. 12) as a spiral axis.
  • the molecular axis of the rod-shaped liquid crystal compound LC in the optically anisotropic layer is horizontal to the surface of the third optically anisotropic layer.
  • the third optically anisotropic layer 22 is preferably a layer in which a chiral nematic phase having a so-called spiral structure is fixed.
  • the third optically anisotropic layer 22 is preferably a layer formed by fixing a liquid crystal compound whose molecular axis is horizontally oriented and twist-oriented with the thickness direction as a spiral axis.
  • a liquid crystal compound showing a nematic liquid crystal phase and a chiral agent described later.
  • the meaning of the "fixed" state is as described above.
  • the definition that the molecular axis is horizontal with respect to the surface of the optically anisotropic layer is as described in the above-described first embodiment.
  • the twist angle of the rod-shaped liquid crystal compound LC (the twist angle in the orientation direction of the rod-shaped liquid crystal compound LC) is preferably 78.6 ⁇ 10.0 °, that is, the twist angle is preferably 68.6 to 88.6 °. Among them, 70.6 to 86.6 ° is more preferable, and 72.6 to 84.6 ° is even more preferable, because the effect of the present invention is more excellent.
  • the twisting orientation of the liquid crystal compound means that the liquid crystal compound from one main surface to the other main surface of the third optically anisotropic layer 22 is twisted about the thickness direction of the third optically anisotropic layer 22. Intended to be.
  • the orientation direction (in-plane slow phase axial direction) of the liquid crystal compound differs depending on the position in the thickness direction of the third optically anisotropic layer 22.
  • twisting directions There are two types of twisting directions, but either right-handed twisting or left-handing twisting may be used.
  • the right-handed twist is the surface of the third optically anisotropic layer 22 on the substituent 10 side, which is the reference axis when observed from the polarizing element 10 toward the third optically anisotropic layer 22. It means that the in-plane slow phase axis on the side opposite to the polarizing element 10 side of the third optically anisotropic layer 22 is located clockwise with respect to the in-plane slow phase axis in the above.
  • the twist angle is measured by using an AxoScan (polarimeter) device manufactured by Axometrics and using the device analysis software of the same company.
  • Equation (3) 110 nm ⁇ ⁇ n3d3 ⁇ 170 nm Above all, it is more preferable to satisfy the relation of the formula (3A), and it is further preferable to satisfy the relation of the formula (3B).
  • Equation (3A) 120 nm ⁇ ⁇ n 3d3 ⁇ 160 nm
  • Equation (3B) 130 nm ⁇ ⁇ n 3d3 ⁇ 150 nm
  • the above ⁇ n3d3 is measured by using an AxoScan (polarimeter) device manufactured by Axometrics and using the device analysis software of the same company as the method for measuring the twist angle.
  • the fourth optically anisotropic layer 24 is a layer formed by fixing a rod-shaped liquid crystal compound LC twist-oriented with the thickness direction (in the z-axis direction in FIG. 12) as a spiral axis.
  • the molecular axis of the rod-shaped liquid crystal compound LC in the optically anisotropic layer is horizontal with respect to the surface of the fourth optically anisotropic layer.
  • the fourth optically anisotropic layer 24 is preferably a layer in which a chiral nematic phase having a so-called spiral structure is fixed.
  • the fourth optically anisotropic layer 24 is preferably a layer formed by fixing a liquid crystal compound whose molecular axis is horizontally oriented and twist-oriented with the thickness direction as a spiral axis.
  • a liquid crystal compound showing a nematic liquid crystal phase and a chiral agent described later.
  • the meaning of the "fixed" state is as described above.
  • the definition that the molecular axis is horizontal with respect to the surface of the optically anisotropic layer is as described in the above-described first embodiment.
  • the twist angle of the rod-shaped liquid crystal compound LC (the twist angle in the orientation direction of the rod-shaped liquid crystal compound LC) is preferably in the range of 26.5 ⁇ 10.0 °. That is, the twist angle is preferably 16.5 to 36.5 °. Among them, 18.5 to 34.5 ° is more preferable, and 20.5 to 32.5 ° is even more preferable, because the effect of the present invention is more excellent.
