WO2023127537A1 - 積層体、光学素子、導光素子 - Google Patents

積層体、光学素子、導光素子 Download PDF

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WO2023127537A1
WO2023127537A1 PCT/JP2022/046328 JP2022046328W WO2023127537A1 WO 2023127537 A1 WO2023127537 A1 WO 2023127537A1 JP 2022046328 W JP2022046328 W JP 2022046328W WO 2023127537 A1 WO2023127537 A1 WO 2023127537A1
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Prior art keywords
compound
liquid crystalline
formula
group
optically anisotropic
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English (en)
French (fr)
Japanese (ja)
Inventor
悠貴 福島
啓祐 小玉
峻也 加藤
秀樹 兼岩
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202280086842.6A priority Critical patent/CN118511099A/zh
Priority to JP2023570850A priority patent/JPWO2023127537A1/ja
Publication of WO2023127537A1 publication Critical patent/WO2023127537A1/ja
Priority to US18/756,434 priority patent/US20240345301A1/en
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2021—Compounds containing at least one asymmetric carbon atom
    • C09K19/2028—Compounds containing at least one asymmetric carbon atom containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -COO-CH*-CH3
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
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    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
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    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms
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    • C09K19/38—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133524—Light-guides, e.g. fibre-optic bundles, louvered or jalousie light-guides
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C09K2019/181—Ph-C≡C-Ph
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K2019/2035—Ph-COO-Ph
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    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C09K2323/021—Inorganic, e.g. glass or silicon oxide

Definitions

  • the present invention relates to laminates, optical elements, and light guide elements.
  • Patent Document 1 an optical element capable of obtaining diffracted light with a large diffraction angle and high diffraction efficiency is composed of a cured layer of a liquid crystalline composition containing a tolan compound as a liquid crystalline compound, and a predetermined liquid crystal
  • An optical element with an optically anisotropic layer having an orientation pattern is disclosed.
  • the present inventors produced and examined the optical element described in Patent Document 1, and found that a liquid crystalline composition containing a tolan compound exhibits a high refractive index anisotropy ⁇ n, and a cured product of this liquid crystalline composition.
  • the optical element provided with the optically anisotropic layer has a high diffraction efficiency, it is difficult to maintain the above optical properties due to photodegradation of the tolane compound (in other words, the diffraction efficiency is reduced due to photodegradation of the tolane compound. may be significantly reduced). In other words, it has been clarified that there is room for improving the light resistance of the optical element.
  • this invention makes it a subject to provide the laminated body which is excellent in light resistance.
  • Another object of the present invention is to provide an optical element and a light guide element having the laminate.
  • an optically anisotropic layer comprising a cured layer of a composition containing a liquid crystalline compound; A laminate having a pair of oxygen barrier layers disposed on both sides of the optically anisotropic layer, The optically anisotropic layer has a liquid crystal orientation pattern in which the orientation of the optical axis derived from the liquid crystalline compound is continuously changed along at least one in-plane direction,
  • the composition contains a compound having a partial structure represented by formula (I) described later, The composition contains a compound having a partial structure represented by the above formula (I) as the liquid crystalline compound, or the composition is a compound represented by the above formula (I) as a compound that is not the liquid crystalline compound.
  • the composition contains, as the liquid crystalline compound, only a compound having a partial structure represented by the formula (I), or The composition further contains, as the liquid crystalline compound, another liquid crystalline compound having a structure different from the compound having the partial structure represented by the formula (I), and is represented by the formula (I).
  • the content of the compound having a partial structure is 50% by mass or more with respect to the total content of the compound having a partial structure represented by the formula (I) and the other liquid crystalline compound, [2]- [4] The laminate according to any one of [4].
  • the composition contains only the compound having the partial structure represented by the formula (I) as the liquid crystalline compound, the Hansen solubility parameter of the main component contained in the oxygen barrier layer and the optical difference
  • the distance ⁇ HSP from the Hansen solubility parameter of the compound having the partial structure represented by the above formula (I) contained in the anisotropic layer is greater than 3.5 MPa 0.5
  • the composition includes a compound having a partial structure represented by the formula (I) as a compound other than the liquid crystalline compound, and a compound having the partial structure represented by the formula (I);
  • the content of the compound having the partial structure represented by formula (I) is relative to the total content of the compound having the partial structure represented by formula (I) and the other liquid crystalline compound , 50% by mass or more, the laminate according to [8].
  • the value obtained by dividing the oxygen permeability coefficient [cm 3 cm/(cm 2 s mmHg)] at 25°C and 50% RH by the film thickness [ ⁇ m] is The laminate according to any one of [1] to [15], which is 1.0 ⁇ 10 ⁇ 13 or less.
  • [19] further comprising a water vapor barrier layer having a water vapor permeability of 100 g/(m 2 day) or less at 40° C. and 90% RH;
  • An optical element comprising the laminate according to any one of [1] to [19].
  • a light guide element including the optical element according to [20] and a light guide plate.
  • the laminated body excellent in light resistance can be provided. Further, according to the present invention, it is possible to provide an optical element and a light guide element having the laminate.
  • FIG. 2 is a schematic diagram of an optically anisotropic layer included in the laminate shown in FIG. 1.
  • FIG. 2 is a schematic plan view of an optically anisotropic layer included in the laminate shown in FIG. 1.
  • FIG. 3 is a conceptual diagram showing the action of the optically anisotropic layer shown in FIG. 2;
  • FIG. 3 is a conceptual diagram showing the action of the optically anisotropic layer shown in FIG. 2;
  • 2 is a schematic diagram showing another example of an optically anisotropic layer included in the laminate shown in FIG. 1.
  • FIG. 2 is a schematic diagram showing another example of an optically anisotropic layer included in the laminate shown in FIG. 1.
  • FIG. 1 is a schematic diagram showing another example of an optically anisotropic layer included in the laminate shown in FIG. 1.
  • (meth)acryloyloxy group is a notation representing both an acryloyloxy group and a methacryloyloxy group
  • “(meth)acrylate” is a notation representing both acrylate and methacrylate.
  • a description that does not describe substitution or unsubstituted includes a group having a substituent as well as a group having no substituent.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • substituent when simply referred to as a "substituent", the substituent includes, for example, the following substituent L.
  • substituent L examples include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms.
  • alkanoyl group alkanoyl group, alkanoyloxy group having 1 to 10 carbon atoms, alkanoylamino group having 1 to 10 carbon atoms, alkanoylthio group having 1 to 10 carbon atoms, alkyloxycarbonyl group having 2 to 10 carbon atoms, 2 to 10 carbon atoms
  • Substituent L also includes a group substituted with CH— or —C ⁇ C—.
  • the above group has two or more —CH 2 —, one —CH 2 — is replaced by —O—, and the adjacent one —CH 2 — is replaced by —CO—, resulting in an ester group ( -O-CO-) may be formed.
  • the group described as the substituent L has a hydrogen atom
  • at least one of the hydrogen atoms contained in the group is replaced with at least one selected from the group consisting of a fluorine atom and a polymerizable group.
  • group is also included in the substituent L.
  • the polymerizable group include an ethylenically unsaturated group and a ring-polymerizable group, among which substituents selected from polymerizable groups P described later are preferable.
  • substituent L examples include, among others, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, and a alkanoyloxy group having 1 to 10 carbon atoms.
  • alkyloxycarbonyl group trifluoromethyl group, hydroxy group, carboxy group, cyano group, nitro group, or halogen atom
  • alkyl group having 1 to 10 carbon atoms alkoxy group having 1 to 10 carbon atoms, carbon number 2 to 10 alkanoyl groups, alkanoyloxy groups having 2 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, trifluoromethyl groups, or halogen atoms are more preferable, alkyl groups having 1 to 6 carbon atoms, carbon More preferred are an alkoxy group having 1 to 6 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, an alkanoyloxy group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, a trifluoromethyl group, or a fluorine atom.
  • the polymerizable group when simply referred to as a "polymerizable group", includes, for example, the following polymerizable group P.
  • Polymerizable group P examples include groups represented by any one of the following formulas (P-1) to (P-19).
  • * in the following formula represents a bonding position
  • Me represents a methyl group
  • Et represents an ethyl group.
  • formula (P-1) or formula (P-2) ((meth)acryloyloxy group) is preferable.
  • the "solid content" of the composition means a component that forms a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.) , means all components except solvent.
  • a liquid component is also regarded as a solid content.
  • the thickness of the layer is measured at 10 points by observing a cross section cut by a microtome with a SEM (scanning electron microscope) or a TEM (transmission electron microscope). It is a value using the average value.
  • the laminate of the present invention is an optically anisotropic layer comprising a cured layer of a composition containing a liquid crystalline compound; A laminate having a pair of oxygen barrier layers disposed on both sides of the optically anisotropic layer, The optically anisotropic layer has a liquid crystal orientation pattern in which the orientation of the optical axis derived from the liquid crystalline compound is continuously changed along at least one in-plane direction,
  • the composition contains a compound having a partial structure represented by formula (I) described below (hereinafter also referred to as a "specific tolan compound"),
  • the composition contains the above specific tolan compound as the liquid crystalline compound, or the composition contains the above specific tolan compound as a compound that is not the liquid crystalline compound,
  • the oxygen permeability coefficient of the oxygen barrier layer at 25° C. and 50% RH is 1.0 ⁇ 10 ⁇ 11 cm 3 ⁇ cm/(cm 2 ⁇ s ⁇ mmHg) or less.
  • compositions contains the above-described specific tolan compound as a liquid crystalline compound corresponds to the case where the liquid crystalline composition is a liquid crystalline composition in any one of the first mode and the second mode described later.
  • the case where the composition contains the above-described specific tolan compound as a compound that is not a liquid crystalline compound corresponds to the case where the liquid crystalline composition is the liquid crystalline composition of the third aspect described later.
  • the laminate of the present invention having the above structure includes an optically anisotropic layer made of a cured liquid crystalline composition containing a tolan compound, it has a high diffraction efficiency, and at the same time, a high diffraction efficiency is maintained over a long period of time due to suppression of photodegradation. Diffraction efficiency can be maintained (in other words, excellent light resistance).
  • an optically anisotropic layer made of a cured liquid crystalline composition containing a tolane compound exhibits photodegradation of the tolane compound caused by singlet oxygen generated by light irradiation (for example, oxidation and radical (decomposition, etc.) reduces the diffraction efficiency.
  • the laminate of the present invention comprises an oxygen barrier layer having a predetermined oxygen permeability coefficient on both sides of the optically anisotropic layer. The generation of singlet oxygen is suppressed, and as a result, it is considered to be excellent in light resistance.
