WO2021090804A1 - Optical laminate, polarizing plate, and image display device - Google Patents

Optical laminate, polarizing plate, and image display device Download PDF

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Publication number
WO2021090804A1
WO2021090804A1 PCT/JP2020/041054 JP2020041054W WO2021090804A1 WO 2021090804 A1 WO2021090804 A1 WO 2021090804A1 JP 2020041054 W JP2020041054 W JP 2020041054W WO 2021090804 A1 WO2021090804 A1 WO 2021090804A1
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group
carbon atoms
layer
optically anisotropic
liquid crystal
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PCT/JP2020/041054
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French (fr)
Japanese (ja)
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晃治 飯島
義明 久門
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富士フイルム株式会社
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Priority to JP2021554938A priority Critical patent/JP7417623B2/en
Publication of WO2021090804A1 publication Critical patent/WO2021090804A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating 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
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/02Details
    • H05B33/04Sealing arrangements, e.g. against humidity
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to an optical laminate, a polarizing plate, and an image display device.
  • a polarizing plate having an optical laminate including an optically anisotropic layer and a polarizer has been used for a liquid crystal display device and organic electroluminescence (hereinafter, also abbreviated as "EL") for the purpose of optical compensation and antireflection. It is used for display devices and the like.
  • an optical laminate for example, a broadband ⁇ / 4 wave plate
  • a broadband ⁇ / 4 wave plate capable of giving the same effect to light rays of all wavelengths with respect to white light, which is a synthetic wave in which light rays in the visible light region are mixed.
  • Patent Documents 1 and 2 propose the use of an inverse wavelength-dispersible polymerizable liquid crystal compound as a polymerizable compound particularly used for forming an optically anisotropic layer. ..
  • the present inventors have studied an optical laminate having an optically anisotropic layer obtained by polymerizing a polymerizable liquid crystal composition containing the compounds (polymerizable liquid crystal compounds) described in Patent Documents 1 and 2.
  • the durability against ammonia which is a basic nucleating substance, is very weak.
  • the durability against ammonia is simply referred to as "durability". It is known that ammonia is generated from certain members and the like, and it is necessary to improve the durability.
  • the present inventors have changed from a type in which a film on which a touch sensor is formed externally attached to an organic EL element (out-cell type) to a type in which a touch sensor is directly formed on the organic EL element (out-cell type). It was clarified that the problem of durability of the optically anisotropic layer became apparent when the type was changed to the on-cell type.
  • An object of the present invention is to provide an optical laminate having excellent durability. Another object of the present invention is to provide a polarizing plate and an image display device.
  • the optically anisotropic layer is a layer formed by using a composition for forming an optically anisotropic layer containing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility.
  • An optical laminate in which the barrier layer is a layer formed from a composition for forming a barrier layer containing a polyfunctional (meth) acrylamide monomer.
  • the barrier layer is formed from a composition containing a polyfunctional (meth) acrylamide compound having a (meth) acrylic equivalent of 100 or less.
  • the optically anisotropic layer is a ⁇ / 4 wave plate, and the angle formed by the slow axis of the optically anisotropic layer and the absorption axis of the polarizer is 45 ° ⁇ 10 ° (7).
  • Polarizing plate is 45 ° ⁇ 10 ° (7).
  • the polarizing plate is the polarizing plate according to (8).
  • the polarizing plate is provided so that the barrier layer side of the polarizing plate faces the image display panel side.
  • the image display panel is an organic electroluminescence panel including an organic electroluminescence element.
  • the present invention it is possible to provide an optical laminate having excellent durability. Further, according to the present invention, a polarizing plate and an image display device can be provided.
  • the present invention will be described in detail.
  • the description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • a substance corresponding to each component may be used alone or in combination of two or more.
  • the content of the component means the total content of the substances used in combination unless otherwise specified.
  • the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited unless the bonding position is specified, and for example, the formula (for example, which will be described later) will be described.
  • D 1 in II) is -CO-O-, assuming that the position bonded to the G 1 side is * 1 and the position bonded to the Ar side is * 2, D 1 is * 1-. It may be CO-O- * 2 or * 1-O-CO- * 2.
  • (meth) acrylate is a general term for “acrylate” and “methacrylate”
  • (meth) acrylic is a general term for “acrylic” and “methacrylic”
  • (meth) acrylic is a general term for "(meth) acrylic”.
  • Acryloyl is a general term for "acryloyl” and “methacryloyl”.
  • “orthogonal” and “parallel” with respect to an angle mean a range of a strict angle of ⁇ 10 °, and “same” and “different” with respect to an angle have a difference of less than 5 °. It can be judged based on whether or not it is.
  • “visible light” means 380 to 780 nm.
  • the measurement wavelength is 550 nm.
  • slow phase axis means the direction in which the refractive index becomes maximum in the plane.
  • the slow axis of the optically anisotropic layer is intended to be the slow axis of the entire optically anisotropic layer.
  • Re ( ⁇ ) and “Rth ( ⁇ )” represent in-plane retardation at wavelength ⁇ and retardation in the thickness direction, respectively.
  • the values of in-plane retardation and retardation in the thickness direction refer to values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Optoscience). Specifically, by inputting the average refractive index ((nx + ny + nz) / 3) and the film thickness (d ( ⁇ m)) in AxoScan OPMF-1.
  • Slow phase axial direction (°) Re ( ⁇ ) R0 ( ⁇ )
  • Rth ( ⁇ ) ((nx + ny) /2-nz) ⁇ d Is calculated.
  • R0 ( ⁇ ) is displayed as a numerical value calculated by AxoScan OPMF-1, it means Re ( ⁇ ).
  • the optical laminate of the present invention has an optically anisotropic layer and a barrier layer in this order.
  • the optically anisotropic layer is a layer formed from a composition for forming an optically anisotropic layer containing a polymerizable liquid crystal compound (hereinafter, also simply referred to as “specific liquid crystal compound”) exhibiting anti-wavelength dispersibility.
  • the barrier layer is a layer formed from a composition for forming a barrier layer containing a polyfunctional (meth) acrylamide monomer.
  • optical laminate of the present invention having a predetermined optically anisotropic layer and a predetermined barrier layer is excellent in durability (ammonia durability). This is not clear in detail, but the present inventors speculate as follows.
  • Polymerizable liquid crystal compounds exhibiting reverse wavelength dispersibility are susceptible to decomposition by nucleophiles such as water and ammonia, and this problem tends to become more prominent especially in the presence of ammonia, which is a basic compound.
  • nucleophiles such as water and ammonia
  • ammonia which is a basic compound.
  • the present inventors decompose the structure derived from the specific liquid crystal compound contained in the optically anisotropic layer. It has been found that it occurs abruptly, the fluctuation of the in-plane retardation value becomes large, and the inverse wavelength anisotropy decreases. The reason for this is presumed to be the following phenomenon.
  • the specific liquid crystal compound may have an electron attracting property.
  • the present invention by blocking the infiltration of ammonia into the optically anisotropic layer by a predetermined barrier layer, the decomposition reaction of the structure derived from the specific liquid crystal compound is suppressed, and the improvement effect is obtained. Conceivable.
  • FIG. 2 and FIG. 3 show a schematic cross-sectional view showing an example of the optical laminate of the present invention.
  • the optical laminate 10 shown in FIG. 1 is an optical laminate having a layer structure having a support 11, an alignment film 12, a positive A plate 13, and a barrier layer 14 in this order.
  • the optical laminate 20 shown in FIG. 2 is an optical laminate having a layer structure having a support 11, a positive C plate 15, and a barrier layer 14 in this order.
  • the optical laminate 30 shown in FIG. 3 has a layered optical laminate having a support 11, an alignment film 12, a positive A plate 13, a vertically oriented forward wavelength dispersive liquid crystal curing layer 16 and a barrier layer 14 in this order.
  • the body is an optical laminate having a layer structure having a support 11, an alignment film 12, a positive A plate 13, a vertically oriented forward wavelength dispersive liquid crystal curing layer 16 and a barrier layer 14 in this order.
  • FIG. 4 shows a schematic cross-sectional view showing an example of an embodiment of the polarizing plate of the present invention
  • FIG. 5 shows a schematic cross-sectional view showing an example of an embodiment of the image display device of the present invention
  • the polarizing plate 40 shown in FIG. 4 includes a polarizing element protective film 41, a polarizing element 42, a support 11, an alignment film 12, a positive A plate 13, a vertically oriented forward wavelength dispersive liquid crystal curing layer 16 and a barrier layer. It is a polarizing plate having a layer structure having 14 in this order.
  • polarizer protective film 41 includes a polarizer protective film 41, a polarizer 42, a support 11, an alignment film 12, a positive A plate 13, a vertically oriented forward wavelength dispersive liquid crystal curing layer 16, and a barrier layer.
  • An image display device having a layer structure having 14, a silicon nitride layer 53, a touch sensor 52, and an organic electroluminescence element 51 in this order.
  • the positive A plate corresponds to the optically anisotropic layer contained in the optical laminate of the present invention.
  • the positive C plate corresponds to the optically anisotropic layer contained in the optical laminate of the present invention.
  • an adhesive layer, an easy-adhesive layer, or the like may be included.
  • the optical laminate of the present invention includes at least an optically anisotropic layer and a barrier layer.
  • the barrier layer is formed from a composition for forming a barrier layer containing a polyfunctional (meth) acrylamide monomer.
  • the composition for forming a barrier layer may contain a polymerization initiator, other monomers, additives and the like, if necessary.
  • (meth) acrylamide monomers and polymers formed from them are used for various purposes due to their high hydrophilicity.
  • Highly hydrophobic resin materials for example, olefin-based polymers
  • olefin-based polymers have been considered suitable as barriers for highly polar molecules such as ammonia, but as a result of studies, the present inventors have made polyfunctional (meth) acrylamide. It has been found that by forming a barrier layer using a composition for forming a barrier layer containing a monomer, an optical laminate having an excellent barrier ability against highly polar molecules such as ammonia can be obtained.
  • the number of functional groups of the polyfunctional (meth) acrylamide monomer is preferably bifunctional or higher, more preferably trifunctional or higher, and even more preferably 3 to 4 functional.
  • the polyfunctional (meth) acrylamide monomer is preferably a (meth) acrylate compound having a (meth) acrylic equivalent of 150 or less, and a (meth) acrylic equivalent, for the reason of better durability. More preferably, it is a (meth) acrylate compound having a value of 100 or less.
  • the lower limit of the (meth) acrylic equivalent is not particularly limited, but is often 80 or more.
  • the (meth) acrylic equivalent means the molecular weight per (meth) acryloyl group. That is, the (meth) acrylic equivalent is the molecular weight divided by the number of (meth) acryloyl groups.
  • the molecular weight of the polyfunctional (meth) acrylamide monomer is not particularly limited, but 1000 or less is preferable, and 600 or less is more preferable, because the effect of the present invention is more excellent.
  • the lower limit is not particularly limited, but is preferably 200 or more.
  • the polyfunctional (meth) acrylamide monomer can be obtained from, for example, a polyvalent amine compound (for example, diethylenetriamine, triethylenetetramine, etc.), polyethyleneimine, and the like, and (meth) acrylic acid. It can also be obtained as (meth) acrylamide obtained from various compounds containing a plurality of primary or secondary amino groups and (meth) acrylic acid. Specific examples of polyfunctional (meth) acrylamide monomers include N, N', N "-triacryloyl diethylenetriamine, N, N', N" -triacryloyl-3, 3'-diaminodipropylamine, N, N'.
  • the content of the polyfunctional (meth) acrylamide monomer in the barrier layer forming composition is not particularly limited, but is preferably 50% by mass or more, preferably 75% by mass or more, based on the solid content in the barrier layer forming composition. More preferably, 90% by mass or more is further preferable.
  • the upper limit of the content of the polyfunctional (meth) acrylamide monomer with respect to the solid content in the composition is not particularly limited, and may be 100% by mass.
  • other monomers may be added to the barrier layer forming composition.
  • the other monomer may be copolymerizable with the polyfunctional (meth) acrylamide monomer described above.
  • Other copolymerizable monomers include known (meth) acrylate compounds and monofunctional (meth) acrylamide monomers.
  • the composition for forming a barrier layer may contain a polymerization initiator.
  • a polymerization initiator when the barrier layer is hardened by light or heat, it is preferable to add a photopolymerization initiator or a thermal polymerization initiator. It is preferable to use a radical polymerization initiator as the polymerization initiator because the reaction between the monomers proceeds sufficiently and desired durability can be imparted.
  • a known radical polymerization initiator can be used.
  • the content of the polymerization initiator in the barrier layer forming composition is not particularly limited, but is preferably 0.1 to 15% by mass, preferably 0.3 to 5% by mass, based on the solid content in the barrier layer forming composition. 0% by mass is more preferable.
  • the composition for forming a barrier layer may contain a solvent.
  • the solvent include water and organic solvents.
  • the organic solvent include various solvents exemplified as organic solvents which may be contained in the polymerizable liquid crystal composition described later.
  • the solvent may be used alone or in combination of two or more.
  • the composition for forming a barrier layer may contain components other than those described above.
  • Other components include surfactants (including so-called leveling agents). By adding a surfactant, the occurrence of surface defects such as unevenness and repellent can be suppressed, and a high-quality optical laminate having an excellent appearance can be obtained.
  • the method for forming the barrier layer using the composition for forming the barrier layer is not particularly limited, but as a preferred embodiment, the composition for forming the barrier layer is applied onto a predetermined base material (for example, an optically anisotropic layer described later). Then, a coating film is formed, and the coating film is cured.
  • a predetermined base material for example, an optically anisotropic layer described later.
  • the above coating can be carried out by known methods (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, and die coating method).
  • Examples of the curing treatment for the coating film include known methods, and energy ray irradiation, light irradiation treatment or heat treatment is preferable, and light irradiation treatment is particularly preferable. It is preferable to use ultraviolet rays in the light irradiation treatment.
  • the conditions of the light irradiation treatment are not particularly limited, but 10 mJ / cm 2 to 50 J / cm 2 is preferable, and 20 mJ / cm 2 to 5 J / cm 2 is more preferable. Further, in order to promote the polymerization reaction, the light irradiation treatment may be carried out under heating conditions.
  • the film thickness of the barrier layer is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more.
  • the upper limit is not particularly limited, but is preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less, from the viewpoint of ensuring the flexibility of the optical laminate.
  • a composition for forming a barrier layer is applied onto a temporary support for transfer to form a coating film, and the coating film is cured, and then the transferred body (transferred body ()
  • a method of transferring a barrier layer formed on an optically anisotropic layer (described later) to remove a temporary support for transfer, for forming a barrier layer on a predetermined base material (support or temporary support for transfer).
  • Examples thereof include a method in which the composition is applied to form a coating film, the coating film is subjected to a curing treatment, and then the composition for forming an optically anisotropic layer, which will be described later, is applied and cured.
  • the optically anisotropic layer is a layer formed by using a composition for forming an optically anisotropic layer containing a specific liquid crystal compound (hereinafter, also referred to as “polymerizable liquid crystal composition”).
  • the specific liquid crystal compound is a polymerizable liquid crystal compound, and is a compound exhibiting "reverse wavelength dispersibility".
  • the compound exhibiting "reverse wavelength dispersibility" in the present specification refers to an in-plane retardation (Re) value at a specific wavelength (visible light range) of an optically anisotropic layer produced using the compound. When measured, the Re value becomes equal or higher as the measurement wavelength increases.
  • One of the preferred embodiments of the specific liquid crystal compound is a compound represented by the following formula (II).
  • 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.
  • 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.
  • the group formed by linking a plurality of the alicyclic hydrocarbon groups means a group formed by connecting divalent alicyclic hydrocarbon groups having 5 to 8 carbon atoms in a single bond. Further, 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 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). In the following formulas (Ar-1) to (Ar-7), * represents the bonding position with D 1 or D 2.
  • 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. Represent.
  • 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 can be 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.
  • the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, 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).
  • 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 carbons, respectively.
  • 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.
  • 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, and tert are 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 .
  • 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 (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 represented 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 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 to which a hydrogen atom or a substituent may be bonded.
  • RC1 represents a hydrogen atom or a substituent. ] Can be mentioned.
  • substituents include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl group.
  • substituents include a carbonyl group, a sulfo group, and a 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.
  • 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, linear or branched alkylene groups having 1 to 12 carbon atoms, or 1 to 12 carbon atoms.
  • One or more of -CH 2- constituting the linear or branched alkylene group was replaced 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.
  • a petitene group is 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 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 aromatic. It 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.
  • the 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 1 (International Publication No. 2014/010325).
  • each substituent of the polymerizable liquid crystal compound represented by the above formula (II) refers to D 1 , D 2 , G 1 , G regarding the compound (A) described in JP2012-021068. 2 , L 1 , L 2 , R 4 , R 5 , R 6 , R 7 , X 1 , Y 1 , Q 1 , Q 2 respectively D 1 , D 2 , G 1 , G 2 , L 1 , L 2 , R 1 , R 2 , R 3 , R 4 , Q 1 , Y 1 , Z 1 , and Z 2 can be referred to, and are represented by the general formula (I) described in JP-A-2008-107767.
  • references to A 1 , A 2 , and X for compounds can be found for A 1 , A 2 , and X, respectively, and Ax for compounds represented by the general formula (I) in WO 2013/018526.
  • Ay the description with respect to Q 1 can refer Ax, Ay, for Q 3 respectively.
  • Z 3 can refer to the description for Q 1 relates to compounds (A) described in JP-A-2012-21068.
  • the organic group represented by L 1 and L 2 is preferably a group represented by -D 3- G 3- Sp-P 3, respectively.
  • 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 aromatic ring groups or heterocyclic groups, and a divalent aromatic ring group having 5 to 8 carbon atoms. It represents an alicyclic hydrocarbon group or a group formed by linking a plurality of the alicyclic hydrocarbon groups, and the methylene group contained in the alicyclic hydrocarbon group is -O-, -S- or-.
  • 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 group in which divalent aromatic ring groups or heterocyclic groups having 6 to 12 carbon atoms are linked by a single bond.
  • the group in which a plurality of the 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.
  • the group adjacent to the acryloyloxy group in the above formulas II-2-8 and II-2-9 represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and the positions of the methyl groups are different. Represents a mixture of bodies.
  • a compound represented by the following formula (V) can also be mentioned.
  • A is a non-aromatic carbocyclic or heterocyclic group having 5 to 8 carbon atoms, or an aromatic or heteroaromatic group having 6 to 20 carbon atoms;
  • E 1 , E 2 , D 1 and D 2 are independently single-bonded or divalent linking groups;
  • m and n are independently integers from 1 to 5; if m or n is 2 or more, they are repeated 2 or more-(D 1- G 1 )-or-(G 2- D 2 ).
  • -Each repeating unit may be the same or different from each other;
  • G 1 and G 2 are independently non-aromatic carbocyclic groups or heterocyclic groups having 5 to 8 carbon atoms, or aromatic groups or heteroaromatic groups having 6 to 20 carbon atoms.
  • G 1 and G 2 are at least one carbocyclic group or heterocyclic group, and any one hydrogen atom contained in the carbocyclic group or heterocyclic group is described below.
  • R 1 and R 2 are independently alkyls having ⁇ H or 1 to 12 carbon atoms.
  • the content of the specific liquid crystal compound in the polymerizable liquid crystal composition is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 99% by mass, based on the total solid content in the polymerizable liquid crystal composition.
  • the specific liquid crystal compound may be used alone or in combination of two or more.
  • the solid content means other components in the polymerizable liquid crystal composition excluding the solvent, and is calculated as a solid content even if the property is liquid.
  • the polymerizable liquid crystal composition may contain a polymerizable rod-shaped compound in addition to the above-mentioned specific liquid crystal compound from the viewpoint of controlling the liquid crystal orientation.
  • the polymerizable rod-like compound may or may not be liquid crystal.
  • the above-mentioned polymerizable rod-shaped compound is a compound having a cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group (hereinafter, "alkylcyclohexane ring”) from the viewpoint of compatibility with the above-mentioned specific liquid crystal compound. It is also abbreviated as “containing compound”).
  • alkylcyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group
  • the "cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group” is, for example, as shown in the following formula (2), when it has two cyclohexane rings, it is on the molecular terminal side.
  • a cyclohexane ring in which one hydrogen atom of the cyclohexane ring present in is substituted with a linear alkyl group.
  • alkylcyclohexane ring-containing compound examples include compounds having a group represented by the following formula (2).
  • a (meth) acryloyl group is used from the viewpoint of imparting moist heat durability to the optically anisotropic layer. It is preferably a compound represented by the following formula (3).
  • * represents a coupling position.
  • R 2 represents an alkyl group having 1 to 10 carbon atoms
  • n represents 1 or 2
  • W 1 and W 2 independently represent an alkyl group and an alkoxy. It represents a group or halogen atom, and W 1 and W 2 may be bonded to each other to form a ring structure which may have a substituent.
  • Z represents -COO-
  • L represents an alkylene group having 1 to 6 carbon atoms
  • R 3 represents a hydrogen atom or a methyl group.
  • alkylcyclohexane ring-containing compound examples include compounds represented by the following formulas A-1 to A-5.
  • R 4 represents an ethyl group or a butyl group.
  • the content of the above-mentioned polymerizable rod-like compound is preferably 1 to 30% by mass with respect to the total mass of the above-mentioned specific liquid crystal compound and the above-mentioned polymerizable rod-like compound. More preferably, 1 to 20% by mass.
  • the polymerizable liquid crystal composition may contain a polymerizable liquid crystal compound (hereinafter, also abbreviated as “another polymerizable liquid crystal compound”) other than the above-mentioned specific liquid crystal compound and the polymerizable rod-shaped compound.
  • a polymerizable liquid crystal compound hereinafter, also abbreviated as “another polymerizable liquid crystal compound”
  • the polymerizable group contained in the other polymerizable liquid crystal compound is not particularly limited, and examples thereof include a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, the (meth) acryloyl group is preferable.
  • the other polymerizable liquid crystal compound is preferably a polymerizable compound having 2 to 4 polymerizable groups, and more preferably a polymerizable compound having 2 polymerizable groups. preferable.
  • Examples of such other polymerizable liquid crystal compounds include compounds represented by the formula (M1) and compounds represented by the formula (M2) described in paragraphs 0030 to 0033 of JP-A-2014-0770668.
  • a compound represented by the formula (M3) can be mentioned, and more specifically, specific examples described in paragraphs 0046 to 0055 of the same publication can be mentioned.
  • Other polymerizable liquid crystal compounds may be used alone or in combination of two or more.
  • the content of the other polymerizable liquid crystal compound is based on the total mass of the specific liquid crystal compound, the polymerizable rod-shaped compound and the other polymerizable liquid crystal compound described above. 1 to 40% by mass is preferable, and 1 to 10% by mass is more preferable.
  • the polymerizable liquid crystal composition preferably contains a non-liquid crystal polyfunctional polymerizable compound from the viewpoint of further improving the durability of the polarizing plate having the optically anisotropic layer to be formed. This is because the increase in the density of cross-linking points suppresses the movement of the compound that catalyzes the hydrolysis reaction (presumed to be a liquid crystal decomposition product), and as a result, the rate of the hydrolysis reaction slows down, while the water ends It is presumed that this is due to the progress of diffusion.
  • the non-liquid crystal polyfunctional polymerizable compound is preferably a compound having a low acrylic equivalent from the viewpoint of the orientation of the specific liquid crystal compound described above. Specifically, a compound having a (meth) acrylic equivalent of 120 or less is preferable, a compound having a (meth) acrylic equivalent of 100 or less is more preferable, and a compound having a (meth) acrylic equivalent of 90 or less is further preferable.
  • Non-liquid polyfunctional polymerizable compounds include esters of polyhydric alcohols with (meth) acrylic acid, vinylbenzene and its derivatives, vinylsulfone, acrylamide, and methacrylamide.
  • ester of the polyhydric alcohol and the (meth) acrylic acid specifically, for example, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, penta.
  • vinylbenzene and its derivatives include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, and 1,4-divinylcyclohexanone.
  • vinyl sulfone include divinyl sulfone.
  • acrylamide include methylenebisacrylamide and the like.
  • the content of the non-liquid crystal polyfunctional polymerizable compound is determined from the viewpoint of expressing the phase difference of the formed optically anisotropic layer. It is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, still more preferably 1 to 6% by mass, based on the total solid content in the polymerizable liquid crystal composition.
  • the polymerizable liquid crystal composition preferably contains a polymerization initiator.
  • a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
  • the photopolymerization initiator include ⁇ -carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670), acidoin ether (described in US Pat. No. 2,448,828), and ⁇ -hydrogen-substituted fragrance.
  • Group acidoine compounds described in US Pat. No. 2722512
  • polynuclear quinone compounds described in US Pat. Nos.
  • an oxime-type polymerization initiator is preferable as the polymerization initiator, and a polymerization initiator represented by the following formula (III) is more preferable.
  • X represents a hydrogen atom or a halogen atom
  • Y represents a monovalent organic group.
  • Ar 3 represents a divalent aromatic group
  • L 6 represents a divalent organic group having 1 to 12 carbon atoms
  • R 10 represents an alkyl group having 1 to 12 carbon atoms.
  • examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
  • examples of the divalent aromatic group represented by Ar 3 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; a furan ring.
  • examples thereof include a divalent group having an aromatic heterocycle such as a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.
  • examples of the divalent organic group having 1 to 12 carbon atoms represented by L 6 include a linear or branched alkylene group having 1 to 12 carbon atoms, and specific examples thereof. Examples include a methylene group, an ethylene group, and a propylene group.
  • examples of the alkyl group having 1 to 12 carbon atoms represented by R 10 include a methyl group, an ethyl group, and a propyl group.
  • examples of the monovalent organic group represented by Y include a functional group containing a benzophenone skeleton ((C 6 H 5 ) 2 CO). Specifically, a functional group containing a benzophenone skeleton in which the terminal benzene ring is unsubstituted or monosubstituted, such as the group represented by the following formula (3a) and the group represented by the following formula (3b), is preferable. ..
  • * represents the bond position, that is, the bond position of the carbonyl group in the above formula (III) with the carbon atom.
  • Examples of the oxime-type polymerization initiator represented by the above formula (III) include a compound represented by the following formula S-1 and a compound represented by the following formula S-2.
  • the content of the polymerization initiator is not particularly limited, but the content of the polymerization initiator is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the specific liquid crystal compound contained in the polymerizable liquid crystal composition. Up to 5 parts by mass is more preferable.
  • the polymerizable liquid crystal composition may contain an orientation control agent, if necessary.
  • the orientation control agent include a low molecular weight orientation control agent and a polymer orientation control agent.
  • the low-molecular-weight orientation control agent include paragraphs 0009 to 0083 of JP-A-2002-020363, paragraphs 0111 to 0120 of JP-A-2006-106662, and paragraphs 0021- of JP-2012-2011306A. The description of 0029 can be taken into consideration and this content is incorporated herein by reference.
  • the polymer orientation control agent for example, paragraphs 0021 to 0057 of JP-A-2004-198511 and paragraphs 0121 to 0167 of JP-A-2006-106662 can be referred to.
  • the amount of the orientation control agent used is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the polymerizable liquid crystal composition.
  • the orientation control agent for example, a homogeneous orientation state oriented parallel to the surface of the optically anisotropic layer can be formed.
  • the polymerizable liquid crystal composition preferably contains an organic solvent from the viewpoint of workability for forming an optically anisotropic layer.
  • organic solvent include ketones (for example, acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone), ethers (for example, dioxane and tetrahydrofuran), and aliphatic hydrocarbons.
  • hexane alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, and trimethylbenzene), carbon halides (eg, dichloromethane, dichloroethane, dichlorobenzene, etc.) And chlorotoluene), esters (eg, methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (eg, methyl cellosolves, etc.) And ethyl cellosolve), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide), amides (eg, dimethylformamide, and dimethylacetamide), and these may be used alone or in combination of two or more. May be used together.
  • sulfoxides
  • the polymerizable liquid crystal composition may contain components other than the above-mentioned components, for example, liquid crystal compounds other than the above-mentioned specific liquid crystal compounds, surfactants, tilt angle control agents, orientation aids, plasticizers, and Examples include cross-linking agents.
  • the optically anisotropic layer is formed by using the above-mentioned polymerizable liquid crystal composition.
  • the method for producing the optically anisotropic layer is not particularly limited, but for example, on a predetermined substrate (for example, a polarizer described later, a support described later or an alignment layer provided on the support, or a barrier layer described above).
  • a predetermined substrate for example, a polarizer described later, a support described later or an alignment layer provided on the support, or a barrier layer described above.
  • a method in which a polymerizable liquid crystal composition is applied to form a coating film, the coating film is subjected to an orientation treatment to bring a specific liquid crystal compound into a predetermined orientation state, and then the coating film is cured. Be done.
  • the above coating can be carried out by a known method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, etc.).
  • the orientation treatment can be carried out by drying or heating at room temperature (for example, 20 to 25 ° C.).
  • room temperature for example, 20 to 25 ° C.
