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  • 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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  • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
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  • C09K19/16—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 double bonds, e.g. stilbenes
• • G—PHYSICS
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  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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• • 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
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  • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
  • C09K2019/0414—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a heterocyclic ring
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  • 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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  • C09K19/06—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
  • C09K19/16—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 double bonds, e.g. stilbenes
  • C09K2019/168—Ph-CH=CH-Ph-CH=CH-Ph
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  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
  • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
  • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
  • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
  • C09K2019/2042—Ph-Ph-COO-Ph
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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
  • C09K2019/2078—Ph-COO-Ph-COO-Ph
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  • C09K2019/528—Surfactants

Definitions

• the present invention relates to compounds and liquid crystal compositions.
• a compound exhibiting liquid crystallinity can be applied to various uses.
• the liquid crystal compound is applied to the production of an optically anisotropic substance represented by a retardation film or the production of a reflective film formed by immobilizing a cholesteric liquid crystal phase.
• the cholesteric liquid crystal phase is formed by adding a chiral compound to a nematic liquid crystal.
• Patent Document 1 discloses a chiral compound having a helical twisting power (HTP) with respect to a liquid crystal compound.
• the chiral compound described in Patent Document 1 has photosensitivity, and HTP changes by light irradiation.
• photosensitive chiral compounds are required to have a large amount of change in HTP. Specifically, when the chiral compound is exposed to ultraviolet rays or the like, it is required that the amount of change in HTP before and after the exposure is large.
• a large amount of change in HTP of a chiral compound before and after exposure is referred to as an excellent amount of change in HTP.
• the photosensitive chiral compound easily changes HTP at the time of exposure. Specifically, it is required that the HTP changes quickly with a small amount of exposure, and the change in HTP easily reaches the saturation point.
• the change in HTP of the chiral compound easily reaches the saturation point with a small amount of exposure, which is excellent in the HTP saturation rate.
• Y represents a group represented by the general formula (C-1) described later, and represents The compound according to any one of (1) to (5), wherein A 2 in the group represented by the general formula (C-1) represents an aromatic group which may have a substituent.
• Y represents a group represented by the general formula (C-1) described later, and represents Among the groups represented by the general formula (C-1), R 1 represents a hydrogen atom, a halogen atom, -CN, -COR, -POR 2 , -SOR, -SO 2 R, or -NO 2 .
• R 1 represents a hydrogen atom, a halogen atom, -CN, -COR, -POR 2 , -SOR, -SO 2 R, or -NO 2 .
• R represents a hydrogen atom, a halogen atom, -CN, -COR, -POR 2 , -SOR, -SO 2 R, or -NO 2 .
• R
• a liquid crystal composition containing the above compound can be provided.
• the present invention will be described in detail.
• the description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
• the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• (meth) acrylate is a notation representing both acrylate and methacrylate.
• the substituent when it is simply referred to as a substituent, the substituent includes, for example, the following substituent T.
• substituent T include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, and a heterocyclic group.
• Cyano group hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino Group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group , Alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo
• L T represents a single bond or a divalent linking group.
• PT represents any of the polymerizable groups represented by the general formulas (P-1) to (P-20) described later.
• the divalent linking group represented by L T is not particularly limited, is preferably an alkylene group which may contain a hetero atom, more alkylene groups contain an ⁇ 1 carbon atoms which may 10 oxygen atoms
• Ra represents a hydrogen atom or a methyl group.
• Me represents a methyl group and Et represents an ethyl group.
• those having a hydrogen atom may be further substituted with any of the above-mentioned substituents in the portion of the hydrogen atom in the substituent.
• the bonding direction of the divalent group described in the present specification is not limited unless otherwise specified.
• G is a group represented by the general formula (B-1) or a general formula (B-2).
• the group represented may be selected, and the group represented by the general formula (C-1) or the group represented by the general formula (C-2) may be selected as Y.