  • the twisting orientation of the liquid crystal compound means that the liquid crystal compound from one main surface to the other main surface of the fourth optically anisotropic layer 24 is twisted about the thickness direction of the fourth optically anisotropic layer 24. Intended to be.
  • the orientation direction (in-plane slow phase axial direction) of the liquid crystal compound differs depending on the position in the thickness direction of the fourth optically anisotropic layer 24.
  • twisting directions There are two types of twisting directions, but either right-handed twisting or left-handing twisting may be used.
  • the right-handed twist is the surface of the fourth optically anisotropic layer 24 on the substituent 10 side, which is the reference axis when observed from the polarizing element 10 toward the fourth optically anisotropic layer 24. It means that the in-plane slow phase axis on the side opposite to the polarizing element 10 side of the fourth optically anisotropic layer 24 is located clockwise with respect to the in-plane slow phase axis in the above.
  • Equation (4) 252 nm ⁇ ⁇ n 4d4 ⁇ 312 nm Above all, it is more preferable to satisfy the relation of the formula (4A), and it is further preferable to satisfy the relation of the formula (4B).
  • Equation (4A) 262 nm ⁇ ⁇ n 4d 4 ⁇ 302 nm Equation (4B) 272 nm ⁇ ⁇ n 4d 4 ⁇ 292 nm
  • AxoScan polarimeter
  • the definition of parallelism is as described above. That is, the in-plane slow phase axis on the surface of the third optically anisotropic layer 22 on the side of the fourth optically anisotropic layer 24 and the third optically anisotropic layer 22 side of the fourth optically anisotropic layer 24.
  • the angle formed by the in-plane slow phase axis on the surface is within 10 ° (0 to 10 °).
  • the twisting direction of the liquid crystal compound in the third optically anisotropic layer 22 and the twisting direction of the liquid crystal compound in the fourth optically anisotropic layer 24 are the same direction.
  • the in-plane slow phase axis on the surface of the third optically anisotropic layer 22 opposite to the fourth optically anisotropic layer 24 is used as a reference.
  • the in-plane slow phase axis of the third optically anisotropic layer 22 is rotated clockwise, the in-plane retard on the surface of the fourth optically anisotropic layer 24 on the third optically anisotropic layer 22 side.
  • the in-plane slow phase axis on the surface of the fourth optically anisotropic layer 24 opposite to the third optically anisotropic layer 22 side is rotated clockwise with respect to the phase axis.
  • the in-plane slow phase axis on the surface of the third optically anisotropic layer 22 opposite to the fourth optically anisotropic layer 24 is used as a reference.
  • the in-plane slow-phase axis of the third optically anisotropic layer 22 is rotated counterclockwise, the in-plane on the surface of the fourth optically anisotropic layer 24 on the third optically anisotropic layer 22 side.
  • the in-plane slow phase axis on the surface of the fourth optically anisotropic layer 24 opposite to the third optically anisotropic layer 22 side is rotated counterclockwise with respect to the slow axis. ..
  • An alignment film described later may be arranged between the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24, but as shown in FIG. 12, the third optically anisotropic layer 24 may be arranged. It is preferable that the layer 22 and the fourth optically anisotropic layer 24 are adjacent to each other and substantially no alignment film is provided between the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24. .. When there is substantially no alignment film between the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24, covalent bonds between the compounds contained in the respective optically anisotropic layers can be used. , Excellent in adhesion.
  • a rod-shaped liquid crystal compound is used for forming the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24, but the present invention is not limited to this embodiment.
  • the liquid crystal compound include the liquid crystal compound described in the first embodiment.
  • the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 can reduce the temperature change or the humidity change, it is more preferable to form the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 by using a liquid crystal compound having a polymerizable group and having a reverse wavelength dispersibility. .. That is, the third optically anisotropic layer 22 or the fourth optically anisotropic layer 24 is preferably a layer formed by fixing a liquid crystal compound having a polymerizable group and having a reverse wavelength dispersibility by polymerization or the like.
  • the type of the polymerizable group is not particularly limited, and a functional group capable of an addition polymerization reaction is preferable, a polymerizable ethylenically unsaturated group or a ring-polymerizable group is more preferable, and a (meth) acryloyl group, a vinyl group, a styryl group, etc. Alternatively, an allyl group is more preferred, and a (meth) acryloyl group is particularly preferred.
