WO2022045243A1 - 液晶組成物、液晶硬化層、光学フィルム、偏光板および画像表示装置 - Google Patents

液晶組成物、液晶硬化層、光学フィルム、偏光板および画像表示装置 Download PDF

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WO2022045243A1
WO2022045243A1 PCT/JP2021/031332 JP2021031332W WO2022045243A1 WO 2022045243 A1 WO2022045243 A1 WO 2022045243A1 JP 2021031332 W JP2021031332 W JP 2021031332W WO 2022045243 A1 WO2022045243 A1 WO 2022045243A1
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liquid crystal
group
carbon atoms
crystal composition
substituent
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French (fr)
Japanese (ja)
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聡一 鷲見
達也 岩▲崎▼
祐貴 中村
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202180052487.6A priority Critical patent/CN115989299A/zh
Priority to JP2022545697A priority patent/JP7440647B2/ja
Publication of WO2022045243A1 publication Critical patent/WO2022045243A1/ja
Priority to US18/166,910 priority patent/US20230183574A1/en
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    • 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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    • C09K19/60—Pleochroic dyes
    • C09K19/601—Azoic
    • 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
    • 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
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    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/35—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being liquid crystals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
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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
    • C—CHEMISTRY; METALLURGY
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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
    • C09K19/20—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
    • C09K2019/205—Ph-Ph-Ph-COO-Ph
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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
    • C09K19/20—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
    • C09K2019/2078—Ph-COO-Ph-COO-Ph
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a liquid crystal composition, a liquid crystal curing layer, an optical film, a polarizing plate, and an image display device.
  • Optical films such as optical compensation sheets and retardation films are used in various image display devices for eliminating image coloring or expanding the viewing angle.
  • a stretched birefringence film has been used as the optical film, but in recent years, it has been proposed to use an optical film having an optically anisotropic layer made of a liquid crystal compound instead of the stretched birefringence film.
  • Patent Document 1 describes a polymerizable composition containing one or more kinds of polymerizable rod-shaped liquid crystal compounds showing a smectic phase ([claim]. 1] [0048]), and it is described that a non-liquid crystal polyfunctional polymerizable compound is blended as an optional component ([0050]).
  • Patent Document 2 describes a composition containing a liquid crystal compound exhibiting a smectic phase and a non-liquid crystal compound satisfying a predetermined condition ([0022] [0023]).
  • the present inventors have examined the compositions described in Patent Documents 1 and 2.
  • an additive for example, a non-liquid crystal compound
  • the additive is added. It was clarified that the phase transition temperature from the smectic phase to the nematic phase becomes low depending on the type of the liquid crystal, and that an orientation defect occurs in the formed liquid crystal cured layer (for example, an optically anisotropic layer).
  • the present invention relates to a liquid crystal composition, a liquid crystal cured layer, an optical film, which can suppress a decrease in the phase transition temperature from a smectic phase to a nematic phase and suppress an orientation defect in the formed liquid crystal cured layer.
  • An object of the present invention is to provide a polarizing plate and an image display device.
  • the present inventors have a predetermined relationship between the I / O values of the liquid crystal compound and the freezing point lowering agent in the liquid crystal composition containing the liquid crystal compound showing the smectic phase and the freezing point lowering agent.
  • the liquid crystal compound is a compound represented by the following formula (I).
  • SP1 and SP2 each independently represent a spacer group.
  • MG represents a mesogen group.
  • Am represents the I / O value of the mesogen group of the liquid crystal compound.
  • As represents the I / O value of the spacer group of the liquid crystal compound.
  • Am ⁇ As it represents the I / O value of the spacer group having the larger I / O value, and if Am> As.
  • Aa represents the I / O value of the freezing point depression agent.
  • the liquid crystal composition according to [1], wherein the freezing point depressant is a non-liquid crystal compound.
  • the liquid crystal composition according to any one of [1] to [5], wherein the molar extinction coefficient of the freezing point depressant at a wavelength of 350 to 750 nm is 100 (l / mol ⁇ cm) or less.
  • Re (450) represents an in-plane lettering of the optically anisotropic layer at a wavelength of 450 nm
  • Re (550) represents an in-plane letter of the optically anisotropic layer at a wavelength of 550 nm. Represents the optics.
  • [12] A liquid crystal curing layer obtained by immobilizing the orientation state of the liquid crystal composition according to any one of [1] to [11].
  • the liquid crystal cured layer according to [12] which shows a diffraction peak derived from a periodic structure in an X-ray diffraction measurement.
  • the liquid crystal compound is a compound represented by the following formula (I).
  • SP1 and SP2 each independently represent a spacer group.
  • MG represents a mesogen group.
  • Am represents the I / O value of the mesogen group of the liquid crystal compound.
  • As represents the I / O value of the spacer group of the liquid crystal compound.
  • the structures of SP1 and SP2 in the above formula (I) are different from each other, if Am ⁇ As, it represents the I / O value of the spacer group having the larger I / O value, and if Am> As.
  • Aa represents the I / O value of the freezing point depression agent.
  • a liquid crystal composition a liquid crystal cured layer, an optical film, which can suppress a decrease in the phase transition temperature from a smectic phase to a nematic phase and suppress an orientation defect in the formed liquid crystal cured layer.
  • a polarizing plate and an image display device can be provided.
  • the present invention will be described in detail.
  • the description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • a substance corresponding to each component may be used alone or in combination of two or more.
  • the content of the component means the total content of the substances used in combination unless otherwise specified.
  • the bonding direction of the divalent group (for example, -CO-O-) described is not particularly limited unless the bonding position is specified, and for example, the formula (for example) described later will be used.
  • D 1 in II) is -CO-NR-, if the position bonded to the G 1 side is * 1 and the position bonded to the Ar side is * 2, D 1 is * 1-. It may be CO-NR- * 2 or * 1-NR-CO- * 2.
  • the liquid crystal composition of the present invention is a liquid crystal composition containing a liquid crystal compound exhibiting a smectic phase and a freezing point lowering agent, wherein the liquid crystal compound is a compound represented by the following formula (I) and the liquid crystal composition is described below.
  • the liquid crystal composition of the present invention contains two or more liquid crystal compounds exhibiting a smectic phase
  • the liquid crystal composition has the following formulas (1) and the following formulas in relation to any one of the liquid crystal compounds. (2-1) or (2-2) may be satisfied.
  • the liquid crystal composition of the present invention contains two or more kinds of freezing point depressants
  • the liquid crystal composition has the following formulas (1) and the following formulas (1) in relation to any one of the freezing point depressants. 2-1) or (2-2) may be satisfied.
  • SP1 and SP2 each independently represent a spacer group.
  • MG represents a mesogen group.
  • Am represents the I / O value of the mesogen group of the liquid crystal compound.
  • As represents the I / O value of the spacer group of the liquid crystal compound.
  • Am ⁇ As it represents the I / O value of the spacer group having the larger I / O value, and if Am> As.
  • Aa represents the I / O value of the freezing point depression agent.
  • the "I / O value” is used as a means for predicting various physicochemical properties of an organic compound.
  • Organic matter can be obtained by comparing the number of carbon atoms, and inorganic matter can be obtained by comparing the boiling points of hydrocarbons having the same number of carbon atoms.
  • one (-CH 2- ) (actually C) is determined to have an organic value of 20, and the inorganic value is determined to be 100 because of the influence of the hydroxyl group (-OH) on the boiling point.
