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  • C09K19/56—Aligning agents
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
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  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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  • C09K19/00—Liquid crystal materials
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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
  • C09K19/14—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
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  • C09K19/00—Liquid crystal materials
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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
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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
  • C09K19/34—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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  • C09K19/00—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
  • C09K19/34—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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  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3833—Polymers with mesogenic groups in the side chain
  • C09K19/3842—Polyvinyl derivatives
  • C09K19/3852—Poly(meth)acrylate derivatives
• • 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
  • G02B5/18—Diffraction gratings
  • G02B5/1833—Diffraction gratings comprising birefringent materials
• • 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
  • G02B5/32—Holograms used as optical elements
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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
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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
  • C09K2019/2078—Ph-COO-Ph-COO-Ph

Definitions

• the present invention relates to a composition, an optically anisotropic layer, a cured film, and a diffraction element.
• Optically anisotropic layers formed by using a composition containing a liquid crystal compound (hereinafter also referred to as “liquid crystal composition”) and orienting the liquid crystal compound in a predetermined orientation state are used in various applications such as diffraction elements.
• the liquid crystal composition may contain an alignment agent (hereinafter also referred to as “air interface side alignment agent”) that can regulate the alignment of the liquid crystal compound from the air interface side, and as such an alignment agent, a fluorine-based alignment agent having a perfluoroalkyl chain, which has low surface free energy and is easily unevenly distributed on the surface, has been widely used.
• air interface side alignment agent an alignment agent
• a fluorine-based alignment agent having a perfluoroalkyl chain which has low surface free energy and is easily unevenly distributed on the surface, has been widely used.
• PFAS-free alternative materials are required from the viewpoint of environmental pollution, and silicon-based alignment agents are expected to be a substitute for them.
• Patent Document 1 discloses a liquid crystal align
• an alignment agent capable of controlling the alignment of a liquid crystal compound from the air interface side (air interface side alignment agent) is generally used that tends to be unevenly distributed on the air interface side in a liquid crystal layer formed from a liquid crystal composition.
• the present inventors have investigated silicon-containing compounds as alignment agents capable of favorably controlling the alignment of a liquid crystal compound, and have found that when another layer (adjacent layer) is formed on the surface of the liquid crystal layer on the side where the air interface side alignment agent is unevenly distributed, problems such as repelling and/or alignment defects in the adjacent layer may occur (hereinafter also referred to as "poor lamination") depending on the structure of the silicon-containing compound.
• a polymerizable liquid crystal compound, and a silicon-containing compound A composition, wherein the silicon-containing compound satisfies all of requirements 1 to 4.
• Requirement 1 The compound has no polymerizable group.
• Requirement 2 The molecule contains two or more ring structures.
• Requirement 3 Contains a siloxane bond.
• Requirement 4 The molecular weight is less than 5,000.
• composition according to [1] or [2], wherein the silicon-containing compound has a group selected from the group consisting of groups represented by formulas (C-1) to (C-3) described below.
• the silicon-containing compound is a compound represented by the formula (1) described below, provided that the compound represented by the formula (1) does not have a polymerizable group and has a molecular weight of less than 5,000.
• the silicon-containing compound is a compound represented by the formula (2) described below, provided that the compound represented by the formula (2) does not have a polymerizable group and has a molecular weight of less than 5,000.
• the divalent linking groups represented by Z 21 and Z 22 are each independently -O-, -S-, -OCH 2 -, -CH 2 CH 2 -, -CO-, -CS-, -COO-, -CSO-, -CSS-, -CO-S-, -O-CO-O-, -CO-CO-, -CO-NH-, -SCH 2 -, -CF 2 O-, -CF 2 S-, -COO-CH 2 CH 2 -, -OCO-CH 2 CH 2 -, -COO-CH 2 -, -OCO-CH 2
• the optically anisotropic layer is a diffraction element having a liquid crystal alignment pattern in which the direction of the optical axis derived from the liquid crystal compound changes while rotating continuously along at least one direction in the plane.
• the present invention it is possible to provide a composition which, when a liquid crystal layer is formed, exhibits excellent alignment of a liquid crystal compound and which exhibits excellent lamination properties of the liquid crystal layer after a surface treatment is applied. Furthermore, according to the present invention, an optically anisotropic layer, a cured film, and a diffraction element can be provided.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower and upper limits.
• an "alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).
• each component may be a single substance corresponding to the component, or two or more substances may be used in combination.
• the content of that component refers to the total content of the substances used in combination, unless otherwise specified.
• the specific compound contains two or more ring structures in the molecule.
• the ring structure may be either an aromatic ring structure or an alicyclic structure.
• the alicyclic structure is preferably a saturated alicyclic structure (a saturated aliphatic hydrocarbon ring structure or a saturated aliphatic heterocyclic structure).
• the aliphatic hydrocarbon ring examples include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a norbornene ring, and an adamantane ring. Of these, a cyclopentane ring or a cyclohexane ring is preferable.
• heteroatoms contained in the aliphatic heterocycle include a nitrogen atom, an oxygen atom, and a sulfur atom.
• the number of ring members in the aliphatic heterocycle is not particularly limited, but is preferably 5 to 15, more preferably 5 to 10, and even more preferably 5 or 6.
• the specific compound contains a siloxane bond (--Si--O--Si--).
• the number of siloxane bonds in a molecule is not limited and may be, for example, from 1 to 20.
• the number of siloxane bonds in a specific compound is preferably adjusted to a value within the range of the silicon atom content described below.
• the specific compound preferably has a linking group containing two or more ring structures (hereinafter also simply referred to as "linking group T”) and a plurality of structural moieties containing siloxane bonds (hereinafter also simply referred to as "structural moieties XS”), and has a structure in which the plurality of structural moieties XS are bonded via the linking group T.
• linking group T a linking group containing two or more ring structures
• structural moieties XS structural moieties containing siloxane bonds
• the structural moiety XS is preferably a structural moiety containing a group selected from the group consisting of groups represented by formulae (C-1) to (C-3).
• the specific compound preferably has a group selected from the group consisting of groups represented by formulae (C-1) to (C-3), and in terms of better effects of the present invention, it is more preferable for the specific compound to have a group represented by formula (C-2) or formula (C-3), and even more preferable for the specific compound to have a group represented by formula (C-3).
• the groups represented by formulae (C-1) to (C-3) will be described below.
• R C1 to R C3 each independently represent an alkyl group having 1 to 10 carbon atoms.
• a plurality of R C1s , a plurality of R C2s , and a plurality of R C3s may be the same or different from each other.
• R C4 represents an alkyl group having 1 to 10 carbon atoms.
• R C5 and R C6 each independently represent an alkyl group having 1 to 10 carbon atoms or a group represented by formula (C-1X).
• a plurality of R C5s and a plurality of R C6s may be the same or different from each other.
• R C10 to R C12 each independently represent an alkyl group having 1 to 10 carbon atoms. 1 represents an integer of 0 to 20.