  • the liquid crystal phase formed by the orientation treatment can generally be transferred by a change in temperature or pressure.
  • the transfer can also be carried out by the composition ratio of the amount of the solvent.
  • the heating time heat aging time
  • the heating time is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, still more preferably 10 seconds to 2 minutes.
  • the curing treatment (irradiation of active energy rays (light irradiation treatment) and / or heat treatment) on the coating film can also be said to be an immobilization treatment for fixing the orientation of the specific liquid crystal compound. Above all, it is preferable to carry out the light irradiation treatment. In the polymerization by light irradiation, it is preferable to use ultraviolet rays. Irradiation dose is preferably 10mJ / cm 2 ⁇ 50J / cm 2, more preferably 20mJ / cm 2 ⁇ 5J / cm 2, more preferably 30mJ / cm 2 ⁇ 3J / cm 2, particularly 50 ⁇ 1000mJ / cm 2 preferable.
  • the light irradiation treatment may be carried out under heating conditions.
  • the optically anisotropic layer can be formed on the support described later, on the polarizer described later, and on the barrier layer described above.
  • the thickness of the optically anisotropic layer is not particularly limited, and is preferably 1 to 5 ⁇ m, more preferably 1 to 4 ⁇ m, and even more preferably 1 to 3 ⁇ m.
  • the optically anisotropic layer preferably satisfies the following formula (IV) because the display quality in the viewing angle direction of the image display device having the optical laminate is improved.
  • Re (450) ⁇ Re (550) ⁇ Re (650) ...
  • Re (IV) represents the in-plane lettering of the optically anisotropic film at a wavelength of 450 nm
  • Re (550) represents the in-plane letter of the optically anisotropic film at a wavelength of 550 nm
  • Re (650) represents the in-plane retardation of the optically anisotropic film at a wavelength of 650 nm.
  • the optically anisotropic layer is preferably a positive A plate.
  • the positive A plate is defined as follows.
  • the positive A plate (positive A plate) has a refractive index of nx in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized), and is orthogonal to the slow axis in the plane in the plane.
  • the refractive index in the direction is ny and the refractive index in the thickness direction is nz
  • the positive A plate shows a positive value for Rth. Equation (A1) nx> ny ⁇ nz
  • Equation (A1) nx> ny ⁇ nz
  • the above " ⁇ " includes not only the case where both are completely the same, but also the case where both are substantially the same.
  • ny ⁇ nz when (ny-nz) ⁇ d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. include.
  • a positive A plate can be obtained by horizontally orienting a rod-shaped polymerizable liquid crystal compound.
  • Japanese Patent Application Laid-Open No. 2008-225281 and Japanese Patent Application Laid-Open No. 2008-026730 can be referred to.
  • the optically anisotropic layer (positive A plate) preferably functions as a ⁇ / 4 plate.
  • the ⁇ / 4 plate is a plate having a function of converting linearly polarized light of a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light), and has an in-plane retardation Re ( ⁇ ) at a specific wavelength of ⁇ nm.
  • a plate that satisfies Re ( ⁇ ) ⁇ / 4. This equation may be achieved at any wavelength in the visible light region (for example, 550 nm), but the in-plane retardation Re (550) at a wavelength of 550 nm has a relationship of 110 nm ⁇ Re (550) ⁇ 160 nm. It is preferable to satisfy, and it is more preferable to satisfy 110 nm ⁇ Re (550) ⁇ 150 nm.
  • the optically anisotropic layer may be used as a positive C plate.
  • the positive C plate is defined as follows.
  • the positive C plate (positive C plate) has a refractive index of nx in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized), and is orthogonal to the slow axis in the plane in the plane.
  • the refractive index in the direction is ny and the refractive index in the thickness direction is nz
  • the positive C plate shows a negative value for Rth.
  • Equation (A2) nx ⁇ ny ⁇ nz
  • includes not only the case where both are completely the same, but also the case where both are substantially the same. “Substantially the same” means, for example, “nx ⁇ ny” when (nx ⁇ ny) ⁇ d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. include. Further, in the positive C plate, Re ⁇ 0 is obtained from the above definition.
  • a positive C plate can be obtained by vertically orienting a rod-shaped polymerizable liquid crystal compound.
  • JP-A-2017-187732, JP-A-2016-53709, and JP-A-2015-200861 can be referred to.
  • the optical laminate of the present invention further comprises one or more liquid crystals between the optically anisotropic layer and the barrier layer for the reason that the display quality in the viewing angle direction of the image display device having the optical laminate is improved. It is preferable to have a cured layer.
  • the liquid crystal curing layer for example, when the optically anisotropic layer is a positive A plate, the above-mentioned positive C plate is preferably mentioned, and when the optically anisotropic layer is a positive C plate, the above is described. Positive A plates are preferred.
  • the optical laminate of the present invention may have a support for supporting the optical laminate.
  • the support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.
  • the support may have optical anisotropy or may be optically isotropic.
  • a polymer film is preferable from the viewpoint of making the optical laminate flexible.
  • Materials for the polymer film include cellulose-based polymers; (meth) acrylic polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and , Polyester-based polymers such as polyethylene naphthalate; Polystyrene and styrene-based polymers such as acrylonitrile-styrene copolymer (AS resin); Polyethylene-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; Vinyl-based polymers; Nylon and amide-based polymers such as aromatic polyamides; Imid-based polymers; Sulfon-based polymers; polyether sulfone-based polymers; polyether ether ketone-based polymers; Polyphenylene sulfide-based polymers;
  • the thickness of the support is not particularly limited, but is preferably 5 to 80 ⁇ m, more preferably 10 to 40 ⁇ m, from the viewpoint of imparting independence and flexibility to the optical laminate.
  • the support may be adjacent to the optically anisotropic layer (or adjacent via an alignment film described later), or may be adjacent to the barrier layer.
  • the optical laminate of the present invention has an alignment film between the support and the optically anisotropic layer when the above-mentioned arbitrary support is provided on the surface opposite to the barrier layer of the optically anisotropic layer. Is preferable.
  • the support described above may also serve as an alignment film.
  • a technique for aligning the molecules of the specific liquid crystal compound in a desired orientation state is used.
  • a specific liquid crystal is used by using an alignment film.
  • a technique for orienting a compound in a desired direction is common.
  • the alignment film a rubbing-treated film of a layer containing an organic compound such as a polymer, an oblique vapor-deposited film of an inorganic compound, a film having microgrooves, or ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearylate.
  • Examples thereof include a membrane obtained by accumulating LB (Langmuir-Blodgett) membranes obtained by the Langmuir-Blodget method of organic compounds such as.
  • LB Liuir-Blodgett
  • the alignment film there is also a photoalignment film in which an alignment function is generated by irradiation with light.
  • the alignment film a film formed by rubbing the surface of a layer (polymer layer) containing an organic compound such as a polymer can be preferably used.
  • the rubbing treatment is carried out by rubbing the surface of the polymer layer with paper or cloth several times in a certain direction (preferably in the longitudinal direction of the support).
  • the polymer used for forming the alignment film include polyimide, polyvinyl alcohol, modified polyvinyl alcohol described in paragraphs 0071 to 0095 of Japanese Patent No. 3907735, and polymerizable groups described in JP-A-9-152509.
  • the polymer having is preferable.
  • the barrier layer described above may also serve as an alignment film.
  • the thickness of the alignment film is not particularly limited as long as it can exhibit the alignment function, but is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 2 ⁇ m.
  • the alignment film it is also preferable to use a so-called photo-alignment film (photo-alignment layer) in which a photo-alignable material is irradiated with polarized light or non-polarized light to form an alignment layer. It is preferable to impart an orientation regulating force to the photoalignment film by a step of irradiating polarized light from a vertical direction or an oblique direction or a step of irradiating non-polarized light from an oblique direction. By using the photoalignment film, it is possible to horizontally orient the specific liquid crystal compound with excellent symmetry.
  • the positive A plate formed by using the photoalignment film can be used for optical compensation in a liquid crystal display device that does not require a pre-tilt angle of the driving liquid crystal, such as an IPS (In-Place-Switching) mode liquid crystal display device. It is useful for ⁇ / 4 wave plates used for circularly polarizing plates that require uniform circular polarization conversion when observed from any direction.
  • IPS In-Place-Switching
  • Examples of the photoalignment material used for the photoalignment film include JP-A-2006-285197, JP-A-2007-076839, JP-A-2007-138138, JP-A-2007-094071, and JP-A-2007-.
  • photodimerizable compounds particularly cinnamate compounds, chalcone compounds, and coumarin compounds.
  • Particularly preferred examples include azo compounds, photocrosslinkable polyimides, polyamides, polyesters, synnate compounds, and chalcone compounds.
  • the thickness of the photoalignment film is not particularly limited, but is preferably 0.01 to 10 ⁇ m, preferably 0, from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic layer having a uniform film thickness. 0.01 to 1 ⁇ m is more preferable, and 0.01 to 0.5 ⁇ m is even more preferable.
  • the optical laminate of the present invention may be provided with a layer having optical anisotropy, which is different from the adhesive layer, the easy-adhesion layer, and the above-mentioned optically anisotropic layer, as other layers.
  • the layer having optical anisotropy can be composed of any material such as a polymer film, a liquid crystal cured layer, and an inorganic layer, but from the viewpoint of thinning the optical laminate and achieving both flexibility and toughness, the liquid crystal cured layer. Is preferable.
  • a liquid crystal composition containing a polymerizable rod-shaped liquid crystal compound or a discotic liquid crystal compound having forward dispersibility or flat dispersibility was oriented and fixed in the same manner as the above-mentioned optically anisotropic layer. Things can be applied.
  • the orientation state, optical characteristics, strength, and the like of these liquid crystal cured layers can be appropriately designed so that desired characteristics can be imparted to the optical laminate of the present invention.
  • an optical laminate including an optically anisotropic layer / vertically oriented forward wavelength dispersive liquid crystal cured layer / barrier layer (for example, the optical laminate shown in FIG. 3) can be mentioned.
  • the optical laminate of the present invention can form a highly functional polarizing plate by laminating it with a polarizer.
  • the polarizing plate of the present invention has the above-mentioned optical laminate of the present invention and a polarizer, and the polarizer, the optically anisotropic layer of the optical laminate, and the barrier layer of the optical laminate are in this order. Included is a polarizing plate.
  • the polarizer is a so-called linear polarized light having a function of converting light into specific linearly polarized light.
  • the polarizer is not particularly limited, but an absorption type polarizer can be used.
  • the type of the polarizer is not particularly limited, and examples thereof include a commonly used polarizer containing a polyvinyl alcohol-based resin as a main component. For example, it is produced by adsorbing iodine or a dichroic dye on a polyvinyl alcohol-based resin and stretching it.
  • the fact that the polyvinyl alcohol-based resin is the main component means that the content of the polyvinyl alcohol-based resin with respect to the total mass of the polarizer is 50% by mass or more.
  • Polyvinyl alcohol resin is a resin containing a repeating unit of -CH 2 -CHOH-, e.g., polyvinyl alcohol, and an ethylene - vinyl alcohol copolymer.
  • a liquid crystal compound and a dichroic azo dye for example, a light-absorbing anisotropic film described in WO2017 / 195833
  • a coating type polarizer produced by coating using the dichroic azo dye used is also preferable.
  • it may be a polyene polarizer, a reflection polarizer, a wire grid polarizer, or the like.
  • the thickness of the polarizer is not particularly limited, but is preferably 5 to 20 ⁇ m, more preferably 3 to 15 ⁇ m, and even more preferably 2 to 13 ⁇ m. By reducing the thickness of the polarizer, a lighter and thinner display device can be obtained when mounted on the display device. Further, when the display device is flexible or curved, a thin polarizing plate can be more preferably applied.
  • the relationship between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer in the polarizing plate is not particularly limited and can be appropriately set according to a desired function.
  • the optically anisotropic layer is a ⁇ / 4 wave plate, and the angle between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45 ⁇ 10 °.
  • the range of (35 to 55 °) is preferable.
  • the optically anisotropic layer is a multi-layer of a positive A plate and a positive C plate of a ⁇ / 4 wave plate.
  • the structure and the angle formed by the transmission axis of the polarizer and the slow axis of the optically anisotropic layer are in the range of 0 ⁇ 10 ° (-10 to 10 °) or 90 ⁇ 10 ° (80 to 100). °) is preferred.
  • the polarizing plate may have a polarizer protective film on the surface of the polarizer.
  • the polarizer protective film may be arranged only on one side of the polarizer (on the surface opposite to the optically anisotropic layer side), or may be arranged on both sides of the polarizer.
  • the support constituting the optical laminate may also serve as a polarizing plate protective film.
  • the structure of the polarizer protective film is not particularly limited, and may be, for example, a so-called transparent support or a hard coat layer, or a laminate of a transparent support and a hard coat layer.
  • As the hard coat layer a known layer can be used, and for example, a layer obtained by polymerizing and curing a known polyfunctional monomer may be used.
  • the coating may have antiglare, antifouling and antireflection properties.
  • a known transparent support can be used as the transparent support.
  • the material for forming the transparent support is a cellulosic polymer represented by triacetyl cellulose (hereinafter, referred to as "cellulose acylate”. ), Thermoplastic norbornen-based resin (Zeonex and Zeonoa manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Co., Ltd.), acrylic resin, polyester resin, and polystyrene resin.
  • the thickness of the polarizer protective film is not particularly limited, but is preferably 40 ⁇ m or less, more preferably 25 ⁇ m or less, further preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less, from the viewpoint that the thickness of the polarizing plate can be reduced.
  • the lower limit is not particularly limited, but is often 1 ⁇ m or more.
  • An adhesive layer or an adhesive layer may be arranged between the layers to ensure the adhesion between the layers. Further, a transparent support may be arranged between the layers.
  • the polarizing plate has another optical laminate of the present invention or an optically anisotropic layer other than the optical laminate of the present invention on the side opposite to the side having the optical laminate of the present invention. You may be.
  • the polarizing plate can be preferably used in an image display device, for example, a liquid crystal display device, an organic electroluminescence display device, a micro LED display device, electronic paper, or the like.
  • the image display device of the present invention is an image display device having the above-mentioned optical laminate of the present invention or the polarizing plate of the present invention, and is, for example, an organic electroluminescence display device even if it is a liquid crystal display device. May be good.
  • the liquid crystal display device of the present invention is an example of an image display device, and includes the above-mentioned polarizing plate of the present invention and a liquid crystal cell.
  • the polarizing element in the polarizing plate of the present invention among the polarizing elements provided on both sides of the liquid crystal cell, it is preferable to use the polarizing element in the polarizing plate of the present invention as the front side polarizing element, and either the front side or the rear side polarizing element. It is more preferable to use the polarizer in the polarizing plate of the present invention.
  • the optical laminate of the present invention contained in the polarizing plate can be arranged on the liquid crystal cell side of the polarizing element.
  • the barrier layer included in the optical laminate can be arranged closer to the liquid crystal cell than the above-mentioned optically anisotropic layer.
  • the optically anisotropic layer contains deterioration source substances such as trace amounts of ammonia molecules that may be generated from the liquid crystal cell and its constituent members, a touch sensor that can be provided between the liquid crystal cell and the optically anisotropic layer, and an adhesive. It is possible to prevent the infiltration into the liquid crystal and impart preferable durability.
  • the optically anisotropic layer acts as an optical compensation function.
  • the liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Optical Compensated Bend) mode, an IPS (In-Place-Switching) mode, or a TN (Twisted Nematic) mode. , Not limited to these.
  • VA Vertical Alignment
  • OCB Optical Compensated Bend
  • IPS In-Place-Switching
  • TN Transmission Nematic
  • the optically anisotropic layer can have optical characteristics suitable for improving or controlling its viewing angle characteristics according to each of these modes.
  • the optical laminate of the present invention contained in the polarizing plate can be arranged outside the polarizer when viewed from the liquid crystal cell.
  • the barrier layer included in the optical laminate can be arranged on the side farther from the liquid crystal cell than the above-mentioned optically anisotropic layer.
  • polar molecules such as ammonia generated and infiltrated from the external environment on the front side and from the backlight on the rear side are prevented from reaching the optically anisotropic layer, and preferable durability is imparted. can do.
  • the optically anisotropic layer is, for example, a ⁇ / 4 wave plate, so that when it is arranged on the front side, the effect of improving visibility due to wearing polarized sunglasses is improved, and when it is arranged on the rear side, polarized light is recycled. It is possible to impart the effect of enhancing the effect of improving the brightness due to the above or the effect of improving the color unevenness caused by the backlight member. Further, by using a ⁇ / 2 wave plate, it is possible to provide a function of preventing reflection on a window or a windshield of an automobile.
  • the organic electroluminescence display device of the present invention preferably has a structure in which the polarizing plate of the present invention and the image display panel are provided in this order from the visual side, that is, the polarizer and the optical laminate of the present invention. And an organic EL display panel in this order.
  • the optically anisotropic layer is a ⁇ / 4 wave plate, and the angle formed by the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45 ⁇ 10 °.
  • the barrier layer contained in the polarizing plate is arranged on the organic EL display panel side.
  • ammonia that can be generated from the silicon nitride layer is transferred to the optically anisotropic layer.
  • the desired durability can be obtained by preventing the barrier layer from infiltrating. That is, the polarizing plate of the present invention can be used as a so-called antireflection film.
  • the organic EL display panel is a display panel configured by using an organic EL element having an organic light emitting layer (organic electroluminescence layer) sandwiched between electrodes (between the cathode and the anode).
  • the configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
  • an adhesive layer is present between the polarizing plate and the silicon nitride layer, but another layer, for example, a metal mesh electrode or the like is provided. You can also. Since the effect of the present invention is remarkably exhibited, the thickness of the layer existing between the circularly polarizing plate and the silicon nitride layer is preferably less than 40 ⁇ m, and more preferably 1 to 30 ⁇ m.
  • the optical laminate of the present invention can be arranged on the visible side of the polarizing element of the circularly polarizing plate arranged on the visible side of the organic EL panel.
  • the effect of the optical laminate of the present invention obtained at this time and the gain as a display device obtained at this time are the same as those when arranged on the front side of the liquid crystal display device.
  • ⁇ Production example 1> (Preparation of support) The following composition was put into a mixing tank and stirred to prepare a cellulose acetate solution to be used as a core layer cellulose acylate dope.
  • Core layer Cellulose acylate dope ⁇ 100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.88 ⁇ 12 parts by mass of the polyester compound B described in Examples of JP-A-2015-227955 ⁇ 2 parts by mass of the following compound G ⁇ Methylene chloride (first solvent) 430 Parts by mass / methanol (second solvent) 64 parts by mass ⁇
  • the following matting solution was added to 90 parts by mass of the above core layer cellulose acylate dope to prepare a cellulose acetate solution to be used as the outer layer cellulose acylate dope.
  • Matte solution ⁇ -Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass-Methylene chloride (first solvent) 76 parts by mass-Methanol (second solvent) 11 parts by mass-The above core layer cellulose acid Rate Dope 1 part by mass ⁇
  • the core layer cellulose acylate dope and the outer layer cellulose acylate dope are filtered through a filter paper having an average pore size of 34 ⁇ m and a sintered metal filter having an average pore size of 10 ⁇ m, and then the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides thereof. And three layers were simultaneously cast on a drum at 20 ° C. from the casting port (band casting machine). The film was peeled off from the drum with a solvent content of about 20% by mass, both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched in the lateral direction.
  • the obtained film was conveyed between the rolls of the heat treatment apparatus to be further dried to prepare a cellulose acylate film 1 having a thickness of 20 ⁇ m.
  • the Re (550) of the obtained cellulose acylate film 1 was 0 nm.
  • a coating liquid 1 for a photoalignment film was prepared and coated on a cellulose acylate film 1 with a wire bar. Then, the obtained cellulose acylate film 1 was dried with warm air at 60 ° C. for 60 seconds to prepare a coating film 1 having a thickness of 300 nm.
  • composition A1 for forming a positive A plate having the following composition was prepared.
  • ⁇ Composition of composition A1 for forming a positive A plate ⁇ -The following polymerizable liquid crystal compound X-1 16.00 parts by mass-The following specific liquid crystal compound L-1 42.00 parts by mass-The following specific liquid crystal compound L-2 42.00 parts by mass-The following polymerization initiator S-1 0. 50 parts by mass, the following polymerizable compound B-1 2.00 parts by mass, the leveling agent (the following compound T-1) 0.20 parts by mass, methyl ethyl ketone (solvent) 230.00 parts by mass, cyclopentanone (solvent) 70. 00 parts by mass ⁇
  • each repeating unit in compound T-1 represents the content (mass%) of each repeating unit with respect to all the repeating units.
  • the prepared coating film 1 was irradiated with ultraviolet rays in the atmosphere using an ultra-high pressure mercury lamp.
  • a wire grid polarizer (ProFlux PPL02 manufactured by Moxtek, Inc.) was set so as to be parallel to the surface of the coating film 1 and exposed, and photoalignment treatment was performed to obtain a photoalignment film 1.
  • the illuminance of the ultraviolet rays was set to 10 mJ / cm 2 in the UV-A region (ultraviolet A wave, integration of wavelengths of 320 to 380 nm).
  • the positive A plate forming composition A1 was applied onto the photoalignment film 1 using a bar coater.
  • the obtained coating film is heat-aged at a film surface temperature of 100 ° C. for 20 seconds, cooled to 90 ° C., and then exposed to ultraviolet rays of 300 mJ / cm 2 using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under air.
  • a positive A plate A1 (corresponding to an optically anisotropic layer) was formed by immobilizing the nematic orientation state, and an optical film L containing the positive A plate A1 was produced.
  • the formed positive A plate A1 had a film thickness of 2.5 ⁇ m.
  • Re (550) of positive A plate A1 is 145 nm, Rth (550) is 73 nm, Re (550) / Re (450) is 1.13, Re (650) / Re (550) is 1.01, and the optical axis is The tilt angle was 0 °, and the liquid crystal compound had a homogeneous orientation.
  • composition C-1) ⁇ -The following forward wavelength-dispersible rod-shaped liquid crystal compound M-1 83 parts by mass-The following forward wavelength-dispersible rod-shaped liquid crystal compound M-2 15 parts by mass-The following forward wavelength-dispersible rod-shaped liquid crystal compound M-3 2 parts by mass-The following Compound B1 4.5 parts by mass-The following polymerization initiator (IrgacureOXE01, BASF) 5 parts by mass ⁇ Viscote # 360 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 8 parts by mass ⁇
  • the following surfactant T-2 0.3 parts by mass ⁇
  • the following surfactant T-3 0.5 parts by mass ⁇ The following onium compound S01 2.0 parts by mass, acetone 229.6 parts by mass, propylene glycol monomethyl ether acetate 42.0 parts by mass, methanol 8.4 parts by mass ⁇ ⁇
  • Surfactant T-2 [Mw: 15k. In the formula, the numerical value described in each repeating unit represents the content (mass%) of each repeating unit with respect to all repeating units. ]
  • Surfactant T-3 Weight average molecular weight: 11,200 (the numerical value described in each repeating unit represents the content (mass%) of each repeating unit with respect to all repeating units)]
  • composition B1 for forming a barrier layer having the following composition was prepared.
  • Barrier layer forming composition B1 ⁇ -The following polyfunctional (meth) acrylamide compound BM-1 14.35 parts by mass-The following polymerization initiator S-2 0.57 parts by mass-The above surfactant T-3 0.07 parts by mass-Methanol (solvent) 85. 00 parts by mass ⁇
  • Polyfunctional (meth) acrylamide compound BM-1 (Number of functional groups: 3, molecular weight: 265, acrylic equivalent: 88)
  • the surface of the optical film M produced above on the positive C plate C1 side is corona-treated, and the barrier layer forming composition B1 is coated thereto with a wire bar coater, and 1 in a drying oven at 120 ° C. Allowed to stand for minutes. Then, using a high-pressure mercury lamp of 150 mW / cm 2 , the obtained coating film was cured to form a barrier layer B1 to form a cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate. An optical laminate 1 in which A1 (optically anisotropic layer) / positive C plate C1 / barrier layer B1 was laminated in this order was obtained. The thickness of the barrier layer was 1.0 ⁇ m.
  • the cellulose acylate film 1 (support) / photoalignment film 1 / positive was the same as in Production Example 1 except that the bar coater count was changed and the thickness of the barrier layer was 0.5 ⁇ m.
  • An optical laminate 4 in which A plate A1 (optically anisotropic layer) / positive C plate C1 / barrier layer B1 was laminated in this order was obtained.
  • Polyfunctional (meth) acrylamide compound BM-4 (Number of functional groups: 4, molecular weight: 509, acrylic equivalent: 127)
  • a sheet-like pressure-sensitive adhesive (Soken) is applied to the surface of the obtained optical laminates 1 to 5 on the support side and the side of the polyvinyl alcohol polarizer having the polarizing plate protective film on only one side and not provided with the polarizing plate protective film.
  • SK2057) manufactured by Kagaku Co., Ltd. is used for bonding, and polarizing plate protective film / polarizer / cellulose acylate film 1 (support) / photoalignment film 1 / positive
  • a plate A1 (optically anisotropic layer) / positive C Polarizing plates (Examples 1 to 5) laminated in the order of plate C1 / barrier layer B1 were obtained.
  • a polarizing plate (Comparative Example 1) was obtained in the same manner as described above except that the optical laminate 6 was used instead of the optical laminate 1.
  • the polarizing element protective film side of the polarizing plates of Examples 1 to 5 and Comparative Example 1 cut into 40 mm squares was attached to a glass plate, and a screw cap bottle containing a methanol solution of 2 mol% ammonia. By placing on top, it was exposed to ammonia for 16 hours. The exposed surface was arranged on the screw cap bottle so that the optical laminate side (that is, the barrier layer B1) was the exposed surface.
  • the values of in-plane retardation Re (450) and Re (550) at wavelengths of 450 nm and 550 nm were measured using an Axo Scan (0PMF-1, manufactured by Axometrics) for the polarizing plate after exposure.
  • the optical laminate and the polarizing plate of the present invention show excellent durability even under exposure conditions of a deterioration source substance such as ammonia. Therefore, it is clear that it exhibits excellent durability even when it is incorporated into various image display devices and the like. Further, from the comparison between Example 1 and Example 5, when the barrier layer is formed from a composition containing a polyfunctional (meth) acrylamide compound having an acrylic equivalent of 100 or less, the durability is further improved. I found out.
  • ⁇ Production example 7> Among the components of the positive A plate forming composition A1 used for forming the optically anisotropic layer, the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1, and the specific liquid crystal compound L-2 (total 100 parts by mass). Instead, 100 parts by mass of the polymerizable liquid crystal compound shown below was used to form a positive A plate A2 (corresponding to an optically anisotropic layer). Cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A2 (optical anisotropic) in the same manner as in Production Example 1 except that the positive A plate A2 was used instead of the positive A plate A1. An optical laminate 7 in which the sex layer) / positive C plate C1 / barrier layer B1 was laminated in this order was obtained.
  • ⁇ Production example 8> Among the components of the positive A plate forming composition A1 used for forming the optically anisotropic layer, the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1, and the specific liquid crystal compound L-2 (total 100 parts by mass). Instead, 100 parts by mass of the polymerizable liquid crystal compound shown below was used to form a positive A plate A3 (corresponding to an optically anisotropic layer). Cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A3 (optical anisotropic) in the same manner as in Production Example 1 except that the positive A plate A3 was used instead of the positive A plate A1. An optical laminate 8 laminated in the order of (sexual layer) / positive C plate C1 / barrier layer B1 was obtained.
  • a sheet-like pressure-sensitive adhesive (Soken Kagaku Co., Ltd.) is used to attach the surface of the obtained optical laminate 7 on the support side and the side of the polyvinyl alcohol polarizer having the polarizing plate protective film on only one side without the polarizing plate protective film.
  • a polarizing plate (Example 6) laminated in the order of / barrier layer B1 was obtained.
  • the surface of the obtained optical laminate 8 on the support side and the side of the polyvinyl alcohol polarizer having the polarizing plate protective film on only one side are not provided with the polarizing plate protective film in the form of a sheet.
  • SK2057) manufactured by Soken Kagaku Co., Ltd. is used for bonding, and polarizing plate protective film / polarizing element / cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A3 (optically anisotropic layer) / positive A polarizing plate (Example 7) in which the C plate C1 / barrier layer B1 was laminated in this order was obtained.
  • a polarizing plate (Comparative Example 2) was obtained in the same manner as described above except that the optical laminate 9 was used instead of the optical laminate 7.
  • a polarizing plate (Comparative Example 3) was obtained in the same manner as above except that the optical laminate 10 was used instead of the optical laminate 8.
  • the polarizing element protective film side of the polarizing plates of Examples 6 to 7 and Comparative Examples 2 to 3 cut into 40 mm squares was attached to a glass plate, and a screw containing a methanol solution of 2 mol% ammonia. By placing on a mouth bottle, ammonia was exposed for 36 hours. The exposed surface was arranged on the screw cap bottle so that the exposed surface was the exposed surface on the optical laminate side (that is, the barrier layer B1).