  • the "inorganic group table” is shown in which the values of other substituents (inorganic groups) are obtained based on the inorganic value 100 of ( ⁇ OH).
  • the ratio I / O of the inorganic value (I) and the organic value (O) obtained for each molecule is defined as "I / O value”. It is shown that the hydrophilicity increases as the I / O value increases, and the hydrophobicity increases as the I / O value decreases.
  • the "I / O value” is determined by the method described in "New Edition: Organic Conceptual Diagram-Basics and Applications” by Yoshio Koda et al., November 2008, Sankyo Publishing. (I) / organic (O) ”value.
  • the liquid crystal compound is a compound represented by the above formula (I), and the liquid crystal composition containing the liquid crystal compound and the freezing point lowering agent is the above formula (1) and the above formula (2-1) or (2).
  • the liquid crystal compound is a compound represented by the above formula (I), and by satisfying the above formula (1), the mesogen group and the spacer group are difficult to be compatible with each other.
  • the freezing point depression agent inhibits the arrangement of spacer portions in the liquid crystal compound without inhibiting the packing of mesogen groups in the liquid crystal compound required for the expression of the smectic phase, and suppresses crystallization. It is thought that there is. It is considered that such an action by the freezing point depressant makes it possible to stably lower the aging temperature of the liquid crystal layer before curing to a low temperature, and as a result, the orientation defect in the formed liquid crystal cured layer can be suppressed. ..
  • each component of the liquid crystal composition of the present invention will be described in detail.
  • the liquid crystal compound contained in the liquid crystal composition of the present invention is a liquid crystal compound exhibiting smectic properties.
  • the smectic phase indicated by the liquid crystal compound means a state in which molecules aligned in one direction have a layered structure.
  • the smectic phase is not particularly limited, but a higher-order smectic phase is preferable.
  • the high-order smectic phase referred to here is the smectic A phase, the smectic B phase, the smectic D phase, the smectic E phase, the smectic F phase, the smectic G phase, the smectic H phase, the smectic I phase, the smectic J phase, and the smectic K phase.
  • the smectic L phase among which the smectic A phase, the smectic B phase, the smectic F phase, the smectic I phase, the slanted smectic F phase and the slanted smectic I phase are more preferable, and the smectic A phase and the smectic B phase are particularly preferable. ..
  • the liquid crystal compound contained in the liquid crystal composition of the present invention is a compound represented by the following formula (I).
  • SP1 and SP2 each independently represent a spacer group.
  • MG represents a mesogen group.
  • the mesogen group is a group showing the main skeleton of the liquid crystal molecule that contributes to the formation of the liquid crystal, and is a group composed of a continuous portion of the ring structure.
  • the mesogen group for example, "Frussige Crystal in Tablelen II” (VEB Manual Verlag fur Grundstoff Industrie, Leipzig, 1984), especially the description on pages 7 to 16 and the liquid crystal, and the liquid crystal. You can refer to the edition, LCD Handbook (Maruzen, 2000), especially the description in Chapter 3.
  • the mesogen group for example, a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group is preferable.
  • the spacer group is a structure other than the mesogen group contained in the liquid crystal compound, and refers to a group from the tip of the ring structure constituting the mesogen group to the end of the molecule.
  • the absolute value of the difference between the I / O value of the mesogen group and the I / O value of the spacer group is 0.2. It is the above-mentioned compound, and it is preferable that it is a compound having a value of 0.2 to 2.0.
  • the definition of the I / O value is as described above, but when calculating the I / O value of the mesogen group and the I / O value of the spacer group in the liquid crystal compound, the boundary between the mesogen group and the spacer group is used. The binding portion located at is included in both the mesogen group and the spacer group.
  • the liquid crystal compound represented by the following formula (L-1) is an I / O having a mesogen group represented by the following formula (mL-1) and a spacer group represented by the following formula (sL-1). Calculate the value.
  • the optically anisotropic layer prepared by using the above liquid crystal compound satisfies the following formula (3) for the reason that the liquid crystal orientation of the produced liquid crystal cured layer becomes better.
  • Re (450) represents an in-plane lettering of the optically anisotropic layer at a wavelength of 450 nm
  • Re (550) represents an in-plane letter of the optically anisotropic layer at a wavelength of 550 nm.
  • the in-plane retardation value is a value measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Optoscience).
  • the optically anisotropic layer to be measured for the in-plane retardation that is, the optically anisotropic layer prepared by using the above liquid crystal compound
  • the optically anisotropic layer prepared by the following procedure is used. That is, the liquid crystal composition L having the following composition is applied to a glass substrate with a rubbing-treated polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.) by spin coating. Next, the coating film is heated and oriented at a temperature indicating liquid crystal property to form a liquid crystal layer. Next, the film is cooled from a temperature exhibiting liquid crystallinity to a temperature 40 ° C. lower, and the orientation is fixed by irradiation with ultraviolet rays of 1000 mJ / cm 2 , to produce an optically anisotropic film.
  • SE-150 rubbing-treated polyimide alignment film
  • the optically anisotropic layer produced by using the above liquid crystal compound has the following formula (4) for the reason that the optical compensatory property of the produced liquid crystal cured layer (particularly the optically anisotropic layer) is further improved. It is preferable to meet.
  • the optically anisotropic layer to be measured for the in-plane retardation the optically anisotropic layer prepared by the above procedure is used. Re (450) / Re (550) ⁇ 1.0 ...
  • Re (450) represents an in-plane lettering of the optically anisotropic layer at a wavelength of 450 nm
  • Re (550) represents an in-plane letter of the optically anisotropic layer at a wavelength of 550 nm. Represents the optics.
  • the liquid crystal compound is preferably a compound represented by the following formula (II) for the reason that the liquid crystal orientation of the produced liquid crystal cured layer becomes better.
  • P 1 -L 1 -D 5- (A 1 ) a1 -D 3- (G 1 ) g1 -D 1- [Ar-D 2 ] q1- (G 2 ) g2 -D 4- (A 2 ) a2- D 6 -L 2 -P 2 ... (II)
  • G 5 independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. However, when q1 is 2 , the plurality of D2s may be the same or different. Further, in the above formula (II), G 1 and G 2 each independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or carbon which may have a substituent. Representing a divalent alicyclic hydrocarbon group of number 5 to 20, one or more of -CH 2- constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. May be.
  • a 1 and A 2 each independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or carbon which may have a substituent. Representing a divalent alicyclic hydrocarbon group of number 5 to 20, one or more of -CH 2- constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. May be.
  • L 1 and L 2 are independently single-bonded, a linear or branched alkylene group having 1 to 14 carbon atoms, or a linear chain having 1 to 14 carbon atoms.
  • Q represents a substituent.
  • P 1 and P 2 each independently represent a monovalent organic group, and at least one of P 1 and P 2 represents a polymerizable group.
  • Ar is an aromatic ring represented by the formula (Ar- 3 ) described later, at least one of P1 and P2 and P3 and P4 in the formula (Ar- 3 ) described later is polymerized. Represents a sex group.
  • Ar is an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a divalent ring having 5 to 20 carbon atoms which may have a substituent.
  • Representing an alicyclic hydrocarbon group one or more of —CH 2 ⁇ constituting the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—.
  • q1 the plurality of Ars may be the same or different.