• a plurality of R C10 's, a plurality of R C11 's, and a plurality of R C12 's may be the same or different from each other.
• the alkyl group having 1 to 10 carbon atoms represented by R C1 to R C12 is preferably a chain (straight-chain or branched-chain) alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain alkyl group having 1 to 10 carbon atoms.
• the alkyl group having 1 to 10 carbon atoms, represented by R C1 to R C12 preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.
• the alkyl group having 1 to 10 carbon atoms represented by R C1 to R C12 may have a substituent (preferably the substituent S1 described below), but preferably does not have one.
• the group represented by formula (B-1) is preferred in that it provides a better effect for the present invention, and groups selected from the group consisting of the groups represented by formulas (B-1-1) to (B-1-5) are more preferred.
• m and n each independently represent an integer of 1 or more.
• Each of m and n independently preferably represents an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, and particularly preferably 1 or 2.
• the amino group may be either an unsubstituted amino group (-NH 2 ) or a substituted amino group (-NHR or -N(R) 2 ).
• the substituent (R) in the substituted amino group is preferably an alkyl group or the like.
• the alkyl group is preferably linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group.
• the silyl group is preferably a group represented by -Si(R) 3 .
• Each R in the silyl group independently represents a substituent.
• the substituent represented by R is preferably an alkyl group or an aryl group.
• the alkyl group is preferably linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• the aryl group is preferably the same as the aryl group described above, and a phenyl group is more preferable.
• the silyl group portion in the silyloxy group preferably has the same form as the above-mentioned silyl group.
• the content of the specific compound in the composition is preferably from 0.01 to 5.00 mass %, more preferably from 0.03 to 3.00 mass %, and even more preferably from 0.05 to 1.00 mass %, based on the mass of the total solid content of the composition.
• the specific compounds may be used alone or in combination of two or more. When two or more specific compounds are used, the total content thereof is preferably within the above-mentioned numerical range.
• the specific compound is capable of reducing the tilt angle of the molecules of the liquid crystal compound at the air interface of the layer, or of aligning the liquid crystal compound substantially horizontally.
• horizontal alignment refers to 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-shaped liquid crystal compound) being parallel to the film surface, but does not require strict parallelism, and in this specification, it means an alignment with an inclination angle of less than 20 degrees with respect to the film surface.
• the molecules of the liquid crystal compound are aligned at a large tilt angle, for example, in the case of a cholesteric phase, the helical axis is deviated from the film surface normal, which is undesirable because it reduces reflectance, generates a fingerprint pattern, increases haze or shows diffraction.
• the composition includes a polymerizable liquid crystal compound.
• the polymerizable liquid crystal compound means a compound that has a polymerizable group and exhibits liquid crystallinity.
• a compound shows liquid crystallinity, it is intended that the compound has a property of expressing an intermediate phase between a crystalline phase (low temperature side) and an isotropic phase (high temperature side) when the temperature is changed.
• the compound is heated or cooled using a hot stage system such as Mettler Toledo FP90, while being observed under a polarizing microscope, and the optical anisotropy and fluidity derived from the liquid crystal phase are observed. It can be confirmed.
• the number of polymerizable groups in the polymerizable liquid crystal compound may be one or more, and is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2.
• a polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into a liquid crystal compound.
• the polymerizable group is preferably an acryloyloxy group (corresponding to the above formula (P-1)), a methacryloyloxy group (corresponding to the above formula (P-2)), an epoxy group (corresponding to the above formula (P-9)), a vinyl ether group (corresponding to the above formula (P-5)), or a vinyl ester group (corresponding to the above formula (P-22)), in terms of the superior effects of the present invention, and is more preferably an acryloyloxy group or a methacryloyloxy group.
• a compound represented by the following formula (3) is preferred.
• P 31 and P 32 each independently represent a hydrogen atom or a substituent, provided that at least one of P 31 and P 32 represents a polymerizable group.
• the polymerizable group is as described above.
• the substituents represented by P 31 and P 32 for example, the above-mentioned substituent S1 is preferable.
• n31 represents an integer of 1 to 10. n31 preferably represents an integer of 2 to 8, and more preferably an integer of 2 to 6.
• Z 31 represents a single bond or a divalent linking group.
• the divalent linking group represented by Z 31 represents one or a combination of two or more selected from the group consisting of -CH 2 -, -O-, -NH-, -S-, -C ⁇ C-, -CO-, -CS-, -CH ⁇ N-, -N ⁇ N-, and -C ⁇ C-, provided that any substitutable hydrogen atom in these groups may be substituted with a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).
• a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• Z 31 is preferably a single bond, —OCH 2 —, —CH 2 CH 2 —, —COO—, —CSO—, —CSS—, —CO-S—, —CO-CO-, —CO-NH-, —SCH 2 —, —CF 2 O—, —CF 2 S—, —CH ⁇ N-, —C ⁇ C-, or —C ⁇ C-C ⁇ C-, and more preferably a single bond, —OCH 2 —, —C ⁇ C-, or —COO-.
• At least one of Z 31 is preferably -C ⁇ C- in that the anisotropy is excellent when used as an optically anisotropic layer.
• the divalent aromatic ring group may be either a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group.
• the divalent aromatic ring group may be either a monocyclic or polycyclic group.
• the number of carbon atoms in the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon ring group is preferably 6 to 10.
• Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, with a benzene ring being more preferred.
• the number of ring members of the aromatic heterocycle constituting the divalent aromatic heterocyclic group is preferably 5 to 10, more preferably 5 or 6.
• heteroatoms contained in the aromatic heterocycle include a nitrogen atom, an oxygen atom, and a sulfur atom.
• the divalent alicyclic group may be either a divalent aliphatic hydrocarbon ring group or a divalent aliphatic heterocyclic group.
• the divalent alicyclic group may be either a monocyclic group or a polycyclic group.
• the number of ring members in the aliphatic hydrocarbon ring constituting the divalent aliphatic hydrocarbon ring group is preferably 5 to 12, more preferably 5 to 10, and even more preferably 5 or 6.
• aliphatic heterocycle examples include an oxolane ring, an oxane ring, a piperidine ring, and a piperazine ring.
• the aliphatic heterocycle may be one in which -CH 2 - constituting the ring is replaced with -CO-, and examples of the aliphatic heterocycle include a phthalimide ring.
• the hydrogen atoms in the divalent aromatic ring group and the divalent alicyclic group may be substituted with other substituents.
• the other substituents include the above-mentioned substituent S1 and the group represented by formula (PA), and the above-mentioned substituent S1 is preferred.
• Formula (PA) *-L A -P A In formula (PA), L 1 A represents a single bond or a divalent linking group.
• a 31 and A 32 are preferably a divalent aromatic hydrocarbon ring group which may have a substituent.
• An embodiment of A 31 and A 32 is a phenylene group bonded at the 1-position and the 4-position.
• a 31 and A 32 includes an embodiment in which one of n31 A 31 and A 32 is any aromatic ring group selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).