  • An organic EL display device was manufactured by laminating on a touch panel so as to be on the side. Further, as another embodiment, the FlexPai manufactured by Royole Co., Ltd. mounted on the organic EL display panel (organic EL display element) was disassembled, and the circularly polarizing plate was peeled off from the organic EL display device. Next, the polarizing plate of the above-described embodiment was attached to the isolated organic EL display panel (the outermost surface is a silicon nitride layer) so that the barrier layer side was on the panel side to prepare an organic EL display device. ..
  • the antireflection effect when observed from the front and the oblique direction is exhibited. Confirmed that it will be done.

Abstract

The present invention addresses the problem of providing: an optical laminate which has excellent durability; a polarizing plate; and an image display device. An optical laminate according to the present invention sequentially comprises an optically anisotropic layer and a barrier layer in this order; the optically anisotropic layer is formed using an optically anisotropic layer-forming composition that contains a polymerizable liquid crystal compound having reverse wavelength dispersion properties; and the barrier layer is formed from a barrier layer-forming composition that contains a multifunctional (meth)acrylamide monomer.

Description

光学積層体、偏光板、および、画像表示装置Optical laminate, polarizing plate, and image display device
 本発明は、光学積層体、偏光板、および、画像表示装置に関する。 The present invention relates to an optical laminate, a polarizing plate, and an image display device.
 従来から、光学異方性層を含む光学積層体と偏光子とを有する偏光板が、光学補償および反射防止などを目的として、液晶表示装置および有機エレクトロルミネッセンス(以下、「EL」とも略す。)表示装置などに用いられている。
 近年、可視光域の光線が混在している合成波である白色光に対して、全ての波長の光線に対応して同様の効果を与えることができる光学積層体(例えば広帯域λ/4波長板)の開発が進められており、特に、偏光板が適用される装置の薄型化の要求から、偏光板に含まれる光学積層体についても薄型化が求められている。
 このような要求に対して、例えば、特許文献1および2においては、特に光学異方性層の形成に使用する重合性化合物として、逆波長分散性の重合性液晶化合物の利用が提案されている。
Conventionally, a polarizing plate having an optical laminate including an optically anisotropic layer and a polarizer has been used for a liquid crystal display device and organic electroluminescence (hereinafter, also abbreviated as "EL") for the purpose of optical compensation and antireflection. It is used for display devices and the like.
In recent years, an optical laminate (for example, a broadband λ / 4 wave plate) capable of giving the same effect to light rays of all wavelengths with respect to white light, which is a synthetic wave in which light rays in the visible light region are mixed. ) Is under development, and in particular, due to the demand for thinning of the device to which the polarizing plate is applied, the optical laminate contained in the polarizing plate is also required to be thinned.
In response to such demands, for example, Patent Documents 1 and 2 propose the use of an inverse wavelength-dispersible polymerizable liquid crystal compound as a polymerizable compound particularly used for forming an optically anisotropic layer. ..
国際公開第2014/010325号International Publication No. 2014/010325 特開2011-207765号公報Japanese Unexamined Patent Publication No. 2011-207765
 本発明者らは、特許文献1および2に記載されている化合物(重合性液晶化合物)を含有する重合性液晶組成物を重合して得られる光学異方性層を有する光学積層体について検討したところ、塩基性の求核物質であるアンモニアに対する耐久性が非常に弱いことを確認した。以下では、アンモニアに対する耐久性を、単に「耐久性」と呼ぶ。
 なお、ある種の部材などからアンモニアが発生することは知られており、上記耐久性の向上が必要である。特に、本発明者らは、有機EL表示装置において、タッチセンサーが形成されたフィルムを有機EL素子に外付けしたタイプ(アウトセルタイプ)から、タッチセンサーを有機EL素子上に直接形成したタイプ(オンセルタイプ)に変更した場合において、光学異方性層の耐久性の問題が顕在化することを明らかとした。
The present inventors have studied an optical laminate having an optically anisotropic layer obtained by polymerizing a polymerizable liquid crystal composition containing the compounds (polymerizable liquid crystal compounds) described in Patent Documents 1 and 2. However, it was confirmed that the durability against ammonia, which is a basic nucleating substance, is very weak. Hereinafter, the durability against ammonia is simply referred to as "durability".
It is known that ammonia is generated from certain members and the like, and it is necessary to improve the durability. In particular, in the organic EL display device, the present inventors have changed from a type in which a film on which a touch sensor is formed externally attached to an organic EL element (out-cell type) to a type in which a touch sensor is directly formed on the organic EL element (out-cell type). It was clarified that the problem of durability of the optically anisotropic layer became apparent when the type was changed to the on-cell type.
 本発明は、耐久性に優れた光学積層体を提供することを課題とする。
 また、本発明は、偏光板、および、画像表示装置を提供することも課題とする。
An object of the present invention is to provide an optical laminate having excellent durability.
Another object of the present invention is to provide a polarizing plate and an image display device.
 本発明者らは、以下の構成により上記課題が解決できることを見出した。 The present inventors have found that the above problems can be solved by the following configuration.
 (1) 光学異方性層と、バリア層とをこの順に有し、
 上記光学異方性層が、逆波長分散性を示す重合性液晶化合物を含む光学異方性層形成用組成物を用いて形成された層であり、
 上記バリア層が、多官能(メタ)アクリルアミドモノマーを含むバリア層形成用組成物から形成された層である、光学積層体。
 (2) 上記バリア層が、(メタ)アクリル当量が100以下の多官能(メタ)アクリルアミド化合物を含む組成物から形成される、(1)に記載の光学積層体。
 (3) 上記バリア層の厚みが0.1~10μmである、(1)または(2)に記載の光学積層体。
 (4) 上記逆波長分散性を示す重合性液晶化合物が、後述する式(II)で表される化合物である、(1)~(3)のいずれかに記載の光学積層体。
 (5) 上記光学異方性層の波長450nmで測定した面内レターデーション値であるRe(450)と、上記光学異方性層の波長550nmで測定した面内レターデーション値であるRe(550)と、上記光学異方性層の波長650nmで測定した面内レターデーションの値であるRe(650)とが、Re(450)≦Re(550)≦Re(650)の関係を満たす、(1)~(4)のいずれかに記載の光学積層体。
 (6) 上記光学異方性層と上記バリア層との間に、さらに1つ以上の液晶硬化層を有する、(1)~(5)のいずれかに記載の光学積層体。
 (7) (1)~(6)のいずれかに記載の光学積層体と偏光子とを有し、上記偏光子と、上記光学積層体が有する光学異方性層と、上記光学積層体が有するバリア層とが、この順に含まれている、偏光板。
 (8) 上記光学異方性層がλ/4波長板であり、上記光学異方性層の遅相軸と上記偏光子の吸収軸とのなす角度が45°±10°である、(7)の偏光板。
 (9) (1)~(6)のいずれかに記載の光学積層体、または、(7)もしくは(8)に記載の偏光板を有する、画像表示装置。
 (10) 液晶表示装置である、(9)に記載の画像表示装置。
 (11) 有機エレクトロルミネッセンス表示装置である、(9)に記載の画像表示装置。
 (12) 視認側から、偏光板と、画像表示パネルと、をこの順で有し、
 上記偏光板が、(8)に記載の偏光板であり、
 上記偏光板が、上記偏光板が有するバリア層側を上記画像表示パネル側に向けて設けられており、
 上記画像表示パネルが、有機エレクトロルミネッセンス素子を含む有機エレクトロルミネッセンスパネルであり、
 上記有機エレクトロルミネッセンス素子と、上記バリア層との間に、窒化ケイ素層を含む、画像表示装置。
 (13) 上記偏光板と上記窒化ケイ素層との間に存在する層の厚みが40μm未満である、(12)に記載の画像表示装置。
(1) An optically anisotropic layer and a barrier layer are provided in this order.
The optically anisotropic layer is a layer formed by using a composition for forming an optically anisotropic layer containing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility.
An optical laminate in which the barrier layer is a layer formed from a composition for forming a barrier layer containing a polyfunctional (meth) acrylamide monomer.
(2) The optical laminate according to (1), wherein the barrier layer is formed from a composition containing a polyfunctional (meth) acrylamide compound having a (meth) acrylic equivalent of 100 or less.
(3) The optical laminate according to (1) or (2), wherein the barrier layer has a thickness of 0.1 to 10 μm.
(4) The optical laminate according to any one of (1) to (3), wherein the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is a compound represented by the formula (II) described later.
(5) Re (450), which is an in-plane retardation value measured at a wavelength of 450 nm of the optically anisotropic layer, and Re (550), which is an in-plane retardation value measured at a wavelength of 550 nm of the optically anisotropic layer. ) And Re (650), which is the value of the in-plane retardation measured at the wavelength of 650 nm of the optically anisotropic layer, satisfy the relationship of Re (450) ≤ Re (550) ≤ Re (650). The optical laminate according to any one of 1) to (4).
(6) The optical laminate according to any one of (1) to (5), further having one or more liquid crystal curing layers between the optically anisotropic layer and the barrier layer.
(7) It has the optical laminate and the polarizer according to any one of (1) to (6), and the polarizer, the optically anisotropic layer of the optical laminate, and the optical laminate A polarizing plate in which the barrier layer having the barrier layer is included in this order.
(8) The optically anisotropic layer is a λ / 4 wave plate, and the angle formed by the slow axis of the optically anisotropic layer and the absorption axis of the polarizer is 45 ° ± 10 ° (7). ) Polarizing plate.
(9) An image display device having the optical laminate according to any one of (1) to (6) or the polarizing plate according to (7) or (8).
(10) The image display device according to (9), which is a liquid crystal display device.
(11) The image display device according to (9), which is an organic electroluminescence display device.
(12) From the visual side, the polarizing plate and the image display panel are provided in this order.
The polarizing plate is the polarizing plate according to (8).
The polarizing plate is provided so that the barrier layer side of the polarizing plate faces the image display panel side.
The image display panel is an organic electroluminescence panel including an organic electroluminescence element.
An image display device including a silicon nitride layer between the organic electroluminescence element and the barrier layer.
(13) The image display device according to (12), wherein the thickness of the layer existing between the polarizing plate and the silicon nitride layer is less than 40 μm.
 本発明によれば、耐久性に優れた光学積層体を提供できる。
 また、本発明によれば、偏光板および画像表示装置を提供できる。
According to the present invention, it is possible to provide an optical laminate having excellent durability.
Further, according to the present invention, a polarizing plate and an image display device can be provided.
本発明の光学積層体の実施形態の一例を示す模式的な断面図である。It is a schematic cross-sectional view which shows an example of embodiment of the optical laminated body of this invention. 本発明の光学積層体の実施形態の一例を示す模式的な断面図である。It is a schematic cross-sectional view which shows an example of embodiment of the optical laminated body of this invention. 本発明の光学積層体の実施形態の一例を示す模式的な断面図である。It is a schematic cross-sectional view which shows an example of embodiment of the optical laminated body of this invention. 本発明の偏光板の実施形態の一例を示す模式的な断面図である。It is a schematic cross-sectional view which shows an example of embodiment of the polarizing plate of this invention. 本発明の画像表示装置の実施形態の一例を示す模式的な断面図である。It is a schematic cross-sectional view which shows an example of embodiment of the image display apparatus of this invention.
 以下、本発明について詳細に説明する。
 以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
 なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
 また、本明細書において、各成分は、各成分に該当する物質を1種単独でも用いても、2種以上を併用してもよい。ここで、各成分について2種以上の物質を併用する場合、その成分についての含有量とは、特段の断りが無い限り、併用した物質の合計の含有量を指す。
 また、本明細書において、表記される二価の基(例えば、-O-CO-)の結合方向は、結合位置を明記している場合を除き、特に制限されず、例えば、後述する式(II)中のDが-CO-O-である場合、G側に結合している位置を*1、Ar側に結合している位置を*2とすると、Dは、*1-CO-O-*2であってもよく、*1-O-CO-*2であってもよい。
 また、本明細書において、「(メタ)アクリレート」は、「アクリレート」および「メタクリレート」の総称であり、「(メタ)アクリル」は、「アクリル」および「メタクリル」の総称であり、「(メタ)アクリロイル」は、「アクリロイル」および「メタクリロイル」の総称である。
 また、本明細書において、角度に関する「直交」および「平行」とは、厳密な角度±10°の範囲を意味するものとし、角度に関する「同一」および「異なる」は、その差が5°未満であるか否かを基準に判断できる。
 また、本明細書において、「可視光」とは、380~780nmのことをいう。
 また、本明細書において、測定波長について特に付記がない場合は、測定波長は550nmである。
Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, as each component, a substance corresponding to each component may be used alone or in combination of two or more. Here, when two or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
Further, in the present specification, the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited unless the bonding position is specified, and for example, the formula (for example, which will be described later) will be described. When D 1 in II) is -CO-O-, assuming that the position bonded to the G 1 side is * 1 and the position bonded to the Ar side is * 2, D 1 is * 1-. It may be CO-O- * 2 or * 1-O-CO- * 2.
Further, in the present specification, "(meth) acrylate" is a general term for "acrylate" and "methacrylate", and "(meth) acrylic" is a general term for "acrylic" and "methacrylic", and "(meth) acrylic" is a general term for "(meth) acrylic". ) Acryloyl is a general term for "acryloyl" and "methacryloyl".
Further, in the present specification, "orthogonal" and "parallel" with respect to an angle mean a range of a strict angle of ± 10 °, and "same" and "different" with respect to an angle have a difference of less than 5 °. It can be judged based on whether or not it is.
Further, in the present specification, "visible light" means 380 to 780 nm.
Further, in the present specification, unless otherwise specified, the measurement wavelength is 550 nm.
 本明細書において、「遅相軸」とは、面内において屈折率が最大となる方向を意味する。なお、光学異方性層の遅相軸という場合は、光学異方性層全体の遅相軸を意図する。 In the present specification, the "slow phase axis" means the direction in which the refractive index becomes maximum in the plane. The slow axis of the optically anisotropic layer is intended to be the slow axis of the entire optically anisotropic layer.
 本明細書において、「Re(λ)」および「Rth(λ)」は、それぞれ、波長λにおける面内のレターデーション、および、厚さ方向のレターデーションを表す。
 ここで、面内レターデーションおよび厚み方向のレターデーションの値は、AxoScan OPMF-1(オプトサイエンス社製)を用い、測定波長の光を用いて測定した値をいう。
 具体的には、AxoScan OPMF-1にて、平均屈折率((nx+ny+nz)/3)と膜厚(d(μm))を入力することにより、
 遅相軸方向(°)
 Re(λ)=R0(λ)
 Rth(λ)=((nx+ny)/2-nz)×d
が算出される。
 なお、R0(λ)は、AxoScan OPMF-1で算出される数値として表示されるものであるが、Re(λ)を意味している。
In the present specification, "Re (λ)" and "Rth (λ)" represent in-plane retardation at wavelength λ and retardation in the thickness direction, respectively.
Here, the values of in-plane retardation and retardation in the thickness direction refer to values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Optoscience).
Specifically, by inputting the average refractive index ((nx + ny + nz) / 3) and the film thickness (d (μm)) in AxoScan OPMF-1.
Slow phase axial direction (°)
Re (λ) = R0 (λ)
Rth (λ) = ((nx + ny) /2-nz) × d
Is calculated.
Although R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, it means Re (λ).
 <光学積層体>
 本発明の光学積層体は、光学異方性層と、バリア層とをこの順に有する。
 また、光学異方性層は、逆波長分散性を示す重合性液晶化合物(以下、単に「特定液晶化合物」ともいう。)を含む光学異方性層形成用組成物から形成された層である。
 また、バリア層は、多官能(メタ)アクリルアミドモノマーを含むバリア層形成用組成物から形成された層である。
<Optical laminate>
The optical laminate of the present invention has an optically anisotropic layer and a barrier layer in this order.
The optically anisotropic layer is a layer formed from a composition for forming an optically anisotropic layer containing a polymerizable liquid crystal compound (hereinafter, also simply referred to as “specific liquid crystal compound”) exhibiting anti-wavelength dispersibility. ..
The barrier layer is a layer formed from a composition for forming a barrier layer containing a polyfunctional (meth) acrylamide monomer.
 所定の光学異方性層および所定のバリア層を有する本発明の光学積層体は、耐久性(アンモニア耐久性)に優れる。
 これは、詳細には明らかではないが、本発明者らは以下のように推測している。
The optical laminate of the present invention having a predetermined optically anisotropic layer and a predetermined barrier layer is excellent in durability (ammonia durability).
This is not clear in detail, but the present inventors speculate as follows.
 逆波長分散性を示す重合性液晶化合物は水およびアンモニアなどの求核種による分解を受けやすく、特に塩基性化合物であるアンモニアが存在する場合において、この問題が顕著になる傾向にある。
 具体的には、本発明者らは、特定液晶化合物を用いて作製した光学異方性層をアンモニアガス下に曝した場合、光学異方性層に含まれる特定液晶化合物由来の構造の分解が急激に起こり、面内のレターデーション値の変動が大きくなること、かつ、逆波長分散性が低下することを知見している。この理由は、以下の現象によるものと推測される。
 すなわち、特定液晶化合物を逆波長分散性にするための1つの方法として、電子求引性の性質を持たせることがある。一方で、そのような分子設計により特定液晶化合物を構成する炭素原子のプラスの分極が大きくなり、求核種(アンモニア)の攻撃を受けやすくなるものと推測される。
Polymerizable liquid crystal compounds exhibiting reverse wavelength dispersibility are susceptible to decomposition by nucleophiles such as water and ammonia, and this problem tends to become more prominent especially in the presence of ammonia, which is a basic compound.
Specifically, when the optically anisotropic layer prepared using the specific liquid crystal compound is exposed to ammonia gas, the present inventors decompose the structure derived from the specific liquid crystal compound contained in the optically anisotropic layer. It has been found that it occurs abruptly, the fluctuation of the in-plane retardation value becomes large, and the inverse wavelength anisotropy decreases. The reason for this is presumed to be the following phenomenon.
That is, as one method for making the specific liquid crystal compound reverse wavelength dispersibility, it may have an electron attracting property. On the other hand, it is presumed that such molecular design increases the positive polarization of the carbon atoms that make up the specific liquid crystal compound, making it more susceptible to attack by nucleophiles (ammonia).
 そのため、本発明においては、アンモニアが光学異方性層へ浸入することを所定のバリア層で遮断することで、特定液晶化合物由来の構造の分解反応が抑制され、改良効果が得られたものと考えられる。 Therefore, in the present invention, by blocking the infiltration of ammonia into the optically anisotropic layer by a predetermined barrier layer, the decomposition reaction of the structure derived from the specific liquid crystal compound is suppressed, and the improvement effect is obtained. Conceivable.
 図1、図2および図3に、本発明の光学積層体の一例を示す模式的な断面図を示す。
 ここで、図1に示す光学積層体10は、支持体11、配向膜12、ポジティブAプレート13およびバリア層14をこの順に有する層構成の光学積層体である。
 また、図2に示す光学積層体20は、支持体11、ポジティブCプレート15およびバリア層14をこの順に有する層構成の光学積層体である。
 また、図3に示す光学積層体30は、支持体11、配向膜12、ポジティブAプレート13、垂直配向した順波長分散性の液晶硬化層16およびバリア層14をこの順に有する層構成の光学積層体である。
1, FIG. 2 and FIG. 3 show a schematic cross-sectional view showing an example of the optical laminate of the present invention.
Here, the optical laminate 10 shown in FIG. 1 is an optical laminate having a layer structure having a support 11, an alignment film 12, a positive A plate 13, and a barrier layer 14 in this order.
Further, the optical laminate 20 shown in FIG. 2 is an optical laminate having a layer structure having a support 11, a positive C plate 15, and a barrier layer 14 in this order.
Further, the optical laminate 30 shown in FIG. 3 has a layered optical laminate having a support 11, an alignment film 12, a positive A plate 13, a vertically oriented forward wavelength dispersive liquid crystal curing layer 16 and a barrier layer 14 in this order. The body.
 図4に、本発明の偏光板の実施形態の一例を示す模式的な断面図を示し、図5に、本発明の画像表示装置の実施形態の一例を示す模式的な断面図を示す。
 ここで、図4に示す偏光板40は、偏光子保護フィルム41、偏光子42、支持体11、配向膜12、ポジティブAプレート13、垂直配向した順波長分散性の液晶硬化層16およびバリア層14をこの順に有する層構成の偏光板である。
 また、図5に示す画像表示装置50は、偏光子保護フィルム41、偏光子42、支持体11、配向膜12、ポジティブAプレート13、垂直配向した順波長分散性の液晶硬化層16、バリア層14、窒化ケイ素層53、タッチセンサー52および有機エレクトロルミネッセンス素子51をこの順に有する層構成の画像表示装置である。
FIG. 4 shows a schematic cross-sectional view showing an example of an embodiment of the polarizing plate of the present invention, and FIG. 5 shows a schematic cross-sectional view showing an example of an embodiment of the image display device of the present invention.
Here, the polarizing plate 40 shown in FIG. 4 includes a polarizing element protective film 41, a polarizing element 42, a support 11, an alignment film 12, a positive A plate 13, a vertically oriented forward wavelength dispersive liquid crystal curing layer 16 and a barrier layer. It is a polarizing plate having a layer structure having 14 in this order.
Further, the image display device 50 shown in FIG. 5 includes a polarizer protective film 41, a polarizer 42, a support 11, an alignment film 12, a positive A plate 13, a vertically oriented forward wavelength dispersive liquid crystal curing layer 16, and a barrier layer. An image display device having a layer structure having 14, a silicon nitride layer 53, a touch sensor 52, and an organic electroluminescence element 51 in this order.
 図1、図3、図4および図5においては、ポジティブAプレートが、本発明の光学積層体に含まれる光学異方性層に該当する。
 また、図2においては、ポジティブCプレートが、本発明の光学積層体に含まれる光学異方性層に該当する。
 また、図1~5においては、必要に応じ、図示しない接着層や易接着層等を含んでもよい。
 本発明の光学積層体においては、少なくとも、光学異方性層、および、バリア層が含まれる。
 以下、本発明の光学積層体の各層および成分について詳細に説明する。
In FIGS. 1, 3, 4 and 5, the positive A plate corresponds to the optically anisotropic layer contained in the optical laminate of the present invention.
Further, in FIG. 2, the positive C plate corresponds to the optically anisotropic layer contained in the optical laminate of the present invention.
Further, in FIGS. 1 to 5, if necessary, an adhesive layer, an easy-adhesive layer, or the like (not shown) may be included.
The optical laminate of the present invention includes at least an optically anisotropic layer and a barrier layer.
Hereinafter, each layer and component of the optical laminate of the present invention will be described in detail.
(バリア層)
 バリア層は、多官能(メタ)アクリルアミドモノマーを含むバリア層形成用組成物から形成される。
 バリア層形成用組成物には、必要に応じ、重合開始剤やその他のモノマー、添加剤等を含むことができる。
(Barrier layer)
The barrier layer is formed from a composition for forming a barrier layer containing a polyfunctional (meth) acrylamide monomer.
The composition for forming a barrier layer may contain a polymerization initiator, other monomers, additives and the like, if necessary.
 一般に(メタ)アクリルアミドモノマーおよびそれらから形成される重合体は親水性が高いことを利用して様々な用途に用いられている。
 アンモニア等の極性の高い分子のバリアには、疎水性の高い樹脂材料(例えば、オレフィン系ポリマーなど)が好適とされてきたが、本発明者らは、検討の結果、多官能(メタ)アクリルアミドモノマーを含むバリア層形成用組成物を用いてバリア層を形成することにより、アンモニア等極性の高い分子に対するバリア能力に優れた光学積層体が得られることを見出した。
Generally, (meth) acrylamide monomers and polymers formed from them are used for various purposes due to their high hydrophilicity.
Highly hydrophobic resin materials (for example, olefin-based polymers) have been considered suitable as barriers for highly polar molecules such as ammonia, but as a result of studies, the present inventors have made polyfunctional (meth) acrylamide. It has been found that by forming a barrier layer using a composition for forming a barrier layer containing a monomer, an optical laminate having an excellent barrier ability against highly polar molecules such as ammonia can be obtained.
 上記多官能(メタ)アクリルアミドモノマーの官能基数は、2官能以上であることが好ましく、3官能以上であることがより好ましく、3~4官能であることが更に好ましい。 The number of functional groups of the polyfunctional (meth) acrylamide monomer is preferably bifunctional or higher, more preferably trifunctional or higher, and even more preferably 3 to 4 functional.
 本発明においては、耐久性がより良好となる理由から、上記多官能(メタ)アクリルアミドモノマーは、(メタ)アクリル当量が150以下の(メタ)アクリレート化合物であることが好ましく、(メタ)アクリル当量が100以下の(メタ)アクリレート化合物であることがより好ましい。上記(メタ)アクリル当量の下限は特に制限されないが、80以上の場合が多い。
 なお、(メタ)アクリル当量とは、(メタ)アクリロイル基1個あたりの分子量を意味する。つまり、(メタ)アクリル当量とは、分子量を(メタ)アクリロイル基の数で割ったものである。
In the present invention, the polyfunctional (meth) acrylamide monomer is preferably a (meth) acrylate compound having a (meth) acrylic equivalent of 150 or less, and a (meth) acrylic equivalent, for the reason of better durability. More preferably, it is a (meth) acrylate compound having a value of 100 or less. The lower limit of the (meth) acrylic equivalent is not particularly limited, but is often 80 or more.
The (meth) acrylic equivalent means the molecular weight per (meth) acryloyl group. That is, the (meth) acrylic equivalent is the molecular weight divided by the number of (meth) acryloyl groups.
 上記多官能(メタ)アクリルアミドモノマーの分子量は特に制限されないが、本発明の効果がより優れる点で、1000以下が好ましく、600以下がより好ましい。下限は特に制限されないが、200以上が好ましい。 The molecular weight of the polyfunctional (meth) acrylamide monomer is not particularly limited, but 1000 or less is preferable, and 600 or less is more preferable, because the effect of the present invention is more excellent. The lower limit is not particularly limited, but is preferably 200 or more.
 上記多官能(メタ)アクリルアミドモノマーは、例えば、多価アミン化合物(例えば、ジエチレントリアミン、トリエチレンテトラミンなど)およびポリエチレンイミン等と、(メタ)アクリル酸とから得ることができる。また、1級または2級アミノ基を複数含む種々の化合物と(メタ)アクリル酸から得られる(メタ)アクリルアミドとして得ることもできる。
 多官能(メタ)アクリルアミドモノマーの具体例としては、N,N′,N″-トリアクリロイルジエチレントリアミン、N,N′,N″-トリアクリロイル-3、3′-ジアミノジプロピルアミン、N,N′,N″,N′″-テトラアクリロイルトリエチレンテトラミン、N,N′,N″,N′″,N″″-ペンタアクリロイルテトラエチレンペンタミン、N,N′‐{[(2-アクリルアミド-2-[(3-アクリルアミドプロポキシ)メチル]プロパン-1,3、-ジイル)ビス(オキシ)]ビス(プロパン-1,3-ジイル)}ジアクリルアミド、N,N′-ジアクリロイル-4,7,10-トリオキサ-1,13-トリデカンジアミンが挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。
The polyfunctional (meth) acrylamide monomer can be obtained from, for example, a polyvalent amine compound (for example, diethylenetriamine, triethylenetetramine, etc.), polyethyleneimine, and the like, and (meth) acrylic acid. It can also be obtained as (meth) acrylamide obtained from various compounds containing a plurality of primary or secondary amino groups and (meth) acrylic acid.
Specific examples of polyfunctional (meth) acrylamide monomers include N, N', N "-triacryloyl diethylenetriamine, N, N', N" -triacryloyl-3, 3'-diaminodipropylamine, N, N'. , N ″, N ′ ″ -tetraacryloyl triethylenetetramine, N, N ′, N ″, N ′ ″, N ″ ″-pentaacryloyl tetraethylenepentamine, N, N ′-{[(2-acrylamide-2) -[(3-acrylamide propoxy) methyl] propane-1,3, -diyl) bis (oxy)] bis (propane-1,3-diyl)} diacrylamide, N, N'-diacryloyl-4,7, Examples thereof include 10-trioxa-1,13-tridecanediamine. These may be used alone or in combination of two or more.
 バリア層形成用組成物中における多官能(メタ)アクリルアミドモノマーの含有量は特に制限されないが、バリア層形成用組成物中の固形分に対して、50質量%以上が好ましく、75質量%以上がより好ましく、90質量%以上がさらに好ましい。組成物中の固形分に対する多官能(メタ)アクリルアミドモノマーの含有量の上限は特に制限されないが、100質量%が挙げられる。 The content of the polyfunctional (meth) acrylamide monomer in the barrier layer forming composition is not particularly limited, but is preferably 50% by mass or more, preferably 75% by mass or more, based on the solid content in the barrier layer forming composition. More preferably, 90% by mass or more is further preferable. The upper limit of the content of the polyfunctional (meth) acrylamide monomer with respect to the solid content in the composition is not particularly limited, and may be 100% by mass.