  • a1, a2, g1 and g2 are preferably 1 for the reason that the liquid crystal composition of the present invention tends to show the liquid crystal state of the smectic phase. Further, it is preferable that both a1 and a2 are 0 and both g1 and g2 are 1 for the reason that the durability of the produced liquid crystal cured layer becomes better.
  • q1 is preferably 1.
  • examples of the divalent linking group represented by one aspect of D 1 , D 2 , D 3 , D 4 , D 5 and D 6 include -CO-, -O-, and -CO-.
  • R 1 , R 2 and R 5 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. Of these, any of -CO-, -O-, and -CO-O- is preferable.
  • examples of the aromatic ring having 6 to 20 carbon atoms represented by one aspect of G 1 and G 2 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring.
  • Aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring; Of these, a benzene ring (for example, a 1,4-phenyl group) is preferable.
  • the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of G 1 and G 2 is preferably a 5-membered ring or a 6-membered ring.
  • the alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferable.
  • the divalent alicyclic hydrocarbon group represented by G 1 and G 2 for example, the description in paragraph [0078] of JP2012-21068A can be referred to, and the content thereof is incorporated in the present specification. ..
  • G 1 and G 2 in the above formula (II) are preferably cycloalkane rings for the reason that the durability of the produced liquid crystal cured layer becomes better.
  • the cycloalkane ring include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, a cyclododecane ring, and the like.
  • a cyclohexane ring is preferred, a 1,4-cyclohexylene group is more preferred, and a trans-1,4-cyclohexylene group is even more preferred.
  • G 1 and G 2 may have a substituent having an aromatic ring having 6 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms.
  • an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamide group, an alkenyl group, an alkynyl group, a halogen atom, a cyano group, a nitro group examples thereof include an alkylthiol group and an N-alkylcarbamate group, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n).
  • -Butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc. are more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group or an ethyl group is particularly preferable.
  • an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and an alkoxy group having 1 carbon atom is preferable.
  • Alkoxy groups of -4 are more preferred, and methoxy or ethoxy groups are particularly preferred.
  • alkoxycarbonyl group examples include a group in which an oxycarbonyl group (—O—CO— group) is bonded to the alkyl group exemplified above, and among them, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group or an isopropoxy.
  • a carbonyl group is preferred, a methoxycarbonyl group is more preferred.
  • alkylcarbonyloxy group examples include a group in which a carbonyloxy group (-CO-O- group) is bonded to the alkyl group exemplified above, and among them, a methylcarbonyloxy group, an ethylcarbonyloxy group, and an n-propylcarbonyloxy group.
  • a group or an isopropylcarbonyloxy group is preferable, and a methylcarbonyloxy group is more preferable.
  • the halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom or a chlorine atom is preferable.
  • the aromatic rings having 6 to 20 or more carbon atoms shown in one aspect of A 1 and A 2 are the same as those described in G 1 and G 2 in the above formula (II). Can be mentioned. Further, in the above formula (II), as the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of A 1 and A 2 , in G 1 and G 2 in the above formula (II). Examples are similar to those described. Regarding A 1 and A 2 , the substituent which the aromatic ring having 6 to 20 carbon atoms or the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms may have is the above formula (II). Examples include the same substituents that G 1 and G 2 may have.
  • examples of the linear or branched alkylene group having 1 to 14 carbon atoms represented by one aspect of L 1 and L 2 include a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene. Preferred examples thereof include a group, a hexylene group, a methylhexylene group, a heptylene group and the like.
  • L 1 and L 2 one or more of -CH 2- constituting a linear or branched alkylene group having 1 to 14 carbon atoms are -O-, -S-, and -NH. It may be a divalent linking group substituted with ⁇ , ⁇ N (Q) ⁇ or —CO—, and the substituent represented by Q includes G1 and G in the above formula (II). Examples thereof include the same substituents that 2 may have.
  • examples of the monovalent organic group represented by P 1 and P 2 include an alkyl group, an aryl group, and a heteroaryl group.
  • the alkyl group may be linear, branched or cyclic, but linear is preferred.
  • the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.
  • the aryl group may be monocyclic or polycyclic, but monocyclic is preferable.
  • the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the heteroaryl group may be monocyclic or polycyclic.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
  • heteroaryl group a nitrogen atom, a sulfur atom and an oxygen atom are preferable.
  • the heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents that G 1 and G 2 in the above formula (II) may have.
  • the polymerizable group represented by at least one of P 1 and P 2 is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
  • a known radically polymerizable group can be used, and suitable examples thereof include an acryloyloxy group and a methacryloyloxy group.
  • the acryloyloxy group is generally faster in terms of the polymerization rate, and the acryloyloxy group is preferable from the viewpoint of improving productivity, but the methacryloyloxy group can also be used as the polymerizable group in the same manner.
  • a known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and vinyloxy.
  • the group can be mentioned.
  • an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
  • particularly preferable polymerizable groups include polymerizable groups represented by any of the following formulas (P-1) to (P-20).
  • both P 1 and P 2 in the above formula (II) are polymerizable groups because the durability of the liquid crystal cured layer produced is good, and acryloyloxy is preferable. More preferably, it is a group or a methacryloyloxy group.
  • examples of the aromatic ring having 6 to 20 or more carbon atoms represented by one aspect of Ar include the same aromatic rings as those described in G1 and G2 in the above formula ( II ). ..
  • the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of Ar is the one described in G1 and G2 in the above formula ( II ). Similar things can be mentioned.
  • the substituent that may be contained in an aromatic ring having 6 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms is G 1 in the above formula (II). And similar substituents that G 2 may have.
  • Ar in the above formula (II) is represented by the following formulas (Ar-1) to (Ar) for the reason that the optical compensatory property of the produced liquid crystal cured layer (particularly the optically anisotropic layer) is further improved. It is preferable to represent any aromatic ring selected from the group consisting of the groups represented by -7). In the following formulas (Ar-1) to (Ar-7), * represents the bonding position with D 1 or D 2 in the above formula (II).
  • Q 1 represents N or CH
  • Q 2 represents -S-, -O-, or -N (R 6 )-
  • R 6 is a hydrogen atom or Represents an alkyl group having 1 to 6 carbon atoms
  • Y1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent and an aromatic group having 3 to 12 carbon atoms which may have a substituent.
  • a group heterocyclic group or an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is represented, and one or more of -CH 2- constituting the alicyclic hydrocarbon group is -O. -, -S- or -NH- may be substituted.
  • alkyl group having 1 to 6 carbon atoms indicated by R 6 include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl.
  • Groups, n-pentyl groups, n-hexyl groups and the like can be mentioned.
  • aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y 1 include an aryl group such as a phenyl group, a 2,6-diethylphenyl group and a naphthyl group.
  • Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y 1 include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group and a pyridyl group.
  • Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms indicated by Y 1 include a cyclohexylene group, a cyclopentylene group, a norbornene group, and an adamantylene group.
  • examples of the substituent that Y 1 may have include the same substituents that G 1 and G 2 in the above formula (I) may have.
  • Z 1 , Z 2 and Z 3 are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon.
  • Nitro group, -OR 7 , -NR 8 R 9 , -SR 10 , -COOR 11 or -COR 12 where R 7 to R 12 are independently hydrogen atoms or 1 to 6 carbon atoms, respectively.
  • Z 1 and Z 2 may be bonded to each other to form an aromatic ring.
  • the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group and an ethyl group.
  • Isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, ethyl group, tert-butyl group. Groups are particularly preferred.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and an ethylcyclohexyl.