• a 31 and A 32 each contain an aromatic ring group selected from the group consisting of groups represented by the following formulae (Ar-1) to (Ar-5)
• an embodiment in which n31 represents 2 and the second A 31 from the P 31 side represents an aromatic ring selected from the group consisting of groups represented by the following formulae (Ar-1) to (Ar-5) or an embodiment in which n31 represents 4 and the third A 31 from the P 31 side represents an aromatic ring selected from the group consisting of groups represented by the following formulae (Ar-1) to (Ar-5) is preferred.
• Q1 represents N or CH.
• Q2 represents -S-, -O- or -N( R6 )-.
• R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms represented by R6 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
• Y1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, in which one or more of -CH 2 - constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or NH-.
• the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y1 include a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group.
• Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y1 include a thienyl group, a thiazolyl group, a benzothiazolyl group, a benzofuryl group, a furyl group, and a pyridyl group.
• Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms represented by Y1 include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group.
• Examples of the substituent that Y 1 may have include the above-mentioned substituent S 1 .
• Examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms represented by Z 1 , Z 2 , and Z 3 include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.
• Examples of the halogen atom represented by Z 1 , Z 2 and Z 3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 which may have a substituent bonded thereto.
• Examples of the non-metallic atom of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom bonded to a hydrogen atom or a substituent [ ⁇ N—R N1 , R N1 represents a hydrogen atom or a substituent], and a carbon atom bonded to a hydrogen atom or a substituent [ ⁇ C—(R C1 ) 2 , R C1 represents a hydrogen atom or a substituent].
• P3 and P4 each independently represent a monovalent organic group, provided that at least one of P3 and P4 represents a polymerizable group.
• the monovalent organic groups represented by P3 and P4 include groups corresponding to the organic groups exemplified as the substituent S1 (preferably an alkyl group, an aryl group, or a heteroaryl group), and polymerizable groups (preferably a monovalent group represented by the above-mentioned formulae (P-1) to (P-22)).
• Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles.
• Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. At least one -CH 2 - in the alkyl group of Ay may be substituted with -O-, -S-, -CO-, -SO-, -SO 2 - or -NH-.
• the polymerizable liquid crystal compound is also preferably a polymerizable liquid crystal compound having reverse wavelength dispersion.
• a liquid crystal compound having reverse wavelength dispersion refers to the property that, when an optically anisotropic layer prepared using such a liquid crystal compound has an in-plane retardation (Re) value measured in the visible light range, the Re value increases as the measured wavelength increases.
• Re in-plane retardation
• polymerizable discotic liquid crystal compounds for example, those described in JP-A-2007-108732 and JP-A-2010-244038 can also be preferably used.
• the birefringence ⁇ n of the liquid crystal compound is preferably 0.15 or more, more preferably 0.20 or more, and even more preferably 0.25 or more, from the viewpoint of excellent anisotropy when used as an optically anisotropic layer, and from the viewpoint of obtaining diffracted light with high diffraction efficiency at a large diffraction angle when used as a diffraction element.
• the upper limit is not particularly limited, but is often 0.50 or less.
• polymerizable liquid crystal compounds having a large refractive index anisotropy include, for example, JP-A-2009-102245, JP-A-4655348, JP-A-4524827, JP-A-4720200, JP-A-2004-091380, JP-A-3972430, JP-A-4517416, JP-A-2002-128742, JP-A-4810750, JP-A-5888544, JP-A-2014-019654, JP-A-6241654, JP-A-6372060, JP-A-6323144, JP-A-2005-015406, JP-A-2007-230968, JP-A-67614 84, Japanese Patent No.
• polymerizable liquid crystal compounds are shown below, but are not limited to these.
• the groups adjacent to the acryloyloxy group and the methacryloyl group, respectively, represent a propylene group (a group in which a methyl group is substituted with an ethylene group), and the structure represents a mixture of positional isomers in which the position of the methyl group is different.
• the composition may include a polymerization initiator.
• the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, and among these, photopolymerization initiators capable of initiating a polymerization reaction by irradiation with ultraviolet light are preferred.
• the photopolymerization initiator include alkylphenone compounds, ⁇ -carbonyl compounds, acyloin ethers, ⁇ -hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, phenazine compounds, and oxadiazole compounds.
• the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 1 to 8% by mass, based on the total mass of the liquid crystal compound.
• the composition may contain one polymerization initiator alone or two or more polymerization initiators. When two or more polymerization initiators are used, the total content thereof is preferably within the above range.
• the content of the solvent in the composition is preferably an amount that makes the solids concentration 0.5 to 30% by mass, and more preferably an amount that makes 1 to 20% by mass.
• the composition may contain one solvent alone or two or more solvents. When two or more solvents are used, the total content is preferably within the above range.
• the composition may include a chiral agent.
• Chiral agents optically active compounds
• Chiral agents have the function of inducing a helical structure in a cholesteric liquid crystal phase.
• Chiral agents can be selected according to the purpose, since the twist direction or helical pitch of the helix induced varies depending on the compound.
• the chiral agent is not particularly limited, and for example, compounds described in "Liquid Crystal Device Handbook, Chapter 3, Section 4-3, Chiral Agents for TN (Twisted Nematic) and STN (Super Twisted Nematic), p. 199, edited by the 142nd Committee of the Japan Society for the Promotion of Science, 1989", isosorbide, isomannide derivatives, and the like can be used.
• Chiral agents generally contain asymmetric carbon atoms, but axially or planarly asymmetric compounds that do not contain asymmetric carbon atoms can also be used as chiral agents.
• Examples of axially or planarly asymmetric compounds include binaphthyl, helicene, paracyclophane, and derivatives thereof.
• the chiral agent may have a polymerizable group.
• a polymer having a repeating unit derived from the polymerizable liquid crystal compound and a repeating unit derived from the chiral agent can be formed by a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound.
• the polymerizable group of the polymerizable chiral agent is preferably the same type of group as the polymerizable group of the polymerizable liquid crystal compound.
• the chiral agent itself may be a liquid crystal compound.
• the chiral agent has a photoisomerizable group
• a pattern of the desired reflection wavelength corresponding to the emission wavelength can be formed by irradiating a photomask with actinic rays or the like after coating and orientation.
• the photoisomerizable group the isomerization site of a compound exhibiting photochromic properties, an azo group, an azoxy group, or a cinnamoyl group is preferable.
• Specific compounds that can be used include those described in 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-A-2002-179682, JP-A-2002-338575, JP-A-2002-338668, JP-A-2003-313189, and JP-A-2003-313292.
• the content of the chiral agent in the composition is not particularly limited, but is preferably 0.01 to 15% by mass, and more preferably 1.0 to 10% by mass, relative to the content of the liquid crystal compound.
• the composition may contain other ingredients in addition to those mentioned above.
• other components include silicon-containing compounds other than the specific compound, non-polymerizable liquid crystal compounds, antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, defoamers, leveling agents, thickeners, flame retardants, surfactants, dispersants, and coloring materials such as dyes and pigments.