• a photosensitive chiral compound can undergo structural change by photoisomerizing so that its side chains are on different sides when exposed to energy irradiation such as ultraviolet rays.
• the specific compound Since the specific compound has a group represented by G and Y, it is presumed that the structural change due to photoisomerization is large and an excellent amount of change in HTP is achieved. Further, the specific compound has an excellent HTP saturation rate because the HTP changes quickly even with a small exposure amount and the change in HTP easily reaches the saturation point.
• the specific compound will be described in detail.
• G represents a group represented by the general formula (B-1) or a group represented by the general formula (B-2). Among them, G has at least one effect of being superior to the amount of change in HPT and being superior to the saturation rate of HPP (hereinafter, also referred to as “the effect of the present invention is more excellent”).
• the group represented by the general formula (B-1) is preferable.
• G is a group represented by the general formula (B-2)
• two Xs may be bonded to each other to form a ring.
• * represents the bond position.
• G is a group represented by the general formula (B-2)
• the specific compound is preferably a compound represented by the following formula.
• X independently represents a hydrogen atom or a monovalent substituent.
• the monovalent substituent represented by X is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned substituent T. Among them, a hydrogen atom is preferable as X in that the effect of the present invention is more excellent.
• Y represents a group represented by the general formula (C-1) or a group represented by the general formula (C-2). Among them, the group represented by the general formula (C-1) is preferable as Y in that the effect of the present invention is more excellent.
• * represents the bond position.
• L 1 independently represents a single bond or a divalent linking group. Among them, a single bond is preferable as L 1 in that the effect of the present invention is more excellent.
• the divalent linking group represented by L 1 is not particularly limited, but for example, a divalent aromatic hydrocarbon group (preferably having 1 to 15 carbon atoms, for example, a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene). A group may be mentioned.)
• a divalent aliphatic hydrocarbon group (which may be linear, branched or cyclic, and preferably has 1 to 10 carbon atoms, for example, an alkylene group or an alkenylene group.
• RA represents a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms). The hydrogen atom in the divalent linking group may be further substituted with a substituent.
• R 1 and R 2 independently represent a hydrogen atom or a monovalent substituent.
• the monovalent substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned substituent T. Among them, hydrogen atom, halogen atom, -CN, -COR, -POR 2 , -SOR, -SO 2 R, or -NO 2 are preferable as R 1 in that the effect of the present invention is more excellent. A hydrogen atom or -CN is more preferred.
• R independently represents a monovalent substituent.
• the monovalent substituent represented by R is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned substituent T. Further, a hydrogen atom is preferable as R 2 in that the effect of the present invention is more excellent.
• a 1 represents an aromatic group which may have a substituent.
• the aromatic group represented by A 1 corresponds to a divalent aromatic group.
• Examples of the aromatic group represented by A 1 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
• the aromatic ring constituting the aromatic group represented by A 1 may have either a monocyclic structure or a polycyclic structure.
• the substituent that the aromatic group represented by A 1 may have is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned Substituent T.
• Examples of the aromatic group represented by A 1 include a phenylene group, a naphthylene group, a fluorenylene group, an anthracenylene group, and a biphenylene group. Among them, in terms of the effect of the present invention is more excellent, as A 1, preferably an arylene group optionally having a substituent, an unsubstituted arylene group is more preferably a phenylene group, or, more preferably a naphthylene group ..
• Z is, -CH 2 - may be substituted by -CO- or -O- - (CH 2) 4 - , a single bond, - (CH 2) 2 - , - COO-, or, -CH 2 Represents O-.
• Z a single bond or -COO- is preferable, and a single bond is more preferable, in that the effect of the present invention is more excellent.
• a 2 represents an aromatic group which may have a substituent or an alicyclic group which may have a substituent.
• the aromatic group represented by A 2 corresponds to a monovalent aromatic group.
• the alicyclic group represented by A 2 corresponds to a monovalent alicyclic group.