  • Monocyclic saturated hydrocarbon groups such as groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as diene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.2.10 2,6 ] decyl group, Tricyclo [3.3.1.1 3,7 ] decyl group, tetracyclo [6.2.1.1 3,6 .
  • Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
  • Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and have 6 to 12 carbon atoms.
  • Aryl groups particularly phenyl groups
  • Specific examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group. Can be mentioned.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
  • alkyl group having 1 to 6 carbon atoms indicated by R 7 to R 10 specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group.
  • Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.
  • Z 1 and Z 2 may be bonded to each other to form an aromatic ring.
  • Z 1 and Z 2 in the above formula (Ar-1) may be bonded to each other to form an aromatic ring.
  • Examples of the structure of the case include a group represented by the following formula (Ar-1a).
  • * represents the bonding position with D 1 or D 2 in the above formula (I).
  • Q 1 , Q 2 and Y 1 are the same as those described in the above formula (Ar-1).
  • A3 and A4 are independently derived from -O-, -N ( R13)-, -S-, and -CO-, respectively.
  • R 13 represents a hydrogen atom or a substituent. Examples of the substituent represented by R 13 include the same substituents that G 1 and G 2 in the above formula (II) may have.
  • X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded.
  • RC1 represents a hydrogen atom or a substituent. ] Can be mentioned.
  • substituents include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl group.
  • substituents include a carbonyl group, a sulfo group and a hydroxyl group.
  • R 2- , -CR 3 CR 4- , -NR 5- , or a divalent linking group consisting of a combination of two or more of these, and R 1 to R 5 are independent hydrogen atoms, respectively. It represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • examples of the divalent linking group include those described in D 1 , D 2 , D 3 , D 4 , D 5 and D 6 in the above formula (II).
  • L 3 and L 4 are independently single-bonded, a linear or branched alkylene group having 1 to 14 carbon atoms, or a direct group having 1 to 14 carbon atoms.
  • One or more of -CH 2- constituting a chain or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-.
  • Examples of the substituent include the same substituents that G 1 and G 2 in the above formula (II) may have.
  • examples of the alkylene group include the same groups as those described in L1 and L2 in the above formula ( II ).
  • P 3 and P 4 independently represent monovalent organic groups, respectively, and at least 1 of P 3 and P 4 and P 1 and P 2 in the above formula (II).
  • the monovalent organic group include the same groups as those described in P1 and P2 in the above formula ( II ).
  • examples of the polymerizable group include the same groups as those described in P1 and P2 in the above formula ( II ).
  • Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
  • Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic. Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
  • the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
  • Q3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • Ax and Ay include those described in paragraphs [0039] to [0995] of International Publication No. 2014/010325.
  • Specific examples of the alkyl group having 1 to 20 carbon atoms indicated by Q3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert.
  • Examples of the compound represented by the above formula (II) include the polymerizable compounds described in paragraphs [0019] to [0023] of JP-A-2019-139222; paragraphs [0059] to International Publication No. 2019/160014.
  • Compound (2-1) to compound (2-5) represented by the following formula; and the like can be mentioned.
  • the group adjacent to the acryloyloxy group represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and compound (1-14) has the position of the methyl group. Represents a mixture of different positional isomers.
  • examples of the compound represented by the above formula (II) include compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, paragraph numbers [0067] to [0073].
  • the compound described the compound represented by the general formula (II) described in JP-A-2016-0537709 (particularly, the compound described in paragraph numbers [0036] to [0043]), and JP-A-2016-081035.
  • the compounds represented by the general formula (1) described in the publication particularly, the compounds described in paragraph numbers [0043] to [0055]
  • those exhibiting smectic properties can be mentioned.
  • K (side chain structure) in (1) to (22) include compounds having side chain structures shown in Tables 1 to 3 below.
  • “*" shown in the side chain structure of K represents the bonding position with the aromatic ring.
  • the group adjacent to the acryloyloxy group and the methacryloyl group is a propylene group (methyl group becomes an ethylene group, respectively). Represents a substituted group) and represents a mixture of positional isomers with different methyl group positions.
  • the freezing point lowering agent contained in the liquid crystal composition of the present invention is related to the above-mentioned liquid crystal compound among the compounds capable of lowering the freezing point of the above-mentioned liquid crystal compound, that is, the temperature at which the liquid crystal undergoes a phase transition to a crystal.
  • the compound is not particularly limited as long as it satisfies the above formula (2-1) or (2-2).
  • the freezing point depressant is preferably a non-liquid crystal compound for the reason that the compatibility with the liquid crystal compound becomes better.
  • the compound having a molecular weight of 2000 or less is preferable, and the compound having a molecular weight of 100 to 1500 is more preferable, because the compatibility with the liquid crystal compound is better.
  • the freezing point depressant is preferably a compound having a polymerizable group because the durability of the produced liquid crystal cured layer is improved.
  • the polymerizable group include the same polymerizable groups as those described in P1 and P2 in the above formula ( II ), and among them, any one of the above formulas (P- 1 ) to (P-20).
  • the polymerizable group represented by is preferably mentioned.
  • the number of the polymerizable group is not particularly limited, but it is preferably 1 to 10 and more preferably 2 to 6.
  • the molar extinction coefficient of the freezing point lowering agent at a wavelength of 350 to 750 nm is preferably 100 (l / mol ⁇ cm) or less because the durability of the produced liquid crystal cured layer becomes better.
  • freezing point depressant examples include compounds shown below that satisfy the above formula (2-1) or (2-2) in relation to the above-mentioned liquid crystal compound.
  • the content of the freezing point depressant is 1 to 30 parts by mass with respect to 100 parts by mass of the above-mentioned liquid crystal compound, for the reason that the orientation defect in the formed liquid crystal cured layer is further suppressed. It is preferably 2 to 15 parts by mass, and more preferably 2 to 15 parts by mass.
  • the polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
  • a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
  • the photopolymerization initiator include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and ⁇ -hydrogen-substituted fragrances.
  • Group acidloin compounds described in US Pat. No. 2,725,512
  • polynuclear quinone compounds described in US Pat. Nos.
  • an oxime-type polymerization initiator is also preferable. Specific examples thereof include the initiators described in paragraphs [0049] to [0052] of International Publication No. 2017/170443.
  • the liquid crystal composition of the present invention preferably contains a dichroic substance from the viewpoint of using the liquid crystal cured layer described later as a polarizing element (light absorption anisotropic film).
  • the above-mentioned bicolor substance is not particularly limited, and is a visible light absorbing substance (bicolor dye), a light emitting substance (fluorescent substance, a phosphorescent substance), an ultraviolet absorbing substance, an infrared absorbing substance, a nonlinear optical substance, a carbon nanotube, and an inorganic substance. (For example, a quantum rod), etc., and conventionally known bicolor substances (bicolor dyes) can be used.
  • two or more kinds of dichroic substances may be used in combination.
  • a wavelength of 370 nm or more and 500 nm or more from the viewpoint of bringing a polarizing element (light absorption anisotropic film) as a liquid crystal cured layer described later into black, a wavelength of 370 nm or more and 500 nm or more. It is preferable to use at least one dichroic substance having a maximum absorption wavelength in the range of less than 500 nm and at least one dichroic substance having a maximum absorption wavelength in the range of 500 nm or more and less than 700 nm.
  • the dichroic substance may have a crosslinkable group.