• the method for producing the composition is not particularly limited, and a known method can be adopted, for example, the composition can be produced by mixing the various components described above. When mixing, the various components may be mixed at once or sequentially.
• a cured product formed using the composition can be used as an optically anisotropic layer.
• the alignment of the liquid crystal compound in the optically anisotropic layer is not particularly limited, and examples thereof include homogeneous alignment, homeotropic alignment, and cholesteric alignment. An example of an optically anisotropic layer and a method for producing the same will be described below.
• Figures 1 and 2 show schematic cross-sectional views of an optically anisotropic layer 1.
• Figure 1 is a side view showing the optically anisotropic layer 1
• Figure 2 is a plan view showing the liquid crystal alignment pattern of the optically anisotropic layer 1 shown in Figure 1.
• the sheet surface of the sheet-like 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 has a liquid crystal alignment pattern (one period length ⁇ ) in which the direction of the optical axis derived from the liquid crystal compound 30 is continuously rotated and changed along at least one direction in the plane. 1 to 4, in order to simplify the drawings and clearly show the configuration of the optically anisotropic layer 1, only the liquid crystal compound present on one main surface side of the optically anisotropic layer 1 is shown.
• the optically anisotropic layer 1 has a structure in which aligned liquid crystal compounds 30 are stacked, similar to an optically anisotropic layer formed using a composition containing a normal liquid crystal compound.
• the layer functions as a general ⁇ /2 plate, that is, imparts a phase difference of half the wavelength, i.e., 180°, to two mutually orthogonal linearly polarized components contained in the light incident on the optically anisotropic layer.
• the optically anisotropic layer 1 has a liquid crystal orientation pattern in which the direction of the optical axis 30A (hereinafter sometimes abbreviated as "optical axis 30A”) originating from the liquid crystal compound 30 changes while rotating continuously in one direction within the plane of the optically anisotropic layer 1.
• optical axis 30A the direction of the optical axis 30A
• the one direction in which the optical axis 30A changes in rotation is made to coincide with the direction of the x-axis in the xy plane.
• the one direction in which the optical axis 30A changes in rotation is referred to as the x-direction.
• the optical axis 30A derived from the liquid crystal compound 30 is the axis along which the refractive index of the liquid crystal compound 30 is the highest, that is, the slow axis. As shown in FIG. 1, when the liquid crystal compound 30 is a rod-shaped liquid crystal compound, the optical axis 30A is along the long axis direction of the rod shape.
• the orientation of the optical axis 30A changes while rotating continuously in the x direction means, specifically, that the angle between the optical axis 30A of the liquid crystal compound 30 aligned along the x direction and the x direction varies depending on the position in the x direction, and the angle between the optical axis 30A and the x direction changes gradually along the x direction from ⁇ to ⁇ +180° or ⁇ -180°.
• the angle changes gradually may mean that the angle changes at regular angle intervals or 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 even more preferably a smaller angle.
• the liquid crystal compounds 30 forming the optically anisotropic layer 1 are arranged at equal intervals with the same orientation of the optical axis 30A.
• the angles between the orientation of the optical axis 30A and the x direction are equal for the liquid crystal compounds 30 arranged in the y direction.
• the length (distance) over which the optical axis 30A of the liquid crystal compound 30 rotates 180° in the x direction in which the orientation of the optical axis 30A continuously rotates and changes in the plane is defined as the length ⁇ of one period in the liquid crystal orientation pattern.
• the length of one period in the liquid crystal orientation pattern is defined as the distance from ⁇ to ⁇ +180°, in which the angle between the optical axis 30A of the liquid crystal compound 30 and the x direction becomes.
• the distance between the centers in the x direction of two liquid crystal compounds 30 whose optical axes 30A coincide with the x direction is the length of one period ⁇ (hereinafter, sometimes referred to as "one period ⁇ " or “period ⁇ ").
• the liquid crystal alignment pattern of the optically anisotropic layer 1 is a pattern in which this one period ⁇ of liquid crystal alignment is repeated in the x direction.
• the liquid crystal compounds 30 aligned in the y direction have the same angle between their optical axes 30A and the x direction in which the optical axes of the liquid crystal compounds 30 rotate.
• a region in which the liquid crystal compounds 30 having the same angle between their optical axes 30A and the x direction are arranged in the y direction is referred to as region R.
• the value of the in-plane retardation (Re) in each region R is preferably half the wavelength of the light (hereinafter referred to as "target light") to be diffracted by the optically anisotropic layer, that is, when the wavelength of the target light is ⁇ , the in-plane retardation Re is ⁇ /2.
• the refractive index difference associated with the refractive index anisotropy of the region R in the optically anisotropic layer is a refractive index difference defined by the difference between the refractive index in the direction of the slow axis in the plane of the region R and the refractive index in the direction perpendicular to the direction of the slow axis.
• the refractive index difference ⁇ n associated with the refractive index anisotropy of the region R is equal to the difference between the refractive index of the liquid crystal compound 30 in the direction of the optical axis 30A and the refractive index of the liquid crystal compound 30 in the direction perpendicular to the optical axis 30A in the plane of the region R. That is, the refractive index difference ⁇ n depends on the liquid crystal compound, and the in-plane retardation of each region R is approximately equal. However, as described above, the direction of the optical axis 30A differs between the regions R.
• the in-plane retardation of the optically anisotropic layer 1 can be estimated from the period and the diffraction efficiency.
• the absolute phase changes according to the direction of the optical axis 30A of each liquid crystal compound 30.
• the direction of the optical axis 30A changes while rotating along the x direction, so the amount of change in the absolute phase of the incident light L1 differs according to the direction of the optical axis 30A.
• the liquid crystal orientation pattern formed in the optically anisotropic layer 1 is a periodic pattern in the x direction, the incident light L1 that passes through the optically anisotropic layer 1 is given an absolute phase Q1 that is periodic in the x direction corresponding to the direction of each optical axis 30A, as shown in FIG. 3.
• the transmitted light L2 is refracted so as to be tilted toward a direction perpendicular to the equiphase surface E1, and travels in a direction different from that of the incident light L1 .
• the incident light L1 which is left-handed circularly polarized light P L
• the transmitted light L2 which is right-handed circularly polarized light P R , which is tilted at a certain angle in the x direction with respect to the incident direction.
• the direction of the optical axis 30A changes while rotating along the x direction, so the amount of change in the absolute phase of the incident light L4 differs depending on the direction of the optical axis 30A .
• the liquid crystal orientation pattern formed in the optically anisotropic layer 1 is a periodic pattern in the x direction, the incident light L4 that passes through the optically anisotropic layer 1 is given an absolute phase Q2 that is periodic in the x direction corresponding to the direction of each optical axis 30A, as shown in FIG.
• the incident light L4 is right-handed circularly polarized light PR , the periodic absolute phase Q2 in the x direction corresponding to the direction of the optical axis 30A is opposite to that of the incident light L1 , which is left-handed circularly polarized light PL .