• Examples of the aromatic group represented by A 2 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
• the aromatic ring constituting the aromatic group represented by A 2 may have either a monocyclic structure or a polycyclic structure.
• the substituent that the aromatic group represented by A 2 may have is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned Substituent T.
• the substituent that the aromatic group represented by A 2 may have is an alkoxy group, an alkoxycarbonyl group, a cyano group, a hydroxyl group, a nitro group, or , A carboxyl group is preferable, and an alkoxy group or an alkoxycarbonyl group is more preferable.
• the alicyclics constituting the alicyclic group may have either a monocyclic structure or a polycyclic structure.
• the number of carbon atoms of the alicyclic group represented by A 2 is not particularly limited, but 3 to 10 is preferable because the effect of the present invention is more excellent.
• the substituent that the alicyclic group represented by A 2 may have is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned Substituent T.
• the alicyclic group represented by A 2 is not particularly limited, but for example, a cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Can be mentioned.
• an aromatic group which may have a substituent is preferable, an aryl group which may have a substituent is more preferable, and a substituent is more preferable.
• a phenyl group which may have a phenyl group is more preferable.
• R 1 , R 2, A 1 and, Z is, R 1 in the general formula (C-1), R 2 , A 1, and, and Z It has the same meaning, and the preferable range is also the same.
• L 2 represents a single bond or -L 3- A 3- **. ** represents the connection position with Z.
• L 3 represents a single bond or a divalent linking group.
• the divalent linking group represented by L 3 is not particularly limited, and examples thereof include the groups exemplified by the divalent linking group represented by L 1.
• a 3 represents an aromatic group which may have a substituent or an alicyclic group which may have a substituent.
• Aromatic group represented by A 3 corresponds to a divalent aromatic group.
• Alicyclic group represented by A 3 corresponds to a divalent alicyclic group.
• Aromatic ring constituting the aromatic group represented by A 3 is a monocyclic structure, and may be any of a polycyclic structure.
• aromatic group represented by A 3 it is not particularly limited substituent which may have, for example, the groups exemplified in substituent group T described above.
• the number of carbon atoms of the alicyclic group represented by A 3 is not particularly limited, in terms of the effect of the present invention is more excellent, preferably 3-10.
• alicyclic group represented by A 3 it is not particularly limited substituent which may have, for example, the groups exemplified in substituent group T described above. Among them, a single bond is preferable as L 2 in that the effect of the present invention is more excellent.
• R 3 represents a hydrogen atom or a monovalent substituent.
• the monovalent substituent represented by R 3 is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned substituent T. Among them, in terms of the effect of the present invention is more excellent, as the R 3, which may have a substituent alkyl group which may have a substituent aromatic group, or has a substituent.
• the alicyclic group which may be present is preferable, the aromatic group which may have a substituent, or the alicyclic group which may have a substituent is more preferable, and the alicyclic group which may have a substituent may be present.
• a cycloalkyl group which may have an aryl group or a substituent is further preferable.
• the specific compound can be synthesized by a known method.
• the specific compound may be R-form, S-form, or a mixture of R-form and S-form. Specific examples of the specific compound are shown below, but the present invention is not limited thereto.
• the specific compound can be applied to various uses and is preferably used as a so-called chiral compound.
• a cholesteric liquid crystal phase can be formed by using a liquid crystal composition obtained by mixing a specific compound and a liquid crystal compound.
• the liquid crystal composition of the present invention hereinafter, also referred to as “specific liquid crystal composition” will be described in detail.
• the specific liquid crystal composition includes a specific compound and a liquid crystal compound.
• various components essential or optionally contained in the specific liquid crystal composition will be described.
• the specific liquid crystal composition contains a specific compound.
• the specific compound is as described above.
• the content of the specific compound in the specific liquid crystal composition is not particularly limited, but is preferably 0.1 to 20% by mass, preferably 0.5 to 15% by mass, based on the total mass of the liquid crystal compound in the specific liquid crystal composition. % Is more preferable, and 1.0 to 10% by mass is further preferable.