  • the crosslinkable group include (meth) acryloyl group, epoxy group, oxetanyl group, styryl group and the like, and among them, (meth) acryloyl group is preferable.
  • the content of the dichroic substance is preferably 1 to 400 parts by mass with respect to 100 parts by mass of the liquid crystal compound, and 2 to 100 parts by mass. Is more preferable, and 5 to 30 parts by mass is further preferable.
  • the content of the dichroic substance is preferably 1 to 50% by mass, more preferably 2 to 40% by mass in the solid content of the liquid crystal composition.
  • the liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability when forming the liquid crystal cured layer.
  • Solvents include, for example, ketones (eg, acetone, 2-butanone, methylisobutylketone, cyclohexanone, and cyclopentanone, etc.), ethers (eg, dioxane, and tetrahydrofuran, etc.), and aliphatic hydrocarbons (eg, eg, dioxane, and tetrahydrofuran, etc.).
  • Hydrocarbons eg, cyclohexane, etc.
  • aromatic hydrocarbons eg, toluene, xylene, and trimethylbenzene, etc.
  • carbon halides eg, dichloromethane, dichloroethane, dichlorobenzene, etc.
  • alicyclic hydrocarbons eg, cyclohexane, etc.
  • esters eg, methyl acetate, ethyl acetate, and butyl acetate, etc.
  • water eg, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol, etc.), cellosolves (eg, methylserosolves, and the like).
  • Ethyl cellosolves, etc. cellosolves, etc.), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide, etc.), and amides (eg, dimethylformamide, dimethylacetamide, etc.) and the like.
  • the solvent may be used alone or in combination of two or more.
  • the liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the liquid crystal cured layer smooth and facilitating orientation control.
  • a leveling agent a fluorine-based leveling agent or a silicon-based leveling agent is preferable because it has a high leveling effect on the amount of addition, and a fluorine-based leveling agent is more preferable because it does not easily cause crying (bloom, bleed). ..
  • the leveling agent is represented by, for example, the compound described in paragraphs [0079] to [0102] of JP-A-2007-069471 and the general formula (I) described in JP-A-2013-047204.
  • the liquid crystal composition of the present invention may contain an orientation control agent, if necessary.
  • the orientation control agent can form various orientation states such as homeotropic orientation (vertical orientation), tilt orientation, hybrid orientation, and cholesteric orientation in addition to homogenius orientation, and can make a specific orientation state more uniform and more precise. It can be controlled and realized.
  • orientation control agent that promotes homogenius orientation for example, a small molecule orientation control agent and a polymer orientation control agent can be used.
  • the small molecule orientation control agent include paragraphs [0009] to [0083] of JP-A-2002-20363, paragraphs [0111]-[0120] of JP-A-2006-106662, and JP-A-2012.
  • paragraphs [0021] to [0029] of Japanese Patent Application Laid-Open No. 211306 can be referred to, and these contents are incorporated in the present specification.
  • orientation control agent for forming or promoting homeotropic orientation examples include a boronic acid compound and an onium salt compound.
  • this orientation control agent examples include paragraphs [0023] to [0032] of JP-A-2008-225281, paragraphs [0052] to [0058] of JP-A-2012-208397, and JP-A-2008-026730.
  • the compounds described in paragraphs [0024] to [0055] and paragraphs [0043] to [0055] of JP-A-2016-193869 can be referred to, and their contents are incorporated in the present specification.
  • the cholesteric orientation can be realized by adding a chiral agent to the liquid crystal composition of the present invention, and the turning direction of the cholesteric orientation can be controlled by the direction of the chiral property.
  • the pitch of the cholesteric orientation may be controlled according to the orientation restricting force of the chiral agent.
  • the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content mass in the composition.
  • the content is in this range, precipitation, phase separation, alignment defects and the like are suppressed while achieving a desired orientation state, and a uniform and highly transparent cured product can be obtained.
  • liquid crystal composition of the present invention may contain components other than those described above.
  • other components include liquid crystal compounds other than the above-mentioned liquid crystal compounds (for example, liquid crystal compounds that do not satisfy the above formula (1)), surfactants, tilt angle control agents, orientation aids, plasticizers, and the like. And a cross-linking agent.
  • the suppression method of the present invention is a method of mixing the above-mentioned freezing point depressant with the above-mentioned liquid crystal compound so as to satisfy the above-mentioned formula (1) and the above-mentioned formula (2-1) or (2-2). be.
  • the liquid crystal curable layer of the present invention is a liquid crystal curable layer obtained by immobilizing the orientation state of the liquid crystal composition of the present invention described above.
  • Examples of the method for forming the liquid crystal cured layer include a method of using the liquid crystal composition of the present invention described above to obtain a desired orientation state and then immobilizing the liquid crystal cured layer by polymerization.
  • the polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation.
  • the irradiation amount is preferably 10 mJ / cm 2 to 50 J / cm 2 , more preferably 20 mJ / cm 2 to 5 J / cm 2 , further preferably 30 mJ / cm 2 to 3 J / cm 2 , and particularly preferably 50 to 1000 mJ / cm 2 . preferable. Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.
  • the liquid crystal cured layer can be formed on an arbitrary support or alignment film in an optical film described later, or on a splitter in a polarizing plate described later.
  • the liquid crystal cured layer of the present invention preferably shows a diffraction peak derived from a periodic structure in X-ray diffraction measurement.
  • a diffraction peak derived from a periodic structure in X-ray diffraction measurement.
  • molecules adjacent to each other in the direction perpendicular to the axis of orientation form a layer, and the layers are laminated in a direction parallel to the axis of orientation, that is, smectic.
  • a mode exhibiting a phase is preferably mentioned.
  • the liquid crystal compound described above is preferably a compound that exhibits the smectic phase both when the temperature is raised and when the temperature is lowered. Whether or not the above-mentioned diffraction peak is exhibited can also be confirmed by observing the texture characteristic of the liquid crystal phase having a periodic structure with a polarizing microscope.
  • the orientation state of the liquid crystal compound in the liquid crystal cured layer of the present invention may be any of horizontal orientation, vertical orientation, inclined orientation, and twisted orientation, and is in a state of being horizontally oriented with respect to the main surface of the liquid crystal cured layer. It is preferable that it is fixed with.
  • horizontal orientation refers to the main surface of the liquid crystal cured layer (or the surface of the member when the liquid crystal cured layer is formed on a member such as a support and an alignment film) and the liquid crystal. It means that the long axis direction of the compound is parallel.
  • the angle formed by the major axis direction of the liquid crystal compound and the main surface of the liquid crystal cured layer is an orientation of less than 10 °.
  • the angle formed by the major axis direction of the liquid crystal compound and the main surface of the liquid crystal cured layer is preferably 0 to 5 °, more preferably 0 to 3 °, still more preferably 0 to 2 °.
  • the liquid crystal cured layer of the present invention is preferably an optically anisotropic layer, more preferably a positive A plate or a positive C plate, and even more preferably a positive A plate.
  • the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
  • the refractive index in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized) is nx
  • the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny
  • the refraction in the thickness direction is nz
  • the positive A plate satisfies the relation of the formula (A1)
  • the positive C plate satisfies the relation of the formula (C1).
  • the positive A plate shows a positive value for Rth
  • the positive C plate shows a negative value for Rth.
  • ⁇ includes not only the case where both are completely the same but also the case where both are substantially the same.