  • the relationship between the absorption axis of the polarizing element 10 and the in-plane slow phase axis of the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 is as follows (Xb) or (Yb). It is preferable to meet the requirements of. (Xb)
  • the angle formed by the in-plane slow phase axis on the surface of the fourth optically anisotropic layer 24 on the polarizing element 10 side and the absorption axis of the polarizing element 10 is in the range of 0 ⁇ 10 ° (-10 to 10 °). Within (preferably within the range of 0 ⁇ 6 °).
  • the angle formed by the in-plane slow phase axis on the surface of the fourth optically anisotropic layer 24 on the polarizing element 10 side and the absorption axis of the polarizing element 10 is within the range of 90 ⁇ 10 ° (80 to 100 °). (Preferably within the range of 90 ⁇ 6 °).
  • the relationship between the above will be described in more detail with reference to FIG.
  • the arrows in the polarizing element 10 in FIG. 13 indicate the absorption axis
  • the arrows in the fourth optically anisotropic layer 24 and the third optically anisotropic layer 22 indicate the in-plane slow-phase axis in each layer. Further, in FIG.
  • the absorption axis of the polarizing element 10 the in-plane slow phase axis of the fourth optically anisotropic layer 24, and the third optical anisotropy when observed from the white arrow in FIG. 13
  • the relationship of the angle of the layer 22 with the in-plane slow phase axis is shown.
  • the rotation angle of the in-plane slow-phase axis is a positive value in the counterclockwise direction and a negative value in the clockwise direction with respect to the absorption axis of the polarizing element 10 when observed from the white arrow in FIG. Expressed as a value.
  • the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 241 of the fourth optically anisotropic layer 24 on the polarizing element 10 side are parallel to each other.
  • the definition of parallelism is as described above. That is, the angle formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 241 on the polarizing element 10 side of the fourth optically anisotropic layer 24 is 0 ⁇ 10 °.
  • the fourth optically anisotropic layer 24 is a layer formed by immobilizing a twist-oriented liquid crystal compound having a spiral axis in the thickness direction. Therefore, as shown in FIG.
  • the in-plane slow phase axis on the surface 221 on the 22 side has the above-mentioned twist angle (26.5 ° in FIG. 13). That is, the in-plane slow phase axis of the fourth optically anisotropic layer 24 rotates by ⁇ 26.5 ° (clockwise 26.5 °). Therefore, the angle ⁇ 2b formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 242 of the fourth optically anisotropic layer 24 is 26.5 °.
  • the in-plane slow phase axis on the surface 242 of the fourth optically anisotropic layer 24 is clockwise with respect to the in-plane slow phase axis on the surface 241 of the fourth optically anisotropic layer 24.
  • the mode of rotation by 26.5 ° is shown, but the mode is not limited to this mode, and the rotation angle may be in the range of 26.5 ⁇ 10.0 ° clockwise.
  • the in-plane slow phase axis on the surface 242 of the fourth optically anisotropic layer 24 on the third optically anisotropic layer 22 side and the fourth optically anisotropic layer 22 of the third optically anisotropic layer 22 are shown. It is parallel to the in-plane slow phase axis on the surface 221 on the layer 24 side. That is, the angle ⁇ 3b formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 221 on the side of the fourth optically anisotropic layer 24 of the third optically anisotropic layer 22 is substantially the same as the above angle ⁇ 2b. Is.
  • the third optically anisotropic layer 22 is a layer formed by immobilizing a twist-oriented liquid crystal compound having a spiral axis in the thickness direction. Therefore, as shown in FIG. 13, the in-plane slow phase axis on the surface 221 of the third optically anisotropic layer 22 on the side of the fourth optically anisotropic layer 24 and the fourth of the third optically anisotropic layer 22.
  • the in-plane slow phase axis on the surface 222 opposite to the optically anisotropic layer 24 side has the above-mentioned twist angle (78.6 ° in FIG. 4).
  • the in-plane slow phase axis of the third optically anisotropic layer 22 rotates by ⁇ 78.6 ° (clockwise 78.6 °). Therefore, the angle ⁇ 4b formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 222 of the third optically anisotropic layer 22 is 105.1 °.
  • the in-plane slow phase axis on the surface 222 of the third optically anisotropic layer 22 is clockwise with respect to the in-plane slow phase axis on the surface 221 of the third optically anisotropic layer 22.