• the specific liquid crystal composition one specific compound may be used alone, or two or more specific compounds may be used. When two or more kinds are used, it is preferable that the total content is within the above range.
• the specific liquid crystal composition contains a liquid crystal compound.
• the liquid crystal compound is a compound other than the specific compound and means a compound exhibiting liquid crystallinity.
• the "liquid crystal-forming compound” is intended to have 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. do.
• the optical anisotropy and fluidity derived from the liquid crystal phase can be confirmed by observing the compound under a polarizing microscope while heating or lowering the temperature of the compound with a hot stage system FP90 manufactured by Metertredo. ..
• the liquid crystal compound is not particularly limited as long as it has a liquid crystal property, and examples thereof include a rod-shaped nematic liquid crystal compound.
• the rod-shaped nematic liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted compounds.
• examples thereof include phenylpyrimidines, phenyldioxans, trans, and alkenylcyclohexylbenzonitriles. Not only low molecular weight liquid crystal compounds but also high molecular weight liquid crystal compounds can be used.
• the liquid crystal compound may be polymerizable or non-polymerizable, and is preferably polymerizable.
• a liquid crystal compound having one or more polymerizable groups is preferable, and a liquid crystal compound having two or more polymerizable groups is more preferable, because the cholesteric liquid crystal phase can be fixed. Liquid crystal compounds having a group are more preferable.
• Rod-shaped liquid crystal compounds having no polymerizable group are described in various documents (for example, Y. Goto et.al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp.23-28). be.
• the polymerizable rod-shaped liquid crystal compound is obtained by introducing a polymerizable group into the rod-shaped liquid crystal compound.
• the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, and an unsaturated polymerizable group is preferable, and an ethylenically unsaturated polymerizable group is more preferable.
• the polymerizable group can be introduced into the molecule of the rod-shaped liquid crystal compound by various methods.
• the number of polymerizable groups contained in the polymerizable rod-shaped liquid crystal compound is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2.
• Two or more kinds of polymerizable rod-shaped liquid crystal compounds may be used in combination. When two or more kinds of polymerizable rod-shaped liquid crystal compounds are used in combination, the orientation temperature can be lowered.
• the liquid crystal compound is preferably a compound represented by the general formula (LC).
• P 11 and P 12 each independently represent a hydrogen atom or a polymerizable group. However, at least one of P 11 and P 12 represents a polymerizable group.
• L 11 and L 12 each independently represent a single bond or a divalent linking group.
• a 11 to A 15 each independently represent an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
• Z 11 to Z 14 each independently represent a single bond or a divalent linking group.
• m 3 and m 4 independently represent an integer of 0 or 1, respectively.
• the polymerizable group represented by P 11 and P 12 is not particularly limited, but for example, the polymerizable group represented by the general formulas (P-1) to (P-20) described above. Can be mentioned.
• the polymerizable groups represented by P 11 and P 12 represent the above-mentioned general formulas (P-1) to (P-20), * in the general formulas (P-1) to (P-20). Represents the bonding position with L 11 or L 12.
• P 11 and P 12 is preferably representative of at least one one of polymerizable group, and more preferably both P 11 and P 12 represents a polymerizable group.
• the divalent linking group represented by L 11 and L 12 is not particularly limited, and for example, a linear or branched alkylene group having 1 to 20 carbon atoms and carbon.
• a linear or branched alkylene group of the number 1 to 20 one or more -CH 2- is -O-, -S-, -NH-, -N (CH 3 )-, -CO.
• Examples include linking groups selected from the group consisting of groups substituted with ⁇ or —COO ⁇ .
• the divalent linking group represented by L 11 and L 12 one or two or more -CH 2- in a linear or branched alkylene group having 1 to 20 carbon atoms is -O-. Groups substituted with are preferred.
• a 11 to A 15 each independently have an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Represents.
• the number of ring members of the aromatic hydrocarbon ring group is preferably 5 to 10.