• the incident light L4 is refracted so as to be tilted toward a direction perpendicular to the equiphase surface E2, and travels in a direction different from the traveling direction of the incident light L4 .
• the incident light L4 is converted into the left-handed circularly polarized transmitted light L5 that is tilted at 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 can be obtained in the diffraction of the target light.
• the angle of refraction of the transmitted light L2 and L5 can be adjusted. Specifically, the shorter one period ⁇ of the liquid crystal orientation pattern is, the stronger the interference between the lights passing through the adjacent liquid crystal compounds 30, and therefore the greater the refraction of the transmitted light L2 and L5 can be achieved. Furthermore, by reversing the direction of rotation of the optical axis 30A of the liquid crystal compound 30, which rotates along the x direction, the direction of refraction of the 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 thickness d of the optically anisotropic layer 1 may be appropriately set to obtain a desired in-plane retardation, but is preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, and even more preferably 0.5 ⁇ m or less.
• the optically anisotropic layer 1 is used as a birefringent mask to form a photo-alignment pattern, the smaller the thickness d, the more preferable. The smaller the thickness d, the more accurate the formation of the photo-alignment pattern can be.
• the ratio of the period ⁇ to the thickness d of the optically anisotropic layer, ⁇ /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 light and dark by observing a periodic pattern of light and dark parts under crossed Nicols conditions using a polarizing microscope.
• the period ⁇ of the liquid crystal alignment pattern corresponds to twice the period of the observed periodic pattern of light and dark.
• the 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. There is no particular upper limit, but a value of 0.8 or less is preferred.
• the optically anisotropic layer a substantially broadband spectrum with respect to the wavelength of incident light by imparting a twist component to the composition and laminating different retardation layers.
• a method for realizing a broadband patterned ⁇ /2 plate by laminating two layers of liquid crystal with different twist directions in an optically anisotropic layer is shown in JP2014-089476A and the like, and can be suitably used in the optically anisotropic layer of the present invention.
• a specific example of a method for producing the optically anisotropic layer 1 includes a process X in which a substrate having an alignment film with a predetermined alignment pattern is brought into contact with a composition to form a composition layer on the alignment film on the substrate, and a process Y in which the composition layer is subjected to a heat treatment to align the liquid crystal compound, and then a curing treatment is performed.
• the above-mentioned substrate may or may not be removed from the optically anisotropic layer after the preparation of the optically anisotropic layer 1.
• the above-mentioned alignment film may or may not be removed from the optically anisotropic layer after the preparation of the optically anisotropic layer 1.
• steps X and Y The specific procedures of steps X and Y will be described in detail below.
• substrate the type of the substrate used is not particularly limited, and examples thereof include known substrates (for example, a resin substrate, a glass substrate, a ceramic substrate, a semiconductor substrate, and a metal substrate).
• Alignment film An alignment film is disposed on the substrate.
• the presence of the alignment film makes it easy to align the liquid crystal compound 30 in a predetermined liquid crystal alignment pattern when the optically anisotropic layer 1 is produced.
• the optically anisotropic layer 1 has a liquid crystal alignment pattern in which the direction of the optical axis 30A (see FIG. 2) originating from the liquid crystal compound 30 changes while continuously rotating along one direction (x direction) in the plane. Therefore, the alignment film is formed so that the optically anisotropic layer can form this liquid crystal alignment pattern.
• alignment films include rubbed films made of organic compounds such as polymers, obliquely evaporated films of inorganic compounds, films with microgrooves, and films formed by accumulating LB (Langmuir-Blodgett) films made by the Langmuir-Blodgett method of organic compounds such as ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, and methyl stearate.
• LB Lightmuir-Blodgett
• the alignment layer formed by rubbing treatment can be formed by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth.
• a material used for the alignment film polyimide, polyvinyl alcohol, a polymer having a polymerizable group described in JP-A-9-152509, and materials used for forming alignment films described in JP-A-2005-097377, JP-A-2005-099228, and JP-A-2005-128503, etc. can be suitably used.
• a so-called photo-alignment film can be suitably used, which is an alignment film formed by irradiating a photo-alignment material with polarized or non-polarized light.
• the photo-alignment material can be irradiated from a vertical direction or an oblique direction, and when the alignment film is formed by irradiating with non-polarized light, the photo-alignment material can be irradiated from an oblique direction.
• photo-alignment materials used in the photo-alignment film include those described in 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, and JP-A-2007 azo compounds described in JP-A-133184, JP-A-2009-109831, JP-B-3883848 and JP-B-4151746; aromatic ester compounds described in JP-A-2002-229039; and malic acid compounds having a photo-orienting unit described in JP-A-2002-265541 and JP-A-2002-317013.
• azo compounds, photocrosslinkable polyimides, photocrosslinkable polyamides, photocrosslinkable esters, cinnamate compounds, chalcone compounds, and the like can be suitably used.
• the thickness of the alignment film there is no limit to the thickness of the alignment film, and the thickness can be set appropriately to obtain the required alignment function depending on the material from which the alignment film is formed.
• the thickness of the alignment film is preferably 0.01 to 5 ⁇ m, and more preferably 0.05 to 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.
• the orientation pattern of the optically anisotropic layer 1 is more easily formed, it is preferable that the photo-alignment film is formed as an alignment film by irradiating a photo-alignment material with polarized or non-polarized light.
• the method described in [0078] to [0080] of International Publication No. 2020/022496 and the method described in FIG. 7 of JP-A-2022-036995 can be suitably applied.
• the method of contacting the composition with a substrate provided with an alignment film having a predetermined alignment pattern is not particularly limited, and examples thereof include a method of applying the composition onto the alignment film on the substrate, and a method of immersing the substrate with alignment film in the composition.
• a drying process may be carried out as necessary to remove the solvent from the composition layer disposed on the alignment film on the substrate.
• the composition layer is heated to align the liquid crystal compound, and then the layer is cured.
• the liquid crystal compound is oriented to form a liquid crystal phase.
• the conditions for the heat treatment are not particularly limited, and the optimum conditions are selected depending on the type of liquid crystal compound.
• the method of the curing treatment is not particularly limited, and examples thereof include photocuring treatment and heat curing treatment. Among these, photoirradiation treatment is preferred, and ultraviolet irradiation treatment is more preferred. For the ultraviolet irradiation, a light source such as an ultraviolet lamp is used.
• the cured product obtained by the above treatment corresponds to a layer in which a liquid crystal phase is fixed.
• a layer in which a cholesteric liquid crystal phase is fixed is formed. It is not necessary for these layers to exhibit liquid crystallinity any more. More specifically, for example, the state in which the cholesteric liquid crystal phase is "fixed" is the most typical and preferred state in which the orientation of the liquid crystal compound in the cholesteric liquid crystal phase is maintained.
• the layer has no fluidity and can stably maintain the fixed orientation without causing any change in the orientation due to an external field or external force, usually in a temperature range of 0 to 50°C, or under more severe conditions, in a temperature range of -30 to 70°C.