  • (ny-nz) x d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. Is also included in “ny ⁇ nz”, and when (nx-nz) x d is -10 to 10 nm, preferably -5 to 5 nm, it is also included in "nx ⁇ nz".
  • (nx-ny) ⁇ d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, it is also included in “nx ⁇ ny”. ..
  • Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, and 130 to 130 to be, from the viewpoint of functioning as a ⁇ / 4 plate. It is more preferably 150 nm, and particularly preferably 130 to 140 nm.
  • the " ⁇ / 4 plate” is a plate having a ⁇ / 4 function, and specifically, a function of converting linear polarization of a specific wavelength into circular polarization (or circular polarization into linear polarization). It is a plate having.
  • the liquid crystal cured layer of the present invention is preferably a polarizing element (light absorption anisotropic film).
  • the optical film of the present invention is an optical film having the liquid crystal curing layer of the present invention.
  • the structure of the optical film will be described with reference to FIG.
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical film. Note that FIG. 1 is a schematic diagram, and the relationship between the thickness and the positional relationship of each layer does not necessarily match the actual ones, and the support and the alignment film shown in FIG. 1 are all arbitrary constituent members.
  • the optical film 10 shown in FIG. 1 has a support 16, an alignment film 14, and a liquid crystal curing layer 12 as a cured product of the liquid crystal composition of the present invention in this order.
  • the liquid crystal curing layer 12 may be a laminated body of two or more different liquid crystal curing layers.
  • the polarizing plate of the present invention described later is used as a circular polarizing plate, or when the optical film of the present invention is used as an optical compensation film for an IPS type or FFS type liquid crystal display device, a positive A plate and a positive C are used. It is preferably a laminate of plates.
  • the liquid crystal cured layer may be peeled off from the support and the liquid crystal cured layer may be used alone as an optical film.
  • various members used in the optical film will be described in detail.
  • the liquid crystal curable layer of the optical film of the present invention is the above-mentioned liquid crystal curable layer of the present invention.
  • the thickness of the liquid crystal cured layer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
  • the optical film may have a support as a base material for forming the liquid crystal cured layer.
  • a support is preferably transparent.
  • the light transmittance is preferably 80% or more.
  • Such a support examples include a glass substrate and a polymer film.
  • Materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and polyethylenena.
  • Polyester polymers such as phthalate; Polystyrene and styrene polymers such as acrylonitrile-styrene copolymer (AS resin); Polyolefin polymers such as polyethylene, polypropylene, and ethylene / propylene copolymers; Vinyl chloride polymers; Nylon, And amide-based polymers such as aromatic polyamides; imide-based polymers; sulfone-based polymers; polyether sulfone-based polymers; polyether ether ketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers. Examples include allylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; and polymers in which these polymers are mixed. Further, the stator described later may also serve as such a support.
  • the thickness of the support is not particularly limited, but is preferably 5 to 60 ⁇ m, more preferably 5 to 40 ⁇ m.
  • the liquid crystal curing layer is preferably formed on the surface of the alignment film.
  • the alignment film may be sandwiched between the support and the liquid crystal cured layer. Further, the support described above may also serve as an alignment film.
  • the alignment film may be any film as long as it has a function of horizontally aligning the polymerizable liquid crystal compound contained in the composition.
  • the alignment film is generally composed of a polymer as a main component.
  • the polymer material for an alignment film has been described in a large number of documents, and a large number of commercially available products are available.
  • As the polymer material for the alignment film polyvinyl alcohol, polyimide, or a derivative thereof is preferable, and modified or unmodified polyvinyl alcohol is more preferable.
  • Examples of the alignment film that the optical film may have include the alignment film described in International Publication No. 01/88574, page 43, lines 24 to 49, line 8; paragraph [0071] to Japanese Patent Application Laid-Open No. 3907735. Examples thereof include an alignment film made of the modified polyvinyl alcohol described in [0995]; and a liquid crystal alignment film formed by a liquid crystal alignment agent described in JP-A-2012-155308.
  • the photoalignment film is not particularly limited, but is an alignment film formed of a polymer material such as the polyamide compound and the polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; JP 2012.
  • a liquid crystal alignment film formed by a liquid crystal alignment agent having a photoaligning group described in Japanese Patent Application Laid-Open No. 155308; and a trade name LPP-JP265CP manufactured by Polyimide Technologies, etc. can be used.
  • the thickness of the alignment film is not particularly limited, but is preferably 0.01 to 10 ⁇ m, preferably 0.01 to 1 ⁇ m, from the viewpoint of alleviating surface irregularities that may exist on the support and forming a liquid crystal cured layer having a uniform film thickness. More preferably, 0.01 to 0.5 ⁇ m is further preferable.
  • the optical film preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (particularly ultraviolet light).
  • the ultraviolet absorber may be contained in the liquid crystal curing layer, or may be contained in a member other than the liquid crystal curing layer constituting the optical film.
  • a support is preferably mentioned.
  • the ultraviolet absorber any conventionally known agent capable of exhibiting ultraviolet absorption can be used.
  • benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorbers are preferable from the viewpoint of obtaining ultraviolet absorbing ability (ultraviolet blocking ability) which is highly ultraviolet absorbing and is used in an image display device. Further, in order to widen the absorption range of ultraviolet rays, it is also preferable to use two or more kinds of ultraviolet absorbers having different maximum absorption wavelengths in combination.
  • Examples of the ultraviolet absorber include the compounds described in paragraphs [0258] to [0259] of JP2012-18395A, and paragraphs [0055] to [0105] of JP2007-72163. Compounds and the like can be mentioned. Further, as commercially available products, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 (all manufactured by BASF) and the like can be used.
  • the polarizing plate according to the first aspect of the present invention is a liquid crystal cured layer (optically different) formed by immobilizing the orientation state of the liquid crystal composition containing no arbitrary dichroic substance in the liquid crystal composition of the present invention described above. It has a square layer) and a polarizing element.
  • the polarizing plate according to the second aspect of the present invention is a liquid crystal obtained by immobilizing the orientation state of the retardation film and the liquid crystal composition containing any dichroic substance among the liquid crystal compositions of the present invention described above. It has a cured layer (light absorption anisotropic layer).
  • the polarizing plate according to the third aspect of the present invention is a liquid crystal cured layer (optically different) formed by immobilizing the orientation state of the liquid crystal composition containing no arbitrary dichroic substance among the liquid crystal compositions of the present invention described above.
  • a square layer and a liquid crystal cured layer (light absorption anisotropic layer) obtained by immobilizing the orientation state of the liquid crystal composition containing an arbitrary dichroic substance among the above-mentioned liquid crystal compositions of the present invention.
  • the polarizing plate according to the first aspect can be used as a circular polarizing plate when the liquid crystal curing layer described above is a ⁇ / 4 plate (positive A plate).
  • the liquid crystal curing layer described above is a ⁇ / 4 plate (positive A plate), and the angle formed by the slow phase axis of the ⁇ / 4 plate and the absorption axis of the splitter described later is 30. It is preferably about 60 °, more preferably 40 to 50 °, even more preferably 42 to 48 °, and particularly preferably 45 °.
  • the "slow-phase axis" of the ⁇ / 4 plate means the direction in which the refractive index becomes maximum in the plane of the ⁇ / 4 plate
  • the "absorption axis" of the substituent means the direction in which the absorbance is highest. do.
  • the polarizing plate can also be used as an optical compensation film for an IPS type or FFS type liquid crystal display device.