• the aromatic hydrocarbon ring constituting the aromatic hydrocarbon ring group may have either a monocyclic structure or a polycyclic structure.
• the number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 18, and more preferably 6 to 10.
• the aromatic hydrocarbon ring is not particularly limited, and examples thereof include a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Of these, the benzene ring is preferable as the aromatic hydrocarbon ring.
• the aromatic hydrocarbon ring group is formed by removing two hydrogen atoms on the ring of the aromatic hydrocarbon ring.
• the number of ring members of the aromatic heterocyclic group is preferably 5 to 10.
• the aromatic heterocycle constituting the aromatic heterocyclic group may have either a monocyclic structure or a polycyclic structure.
• the hetero atom contained in the aromatic heterocyclic group is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom.
• the aromatic heterocycle preferably has 5 to 18 carbon atoms.
• the aromatic heterocycle is not particularly limited, and examples thereof include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiophene ring, a thiazole ring, and an imidazole ring.
• the aromatic heterocyclic group is formed by removing two hydrogen atoms on the ring of the aromatic heterocycle.
• the aromatic hydrocarbon ring group and the aromatic heterocyclic group may have a substituent.
• the type of the substituent is not particularly limited, and examples thereof include known substituents.
• the above-mentioned substituent is not particularly limited, and for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acyl group, an acyloxy group, a cyano group, and the like.
• Examples thereof include a nitro group and an alkoxycarbonyl group.
• Each of the above groups may be further substituted with a substituent.
• the hydrogen atom in the alkyl group may be substituted with a fluorine atom.
• the number of substituents is not particularly limited, and the aromatic hydrocarbon ring group and the aromatic heterocyclic group may have one substituent or may have a plurality of substituents. good.
• the substituent is preferably a fluorine atom, a chlorine atom, a fluoroalkyl group, an alkoxy group, or an alkyl group in that the solubility of the compound represented by the general formula (LC) is further improved.
• the fluoroalkyl group is a group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom, and it is preferable that all hydrogen atoms are substituted with a fluorine atom (so-called perfluoroalkyl group). preferable).
• an aromatic hydrocarbon ring group which may have a substituent is preferable, and a phenylene group bonded at the 1-position and the 4-position is more preferable.
• the divalent linking group represented by Z 11 to Z 14 is not particularly limited, and for example, a divalent aliphatic hydrocarbon group (linear, branched chain, and cyclic) is used. Any of them may be used, and the number of carbon atoms is preferably 1 to 20, and examples thereof include an alkylene group. In addition, an alkaneylene group or an alkynylene group may be used), —O—,.
• RC represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
• the hydrogen atom in the divalent linking group may be substituted with another substituent such as a halogen atom.
• m 3 and m 4 independently represent an integer of 0 or 1, and 0 is preferable.
• the compound represented by the general formula (LC) can be synthesized by a known method. Specific examples of the compound represented by the above general formula (LC) are shown below, but the present invention is not limited thereto.
• the content of the liquid crystal compound in the specific liquid crystal composition is preferably 5 to 99% by mass, more preferably 25 to 99% by mass, and further preferably 75 to 99% by mass with respect to the total solid content of the specific liquid crystal composition.
• the solid content is intended to be a component other than the solvent in the specific liquid crystal composition. If it is not a solvent, even if it is a liquid component, it is regarded as a solid content.
• the specific liquid crystal composition one liquid crystal compound may be used alone, or two or more liquid crystal compounds may be used. When two or more kinds are used, it is preferable that the total content is within the above range.
• the specific liquid crystal composition may contain a surfactant that contributes to the formation of a stable or rapid liquid crystal phase (eg, nematic liquid crystal phase, cholesteric liquid crystal phase).
• a surfactant for example, the compound described in paragraphs 0020 to 0031 of JP2013-047204 (Patent No. 5774518), the fluorine-containing (meth) acrylate-based polymer, and the general formula (X1) described in WO2011 / 162291. )-(X3), and compounds represented by the general formula (I) described in paragraphs 802 to 0090 of JP2014-119605.