• the thickness of the optically anisotropic layer does not reach the desired value, another optically anisotropic layer may be formed on the surface of the optically anisotropic layer obtained in step Y.
• multiple optically anisotropic layers may be laminated by repeating steps X and Y until the thickness of the optically anisotropic layer reaches the desired thickness. Even when multiple optically anisotropic layers are formed, the orientation direction of the alignment film can be reflected from the lower surface to the upper surface of the optically anisotropic layer.
• optically anisotropic layer B another optically anisotropic layer (hereinafter also referred to as “optically anisotropic layer B”) is formed on the surface of the optically anisotropic layer (hereinafter also referred to as “optically anisotropic layer A”) obtained in process Y, it is preferable to apply a surface treatment to the surface of the optically anisotropic layer A on the side where the optically anisotropic layer B is to be placed.
• the surface treatment include a treatment for washing and removing the specific compound by pouring a solvent over the surface of the optically anisotropic layer A on the side where the optically anisotropic layer B is to be disposed, and a treatment for etching and removing the specific compound by subjecting the surface of the optically anisotropic layer A on the side where the optically anisotropic layer B is to be disposed to a corona treatment or the like.
• the optically anisotropic layer B is formed by a coating method, the above operation may or may not be performed as long as the specific compound can be removed from the optically anisotropic layer A by the solvent contained in the coating liquid for forming the optically anisotropic layer B.
• the optically anisotropic layer 2 shown in FIG. 5 is an optically anisotropic layer in which liquid crystal compounds 30 are cholesterically aligned in the thickness direction.
• Cholesteric liquid crystal phases are known to exhibit selective reflectivity at specific wavelengths.
• Cholesteric liquid crystal phases exhibit selective reflection for either left-handed or right-handed circularly polarized light at specific wavelengths. Whether the reflected light is right-handed or left-handed circularly polarized light depends on the twist direction (sense) of the helix of the cholesteric liquid crystal phase. When the helix of the cholesteric liquid crystal phase is twisted to the right, right-handed circularly polarized light is reflected, and when the helix is twisted to the left, left-handed circularly polarized light is reflected.
• the optically anisotropic layer 2 has the function of selectively reflecting light of a specific wavelength range that is a specific circularly polarized light (right-handed 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 similar to the orientation pattern in the optically anisotropic layer 1 shown in FIG. 1, and therefore produces the same effect as the optically anisotropic layer 1. That is, like the optically anisotropic layer 1 described above, the optically anisotropic layer 2 has the effect of changing the absolute phase of incident light and bending it in a predetermined direction. Therefore, the optically anisotropic layer 2 has both the effect of bending incident light in a direction different from the incident direction and the effect of the above-mentioned cholesteric orientation, and reflects light at an angle in a predetermined direction relative to the reflection direction of the specular reflection.
• the cholesteric liquid crystal phase of the optically anisotropic layer 2 is designed to reflect right-handed circularly polarized light.
• Fig. 5 when light L6, which is right-handed circularly polarized light PR , is incident perpendicularly to the main surface of the optically anisotropic layer 2, i.e., along the normal line, reflected light L7 is generated in a direction inclined with respect to the normal line direction.
• the optically anisotropic layer 2 functions as a reflective diffraction grating.
• the optic axes 30A of the liquid crystal compounds 30 in the liquid crystal alignment patterns of the optically anisotropic layers shown in Figures 1 to 5 rotate continuously in-plane along only the x-direction.
• various configurations are possible for the optically anisotropic layer of the present invention, so long as the optical axis 30A of the liquid crystal compound 30 rotates continuously along one direction.
• Fig. 6 is a schematic plan view of the optically anisotropic layer 3 of the design modification.
• the liquid crystal alignment pattern is indicated by the optical axis 30A of the liquid crystal compound.
• the optically anisotropic layer 3 has a liquid crystal alignment pattern in which regions in which the optical axis 30A has the same orientation are arranged concentrically, and one direction in which the orientation of the optical axis 30A changes while continuously rotating is arranged radially from the center of the optically anisotropic layer 3.
• the direction of the optical axis 30A changes while continuously rotating along a number of directions from the center of the optically anisotropic layer 3 toward the outside, for example, the direction indicated by the arrow A1 , the direction indicated by the arrow A2 , the direction indicated by the arrow A3, ....
• the absolute phase of the circularly polarized light incident on the optically anisotropic layer 3 having this liquid crystal orientation pattern changes in each local region having a different optical axis direction of the liquid crystal compound 30.
• the amount of change in each absolute phase differs depending on the optical axis direction of the liquid crystal compound 30 into which the circularly polarized light is incident.
• the liquid crystal orientation pattern of the optically anisotropic layer is concentric and the optically anisotropic layer is made to act as a convex lens
• the angle of refraction of light with respect to the incident direction becomes larger as one period ⁇ in the liquid crystal orientation pattern becomes shorter.
• the light focusing power of the optically anisotropic layer 3 can be further improved, and the performance as a convex lens can be improved.
• the laminate for example when it is used as a concave lens, it is preferable to rotate one period ⁇ in which the optical axis rotates 180° in the liquid crystal orientation pattern in the opposite direction to the direction in which the optical axis continuously rotates from the center of the optically anisotropic layer 3, and gradually shorten it toward the outside in one direction.
• the divergence power of light by the optically anisotropic layer 3 can be further improved, and the performance as a concave lens can be improved.
• the optically anisotropic layer is a concave lens
• one period ⁇ in the concentric liquid crystal alignment pattern may be gradually lengthened from the center of the optically anisotropic layer 3 toward the outside in one direction in which the optical axis rotates continuously.
• the optically anisotropic layer for example when it is desired to provide a light quantity distribution in transmitted light, it is also possible to use a configuration in which, rather than gradually changing one period ⁇ in one direction in which the optical axis rotates continuously, there are regions in which one period ⁇ is partially different in one direction in which the optical axis rotates continuously.
• the light-emitting element may have an optically anisotropic layer in which the period ⁇ is uniform across the entire surface, and an optically anisotropic layer having regions in which the period ⁇ differs.
• the configuration in which the period ⁇ in which the optical axis rotates 180° is changed in one direction in which the optical axis rotates continuously can also be used in the configuration in which the optical axis 30A of the liquid crystal compound 30 rotates and changes continuously in only one direction, the x direction, as shown in Figures 1 to 4.
• an optically anisotropic layer that transmits light so as to be concentrated can be obtained.
• an optically anisotropic layer that transmits light so as to be diffused only in the x direction can be obtained.
• an optically anisotropic layer that transmits light so as to be diffused only in the X direction of the arrow can also be obtained. Furthermore, depending on the application of the optically anisotropic layer, for example when it is desired to provide a light quantity distribution in transmitted light, it is also possible to use a configuration having an area in which one period ⁇ is partially different in the x direction, rather than gradually changing one period ⁇ in the x direction.
• the optical element of the present invention has an optically anisotropic layer formed from the above-mentioned composition.