 バリア層形成用組成物には、必要に応じさらに他のモノマーを添加してもよい。他のモノマーは、上述した多官能(メタ)アクリルアミドモノマーと共重合可能なものであってもよい。共重合可能な他のモノマーとしては、公知の(メタ)アクリレート化合物や、単官能の(メタ)アクリルアミドモノマーが挙げられる。 If necessary, other monomers may be added to the barrier layer forming composition. The other monomer may be copolymerizable with the polyfunctional (meth) acrylamide monomer described above. Other copolymerizable monomers include known (meth) acrylate compounds and monofunctional (meth) acrylamide monomers.
 バリア層形成用組成物は、重合開始剤を含んでいてもよい。特に、光、熱によってバリア層の硬膜を行う場合は、光重合開始剤または熱重合開始剤を添加することが好ましい。重合開始剤としてはラジカル重合開始剤を用いると、モノマー間の反応が十分に進行して望ましい耐久性を付与できるため好ましい。ラジカル重合開始剤としては公知のものを利用することができる。バリア層形成用組成物中における重合開始剤の含有量は特に制限されないが、バリア層形成用組成物中の固形分に対して、0.1~15質量%が好ましく、0.3~5.0質量%がより好ましい。 The composition for forming a barrier layer may contain a polymerization initiator. In particular, when the barrier layer is hardened by light or heat, it is preferable to add a photopolymerization initiator or a thermal polymerization initiator. It is preferable to use a radical polymerization initiator as the polymerization initiator because the reaction between the monomers proceeds sufficiently and desired durability can be imparted. A known radical polymerization initiator can be used. The content of the polymerization initiator in the barrier layer forming composition is not particularly limited, but is preferably 0.1 to 15% by mass, preferably 0.3 to 5% by mass, based on the solid content in the barrier layer forming composition. 0% by mass is more preferable.
 バリア層形成用組成物は、溶媒を含んでいてもよい。
 溶媒としては、水および有機溶媒が挙げられる。有機溶媒としては、後述する重合性液晶組成物が含んでいてもよい有機溶媒として例示される種々の溶媒が挙げられる。溶媒は単独で用いてもよいし、複数を混合して用いることもできる。
The composition for forming a barrier layer may contain a solvent.
Examples of the solvent include water and organic solvents. Examples of the organic solvent include various solvents exemplified as organic solvents which may be contained in the polymerizable liquid crystal composition described later. The solvent may be used alone or in combination of two or more.
 バリア層形成用組成物は、上述した成分以外の他の成分を含んでいてもよい。
 他の成分としては、界面活性剤(いわゆるレベリング剤を含む)が挙げられる。界面活性剤を添加することで、ムラやハジキ等の面状欠陥の発生が抑制され、外観に優れた高品質な光学積層体を得ることができる。
The composition for forming a barrier layer may contain components other than those described above.
Other components include surfactants (including so-called leveling agents). By adding a surfactant, the occurrence of surface defects such as unevenness and repellent can be suppressed, and a high-quality optical laminate having an excellent appearance can be obtained.
 バリア層形成用組成物を用いたバリア層の形成方法は特に制限されないが、好ましい一態様として、所定の基材(例えば、後述する光学異方性層)上にバリア層形成用組成物を塗布して塗膜を形成して、塗膜に対して硬化処理を施す方法が挙げられる。 The method for forming the barrier layer using the composition for forming the barrier layer is not particularly limited, but as a preferred embodiment, the composition for forming the barrier layer is applied onto a predetermined base material (for example, an optically anisotropic layer described later). Then, a coating film is formed, and the coating film is cured.
 上記塗布は、公知の方法(例えば、ワイヤーバーコーティング法、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、および、ダイコーティング法)により実施できる。 The above coating can be carried out by known methods (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, and die coating method).
 塗膜に対する硬化処理としては公知の方法が挙げられ、エネルギー線照射、光照射処理または加熱処理が好ましく、光照射処理が特に好ましい。
 光照射処理の際には、紫外線を用いることが好ましい。
 光照射処理の条件は特に制限されないが、10mJ/cm~50J/cmが好ましく、20mJ/cm~5J/cmがより好ましい。
 また、重合反応を促進するため、加熱条件下で光照射処理を実施してもよい。
Examples of the curing treatment for the coating film include known methods, and energy ray irradiation, light irradiation treatment or heat treatment is preferable, and light irradiation treatment is particularly preferable.
It is preferable to use ultraviolet rays in the light irradiation treatment.
The conditions of the light irradiation treatment are not particularly limited, but 10 mJ / cm 2 to 50 J / cm 2 is preferable, and 20 mJ / cm 2 to 5 J / cm 2 is more preferable.
Further, in order to promote the polymerization reaction, the light irradiation treatment may be carried out under heating conditions.
 バリア層の膜厚は、0.1μm以上が好ましく、0.2μm以上がより好ましい。上限は特に制限されないが、光学積層体の柔軟さを確保する観点から10μm以下が好ましく、8μm以下がより好ましい。 The film thickness of the barrier layer is preferably 0.1 μm or more, more preferably 0.2 μm or more. The upper limit is not particularly limited, but is preferably 10 μm or less, and more preferably 8 μm or less, from the viewpoint of ensuring the flexibility of the optical laminate.
 また、その他の好ましい一態様としては、転写用仮支持体上にバリア層形成用組成物を塗布して塗膜を形成して、塗膜に対して硬化処理を施したのち、被転写体(例えば、後述する光学異方性層)上に形成したバリア層を転写して転写用仮支持体を除去する方法、所定の基材(支持体または転写用仮支持体)上にバリア層形成用組成物を塗布して塗膜を形成して、塗膜に対して硬化処理を施した後、後述する光学異方性層形成用組成物を塗布・硬化する方法が挙げられる。 Further, as another preferred embodiment, a composition for forming a barrier layer is applied onto a temporary support for transfer to form a coating film, and the coating film is cured, and then the transferred body (transferred body () For example, a method of transferring a barrier layer formed on an optically anisotropic layer (described later) to remove a temporary support for transfer, for forming a barrier layer on a predetermined base material (support or temporary support for transfer). Examples thereof include a method in which the composition is applied to form a coating film, the coating film is subjected to a curing treatment, and then the composition for forming an optically anisotropic layer, which will be described later, is applied and cured.
(光学異方性層)
 光学異方性層は、特定液晶化合物を含む光学異方性層形成用組成物(以下、「重合性液晶組成物」ともいう。)を用いて形成された層である。
 特定液晶化合物は、重合性液晶化合物であり、「逆波長分散性」を示す化合物である。
 ここで、本明細書において「逆波長分散性」を示す化合物とは、これを用いて作製された光学異方性層の特定波長(可視光範囲)における面内のレターデーション(Re)値を測定した際に、測定波長が大きくなるにつれてRe値が同等または高くなるものをいう。
(Optically anisotropic layer)
The optically anisotropic layer is a layer formed by using a composition for forming an optically anisotropic layer containing a specific liquid crystal compound (hereinafter, also referred to as “polymerizable liquid crystal composition”).
The specific liquid crystal compound is a polymerizable liquid crystal compound, and is a compound exhibiting "reverse wavelength dispersibility".
Here, the compound exhibiting "reverse wavelength dispersibility" in the present specification refers to an in-plane retardation (Re) value at a specific wavelength (visible light range) of an optically anisotropic layer produced using the compound. When measured, the Re value becomes equal or higher as the measurement wavelength increases.
 特定液晶化合物の好ましい態様のひとつとしては、下記式(II)で表される化合物が挙げられる。
 L-G-D-Ar-D-G-L   ・・・(II)
 上記式(II)中、DおよびDは、それぞれ独立に、単結合、-O-、-CO-、-CO-O-、-C(=S)O-、-CR-、-CR-CR-、-O-CR-、-CR-O-CR-、-CO-O-CR-、-O-CO-CR-、-CR-CR-O-CO-、-CR-O-CO-CR-、-CR-CO-O-CR-、-NR-CR-、または、-CO-NR-を表す。
 R、R、RおよびRは、それぞれ独立に、水素原子、フッ素原子または炭素数1~4のアルキル基を表す。R、R、RおよびRのそれぞれが複数存在する場合には、複数のR、複数のR、複数のRおよび複数のRはそれぞれ、互いに同一でも異なっていてもよい。
 GおよびGは、それぞれ独立に、炭素数5~8の2価の脂環式炭化水素基、複数の上記脂環式炭化水素基が連結してなる基、芳香族炭化水素基、または、複数の上記芳香族炭化水素基が連結してなる基を表し、上記脂環式炭化水素基を構成する-CH-の1個以上が-O-、-S-または-NH-で置換されていてもよい。
 複数の上記脂環式炭化水素基が連結してなる基とは、炭素数5~8の2価の脂環式炭化水素基同士が単結合で連結してなる基を意味する。また、複数の上記芳香族炭化水素基が連結してなる基とは、芳香族炭化水素基同士が単結合で連結してなる基を意味する。
 LおよびLはそれぞれ独立に、1価の有機基を表し、LおよびLの少なくとも一方は、重合性基を有する1価の基を表す。
 Arは、式(Ar-1)~(Ar-7)で表される基からなる群から選択されるいずれかの芳香環を表す。なお、下記式(Ar-1)~(Ar-7)中、*は、DまたはDとの結合位置を表す。
One of the preferred embodiments of the specific liquid crystal compound is a compound represented by the following formula (II).
L 1- G 1- D 1- Ar-D 2- G 2- L 2 ... (II)
In the above formula (II), D 1 and D 2 are independently single-bonded, -O-, -CO-, -CO-O-, -C (= S) O-, and -CR 1 R 2-. , -CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O- CO-CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -O-CO -, - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O- CR 3 R 4 -, - NR 1 -CR 2 R 3 -, or, -CO-NR 1 - represents a.
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. When each of R 1 , R 2 , R 3 and R 4 exists, 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 one or more of -CH 2- constituting the alicyclic hydrocarbon group is replaced with -O-, -S- or -NH-. It may have been.
The group formed by linking a plurality of the alicyclic hydrocarbon groups means a group formed by connecting divalent alicyclic hydrocarbon groups having 5 to 8 carbon atoms in a single bond. Further, 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 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). In the following formulas (Ar-1) to (Ar-7), * represents the bonding position with D 1 or D 2.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
 上記式(Ar-1)中、Qは、NまたはCHを表し、Qは、-S-、-O-、または、-N(R)-を表し、Rは、水素原子または炭素数1~6のアルキル基を表し、Yは、置換基を有してもよい、炭素数6~12の芳香族炭化水素基、または、炭素数3~12の芳香族複素環基を表す。
 Rが示す炭素数1~6のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、および、n-ヘキシル基が挙げられる。
 Yが示す炭素数6~12の芳香族炭化水素基としては、例えば、フェニル基、2,6-ジエチルフェニル基、および、ナフチル基のアリール基が挙げられる。
 Yが示す炭素数3~12の芳香族複素環基としては、例えば、チエニル基、チアゾリル基、フリル基、および、ピリジル基のヘテロアリール基が挙げられる。
 また、Yが有していてもよい置換基としては、例えば、アルキル基、アルコキシ基、および、ハロゲン原子が挙げられる。
 アルキル基としては、炭素数1~18のアルキル基が好ましく、炭素数1~8のアルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、および、シクロヘキシル基)がより好ましく、炭素数1~4のアルキル基がさらに好ましく、メチル基またはエチル基が特に好ましい。アルキル基は、直鎖状、分岐鎖状、および、環状のいずれであってもよい。
 アルコキシ基としては、例えば、炭素数1~18のアルコキシ基が好ましく、炭素数1~8のアルコキシ基(例えば、メトキシ基、エトキシ基、n-ブトキシ基、および、メトキシエトキシ基)がより好ましく、炭素数1~4のアルコキシ基がさらに好ましく、メトキシ基またはエトキシ基が特に好ましい。
 ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、および、ヨウ素原子が挙げられ、中でも、フッ素原子または塩素原子が好ましい。
In the above formula (Ar-1), Q 1 represents N or CH, Q 2 represents -S-, -O-, or -N (R 7 )-, and 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. Represent.
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 can be 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.
Further , examples of the substituent that Y 1 may have include an alkyl group, an alkoxy group, and a halogen atom.
The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, 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). Groups, t-butyl groups, and cyclohexyl groups) are more preferred, 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.
As the alkoxy group, for example, 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.
Examples of 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.
 また、上記式(Ar-1)~(Ar-7)中、Z、ZおよびZは、それぞれ独立に、水素原子、炭素数1~20の1価の脂肪族炭化水素基、炭素数3~20の1価の脂環式炭化水素基、炭素数6~20の1価の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、-OR、-NR10、または、-SR11を表し、R~R11は、それぞれ独立に、水素原子または炭素数1~6のアルキル基を表し、ZおよびZは、互いに結合して芳香環を形成してもよい。
 炭素数1~20の1価の脂肪族炭化水素基としては、炭素数1~15のアルキル基が好ましく、炭素数1~8のアルキル基がより好ましく、メチル基、エチル基、イソプロピル基、tert-ペンチル基(1,1-ジメチルプロピル基)、tert-ブチル基、または、1,1-ジメチル-3,3-ジメチル-ブチル基がさらに好ましく、メチル基、エチル基、または、tert-ブチル基が特に好ましい。
 炭素数3~20の1価の脂環式炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、メチルシクロヘキシル基、および、エチルシクロヘキシル基等の単環式飽和炭化水素基;シクロブテニル基、シクロペンテニル基、シクロヘキセニル基、シクロヘプテニル基、シクロオクテニル基、シクロデセニル基、シクロペンタジエニル基、シクロヘキサジエニル基、シクロオクタジエニル基、および、シクロデカジエン等の単環式不飽和炭化水素基;ビシクロ[2.2.1]ヘプチル基、ビシクロ[2.2.2]オクチル基、トリシクロ[5.2.1.02,6]デシル基、トリシクロ[3.3.1.13,7]デシル基、テトラシクロ[6.2.1.13,6.02,7]ドデシル基、および、アダマンチル基等の多環式飽和炭化水素基;等が挙げられる。
 炭素数6~20の1価の芳香族炭化水素基としては、例えば、フェニル基、2,6-ジエチルフェニル基、ナフチル基、および、ビフェニル基が挙げられ、炭素数6~12のアリール基(特にフェニル基)が好ましい。
 ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、および、ヨウ素原子が挙げられ、中でも、フッ素原子、塩素原子、または、臭素原子が好ましい。
 R~R11が示す炭素数1~6のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、および、n-ヘキシル基が挙げられる。
Further, in the above formulas (Ar-1) to (Ar-7), Z 1 , Z 2 and Z 3 are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbons, respectively. 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.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, 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, and tert are 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.
Examples of 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 (an aryl group having 6 to 12 carbon atoms). Especially phenyl group) is preferable.
Examples of the halogen atom 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.
Examples of the alkyl group having 1 to 6 carbon atoms represented 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.
 また、上記式(Ar-2)および(Ar-3)中、AおよびAは、それぞれ独立に、-O-、-N(R12)-、-S-、および、-CO-からなる群から選択される基を表し、R12は、水素原子または置換基を表す。
 R12が示す置換基としては、上記式(Ar-1)中のYが有していてもよい置換基と同様のものが挙げられる。
Further, in the above formulas (Ar-2) and (Ar-3), A 1 and A 2 are independently derived from -O-, -N (R 12 )-, -S-, and -CO-, respectively. Represents a group selected from the group, where R 12 represents a hydrogen atom or substituent.
Examples of the substituent represented by R 12 include the same substituents that Y 1 in the above formula (Ar-1) may have.
 また、上記式(Ar-2)中、Xは、水素原子または置換基が結合していてもよい、第14~16族の非金属原子を表す。
 また、Xが示す第14~16族の非金属原子としては、例えば、酸素原子、硫黄原子、水素原子または置換基が結合した窒素原子〔=N-RN1,RN1は水素原子または置換基を表す。〕、水素原子または置換基が結合した炭素原子〔=C-(RC1,RC1は水素原子または置換基を表す。〕が挙げられる。
 置換基としては、具体的には、例えば、アルキル基、アルコキシ基、アルキル置換アルコキシ基、環状アルキル基、アリール基(例えば、フェニル基、ナフチル基など)、シアノ基、アミノ基、ニトロ基、アルキルカルボニル基、スルホ基、および、水酸基が挙げられる。
Further, in the above formula (Ar-2), X represents a non-metal atom of Groups 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Further, as the non-metal atom of Group 14 to 16 indicated by X, for example, an oxygen atom, a sulfur atom, a hydrogen atom or a nitrogen atom to which a substituent is bonded [= N- RN1 , RN1 is a hydrogen atom or a substituent. Represents. ], A carbon atom to which a hydrogen atom or a substituent is bonded [= C- ( RC1 ) 2 , RC1 represents a hydrogen atom or a substituent. ] Can be mentioned.
Specific examples of the substituent include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl group. Examples include a carbonyl group, a sulfo group, and a hydroxyl group.
 また、上記式(Ar-3)中、DおよびDは、それぞれ独立に、単結合、または、-CO-、-O-、-S-、-C(=S)-、-CR1a2a-、-CR3a=CR4a-、-NR5a-、もしくは、これらの2つ以上の組み合わせからなる2価の連結基を表し、R1a~R5aは、それぞれ独立に、水素原子、フッ素原子、または、炭素数1~4のアルキル基を表す。
 ここで、2価の連結基としては、例えば、-CO-、-O-、-CO-O-、-C(=S)O-、-CR1b2b-、-CR1b2b-CR1b2b-、-O-CR1b2b-、-CR1b2b-O-CR1b2b-、-CO-O-CR1b2b-、-O-CO-CR1b2b-、-CR1b2b-O-CO-CR1b2b-、-CR1b2b-CO-O-CR1b2b-、-NR3b-CR1b2b-、および、-CO-NR3b-が挙げられる。R1b、R2bおよびR3bは、それぞれ独立に、水素原子、フッ素原子、または、炭素数1~4のアルキル基を表す。
Further, in the above formula (Ar-3), D 4 and D 5 are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR 1a. 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. Represents a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
Here, examples of the divalent linking group, for example, -CO -, - O -, - CO-O -, - C (= S) O -, - CR 1b R 2b -, - CR 1b R 2b -CR 1b R 2b -, - O- CR 1b R 2b -, - CR 1b R 2b -O-CR 1b R 2b -, - CO-O-CR 1b R 2b -, - O-CO-CR 1b R 2b -, -CR 1b R 2b -O-CO- CR 1b R 2b -, - CR 1b R 2b -CO-O-CR 1b R 2b -, - NR 3b -CR 1b R 2b -, and, -CO-NR 3b - Can be mentioned. R 1b , R 2b and R 3b independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
 また、上記式(Ar-3)中、SPおよびSPは、それぞれ独立に、単結合、炭素数1~12の直鎖状もしくは分岐鎖状のアルキレン基、または、炭素数1~12の直鎖状もしくは分岐鎖状のアルキレン基を構成する-CH-の1個以上が-O-、-S-、-NH-、-N(Q)-、もしくは、-CO-に置換された2価の連結基を表し、Qは、置換基を表す。置換基としては、上記式(Ar-1)中のYが有していてもよい置換基と同様のものが挙げられる。
 ここで、炭素数1~12の直鎖状または分岐鎖状のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、メチルヘキシレン基、および、へプチレン基が好ましい。
Further, in the above formula (Ar-3), SP 1 and SP 2 are independently single-bonded, linear or branched alkylene groups having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. One or more of -CH 2- constituting the linear or branched alkylene group was replaced 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.
Here, 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. A petitene group is preferred.
 また、上記式(Ar-3)中、LおよびLは、それぞれ独立に、1価の有機基を表す。
 1価の有機基としては、例えば、アルキル基、アリール基、および、ヘテロアリール基が挙げられる。アルキル基は、直鎖状、分岐鎖状、または、環状であってもよいが、直鎖状が好ましい。アルキル基の炭素数は、1~30が好ましく、1~20がより好ましく、1~10がさらに好ましい。また、アリール基は、単環であっても多環であってもよいが単環が好ましい。アリール基の炭素数は、6~25が好ましく、6~10がより好ましい。また、ヘテロアリール基は、単環であっても多環であってもよい。ヘテロアリール基を構成するヘテロ原子の数は1~3が好ましい。ヘテロアリール基を構成するヘテロ原子は、窒素原子、硫黄原子、または、酸素原子が好ましい。ヘテロアリール基の炭素数は6~18が好ましく、6~12がより好ましい。また、アルキル基、アリール基、および、ヘテロアリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上記式(Ar-1)中のYが有していてもよい置換基と同様のものが挙げられる。
Further, in the above formula (Ar-3), L 3 and L 4 each independently represent a monovalent organic group.
Examples of 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. Further, 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. Further, the alkyl group, the aryl group, and the heteroaryl group may be unsubstituted or have a substituent. Examples of the substituent include the same substituents that Y 1 in the above formula (Ar-1) may have.
 また、上記式(Ar-4)~(Ar-7)中、Axは、芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
 また、上記式(Ar-4)~(Ar-7)中、Ayは、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、または、芳香族炭化水素環および芳香族複素環からなる群から選択される少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
 ここで、AxおよびAyにおける芳香環は、置換基を有していてもよく、AxとAyとが互いに結合して環を形成していてもよい。
 また、Qは、水素原子、または、置換基を有していてもよい炭素数1~6のアルキル基を表す。
 AxおよびAyとしては、特許文献1(国際公開第2014/010325号)の段落[0039]~[0095]に記載されたものが挙げられる。
 また、Qが示す炭素数1~6のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、および、n-ヘキシル基が挙げられ、置換基としては、上記式(Ar-1)中のYが有していてもよい置換基と同様のものが挙げられる。
Further, in the above formulas (Ar-4) to (Ar-7), 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.
Further, in the above formulas (Ar-4) to (Ar-7), 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 aromatic. It 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.
Here, the aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may be bonded to each other to form a ring.
Further, 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 1 (International Publication No. 2014/010325).
The alkyl group having 1 to 6 carbon atoms represented by Q 3, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl radical, n -Pentyl group and n-hexyl group can be mentioned, and examples of the substituent include the same substituents that Y 1 in the above formula (Ar-1) may have.
 上記式(II)で表される重合性液晶化合物の各置換基の定義および好ましい範囲については、特開2012-021068号公報に記載の化合物(A)に関するD、D、G、G、L、L、R、R、R、R、X、Y、Q、Qに関する記載をそれぞれD、D、G、G、L、L、R、R、R、R、Q、Y、Z、およびZについて参照でき、特開2008-107767号公報に記載の一般式(I)で表される化合物についてのA、A、およびXに関する記載をそれぞれA、A、およびXについて参照でき、国際公開第2013/018526号に記載の一般式(I)で表される化合物についてのAx、Ay、Qに関する記載をそれぞれAx、Ay、Qについて参照できる。Zについては特開2012-21068号公報に記載の化合物(A)に関するQの記載を参照できる。 For the definition and preferable range of each substituent of the polymerizable liquid crystal compound represented by the above formula (II), refer to D 1 , D 2 , G 1 , G regarding the compound (A) described in JP2012-021068. 2 , L 1 , L 2 , R 4 , R 5 , R 6 , R 7 , X 1 , Y 1 , Q 1 , Q 2 respectively D 1 , D 2 , G 1 , G 2 , L 1 , L 2 , R 1 , R 2 , R 3 , R 4 , Q 1 , Y 1 , Z 1 , and Z 2 can be referred to, and are represented by the general formula (I) described in JP-A-2008-107767. References to A 1 , A 2 , and X for compounds can be found for A 1 , A 2 , and X, respectively, and Ax for compounds represented by the general formula (I) in WO 2013/018526. , Ay, the description with respect to Q 1 can refer Ax, Ay, for Q 3 respectively. For Z 3 can refer to the description for Q 1 relates to compounds (A) described in JP-A-2012-21068.
 特に、LおよびLで示される有機基としては、それぞれ、-D-G-Sp-Pで表される基であることが好ましい。
 Dは、Dと同義である。
 Gは、単結合、炭素数6~12の2価の芳香環基もしくは複素環基、複数の上記芳香環基もしくは複素環基が連結してなる基、炭素数5~8の2価の脂環式炭化水素基、または、複数の上記脂環式炭化水素基が連結してなる基を表し、上記脂環式炭化水素基に含まれるメチレン基は、-O-、-S-または-NR-で置換されていてもよく、ここでRは水素原子または炭素数1~6のアルキル基を表す。
 複数の上記芳香環基もしくは複素環基が連結してなる基とは、炭素数6~12の2価の芳香環基もしくは複素環基同士が単結合で連結してなる基を意味する。また、複数の上記脂環式炭化水素基が連結してなる基とは、炭素数5~8の2価の脂環式炭化水素基同士が単結合で連結してなる基を意味する。
 Gとしては、2個のシクロヘキサン環が単結合を介して結合した基も好ましい。
 Spは、単結合、-(CH-、-(CH-O-、-(CH-O-)-、-(CHCH-O-)、-O-(CH-、-O-(CH-O-、-O-(CH-O-)-、-O-(CHCH-O-)、-C(=O)-O-(CH-、-C(=O)-O-(CH-O-、-C(=O)-O-(CH-O-)-、-C(=O)-O-(CHCH-O-)、-C(=O)-N(R)-(CH-、-C(=O)-N(R)-(CH-O-、-C(=O)-N(R)-(CH-O-)-、-C(=O)-N(R)-(CHCH-O-)、または、-(CH-O-(C=O)-(CH-C(=O)-O-(CH-で表されるスペーサー基を表す。ここで、nは2~12の整数を表し、mは2~6の整数を表し、Rは水素原子または炭素数1~6のアルキル基を表す。また、上記各基における-CH-の水素原子は、メチル基で置換されていてもよい。
 Pは重合性基を示す。
In particular, the organic group represented by L 1 and L 2 is preferably a group represented by -D 3- G 3- Sp-P 3, respectively.
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 aromatic ring groups or heterocyclic groups, and a divalent aromatic ring group having 5 to 8 carbon atoms. It represents an alicyclic hydrocarbon group or a group formed by linking a plurality of the alicyclic hydrocarbon groups, and the methylene group contained in the alicyclic hydrocarbon group is -O-, -S- or-. It may be substituted with NR 7 −, where 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 group in which divalent aromatic ring groups or heterocyclic groups having 6 to 12 carbon atoms are linked by a single bond. The group in which a plurality of the 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.
Sp is a single bond,-(CH 2 ) n -,-(CH 2 ) n- O-,-(CH 2- O-) n -,-(CH 2 CH 2- O-) m , -O- (CH 2 ) n- , -O- (CH 2 ) n- O-, -O- (CH 2- O-) n- , -O- (CH 2 CH 2- O-) m , -C (= O) -O- (CH 2 ) n- , -C (= O) -O- (CH 2 ) n- O-, -C (= O) -O- (CH 2- O-) n -,- C (= O) -O- (CH 2 CH 2 -O-) m, -C (= O) -N (R 8) - (CH 2) n -, - C (= O) -N (R 8 )-(CH 2 ) n -O-, -C (= O) -N (R 8 )-(CH 2- O-) n- , -C (= O) -N (R 8 )-(CH 2) Spacer represented by CH 2- O-) m or-(CH 2 ) n- O- (C = O)-(CH 2 ) n- C (= O) -O- (CH 2 ) n- Represents a group. Here, n represents an integer of 2 to 12, m represents an integer of 2 to 6, and R 8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Further, -CH 2 in the above group - hydrogen atoms may be substituted with a methyl group.
P 3 represents a polymerizable group.
 重合性基は特に限定されないが、ラジカル重合またはカチオン重合可能な重合性基が好ましい。
 ラジカル重合性基としては、公知のラジカル重合性基が挙げられ、アクリロイル基またはメタクリロイル基が好ましい。重合速度はアクリロイル基が一般的に速いことが知られており、生産性向上の点からアクリロイル基が好ましいが、メタクリロイル基も高複屈折性液晶の重合性基として同様に使用することができる。
 カチオン重合性基としては、公知のカチオン重合性基が挙げられ、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、および、ビニルオキシ基が挙げられる。なかでも、脂環式エーテル基、または、ビニルオキシ基が好ましく、エポキシ基、オキセタニル基、または、ビニルオキシ基がより好ましい。
 特に好ましい重合性基の例としては下記が挙げられる。
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.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
 なお、本明細書において、「アルキル基」は、直鎖状、分枝鎖状および環状のいずれでもよく、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、1,1-ジメチルプロピル基、n-ヘキシル基、イソヘキシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、および、シクロヘキシル基が挙げられる。 In the present specification, the "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, sec-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.
 上記式(II)で表される重合性液晶化合物の好ましい例を以下に示すが、これらの液晶化合物に限定されるものではない。 Preferred examples of the polymerizable liquid crystal compound represented by the above formula (II) are shown below, but the present invention is not limited to these liquid crystal compounds.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
 なお、上記式中、「*」は結合位置を表す。 In the above formula, "*" represents the connection position.