• horizontal orientation means the molecular axis of the liquid crystal compound (when the liquid crystal compound is a rod-shaped liquid crystal compound, it corresponds to the long axis of the liquid crystal compound) and the surface of the layer of the composition (although it means that the liquid crystal surfaces are parallel, it does not require that they are strictly parallel, and in the present specification, it means an orientation in which the inclination angle formed with the liquid crystal surface is less than 20 degrees.
• the spiral axis deviates from the normal of the film surface, resulting in a decrease in reflectance or a finger. It is not preferable because a print pattern is generated and haze is increased or diffractivity is exhibited.
• fluorine-containing (meth) acrylate-based polymer that can be used as a surfactant include the polymers described in paragraphs 0018 to 0043 of JP-A-2007-272185.
• the content of the surfactant is not particularly limited, but is preferably 0.001 to 10% by mass, preferably 0.05 to 3% by mass, based on the total mass of the liquid crystal compound. % Is more preferable.
• the specific liquid crystal composition one type of surfactant may be used alone, or two or more types may be used. When two or more kinds are used, it is preferable that the total content is within the above range.
• the specific liquid crystal composition may contain a solvent.
• the solvent preferably can dissolve each component of the composition.
• the solvent include methyl ethyl ketone, cyclohexanone, and a mixed solvent thereof. Among them, the solvent is preferably methyl ethyl ketone because the effect of the present invention is more excellent.
• the specific liquid crystal composition contains a solvent, the content of the solvent in the specific liquid crystal composition is preferably an amount having a solid content concentration of 5 to 50% by mass, more preferably 10 to 40% by mass. preferable.
• one kind of solvent may be used alone, or two or more kinds of solvents may be used. When two or more kinds are used, it is preferable that the total content is within the above range.
• the specific liquid crystal composition includes a polymerization initiator, an antioxidant, an ultraviolet absorber, a sensitizer, a stabilizer, a plasticizer, a chain transfer agent, a polymerization inhibitor, a defoaming agent, a leveling agent, and a thickening agent. It may contain agents, flame retardants, dispersants, polymerizable monomers, and other additives such as colorants such as dyes and pigments.
• the specific liquid crystal composition may contain a polymerization initiator.
• the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Of these, a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
• the photopolymerization initiator is not particularly limited, and examples thereof include alkylphenone compounds, ⁇ -carbonyl compounds, acidoin ethers, ⁇ -hydrocarbon-substituted aromatic acidoine compounds, polynuclear quinone compounds, phenazine compounds, and oxadiazole compounds. Be done.
• the alkylphenone compound for example, IRGACURE 907 is used.
• the content of the polymerization initiator in the specific liquid crystal composition is not particularly limited, but is preferably 0.1 to 20% by mass with respect to the total mass of the liquid crystal compound. More preferably, 1 to 8% by mass.
• the specific liquid crystal composition one type of polymerization initiator may be used alone, or two or more types may be used. When two or more kinds are used, it is preferable that the total content is within the above range.
• the specific liquid crystal composition may be cured.
• the method for curing (polymerizing and curing) the specific liquid crystal composition is not particularly limited, and a known method can be adopted.
• the liquid crystal compound can be immobilized in an oriented state, and a so-called optically anisotropic substance or a layer formed by immobilizing a cholesteric liquid crystal phase can be formed.
• Step X is a step of bringing the substrate into contact with the specific liquid crystal composition to form a composition layer on the substrate.
• the substrate used is not particularly limited, and examples thereof include known substrates (for example, resin substrates, glass substrates, ceramic substrates, semiconductor substrates, and metal substrates).
• the method of bringing the substrate into contact with the specific liquid crystal composition is not particularly limited, and examples thereof include a method of applying the specific liquid crystal composition on the substrate and a method of immersing the substrate in the specific liquid crystal composition.