• the use of the optical element is not particularly limited, and it can be used for various purposes that transmit light in a direction different from the incident direction, such as an optical path changing member in an optical device, a light focusing element, a light diffusing element in a specified direction, and a diffraction element.
• a preferred application is a light guide element.
• the light guide element typically includes a light guide plate and a diffraction element disposed on the light guide plate (preferably disposed at a distance from the light guide plate).
• the optical element of the present invention is suitably used as a diffraction element.
• Solution A was prepared by dissolving NaH 2 PO 4 dihydrate (2.2 mmol) and tetrabutylammonium hydrogen sulfate (0.08 mmol) in water (2.2 mL).
• solution B was prepared by dissolving compound 1b (7.8 mmol) in ethyl acetate (6 mL) and THF (5 mL), and solution A was added dropwise to solution B.
• hydrogen peroxide 1.3 mmol
• was further added followed by an aqueous solution of NaClO 2 (9.4 mmol) (2.5 mL), and the mixture was stirred at 40° C. for 1 hour.
• Compound A3 was synthesized in the same manner as in the above-mentioned [Synthesis of Compound A2], except that the raw material component, Compound 2a, was changed to Compound 3a.
• Compound A4 was synthesized using the same procedure as described above for [Synthesis of Compound A2], except that the raw material component, compound 2a, was changed to compound 4a.
• Compound A40 was synthesized using the same procedure as in the synthesis of compound A1 described above, except that the raw material compound 1a was replaced with compound 4a and the skeleton raw material was changed to hydroquinone.
• Compound A41 was synthesized using the same procedure as in the synthesis of compound A1 described above, except that the raw material compound 1a was replaced with compound 5a and the skeleton raw material was changed to hydroquinone.
• Example 1 [Preparation of photo-alignment film] A glass substrate was prepared as a support. The coating solution 1 for forming a photo-alignment film was applied onto the support at 2500 rpm for 30 seconds using a spin coater. The support coated with the coating solution 1 for forming a photo-alignment film was then dried on a hot plate at 60° C. for 60 seconds to form a dry film on the support.
• the above-mentioned dried film on the support was irradiated with linearly polarized UV light at 10 mW/cm 2 for 30 seconds using a 365 nm LED-UV irradiation device through a wire grid polarizer to form a photoalignment film.
• optically anisotropic layer 1A was observed under an optical microscope and the alignment was evaluated according to the following criteria. The results are shown in Table 1. (Evaluation Criteria) "A”: No alignment defects; “B”: Slight alignment defects; “C”: Many alignment defects
• the orientation of the optically anisotropic layer 1B in the obtained laminate was observed with an optical microscope, and the presence or absence of repelling was visually observed, and evaluation was performed according to the following criteria.
• the presence of repelling refers to the presence of a portion where the optically anisotropic layer 1B has not been formed and/or a portion where the optically anisotropic layer 1B has uneven coating.
• Cycling resistance evaluation criteria "A”: No repelling.
• B” There is a slight amount of repelling.
• C There are many repellings.
• Orientation defect evaluation criteria "A”: No alignment defect.
• B” There is a slight alignment defect.
• C” There are many alignment defects.
• Examples 2 to 11, Comparative Examples 1 and 2 Except for changing the liquid crystal compound and the alignment agent as shown in Table 1, coating solutions 2 to 11, R1, and R2 for forming an optically anisotropic layer (coating solutions 2 to 11, R1, and R2) were prepared with the same composition as the coating solution 1 for forming an optically anisotropic layer.
• a polyorganosiloxane compound compound CE1 having a polymerizable group (epoxy group) and a molecular weight of 9,500 was synthesized by the method described in [Synthesis Example CE-1] of paragraph 0069 of Japanese Patent No. 6,617,529, and used as an alignment agent.
• Optically anisotropic layers 2A to 11A, R1A, and R2A were prepared in the same manner as in ⁇ Preparation and evaluation of optically anisotropic layer 1A> above, except that coating solution 1 for forming an optically anisotropic layer was changed to coating solutions 2 to 11, R1, and R2 for forming an optically anisotropic layer shown in Table 1, and the alignment properties were evaluated. The results are shown in Table 1.
• liquid crystal compounds used in Table 1 are shown below.
• a glass substrate was prepared as a support.
• the composition 2 for photo-alignment film was applied onto the support by a spin coater.
• the support on which the composition 2 for photo-alignment film was applied was then placed in a dryer at 120° C. for 1 minute to remove the solvent, forming a dry film with a thickness of 0.3 ⁇ m.
• the photo-alignment film was then formed by irradiating the substrate with polarized ultraviolet light (10 mJ/cm, using an ultra-high pressure mercury lamp).
• Coating Solution 12 for Forming Optically Anisotropic Layer (Coating Solution 12)> An optically anisotropic layer forming coating solution 12 having the following composition was prepared.
• Coating liquid 12 for forming optically anisotropic layer ⁇ - 100.00 parts by mass of polymerizable liquid crystal compound LC10 shown below - 0.50 parts by mass of polymerization initiator S1 shown below - 0.09 parts by mass of alignment agent (compound A1) shown in Table 1 - 179.67 parts by mass of cyclopentanone - 53.67 parts by mass of methyl ethyl ketone
• the alignment was fixed by irradiating ultraviolet light (300 mJ/cm 2 , using an ultra-high pressure mercury lamp) in a nitrogen atmosphere (oxygen concentration 100 ppm by volume), to produce an optically anisotropic layer 12A having a thickness of 2.1 ⁇ m.
• the obtained optically anisotropic layer 12A was peeled off from the support, and the phase difference of the optically anisotropic layer 12A was measured.
• the in-plane retardation Re1(550) was 145 nm, and Re1(450)/Re1(550) was 0.83.
• the alignment property of the obtained optically anisotropic layer 12A was evaluated in the same manner as in Example 1. The results are shown in Table 1.
• Leveling agent Y- (The numerical values attached to the repeating units in the following structural formula are based on mass %. The weight average molecular weight of leveling agent Y is 15,300.)
• ⁇ Preparation of Optically Anisotropic Layer 12B> The surface of the optically anisotropic layer 12A opposite to the glass substrate was subjected to a corona treatment at a discharge amount of 150 W ⁇ min/ m2 , and the above-mentioned coating solution 12' for forming an optically anisotropic layer was applied to the corona-treated surface by a spin coater. Next, the resulting laminate with the coating film was heated with hot air at 85°C for 60 seconds to dry the solvent of the composition and to ripen the alignment of the liquid crystal compound.
• the alignment was fixed by irradiating with ultraviolet light (150 mJ/ cm2 ) at 50°C under a nitrogen purge with an oxygen concentration of 100 ppm by volume, to produce an optically anisotropic layer 12B having a thickness of 2.0 ⁇ m.
• a laminate Z1 was obtained which had a support, a photo-alignment film, an optically anisotropic layer 12A, and an optically anisotropic layer 12B in this order.