  • the laminate of the present invention when at least one of the oxygen barrier layers arranged on both sides of the optically anisotropic layer is arranged so as to be in direct contact with the optically anisotropic layer, the light resistance of the laminate It is also clear that the performance can be further improved.
  • the Hansen solubility parameter (HSP) value of the main component of the oxygen barrier layer and the liquid crystalline composition forming the optically anisotropic layer By increasing the distance ⁇ HSP from the average HSP value of the specific tolane compound and other liquid crystalline compounds in the optically anisotropic layer, the specific tolane compound and other liquid crystalline compounds (particularly, , specific tolan compounds and other liquid crystalline compounds) are suppressed from moving to the oxygen barrier layer, and as a result, the light resistance of the laminate can be further improved.
  • more excellent light resistance of the laminate and/or more excellent durability (wet heat durability) of the laminate may also be referred to as "excellent effects of the present invention.
  • FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the laminate of the present invention.
  • the laminate 10 comprises an optically anisotropic layer 1, a pair of oxygen barrier layers 2A and 2B disposed on both sides of the optically anisotropic layer 1 (both sides of the main surface of the optically anisotropic layer), and oxygen barrier layers A water vapor barrier layer 4A arranged on the side opposite to the optically anisotropic layer 1 side of 2A and a water vapor barrier layer 4B arranged on the side opposite to the optically anisotropic layer 1 side of the oxygen barrier layer 2B.
  • the oxygen permeability coefficient of each of the oxygen barrier layers 2A and 2B at 25° C.
  • the optically anisotropic layer 1 is an optically anisotropic layer composed of a cured layer of a composition containing a liquid crystalline compound, and the orientation of the optical axis derived from the liquid crystalline compound is continuous along at least one in-plane direction. It has a liquid crystal alignment pattern that is randomly rotated.
  • the optically anisotropic layer 1 and the oxygen barrier layer 2A, and the optically anisotropic layer 1 and the oxygen barrier layer 2B are in direct contact with each other without intervening other layers.
  • Intermediate layers such as an alignment film, a pressure-sensitive adhesive layer, and an adhesive layer may be interposed between the anisotropic layer 1 and at least one of the oxygen barrier layers 2A and 2B.
  • the alignment film may be an alignment film used for the purpose of forming the liquid crystalline compound in a predetermined alignment pattern in the preparation of the optically anisotropic layer 1 described later.
  • the optically anisotropic layer 1 and the oxygen barrier layer 2A, and the optically anisotropic layer 1 and the oxygen barrier layer 2B are in direct contact with each other without any other layer interposed therebetween, because the effects of the present invention are more excellent.
  • the water vapor barrier layer 4A is arranged on the side opposite to the optically anisotropic layer 1 of the oxygen barrier layer 2A, and the water vapor barrier layer 4B is arranged on the side opposite to the optically anisotropic layer 1 of the oxygen barrier layer 2B.
  • the water vapor barrier layers 4A and 4B may not be arranged. Alternatively, only one of the vapor barrier layers 4A and 4B may be arranged.
  • the optically anisotropic layer 1 is an optically anisotropic layer comprising a cured layer of a composition containing a liquid crystalline compound.
  • 2 and 3 show schematic cross-sectional views of the optically anisotropic layer 1.
  • FIG. 2 is a side view schematically showing the optically anisotropic layer 1
  • FIG. 3 is a plan view schematically showing the liquid crystal alignment pattern of the optically anisotropic layer 1 shown in FIG.
  • the sheet surface of the sheet-shaped optically anisotropic layer 1 is defined as the xy plane, and the thickness direction is defined as the z direction.
  • the optically anisotropic layer 1 shown in FIG. 2 consists of a cured layer of a composition containing a liquid crystalline compound.
  • the optically anisotropic layer 1 has a liquid crystal alignment pattern (one cycle length ⁇ ) in which the direction of the optic axis derived from the liquid crystal compound 30 is continuously rotated along at least one in-plane direction. 2 to 5, in order to simplify the drawings and clearly show the structure of the optically anisotropic layer 1, only the liquid crystal molecules existing on one main surface side of the optically anisotropic layer 1 are shown. ing.
  • the optically anisotropic layer 1 has a structure in which oriented liquid crystalline compounds 30 are stacked, like an optically anisotropic layer formed using a composition containing a normal liquid crystalline compound.
  • the optically anisotropic layer 1 functions as a general ⁇ /2 plate when the in-plane retardation value is set to ⁇ /2, that is, It has a function of giving a phase difference of half a wavelength, that is, 180° to two linearly polarized light components orthogonal to each other.
  • the optically anisotropic layer 1 has an optical axis 30A derived from a liquid crystalline compound 30 (hereinafter sometimes abbreviated as "optical axis 30A") in the plane of the optically anisotropic layer 1. ) has a liquid crystal orientation pattern that changes while continuously rotating in one direction.
  • optical axis 30A one direction in which the optical axis 30A rotates is aligned with the x-axis direction on the xy plane.
  • one direction in which the optical axis 30A rotates is defined as the x direction.
  • the optical axis 30A derived from the liquid crystalline compound 30 is the axis with the highest refractive index in the liquid crystalline compound 30, the so-called slow axis. As shown in FIG. 2, when the liquid crystalline compound 30 is a rod-like liquid crystalline compound, the optic axis 30A is along the long axis direction of the rod shape.
  • That the direction of the optic axis 30A changes while continuously rotating in the x direction specifically means that the optic axis 30A of the liquid crystalline compound 30 arranged along the x direction and the x direction
  • the angle formed varies depending on the position in the x direction, meaning that the angle formed by the optical axis 30A and the x direction gradually changes from ⁇ to ⁇ +180° or ⁇ 180° along the x direction. do.
  • the angle gradually changes may mean that the angle changes at regular angular intervals, or may mean that the angle changes continuously.
  • the difference in angle between the optical axes 30A of the liquid crystal compounds 30 adjacent to each other in the x direction is preferably 45° or less, more preferably 15° or less, and still more preferably a smaller angle. .
  • the liquid crystalline compound 30 forming the optically anisotropic layer 1 has a , liquid crystalline compounds 30 having the same optical axis 30A are arranged at regular intervals.
  • the angles formed by the directions of the optical axes 30A and the x direction are equal between the liquid crystal compounds 30 arranged in the y direction.
  • the optical axis of the liquid crystal compound 30 is changed in the x direction in which the direction of the optical axis 30A rotates continuously within the plane.
  • the length (distance) by which 30A is rotated by 180° is defined as the length ⁇ of one cycle in the liquid crystal alignment pattern.
  • the length of one cycle in the liquid crystal alignment pattern is defined by the distance from ⁇ to ⁇ +180° formed by the optical axis 30A of the liquid crystal compound 30 and the x direction.
  • the distance between the centers in the x direction of two liquid crystalline compounds 30 whose x direction and the direction of the optical axis 30A match is defined as the length of one cycle ⁇ (hereinafter It is sometimes called “one period ⁇ ” or “period ⁇ ”).
  • the liquid crystal alignment pattern of the optically anisotropic layer 1 is a pattern in which the liquid crystal alignment of one period ⁇ is repeated in the x direction.
  • the liquid crystal compounds 30 arranged in the y direction have the same angle between the optic axis 30A and the x direction in which the directions of the optical axes of the liquid crystal compounds 30 rotate.
  • a region R is defined as a region in which the liquid crystalline compound 30 having the same angle formed by the optical axis 30A and the x direction is arranged in the y direction.
  • the value of the in-plane retardation (Re) in each region R is half the wavelength of the light to be diffracted by the optically anisotropic layer (hereinafter referred to as "target light”), i.e., the wavelength of the target light is ⁇ .
  • the in-plane retardation Re is preferably ⁇ /2. These in-plane retardations are calculated from the product of the refractive index anisotropy ⁇ n of the region R and the thickness (film thickness) d of the optically anisotropic layer.
  • the refractive index difference associated with the refractive index anisotropy of the region R in the optically anisotropic layer is the refractive index in the direction of the slow axis in the plane of the region R and the direction orthogonal to the direction of the slow axis is the refractive index difference defined by the difference from the refractive index of That is, the refractive index difference ⁇ n associated with the refractive index anisotropy of the region R is the refractive index of the liquid crystalline compound 30 in the direction of the optical axis 30A and the liquid crystalline compound 30 in the direction perpendicular to the optical axis 30A in the plane of the region R. equal to the difference in refractive index of 30. That is, the refractive index difference ⁇ n depends on the liquid crystalline compound, and the in-plane retardation of each region R is substantially the same. However, as described above, the directions of the optical axes 30A differ between the regions R.
  • the absolute phase changes according to the direction of the optical axis 30 A of each liquid crystalline compound 30 .
  • the orientation of the optical axis 30A changes while rotating along the x-direction
  • the amount of change in the absolute phase of the incident light L1 differs depending on the orientation of the optical axis 30A.
  • the liquid crystal alignment pattern formed on the optically anisotropic layer 1 is a periodic pattern in the x direction
  • the incident light L 1 passing through the optically anisotropic layer 1 has a pattern as shown in FIG. , a periodic absolute phase Q1 is given in the x-direction corresponding to the orientation of each optical axis 30A.
  • the transmitted light L2 is refracted so as to be inclined in a direction perpendicular to the equal phase plane E1, and travels in a direction different from the traveling direction of the incident light L1 .
  • the incident light L 1 of left-hand circularly polarized light P L is converted into the transmitted light L 2 of right-handed circularly polarized light P R which is tilted in the x-direction with respect to the incident direction by a certain angle.
  • the amount of change in the absolute phase of the incident light L4 differs depending on the direction of the optical axis 30A. Furthermore, since the liquid crystal alignment pattern formed on the optically anisotropic layer 1 is a periodic pattern in the x-direction, the incident light L 4 that has passed through the optically anisotropic layer 1 has the following characteristics, as shown in FIG. A periodic absolute phase Q2 is given in the x-direction corresponding to the orientation of each optical axis 30A.
  • the incident light L 4 is right-handed circularly polarized light P R
  • the periodic absolute phase Q2 in the x-direction corresponding to the direction of the optical axis 30A is left-handed circularly polarized light P L .
  • the incident light L4 forms an equiphase surface E2 inclined in the x-direction opposite to the incident light L1 . Therefore, the incident light L4 is refracted so as to be inclined in a direction perpendicular to the equal phase plane E2, and travels in a direction different from the traveling direction of the incident light L4 . In this way, the incident light L4 is converted into left-handed circularly polarized transmitted light L5 which is tilted by a certain angle in the direction opposite to the x-direction with respect to the incident direction.
  • the in-plane retardation value is preferably half the wavelength of the target light. This is because the closer the in-plane retardation value is to the half wavelength of the target light, the higher the diffraction efficiency in the diffraction of the target light.