 II-2-8
Figure JPOXMLDOC01-appb-C000007
II-2-8
Figure JPOXMLDOC01-appb-C000007
 II-2-9
Figure JPOXMLDOC01-appb-C000008
II-2-9
Figure JPOXMLDOC01-appb-C000008
 なお、上記式II-2-8およびII-2-9中のアクリロイルオキシ基に隣接する基は、プロピレン基(メチル基がエチレン基に置換した基)を表し、メチル基の位置が異なる位置異性体の混合物を表す。 The group adjacent to the acryloyloxy group in the above formulas II-2-8 and II-2-9 represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and the positions of the methyl groups are different. Represents a mixture of bodies.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
 上記の好ましい例に加えて、他に好ましい側鎖構造の例を以下に示す。 In addition to the above preferred examples, other preferred side chain structure examples are shown below.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
 また、特定液晶化合物の他の好ましい態様として、下記式(V)で表される化合物も挙げられる。
 L-[D-G-E-A-E-[G-D-L   ・・・(V)
 上記式(V)において、
 Aは、炭素数5~8の非芳香族の炭素環式基もしくはヘテロ環式基、または、炭素数6~20の芳香族基もしくはヘテロ芳香族基であり;
 E、E、DおよびDは、それぞれ独立に、単結合または2価の連結基であり;
 LおよびLは、それぞれ独立に、-H、-F、-Cl、-Br、-I、-CN、-NC、-NCO、-OCN、-SCN、-C(=O)NR、-C(=O)R、-O-C(=O)R、-NH、-SH、-SR、-SOH、-SO、-OH、-NO、-CF、-SF、置換もしくは非置換のシリル、置換もしくは非置換の炭素数1~40のカルビル基もしくはヒドロカルビル基、または、-Sp-Pであって、LおよびLのうちの少なくとも1つは、-Sp-Pであり、Pは、重合性基であり、Spは、スペーサー基または単結合であり、RおよびRは、それぞれ独立に、-Hまたは炭素数1~12のアルキルであり;
 mおよびnは、それぞれ独立に、1~5の整数であって;mまたはnが2以上であれば、2以上繰り返される-(D-G)-または-(G-D)-の各繰り返し単位は、互いに同一であっても異なっていてもよく;
 GおよびGは、それぞれ独立に、炭素数5~8の非芳香族の炭素環式基もしくはヘテロ環式基、または、炭素数6~20の芳香族基もしくはヘテロ芳香族基であって、GおよびGのうちの少なくとも1つは、上記炭素環式基もしくはヘテロ環式基であり、上記炭素環式もしくはヘテロ環式基に含まれているいずれか1つの水素原子は、下記式(VI)で表される基で置換されている:
 *-[Q-B   ・・・(VI)
 上記式(VI)において、
 pは、1~10の整数であって、pが2以上であれば、2以上繰り返される-(Q)-の各繰り返し単位は、互いに同一であっても異なっていてもよく、
 Qは、それぞれ独立に、-C≡C-、-CY=CY-、および、炭素数6~20の置換もしくは非置換の芳香族基またはヘテロ芳香族基からなる群より選択された2価基であって、YおよびYは、それぞれ独立に、-H、-F、-Cl、-CN、または-Rであり、
 Bは、-H、-F、-Cl、-Br、-I、-CN、-NC、-NCO、-OCN、-SCN、-C(=O)NR、-C(=O)R、-NH、-SH、-SR、-SOH、-SO、-OH、-NO、-CF、-SF、重合性基、炭素数2~6のアルケニル基、炭素数2~6のアルキニル基、炭素数2~4のアシル基、末端に炭素数2~4のアシル基が結合した炭素数2~6のアルキニレン基、炭素数1~5のアルコール基、または、炭素数1~12のアルコキシ基であり、
 RおよびRは、それぞれ独立に、-Hまたは炭素数1~12のアルキルである。
Further, as another preferable embodiment of the specific liquid crystal compound, a compound represented by the following formula (V) can also be mentioned.
L 1- [D 1- G 1 ] m- E 1- A-E 2- [G 2- D 2 ] n- L 2 ... (V)
In the above formula (V)
A is a non-aromatic carbocyclic or heterocyclic group having 5 to 8 carbon atoms, or an aromatic or heteroaromatic group having 6 to 20 carbon atoms;
E 1 , E 2 , D 1 and D 2 are independently single-bonded or divalent linking groups;
L 1 and L 2 are independently of -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R. 2 , -C (= O) R 1 , -OC (= O) R 1 , -NH 2 , -SH, -SR 1 , -SO 3 H, -SO 2 R 1 , -OH, -NO 2 , -CF 3 , -SF 3 , substituted or unsubstituted silyl, substituted or unsubstituted carbil group or hydrocarbyl group having 1 to 40 carbon atoms, or -Sp-P, which is of L 1 and L 2 . At least one of is -Sp-P, P is a polymerizable group, Sp is a spacer group or a single bond, and R 1 and R 2 are independently -H or 1 carbon atoms, respectively. ~ 12 alkyls;
m and n are independently integers from 1 to 5; if m or n is 2 or more, they are repeated 2 or more-(D 1- G 1 )-or-(G 2- D 2 ). -Each repeating unit may be the same or different from each other;
G 1 and G 2 are independently non-aromatic carbocyclic groups or heterocyclic groups having 5 to 8 carbon atoms, or aromatic groups or heteroaromatic groups having 6 to 20 carbon atoms. , G 1 and G 2 are at least one carbocyclic group or heterocyclic group, and any one hydrogen atom contained in the carbocyclic group or heterocyclic group is described below. Substituted with a group represented by the formula (VI):
*-[Q 1 ] p- B 1 ... (VI)
In the above formula (VI)
p is an integer of 1 to 10, and if p is 2 or more, each repeating unit of − (Q 1 ) − repeated 2 or more may be the same as or different from each other.
Q 1 was independently selected from the group consisting of -C≡C-, -CY 1 = CY 2- , and a substituted or unsubstituted aromatic group or heteroaromatic group having 6 to 20 carbon atoms. The divalent groups, Y 1 and Y 2 , are independently -H, -F, -Cl, -CN, or -R 1 , respectively.
B 1 is -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR 1 R 2 , -C (= O). ) R 1 , -NH 2 , -SH, -SR 1 , -SO 3 H, -SO 2 R 1 , -OH, -NO 2 , -CF 3 , -SF 3 , polymerizable group, carbon number 2 to 6 Alkoxy group, alkynyl group having 2 to 6 carbon atoms, acyl group having 2 to 4 carbon atoms, alkynylene group having 2 to 6 carbon atoms with an acyl group having 2 to 4 carbon atoms bonded to the end, and alkynylene group having 1 to 5 carbon atoms. It is an alcohol group or an alkoxy group having 1 to 12 carbon atoms.
R 1 and R 2 are independently alkyls having −H or 1 to 12 carbon atoms.
 上記式(V)の好ましい具体例を下記に示す。 A preferable specific example of the above formula (V) is shown below.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
 重合性液晶組成物中における特定液晶化合物の含有量は特に制限されないが、重合性液晶組成物中の全固形分に対して、50~100質量%が好ましく、70~99質量%がより好ましい。
 特定液晶化合物は、1種単独で用いてもよいし、2種以上併用してもよい。
 固形分とは、重合性液晶組成物中の溶媒を除いた他の成分を意味し、その性状が液状であっても固形分として計算する。
The content of the specific liquid crystal compound in the polymerizable liquid crystal composition is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 99% by mass, based on the total solid content in the polymerizable liquid crystal composition.
The specific liquid crystal compound may be used alone or in combination of two or more.
The solid content means other components in the polymerizable liquid crystal composition excluding the solvent, and is calculated as a solid content even if the property is liquid.
 重合性液晶組成物は、液晶配向性を制御する点から、上述した特定液晶化合物以外に、重合性棒状化合物を含んでいてもよい。
 なお、上記重合性棒状化合物は、液晶性の有無を問わない。
The polymerizable liquid crystal composition may contain a polymerizable rod-shaped compound in addition to the above-mentioned specific liquid crystal compound from the viewpoint of controlling the liquid crystal orientation.
The polymerizable rod-like compound may or may not be liquid crystal.
 上記重合性棒状化合物は、上述した特定液晶化合物との相溶性の点から、直鎖状のアルキル基で水素原子が1個置換されたシクロヘキサン環を一部に有する化合物(以下、「アルキルシクロヘキサン環含有化合物」とも略す。)であることが好ましい。
 ここで、「直鎖状のアルキル基で水素原子が1個置換されたシクロヘキサン環」とは、例えば、下記式(2)に示すように、シクロヘキサン環を2つ有する場合には、分子末端側に存在するシクロヘキサン環の水素原子が直鎖状のアルキル基で1個置換されたシクロヘキサン環をいう。
The above-mentioned polymerizable rod-shaped compound is a compound having a cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group (hereinafter, "alkylcyclohexane ring") from the viewpoint of compatibility with the above-mentioned specific liquid crystal compound. It is also abbreviated as "containing compound").
Here, the "cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group" is, for example, as shown in the following formula (2), when it has two cyclohexane rings, it is on the molecular terminal side. A cyclohexane ring in which one hydrogen atom of the cyclohexane ring present in is substituted with a linear alkyl group.
 アルキルシクロヘキサン環含有化合物としては、例えば、下記式(2)で表される基を有する化合物が挙げられ、なかでも、光学異方性層の湿熱耐久性付与の点から、(メタ)アクリロイル基を有する下記式(3)で表される化合物であるのが好ましい。 Examples of the alkylcyclohexane ring-containing compound include compounds having a group represented by the following formula (2). Among them, a (meth) acryloyl group is used from the viewpoint of imparting moist heat durability to the optically anisotropic layer. It is preferably a compound represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
 ここで、上記式(2)中、*は結合位置を表す。
 また、上記式(2)および(3)中、Rは炭素数1~10のアルキル基を表し、nは1または2を表し、WおよびWは、それぞれ独立に、アルキル基、アルコキシ基またはハロゲン原子を表し、また、WおよびWはこれらが互いに結合し、置換基を有していてもよい環構造を形成していてもよい。
 また、上記式(3)中、Zは-COO-を表し、Lは炭素数1~6のアルキレン基を表し、Rは水素原子またはメチル基を表す。
Here, in the above equation (2), * represents a coupling position.
Further, in the above formulas (2) and (3), R 2 represents an alkyl group having 1 to 10 carbon atoms, n represents 1 or 2, and W 1 and W 2 independently represent an alkyl group and an alkoxy. It represents a group or halogen atom, and W 1 and W 2 may be bonded to each other to form a ring structure which may have a substituent.
Further, in the above formula (3), Z represents -COO-, L represents an alkylene group having 1 to 6 carbon atoms, and R 3 represents a hydrogen atom or a methyl group.
 このようなアルキルシクロヘキサン環含有化合物としては、具体的には、例えば、下記式A-1~A-5で表される化合物が挙げられる。なお、下記式A-3中、Rは、エチル基またはブチル基を表す。 Specific examples of such an alkylcyclohexane ring-containing compound include compounds represented by the following formulas A-1 to A-5. Incidentally, in the following formula A-3, R 4 represents an ethyl group or a butyl group.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
 重合性液晶組成物が上記重合性棒状化合物を含む場合、上記重合性棒状化合物の含有量は、上述した特定液晶化合物および上記重合性棒状化合物の合計質量に対して、1~30質量%が好ましく、1~20質量%がより好ましい。 When the polymerizable liquid crystal composition contains the above-mentioned polymerizable rod-like compound, the content of the above-mentioned polymerizable rod-like compound is preferably 1 to 30% by mass with respect to the total mass of the above-mentioned specific liquid crystal compound and the above-mentioned polymerizable rod-like compound. More preferably, 1 to 20% by mass.
 重合性液晶組成物は、上述した特定液晶化合物および重合性棒状化合物以外の重合性液晶化合物(以下、「他の重合性液晶化合物」とも略す。)を含んでいてもよい。
 ここで、他の重合性液晶化合物が有する重合性基は特に限定されず、例えば、(メタ)アクリロイル基、ビニル基、スチリル基、および、アリル基が挙げられる。なかでも、(メタ)アクリロイル基が好ましい。
The polymerizable liquid crystal composition may contain a polymerizable liquid crystal compound (hereinafter, also abbreviated as “another polymerizable liquid crystal compound”) other than the above-mentioned specific liquid crystal compound and the polymerizable rod-shaped compound.
Here, the polymerizable group contained in the other polymerizable liquid crystal compound is not particularly limited, and examples thereof include a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, the (meth) acryloyl group is preferable.
 光学異方性層の耐久性が向上する点から、他の重合性液晶化合物としては、重合性基を2~4個有する重合性化合物が好ましく、重合性基を2個有する重合性化合物がより好ましい。 From the viewpoint of improving the durability of the optically anisotropic layer, the other polymerizable liquid crystal compound is preferably a polymerizable compound having 2 to 4 polymerizable groups, and more preferably a polymerizable compound having 2 polymerizable groups. preferable.
 このような他の重合性液晶化合物としては、例えば、特開2014-077068号公報の段落0030~0033に記載された式(M1)で表される化合物、式(M2)で表される化合物、および、式(M3)で表される化合物が挙げられ、より具体的には、同公報の段落0046~0055に記載された具体例が挙げられる。
 他の重合性液晶化合物は、1種単独で用いてもよいし、2種以上併用してもよい。
Examples of such other polymerizable liquid crystal compounds include compounds represented by the formula (M1) and compounds represented by the formula (M2) described in paragraphs 0030 to 0033 of JP-A-2014-0770668. In addition, a compound represented by the formula (M3) can be mentioned, and more specifically, specific examples described in paragraphs 0046 to 0055 of the same publication can be mentioned.
Other polymerizable liquid crystal compounds may be used alone or in combination of two or more.
 重合性液晶組成物が他の重合性液晶化合物を含む場合、他の重合性液晶化合物の含有量は、上述した特定液晶化合物、重合性棒状化合物および他の重合性液晶化合物の合計質量に対して、1~40質量%が好ましく、1~10質量%がより好ましい。 When the polymerizable liquid crystal composition contains another polymerizable liquid crystal compound, the content of the other polymerizable liquid crystal compound is based on the total mass of the specific liquid crystal compound, the polymerizable rod-shaped compound and the other polymerizable liquid crystal compound described above. 1 to 40% by mass is preferable, and 1 to 10% by mass is more preferable.
 重合性液晶組成物は、形成される光学異方性層を有する偏光板の耐久性がさらに向上する点から、非液晶性の多官能重合性化合物を含むことが好ましい。
 これは、架橋点密度が増えることにより、加水分解反応の触媒となる化合物(液晶分解物と推定)の動きが抑制された結果、加水分解反応の速度が遅くなり、その間に水分の端部への拡散が進行するためと推定している。
The polymerizable liquid crystal composition preferably contains a non-liquid crystal polyfunctional polymerizable compound from the viewpoint of further improving the durability of the polarizing plate having the optically anisotropic layer to be formed.
This is because the increase in the density of cross-linking points suppresses the movement of the compound that catalyzes the hydrolysis reaction (presumed to be a liquid crystal decomposition product), and as a result, the rate of the hydrolysis reaction slows down, while the water ends It is presumed that this is due to the progress of diffusion.
 非液晶性の多官能重合性化合物は、上述した特定液晶化合物の配向性の点から、アクリル当量が低い化合物が好ましい。
 具体的には、(メタ)アクリル当量が120以下である化合物が好ましく、(メタ)アクリル当量が100以下である化合物がより好ましく、(メタ)アクリル当量が90以下である化合物がさらに好ましい。
The non-liquid crystal polyfunctional polymerizable compound is preferably a compound having a low acrylic equivalent from the viewpoint of the orientation of the specific liquid crystal compound described above.
Specifically, a compound having a (meth) acrylic equivalent of 120 or less is preferable, a compound having a (meth) acrylic equivalent of 100 or less is more preferable, and a compound having a (meth) acrylic equivalent of 90 or less is further preferable.
 非液晶性の多官能重合性化合物としては、多価アルコールと(メタ)アクリル酸とのエステル、ビニルベンゼンおよびその誘導体、ビニルスルホン、アクリルアミド、および、メタクリルアミドが挙げられる。
 ここで、多価アルコールと(メタ)アクリル酸とのエステルとしては、具体的には、例えば、エチレングリコールジ(メタ)アクリレート、1,4-シクロヘキサンジアクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,2,3-シクロヘキサンテトラメタクリレート、ポリウレタンポリアクリレート、および、ポリエステルポリアクリレートなどが挙げられる。
 また、ビニルベンゼンおよびその誘導体としては、具体的には、例えば、1,4-ジビニルベンゼン、4-ビニル安息香酸-2-アクリロイルエチルエステル、および、1,4-ジビニルシクロヘキサノンなどが挙げられる。
 また、ビニルスルホンとしては、具体的には、例えば、ジビニルスルホンなどが挙げられる。
 また、アクリルアミドとしては、具体的には、例えば、メチレンビスアクリルアミドなどが挙げられる。
Non-liquid polyfunctional polymerizable compounds include esters of polyhydric alcohols with (meth) acrylic acid, vinylbenzene and its derivatives, vinylsulfone, acrylamide, and methacrylamide.
Here, as the ester of the polyhydric alcohol and the (meth) acrylic acid, specifically, for example, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, penta. Elythritol tri (meth) acrylate, trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate and the like can be mentioned.
Specific examples of vinylbenzene and its derivatives include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, and 1,4-divinylcyclohexanone.
Specific examples of the vinyl sulfone include divinyl sulfone.
Specific examples of acrylamide include methylenebisacrylamide and the like.
 重合性液晶組成物が非液晶性の多官能重合性化合物を含む場合、形成される光学異方性層の位相差の発現の点から、非液晶性の多官能重合性化合物の含有量は、重合性液晶組成物中の全固形分に対して、0.1~20質量%が好ましく、0.1~10質量%がより好ましく、1~6質量%がさらに好ましい。 When the polymerizable liquid crystal composition contains a non-liquid crystal polyfunctional polymerizable compound, the content of the non-liquid crystal polyfunctional polymerizable compound is determined from the viewpoint of expressing the phase difference of the formed optically anisotropic layer. It is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, still more preferably 1 to 6% by mass, based on the total solid content in the polymerizable liquid crystal composition.
 重合性液晶組成物は、重合開始剤を含むことが好ましい。
 重合開始剤としては、紫外線照射によって重合反応を開始可能な光重合開始剤が好ましい。
 光重合開始剤としては、例えば、α-カルボニル化合物(米国特許第2367661号、同2367670号の各明細書記載)、アシロインエーテル(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許第4239850号明細書記載)およびオキサジアゾール化合物(米国特許第4212970号明細書記載)、アシルフォスフィンオキシド化合物(特公昭63-40799号公報、特公平5-29234号公報、特開平10-95788号公報、および、特開平10-29997号公報記載)が挙げられる。
The polymerizable liquid crystal composition preferably contains a polymerization initiator.
As the polymerization initiator, a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670), acidoin ether (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrance. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents). 3549367 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 421,970), acylphosphine. Examples thereof include oxide compounds (described in JP-A-63-40799, JP-A-5-29234, JP-A-10-95788, and JP-A-10-29997).
 光学異方性層の耐久性がより良好となる点から、重合開始剤としてはオキシム型の重合開始剤が好ましく、下記式(III)で表される重合開始剤がより好ましい。 From the viewpoint of improving the durability of the optically anisotropic layer, an oxime-type polymerization initiator is preferable as the polymerization initiator, and a polymerization initiator represented by the following formula (III) is more preferable.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
 上記式(III)中、Xは、水素原子またはハロゲン原子を表し、Yは、1価の有機基を表す。
 また、Arは、2価の芳香族基を表し、Lは、炭素数1~12の2価の有機基を表し、R10は、炭素数1~12のアルキル基を表す。
In the above formula (III), X represents a hydrogen atom or a halogen atom, and Y represents a monovalent organic group.
Further, Ar 3 represents a divalent aromatic group, L 6 represents a divalent organic group having 1 to 12 carbon atoms, and R 10 represents an alkyl group having 1 to 12 carbon atoms.
 上記式(III)中、Xが示すハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、および、ヨウ素原子が挙げられ、塩素原子が好ましい。
 また、上記式(III)中、Arが示す2価の芳香族基としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、および、フェナンスロリン環などの芳香族炭化水素環;フラン環、ピロール環、チオフェン環、ピリジン環、チアゾール環、および、ベンゾチアゾール環などの芳香族複素環;を有する2価の基が挙げられる。
 また、上記式(III)中、Lが示す炭素数1~12の2価の有機基としては、例えば、炭素数1~12の直鎖状または分岐状のアルキレン基が挙げられ、具体的には、メチレン基、エチレン基、および、プロピレン基が挙げられる。
 また、上記式(III)中、R10が示す炭素数1~12のアルキル基としては、例えば、メチル基、エチル基、および、プロピル基が挙げられる。
 また、上記式(III)中、Yが示す1価の有機基としては、例えば、ベンゾフェノン骨格((CCO)を含む官能基が挙げられる。具体的には、下記式(3a)で表される基および下記式(3b)で表される基のように、末端のベンゼン環が無置換または1置換であるベンゾフェノン骨格を含む官能基が好ましい。
In the above formula (III), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
Further, in the above formula (III) , examples of the divalent aromatic group represented by Ar 3 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; a furan ring. Examples thereof include a divalent group having an aromatic heterocycle such as a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.
Further, in the above formula (III) , examples of the divalent organic group having 1 to 12 carbon atoms represented by L 6 include a linear or branched alkylene group having 1 to 12 carbon atoms, and specific examples thereof. Examples include a methylene group, an ethylene group, and a propylene group.
Further, in the above formula (III) , examples of the alkyl group having 1 to 12 carbon atoms represented by R 10 include a methyl group, an ethyl group, and a propyl group.
Further, in the above formula (III), examples of the monovalent organic group represented by Y include a functional group containing a benzophenone skeleton ((C 6 H 5 ) 2 CO). Specifically, a functional group containing a benzophenone skeleton in which the terminal benzene ring is unsubstituted or monosubstituted, such as the group represented by the following formula (3a) and the group represented by the following formula (3b), is preferable. ..
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
 ここで、上記式(3a)および上記式(3b)中、*は結合位置、すなわち、上記式(III)におけるカルボニル基の炭素原子との結合位置を表す。 Here, in the above formula (3a) and the above formula (3b), * represents the bond position, that is, the bond position of the carbonyl group in the above formula (III) with the carbon atom.
 上記式(III)で表されるオキシム型の重合開始剤としては、例えば、下記式S-1で表される化合物、および、下記式S-2で表される化合物が挙げられる。 Examples of the oxime-type polymerization initiator represented by the above formula (III) include a compound represented by the following formula S-1 and a compound represented by the following formula S-2.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
 上記重合開始剤の含有量は特に限定されないが、重合開始剤の含有量は、重合性液晶組成物に含まれる特定液晶化合物100質量部に対して、0.5~10質量部が好ましく、1~5質量部がより好ましい。 The content of the polymerization initiator is not particularly limited, but the content of the polymerization initiator is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the specific liquid crystal compound contained in the polymerizable liquid crystal composition. Up to 5 parts by mass is more preferable.
 重合性液晶組成物は、必要に応じて、配向制御剤を含んでいてもよい。
 配向制御剤としては、例えば、低分子の配向制御剤、および、高分子の配向制御剤が挙げられる。低分子の配向制御剤としては、例えば、特開2002-020363号公報の段落0009~0083、特開2006-106662号公報の段落0111~0120、および、特開2012-211306号公報の段落0021-0029の記載を参酌でき、この内容は本明細書に組み込まれる。また、高分子の配向制御剤としては、例えば、特開2004-198511号公報の段落0021~0057の記載、および、特開2006-106662号公報の段落0121~0167を参酌でき、この内容は本明細書に組み込まれる。
 配向制御剤の使用量は、重合性液晶組成物の全固形分に対して、0.01~10質量%が好ましく、0.05~5質量%がより好ましい。配向制御剤を用いることにより、例えば、光学異方性層の表面と平行に配向したホモジニアス配向状態を形成できる。
The polymerizable liquid crystal composition may contain an orientation control agent, if necessary.
Examples of the orientation control agent include a low molecular weight orientation control agent and a polymer orientation control agent. Examples of the low-molecular-weight orientation control agent include paragraphs 0009 to 0083 of JP-A-2002-020363, paragraphs 0111 to 0120 of JP-A-2006-106662, and paragraphs 0021- of JP-2012-2011306A. The description of 0029 can be taken into consideration and this content is incorporated herein by reference. Further, as the polymer orientation control agent, for example, paragraphs 0021 to 0057 of JP-A-2004-198511 and paragraphs 0121 to 0167 of JP-A-2006-106662 can be referred to. Incorporated into the specification.
The amount of the orientation control agent used is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the polymerizable liquid crystal composition. By using the orientation control agent, for example, a homogeneous orientation state oriented parallel to the surface of the optically anisotropic layer can be formed.
 重合性液晶組成物は、光学異方性層を形成する作業性の点から、有機溶媒を含むことが好ましい。
 有機溶媒としては、例えば、ケトン類(例えば、アセトン、2-ブタノン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、および、シクロペンタノン)、エーテル類(例えば、ジオキサン、および、テトラヒドロフラン)、脂肪族炭化水素類(例えば、ヘキサン)、脂環式炭化水素類(例えば、シクロヘキサン)、芳香族炭化水素類(例えば、トルエン、キシレン、および、トリメチルベンゼン)、ハロゲン化炭素類(例えば、ジクロロメタン、ジクロロエタン、ジクロロベンゼン、および、クロロトルエン)、エステル類(例えば、酢酸メチル、酢酸エチル、および、酢酸ブチル)、水、アルコール類(例えば、エタノール、イソプロパノール、ブタノール、および、シクロヘキサノール)、セロソルブ類(例えば、メチルセロソルブ、および、エチルセロソルブ)、セロソルブアセテート類、スルホキシド類(例えば、ジメチルスルホキシド)、アミド類(例えば、ジメチルホルムアミド、および、ジメチルアセトアミド)が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
The polymerizable liquid crystal composition preferably contains an organic solvent from the viewpoint of workability for forming an optically anisotropic layer.
Examples of the organic solvent include ketones (for example, acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone), ethers (for example, dioxane and tetrahydrofuran), and aliphatic hydrocarbons. (Eg, hexane), alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, and trimethylbenzene), carbon halides (eg, dichloromethane, dichloroethane, dichlorobenzene, etc.) And chlorotoluene), esters (eg, methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (eg, methyl cellosolves, etc.) And ethyl cellosolve), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide), amides (eg, dimethylformamide, and dimethylacetamide), and these may be used alone or in combination of two or more. May be used together.
 重合性液晶組成物は、上述した成分以外の成分を含んでいてもよく、例えば、上述した特定液晶化合物以外の液晶化合物、界面活性剤、チルト角制御剤、配向助剤、可塑剤、および、架橋剤が挙げられる。 The polymerizable liquid crystal composition may contain components other than the above-mentioned components, for example, liquid crystal compounds other than the above-mentioned specific liquid crystal compounds, surfactants, tilt angle control agents, orientation aids, plasticizers, and Examples include cross-linking agents.
 光学異方性層は、上述した重合性液晶組成物を用いて形成される。
 光学異方性層の製造方法は特に制限されないが、例えば、所定の基板(例えば、後述する偏光子、後述する支持体またはその上に設けられた配向層、あるいは、上述したバリア層など)に、重合性液晶組成物を塗布して塗膜を形成し、塗膜に対して配向処理を施して特定液晶化合物を所定の配向状態とした後、塗膜に対して硬化処理を施す方法が挙げられる。
The optically anisotropic layer is formed by using the above-mentioned polymerizable liquid crystal composition.
The method for producing the optically anisotropic layer is not particularly limited, but for example, on a predetermined substrate (for example, a polarizer described later, a support described later or an alignment layer provided on the support, or a barrier layer described above). , A method in which a polymerizable liquid crystal composition is applied to form a coating film, the coating film is subjected to an orientation treatment to bring a specific liquid crystal compound into a predetermined orientation state, and then the coating film is cured. Be done.
 上記塗布は、公知の方法(例えば、ワイヤーバーコーティング法、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、および、ダイコーティング法など)により実施できる。 The above coating can be carried out by a known method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, etc.).
 配向処理は、室温(例えば、20~25℃)で乾燥させる、または、加熱することにより行うことができる。配向処理で形成される液晶相は、サーモトロピック性液晶化合物の場合、一般に温度または圧力の変化により転移させることができる。リオトロピック性をもつ液晶化合物の場合には、溶媒量の組成比によっても転移させることができる。
 配向処理が加熱温度である場合、加熱時間(加熱熟成時間)は、10秒間~5分間が好ましく、10秒間~3分間がより好ましく、10秒間~2分間がさらに好ましい。
The orientation treatment can be carried out by drying or heating at room temperature (for example, 20 to 25 ° C.). In the case of a thermotropic liquid crystal compound, the liquid crystal phase formed by the orientation treatment can generally be transferred by a change in temperature or pressure. In the case of a liquid crystal compound having a lyotropic property, the transfer can also be carried out by the composition ratio of the amount of the solvent.