• the alignment of the optically anisotropic layer 12B in the obtained laminate Z1 and the presence or absence of repelling were evaluated in the same manner as in Example 1.
• the support and the photo-alignment film were peeled off from the prepared laminate, and the phase difference of the laminate (optically anisotropic layer 12A/optically anisotropic layer 12B) was measured.
• the phase difference of the optically anisotropic layer 12B was calculated by subtracting the phase difference of the optically anisotropic layer 12A measured earlier.
• the retardation in the thickness direction Rth(550) was ⁇ 90 nm, and it was confirmed that the optically anisotropic layer 12B was a positive C plate.
• Example 13 ⁇ Preparation of Coating Solution 13 for Forming Optically Anisotropic Layer (Coating Solution 13)> An optically anisotropic layer-forming coating solution 13 having the following composition was prepared.
• ⁇ Coating liquid 13 for forming optically anisotropic layer ⁇ - 100.00 parts by mass of polymerizable liquid crystal compound LC11 shown below - 0.50 parts by mass of polymerization initiator S1 shown above - 0.09 parts by mass of alignment agent (compound A1) shown in Table 1 - 179.67 parts by mass of cyclopentanone - 53.67 parts by mass of methyl ethyl ketone
• optically anisotropic layer 13B was formed on the surface of the optically anisotropic layer 13A by the same procedure as in the above-mentioned ⁇ Preparation and evaluation of optically anisotropic layer 12B> (that is, the optically anisotropic layer 13B is an optically anisotropic layer formed using the coating liquid for forming an optically anisotropic layer 12', like the optically anisotropic layer 12B).
• the prepared laminate was used to carry out evaluation by the same procedure as in ⁇ Preparation and evaluation of optically anisotropic layer 12B>. The results are shown in Table 1.
• Coating Solution 14 for Forming Optically Anisotropic Layer
• An optically anisotropic layer forming coating solution 14 having the following composition was prepared.
• Coating liquid 14 for forming optically anisotropic layer ⁇ - 100.00 parts by mass of polymerizable liquid crystal compound LC12 shown below - 0.50 parts by mass of polymerization initiator S1 shown above - 0.09 parts by mass of alignment agent (compound A1) shown in Table 1 - 179.67 parts by mass of cyclopentanone - 53.67 parts by mass of methyl ethyl ketone
• optically anisotropic layer 14B was formed on the surface of the optically anisotropic layer 14A by the same procedure as in the above-mentioned ⁇ Preparation and evaluation of optically anisotropic layer 12B> (that is, the optically anisotropic layer 14B is an optically anisotropic layer formed using the coating liquid for forming an optically anisotropic layer 12', like the optically anisotropic layer 12B).
• the prepared laminate was used to carry out evaluation by the same procedure as in ⁇ Preparation and evaluation of optically anisotropic layer 12B>. The results are shown in Table 1.
• Example 15 [Preparation and Evaluation of Optically Anisotropic Layer] An optically anisotropic layer forming coating solution 15 having the following composition was prepared.
• Coating liquid 15 for forming optically anisotropic layer ⁇
• the polymerizable liquid crystal compound LC3 100.00 parts by mass Alignment agent (the compound A1) 0.40 parts by mass Polymerization initiator (Omnirad 819 (manufactured by IGM Resins B.V.)) 3.00 parts by mass Chiral agent (Paliocolor LC756 (manufactured by BASF)) 5.70 parts by mass Cyclohexanone Amount to make the solute concentration 30% by mass ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
• a photo-alignment film was formed on a glass substrate by the same procedure as in Example 1 (Preparation of Photo-Alignment Film).
• the coating solution 15 for forming an optically anisotropic layer was measured out using a micropipette, dropped onto the photoalignment film, and spin-coated at a rotation speed of 1500 rpm.
• the resulting coating film was then heated at 100° C. for 1 minute, and irradiated with UV light at an illuminance of 10 mW/cm 2 for 30 seconds using a 365 nm LED-UV irradiation device under a nitrogen atmosphere to form an optically anisotropic layer 15A.
• the optically anisotropic layer 15A showed a central reflection wavelength of 550 nm.
• the haze value of the optically anisotropic layer 15A was measured with a haze meter and found to be less than 1.0. In other words, it was confirmed that the optically anisotropic layer 15A had reduced alignment defects.
• Example 3 Except for changing the alignment agent to compound CE1, an optically anisotropic layer R3A was prepared and evaluated in the same manner as in Example 15.
• the optically anisotropic layer R3A exhibited a central reflection wavelength at about 550 nm, but the spectrum was broad due to scattering, and the haze value was 5.0 or more.
• Example 16 [Preparation of photo-alignment film] A dried film of the coating solution 1 for forming a photo-alignment film described in Example 1 was exposed to light using the exposure device shown in FIG. 7 of JP-A-2022-036995 under an environment of a temperature of 25° C. and a relative humidity of 10%, to form a photo-alignment film P-1 having an alignment pattern.
• a laser emitting laser light with a wavelength of 325 nm was used.
• the exposure amount by the interference light was 3000 mJ/cm 2.
• the crossing angle (crossing angle ⁇ ) of the two laser lights was 9.3°.
• the coating solution 1 for forming an optically anisotropic layer was measured out using a micropipette, dropped onto the photoalignment film, and spin-coated at a rotation speed of 1500 rpm.
• the film was heated at 80° C. for 1 minute, and then irradiated with UV light at 10 mW/cm 2 for 30 seconds using a 365 nm LED-UV irradiation device under a nitrogen atmosphere to form an optically anisotropic layer 16A.
• the following lamination step was repeated three times on the optically anisotropic layer 16A after the above-mentioned solvent washing treatment with cyclohexanone, to prepare a laminate in which four optically anisotropic layers were laminated.
• Lamination process 50 ⁇ L of the coating solution 1 for forming an optically anisotropic layer was measured out using a micropipette, dropped onto the optically anisotropic layer, and spin-coated at a rotation speed of 1500 rpm. The layer was heated at 80° C. for 1 minute, and irradiated with UV light at 10 mW/cm 2 for 30 seconds using a 365 nm LED-UV irradiation device under a nitrogen atmosphere. Next, 200 ⁇ L of cyclohexanone was measured out using a micropipette, dropped onto the optically anisotropic layer, and spin-coated at a rotation speed of 1500 rpm.
• the orientation of the obtained laminate was observed with an optical microscope, and it was confirmed that the stripe pattern was clearly visible. It was also visually confirmed that there was no repelling in the laminate.
• Optically anisotropic layer xy plane Sheet surface z direction Thickness direction 30 Liquid crystal compound ⁇ Length of one period 30A Optical axis derived from liquid crystal compound 30 ⁇ Angle R Region d Thickness (film thickness) of optically anisotropic layer P L left circularly polarized light P R right circularly polarized light L 1 , L 4 , L 6 incident light L 2 , L 5 , L 7 transmitted light Q1, Q2 absolute phase E1, E2 equal phase plane A 1 , A 2 , A 3 directions

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