  • the angles of refraction of the transmitted lights L 2 and L 5 can be adjusted. Specifically, the shorter the period ⁇ of the liquid crystal alignment pattern, the stronger the interference between the lights passing through the liquid crystal compounds 30 adjacent to each other, so that the transmitted lights L 2 and L 5 can be greatly refracted. Furthermore, by reversing the direction of rotation of the optical axis 30A of the liquid crystal compound 30 rotating along the x-direction, the direction of refraction of transmitted light can be reversed.
  • the period ⁇ is preferably 50 ⁇ m or less, more preferably 25 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the film thickness d of the optically anisotropic layer 1 may be appropriately set in order to obtain a desired in-plane retardation. It is more preferably 5 ⁇ m or less.
  • the thickness d is preferably as small as possible. As the film thickness d is smaller, the accuracy of forming the photo-alignment pattern can be improved.
  • ⁇ /d is preferably 1 or more.
  • the period ⁇ of the liquid crystal alignment pattern in the optically anisotropic layer 1 is determined from the period of the light and dark by observing the light and dark periodic patterns of the bright and dark areas under crossed Nicols conditions with a polarizing microscope. Twice the period of the observed light-dark periodic pattern corresponds to the period ⁇ of the liquid crystal orientation pattern. Also, the film thickness d of the optically anisotropic layer 1 can be measured, for example, by observing the cross section of the optically anisotropic layer with a scanning electron microscope.
  • the optically anisotropic layer 1 preferably has a refractive index anisotropy ⁇ n of 0.21 or more at a wavelength of 550 nm.
  • the upper limit is not particularly limited, it is preferably 0.80 or less.
  • the optically anisotropic layer 1 is a cured layer of a composition containing a liquid crystalline compound (liquid crystalline composition).
  • the liquid crystalline composition for forming the optically anisotropic layer 1 will be described in detail below.
  • liquid crystalline composition contains only a specific tolan compound as a liquid crystalline compound.
  • the liquid crystalline composition contains, as liquid crystalline compounds, a specific tolan compound and a liquid crystalline compound having a structure different from that of the specific tolan compound (hereinafter also referred to as "another liquid crystalline compound").
  • the liquid crystalline composition contains a specific tolan compound as a non-liquid crystalline compound, and a liquid crystalline compound (another liquid crystalline compound) having a structure different from that of the specific tolan compound as a liquid crystalline compound.
  • the liquid crystalline compound having a structure different from that of the specific tolan compound is a liquid crystalline compound that does not contain the partial structure represented by the above formula (I).
  • the liquid crystalline composition of the first aspect does not contain other liquid crystalline compounds having a structure different from that of the specific tolan compound.
  • a specific tolan compound exhibiting liquid crystallinity may be referred to as a "specific tolan compound with liquid crystallinity”
  • a specific tolan compound not exhibiting liquid crystallinity may be referred to as a "non-liquid crystal specific tolan compound”.
  • the liquid crystalline composition of the first aspect described above contains only the specific liquid crystalline tolan compound as the liquid crystalline compound.
  • the liquid crystalline composition of the second aspect described above contains a liquid crystalline specific tolan compound and other liquid crystalline compounds.
  • the liquid crystalline composition of the third aspect described above contains a non-liquid crystalline specific tolan compound and another liquid crystalline compound.
  • liquid crystalline composition each component in the liquid crystalline composition will be described below.
  • the liquid crystalline composition may further contain various components such as a polymerization initiator to be described later.
  • the liquid crystalline composition contains a compound (specific tolan compound) having a partial structure represented by formula (I) below.
  • a 1 and A 2 each independently represent an optionally substituted aromatic hydrocarbon ring group or aromatic heterocyclic group. * represents a binding position.
  • the aromatic hydrocarbon ring group may have a monocyclic structure or a polycyclic structure.
  • the aromatic hydrocarbon ring group is not particularly limited, but is preferably an arylene group, more preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and particularly preferably a phenylene group or a naphthylene group. .
  • the aromatic heterocyclic group may have a monocyclic structure or a polycyclic structure. Among them, the aromatic heterocyclic group is preferably a 5- or 6-membered monocyclic aromatic heterocyclic group.
  • the heteroatom contained in the aromatic heterocyclic group is not particularly limited, and examples thereof include nitrogen atom, oxygen atom, sulfur atom and the like.
  • the aromatic heterocyclic group is not particularly limited, but is preferably a heteroarylene group, more preferably a heteroarylene group having 3 to 20 carbon atoms, and still more preferably a heteroarylene group having 3 to 10 carbon atoms.
  • the heteroatom contained in the heteroarylene group is preferably at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • the substituents that the aromatic hydrocarbon ring group and the aromatic heterocyclic group may have are not particularly limited, but substituents selected from the substituents L described above are preferable.
  • the specific tolan compound may or may not exhibit liquid crystallinity.
  • liquid crystalline compounds can be classified into a rod-like type and a disk-like type according to their shape. Furthermore, there are low-molecular-weight and high-molecular-weight types, respectively.
  • Polymers generally refer to those having a degree of polymerization of 100 or more (Polymer Physics: Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
  • the specific tolane compound with liquid crystallinity may be any of the compounds described above, but a rod-like liquid crystalline compound is particularly preferable.
  • the liquid crystalline specific tolan compound is preferably a liquid crystalline compound having a polymerizable group in the molecule (hereinafter also referred to as "polymerizable liquid crystalline compound").
  • the polymerizable group include an ethylenically unsaturated group and a ring-polymerizable group. Specifically, for example, it is selected from a vinyl group, a styryl group, an allyl group, and the polymerizable group P described above. A substituent etc. are mentioned.
  • the specific liquid crystalline tolan compound has a polymerizable group, it is preferred that one molecule has two or more polymerizable groups in order to fix the alignment.
  • the molecular weight of the specific tolan compound is, for example, preferably 200 to 100,000, more preferably 300 to 10,000, even more preferably 400 to 2,500.
  • the above molecular weight means a weight average molecular weight.
  • P 1 and P 2 each independently represent a hydrogen atom, a halogen atom, —CN, —NCS, or a polymerizable group.
  • P 1 and P 2 are each independently preferably a polymerizable group.
  • the polymerizable group is not particularly limited, but includes, for example, an ethylenically unsaturated group and a ring-polymerizable group, and is preferably a substituent selected from the polymerizable groups P described above.
  • Sp 1 and Sp 2 each independently represent a single bond or a divalent linking group.
  • Sp 1 and Sp 2 represent a divalent linking group containing at least one group selected from the group consisting of an aromatic hydrocarbon ring group, an aromatic heterocyclic group, and an aliphatic hydrocarbon ring group. do not have.
  • the divalent linking group represented by Sp 1 and Sp 2 is not particularly limited, but an alkylene group (preferably an alkylene group having 1 to 20 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 20 carbon atoms ), -O-, -S-, -CO-, -SO-, -SO2- , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O- , or a divalent linking group in which a plurality of these are combined is preferred.
  • an alkylene group preferably an alkylene group having 1 to 20 carbon atoms
  • an alkenylene group preferably an alkenylene group having 2 to 20 carbon atoms
  • -O-, -S-, -CO- preferably an alkenylene group having 2 to 20 carbon atoms
  • -O-, -S-, -CO- preferably an alkenylene group having 2 to 20 carbon atom
  • Sp 1 and Sp 2 are each independently a single bond, or an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -CO-, -COO-, -OCO-, or A divalent linking group combining a plurality of these is preferred, and a single bond, or an alkylene group having 1 to 6 carbon atoms, -O-, -S-, or a divalent linking group combining a plurality of these is more preferred.
  • a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, or a divalent linking group combining a plurality of these is more preferable.
  • Z 1 and Z 2 each independently represent a single bond or a divalent linking group.
  • the multiple Z 1 and the multiple Z 2 may be the same or different.
  • Z 1 and Z 2 represent a divalent linking group containing at least one group selected from the group consisting of an aromatic hydrocarbon ring group, an aromatic heterocyclic group, and an aliphatic hydrocarbon ring group. do not have.
  • the divalent linking group represented by Z 1 and Z 2 is not particularly limited, but an alkylene group (preferably an alkylene group having 1 to 20 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 20 carbon atoms ), an alkynylene group (preferably an alkynylene group having 2 to 20 carbon atoms), -O-, -S-, -CO-, -SO-, -SO 2 -, -COO-, -OCO-, -CO-S -, -S-CO-, -O-CO-O-, or a divalent linking group combining a plurality of these is preferred.
  • an alkylene group preferably an alkylene group having 1 to 20 carbon atoms
  • an alkenylene group preferably an alkenylene group having 2 to 20 carbon atoms
  • an alkynylene group preferably an alkynylene group having 2 to 20 carbon atoms
  • R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.
  • R may each be same or different.
  • Z 1 and Z 2 are each independently -CHRCHR-, -OCHR-, -CHRO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, or - C ⁇ C- is preferred, and -CHRCHR-, -OCHR-, -CHRO- or -C ⁇ C- is more preferred.
  • a 1 and A 2 each independently represent an optionally substituted aromatic hydrocarbon ring group or aromatic heterocyclic group.
  • a 1 and A 2 have the same meanings as A 1 and A 2 in formula (I), and the preferred embodiments are also the same.
  • B 1 and B 2 each independently represent an optionally substituted aromatic hydrocarbon ring group, aromatic heterocyclic group, or aliphatic hydrocarbon ring group.
  • the plurality of B 1 's and the plurality of B 2 's may be the same or different.
  • the aromatic hydrocarbon ring group may have a monocyclic structure or a polycyclic structure.
  • the aromatic hydrocarbon ring group is not particularly limited, but is preferably an arylene group, more preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and particularly preferably a phenylene group or a naphthylene group. .
  • the aromatic heterocyclic group may have a monocyclic structure or a polycyclic structure. Among them, the aromatic heterocyclic group is preferably a 5- or 6-membered monocyclic aromatic heterocyclic group.
  • the heteroatom contained in the aromatic heterocyclic group is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom and the like.
  • the aromatic heterocyclic group is not particularly limited, but is preferably a heteroarylene group, more preferably a heteroarylene group having 3 to 20 carbon atoms, and still more preferably a heteroarylene group having 3 to 10 carbon atoms.
  • the heteroatom contained in the heteroarylene group is preferably at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • the aliphatic hydrocarbon ring group may have a monocyclic structure or a polycyclic structure.
  • the aliphatic hydrocarbon ring group is not particularly limited and includes, for example, a cycloalkylene group.
  • a cycloalkylene group having 3 to 20 carbon atoms is preferable, and a cycloalkylene group having 3 to 10 carbon atoms is more preferable.