  • the mode of rotation by 78.6 ° is shown, but the mode is not limited to this mode, and the rotation angle may be in the range of 78.6 ⁇ 10.0 in the clockwise direction.
  • the twisting directions of the liquid crystal compounds in the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 are both clockwise with respect to the absorption axis of the polarizing element 10. (Right twist) is shown.
  • the mode in which the twisting direction is clockwise (clockwise twisting) has been described in detail, but the twisting directions of the liquid crystal compounds in the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 are both opposite to each other. It may be in a clockwise mode.
  • the absorption axis of the polarizing element 10 in the embodiment represented by (Yb) above, the in-plane slow phase axis of the third optically anisotropic layer 22, and the in-plane retard of the fourth optically anisotropic layer 24 The relationship with the phase axis will be described in more detail with reference to FIG.
  • the arrows in the polarizing element 10 in FIG. 15 indicate the absorption axis, and the arrows in the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 represent the in-plane slow-phase axis in each layer. Further, in FIG.
  • the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 221 and the surface 222 of the third optically anisotropic layer 22 when observed from the white arrow in FIG. The relationship between the angles of the fourth optically anisotropic layer 24 with the in-plane slow phase axis on the surface 241 and the surface 242 is shown.
  • the rotation angle of the in-plane slow-phase axis is positive in the counterclockwise direction with respect to the absorption axis of the polarizing element 10 (0 °). It is represented by a negative angle value around it.
  • the embodiment shown in FIG. 15 has the same configuration as the embodiment shown in FIG. 13, except that the absorption axis of the polarizing element 10 differs from the absorption axis of the polarizing element 10 in FIG. 15 by 90 °.
  • the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 241 of the fourth optically anisotropic layer 24 are orthogonal to each other. That is, the angle ⁇ 1b formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 241 of the fourth optically anisotropic layer 24 is 90 °.
  • the definition of orthogonality is as described above.
  • the in-plane slow phase axis has the above-mentioned twist angle (26.5 ° in FIG. 15). That is, the in-plane slow phase axis of the fourth optically anisotropic layer 24 rotates by ⁇ 26.5 ° (clockwise 26.5 °).
  • the angle ⁇ 2b formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 242 of the fourth optically anisotropic layer 24 is 116.5 °.
  • the in-plane slow phase axis on the surface 242 of the fourth optically anisotropic layer 24 is clockwise with respect to the in-plane slow phase axis on the surface 241 of the fourth optically anisotropic layer 24.
  • the mode of rotation by 26.5 ° is shown, but the mode is not limited to this mode, and the rotation angle may be in the range of 26.5 ⁇ 10 ° clockwise.
  • the in-plane slow phase axis on the surface 242 of the fourth optically anisotropic layer 24 on the third optically anisotropic layer 22 side and the fourth optically anisotropic layer 22 of the third optically anisotropic layer 22 are shown. It is parallel to the in-plane slow phase axis on the surface 221 on the layer 24 side. That is, the angle ⁇ 3b formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 221 on the side of the fourth optically anisotropic layer 24 of the third optically anisotropic layer 22 is substantially the same as ⁇ 2b. be.
  • the in-plane slow phase axis on the opposite surface 222 has the above-mentioned twist angle (78.6 ° in FIG. 15). That is, the in-plane slow phase axis of the third optically anisotropic layer 22 rotates by ⁇ 78.6 ° (clockwise 78.6 °).
  • the angle ⁇ 4b formed by the absorption axis of the polarizing element 10 and the in-plane slow phase axis on the surface 222 of the third optically anisotropic layer 22 is 195.1 °.
  • the in-plane slow phase axis on the surface 222 of the third optically anisotropic layer 22 is clockwise with respect to the in-plane slow phase axis on the surface 221 of the third optically anisotropic layer 22.
  • the mode of rotation by 78.6 ° is shown, but the mode is not limited to this mode, and the rotation angle may be in the range of 78.6 ⁇ 10 ° clockwise.
  • the twisting directions of the liquid crystal compounds in the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 are both clockwise with respect to the absorption axis of the polarizing element 10. (Right twist) is shown.