When the orientation treatment is a heating temperature, the heating time (heat aging time) is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, still more preferably 10 seconds to 2 minutes.
 塗膜に対する硬化処理(活性エネルギー線の照射(光照射処理)および/または加熱処理)は、特定液晶化合物の配向を固定するための固定化処理ということもできる。
 なかでも、光照射処理を実施することが好ましい。光照射による重合においては、紫外線を用いることが好ましい。
 照射量は、10mJ/cm~50J/cmが好ましく、20mJ/cm~5J/cmがより好ましく、30mJ/cm~3J/cmがさらに好ましく、50~1000mJ/cmが特に好ましい。
 また、重合反応を促進するため、加熱条件下で光照射処理を実施してもよい。
 なお、上述したように、光学異方性層は、後述する支持体上、後述する偏光子上、および、上述したバリア層上に形成できる。
The curing treatment (irradiation of active energy rays (light irradiation treatment) and / or heat treatment) on the coating film can also be said to be an immobilization treatment for fixing the orientation of the specific liquid crystal compound.
Above all, it is preferable to carry out the light irradiation treatment. In the polymerization by light irradiation, it is preferable to use ultraviolet rays.
Irradiation dose is preferably 10mJ / cm 2 ~ 50J / cm 2, more preferably 20mJ / cm 2 ~ 5J / cm 2, more preferably 30mJ / cm 2 ~ 3J / cm 2, particularly 50 ~ 1000mJ / cm 2 preferable.
Further, in order to promote the polymerization reaction, the light irradiation treatment may be carried out under heating conditions.
As described above, the optically anisotropic layer can be formed on the support described later, on the polarizer described later, and on the barrier layer described above.
 光学異方性層の厚みは特に制限されず、1~5μmが好ましく、1~4μmがより好ましく、1~3μmがさらに好ましい。 The thickness of the optically anisotropic layer is not particularly limited, and is preferably 1 to 5 μm, more preferably 1 to 4 μm, and even more preferably 1 to 3 μm.
 光学異方性層は、光学積層体を有する画像表示装置の視野角方向の表示品質が向上する理由から、下記式(IV)を満たしていることが好ましい。
 Re(450)≦Re(550)≦Re(650) ・・・(IV)
 ここで、上記式(IV)中、Re(450)は、光学異方性膜の波長450nmにおける面内レターデーションを表し、Re(550)は、光学異方性膜の波長550nmにおける面内レターデーションを表し、Re(650)は、光学異方性膜の波長650nmにおける面内レターデーションを表す。
The optically anisotropic layer preferably satisfies the following formula (IV) because the display quality in the viewing angle direction of the image display device having the optical laminate is improved.
Re (450) ≤ Re (550) ≤ Re (650) ... (IV)
Here, in the above formula (IV), Re (450) represents the in-plane lettering of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents the in-plane letter of the optically anisotropic film at a wavelength of 550 nm. Re (650) represents the in-plane retardation of the optically anisotropic film at a wavelength of 650 nm.
 光学異方性層は、ポジティブAプレートであることが好ましい。
 なお、本明細書において、ポジティブAプレートは以下のように定義する。ポジティブAプレート(正のAプレート)は、フィルム面内の遅相軸方向(面内での屈折率が最大となる方向)の屈折率をnx、面内の遅相軸と面内で直交する方向の屈折率をny、厚さ方向の屈折率をnzとしたとき、式(A1)の関係を満たすものである。なお、ポジティブAプレートはRthが正の値を示す。
 式(A1)  nx>ny≒nz
 なお、上記「≒」とは、両者が完全に同一である場合だけでなく、両者が実質的に同一である場合も包含する。「実質的に同一」とは、例えば、(ny-nz)×d(ただし、dはフィルムの厚みである)が、-10~10nm、好ましくは-5~5nmの場合も「ny≒nz」に含まれる。
The optically anisotropic layer is preferably a positive A plate.
In this specification, the positive A plate is defined as follows. The positive A plate (positive A plate) has a refractive index of nx in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized), and is orthogonal to the slow axis in the plane in the plane. When the refractive index in the direction is ny and the refractive index in the thickness direction is nz, the relationship of the formula (A1) is satisfied. The positive A plate shows a positive value for Rth.
Equation (A1) nx> ny≈nz
The above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same. “Substantially the same” means, for example, “ny ≈ nz” when (ny-nz) × d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. include.
 ポジティブAプレートを得るには、棒状の重合性液晶化合物を水平配向させることにより得ることができる。ポジティブAプレートの製造方法の詳細は、例えば、特開2008-225281号公報、および、特開2008-026730号公報などの記載を参酌できる。 A positive A plate can be obtained by horizontally orienting a rod-shaped polymerizable liquid crystal compound. For details of the method for producing a positive A plate, for example, Japanese Patent Application Laid-Open No. 2008-225281 and Japanese Patent Application Laid-Open No. 2008-026730 can be referred to.
 上記光学異方性層(ポジティブAプレート)は、λ/4板として機能することが好ましい。
 λ/4板は、ある特定の波長の直線偏光を円偏光に(または、円偏光を直線偏光に)変換する機能を有する板であり、特定の波長λnmにおける面内レターデーションRe(λ)がRe(λ)=λ/4を満たす板のことをいう。
 この式は、可視光域のいずれかの波長(例えば、550nm)において達成されていればよいが、波長550nmにおける面内レターデーションRe(550)が、110nm≦Re(550)≦160nmの関係を満たすことが好ましく、110nm≦Re(550)≦150nmを満たすことがより好ましい。
The optically anisotropic layer (positive A plate) preferably functions as a λ / 4 plate.
The λ / 4 plate is a plate having a function of converting linearly polarized light of a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light), and has an in-plane retardation Re (λ) at a specific wavelength of λnm. A plate that satisfies Re (λ) = λ / 4.
This equation may be achieved at any wavelength in the visible light region (for example, 550 nm), but the in-plane retardation Re (550) at a wavelength of 550 nm has a relationship of 110 nm ≤ Re (550) ≤ 160 nm. It is preferable to satisfy, and it is more preferable to satisfy 110 nm ≦ Re (550) ≦ 150 nm.
 また、光学異方性層をポジティブCプレートとしてもよい。
 なお、本明細書において、ポジティブCプレートは以下のように定義する。ポジティブCプレート(正のCプレート)は、フィルム面内の遅相軸方向(面内での屈折率が最大となる方向)の屈折率をnx、面内の遅相軸と面内で直交する方向の屈折率をny、厚さ方向の屈折率をnzとしたとき、式(A2)の関係を満たすものである。なお、ポジティブCプレートはRthが負の値を示す。
 式(A2)  nx≒ny<nz
 なお、上記「≒」とは、両者が完全に同一である場合だけでなく、両者が実質的に同一である場合も包含する。「実質的に同一」とは、例えば、(nx-ny)×d(ただし、dはフィルムの厚みである)が、-10~10nm、好ましくは-5~5nmの場合も「nx≒ny」に含まれる。
 また、ポジティブCプレートでは、上記の定義より、Re≒0となる。
Further, the optically anisotropic layer may be used as a positive C plate.
In this specification, the positive C plate is defined as follows. The positive C plate (positive C plate) has a refractive index of nx in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized), and is orthogonal to the slow axis in the plane in the plane. When the refractive index in the direction is ny and the refractive index in the thickness direction is nz, the relationship of the formula (A2) is satisfied. The positive C plate shows a negative value for Rth.
Equation (A2) nx≈ny <nz
The above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same. “Substantially the same” means, for example, “nx ≈ ny” when (nx−ny) × d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. include.
Further, in the positive C plate, Re≈0 is obtained from the above definition.
 ポジティブCプレートを得るには、棒状の重合性液晶化合物を垂直配向させることにより得ることができる。ポジティブCプレートの製造方法の詳細は、例えば、特開2017-187732号公報、特開2016-53709号公報、および、特開2015-200861号公報の記載を参酌できる。 A positive C plate can be obtained by vertically orienting a rod-shaped polymerizable liquid crystal compound. For details of the method for producing a positive C plate, for example, JP-A-2017-187732, JP-A-2016-53709, and JP-A-2015-200861 can be referred to.
(液晶硬化層)
 本発明の光学積層体は、光学積層体を有する画像表示装置の視野角方向の表示品質が向上する理由から、上記光学異方性層と上記バリア層との間に、さらに1つ以上の液晶硬化層を有していることが好ましい。
 上記液晶硬化層としては、例えば、上記光学異方性層がポジティブAプレートである場合、上述したポジティブCプレートが好適に挙げられ、上記光学異方性層がポジティブCプレートである場合、上述したポジティブAプレートが好適に挙げられる。
(Liquid crystal cured layer)
The optical laminate of the present invention further comprises one or more liquid crystals between the optically anisotropic layer and the barrier layer for the reason that the display quality in the viewing angle direction of the image display device having the optical laminate is improved. It is preferable to have a cured layer.
As the liquid crystal curing layer, for example, when the optically anisotropic layer is a positive A plate, the above-mentioned positive C plate is preferably mentioned, and when the optically anisotropic layer is a positive C plate, the above is described. Positive A plates are preferred.
(支持体)
 本発明の光学積層体は、上記光学積層体を支持するための支持体を有していてもよい。
 支持体は、透明であるのが好ましく、具体的には光透過率が80%以上であるのが好ましい。
 支持体は光学異方性を有していてもよく、光学的に等方的であってもよい。
(Support)
The optical laminate of the present invention may have a support for supporting the optical laminate.
The support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.
The support may have optical anisotropy or may be optically isotropic.
 支持体としては、光学積層体をフレキシブルにする観点から、ポリマーフィルムが好ましい。
 ポリマーフィルムの材料としては、セルロース系ポリマー;ポリメチルメタクリレート、ラクトン環含有重合体などのアクリル酸エステル重合体を有する(メタ)アクリル系ポリマー;熱可塑性ノルボルネン系ポリマー;ポリカーボネート系ポリマー;ポリエチレンテレフタレート、および、ポリエチレンナフタレートなどのポリエステル系ポリマー;ポリスチレン、および、アクリロニトリル・スチレン共重合体(AS樹脂)などのスチレン系ポリマー;ポリエチレン、ポリプロピレン、および、エチレン・プロピレン共重合体などのポリオレフィン系ポリマー;、塩化ビニル系ポリマー;ナイロン、および、芳香族ポリアミドなどのアミド系ポリマー;イミド系ポリマー;スルホン系ポリマー;ポリエーテルスルホン系ポリマー;ポリエーテルエーテルケトン系ポリマー;ポリフェニレンスルフィド系ポリマー;塩化ビニリデン系ポリマー;ビニルアルコール系ポリマー;ビニルブチラール系ポリマー;アリレート系ポリマー;ポリオキシメチレン系ポリマー;エポキシ系ポリマー;またはこれらのポリマーを混合したポリマーが挙げられる。
 また、後述する偏光子がこのような支持体を兼ねる態様であってもよい。
As the support, a polymer film is preferable from the viewpoint of making the optical laminate flexible.
Materials for the polymer film include cellulose-based polymers; (meth) acrylic polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and , Polyester-based polymers such as polyethylene naphthalate; Polystyrene and styrene-based polymers such as acrylonitrile-styrene copolymer (AS resin); Polyethylene-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; Vinyl-based polymers; Nylon and amide-based polymers such as aromatic polyamides; Imid-based polymers; Sulfon-based polymers; polyether sulfone-based polymers; polyether ether ketone-based polymers; Polyphenylene sulfide-based polymers; Vinylidene chloride-based polymers; Vinyl alcohol Examples include polymer; vinyl butyral polymer; allylate polymer; polyoxymethylene polymer; epoxy polymer; or a polymer in which these polymers are mixed.
Further, the polarizer described later may also serve as such a support.
 支持体の厚みは特に制限されないが、光学積層体に自立性とフレキシビリティを付与する観点から5~80μmが好ましく、10~40μmがより好ましい。
 支持体は、光学異方性層に隣接して(あるいは後述する配向膜を介して隣接して)いてもよく、バリア層に隣接していてもよい。
The thickness of the support is not particularly limited, but is preferably 5 to 80 μm, more preferably 10 to 40 μm, from the viewpoint of imparting independence and flexibility to the optical laminate.
The support may be adjacent to the optically anisotropic layer (or adjacent via an alignment film described later), or may be adjacent to the barrier layer.
(配向膜)
 本発明の光学積層体は、上述した任意の支持体を光学異方性層のバリア層とは逆側の面に有する場合、支持体と光学異方性層との間に、配向膜を有するのが好ましい。なお、上述した支持体が配向膜を兼ねる態様であってもよい。
(Alignment film)
The optical laminate of the present invention has an alignment film between the support and the optically anisotropic layer when the above-mentioned arbitrary support is provided on the surface opposite to the barrier layer of the optically anisotropic layer. Is preferable. The support described above may also serve as an alignment film.
 光学異方性層の一態様であるポジティブAプレートを形成するためには、特定液晶化合物の分子を所望の配向状態にするための技術が用いられ、例えば、配向膜を利用して、特定液晶化合物を所望の方向に配向させる技術が一般的である。
 配向膜としては、ポリマーなどの有機化合物を含む層のラビング処理膜や無機化合物の斜方蒸着膜、マイクログルーブを有する膜、または、ω-トリコサン酸、ジオクタデシルメチルアンモニウムクロライド、もしくは、ステアリル酸メチルなどの有機化合物のラングミュア・ブロジェット法によるLB(Langmuir-Blodgett)膜を累積させた膜が挙げられる。
 さらに、配向膜としては、光の照射で配向機能が生じる光配向膜も挙げられる。
In order to form the positive A plate, which is one aspect of the optically anisotropic layer, a technique for aligning the molecules of the specific liquid crystal compound in a desired orientation state is used. For example, a specific liquid crystal is used by using an alignment film. A technique for orienting a compound in a desired direction is common.
As the alignment film, a rubbing-treated film of a layer containing an organic compound such as a polymer, an oblique vapor-deposited film of an inorganic compound, a film having microgrooves, or ω-tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearylate. Examples thereof include a membrane obtained by accumulating LB (Langmuir-Blodgett) membranes obtained by the Langmuir-Blodget method of organic compounds such as.
Further, as the alignment film, there is also a photoalignment film in which an alignment function is generated by irradiation with light.
 配向膜としては、ポリマーなどの有機化合物を含む層(ポリマー層)の表面をラビング処理して形成されたものを好ましく用いることができる。ラビング処理は、ポリマー層の表面を紙または布で一定方向(好ましくは支持体の長手方向)に数回こすることにより実施される。配向膜の形成に使用するポリマーとしては、ポリイミド、ポリビニルアルコール、特許第3907735号公報の段落0071~0095に記載の変性ポリビニルアルコール、および、特開平9-152509号公報に記載された重合性基を有するポリマーが好ましい。上述したバリア層が配向膜を兼ねてもよい。
 配向膜の厚さは、配向機能を発揮することができれば特に制限されないが、0.01~5μmが好ましく、0.05~2μmがより好ましい。
As the alignment film, a film formed by rubbing the surface of a layer (polymer layer) containing an organic compound such as a polymer can be preferably used. The rubbing treatment is carried out by rubbing the surface of the polymer layer with paper or cloth several times in a certain direction (preferably in the longitudinal direction of the support). Examples of the polymer used for forming the alignment film include polyimide, polyvinyl alcohol, modified polyvinyl alcohol described in paragraphs 0071 to 0095 of Japanese Patent No. 3907735, and polymerizable groups described in JP-A-9-152509. The polymer having is preferable. The barrier layer described above may also serve as an alignment film.
The thickness of the alignment film is not particularly limited as long as it can exhibit the alignment function, but is preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm.
 配向膜としては、光配向性の素材に偏光または非偏光を照射して配向層とした、いわゆる光配向膜(光配向層)を用いることも好ましい。
 光配向膜には、垂直方向または斜め方向から偏光照射する工程、または、斜め方向から非偏光照射する工程により配向規制力を付与することが好ましい。
 光配向膜を利用することで、特定液晶化合物を優れた対称性で水平配向させることが可能である。そのため、光配向膜を利用して形成されたポジティブAプレートは、特にIPS(In-Place-Switching)モード液晶表示装置のように駆動液晶のプレ傾斜角が必要ない液晶表示装置における光学補償や、どの方位から観察しても均一に円偏光変換されることが必要な円偏光板に用いるλ/4波長板に有用である。
As the alignment film, it is also preferable to use a so-called photo-alignment film (photo-alignment layer) in which a photo-alignable material is irradiated with polarized light or non-polarized light to form an alignment layer.
It is preferable to impart an orientation regulating force to the photoalignment film by a step of irradiating polarized light from a vertical direction or an oblique direction or a step of irradiating non-polarized light from an oblique direction.
By using the photoalignment film, it is possible to horizontally orient the specific liquid crystal compound with excellent symmetry. Therefore, the positive A plate formed by using the photoalignment film can be used for optical compensation in a liquid crystal display device that does not require a pre-tilt angle of the driving liquid crystal, such as an IPS (In-Place-Switching) mode liquid crystal display device. It is useful for λ / 4 wave plates used for circularly polarizing plates that require uniform circular polarization conversion when observed from any direction.
 光配向膜に用いられる光配向材料としては、例えば、特開2006-285197号公報、特開2007-076839号公報、特開2007-138138号公報、特開2007-094071号公報、特開2007-121721号公報、特開2007-140465号公報、特開2007-156439号公報、特開2007-133184号公報、特開2009-109831号公報、特許第3883848号、特許第4151746号に記載のアゾ化合物、特開2002-229039号公報に記載の芳香族エステル化合物、特開2002-265541号公報、特開2002-317013号公報に記載の光配向性単位を有するマレイミドおよび/またはアルケニル置換ナジイミド化合物、特許第4205195号、特許第4205198号に記載の光架橋性シラン誘導体、特表2003-520878号公報、特表2004-529220号公報、特許第4162850号に記載の光架橋性ポリイミド、ポリアミド、またはエステル、特開平9-118717号公報、特表平10-506420号公報、特表2003-505561号公報、国際公開第2010/150748号、特開2013-177561号公報、特開2014-12823号公報に記載の光二量化可能な化合物、特にシンナメート化合物、カルコン化合物、および、クマリン化合物が挙げられる。
 特に好ましい例としては、アゾ化合物、光架橋性ポリイミド、ポリアミド、ポリエステル、シンナメート化合物、および、カルコン化合物が挙げられる。
Examples of the photoalignment material used for the photoalignment film include JP-A-2006-285197, JP-A-2007-076839, JP-A-2007-138138, JP-A-2007-094071, and JP-A-2007-. The azo compounds described in JP-A-121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Patent No. 3883848, and Patent No. 4151746. , Aromatic ester compounds described in JP-A-2002-229039, maleimide and / or alkenyl-substituted nadiimide compounds having photoorientation units described in JP-A-2002-265541 and JP-A-2002-317013, patents. Photocrossable silane derivatives described in No. 4205195, Patent No. 4205198, Photocrossable polyimides, polyamides, or esters described in JP-A-2003-520878, JP-A-2004-522220, and Patent No. 4162850. Described in JP-A-9-118717, JP-A-10-506420, JP-A-2003-505561, International Publication No. 2010/150748, JP-A-2013-177561, and JP-A-2014-12823. Examples of photodimerizable compounds, particularly cinnamate compounds, chalcone compounds, and coumarin compounds.
Particularly preferred examples include azo compounds, photocrosslinkable polyimides, polyamides, polyesters, synnate compounds, and chalcone compounds.
 光配向膜の厚さは特に制限されないが、支持体に存在しうる表面凹凸を緩和して均一な膜厚の光学異方性層を形成するという点から、0.01~10μmが好ましく、0.01~1μmがより好ましく、0.01~0.5μmがさらに好ましい。 The thickness of the photoalignment film is not particularly limited, but is preferably 0.01 to 10 μm, preferably 0, from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic layer having a uniform film thickness. 0.01 to 1 μm is more preferable, and 0.01 to 0.5 μm is even more preferable.
(その他の層)
 本発明の光学積層体には、その他の層として、粘接着層や易接着層、上述した光学異方性層とは別の、光学異方性を有する層を設けてもよい。例えば光学異方性を有する層は、ポリマーフィルムや液晶硬化層、無機層等任意の材料から構成されうるが、光学積層体を薄くしフレキシビリティと靭性とを両立する観点からは、液晶硬化層であることが好ましい。
 こうした液晶硬化層としては、順分散性またはフラット分散性を有する、重合性の棒状液晶化合物やディスコティック液晶化合物を含む液晶組成物を、上述した光学異方性層と同様にして配向させ固定したものが適用できる。これら液晶硬化層の配向状態や光学特性、強度等は、本発明の光学積層体に所望の特性が付与できるよう、適宜設計することができる。好ましい一態様として、光学異方性層/垂直配向した順波長分散性の液晶硬化層/バリア層の構成を含む光学積層体(例えば、図3に示す光学積層体など)が挙げられる。
(Other layers)
The optical laminate of the present invention may be provided with a layer having optical anisotropy, which is different from the adhesive layer, the easy-adhesion layer, and the above-mentioned optically anisotropic layer, as other layers. For example, the layer having optical anisotropy can be composed of any material such as a polymer film, a liquid crystal cured layer, and an inorganic layer, but from the viewpoint of thinning the optical laminate and achieving both flexibility and toughness, the liquid crystal cured layer. Is preferable.
As such a liquid crystal cured layer, a liquid crystal composition containing a polymerizable rod-shaped liquid crystal compound or a discotic liquid crystal compound having forward dispersibility or flat dispersibility was oriented and fixed in the same manner as the above-mentioned optically anisotropic layer. Things can be applied. The orientation state, optical characteristics, strength, and the like of these liquid crystal cured layers can be appropriately designed so that desired characteristics can be imparted to the optical laminate of the present invention. As a preferred embodiment, an optical laminate including an optically anisotropic layer / vertically oriented forward wavelength dispersive liquid crystal cured layer / barrier layer (for example, the optical laminate shown in FIG. 3) can be mentioned.
<偏光板>
 本発明の光学積層体は、偏光子と積層することにより、高機能な偏光板を構成することができる。
 本発明の偏光板は、上述した本発明の光学積層体と偏光子とを有し、偏光子と、光学積層体が有する光学異方性層と、光学積層体が有するバリア層とがこの順に含まれている、偏光板である。
<Polarizer>
The optical laminate of the present invention can form a highly functional polarizing plate by laminating it with a polarizer.
The polarizing plate of the present invention has the above-mentioned optical laminate of the present invention and a polarizer, and the polarizer, the optically anisotropic layer of the optical laminate, and the barrier layer of the optical laminate are in this order. Included is a polarizing plate.
(偏光子)
 偏光子は、光を特定の直線偏光に変換する機能を有するいわゆる直線偏光子である。偏光子としては、特に限定されないが、吸収型偏光子を利用できる。
 偏光子の種類は特に制限されず、通常用いられているポリビニルアルコール系樹脂を主成分とする偏光子が挙げられる。例えば、ポリビニルアルコール系樹脂にヨウ素または二色性染料を吸着させ、延伸することで作製される。ポリビニルアルコール系樹脂を主成分とするとは、偏光子の全質量に対するポリビニルアルコール系樹脂の含有量が50質量%以上であることを意味する。
 ポリビニルアルコール系樹脂は、-CH-CHOH-という繰り返し単位を含む樹脂であり、例えば、ポリビニルアルコール、および、エチレン-ビニルアルコール共重合体が挙げられる。
(Polarizer)
The polarizer is a so-called linear polarized light having a function of converting light into specific linearly polarized light. The polarizer is not particularly limited, but an absorption type polarizer can be used.
The type of the polarizer is not particularly limited, and examples thereof include a commonly used polarizer containing a polyvinyl alcohol-based resin as a main component. For example, it is produced by adsorbing iodine or a dichroic dye on a polyvinyl alcohol-based resin and stretching it. The fact that the polyvinyl alcohol-based resin is the main component means that the content of the polyvinyl alcohol-based resin with respect to the total mass of the polarizer is 50% by mass or more.
Polyvinyl alcohol resin is a resin containing a repeating unit of -CH 2 -CHOH-, e.g., polyvinyl alcohol, and an ethylene - vinyl alcohol copolymer.
 また、WO2017/195833号公報および特開2017-83843号公報に記載されているような、液晶化合物および二色性アゾ色素(例えば、WO2017/195833号公報に記載の光吸収性異方性膜に用いられる二色性アゾ色素)を用い、塗布により作製した塗布型偏光子も好ましい。その他、ポリエン偏光子、反射偏光子、ワイヤグリッド偏光子などであってもよい。 Further, on a liquid crystal compound and a dichroic azo dye (for example, a light-absorbing anisotropic film described in WO2017 / 195833) as described in WO2017 / 195833 and Japanese Patent Application Laid-Open No. 2017-83843. A coating type polarizer produced by coating using the dichroic azo dye used) is also preferable. In addition, it may be a polyene polarizer, a reflection polarizer, a wire grid polarizer, or the like.
 偏光子の厚みは特に制限されないが、5~20μmが好ましく、3~15μmがより好ましく、2~13μmがさらに好ましい。偏光子厚みを薄くすることで、表示装置に実装した際により軽量で薄型の表示装置を得ることができる。また、表示装置が可撓性あるいは曲面である場合、薄い偏光板のほうがより好ましく適用できる。 The thickness of the polarizer is not particularly limited, but is preferably 5 to 20 μm, more preferably 3 to 15 μm, and even more preferably 2 to 13 μm. By reducing the thickness of the polarizer, a lighter and thinner display device can be obtained when mounted on the display device. Further, when the display device is flexible or curved, a thin polarizing plate can be more preferably applied.
 なお、偏光板中において偏光子の透過軸と光学異方性層の遅相軸との関係は特に制限なく、所望の機能に応じ適宜設定することができる。
 偏光板を反射防止用途に適用する場合、光学異方性層がλ/4波長板で、かつ、偏光子の透過軸と光学異方性層の遅相軸とのなす角度は45±10°の範囲(35~55°)が好ましい。
 また、偏光板をIPS(In-Plane-Switching)液晶の斜め視野角の光学補償用途に適用する場合、光学異方性層がλ/4波長板のポジティブAプレートとポジティブCプレートとの複層構造であり、かつ、偏光子の透過軸と光学異方性層の遅相軸とのなす角度は0±10°の範囲(-10~10°)または90±10°の範囲(80~100°)が好ましい。
The relationship between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer in the polarizing plate is not particularly limited and can be appropriately set according to a desired function.
When the polarizing plate is applied to antireflection applications, the optically anisotropic layer is a λ / 4 wave plate, and the angle between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45 ± 10 °. The range of (35 to 55 °) is preferable.
Further, when the polarizing plate is applied to an optical compensation application for an oblique viewing angle of an IPS (In-Plane-Switching) liquid crystal, the optically anisotropic layer is a multi-layer of a positive A plate and a positive C plate of a λ / 4 wave plate. The structure and the angle formed by the transmission axis of the polarizer and the slow axis of the optically anisotropic layer are in the range of 0 ± 10 ° (-10 to 10 °) or 90 ± 10 ° (80 to 100). °) is preferred.
(偏光子保護フィルム)
 偏光板は、偏光子の表面上に、偏光子保護フィルムを有していてもよい。
 偏光子保護フィルムは、偏光子の片面上(光学異方性層側とは反対側の表面上)にのみ配置されていてもよいし、偏光子の両面上に配置されていてもよい。光学積層体を構成する支持体が、偏光板保護フィルムを兼ねる構成であってもよい。
 偏光子保護フィルムの構成は特に制限されず、例えば、いわゆる透明支持体またはハードコート層であっても、透明支持体とハードコート層との積層体であってもよい。
 ハードコート層としては、公知の層を使用でき、例えば、公知の多官能モノマーを重合硬化して得られる層であってもよい。また、防眩性や防汚性、反射防止性を有するコーティングであってもよい。
 また、透明支持体としては、公知の透明支持体を使用でき、例えば、透明支持体を形成する材料としては、トリアセチルセルロースに代表される、セルロース系ポリマー(以下、「セルロースアシレート」という。)、熱可塑性ノルボルネン系樹脂(日本ゼオン(株)製のゼオネックス、ゼオノア、JSR(株)製のアートン)、アクリル系樹脂、ポリエステル系樹脂、および、ポリスチレン系樹脂が挙げられる。
 偏光子保護フィルムの厚みは特に制限されないが、偏光板の厚みを薄くできる点から、40μm以下が好ましく、25μm以下がより好ましく、10μm以下がさらに好ましく、5μm以下が特に好ましい。下限は特に制限されないが、1μm以上の場合が多い。
(Polarizer protective film)
The polarizing plate may have a polarizer protective film on the surface of the polarizer.
The polarizer protective film may be arranged only on one side of the polarizer (on the surface opposite to the optically anisotropic layer side), or may be arranged on both sides of the polarizer. The support constituting the optical laminate may also serve as a polarizing plate protective film.