  • the substituent that the aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the aliphatic hydrocarbon ring group may have is not particularly limited, but a substituent selected from the substituent L described above It is preferable to have
  • n and m each independently represent an integer of 0-4. n and m preferably each independently represent an integer of 0 to 3, more preferably an integer of 0 to 2.
  • T 1 and T 2 each independently represent a hydrogen atom or a methyl group.
  • X 1 and X 2 each independently represent a methylene group, an oxygen atom, or a sulfur atom.
  • r represents an integer of 1 to 5;
  • t and v each independently represent 0 or 1;
  • u represents 1 or 2;
  • w represents an integer of 1-5.
  • Q 1 to Q 16 each independently represent a hydrogen atom or a substituent.
  • E 1 to E 6 each independently represent a hydrogen atom or a substituent.
  • the substituents represented by Q 1 to Q 16 are not particularly limited, but substituents selected from the substituents L described above are preferred.
  • the substituents represented by E 1 to E 6 are not particularly limited, but are preferably substituents selected from the substituents L described above.
  • Specific examples of the specific tolan compound are not particularly limited. 4517416, JP 2002-128742, JP 4810750, JP 5888544, JP 2014-019654, JP 6241654, JP 6372060, JP 6323144, JP 2005-015406 JP, JP 2007-230968, JP 6761484, JP 6681992, WO 19/182129, CN1134217A, KR101069555B, KR101690767B, CN20120229730A, JP 4053782, JP 200 9-249406, Japanese Patent No. 4121075, Japanese Patent Publication No. 2005-528416, US6514578, International Publication No. 06/006819, Japanese Unexamined Patent Publication No.
  • specific tolan compounds include the following compounds.
  • the specific tolan compound can include liquid crystalline specific tolan compounds (specific tolan compounds exhibiting liquid crystallinity) and non-liquid crystal specific tolan compounds (specific tolan compounds not exhibiting liquid crystallinity).
  • the specific liquid crystalline tolan compound is intended to be a compound having a partial structure represented by the above formula (I) and having a transition temperature to a liquid crystal phase of 1° C. or higher when the temperature is lowered.
  • the refractive index anisotropy ⁇ n of the specific liquid crystalline tolan compound ⁇ n at a wavelength of 550 nm is preferably 0.20 or more, more preferably 0.24 or more, and still more preferably 0.28 or more.
  • the liquid crystalline composition may contain another liquid crystalline compound (another liquid crystalline compound) having a structure different from that of the specific tolan compound.
  • liquid crystalline compounds can be classified into a rod-like type and a disk-like type according to their shape. Furthermore, there are low-molecular-weight and high-molecular-weight types, respectively.
  • Polymers generally refer to those having a degree of polymerization of 100 or more (Polymer Physics: Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
  • the other liquid crystalline compound is not particularly limited and may be any compound. Among them, a rod-like liquid crystalline compound or a discotic liquid crystalline compound (discotic liquid crystalline compound) is preferable, and a rod-like liquid crystalline compound is more preferable, because the effects of the present invention are more excellent.
  • a liquid crystalline compound having a polymerizable group in the molecule (polymerizable liquid crystalline compound) is preferable.
  • the polymerizable group include an ethylenically unsaturated group and a ring-polymerizable group. Specifically, for example, it is selected from a vinyl group, a styryl group, an allyl group, and the polymerizable group P described above. A substituent etc. are mentioned.
  • the other liquid crystalline compound contains a polymerizable group, the number of polymerizable groups is not particularly limited, but is, for example, one or more. It is preferable to have two or more polymerizable groups in one molecule. In addition, as an upper limit, 6 or less are preferable, and 3 or less are more preferable, for example.
  • liquid crystalline compounds may be used singly or in combination of two or more.
  • two or more other liquid crystalline compounds are used in combination, two or more rod-like liquid crystalline compounds, two or more discotic liquid crystalline compounds, and a mixture of a rod-like liquid crystalline compound and a discotic liquid crystalline compound. It can be in any form.
  • Known compounds can be used as other liquid crystalline compounds.
  • the rod-like liquid crystalline compound for example, the compounds described in [Claim 1] of JP-A-11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be suitably used.
  • the discotic liquid crystalline compound for example, compounds described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038, etc. can be preferably used.
  • liquid crystalline compounds rod-like liquid crystalline compounds are preferable in that the effects of the present invention are more excellent.
  • Acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, or alkenylcyclohexylbenzonitriles are more preferred.
  • liquid crystalline compounds preferably have a higher refractive index anisotropy ⁇ n.
  • ⁇ n at a wavelength of 550 nm is preferably 0.15 or more, more preferably 0.18 or more. It is more preferably 0.22 or more. Although the upper limit is not particularly limited, it is often 0.20 or less.
  • the content of the liquid crystalline compound in the liquid crystalline composition is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, and further preferably 80 to 100% by mass, based on the solid content of the liquid crystalline composition. preferable.
  • the content of the specific tolan compound in the liquid crystalline composition (the total content of the specific liquid crystalline tolan compound and the non-liquid crystalline specific tolan compound) is 20 to 100 with respect to the total solid content of the liquid crystalline composition. % by mass is preferable, 50 to 100% by mass is more preferable, and 70 to 100% by mass is even more preferable.
  • the specific liquid crystalline tolan compound is preferably a polymerizable liquid crystalline compound having two or more polymerizable groups. Further, when the liquid crystalline composition is the liquid crystalline composition of the first aspect, the specific liquid crystalline tolan compound is preferably a rod-like liquid crystalline compound.
  • the liquid crystalline composition is the liquid crystalline composition of the second embodiment
  • at least one of the specific liquid crystalline tolan compound and the other liquid crystalline compound is a polymerizable liquid crystalline compound having two or more polymerizable groups. More preferably, both are polymerizable liquid crystalline compounds having two or more polymerizable groups.
  • the content of the specific liquid crystalline tolan compound is 50% by mass with respect to the total content of the specific liquid crystalline tolan compound and other liquid crystalline compounds. It is preferably 70% by mass or more, more preferably 70% by mass or more, and even more preferably 85% by mass or more. Although the upper limit is not particularly limited, it is preferably 95% by mass or less.
  • both the specific liquid crystalline tolan compound and the other liquid crystalline compound are preferably rod-like liquid crystalline compounds.
  • the liquid crystalline composition is the liquid crystalline composition of the third embodiment
  • at least one of the non-liquid crystalline specific tolan compound and the other liquid crystalline compound preferably has two or more polymerizable groups, and both are polymerized. More preferably, it has two or more functional groups.
  • the content of the non-specific tolan compound is 20% by mass with respect to the total content of the non-specific tolan compound and other liquid crystalline compounds. It is preferably at least 30% by mass, more preferably at least 30% by mass, even more preferably at least 40% by mass, and particularly preferably at least 50% by mass.
  • the upper limit is not particularly limited, it is preferably 80% by mass or less, more preferably 60% by mass or less.
  • the other liquid crystalline compound is preferably a rod-like liquid crystalline compound.
  • the liquid crystalline composition preferably contains a polymerization initiator.
  • a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation is preferred.
  • photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), and ⁇ -hydrocarbon-substituted aromatic compounds. group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. No.
  • the liquid crystalline composition contains a polymerization initiator
  • the content of the polymerization initiator in the liquid crystalline composition is preferably 0.1 to 20% by mass with respect to the content of the liquid crystalline compound. It is more preferably 1 to 10% by mass.
  • the polymerization initiator may be used singly or in combination of two or more. When two or more kinds are used, the total content is preferably within the above range.
  • the liquid crystalline composition may contain a surfactant that contributes to stable or rapid formation of a liquid crystal phase.
  • surfactants include fluorine-containing (meth)acrylate polymers, compounds represented by general formulas (X1) to (X3) described in International Publication No. 2011/162291, paragraph [ 0082] to [0090], compounds represented by general formula (I), and compounds described in paragraphs [0020] to [0031] of JP-A-2013-047204. These compounds can reduce the tilt angle of the molecules of the liquid crystalline compound or align the liquid crystalline compound substantially horizontally at the air interface of the layer.
  • the term “horizontal alignment” means that the molecular axis of the liquid crystal compound (corresponding to the long axis of the liquid crystal compound when the liquid crystal compound is a rod-like liquid crystal compound) is parallel to the film surface. However, it is not required to be strictly parallel, and in this specification, it means an orientation with an inclination angle of less than 20 degrees with respect to the film surface.
  • the liquid crystalline compound is horizontally aligned in the vicinity of the air interface, alignment defects are less likely to occur, resulting in high transparency in the visible light region.
  • the molecules of the liquid crystalline compound are oriented at a large tilt angle, for example, in the case of a cholesteric phase, the helical axis deviates from the normal to the film surface, resulting in a decrease in reflectance or the occurrence of a fingerprint pattern. It is not preferable because it increases haze or exhibits diffractive properties.
  • fluorine-containing (meth)acrylate polymers that can be used as surfactants include polymers described in paragraphs [0018] to [0043] of JP-A-2007-272185.
  • the content of the surfactant in the liquid crystalline composition is not particularly limited. Preferably, 0.05 to 3% by mass is more preferable.
  • the liquid crystalline composition may use one surfactant alone, or two or more surfactants. When two or more kinds are used, the total content is preferably within the above range.
  • the liquid crystalline composition may contain a solvent.
  • the solvent is preferably a solvent capable of dissolving each component to be mixed in the liquid crystalline composition. etc.), ethers (e.g., dioxane and tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene , and trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, and butyl acetate, etc.), water, alcohols (e.g., , ethanol, isopropanol, butanol, and
  • the content of the solvent in the liquid crystalline composition is preferably an amount that makes the solid content concentration 0.5 to 30% by mass, more preferably 1 to 20% by mass. preferable.
  • the liquid crystalline composition may use one solvent alone, or two or more solvents. When two or more kinds are used, the total content is preferably within the above range.
  • the liquid crystalline composition may contain a chiral agent.
  • a chiral agent (optically active compound) has a function of inducing a helical structure of a cholesteric liquid crystal phase.
  • the chiral agent may be selected depending on the purpose, since the helical twist direction or helical pitch induced by the compound differs.
  • the chiral agent is not particularly limited. Committee, 1989", isosorbide, isomannide derivatives and the like can be used.
  • Chiral agents generally contain an asymmetric carbon atom, but axially or planarly chiral compounds that do not contain an asymmetric carbon atom can also be used as chiral agents.
  • Examples of axially or planarly chiral compounds include binaphthyl, helicene, paracyclophane, and derivatives thereof.
  • the chiral agent may have a polymerizable group.
  • the polymerization reaction of the polymerizable chiral agent and the polymerizable liquid crystalline compound produces repeating units derived from the polymerizable liquid crystalline compound and the chiral agent.