  • the mode in which the twisting direction is clockwise (clockwise twisting) is described in detail, but the twisting directions of the liquid crystal compounds in the third optically anisotropic layer 22 and the fourth optically anisotropic layer 24 are both opposite to each other. It may be in a clockwise mode.
  • the aspect shown in FIG. 13 is more preferable.
  • the circularly polarizing plate 100C may have a layer other than the polarizing element 10, the third optically anisotropic layer 22, and the fourth optically anisotropic layer 24.
  • the circularly polarizing plate 100C may have a support. The embodiment of the support is as described in the first embodiment described above.
  • the circularly polarizing plate 100C may have a support between the polarizing element 10 and the third optically anisotropic layer 22.
  • the circularly polarizing plate 100C may have an alignment film. The aspect of the alignment film is as described in the first embodiment described above.
  • the circularly polarizing plate 100C may have an adhesive layer.
  • the pressure-sensitive adhesive layer may be provided on the surface of the third optically anisotropic layer 22 opposite to the polarizing element 10 side.
  • a known pressure-sensitive adhesive is used as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer.
  • the method for producing the circularly polarizing plate is not particularly limited, and known methods can be mentioned.
  • the circularly polarizing plate may be continuously manufactured by roll-to-roll.
  • a third optically anisotropic layer and a fourth optically anisotropic layer exhibiting predetermined optical characteristics are respectively produced, and the optically anisotropic layer and the polarizing element are attached to an adhesive layer (for example, an adhesive layer or an adhesive layer).
  • the circularly polarizing plate can be manufactured by laminating them in a predetermined order.
  • a third optically anisotropic layer and a fourth optically anisotropic layer were sequentially prepared on the support using the polymerizable liquid crystal composition to produce an optical film, and the obtained optical film was produced.
  • a circularly polarizing plate may be manufactured by bonding with a polarizing element.
  • a polymerizable liquid crystal composition is applied onto a support to form a fourth optically anisotropic layer, and then a polymerizable liquid crystal composition is applied onto the fourth optically anisotropic layer to form a third optical.
  • An anisotropic layer may be formed.
  • the embodiment of the polymerizable liquid crystal composition and the procedure of the method for producing the optically anisotropic layer using the polymerizable liquid crystal composition are as described in the first embodiment.
  • the display device of the present invention has a display element and the above-mentioned circularly polarizing plate.
  • the optically anisotropic layer in the circularly polarizing plate is arranged on the display element side. That is, the polarizing element in the circularly polarizing plate is arranged on the visual recognition side.
  • the display element include an organic EL display element and a liquid crystal display element.
  • the organic EL display device has at least an organic EL display element and a circularly polarizing plate. The circularly polarizing plate is arranged so that the optically anisotropic layer faces the organic EL display element side.
  • the organic EL display element is a member in which a plurality of organic compound thin films including a light emitting layer or a light emitting layer are formed between a pair of electrodes of an anode and a cathode, and is a hole injection layer, a hole transport layer, and an electron injection in addition to the light emitting layer. It may have a layer, an electron transport layer, a protective layer, and the like, and each of these layers may have other functions. Various materials can be used to form each layer.
  • Example A1> Preparation of Cellulose Achillate Film (Substrate)
  • the following components are put into a mixing tank, stirred, heated at 90 ° C. for 10 minutes, filtered through a filter paper having an average pore diameter of 34 ⁇ m and a sintered metal filter having an average pore diameter of 10 ⁇ m, and subjected to cellulose acylate dope (hereinafter, simply “”. Also called “dope”) was manufactured.
  • Cellulose acylate dope ⁇ Cellulose acylate (acetyl substitution degree 2.86, viscosity average polymerization degree 310) 100 parts by mass sugar ester compound 1 (represented by chemical formula (S4)) 6.0 parts by mass sugar ester compound 2 (represented by chemical formula (S5)) 2.0 parts by mass silica particle dispersion (AEROSIL R972, Nippon Aerosil Co., Ltd.) Made) 0.1 part by mass Solvent (methylene chloride / methanol / butanol) Predetermined amount ⁇
  • the above-mentioned dope was cast using a drum film forming machine.
  • the above-mentioned doping for forming the core layer so as to be in contact with the metal substrate cooled to 0 ° C. and the above-mentioned doping for forming the surface layer on the core layer were co-injected from the die, and then obtained.