The structure of the polarizer protective film is not particularly limited, and may be, for example, a so-called transparent support or a hard coat layer, or a laminate of a transparent support and a hard coat layer.
As the hard coat layer, a known layer can be used, and for example, a layer obtained by polymerizing and curing a known polyfunctional monomer may be used. Further, the coating may have antiglare, antifouling and antireflection properties.
A known transparent support can be used as the transparent support. For example, the material for forming the transparent support is a cellulosic polymer represented by triacetyl cellulose (hereinafter, referred to as "cellulose acylate". ), Thermoplastic norbornen-based resin (Zeonex and Zeonoa manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Co., Ltd.), acrylic resin, polyester resin, and polystyrene resin.
The thickness of the polarizer protective film is not particularly limited, but is preferably 40 μm or less, more preferably 25 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less, from the viewpoint that the thickness of the polarizing plate can be reduced. The lower limit is not particularly limited, but is often 1 μm or more.
 各層の間の密着性担保のために、各層の間に粘着層または接着層を配置してもよい。さらに、各層の間に透明支持体を配置してもよい。
 偏光板は、本発明の光学積層体を有する側とは反対側に、本発明の光学積層体をもう一つ、あるいは、本発明の光学積層体以外の他の光学異方性層を有していてもよい。
An adhesive layer or an adhesive layer may be arranged between the layers to ensure the adhesion between the layers. Further, a transparent support may be arranged between the layers.
The polarizing plate has another optical laminate of the present invention or an optically anisotropic layer other than the optical laminate of the present invention on the side opposite to the side having the optical laminate of the present invention. You may be.
<画像表示装置>
 上記偏光板は、画像表示装置、例えば、液晶表示装置、有機エレクトロルミネッセンス表示装置、マイクロLED表示装置、電子ペーパー等などに好ましく用いることができる。
 本発明の画像表示装置は、上述した本発明の光学積層体、または、本発明の偏光板を有する、画像表示装置であり、例えば、液晶表示装置であっても有機エレクトロルミネッセンス表示装置であってもよい。
<Image display device>
The polarizing plate can be preferably used in an image display device, for example, a liquid crystal display device, an organic electroluminescence display device, a micro LED display device, electronic paper, or the like.
The image display device of the present invention is an image display device having the above-mentioned optical laminate of the present invention or the polarizing plate of the present invention, and is, for example, an organic electroluminescence display device even if it is a liquid crystal display device. May be good.
(液晶表示装置)
 本発明の液晶表示装置は、画像表示装置の一例であり、上述した本発明の偏光板と、液晶セルとを有する。
 なお、本発明においては、液晶セルの両側に設けられる偏光子のうち、フロント側の偏光子として本発明の偏光板中の偏光子を用いるのが好ましく、フロント側およびリア側の偏光子のいずれにも本発明の偏光板中の偏光子を用いるのがより好ましい。
(Liquid crystal display device)
The liquid crystal display device of the present invention is an example of an image display device, and includes the above-mentioned polarizing plate of the present invention and a liquid crystal cell.
In the present invention, among the polarizing elements provided on both sides of the liquid crystal cell, it is preferable to use the polarizing element in the polarizing plate of the present invention as the front side polarizing element, and either the front side or the rear side polarizing element. It is more preferable to use the polarizer in the polarizing plate of the present invention.
 好ましい一態様として、偏光板に含まれる本発明の光学積層体は、偏光子より液晶セル側に配置することができる。この場合、光学積層体に含まれる上記バリア層は、上述した光学異方性層より液晶セルに近い側に配置することができる。この配置では、液晶セルおよびその構成部材、液晶セルと光学異方性層との間に設けられうるタッチセンサー、粘着剤等から生じ得る微量のアンモニア分子等の劣化源物質が光学異方性層に浸入することを防ぎ、好ましい耐久性を付与することができる。この態様では、光学異方性層は、光学補償機能として作用している。 As a preferred embodiment, the optical laminate of the present invention contained in the polarizing plate can be arranged on the liquid crystal cell side of the polarizing element. In this case, the barrier layer included in the optical laminate can be arranged closer to the liquid crystal cell than the above-mentioned optically anisotropic layer. In this arrangement, the optically anisotropic layer contains deterioration source substances such as trace amounts of ammonia molecules that may be generated from the liquid crystal cell and its constituent members, a touch sensor that can be provided between the liquid crystal cell and the optically anisotropic layer, and an adhesive. It is possible to prevent the infiltration into the liquid crystal and impart preferable durability. In this aspect, the optically anisotropic layer acts as an optical compensation function.
 液晶表示装置に利用される液晶セルは、VA(Vertical Alignment)モード、OCB(Optical Compensated Bend)モード、IPS(In-Place-Switching)モード、または、TN(Twisted Nematic)モードであることが好ましいが、これらに限定されるものではない。光学異方性層は、これらの各モードに合わせ、その視野角特性を改良あるいは制御するために適した光学特性を有することができる。 The liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Optical Compensated Bend) mode, an IPS (In-Place-Switching) mode, or a TN (Twisted Nematic) mode. , Not limited to these. The optically anisotropic layer can have optical characteristics suitable for improving or controlling its viewing angle characteristics according to each of these modes.
 好ましい別の一態様として、偏光板に含まれる本発明の光学積層体は、液晶セルから見て偏光子より外側に配置することができる。この場合、光学積層体に含まれる上記バリア層は、上述した光学異方性層より液晶セルに遠い側に配置することができる。この配置では、例えばフロント側であれば外部環境から、リア側であればバックライト等から発生し浸入してくるアンモニア等極性分子が光学異方性層に達するのを防ぎ、好ましい耐久性を付与することができる。 As another preferred embodiment, the optical laminate of the present invention contained in the polarizing plate can be arranged outside the polarizer when viewed from the liquid crystal cell. In this case, the barrier layer included in the optical laminate can be arranged on the side farther from the liquid crystal cell than the above-mentioned optically anisotropic layer. In this arrangement, for example, polar molecules such as ammonia generated and infiltrated from the external environment on the front side and from the backlight on the rear side are prevented from reaching the optically anisotropic layer, and preferable durability is imparted. can do.
 この場合、光学異方性層は、例えばλ/4波長板とすることにより、フロント側に配置した場合は偏光サングラス装着による視認性阻害を改良する効果を、リア側に配置した場合は偏光リサイクルによる輝度向上効果を増強する効果あるいはバックライト部材に起因する色ムラを改善する効果を付与することができる。また、λ/2波長板とすることで窓や自動車のフロントガラスへの映り込み防止機能を付与することができる。 In this case, the optically anisotropic layer is, for example, a λ / 4 wave plate, so that when it is arranged on the front side, the effect of improving visibility due to wearing polarized sunglasses is improved, and when it is arranged on the rear side, polarized light is recycled. It is possible to impart the effect of enhancing the effect of improving the brightness due to the above or the effect of improving the color unevenness caused by the backlight member. Further, by using a λ / 2 wave plate, it is possible to provide a function of preventing reflection on a window or a windshield of an automobile.
(有機エレクトロルミネッセンス表示装置)
 本発明の有機エレクトロルミネッセンス表示装置としては、好ましい一態様として、視認側から、本発明の偏光板と、画像表示パネルとをこの順で有する構成、すなわち、偏光子と、本発明の光学積層体と、有機EL表示パネルとをこの順で有する構成が挙げられる。その際、本発明の偏光板は、光学異方性層がλ/4波長板であり、かつ、偏光子の透過軸と光学異方性層の遅相軸とのなす角度が45±10°の範囲(35~55°)となる偏光板を用いることが好ましく、また、偏光板に含まれるバリア層は、有機EL表示パネル側に配置されることが好ましい。こうした配置にすることで、特に有機ELパネルが、有機エレクトロルミネッセンス層と光学積層体との間に窒化ケイ素層を有する構成である場合、窒化ケイ素層から発生しうるアンモニアが光学異方性層へ浸入することをバリア層が防ぐことで、所望の耐久性を得ることができる。
 すなわち、本発明の偏光板は、いわゆる反射防止フィルムとして使用されうる。
(Organic electroluminescence display device)
The organic electroluminescence display device of the present invention preferably has a structure in which the polarizing plate of the present invention and the image display panel are provided in this order from the visual side, that is, the polarizer and the optical laminate of the present invention. And an organic EL display panel in this order. At that time, in the polarizing plate of the present invention, the optically anisotropic layer is a λ / 4 wave plate, and the angle formed by the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45 ± 10 °. It is preferable to use a polarizing plate having a range of (35 to 55 °), and it is preferable that the barrier layer contained in the polarizing plate is arranged on the organic EL display panel side. With such an arrangement, particularly when the organic EL panel has a silicon nitride layer between the organic electroluminescence layer and the optical laminate, ammonia that can be generated from the silicon nitride layer is transferred to the optically anisotropic layer. The desired durability can be obtained by preventing the barrier layer from infiltrating.
That is, the polarizing plate of the present invention can be used as a so-called antireflection film.
 有機EL表示パネルは、電極間(陰極および陽極間)に有機発光層(有機エレクトロルミネッセンス層)を挟持してなる有機EL素子を用いて構成された表示パネルである。有機EL表示パネルの構成は特に制限されず、公知の構成が採用される。 The organic EL display panel is a display panel configured by using an organic EL element having an organic light emitting layer (organic electroluminescence layer) sandwiched between electrodes (between the cathode and the anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
 本発明の有機エレクトロルミネッセンス表示装置において、偏光板と窒化ケイ素層の間には粘着層が存在することが、好ましい態様の一つであるが、その他の層、例えば、メタルメッシュ電極などを有することもできる。
 本発明の効果が顕著に現れることから、円偏光板と窒化ケイ素層との間に存在する層の厚みが40μm未満であることが好ましく、1~30μmであることがより好ましい。
In the organic electroluminescence display device of the present invention, it is one of the preferable embodiments that an adhesive layer is present between the polarizing plate and the silicon nitride layer, but another layer, for example, a metal mesh electrode or the like is provided. You can also.
Since the effect of the present invention is remarkably exhibited, the thickness of the layer existing between the circularly polarizing plate and the silicon nitride layer is preferably less than 40 μm, and more preferably 1 to 30 μm.
 また好ましい別の一態様としては、有機ELパネルの視認側に配置された円偏光板の、偏光子より視認側に本発明の光学積層体を配置することができる。この際に得られる本発明の光学積層体の効果や得られる表示装置としての利得は、液晶表示装置におけるフロント側に配置した場合のそれらと同じである。 In another preferred embodiment, the optical laminate of the present invention can be arranged on the visible side of the polarizing element of the circularly polarizing plate arranged on the visible side of the organic EL panel. The effect of the optical laminate of the present invention obtained at this time and the gain as a display device obtained at this time are the same as those when arranged on the front side of the liquid crystal display device.
 以下に実施例に基づいて本発明をさらに詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、および、処理手順などは、本発明の趣旨を逸脱しない限り適宜変更できる。従って、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。 The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
<作製例1>
(支持体の作製)
 下記の組成物をミキシングタンクに投入し、攪拌して、コア層セルロースアシレートドープとして用いるセルロースアセテート溶液を調製した。
──────────────────────────―──────
コア層セルロースアシレートドープ
──────────────────────────―──────
・アセチル置換度2.88のセルロースアセテート    100質量部
・特開2015-227955号公報の実施例に
記載されたポリエステル化合物B             12質量部
・下記化合物G                      2質量部
・メチレンクロライド(第1溶媒)           430質量部
・メタノール(第2溶媒)                64質量部
───────────────────────―─────────
<Production example 1>
(Preparation of support)
The following composition was put into a mixing tank and stirred to prepare a cellulose acetate solution to be used as a core layer cellulose acylate dope.
─────────────────────────────────
Core layer Cellulose acylate dope ─────────────────────────────────
100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.88 ・ 12 parts by mass of the polyester compound B described in Examples of JP-A-2015-227955 ・ 2 parts by mass of the following compound G ・ Methylene chloride (first solvent) 430 Parts by mass / methanol (second solvent) 64 parts by mass ─────────────────────────────────
 化合物G
Figure JPOXMLDOC01-appb-C000026
Compound G
Figure JPOXMLDOC01-appb-C000026
 上記のコア層セルロースアシレートドープ90質量部に下記のマット剤溶液を10質量部加え、外層セルロースアシレートドープとして用いるセルロースアセテート溶液を調製した。
─────────────────────────―───────
マット剤溶液
─────────────────────────―───────
・平均粒子サイズ20nmのシリカ粒子
(AEROSIL R972、日本アエロジル(株)製)    2質量部
・メチレンクロライド(第1溶媒)            76質量部
・メタノール(第2溶媒)                11質量部
・上記のコア層セルロースアシレートドープ         1質量部
────────────────────────―────────
The following matting solution was added to 90 parts by mass of the above core layer cellulose acylate dope to prepare a cellulose acetate solution to be used as the outer layer cellulose acylate dope.
─────────────────────────────────
Matte solution ─────────────────────────────────
-Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass-Methylene chloride (first solvent) 76 parts by mass-Methanol (second solvent) 11 parts by mass-The above core layer cellulose acid Rate Dope 1 part by mass ─────────────────────────────────
 上記コア層セルロースアシレートドープおよび上記外層セルロースアシレートドープを平均孔径34μmのろ紙および平均孔径10μmの焼結金属フィルターでろ過した後、上記コア層セルロースアシレートドープとその両側に外層セルロースアシレートドープとを3層同時に流延口から20℃のドラム上に流延した(バンド流延機)。溶媒含有率略20質量%の状態でフィルムをドラム上から剥ぎ取り、フィルムの幅方向の両端をテンタークリップで固定し、横方向に延伸しつつ乾燥した。その後、得られたフィルムを熱処理装置のロール間を搬送することにより、さらに乾燥し、厚み20μmのセルロースアシレートフィルム1を作製した。得られたセルロースアシレートフィルム1のRe(550)は0nmであった。 The core layer cellulose acylate dope and the outer layer cellulose acylate dope are filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, and then the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides thereof. And three layers were simultaneously cast on a drum at 20 ° C. from the casting port (band casting machine). The film was peeled off from the drum with a solvent content of about 20% by mass, both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched in the lateral direction. Then, the obtained film was conveyed between the rolls of the heat treatment apparatus to be further dried to prepare a cellulose acylate film 1 having a thickness of 20 μm. The Re (550) of the obtained cellulose acylate film 1 was 0 nm.
(光配向膜の作製)
 次に、特開2012-155308号公報の実施例3の記載を参考に、光配向膜用塗布液1を調製し、セルロースアシレートフィルム1にワイヤーバーで塗布した。その後、得られたセルロースアシレートフィルム1を60℃の温風で60秒間乾燥し、厚み300nmの塗膜1を作製した。
(Preparation of photo-alignment film)
Next, referring to the description of Example 3 of JP2012-155308A, a coating liquid 1 for a photoalignment film was prepared and coated on a cellulose acylate film 1 with a wire bar. Then, the obtained cellulose acylate film 1 was dried with warm air at 60 ° C. for 60 seconds to prepare a coating film 1 having a thickness of 300 nm.
(光学異方性層の作製)
 続いて、下記組成のポジティブAプレート形成用組成物A1を調製した。
―――――――――――――――――――――――――――――――――
ポジティブAプレート形成用組成物A1の組成
―――――――――――――――――――――――――――――――――
・下記重合性液晶化合物X-1           16.00質量部
・下記特定液晶化合物L-1            42.00質量部
・下記特定液晶化合物L-2            42.00質量部
・下記重合開始剤S-1               0.50質量部
・下記重合性化合物B-1              2.00質量部
・レベリング剤(下記化合物T-1)         0.20質量部
・メチルエチルケトン(溶媒)          230.00質量部
・シクロペンタノン(溶媒)            70.00質量部
―――――――――――――――――――――――――――――――――
(Preparation of optically anisotropic layer)
Subsequently, the composition A1 for forming a positive A plate having the following composition was prepared.
―――――――――――――――――――――――――――――――――
Composition of composition A1 for forming a positive A plate ――――――――――――――――――――――――――――――――――
-The following polymerizable liquid crystal compound X-1 16.00 parts by mass-The following specific liquid crystal compound L-1 42.00 parts by mass-The following specific liquid crystal compound L-2 42.00 parts by mass-The following polymerization initiator S-1 0. 50 parts by mass, the following polymerizable compound B-1 2.00 parts by mass, the leveling agent (the following compound T-1) 0.20 parts by mass, methyl ethyl ketone (solvent) 230.00 parts by mass, cyclopentanone (solvent) 70. 00 parts by mass ――――――――――――――――――――――――――――――――――
 重合性液晶化合物X-1
Figure JPOXMLDOC01-appb-C000027
Polymerizable liquid crystal compound X-1
Figure JPOXMLDOC01-appb-C000027
 特定液晶化合物L-1
Figure JPOXMLDOC01-appb-C000028
Specific liquid crystal compound L-1
Figure JPOXMLDOC01-appb-C000028
 特定液晶化合物L-2
Figure JPOXMLDOC01-appb-C000029
Specific liquid crystal compound L-2
Figure JPOXMLDOC01-appb-C000029
 化合物T-1
Figure JPOXMLDOC01-appb-C000030
Compound T-1
Figure JPOXMLDOC01-appb-C000030
 化合物T-1中の各繰り返し単位に記載の数値は、全繰り返し単位に対する各繰り返し単位の含有量(質量%)を表す。 The numerical value described in each repeating unit in compound T-1 represents the content (mass%) of each repeating unit with respect to all the repeating units.
 重合開始剤S-1
Figure JPOXMLDOC01-appb-C000031
Polymerization Initiator S-1
Figure JPOXMLDOC01-appb-C000031
 重合性化合物B-1
Figure JPOXMLDOC01-appb-C000032
Polymerizable compound B-1
Figure JPOXMLDOC01-appb-C000032
 作製した塗膜1に、大気下にて超高圧水銀ランプを用いて紫外線を照射した。このとき、ワイヤーグリッド偏光子(Moxtek社製, ProFlux PPL02)を塗膜1の面と平行になるようにセットして露光し、光配向処理を行い、光配向膜1を得た。
 この際、紫外線の照度はUV-A領域(紫外線A波、波長320~380nmの積算)において10mJ/cmとした。
The prepared coating film 1 was irradiated with ultraviolet rays in the atmosphere using an ultra-high pressure mercury lamp. At this time, a wire grid polarizer (ProFlux PPL02 manufactured by Moxtek, Inc.) was set so as to be parallel to the surface of the coating film 1 and exposed, and photoalignment treatment was performed to obtain a photoalignment film 1.
At this time, the illuminance of the ultraviolet rays was set to 10 mJ / cm 2 in the UV-A region (ultraviolet A wave, integration of wavelengths of 320 to 380 nm).
 次いで、光配向膜1上にポジティブAプレート形成用組成物A1を、バーコーターを用いて塗布した。得られた塗膜を膜面温度100℃で20秒間加熱熟成し、90℃まで冷却した後に、空気下にて空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて300mJ/cmの紫外線を照射して、ネマチック配向状態を固定化することによりポジティブAプレートA1(光学異方性層に該当)を形成し、ポジティブAプレートA1を含む光学フィルムLを製造した。 Next, the positive A plate forming composition A1 was applied onto the photoalignment film 1 using a bar coater. The obtained coating film is heat-aged at a film surface temperature of 100 ° C. for 20 seconds, cooled to 90 ° C., and then exposed to ultraviolet rays of 300 mJ / cm 2 using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under air. A positive A plate A1 (corresponding to an optically anisotropic layer) was formed by immobilizing the nematic orientation state, and an optical film L containing the positive A plate A1 was produced.
 形成されたポジティブAプレートA1は、膜厚が2.5μmであった。ポジティブAプレートA1のRe(550)は145nm、Rth(550)は73nm、Re(550)/Re(450)は1.13、Re(650)/Re(550)は1.01、光軸のチルト角は0°であり、液晶化合物はホモジニアス配向であった。 The formed positive A plate A1 had a film thickness of 2.5 μm. Re (550) of positive A plate A1 is 145 nm, Rth (550) is 73 nm, Re (550) / Re (450) is 1.13, Re (650) / Re (550) is 1.01, and the optical axis is The tilt angle was 0 °, and the liquid crystal compound had a homogeneous orientation.
(ポジティブCプレートフィルム1の形成)
 上記で形成したポジティブAプレートA1の表面をコロナ処理し、コロナ処理を行った面に、下記のポジティブCプレート形成用組成物C1を塗布し、70℃の温風で90秒間熟成させた。
 次いで、窒素パージ下酸素濃度0.1%で40℃にて紫外線照射(300mJ/cm2)を行って液晶化合物の配向を固定したポジティブCプレートC1を作製し、支持体/配向膜/ポジティブAプレートA1(光学異方性層)/ポジティブCプレートC1をこの順を含む光学フィルムMを作製した。ポジティブCプレートC1の厚みは0.4μmであった。ポジティブCプレートC1は、本発明におけるその他の光学異方性を有する層に該当する。
(Formation of Positive C Plate Film 1)
The surface of the positive A plate A1 formed above was corona-treated, and the following positive C plate-forming composition C1 was applied to the corona-treated surface and aged for 90 seconds with warm air at 70 ° C.
Next, ultraviolet irradiation (300 mJ / cm 2 ) was performed at 40 ° C. under a nitrogen purge at an oxygen concentration of 0.1% to prepare a positive C plate C1 in which the orientation of the liquid crystal compound was fixed, and the support / alignment film / positive A was prepared. An optical film M containing the plate A1 (optically anisotropic layer) / positive C plate C1 in this order was produced. The thickness of the positive C plate C1 was 0.4 μm. The positive C plate C1 corresponds to the other layers having optical anisotropy in the present invention.
―――――――――――――――――――――――――――――――――
(組成物C-1)
―――――――――――――――――――――――――――――――――
・下記順波長分散性の棒状液晶化合物M-1        83質量部
・下記順波長分散性の棒状液晶化合物M-2        15質量部
・下記順波長分散性の棒状液晶化合物M-3         2質量部
・下記化合物B1                   4.5質量部
・下記重合開始剤(IrgacureOXE01,
 BASF社製)                     5質量部
・ビスコート#360(大阪有機化学工業株式会社製)    8質量部
・下記界面活性剤T-2                0.3質量部
・下記界面活性剤T-3                0.5質量部
・下記オニウム化合物S01              2.0質量部
・アセトン                    229.6質量部
・プロピレングリコールモノメチルエーテルアセテート 42.0質量部
・メタノール                     8.4質量部
―――――――――――――――――――――――――――――――――
―――――――――――――――――――――――――――――――――
(Composition C-1)
―――――――――――――――――――――――――――――――――
-The following forward wavelength-dispersible rod-shaped liquid crystal compound M-1 83 parts by mass-The following forward wavelength-dispersible rod-shaped liquid crystal compound M-2 15 parts by mass-The following forward wavelength-dispersible rod-shaped liquid crystal compound M-3 2 parts by mass-The following Compound B1 4.5 parts by mass-The following polymerization initiator (IrgacureOXE01,
BASF) 5 parts by mass ・ Viscote # 360 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 8 parts by mass ・ The following surfactant T-2 0.3 parts by mass ・ The following surfactant T-3 0.5 parts by mass ・The following onium compound S01 2.0 parts by mass, acetone 229.6 parts by mass, propylene glycol monomethyl ether acetate 42.0 parts by mass, methanol 8.4 parts by mass ―――――――――――――――― ―――――――――――――――――
 順波長分散性の棒状液晶化合物M-1
Figure JPOXMLDOC01-appb-C000033
Forward wavelength dispersible rod-shaped liquid crystal compound M-1
Figure JPOXMLDOC01-appb-C000033
 順波長分散性の棒状液晶化合物M-2
Figure JPOXMLDOC01-appb-C000034
Forward wavelength dispersible rod-shaped liquid crystal compound M-2
Figure JPOXMLDOC01-appb-C000034
 順波長分散性の棒状液晶化合物M-3
Figure JPOXMLDOC01-appb-C000035
Forward wavelength dispersible rod-shaped liquid crystal compound M-3
Figure JPOXMLDOC01-appb-C000035
 化合物B1
Figure JPOXMLDOC01-appb-C000036
Compound B1
Figure JPOXMLDOC01-appb-C000036
 重合開始剤
Figure JPOXMLDOC01-appb-C000037
Polymerization initiator
Figure JPOXMLDOC01-appb-C000037
 界面活性剤T-2〔Mw:15k。式中、各繰り返し単位に記載の数値は、全繰り返し単位に対する各繰り返しの含有量(質量%)を表す。〕
Figure JPOXMLDOC01-appb-C000038
Surfactant T-2 [Mw: 15k. In the formula, the numerical value described in each repeating unit represents the content (mass%) of each repeating unit with respect to all repeating units. ]
Figure JPOXMLDOC01-appb-C000038
 界面活性剤T-3〔重量平均分子量:11,200(各繰り返し単位に記載の数値は、全繰り返し単位に対する各繰り返し単位の含有量(質量%)を表す。)〕
Figure JPOXMLDOC01-appb-C000039
Surfactant T-3 [Weight average molecular weight: 11,200 (the numerical value described in each repeating unit represents the content (mass%) of each repeating unit with respect to all repeating units)]
Figure JPOXMLDOC01-appb-C000039
 オニウム塩化合物S01
Figure JPOXMLDOC01-appb-C000040
Onium salt compound S01
Figure JPOXMLDOC01-appb-C000040
(バリア層の作製)
 下記組成のバリア層形成用組成物B1を調製した。
―――――――――――――――――――――――――――――――――
バリア層形成用組成物B1
―――――――――――――――――――――――――――――――――
・下記多官能(メタ)アクリルアミド化合物BM-1 14.35質量部
・下記重合開始剤S-2               0.57質量部
・上記界面活性剤T-3               0.07質量部
・メタノール(溶媒)               85.00質量部
―――――――――――――――――――――――――――――――――
(Preparation of barrier layer)
A composition B1 for forming a barrier layer having the following composition was prepared.
―――――――――――――――――――――――――――――――――
Barrier layer forming composition B1
―――――――――――――――――――――――――――――――――
-The following polyfunctional (meth) acrylamide compound BM-1 14.35 parts by mass-The following polymerization initiator S-2 0.57 parts by mass-The above surfactant T-3 0.07 parts by mass-Methanol (solvent) 85. 00 parts by mass ――――――――――――――――――――――――――――――――――
 多官能(メタ)アクリルアミド化合物BM-1
(官能基数:3、分子量:265、アクリル当量:88)
Figure JPOXMLDOC01-appb-C000041
Polyfunctional (meth) acrylamide compound BM-1
(Number of functional groups: 3, molecular weight: 265, acrylic equivalent: 88)
Figure JPOXMLDOC01-appb-C000041
 重合開始剤S-2
Figure JPOXMLDOC01-appb-C000042
Polymerization Initiator S-2
Figure JPOXMLDOC01-appb-C000042
 上記で作製した光学フィルムMの、ポジティブCプレートC1側の表面をコロナ処理し、その上に上記バリア層形成用組成物B1を、ワイヤーバーコーターを用いてコーティングし、120℃の乾燥オーブンで1分間静置した。その後、150mW/cmの高圧水銀ランプを用いて、得られた塗膜を硬化させて、バリア層B1を形成して、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA1(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された光学積層体1を得た。バリア層の厚みは、1.0μmであった。 The surface of the optical film M produced above on the positive C plate C1 side is corona-treated, and the barrier layer forming composition B1 is coated thereto with a wire bar coater, and 1 in a drying oven at 120 ° C. Allowed to stand for minutes. Then, using a high-pressure mercury lamp of 150 mW / cm 2 , the obtained coating film was cured to form a barrier layer B1 to form a cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate. An optical laminate 1 in which A1 (optically anisotropic layer) / positive C plate C1 / barrier layer B1 was laminated in this order was obtained. The thickness of the barrier layer was 1.0 μm.
<作製例2~4>
 作製例2~3として、多官能(メタ)アクリルアミド化合物BM-1に代えて、それぞれ多官能(メタ)アクリルアミド化合物BM-2および多官能(メタ)アクリルアミド化合物BM-3を使用した以外は、作製例1と同様にして、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA1(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された光学積層体2および3を得た。
 また、作製例4として、バーコーターの番手を変えてバリア層の厚みを0.5μmとした以外は作製例1と同様にして、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA1(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された光学積層体4を得た。
<Production Examples 2-4>
As Production Examples 2 to 3, preparations were made except that the polyfunctional (meth) acrylamide compound BM-2 and the polyfunctional (meth) acrylamide compound BM-3 were used instead of the polyfunctional (meth) acrylamide compound BM-1, respectively. An optical laminate in which cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A1 (optically anisotropic layer) / positive C plate C1 / barrier layer B1 are laminated in this order in the same manner as in Example 1. 2 and 3 were obtained.
Further, as Production Example 4, the cellulose acylate film 1 (support) / photoalignment film 1 / positive was the same as in Production Example 1 except that the bar coater count was changed and the thickness of the barrier layer was 0.5 μm. An optical laminate 4 in which A plate A1 (optically anisotropic layer) / positive C plate C1 / barrier layer B1 was laminated in this order was obtained.