  • a polymer can be formed having derivatized repeat units.
  • the polymerizable group possessed by the polymerizable chiral agent is preferably the same kind of group as the polymerizable group possessed by the polymerizable liquid crystalline compound.
  • the chiral agent itself may be a liquid crystalline compound.
  • the chiral agent has a photoisomerizable group
  • the photoisomerizable group is preferably an isomerization site of a compound exhibiting photochromic properties, an azo group, an azoxy group, or a cinnamoyl group.
  • Specific compounds include JP-A-2002-080478, JP-A-2002-080851, JP-A-2002-179668, JP-A-2002-179669, JP-A-2002-179670, JP-A-2002- 179681, JP 2002-179682, JP 2002-338575, JP 2002-338668, JP 2003-313189, and compounds described in JP 2003-313292, etc. Available.
  • the content of the chiral agent in the liquid crystalline composition is not particularly limited, but is 0.01% by mass to 15% by mass based on the content of the liquid crystalline compound. Preferably, 1.0% by mass to 10% by mass is more preferable.
  • the liquid crystalline composition may contain additives other than the components described above.
  • additives include antioxidants, UV absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, antifoaming agents, leveling agents, thickeners, flame retardants, surfactants. , dispersants, and coloring materials such as dyes and pigments.
  • ⁇ n of liquid crystalline composition As the refractive index anisotropy ⁇ n of the liquid crystalline composition, ⁇ n at a wavelength of 550 nm is preferably 0.21 or more, more preferably 0.25 or more, from the viewpoint that the diffraction efficiency of the laminate becomes higher. is more preferable, 0.28 or more is still more preferable, and 0.30 or more is particularly preferable. Although the upper limit is not particularly limited, for example, 0.80 or less is preferable.
  • the refractive index anisotropy ⁇ n of the liquid crystalline composition can be measured by the following method. As described below, when the liquid crystalline composition contains a solvent, ⁇ n is measured after removing the solvent from the liquid crystalline composition.
  • ⁇ n of each liquid crystalline composition is measured by the method using a wedge-shaped liquid crystal cell described in Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Editing Committee, published by Maruzen Co., Ltd.), page 202.
  • the liquid crystalline composition contains a solvent
  • the liquid crystalline composition is dried in advance on a hot plate at 120° C., and ⁇ n is measured using the composition obtained by removing the solvent.
  • the optically anisotropic layer substantially broadband with respect to the wavelength of incident light by imparting a twist component to the liquid crystalline composition or by laminating different retardation layers.
  • Japanese Unexamined Patent Application Publication No. 2014-089476 discloses a method of realizing a broadband patterned ⁇ /2 plate by laminating two layers of liquid crystal having different twist directions in an optically anisotropic layer. , can be suitably used in the laminate of the present invention.
  • the optically anisotropic layer 1 is a layer obtained by curing the liquid crystalline composition described above.
  • a substrate provided with an alignment film having a predetermined alignment pattern is brought into contact with the liquid crystalline composition to form a composition layer on the alignment film of the substrate. and a step Y of subjecting the composition layer to a heat treatment to align the liquid crystalline compound and then subjecting the composition layer to a curing treatment.
  • the substrate may or may not be removed from the optically anisotropic layer.
  • the alignment film described above may or may not be removed from the optically anisotropic layer after the preparation of the optically anisotropic layer 1 .
  • the substrate described above may be an oxygen barrier layer (for example, a glass substrate, etc.) described later.
  • an alignment film is provided between the optically anisotropic layer 1 and the oxygen barrier layer 2A or between the optically anisotropic layer 1 and the oxygen barrier layer 2B. may intervene.
  • an alignment film may be formed on the oxygen barrier layer, and an optically anisotropic layer may be formed on the alignment film.
  • step X substrate
  • known substrates for example, resin substrates, glass substrates, ceramic substrates, semiconductor substrates, and metal substrates.
  • Alignment film An alignment film is arranged on the substrate. The presence of the alignment film facilitates alignment of the liquid crystal compound 30 in a predetermined liquid crystal alignment pattern when the optically anisotropic layer 1 is produced. As described above, in the optically anisotropic layer 1, the direction of the optical axis 30A (see FIG. 3) derived from the liquid crystalline compound 30 continuously rotates along one in-plane direction (x direction). It has a varying liquid crystal alignment pattern. Therefore, the alignment film is formed so that the optically anisotropic layer can form this liquid crystal alignment pattern.
  • Alignment films include, for example, rubbing-treated films made of organic compounds such as polymers, oblique deposition films of inorganic compounds, films having microgrooves, and films made of ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate, and the like. Examples thereof include a film obtained by accumulating LB (Langmuir-Blodgett) films by the Langmuir-Blodgett method of an organic compound.
  • the alignment film by rubbing treatment can be formed by rubbing the surface of the polymer layer with paper or cloth several times in one direction.
  • Materials used for the alignment film include polyimide, polyvinyl alcohol, polymers having a polymerizable group described in JP-A-9-152509, JP-A-2005-097377, JP-A-2005-099228, and JP-A-2005-099228. Materials used for forming alignment films described in JP-A-2005-128503 and the like can be preferably used.
  • the alignment film a so-called photo-alignment film obtained by irradiating a photo-alignment material with polarized or non-polarized light to form an alignment film can be suitably used.
  • the alignment film is formed by irradiating polarized light
  • the alignment film is formed by irradiating the photo-alignment material from a vertical direction or an oblique direction
  • the alignment film is formed by irradiating the photo-alignment material with unpolarized light. can be formed by performing irradiation from an oblique direction.
  • photo-alignment material used in the photo-alignment film for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007- 121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, JP-A-3883848 and JP-A-4151746.
  • azo compounds, photocrosslinkable polyimides, photocrosslinkable polyamides, photocrosslinkable esters, cinnamate compounds, chalcone compounds, and the like can be preferably used.
  • the thickness of the alignment film there is no limit to the thickness of the alignment film, and the thickness that can obtain the required alignment function can be set as appropriate according to the material for forming the alignment film.
  • the thickness of the alignment film is preferably 0.01-5 ⁇ m, more preferably 0.05-2 ⁇ m.
  • the method for forming the alignment film is not particularly limited, and various known methods can be used depending on the material for forming the alignment film.
  • a photo-alignment film formed as an alignment film by irradiating a photo-alignment material with polarized or non-polarized light is preferable because the alignment pattern of the optically anisotropic layer 1 is more easily formed.
  • the method of bringing the liquid crystalline composition into contact with a substrate provided with an alignment film having a predetermined alignment pattern is not particularly limited.
  • a method of coating the composition thereon and a method of immersing the alignment film-attached substrate in the composition may be mentioned.
  • a drying treatment may be carried out, if necessary, in order to remove the solvent from the composition layer disposed on the alignment film of the substrate.
  • Step Y is a step of subjecting the composition layer to heat treatment to align the liquid crystalline compound and then subjecting the composition layer to curing treatment.
  • the liquid crystalline compound is oriented and a liquid crystal phase is formed.
  • the conditions for the heat treatment are not particularly limited, and optimal conditions are selected according to the type of liquid crystalline compound.
  • the curing treatment method is not particularly limited, and includes photocuring treatment and heat curing treatment. Among them, light irradiation treatment is preferable, and ultraviolet irradiation treatment is more preferable.
  • a light source such as an ultraviolet lamp is used for ultraviolet irradiation.
  • the cured product obtained by the above treatment corresponds to a layer having a fixed liquid crystal phase.
  • a layer having a fixed cholesteric liquid crystal phase is formed.
  • These layers no longer need to exhibit liquid crystallinity.
  • the state in which the cholesteric liquid crystal phase is "fixed” is the most typical and preferable mode in which the alignment of the liquid crystal compound in the cholesteric liquid crystal phase is maintained.
  • the layer has no fluidity in the temperature range of 0 to 50°C normally, and -30 to 70°C under more severe conditions, and the orientation is changed by an external field or force. It is preferably in a state in which the fixed alignment form can be stably maintained.
  • a semi-cured optically anisotropic layer may be formed by a curing treatment, and after placing an oxygen barrier layer on the optically anisotropic layer, additional curing of the optically anisotropic layer may be performed. good.
  • the optically anisotropic layer is additionally cured after the oxygen barrier layer is placed, the optically anisotropic layer is cured in the absence of singlet oxygen, which is a polymerization inhibitor. The light resistance of the body is more likely to be improved.
  • the substrate is an oxygen barrier layer (an oxygen barrier layer having an oxygen permeability coefficient of 1.0 ⁇ 10 ⁇ 11 cm 3 cm/(cm 2 s mmHg) or less at 25° C. and 50% RH). ).
  • the laminate 10 has a pair of oxygen barrier layers (2A, 2B) arranged on both sides of the optically anisotropic layer 1. As shown in FIG. Each oxygen barrier layer of the oxygen barrier layers 2A and 2B has an oxygen permeability coefficient of 1.0 ⁇ 10 ⁇ 11 cm 3 cm/(cm 2 s mmHg) or less at 25° C. and 50% RH. 1.0 ⁇ 10 ⁇ 12 cm 3 ⁇ cm/(cm 2 ⁇ s ⁇ mmHg) or less is preferable, and 1.0 ⁇ 10 ⁇ 13 cm 3 ⁇ cm/(cm 2 ⁇ s * mmHg) or less is more preferable.
  • the lower limit is not particularly limited, it is preferably 1.0 ⁇ 10 ⁇ 20 cm 3 ⁇ cm/(cm 2 ⁇ s ⁇ mmHg) or more.
  • the oxygen permeability coefficient of each of the oxygen barrier layers 2A and 2B at 25° C. and 50% RH can be measured by the isobaric method according to ISO 15105-2.
  • the value obtained by dividing the oxygen permeability coefficient [cm 3 cm/(cm 2 s mmHg)] at 25° C. and 50% RH by the film thickness [ ⁇ m]. is preferably 1.0 ⁇ 10 ⁇ 11 or less, more preferably 1.0 ⁇ 10 ⁇ 12 or less, and even more preferably 1.0 ⁇ 10 ⁇ 13 or less.
  • the lower limit is not particularly limited, it is preferably 1.0 ⁇ 10 ⁇ 20 or more, for example.
  • the transmittance is preferably 70% or more, more preferably 75% or more, and even more preferably 80% or more.
  • the transmittance refers to the average transmittance of visible light with wavelengths of 400-700 nm.
  • the above transmittance is a value measured at 25° C. using a spectrophotometer (for example, spectrophotometer UV-3100PC manufactured by Shimadzu Corporation).