  • the film was stripped off.
  • the drum was made of SUS (Steel Use Stainless).
  • the film stripped from the drum was dried at 30-40 ° C. for 20 minutes during transport using a tenter device that clips and transports both ends of the film with clips.
  • a tenter device that clips and transports both ends of the film with clips.
  • the obtained film was rolled and conveyed, it was post-dried by zone heating. Then, the obtained film was knurled and then wound up.
  • the film thickness of the obtained long cellulose acylate film was 40 ⁇ m, Re (550) was 1 nm, and Rth (550) was 26 nm.
  • optically anisotropic layer The cellulose acylate film produced above was continuously subjected to a rubbing treatment. At this time, the longitudinal direction and the conveying direction of the long film are parallel to each other, and the angle between the longitudinal direction of the film (the conveying direction) and the rotation axis of the rubbing roller is set to 90 °.
  • the following optically anisotropic layer coating liquid (A) was applied onto the rubbing-treated film using a Geeser coating machine, and heated at 80 ° C. for 60 seconds.
  • the film on which the coating film was formed was irradiated with light of a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) having an irradiation amount of 500 mJ at 80 ° C. to fix the orientation state of the liquid crystal compound.
  • a metal halide lamp manufactured by Eye Graphics Co., Ltd.
  • An optically anisotropic layer A1 was produced.
  • the product ⁇ nd of ⁇ n and d at a wavelength of 550 nm of the optically anisotropic layer A1 is 200 nm
  • the direction of the in-plane slow axis on the surface of the optically anisotropic layer A1 on the cellulose acylate film side is 90 °
  • the optics are optical.
  • the direction of the in-plane slow-phase axis is based on the width direction of the cellulose acylate film by observing the laminate of the cellulose acylate film and the optically anisotropic layer A1 from the cellulose acylate film side (0 °).
  • the counterclockwise direction is represented by a positive value.
  • the molecular axis of the liquid crystal compound was horizontal with respect to the surface of the cellulose acylate film (or the surface of the optically anisotropic layer).
  • composition of optically anisotropic layer coating liquid (A) ⁇ 40 parts by mass of the following rod-shaped liquid crystal compound (A) ⁇ 40 parts by mass of the following rod-shaped liquid crystal compound (B) ⁇ 20 parts by mass of the following rod-shaped liquid crystal compound (C) ⁇ Ethylene oxide-modified trimethyl propantriacrylate (V # 360, Osaka Organic Chemical Co., Ltd.) 4 parts by mass, photopolymerization initiator (Irgacure 819, manufactured by Ciba Japan) 3 parts by mass, the following chiral agent (A) 0.46 parts by mass, the following polymerizable polymer (manufactured by Ciba Japan) X) 0.5 parts by mass, the following polymer (A) 0.1 parts by mass, methyl isobutyl ketone 325 parts by mass ⁇ ⁇
  • Rod-shaped liquid crystal compound (C) (hereinafter, corresponds to a mixture of liquid crystal compounds)
  • a polyvinyl alcohol (PVA) film having a thickness of 80 ⁇ m is immersed in an aqueous solution of iodine having an iodine concentration of 0.05% by mass at 30 ° C. for 60 seconds for dyeing, and then 60 in an aqueous solution of boric acid having a boric acid concentration of 4% by mass. After being longitudinally stretched to 5 times the original length during the second immersion, it was dried at 50 ° C. for 4 minutes to obtain a polarizing element having a thickness of 20 ⁇ m.
  • PVA polyvinyl alcohol
  • a commercially available cellulose acylate film "TD80UL" (manufactured by FUJIFILM Corporation) was prepared, immersed in a sodium hydroxide aqueous solution at 55 ° C. at 1.5 mol / liter, and then the sodium hydroxide was thoroughly washed away with water. .. Then, it was immersed in a dilute sulfuric acid aqueous solution at 35 ° C. at 0.005 mol / liter for 1 minute, and then immersed in water to thoroughly wash away the dilute sulfuric acid aqueous solution. Finally, the sample was sufficiently dried at 120 ° C. to prepare a polarizing element protective film.
  • a laminate containing a polarizing element and a polarizing element protective film arranged on one side of the polarizing element by laminating the polarizing element protective film produced above on one side of the polarizing element produced above with a polyvinyl alcohol-based adhesive. was produced.