  • the polarizing plate is used as an optical compensation film for an IPS type or FFS type liquid crystal display device
  • the above-mentioned liquid crystal curing layer is used as at least one plate of a laminate of a positive A plate and a positive C plate, and the positive A plate layer is used.
  • the angle formed by the slow axis of the above and the absorption axis of the polarizing element described later is orthogonal or parallel, and specifically, the slow axis of the positive A plate layer and the absorption axis of the polarizing element described later It is more preferable that the angle formed by the light is 0 to 5 ° or 85 to 95 °.
  • the angle formed by the slow axis of the liquid crystal cured layer and the absorption axis of the polarizing element described later is parallel or orthogonal. It is preferable to have.
  • parallel does not require that it is strictly parallel, but means that the angle between one and the other is less than 10 °.
  • orthogonal does not require that they are strictly orthogonal, but means that the angle between one and the other is more than 80 ° and less than 100 °.
  • the polarizing element of the polarizing plate according to the first aspect of the present invention is not particularly limited as long as it is a member having a function of converting light into specific linear polarization, and conventionally known absorption-type and reflective-type polarizing elements. Can be used.
  • an iodine-based splitter, a dye-based splitter using a dichroic dye, a polyene-based splitter, and the like are used.
  • Iodine-based splitters and dye-based splitters include coated and stretched splitters, both of which can be applied, but polarized light produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching it. Children are preferred.
  • Japanese Patent No. 5048120 Japanese Patent No. 5143918, Japanese Patent No. 4691205, and Patent No. 5048120, Patent No. Japanese Patent No. 4751481 and Japanese Patent No. 4751486 are mentioned, and known techniques relating to these substituents can also be preferably used.
  • coated polarizing element examples include WO2018 / 124198, WO2018 / 186553, WO2019 / 132020, WO2019 / 132018, WO2019 / 189345, JP-A-2019-197168, JP-A-2019-194685, and JP-A-2019-139222. Publications are mentioned, and known techniques relating to these substituents can also be preferably used.
  • the reflective classifier a splitter in which thin films having different birefringences are laminated, a wire grid type splitter, and a splitter in which a cholesteric liquid crystal having a selective reflection range and a 1/4 wave plate are combined are used.
  • a polymer containing a polyvinyl alcohol-based resin ( -CH2 -CHOH- as a repeating unit.
  • a polyvinyl alcohol-based resin -CH2 -CHOH- as a repeating unit.
  • a polarizing element containing 1) is preferable.
  • the polarizing element may have a depolarizing portion formed along the opposite end edges. Examples of the depolarization unit include Japanese Patent Application Laid-Open No. 2014-240970.
  • the splitter may have non-polarizing portions arranged at predetermined intervals in the longitudinal direction and / or the width direction. The non-polarized portion is a partially decolorized decolorized portion.
  • the arrangement pattern of the non-polarized portion can be appropriately set according to the purpose.
  • the non-polarizing unit is arranged at a position corresponding to the camera unit of the image display device when the polarizing element is cut (cut, punched, etc.) to a predetermined size in order to attach it to an image display device of a predetermined size.
  • Examples of the arrangement pattern of the non-polarized portion include Japanese Patent Application Laid-Open No. 2016-27392.
  • the thickness of the splitter is not particularly limited, but is preferably 3 to 60 ⁇ m, more preferably 3 to 30 ⁇ m, and even more preferably 3 to 10 ⁇ m.
  • the pressure-sensitive adhesive layer may be arranged between the liquid crystal curing layer in the optical film and the polarizing element.
  • the ratio of the storage elastic modulus G'and the loss elastic modulus G'measured by a dynamic viscoelasticity measuring device (tan ⁇ ). G "/ G') includes members made of a substance having a value of 0.001 to 1.5, and includes so-called adhesives, substances that easily creep, and the like.
  • the pressure-sensitive adhesive include, but are not limited to, polyvinyl alcohol-based pressure-sensitive adhesives.
  • an adhesive layer may be arranged between the liquid crystal curing layer and the polarizing element in the optical film.
  • a curable adhesive composition that is cured by irradiation with active energy rays or heating is preferable.
  • the curable adhesive composition include a curable adhesive composition containing a cationically polymerizable compound, a curable adhesive composition containing a radically polymerizable compound, and the like.
  • the thickness of the adhesive layer is preferably 0.01 to 20 ⁇ m, more preferably 0.01 to 10 ⁇ m, and even more preferably 0.05 to 5 ⁇ m.
  • the thickness of the adhesive layer is within this range, floating or peeling does not occur between the protective layer or the liquid crystal curing layer to be laminated and the polarizing element, and a practically acceptable adhesive force can be obtained.
  • the thickness of the adhesive layer is preferably 0.4 ⁇ m or more from the viewpoint of suppressing the generation of bubbles.
  • the bulk water absorption rate of the adhesive layer may be adjusted to 10% by mass or less, preferably 2% by mass or less. The bulk water absorption rate is measured according to the water absorption rate test method described in JIS K 7209.
  • the adhesive layer for example, paragraphs [0062] to [0080] of JP-A-2016-35579 can be referred to, and these contents are incorporated in the present specification.
  • an easy-adhesion layer may be arranged between the liquid crystal curing layer and the polarizing element in the optical film.
  • the storage elastic modulus of the easy-adhesion layer at 85 ° C. is 1.0 ⁇ 10 6 Pa to 1. It is preferably 0 ⁇ 10 7 Pa.
  • the constituent material of the easy-adhesion layer include a polyolefin-based component and a polyvinyl alcohol-based component.
  • the thickness of the easy-adhesion layer is preferably 500 nm to 1 ⁇ m.
  • paragraphs [0048] to [0053] of JP-A-2018-36345 can be referred to, and these contents are incorporated in the present specification.
  • the image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
  • the display element used in the image display device is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter, abbreviated as “EL (Electro Luminescence)”) display panel, and a plasma display panel.
  • EL Electro Luminescence
  • a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, as the image display device, a liquid crystal display device using a liquid crystal cell as a display element or an organic EL display device using an organic EL display panel as a display element is preferable, and a liquid crystal display device is more preferable.
  • a liquid crystal display device which is an example of an image display device, is a liquid crystal display device having the above-mentioned polarizing plate and a liquid crystal cell.
  • the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the above-mentioned polarizing plate as the front side polarizing plate, and more preferably to use the above-mentioned polarizing plate as the front side and rear side polarizing plates.
  • the liquid crystal cells constituting the liquid crystal display device will be described in detail below.
  • the liquid crystal cell used in the liquid crystal display device is VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, FFS (Fringe-Field-Switching) mode, or TN (Twisted). Nematic) mode is preferred, but is not limited to these.
  • the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °.
  • the TN mode liquid crystal cell is most often used as a color TFT liquid crystal display device, and has been described in many documents.
  • the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied.
  • a VA mode liquid crystal cell in a narrow sense (1) in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied
  • 176625 Japanese Patent Publication No. 176625
  • SID97 Digest of tech. Papers (Proceedings) 28 (1997) 845, in which the VA mode is multi-domainized to expand the viewing angle.
  • liquid crystal cell in the VA mode may be any of PVA (Patterned Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment). Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819.
  • the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane by applying an electric field parallel to the substrate surface.
  • the display is black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other.
  • Methods for reducing leakage light when displaying black in an oblique direction and improving the viewing angle by using an optical compensation sheet are described in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. It is disclosed in JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.