  • Materials constituting the oxygen barrier layers 2A and 2B include, for example, glass and resin. Resins constituting the oxygen barrier layers 2A and 2B are not particularly limited, and examples thereof include ethylene-vinyl alcohol copolymer, polyamide, polyvinyl alcohol, polyacrylonitrile, and polyvinylidene chloride.
  • the organic molecular film described in JP-A-2014-218444 and JP-A-2014-218548, the barrier film described in JP-A-2020-188047, and the coating described in JP-A-2020-186281 A film or the like can also be applied as the oxygen barrier layers 2A and 2B.
  • a polarizing plate may be used as the oxygen barrier layers 2A and 2B.
  • the oxygen barrier layers 2A and 2B may contain an inorganic filler. The inorganic filler is the same as the inorganic filler contained in the water vapor barrier layer, which will be described later.
  • one of the oxygen barrier films 2A and 2B is made of glass and the other is made of non-glass (for example, resin or the like).
  • the lower limit of the thickness of the oxygen barrier layer is not particularly limited, it is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or more in terms of better oxygen barrier properties.
  • the upper limit of the thickness of the oxygen barrier layer is not particularly limited. , is preferably 2 cm or less, more preferably 1 cm or less, and even more preferably 5 mm or less.
  • the thickness is preferably 2 cm or less, more preferably 1 cm or less, and even more preferably 5 mm or less in order to reduce the thickness of the entire laminate and to improve productivity. , 100 ⁇ m or less is even more preferable, 50 ⁇ m or less is particularly preferable, 30 ⁇ m or less is particularly preferable, and 10 ⁇ m or less is most preferable.
  • the liquid crystalline composition for forming the optically anisotropic layer 1 is the liquid crystalline composition of Embodiment 1 described above
  • the HSP value of the main component contained in the oxygen barrier layer 2A (and/or the oxygen barrier layer 2B) and , the distance ⁇ HSP from the HSP value of the specific tolan compound is preferably greater than 3.5 MPa 0.5 , preferably 4.0 MPa 0.5 or more, more preferably 5.0 MPa 0.5 or more, and 7.0 MPa 0 0.5 or more is particularly preferred.
  • the upper limit is not particularly limited, for example, 13.0 MPa 0.5 or less is preferable.
  • the oxygen barrier layer 2A (and/or the oxygen barrier layer 2B) contains
  • the distance ⁇ HSP between the HSP value of the component and the average HSP value of the specific tolan compound and other liquid crystalline compounds is 3.5 MPa, preferably greater than 0.5 , and 4.0 MPa, preferably 0.5 or more, and 5.0 MPa. 0.5 or more is more preferable, and 7.0 MPa 0.5 or more is particularly preferable.
  • the upper limit is not particularly limited, for example, 13.0 MPa 0.5 or less is preferable.
  • the migration of molecules of the specific tolane compound and other liquid crystalline compounds (in particular, the specific tolane compound and other liquid crystalline compounds that are not immobilized by polymerization) to the oxygen barrier layer is suppressed, resulting in lamination.
  • the light resistance of the body can be further improved.
  • the distance ⁇ HSP value is obtained by the following procedure.
  • three vectors of Hansen solubility parameters (Hansen solubility parameter vector variance A term component: ⁇ D, a polar term component of the Hansen solubility parameter vector: ⁇ P, and a hydrogen bond term component of the Hansen solubility parameter vector: ⁇ H) are obtained.
  • the main component constituting the oxygen barrier layer corresponds to, for example, SiO 2 when the oxygen barrier layer is glass.
  • the ⁇ D, ⁇ P, and ⁇ H of each raw material monomer constituting the resin and the content of each raw material monomer are obtained by the same method as the procedure (2) described later.
  • the average ⁇ D, average ⁇ P, and average ⁇ H calculated from the amount are compared with ⁇ D, ⁇ P, and ⁇ H of the main components constituting the oxygen barrier layer. I reckon.
  • the average ⁇ Dx of the specific tolan compound and the other liquid crystalline compound is calculated according to the following formula.
  • Average ⁇ D x ⁇ D 1 ⁇ W 1 + ⁇ D 2 ⁇ W 2 + . . . ⁇ Dn ⁇ Wn
  • ⁇ Dn represents the ⁇ D of each compound corresponding to the specific tolan compound and other liquid crystalline compounds
  • Wn is the content of each compound (mass fraction: relative to the total content of each compound, compound content ratio).
  • the optically anisotropic layer contains a specific tolan compound and another liquid crystalline compound in equal amounts
  • the average ⁇ D x ⁇ D 1 ⁇ W 1 + ⁇ D 2 ⁇ W 2 (where ⁇ D 1 and ⁇ D 2 are , respectively represent ⁇ D of the specific tolan compound and other liquid crystalline compounds, and W 1 and W 2 represent 0.5).
  • ⁇ HSP value ⁇ 4 ⁇ ( ⁇ D A - ⁇ D B ) 2 + ( ⁇ P A - ⁇ P B ) 2 + ( ⁇ H A - ⁇ H B ) 2 ⁇ 0.5
  • ⁇ D A , ⁇ P A and ⁇ H A are the average ⁇ D x and the average ⁇ P of the specific tolan compound and the other liquid crystalline compound.
  • ⁇ D A , ⁇ P A and ⁇ H A represent ⁇ D, ⁇ P and ⁇ H of the specific tolan compound, respectively.
  • ⁇ D B , ⁇ P B , and ⁇ H B represent ⁇ D, ⁇ P, and ⁇ H, which are the main components of the oxygen barrier layer.
  • the layered product 10 is provided with the water vapor barrier layers 4A and 4B, so that the light resistance is further improved.
  • Resins constituting the water vapor barrier layers 4A and 4B are not particularly limited, and examples thereof include polyolefin resins such as polypropylene, polyethylene, high-density polyethylene, cyclic olefin polymers, and cyclic olefin copolymers; polyvinylidene chloride and polychlorotrifluoroethylene. and resins containing halogen atoms such as.
  • the water vapor barrier layers 4A and 4B may contain an inorganic filler. When the water vapor barrier layers 4A and 4B contain an inorganic filler, the water vapor barrier properties are further improved.
  • Examples of inorganic fillers contained in the water vapor barrier layers 4A and 4B include layered silicates such as talc, mica, kaolin, clay, and bentonite, silica, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, Examples include glass fillers, glass fibers, glass beads, titanium oxide, aluminum oxide, iron, zinc, and aluminum.
  • the water vapor permeability at 40° C. and 90% RH is preferably 100 g/(m 2 ⁇ day) or less, more preferably 40 g/(m 2 ⁇ day) or less. , 20 g/(m 2 ⁇ day) or less is more preferable. Although the lower limit is not particularly limited, it is preferably 0.01 g/(m 2 ⁇ day) or more, for example.
  • the water vapor barrier degree of the water vapor barrier layers 4A and 4B at 40° C. and 90% RH can be measured by the cup method with reference to JIS-Z-0208 (1976).
  • the thickness of the water vapor barrier layers 4A and 4B is not particularly limited, it is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or more in terms of better water vapor barrier properties.
  • optically anisotropic layer 1 included in the laminate 10 shown in FIG. 1 Modifications of the optically anisotropic layer 1 included in the laminate 10 shown in FIG. 1 are shown below.
  • the optically anisotropic layer 2 shown in FIG. 6 is an optically anisotropic layer in which the liquid crystalline compound 30 is cholesterically aligned in the thickness direction.
  • Cholesteric liquid crystal phases are known to exhibit selective reflectivity at specific wavelengths.
  • the cholesteric liquid crystal phase exhibits selective reflectivity for either left or right circularly polarized light at a specific wavelength. Whether the reflected light is right-handed circularly polarized light or left-handed circularly polarized light depends on the twist direction (sense) of the cholesteric liquid crystal phase.
  • the selective reflection of circularly polarized light by the cholesteric liquid crystal phase reflects right circularly polarized light when the spiral of the cholesteric liquid crystal phase is twisted to the right, and reflects left circularly polarized light when the spiral is twisted to the left.
  • the optically anisotropic layer 2 has a function of selectively reflecting light in a predetermined wavelength range of specific circularly polarized light (right-handed circularly polarized light or left-handed circularly polarized light).
  • the orientation pattern of the optical axis 30A in the in-plane direction of the optically anisotropic layer 2 is the same as the orientation pattern of the optically anisotropic layer 1 shown in FIG. produce an effect. That is, the optically anisotropic layer 2 has the effect of changing the absolute phase of incident light to bend it in a predetermined direction, like the optically anisotropic layer 1 described above. Therefore, the optically anisotropic layer 2 has both the action of bending incident light in a direction different from the direction of incidence and the action of the cholesteric orientation, so that the light is reflected at an angle in a predetermined direction with respect to the direction of specular reflection. reflect.
  • the cholesteric liquid crystal phase of the optically anisotropic layer 2 is designed to reflect right-handed circularly polarized light.
  • the optically anisotropic layer 2 functions as a reflective diffraction grating.
  • optical axis 30A of the liquid crystal compound 30 in the liquid crystal alignment patterns of the optically anisotropic layers shown in FIGS. 2 to 6 continuously rotates only along the x direction in the plane.
  • various configurations are available as long as the optical axis 30A of the liquid crystalline compound 30 rotates continuously along one direction.
  • FIG. 7 is a schematic plan view of the optically anisotropic layer 3 of the modified design.
  • the liquid crystal alignment pattern is indicated by the optical axis 30A of the liquid crystal compound.
  • the optically anisotropic layer 3 is provided with concentric regions in which the directions of the optical axes 30A are the same. It has a liquid crystal alignment pattern radially provided from the center.
  • the optic axis 30A is oriented in a number of directions outward from the center of the optically anisotropic layer 3, such as the direction indicated by arrow A1 , the direction indicated by arrow A2 , the direction indicated by arrow A3, and the direction indicated by arrow A3 . It changes while rotating continuously along the directions indicated by .
  • Circularly polarized light incident on the optically anisotropic layer 3 having this liquid crystal alignment pattern changes its absolute phase in individual local regions where the orientation of the optical axis of the liquid crystal compound 30 is different. At this time, the amount of change in each absolute phase differs depending on the direction of the optical axis of the liquid crystal compound 30 on which the circularly polarized light is incident.
  • the optically anisotropic layer 3 having such a concentric liquid crystal orientation pattern that is, a liquid crystal orientation pattern in which the optic axis rotates continuously and changes radially, has a rotation direction of the optic axis of the liquid crystalline compound 30 and Depending on the direction of the incident circularly polarized light, the incident light can be transmitted as divergent or convergent light. That is, by making the liquid crystal alignment pattern of the optically anisotropic layer concentric, the optically anisotropic layer functions as, for example, a convex lens or a concave lens.