  • An adhesive (SK-2057, manufactured by Soken Kagaku Co., Ltd.) is applied to the polarizing element (without the polarizing element protective film) side of the prepared laminate to form an adhesive layer, and the prepared cellulose acylate is formed.
  • the film and the film having the optically anisotropic layer A1 were bonded so that the pressure-sensitive adhesive layer and the cellulose acylate film were in close contact with each other.
  • the absorption axis of the polarizing element was parallel to the in-plane slow phase axis of the surface of the optically anisotropic layer A1 on the polarizing element side.
  • an adhesive was applied to the optically anisotropic layer A1 in the obtained laminate to form an adhesive layer.
  • Examples A2-A15> The amount of chiral agent used and the thickness of the optically anisotropic layer are adjusted so that the retardation and the twist angle are as shown in Table 1, and the axial relationship of each layer is as shown in Table 1.
  • Circularly polarized light plates A2 to A15 were produced according to the same procedure as in Example A1 except that the rubbing axis angle and the like were adjusted.
  • the molecular axis of the liquid crystal compound in the optically anisotropic layer in the circularly polarizing plates A2 to A15 was horizontal with respect to the surface of the optically anisotropic layer.
  • the GALAXY S4 manufactured by SAMSUNG equipped with an organic EL panel (organic EL display element) is disassembled, the touch panel with a circular polarizing plate is peeled off from the organic EL display device, and the circular polarizing plates A1 to A15 or AC1 produced above are air-conditioned.
  • An organic EL display device was manufactured by laminating them so that they would not enter.
  • the organic EL display device with a circularly polarizing plate manufactured above is tilted 40 ° and fixed to SR-3 (manufactured by Topcon), and the reflectance (Y) and color (a * / b *) under fluorescent lamps are ) Was measured.
  • the average reflectance (Y) was evaluated according to the following criteria. Practically, it is preferably D or more.
  • ⁇ a * was evaluated according to the following criteria. Practically, A is preferable. A: Less than 25 B: 25 or more In addition, ⁇ b * was evaluated according to the following criteria. Practically, A is preferable.
  • axis [°] in the “polarizer” column refers to the position of the absorption axis of the polarizing element with respect to the width direction of the circular polarizing plate by observing the circular polarizing plate from the polarizing element side (0 °).
  • the counterclockwise direction is represented by a positive value.
  • the "LC dispersion” column is "reverse dispersion” when the liquid crystal compound used is a liquid crystal compound having a reverse wavelength dispersibility, and when the liquid crystal compound used is a liquid crystal compound having a forward wavelength dispersibility. Shown as "forward dispersion".
  • the position of the in-plane slow-phase axis on the surface of the optically anisotropic layer on the polarizing element side is observed by observing the circularly polarizing plate from the polarizing plate side.
  • the counterclockwise direction is represented by a positive value with respect to the width direction of (0 °).
  • the “ ⁇ nd [nm]” column represents the product ⁇ nd (nm) of ⁇ n and d (thickness) at a wavelength of 550 nm of the optically anisotropic layer.
  • the “twist angle [°]” column represents the twist angle (°) of the twist-oriented liquid crystal compound.
  • the "average Y [%]” column represents the average reflectance (Y) (%).
  • the desired effect can be obtained by using the circularly polarizing plate of the present invention (corresponding to the first embodiment).
  • the twist angle of the liquid crystal compound was 54 to 74 ° (preferably 59 to 69 °).
  • the product ⁇ nd of ⁇ n and d at the wavelength of 550 nm of the optically anisotropic layer is 170 to 230 nm (preferably 180 to 220 nm, more preferably 190 to 210 nm). In the case of the range of), it was confirmed that the effect was more excellent.
  • Example B1> The cellulose acylate film produced above was continuously subjected to a rubbing treatment. At this time, the longitudinal direction of the long film and the conveying direction were parallel, and the angle formed by the film longitudinal direction (conveying direction) and the rotation axis of the rubbing roller was 76 °.
  • the longitudinal direction of the film (transportation direction) is 90 ° and the counterclockwise direction is represented by a positive value with respect to the width direction of the cellulose acylate film as a reference (0 °) when observed from the cellulose acylate film side, rubbing.