 多官能(メタ)アクリルアミド化合物BM-2
(官能基数:4、分子量:362、アクリル当量:91)
Figure JPOXMLDOC01-appb-C000043
Polyfunctional (meth) acrylamide compound BM-2
(Number of functional groups: 4, molecular weight: 362, acrylic equivalent: 91)
Figure JPOXMLDOC01-appb-C000043
 多官能(メタ)アクリルアミド化合物BM-3
(官能基数:3、分子量:293、アクリル当量:98)
Figure JPOXMLDOC01-appb-C000044
Polyfunctional (meth) acrylamide compound BM-3
(Number of functional groups: 3, molecular weight: 293, acrylic equivalent: 98)
Figure JPOXMLDOC01-appb-C000044
<作製例5>
 作製例5として、多官能(メタ)アクリルアミド化合物BM-1に代えて、多官能(メタ)アクリルアミド化合物BM-4を使用した以外は、作製例1と同様にして、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA1(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された光学積層体2および3を得た。
<Production example 5>
Cellulose acylate film 1 (supported) in the same manner as in Production Example 1 except that the polyfunctional (meth) acrylamide compound BM-4 was used in place of the polyfunctional (meth) acrylamide compound BM-1 as Production Example 5. (Body) / Photoalignment film 1 / Positive A plate A1 (optically anisotropic layer) / Positive C plate C1 / Barrier layer B1 were laminated in this order to obtain optical laminates 2 and 3.
 多官能(メタ)アクリルアミド化合物BM-4
(官能基数:4、分子量:509、アクリル当量:127)
Figure JPOXMLDOC01-appb-C000045
Polyfunctional (meth) acrylamide compound BM-4
(Number of functional groups: 4, molecular weight: 509, acrylic equivalent: 127)
Figure JPOXMLDOC01-appb-C000045
<作製例6>
 バリア層B1を形成しなかった以外は、作製例1と同様の方法で、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA1(光学異方性層)/ポジティブCプレートC1の順に積層された光学積層体6を得た。
<Production example 6>
Cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A1 (opticallyotropic layer) / positive C plate in the same manner as in Production Example 1 except that the barrier layer B1 was not formed. An optical laminate 6 laminated in the order of C1 was obtained.
<偏光板の作製>
 得られた光学積層体1~5の支持体側の表面と、片面のみ偏光板保護フィルムを備えたポリビニルアルコール偏光子の偏光板保護フィルムが設けられていない側とを、シート状の粘着剤(綜研化学社製、SK2057)を用いて貼合し、偏光板保護フィルム/偏光子/セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA1(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された偏光板(実施例1~5)を得た。
 また、光学積層体1に代えて光学積層体6を用いた以外は上記と同様にして、偏光板(比較例1)を得た。
<Manufacturing of polarizing plate>
A sheet-like pressure-sensitive adhesive (Soken) is applied to the surface of the obtained optical laminates 1 to 5 on the support side and the side of the polyvinyl alcohol polarizer having the polarizing plate protective film on only one side and not provided with the polarizing plate protective film. SK2057) manufactured by Kagaku Co., Ltd. is used for bonding, and polarizing plate protective film / polarizer / cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A1 (optically anisotropic layer) / positive C Polarizing plates (Examples 1 to 5) laminated in the order of plate C1 / barrier layer B1 were obtained.
Further, a polarizing plate (Comparative Example 1) was obtained in the same manner as described above except that the optical laminate 6 was used instead of the optical laminate 1.
<耐久性評価>
 粘着剤付きフィルムを用いて、40mm角に切り出した実施例1~5および比較例1の偏光板の偏光子保護フィルム側をガラス板に貼り合わせ、アンモニア2mol%のメタノール溶液を入れたネジ口瓶上に配置することで、アンモニアに16時間曝露した。曝露面は、光学積層体側(すなわち、バリア層B1)が曝露面となるようにネジ口瓶上に配置された。
 曝露後の偏光板を、Axo Scan(0PMF-1、Axometrics社製)を用いて、波長450nmおよび550nmにおける面内レターデーションRe(450)、Re(550)の値を測定した。
 H=Re(550)とするとき、アンモニア暴露前のHをH0、アンモニア暴露後のHをH1とし、ΔH(%)=|H1-H0|/H0×100を指標とし、下記のように評価した。結果を下記表3に示す。
 AA:ΔHが2%未満
 A:ΔHが2%以上5%未満
 B:ΔHが5%以上10%未満
 C:ΔHが10%以上
<Durability evaluation>
Using a film with an adhesive, the polarizing element protective film side of the polarizing plates of Examples 1 to 5 and Comparative Example 1 cut into 40 mm squares was attached to a glass plate, and a screw cap bottle containing a methanol solution of 2 mol% ammonia. By placing on top, it was exposed to ammonia for 16 hours. The exposed surface was arranged on the screw cap bottle so that the optical laminate side (that is, the barrier layer B1) was the exposed surface.
The values of in-plane retardation Re (450) and Re (550) at wavelengths of 450 nm and 550 nm were measured using an Axo Scan (0PMF-1, manufactured by Axometrics) for the polarizing plate after exposure.
When H = Re (550), H before ammonia exposure is H0, H after ammonia exposure is H1, and ΔH (%) = | H1-H0 | / H0 × 100 is used as an index, and the evaluation is performed as follows. did. The results are shown in Table 3 below.
AA: ΔH is less than 2% A: ΔH is 2% or more and less than 5% B: ΔH is 5% or more and less than 10% C: ΔH is 10% or more
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
 表3に示す評価結果から分かるように、本発明の光学積層体、および、偏光板は、アンモニア等の劣化源物質の曝露条件下でも優れた耐久性を示す。したがって、様々な画像表示装置等に組み込んだ場合でも優れた耐久性を示すことが明らかである。
 また、実施例1と実施例5との対比から、バリア層が、アクリル当量が100以下の多官能(メタ)アクリルアミド化合物を含む組成物から形成されていると、耐久性がより良好となることが分かった。
As can be seen from the evaluation results shown in Table 3, the optical laminate and the polarizing plate of the present invention show excellent durability even under exposure conditions of a deterioration source substance such as ammonia. Therefore, it is clear that it exhibits excellent durability even when it is incorporated into various image display devices and the like.
Further, from the comparison between Example 1 and Example 5, when the barrier layer is formed from a composition containing a polyfunctional (meth) acrylamide compound having an acrylic equivalent of 100 or less, the durability is further improved. I found out.
<作製例7>
 光学異方性層の形成に用いたポジティブAプレート形成用組成物A1の成分のうち、重合性液晶化合物X-1、特定液晶化合物L-1および特定液晶化合物L-2(合計100質量部)に代えて、以下に示す重合性液晶化合物を100質量部用いて、ポジティブAプレートA2(光学異方性層に該当)を形成した。
 ポジティブAプレートA1に代えて、ポジティブAプレートA2を用いた以外は、作製例1と同様の方法で、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA2(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された光学積層体7を得た。
Figure JPOXMLDOC01-appb-C000047
<Production example 7>
Among the components of the positive A plate forming composition A1 used for forming the optically anisotropic layer, the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1, and the specific liquid crystal compound L-2 (total 100 parts by mass). Instead, 100 parts by mass of the polymerizable liquid crystal compound shown below was used to form a positive A plate A2 (corresponding to an optically anisotropic layer).
Cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A2 (optical anisotropic) in the same manner as in Production Example 1 except that the positive A plate A2 was used instead of the positive A plate A1. An optical laminate 7 in which the sex layer) / positive C plate C1 / barrier layer B1 was laminated in this order was obtained.
Figure JPOXMLDOC01-appb-C000047
<作製例8>
 光学異方性層の形成に用いたポジティブAプレート形成用組成物A1の成分のうち、重合性液晶化合物X-1、特定液晶化合物L-1および特定液晶化合物L-2(合計100質量部)に代えて、以下に示す重合性液晶化合物を100質量部用いて、ポジティブAプレートA3(光学異方性層に該当)を形成した。
 ポジティブAプレートA1に代えて、ポジティブAプレートA3を用いた以外は、作製例1と同様の方法で、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA3(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された光学積層体8を得た。
Figure JPOXMLDOC01-appb-C000048
<Production example 8>
Among the components of the positive A plate forming composition A1 used for forming the optically anisotropic layer, the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1, and the specific liquid crystal compound L-2 (total 100 parts by mass). Instead, 100 parts by mass of the polymerizable liquid crystal compound shown below was used to form a positive A plate A3 (corresponding to an optically anisotropic layer).
Cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A3 (optical anisotropic) in the same manner as in Production Example 1 except that the positive A plate A3 was used instead of the positive A plate A1. An optical laminate 8 laminated in the order of (sexual layer) / positive C plate C1 / barrier layer B1 was obtained.
Figure JPOXMLDOC01-appb-C000048
<作製例9>
 バリア層B1を形成しなかった以外は、作製例7と同様の方法で、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA2(光学異方性層)/ポジティブCプレートC1の順に積層された光学積層体9を得た。
<Production example 9>
Cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A2 (opticallyotropic layer) / positive C plate by the same method as in Production Example 7 except that the barrier layer B1 was not formed. An optical laminate 9 laminated in the order of C1 was obtained.
<作製例10>
 バリア層B1を形成しなかった以外は、作製例8と同様の方法で、セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA3(光学異方性層)/ポジティブCプレートC1の順に積層された光学積層体10を得た。
<Production example 10>
Cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A3 (opticallyotropic layer) / positive C plate in the same manner as in Production Example 8 except that the barrier layer B1 was not formed. An optical laminate 10 laminated in the order of C1 was obtained.
<偏光板の作製>
 得られた光学積層体7の支持体側の表面と、片面のみ偏光板保護フィルムを備えたポリビニルアルコール偏光子の偏光板保護フィルムが設けられていない側とを、シート状の粘着剤(綜研化学社製、SK2057)を用いて貼合し、偏光板保護フィルム/偏光子/セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA2(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された偏光板(実施例6)を得た。
 同様に、得られた光学積層体8の支持体側の表面と、片面のみ偏光板保護フィルムを備えたポリビニルアルコール偏光子の偏光板保護フィルムが設けられていない側とを、シート状の粘着剤(綜研化学社製、SK2057)を用いて貼合し、偏光板保護フィルム/偏光子/セルロースアシレートフィルム1(支持体)/光配向膜1/ポジティブAプレートA3(光学異方性層)/ポジティブCプレートC1/バリア層B1の順に積層された偏光板(実施例7)を得た。
 また、光学積層体7に代えて光学積層体9を用いた以外は上記と同様にして、偏光板(比較例2)を得た。
 同様に、光学積層体8に代えて光学積層体10を用いた以外は上記と同様にして、偏光板(比較例3)を得た。
<Manufacturing of polarizing plate>
A sheet-like pressure-sensitive adhesive (Soken Kagaku Co., Ltd.) is used to attach the surface of the obtained optical laminate 7 on the support side and the side of the polyvinyl alcohol polarizer having the polarizing plate protective film on only one side without the polarizing plate protective film. SK2057), polarizing plate protective film / polarizing element / cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A2 (optically anisotropic layer) / positive C plate C1 A polarizing plate (Example 6) laminated in the order of / barrier layer B1 was obtained.
Similarly, the surface of the obtained optical laminate 8 on the support side and the side of the polyvinyl alcohol polarizer having the polarizing plate protective film on only one side are not provided with the polarizing plate protective film in the form of a sheet. SK2057) manufactured by Soken Kagaku Co., Ltd. is used for bonding, and polarizing plate protective film / polarizing element / cellulose acylate film 1 (support) / photoalignment film 1 / positive A plate A3 (optically anisotropic layer) / positive A polarizing plate (Example 7) in which the C plate C1 / barrier layer B1 was laminated in this order was obtained.
Further, a polarizing plate (Comparative Example 2) was obtained in the same manner as described above except that the optical laminate 9 was used instead of the optical laminate 7.
Similarly, a polarizing plate (Comparative Example 3) was obtained in the same manner as above except that the optical laminate 10 was used instead of the optical laminate 8.
<耐久性評価>
 粘着剤付きフィルムを用いて、40mm角に切り出した実施例6~7および比較例2~3の偏光板の偏光子保護フィルム側をガラス板に貼り合わせ、アンモニア2mol%のメタノール溶液を入れたネジ口瓶上に配置することで、アンモニアを36時間曝露した。暴露面は、曝露面は、光学積層体側(すなわち、バリア層B1)が曝露面となるようにネジ口瓶上に配置された。
 曝露後の偏光板を、Axo Scan(0PMF-1、Axometrics社製)を用いて、波長450nmおよび550nmにおける面内レターデーションRe(450)、Re(550)の値を測定した。
 H=Re(550)とするとき、アンモニア暴露前のHをH0、アンモニア暴露後のHをH1とし、ΔH(%)=|H1-H0|/H0×100を指標とし、下記のように評価した。結果を下記表4に示す。
 AA:ΔHが2%未満
 A:ΔHが2%以上5%未満
 B:ΔHが5%以上10%未満
 C:ΔHが10%以上
<Durability evaluation>
Using a film with an adhesive, the polarizing element protective film side of the polarizing plates of Examples 6 to 7 and Comparative Examples 2 to 3 cut into 40 mm squares was attached to a glass plate, and a screw containing a methanol solution of 2 mol% ammonia. By placing on a mouth bottle, ammonia was exposed for 36 hours. The exposed surface was arranged on the screw cap bottle so that the exposed surface was the exposed surface on the optical laminate side (that is, the barrier layer B1).
The values of in-plane retardation Re (450) and Re (550) at wavelengths of 450 nm and 550 nm were measured using an Axo Scan (0PMF-1, manufactured by Axometrics) for the polarizing plate after exposure.
When H = Re (550), H before ammonia exposure is H0, H after ammonia exposure is H1, and ΔH (%) = | H1-H0 | / H0 × 100 is used as an index, and the evaluation is performed as follows. did. The results are shown in Table 4 below.
AA: ΔH is less than 2% A: ΔH is 2% or more and less than 5% B: ΔH is 5% or more and less than 10% C: ΔH is 10% or more
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
 表4に示す評価結果から分かるように、光学異方性層の形成に用いる重合性液晶化合物の種類を変えても、表3に示す評価結果と同様の結果が得られることが分かった。 As can be seen from the evaluation results shown in Table 4, it was found that the same results as the evaluation results shown in Table 3 can be obtained even if the type of the polymerizable liquid crystal compound used for forming the optically anisotropic layer is changed.
<有機EL表示装置の作製>
 有機EL表示パネル(有機EL表示素子)搭載のSAMSUNG社製GALAXY S5を分解し、有機EL表示装置から、円偏光板付きタッチパネルを剥離し、さらにタッチパネルから円偏光板を剥がし、有機EL表示パネル、タッチパネルおよび円偏光板をそれぞれ単離した。次いで、単離したタッチパネル表面にスパッタリングにより窒化ケイ素層(厚さ50nm)を設けた後、有機EL表示パネルと再度貼合し、さらに上記で作製した実施例の偏光板をポジティブCプレートC1側がパネル側になるようにタッチパネル上に貼合し、有機EL表示装置を作製した。
 また、別の態様として、有機EL表示パネル(有機EL表示素子)搭載のRoyole社製FlexPaiを分解し、有機EL表示装置から、円偏光板を剥離した。次いで、単離した有機EL表示パネル(最表面は、窒化ケイ素層)に、上記で作製した実施例の偏光板をバリア層側がパネル側になるように貼合し、有機EL表示装置を作製した。
<Manufacturing of organic EL display device>
The SAMSUNG GALAXY S5 equipped with an organic EL display 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 plate is further peeled off from the touch panel. A touch panel and a circular polarizing plate were isolated, respectively. Next, a silicon nitride layer (thickness 50 nm) was provided on the isolated touch panel surface by sputtering, and then reattached to the organic EL display panel, and the polarizing plate of the above-mentioned embodiment was further attached to the panel on the positive C plate C1 side. An organic EL display device was manufactured by laminating on a touch panel so as to be on the side.
Further, as another embodiment, the FlexPai manufactured by Royole Co., Ltd. mounted on the organic EL display panel (organic EL display element) was disassembled, and the circularly polarizing plate was peeled off from the organic EL display device. Next, the polarizing plate of the above-described embodiment was attached to the isolated organic EL display panel (the outermost surface is a silicon nitride layer) so that the barrier layer side was on the panel side to prepare an organic EL display device. ..
 作製した有機EL表示装置について、ポジティブAプレートA1とポジティブCプレートC1、バリア層の光学積層体を含む実施例の偏光板を用いることにより、正面および斜め方向から観察した場合の反射防止効果が発揮されることを確認した。 By using the polarizing plate of the example including the positive A plate A1, the positive C plate C1, and the optical laminate of the barrier layer for the produced organic EL display device, the antireflection effect when observed from the front and the oblique direction is exhibited. Confirmed that it will be done.
 10、20、30 光学積層体
 11 支持体
 12 配向膜
 13 ポジティブAプレート(光学異方性層)
 14 バリア層
 15 ポジティブCプレート(光学異方性層)
 16 垂直配向した順波長分散性の液晶硬化層
 40 偏光板
 41 偏光子保護フィルム
 42 偏光子
 50 画像表示装置
 51 有機エレクトロルミネッセンス素子
 52 タッチセンサー
 53 窒化ケイ素層
10, 20, 30 Optical laminate 11 Support 12 Alignment film 13 Positive A plate (optical anisotropic layer)
14 Barrier layer 15 Positive C plate (opticallyotropic layer)
16 Vertically oriented forward wavelength dispersive liquid crystal curing layer 40 Polarizing plate 41 Polarizer protective film 42 Polarizer 50 Image display device 51 Organic electroluminescence element 52 Touch sensor 53 Silicon nitride layer

Claims (13)

  1.  光学異方性層と、バリア層とをこの順に有し、
     前記光学異方性層が、逆波長分散性を示す重合性液晶化合物を含む光学異方性層形成用組成物を用いて形成された層であり、
     前記バリア層が、多官能(メタ)アクリルアミドモノマーを含むバリア層形成用組成物から形成された層である、光学積層体。
    It has an optically anisotropic layer and a barrier layer in this order.
    The optically anisotropic layer is a layer formed by using a composition for forming an optically anisotropic layer containing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility.
    An optical laminate in which the barrier layer is a layer formed from a composition for forming a barrier layer containing a polyfunctional (meth) acrylamide monomer.
  2.  前記バリア層が、(メタ)アクリル当量が100以下の多官能(メタ)アクリルアミド化合物を含む組成物から形成される、請求項1に記載の光学積層体。 The optical laminate according to claim 1, wherein the barrier layer is formed from a composition containing a polyfunctional (meth) acrylamide compound having a (meth) acrylic equivalent of 100 or less.
  3.  前記バリア層の厚みが0.1~10μmである、請求項1または2に記載の光学積層体。 The optical laminate according to claim 1 or 2, wherein the barrier layer has a thickness of 0.1 to 10 μm.
  4.  前記逆波長分散性を示す重合性液晶化合物が、下記式(II)で表される化合物である、請求項1~3のいずれか1項に記載の光学積層体。
     L-G-D-Ar-D-G-L   ・・・(II)
     ここで、前記式(II)中、
     DおよびDは、それぞれ独立に、単結合、-O-、-CO-、-CO-O-、-C(=S)O-、-CR-、-CR-CR-、-O-CR-、-CR-O-CR-、-CO-O-CR-、-O-CO-CR-、-CR-CR-O-CO-、-CR-O-CO-CR-、-CR-CO-O-CR-、-NR-CR-、または、-CO-NR-を表す。
     R、R、RおよびRは、それぞれ独立に、水素原子、フッ素原子、または、炭素数1~4のアルキル基を表す。R、R、R及びRのそれぞれが複数存在する場合には、複数のR、複数のR、複数のR及び複数のRはそれぞれ、互いに同一でも異なっていてもよい。
     GおよびGは、それぞれ独立に、炭素数5~8の2価の脂環式炭化水素基、複数の前記脂環式炭化水素基が連結してなる基、芳香族炭化水素基、または、複数の前記芳香族炭化水素基が連結してなる基を表し、前記脂環式炭化水素基を構成する-CH-の1個以上が-O-、-S-または-NH-で置換されていてもよい。
     LおよびLは、それぞれ独立に、1価の有機基を表し、LおよびLの少なくとも一方は、重合性基を有する1価の基を表す。
     Arは、式(Ar-1)~(Ar-7)で表される基からなる群から選択されるいずれかの芳香環を表す。
    Figure JPOXMLDOC01-appb-C000001

     前記式(Ar-1)~(Ar-7)中、
     *は、DまたはDとの結合位置を表す。
     Qは、NまたはCHを表す。
     Qは、-S-、-O-、または、-N(R)-を表し、Rは、水素原子、または、炭素数1~6のアルキル基を表す。
     Yは、置換基を有してもよい、炭素数6~12の芳香族炭化水素基、または、炭素数3~12の芳香族複素環基を表す。
     Z、ZおよびZは、それぞれ独立に、水素原子、炭素数1~20の1価の脂肪族炭化水素基、炭素数3~20の1価の脂環式炭化水素基、炭素数6~20の1価の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、-OR、-NR10、または、-SR11を表し、R~R11は、それぞれ独立に、水素原子、または、炭素数1~6のアルキル基を表し、ZおよびZは、互いに結合して芳香環を形成してもよい。
     AおよびAは、それぞれ独立に、-O-、-N(R12)-、-S-、および、-CO-からなる群から選択される基を表し、R12は、水素原子または置換基を表す。
     Xは、水素原子または置換基が結合していてもよい、第14~16族の非金属原子を表す。
     DおよびDは、それぞれ独立に、単結合、または、-CO-、-O-、-S-、-C(=S)-、-CR1a2a-、-CR3a=CR4a-、-NR5a-、もしくは、これらの2つ以上の組み合わせからなる2価の連結基を表し、R1a~R5aは、それぞれ独立に、水素原子、フッ素原子、または、炭素数1~4のアルキル基を表す。
     SPおよびSPは、それぞれ独立に、単結合、炭素数1~12の直鎖状もしくは分岐鎖状のアルキレン基、または、炭素数1~12の直鎖状もしくは分岐鎖状のアルキレン基を構成する-CH-の1個以上が-O-、-S-、-NH-、-N(Q)-、もしくは、-CO-に置換された2価の連結基を表し、Qは、置換基を表す。
     LおよびLは、それぞれ独立に、1価の有機基を表す。
     Axは、芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
     Ayは、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、または、芳香族炭化水素環および芳香族複素環からなる群から選択される少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
     AxおよびAyにおける芳香環は、置換基を有していてもよく、AxとAyとが互いに結合して環を形成していてもよい。
     Qは、水素原子、または、置換基を有していてもよい炭素数1~6のアルキル基を表す。
    The optical laminate according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is a compound represented by the following formula (II).
    L 1- G 1- D 1- Ar-D 2- G 2- L 2 ... (II)
    Here, in the above formula (II),
    D 1 and D 2 are independently single-bonded, -O-, -CO-, -CO-O-, -C (= S) O-, -CR 1 R 2- , -CR 1 R 2- CR 3 R 4 -, - O -CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O-CO-CR 1 R 2 - , -CR 1 R 2 -CR 3 R 4 -O-CO -, - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - It represents NR 1- CR 2 R 3- or -CO-NR 1- .
    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. When each of R 1 , R 2 , R 3 and R 4 exists, 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 each independently a divalent alicyclic hydrocarbon group 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 one or more of -CH 2- constituting the alicyclic hydrocarbon group is replaced with -O-, -S- or -NH-. It may have been.
    L 1 and L 2 each independently represent a monovalent organic group, and at least one 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).
    Figure JPOXMLDOC01-appb-C000001

    In the formulas (Ar-1) to (Ar-7),
    * Represents the bonding position with D 1 or D 2.
    Q 1 represents an N or CH.
    Q 2 is, -S -, - O-, or, -N (R 7) - represents, R 7 is a hydrogen atom or 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.
    Z 1 , Z 2 and Z 3 independently have a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a carbon number of carbon atoms. Represents 6 to 20 monovalent aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -OR 8 , -NR 9 R 10 , or -SR 11 , where R 8 to R 11 are independent of each other. , 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.
    A 1 and A 2 each independently represent a group selected from the group consisting of -O-, -N (R 12 )-, -S-, and -CO-, where R 12 is a hydrogen atom or Represents a substituent.
    X represents a non-metal atom of Group 14-16 to which a hydrogen atom or a substituent may be bonded.
    D 4 and D 5 are independently single-bonded or -CO-, -O-, -S- , -C (= S)-, -CR 1a R 2a-, -CR 3a = CR 4a- , -NR 5a- , or a divalent linking group consisting of two or more of these, and R 1a to R 5a are independently hydrogen atoms, fluorine atoms, or carbon atoms 1 to 4, respectively. Represents an alkyl group.
    SP 1 and SP 2 independently have a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of the constituent -CH 2- represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where Q represents a divalent linking group. Represents a substituent.
    L 3 and L 4 each independently represent a monovalent organic group.
    Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
    Ay has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , Represents an organic group having 2 to 30 carbon atoms.
    The aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may be bonded to each other to form a ring.
    Q 3 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  5.  前記光学異方性層の波長450nmで測定した面内レターデーション値であるRe(450)と、前記光学異方性層の波長550nmで測定した面内レターデーション値であるRe(550)と、前記光学異方性層の波長650nmで測定した面内レターデーションの値であるRe(650)とが、Re(450)≦Re(550)≦Re(650)の関係を満たす、請求項1~4のいずれか1項に記載の光学積層体。 Re (450), which is an in-plane retardation value measured at a wavelength of 450 nm of the optically anisotropic layer, and Re (550), which is an in-plane retardation value measured at a wavelength of 550 nm of the optically anisotropic layer, Claims 1 to 1, wherein Re (650), which is a value of in-plane retardation measured at a wavelength of 650 nm of the optically anisotropic layer, satisfies the relationship of Re (450) ≤ Re (550) ≤ Re (650). The optical laminate according to any one of 4.
  6.  前記光学異方性層と前記バリア層との間に、さらに1つ以上の液晶硬化層を有する、請求項1~5のいずれか1項に記載の光学積層体。 The optical laminate according to any one of claims 1 to 5, further comprising one or more liquid crystal curing layers between the optically anisotropic layer and the barrier layer.
  7.  請求項1~6のいずれか1項に記載の光学積層体と偏光子とを有し、前記偏光子と、前記光学積層体が有する光学異方性層と、前記光学積層体が有するバリア層とが、この順に含まれている、偏光板。 A barrier layer having the optical laminate and the polarizer according to any one of claims 1 to 6, the polarizer, the optically anisotropic layer of the optical laminate, and the optical laminate. And are included in this order, polarizing plates.
  8.  前記光学異方性層がλ/4波長板であり、前記光学異方性層の遅相軸と前記偏光子の吸収軸とのなす角度が45°±10°である、請求項7の偏光板。 The polarized light according to claim 7, wherein the optically anisotropic layer is a λ / 4 wave plate, and the angle formed by the slow axis of the optically anisotropic layer and the absorption axis of the polarizer is 45 ° ± 10 °. Board.
  9.  請求項1~6のいずれか1項に記載の光学積層体、または、請求項7もしくは8に記載の偏光板を有する、画像表示装置。 An image display device having the optical laminate according to any one of claims 1 to 6 or the polarizing plate according to claim 7 or 8.
  10.  液晶表示装置である、請求項9に記載の画像表示装置。 The image display device according to claim 9, which is a liquid crystal display device.
  11.  有機エレクトロルミネッセンス表示装置である、請求項9に記載の画像表示装置。 The image display device according to claim 9, which is an organic electroluminescence display device.
  12.  視認側から、偏光板と、画像表示パネルと、をこの順で有し、
     前記偏光板が、請求項8に記載の偏光板であり、
     前記偏光板が、前記偏光板が有するバリア層側を前記画像表示パネル側に向けて設けられており、
     前記画像表示パネルが、有機エレクトロルミネッセンス素子を含む有機エレクトロルミネッセンスパネルであり、
     前記有機エレクトロルミネッセンス素子と、前記バリア層との間に、窒化ケイ素層を含む、画像表示装置。
    From the viewing side, the polarizing plate and the image display panel are provided in this order.
    The polarizing plate is the polarizing plate according to claim 8.
    The polarizing plate is provided so that the barrier layer side of the polarizing plate faces the image display panel side.
    The image display panel is an organic electroluminescence panel including an organic electroluminescence element.
    An image display device including a silicon nitride layer between the organic electroluminescence element and the barrier layer.
  13.  前記偏光板と前記窒化ケイ素層との間に存在する層の厚みが40μm未満である、請求項12に記載の画像表示装置。 The image display device according to claim 12, wherein the thickness of the layer existing between the polarizing plate and the silicon nitride layer is less than 40 μm.
PCT/JP2020/041054 2019-11-06 2020-11-02 Optical laminate, polarizing plate, and image display device WO2021090804A1 (en)

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