  • one period ⁇ in which the optical axis rotates 180° in the liquid crystal alignment pattern is defined as the optical anisotropy. It is preferable to gradually shorten from the center of the optical layer 3 outward in one direction in which the optical axis rotates continuously. The angle of refraction of light with respect to the incident direction increases as one period ⁇ in the liquid crystal alignment pattern becomes shorter.
  • the optically anisotropic layer 3 can further improve the light focusing power, and the performance as a convex lens can be improved.
  • the optic axis rotates continuously from the center of the optically anisotropic layer 3 in one cycle ⁇ in which the optic axis rotates 180° in the liquid crystal orientation pattern. It is preferable to rotate the direction in the opposite direction and gradually shorten in the outward direction in one direction. The angle of refraction of light with respect to the incident direction increases as one period ⁇ in the liquid crystal alignment pattern becomes shorter.
  • the optically anisotropic layer by gradually shortening one period ⁇ in the liquid crystal alignment pattern from the center of the optically anisotropic layer 3 toward the outer direction in which the optical axis continuously rotates, the optically anisotropic layer
  • the light divergence power of 3 can be further improved, and the performance as a concave lens can be improved.
  • one period ⁇ of the concentric liquid crystal alignment pattern may be gradually lengthened from the center of the optically anisotropic layer 3 toward the outer direction in which the optical axis continuously rotates. good.
  • the optical axis it is also possible to use a configuration having regions with partially different periods ⁇ in one continuously rotating direction.
  • the laminate may have an optically anisotropic layer with a uniform period ⁇ over the entire surface and an optically anisotropic layer having regions with different periods ⁇ .
  • FIGS. 1 In this way, in one direction in which the optic axis rotates continuously, the configuration in which one period ⁇ in which the optic axis rotates 180° is changed is shown in FIGS. It is also possible to use a configuration in which the optical axis 30A of is continuously rotated and changed. For example, by gradually shortening one period ⁇ of the liquid crystal alignment pattern in the x-direction, it is possible to obtain a laminate that transmits light so as to condense the light. Further, by reversing the direction in which the optical axis is rotated by 180° in the liquid crystal alignment pattern, it is possible to obtain a laminate that transmits light so as to diffuse only in the x direction.
  • An optical element of the present invention has the laminate described above.
  • the use of the optical element is not particularly limited, for example, an optical path changing member, a light condensing element, a light diffusing element in a predetermined direction, a diffraction element, etc. in an academic device, which transmits light in a direction different from the incident direction, It can be used for various purposes.
  • a particularly preferred use is a light guide element.
  • the light guide element typically includes a light guide plate and a diffractive element disposed on the light guide plate (preferably spaced from the light guide plate).
  • the optical element of the present invention is suitable for use as a diffraction element.
  • the exposed film was exposed using the exposure apparatus of FIG. 5 of WO 2020/022496 to form an alignment film P-1 having an alignment pattern.
  • a laser that emits laser light with a wavelength of 325 nm was used.
  • the amount of exposure by interference light was set to 2000 mJ/cm 2 .
  • One cycle of the alignment pattern formed by the interference of the two laser beams (the length of the 180° rotation of the optical axis derived from the liquid crystalline compound) changes the crossing angle (crossing angle ⁇ ) of the two lights. controlled by
  • composition E-1 ⁇ ⁇ The following polymerizable liquid crystalline compound L-1 90 parts by mass ⁇ The following polymerizable liquid crystalline compound L-2 10 parts by mass ⁇ Polymerization initiator (manufactured by BASF, Irgacure (registered trademark) 819) 3.00 parts by mass Leveling agent T-1 below 0.08 parts by mass Methyl ethyl ketone 927.7 parts by mass ⁇ ⁇
  • Polymerizable liquid crystalline compound L-1 (corresponding to a specific liquid crystalline tolan compound)
  • the optically anisotropic layer was formed by coating the composition E-1 on the alignment film P-1 in multiple layers.
  • Multi-layer coating means that the first layer composition E-1 is first applied on the alignment film, heated, cooled, and then UV-cured to prepare a liquid crystal fixing layer. It refers to repeating the process of coating in multiple layers, heating and cooling in the same way, and then UV curing.
  • the above composition E-1 was applied on the alignment film P-1, the coating film was heated on a hot plate to 80 ° C., then cooled to 80 ° C., and then under a nitrogen atmosphere.
  • the orientation of the liquid crystalline compound was fixed by irradiating the coating film with ultraviolet rays having a wavelength of 365 nm at an irradiation amount of 300 mJ/cm 2 using a high-pressure mercury lamp. At this time, the film thickness of the first liquid crystal layer was 0.3 ⁇ m.
  • the second and subsequent layers were overcoated on this liquid crystal layer, heated under the same conditions as the first layer, cooled, and then UV-cured to prepare a liquid crystal fixing layer (cured layer). In this manner, multiple coatings were repeated until the in-plane retardation (Re) reached 325 nm to form an optically anisotropic layer H-1.
  • the optically anisotropic layer of this example had a periodically oriented surface as shown in FIGS. 2 and 3 described above.
  • one period ⁇ for rotating the optical axis derived from the liquid crystal compound by 180° was 1.0 ⁇ m.
  • the period ⁇ was obtained by measuring the period of the light-dark pattern observed under crossed Nicols conditions using a polarizing microscope.
  • composition E-2 used in forming optically anisotropic layer H-1
  • composition E-2 was used.
  • An optically anisotropic layer H-2 was formed according to the same procedure as that for forming the optically anisotropic layer H-1.
  • composition E-2 ⁇ ⁇
  • the following polymerizable liquid crystalline compound L-3 100 parts by mass ⁇ Polymerization initiator (manufactured by BASF, Irgacure (registered trademark) 819) 3.00 parts by mass 0.08 parts by mass of leveling agent T-1 Methyl ethyl ketone 927.7 parts by mass ⁇ ⁇
  • Polymerizable liquid crystalline compound L-3 (corresponding to a specific liquid crystalline tolan compound)
  • optically anisotropic layer H-3 instead of composition E-1 used in forming optically anisotropic layer H-1, the following composition E-3 was used.
  • An optically anisotropic layer H-3 was formed according to the same procedure as that for forming the optically anisotropic layer H-1.
  • composition E-3 ⁇
  • the following polymerizable liquid crystalline compound L-4 100 parts by mass ⁇ Polymerization initiator (manufactured by BASF, Irgacure (registered trademark) 819) 3.00 parts by mass 0.08 parts by mass of leveling agent T-1 Methyl ethyl ketone 927.7 parts by mass ⁇ ⁇
  • Polymerizable liquid crystalline compound L-4 (corresponding to a specific liquid crystalline tolan compound)
  • Oxygen Barrier Layer B-2 An oxygen barrier layer coating solution O-2 having the following composition was prepared and spin-coated onto an optically anisotropic layer that had been plasma-treated using a plasma cleaner PDC-32G manufactured by Harrick Plasma. It was applied and dried on a hot plate at 100° C. for 60 seconds to form an oxygen barrier layer B-2. The thickness of the formed oxygen barrier layer B-2 was 0.97 ⁇ m.
  • Modified polyvinyl alcohol V-1 (The ratio of repeating units in the structural formula below is the mass ratio.)
  • Oxygen Barrier Layer B-3 An oxygen barrier layer coating solution O-3 having the following composition was prepared and spin-coated onto an optically anisotropic layer that had been plasma-treated using a plasma cleaner PDC-32G manufactured by Harrick Plasma. Then, an oxygen barrier layer B-3 was formed by irradiating ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 300 mJ/cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere. The thickness of the formed oxygen barrier layer B-3 was 0.95 ⁇ m.
  • Surfactant F-1 (The ratio of repeating units in the following structural formula is the mass ratio.)
  • an oxygen barrier layer coating solution O-4 having the following composition was used.
  • An oxygen barrier layer B-4 was formed in the same procedure as that for forming the oxygen barrier layer B-3, except that the oxygen barrier layer B-3 was used.
  • the thickness of the formed oxygen barrier layer B-4 was 1.01 ⁇ m.
  • Oxygen Barrier Layer B-5 An oxygen barrier layer coating solution O-5 having the following composition was prepared and spin-coated onto the optically anisotropic layer that had been plasma-treated with a plasma cleaner PDC-32G manufactured by Harrick Plasma. An operation of coating and drying on a hot plate at 100° C. for 60 seconds was repeated three times to form an oxygen barrier layer B-5. The thickness of the formed oxygen barrier layer B-5 was 1.03 ⁇ m.
  • Formation of oxygen barrier layer B-6 An operation of spin-coating the oxygen barrier layer coating solution O-2 onto the oxygen barrier layer B-2 and drying on a hot plate at 100° C. for 60 seconds. was repeated twice to form an oxygen barrier layer B-6.
  • the thickness of the formed oxygen barrier layer B-6 was 3.12 ⁇ m.
  • Oxygen Barrier Layer B-7 On a commercially available triacetyl cellulose film (Z-TAC, manufactured by Fujifilm Corporation), the oxygen barrier layer coating solution O-2 was applied by spin coating, and the temperature was adjusted to 100°C. An operation of drying on a hot plate of 60 seconds for 60 seconds was repeated three times to form an oxygen barrier layer on Z-TAC.
  • the oxygen barrier layer B-7 was formed by laminating the oxygen barrier layer on Z-TAC on the optically anisotropic layer using Soken Kagaku Co., Ltd. adhesive SK2057, and then peeling off the triacetyl cellulose film. formed. The thickness of the formed oxygen barrier layer B-7 was 3.05 ⁇ m.
  • Oxygen Barrier Layer B-8 On a commercially available triacetyl cellulose film (Z-TAC, manufactured by Fujifilm Corporation), the oxygen barrier layer coating solution O-2 was applied by spin coating at 100°C. hot plate for 60 seconds to form an oxygen barrier layer on the Z-TAC.
  • the glass and alignment film P-1 are peeled off from the optically anisotropic layer, and an oxygen barrier layer on Z-TAC is formed on the peeled surface side of the optically anisotropic layer using Soken Kagaku Co., Ltd.'s adhesive SK2057. was laminated, and then Z-TAC was peeled off to form an oxygen barrier layer B-8.
  • the thickness of the formed oxygen barrier layer B-8 was 0.99 ⁇ m.
  • a lidded measuring cup was then prepared by placing 20 g of dried calcium chloride in the measuring cup and then lidding with the circular sample. This lidded measuring cup was left for 24 hours under conditions of 40° C. and 90% RH in a constant temperature and humidity chamber.
  • the water vapor transmission rate (unit: g/(m2 ⁇ day)) of the circular sample was calculated from the change in the mass of the measuring cup with lid before and after the standing. After the above measurements were performed three times, the average value of the three measurements was calculated and taken as the water vapor transmission rate of the water vapor barrier layer.