  • the axis of rotation of the rollers was 14 °. In other words, the position of the rotation axis of the rubbing roller was a position rotated by 76 ° clockwise with respect to the longitudinal direction of the cellulose acylate film.
  • the optically anisotropic layer coating liquid (B) containing the following rod-shaped liquid crystal compound was applied onto the rubbing-treated film using a Geeser coating machine, and heated at 80 ° C. for 60 seconds. Then, under air, at 40 ° C., the light of a 365 nm LED lamp (manufactured by Acroedge Co., Ltd.) having an irradiation amount of 40 mJ was irradiated, and the orientation state of the liquid crystal compound in the half region on the cellulose acylate film side in the coating film. was fixed. Further, after heating at 80 ° C.
  • the liquid crystal compound in the region of No. 1 was immobilized to prepare an optically anisotropic layer.
  • the optically anisotropic layer is composed of two layers exhibiting different optical anisotropies, and the layer on the cellulose acylate film side (second optically anisotropic layer) in the optically anisotropic layer is homogenically oriented.
  • the air-side layer (first optically anisotropic layer) in the optically anisotropic layer is a layer in which a liquid crystal compound having a reverse wavelength dispersibility twisted and oriented with the thickness direction as a spiral axis is fixed.
  • the above angle represents a counterclockwise direction as a positive value with respect to the width direction of the cellulose acylate film as a reference (0 °) when the optically anisotropic layer is observed from the cellulose acylate film side.
  • Example A1 Manufacturing of circularly polarizing plate
  • An adhesive (SK-2057, manufactured by Soken Kagaku Co., Ltd.) is applied to the polarizing element (without the polarizing element protective film) side of the prepared laminate to form an adhesive layer, and the prepared cellulose acylate is formed.
  • the film and the film having the optically anisotropic layer were bonded so that the pressure-sensitive adhesive layer and the cellulose acylate film were in close contact with each other.
  • the absorption axes of the polarizing elements were bonded so as to be at the angular positions in Table 2 described later.
  • an adhesive was applied onto the optically anisotropic layer in the obtained laminate to form an adhesive layer.
  • a long circular polarizing plate B1 in which a polarizing element, a cellulose acylate film, an optically anisotropic layer, and an adhesive layer are arranged in this order was produced.
  • Examples B2-B19> The amount of chiral agent used and the thickness of the optically anisotropic layer are adjusted so that the retardation and the twist angle are as shown in Table 2, and the axial relationship of each layer is as shown in Table 2.
  • Circularly polarizing plates B2 to B19 were produced according to the same procedure as in Example B1 except that the rubbing axis angle and the like were adjusted.
  • the molecular axis of the liquid crystal compound in the first optically anisotropic layer in the circularly polarizing plates A2 to A15 was horizontal with respect to the surface of the first optically anisotropic layer.
  • Example A1 Using the circularly polarizing plates B1 to B19 or BC1 produced above, the ⁇ evaluation> carried out in Example A1 described above was carried out. The results are summarized in Table 2.
  • axis [°] in the “polarizer” column refers to the position of the absorption axis of the polarizing element with respect to the width direction of the circular polarizing plate by observing the circular polarizing plate from the polarizing element side (0 °). The counterclockwise direction is represented by a positive value.
  • the "LC dispersion” column is "reverse dispersion” when the liquid crystal compound used is a liquid crystal compound having a reverse wavelength dispersibility, and when the liquid crystal compound used is a liquid crystal compound having a forward wavelength dispersibility. Shown as "forward dispersion".
  • the “ ⁇ nd [nm]” column represents the product ⁇ nd (nm) of ⁇ n and d (thickness) at a wavelength of 550 nm of the optically anisotropic layer.
  • the position of the in-plane slow-phase axis on the surface of the optically anisotropic layer on the polarizing element side is observed by observing the circularly polarizing plate from the polarizing plate side.
  • the counterclockwise direction is represented by a positive value with respect to the width direction of (0 °).
  • Polarizer Optically anisotropic layer 14
  • First optically anisotropic layer 16
  • Second optically anisotropic layer 18
  • Support 20
  • Composition layer 20A
  • First region 20B
  • Third optically anisotropic layer 24th 4
  • Optically anisotropic layer 100A, 100B, 100C Circular polarizing plate

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