  • Organic EL display device As an organic EL display device which is an example of an image display device, for example, from the visual recognition side, a polarizing element, a ⁇ / 4 plate (positive A plate) made of the liquid crystal curing layer described above, and an organic EL display panel are arranged in this order. Examples thereof include the aspect having the above. Further, the organic EL display panel is a display panel configured by using an organic EL element formed by sandwiching an organic light emitting layer (organic electroluminescence layer) between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
  • Polyester (number average molecular weight 800)
  • ⁇ Making protective film 1> The core layer cellulose acylate dope 1 and the outer layer cellulose acylate dope 1 were filtered using a filter paper having an average pore diameter of 34 ⁇ m and a sintered metal filter having an average pore diameter of 10 ⁇ m. Then, using a band spreading machine, the core layer cellulose acylate dope 1 and the outer layer cellulose acylate dope 1 on both sides thereof were spread simultaneously on a drum at 20 ° C. from the spreading port in three layers. Next, the film was peeled off from the drum with the solvent content of the film on the drum being approximately 20% by mass.
  • liquid crystal composition 1 for forming an optically anisotropic layer having the following composition was prepared.
  • Liquid crystal composition 1 ⁇ -The following liquid crystal compound R1 80.00 parts by mass-The following liquid crystal compound R2 20.00 parts by mass-The following freezing point depression agent A1 10.00 parts by mass-The following polymerization initiator S1 0.50 parts by mass-The following leveling agent P1 0.23 Part by mass ⁇ Cyclopentanone 284.73 parts by mass ⁇
  • Leveling agent P1 (in the following formula: 32.5 and 67.5 indicate the content (% by mass) of each repeating unit with respect to all the repeating units in the leveling agent P1).
  • composition 1 for a photoalignment film prepared above was continuously applied to one side of the prepared cellulose acylate film 1 with a bar coater. After the coating, the solvent was removed by drying in a heating zone at 120 ° C. for 1 minute to form a photoisomerized composition layer having a thickness of 0.3 ⁇ m. Subsequently, a photoalignment film was formed by irradiating with polarized ultraviolet rays (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) while winding the mirror-treated back appol.
  • polarized ultraviolet rays (10 mJ / cm 2 , using an ultra-high pressure mercury lamp
  • the liquid crystal composition 1 prepared above was coated on the photoalignment film formed in a long shape with a bar coater to form a composition layer.
  • the temperature of the coating chamber was set to 23 ° C.
  • the formed composition layer was heated to a temperature indicating a nematic phase in a heating zone and then cooled to stabilize the orientation at a temperature indicating a smectic phase.
  • the orientation was fixed by irradiating with ultraviolet rays (500 mJ / cm 2 , using an ultrahigh pressure mercury lamp) under a nitrogen atmosphere (oxygen concentration 100 ppm), and an optically anisotropic layer having a thickness of 2.2 ⁇ m was used. 1 was produced.
  • the in-plane retardation Re1 (550) was 117 nm, and Re1 (450) /. Re1 (550) was 0.68, confirming that the optically anisotropic layer 1 was a positive A plate.
  • phase transition temperature of the liquid crystal composition 1 was confirmed by observing the texture with a polarizing microscope.
  • the liquid crystal composition 1 changed from a crystal to a liquid crystal phase having a texture peculiar to the smectic phase at around 84 ° C. when the temperature was raised to 200 ° C. and when the temperature was lowered. It was confirmed that when the temperature was further increased, the nematic phase changed to around 136 ° C, and the nematic phase was maintained up to around 200 ° C. Further, the phase transition temperature of the liquid crystal composition 1'excluding only the freezing point depressant 1 from the liquid crystal composition 1 was also confirmed.
  • phase transitioned from the crystal to the smectic phase at around 91 ° C. changed to the nematic phase at around 136 ° C., and maintained the nematic phase up to around 200 ° C. when the temperature was raised to 200 ° C. and when the temperature was lowered.
  • the phase transition temperature from the smectic phase to the nematic phase of the liquid crystal composition 1 is T1 (SN)
  • the phase transition temperature from the smectic phase to the nematic phase of the liquid crystal composition 1' is T1'(SN).
  • the prepared optically anisotropic layer 1 is observed with a polarizing microscope, and the laminated body obtained by inserting the optically anisotropic layer 1 between two polarizing plates arranged in a cross Nicol state is visually observed. Each observation was carried out, and the defect of the optically anisotropic layer 1 was evaluated according to the following criteria.
  • Examples 2 to 9 The same method as in Example 1 was carried out except that the liquid crystal compounds R1 and R2 contained in the liquid crystal composition 1 and the liquid crystal compounds and the freezing point depressant A1 in Table 4 below were used instead of the liquid crystal compounds R1 and R2 and the freezing point depressant A1.
  • Optically anisotropic layers 2 to 9 of Examples 2 to 9 were prepared and evaluated.
  • Example 10 The light absorption anisotropic layer 10 of Example 10 was prepared by the same method as in Example 1 except that the following liquid crystal composition 10 was used instead of the liquid crystal composition 1, and each evaluation was performed.
  • Table 4 shows the liquid crystal compositions used for forming the optically anisotropic layer (referred to as the light absorption anisotropic layer in Example 10; the same applies hereinafter) in Examples 1 to 10 and Comparative Examples 1 to 8.
  • the evaluation results of the composition of the substance, the phase transition temperature of the liquid crystal composition, and the orientation defect of the formed optically anisotropic layer are shown.
  • the structures of the liquid crystal compound and the freezing point depressant in Table 4 are shown below. Further, the above-mentioned liquid crystal composition L is prepared using this liquid crystal compound, and the values of Re (450) / Re (550) of the optically anisotropic layer prepared by the above-mentioned method are shown below. The molar extinction coefficient of this freezing point depressant at a wavelength of 350 to 750 nm is shown below.
  • Liquid crystal compound R1 [Re (450) / Re (550): 0.58]
  • Liquid crystal compound R2 [Re (450) / Re (550): 0.68]
  • Liquid crystal compound R3 [Re (450) / Re (550): 0.82]
  • Liquid crystal compound R4 [Re (450) / Re (550): 0.83]
  • Liquid crystal compound R5 [Re (450) / Re (550): 1.09]
  • Liquid crystal compound R6 [Re (450) / Re (550): 0.80]
  • Liquid crystal compound R7 [Re (450) / Re (550): 1.10]
  • Freezing point depression agent A1 [molar extinction coefficient: 0.8 (l / mol ⁇ cm)]
  • Freezing point depression agent A2 [molar extinction coefficient: 1.2 (l / mol ⁇ cm)]
  • Freezing point depression agent A3 [molar extinction coefficient: 0.7 (l / mol ⁇ cm)]
  • Freezing point depression agent A4 [molar extinction coefficient: 0.8 (l / mol ⁇ cm)]
  • Freezing point depression agent A5 [molar extinction coefficient: 1.0 (l / mol ⁇ cm)]
  • Freezing point depression agent A6 [molar extinction coefficient: 2.4 (l / mol ⁇ cm)]
  • Freezing point depression agent A7 [molar extinction coefficient: 1.9 (l / mol ⁇ cm)]
  • Freezing point depression agent A8 [molar extinction coefficient: 1.5 (l / mol ⁇ cm)]
  • Freezing point depression agent A9 [molar extinction coefficient: 1.8 (l / mol ⁇ cm)]

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