  • the water vapor transmission rate of Zeonor Film (registered trademark) ZB12 manufactured by Zeon Corp. at 40° C. and 90% RH determined by the above measurement method was 20 g/(m 2 ⁇ day) or less.
  • Laminates of Examples 1-9 Oxygen barrier layer (lower side)/optically anisotropic layer/oxygen barrier layer (upper side)
  • Laminate of Example 10 Oxygen barrier layer (lower side)/optically anisotropic layer/oxygen barrier layer (upper side)/water vapor barrier layer (upper side)
  • Laminates of Comparative Examples 1-3 Oxygen barrier layer (lower side)/optically anisotropic layer
  • the oxygen permeability coefficient of the oxygen barrier layer was measured under the following conditions. In measuring the oxygen permeability coefficient, the oxygen permeability coefficient of the oxygen barrier layer alone, excluding B-1 (corresponding to glass), was determined by the following procedure. Following “(6) Formation of oxygen barrier layer B-7”, an oxygen barrier layer was formed on Z-TAC (the thickness of each oxygen barrier layer was set to the predetermined thickness described above (for example, oxygen barrier layer B-7). 0.97 ⁇ m for layer B-2)). Next, the oxygen permeability coefficient of the obtained Z-TAC with an oxygen barrier layer was obtained by the following procedure.
  • the oxygen permeability coefficient of Z-TAC is also determined by the following procedure, and the oxygen permeability coefficient of Z-TAC with an oxygen barrier layer is divided by the oxygen permeability coefficient of Z-TAC to obtain the oxygen permeability of the oxygen barrier layer alone. Permeability coefficients were calculated. Test method: ISO 15105-2 (isobaric method) Tester: Oxygen permeability tester made by partially remodeling the model 3600 oxygen concentration meter manufactured by Huck Ultra Analytical (calibration and calibration by Mocon oxygen permeability tester OX-TRAN 2/10 type) Test temperature: 25°C Test humidity: relative humidity 50% RH Test gas: Air (oxygen content)
  • the measured oxygen permeability coefficient was evaluated based on the following evaluation criteria. ⁇ Evaluation Criteria> “A”: oxygen permeability coefficient of 1.0 ⁇ 10 ⁇ 13 [cm 3 cm/(cm 2 s mmHg)] or less “B”: oxygen permeability coefficient of 1.0 ⁇ 10 ⁇ 13 [cm 3 ⁇ cm / (cm 2 ⁇ s ⁇ mmHg)] more than 1.0 ⁇ 10 -12 [cm 3 ⁇ cm / (cm 2 ⁇ s ⁇ mmHg)] or less "C”: oxygen permeability coefficient is 1.0 ⁇ 10 -12 [ cm3 ⁇ cm/( cm2 ⁇ s ⁇ mmHg)] over
  • the value obtained by dividing the measured oxygen permeability coefficient by the film thickness was evaluated based on the following evaluation criteria.
  • A The value obtained by dividing the oxygen permeability coefficient [cm 3 ⁇ cm / (cm 2 ⁇ s ⁇ mmHg)] by the film thickness [ ⁇ m] is 1.0 ⁇ 10 -13 or less
  • B Oxygen permeability coefficient [ cm 3 ⁇ cm / (cm 2 ⁇ s ⁇ mmHg)] divided by the film thickness [ ⁇ m] is more than 1.0 ⁇ 10 -13 and 1.0 ⁇ 10 -12 or less
  • C oxygen permeability coefficient [ cm 3 cm/(cm 2 s mmHg)] divided by film thickness [ ⁇ m] exceeds 1.0 ⁇ 10 ⁇ 12
  • the optically anisotropic layer contains a specific tolan compound and another liquid crystalline compound in equal amounts
  • the average ⁇ D x ⁇ D 1 ⁇ W 1 + ⁇ D 2 ⁇ W 2 (where ⁇ D 1 and ⁇ D 2 are , respectively represent ⁇ D of the specific tolan compound and other liquid crystalline compounds, and W 1 and W 2 represent 0.5).
  • ⁇ HSP value ⁇ 4 ⁇ ( ⁇ D A - ⁇ D B ) 2 + ( ⁇ P A - ⁇ P B ) 2 + ( ⁇ H A - ⁇ H B ) 2 ⁇ 0.5
  • ⁇ D A , ⁇ P A and ⁇ H A are the average ⁇ D x and the average ⁇ P of the specific tolan compound and the other liquid crystalline compound.
  • ⁇ D A , ⁇ P A and ⁇ H A represent ⁇ D, ⁇ P and ⁇ H of the specific tolan compound, respectively.
  • ⁇ D B , ⁇ P B , and ⁇ H B represent ⁇ D, ⁇ P, and ⁇ H, which are the main components of the oxygen barrier layer.
  • ⁇ HSP was evaluated according to the following evaluation criteria. ⁇ Evaluation Criteria> "A”: ⁇ HSP is 5.0 MPa 0.5 or more "B”: ⁇ HSP is 5.0 MPa less than 0.5
  • the transmittance of the oxygen barrier layer was measured under the following conditions. In measuring the transmittance, the transmittance of the oxygen barrier layer alone, excluding B-1 (corresponding to glass), was obtained by the following procedure. Following “(6) Formation of oxygen barrier layer B-7”, an oxygen barrier layer was formed on Z-TAC (the thickness of each oxygen barrier layer was set to the predetermined thickness described above (for example, oxygen barrier layer B-7). 0.97 ⁇ m for layer B-2)). Next, the transmittance of Z-TAC with an oxygen barrier layer was measured using a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation.
  • the transmittance of Z-TAC was separately measured and corrected to calculate the average transmittance of visible light with a wavelength of 400 to 700 nm for the oxygen barrier layer alone.
  • the measurement was implemented in a 25 degreeC environment.
  • the transmittance of each of the oxygen barrier layers B-1 to B-8 was 80% or more.
  • An evaluation optical system was prepared in which a light source for evaluation, a polarizer, a quarter-wave plate, an optical element G (corresponding to each laminate of Examples and Comparative Examples), and a screen were arranged in this order.
  • a laser pointer with a wavelength of 650 nm was used as a light source for evaluation, and SAQWP05M-700 manufactured by Thorlab was used as a quarter-wave plate.
  • the slow axis of the quarter-wave plate was arranged at an angle of 45° with respect to the absorption axis of the polarizer.
  • the optical element G was arranged with the lower oxygen barrier layer facing the light source.
  • the diffraction efficiency was measured at a point 1 cm from the outer circumference of the optical element toward the center, and evaluation was performed based on the following evaluation criteria. The higher the diffraction efficiency after the test, the better the light resistance. In other words, it means that photodegradation is suppressed and high diffraction efficiency is exhibited even after the test. Table 1 shows the results. "A”: Diffraction efficiency is 97% or more. "B”: The diffraction efficiency is 95% or more and less than 97%. “C”: The diffraction efficiency is 90% or more and less than 95%. “D”: The diffraction efficiency is 80% or more and less than 90%. “E”: The diffraction efficiency is less than 80%.
  • the column "Direct lamination with optically anisotropic layer” indicates the state of arrangement of the optically anisotropic layer and the upper (or lower) oxygen barrier layer, and "No” indicates direct lamination. It represents the case of non-bonding (in other words, the case of intervening another layer), and "to” represents the case of direct lamination.
  • “no” means that no water vapor barrier layer is provided
  • “yes” means that the upper oxygen barrier layer is provided on the side opposite to the optically anisotropic layer. This indicates that a water vapor barrier layer has been placed on the surface.
  • both of the pair of oxygen barrier layers have an oxygen permeability coefficient of 1.0 ⁇ 10 ⁇ 12 [cm 3 cm/(cm 2 s mmHg)] at 25° C. and 50% RH. It was confirmed that the light resistance was further improved when the ratio was below (see Example 5, etc.). Moreover, it was confirmed from the comparison with the examples that the light resistance was further improved when the distance ⁇ HSP value obtained from the predetermined formula was set to 0.5 or more at 5.0 MPa (see Example 6, etc.).
  • the light resistance is further improved when the laminate further includes a water vapor barrier layer having a predetermined physical property (see Example 10, etc.). Further, from the comparison of Examples, it was confirmed that when at least one of the oxygen barrier layers and the optically anisotropic layer were arranged so as to be in direct contact with each other, the light resistance was further improved (Examples 4 and 12, etc.). reference).

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025013901A1 (ja) * 2023-07-11 2025-01-16 富士フイルム株式会社 液晶組成物、光学異方性層、硬化膜、回折素子、化合物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0959219A (ja) * 1995-08-24 1997-03-04 Citizen Watch Co Ltd トラン化合物およびそれを含有する液晶組成物
JP2001249222A (ja) * 2000-03-02 2001-09-14 Teijin Ltd 反射防止フィルム及びそれを用いてなる発光表示素子
JP2008505235A (ja) * 2004-07-02 2008-02-21 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 液晶媒体
WO2018034216A1 (ja) * 2016-08-17 2018-02-22 富士フイルム株式会社 化合物、組成物、硬化物、光学異方体、反射膜
JP2019028196A (ja) * 2017-07-28 2019-02-21 株式会社サンリッツ 偏光板および画像表示装置
WO2020022496A1 (ja) * 2018-07-27 2020-01-30 富士フイルム株式会社 光学素子、光配向パターンの形成方法および光学素子の製造方法
WO2020175448A1 (ja) * 2019-02-27 2020-09-03 富士フイルム株式会社 光学異方性膜、積層体、円偏光板、表示装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0959219A (ja) * 1995-08-24 1997-03-04 Citizen Watch Co Ltd トラン化合物およびそれを含有する液晶組成物
JP2001249222A (ja) * 2000-03-02 2001-09-14 Teijin Ltd 反射防止フィルム及びそれを用いてなる発光表示素子
JP2008505235A (ja) * 2004-07-02 2008-02-21 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 液晶媒体
WO2018034216A1 (ja) * 2016-08-17 2018-02-22 富士フイルム株式会社 化合物、組成物、硬化物、光学異方体、反射膜
JP2019028196A (ja) * 2017-07-28 2019-02-21 株式会社サンリッツ 偏光板および画像表示装置
WO2020022496A1 (ja) * 2018-07-27 2020-01-30 富士フイルム株式会社 光学素子、光配向パターンの形成方法および光学素子の製造方法
WO2020175448A1 (ja) * 2019-02-27 2020-09-03 富士フイルム株式会社 光学異方性膜、積層体、円偏光板、表示装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025013901A1 (ja) * 2023-07-11 2025-01-16 富士フイルム株式会社 液晶組成物、光学異方性層、硬化膜、回折素子、化合物

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