• a drying treatment may be carried out in order to remove the solvent from the composition layer on the substrate, if necessary. Further, heat treatment may be carried out in order to promote the orientation of the liquid crystal compound and bring it into the state of the liquid crystal phase.
• Step Y is a step of exposing the composition layer to an exposure process using a wavelength of 315 nm, an i-line (wavelength of 365 nm), or the like. It is preferable that the specific compound undergoes photoisomerization by the exposure treatment and the HTP thereof changes. In this exposure process, the degree of change in HTP can also be adjusted by appropriately adjusting the exposure amount and / or the exposure wavelength and the like. After the exposure, heat treatment may be further carried out in order to further promote the orientation of the liquid crystal compound and bring it into the state of the liquid crystal phase.
• the spiral pitch (and thus the selective reflection wavelength, etc.) of the liquid crystal phase obtained here reflects the HTP adjusted in the above-mentioned exposure process.
• Step Z is a step of applying a hardening treatment to the composition layer that has undergone the step Y.
• the method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment and a thermosetting treatment. Of these, photocuring treatment is preferable.
• the specific liquid crystal composition preferably contains a photopolymerization initiator.
• the wavelength of the light irradiated in the photocuring treatment is preferably different from the wavelength of the light used in the above-mentioned exposure treatment, and the photopolymerization initiator is sensitive to the wavelength of the light used in the exposure treatment. It is preferable not to show.
• a layer formed by immobilizing the cholesteric liquid crystal phase is formed.
• the layer formed by immobilizing the cholesteric liquid crystal phase no longer needs to exhibit liquid crystallinity. More specifically, for example, the state in which the cholesteric liquid crystal phase is "immobilized” is the most typical and preferable mode in which the orientation of the liquid crystal compound which is the cholesteric liquid crystal phase is maintained. More specifically, in the temperature range of 0 to 50 ° C., usually 0 to 50 ° C., and -30 to 70 ° C. under more severe conditions, the layer has no fluidity, and the orientation morphology is not changed by an external field or an external force. , It is preferable that the fixed orientation form can be kept stable.
• the specific liquid crystal composition can be applied to various uses. For example, using a specific liquid crystal composition, a polarizing element, a reflective film (reflective layer), an antireflection film, a viewing angle compensation film, a holography, a security, a sensor, and a mirror for real image projection (front projection), which are constituent elements of an optical element, are used. , Rear projection), virtual image projection mirror, decorative sheet, heat shield sheet, light shield sheet, screen, optical variant, alignment film, etc. can be formed.
• a cured product can be obtained by subjecting the specific liquid crystal composition to a curing treatment (light irradiation treatment, heat treatment, etc.), and the cured product is a component of the optical element.
• Polarizing element, reflective film (reflective layer), antireflection film, viewing angle compensation film, holography, security, sensor, real image projection mirror (front projection, rear projection), virtual image projection mirror, decorative sheet, shield It can be suitably applied to a heat sheet, a light-shielding sheet, a screen, an optical variant, an alignment film, and the like.
• the optical anisotropy is intended to be a substance having optical anisotropy.
• the reflective film corresponds to a layer formed by fixing the cholesteric liquid crystal phase, and can reflect light in a predetermined reflection band.
• Compound CD-8 was synthesized in the same procedure as in [Synthesis of compound CD-1] except that malonic acid was used instead of cyanoacetic acid.
• Surfactant S-1 is a compound described in Japanese Patent No. 5774518 and has the following structure. * Represents the bond position.
• a polyimide alignment film material SE-130 (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the washed glass substrate to form a coating film.
• the obtained coating film was fired and then subjected to a rubbing treatment to prepare a substrate with an alignment film.
• the liquid crystal composition (30 ⁇ L) was spin-coated on the rubbing-treated surface of the alignment film under the conditions of 1500 rpm and 10 seconds, and the obtained coating film was heat-dried at 90 ° C. for 1 minute to dry the liquid crystal layer of Example 1.
• 1 (cholesteric liquid crystal layer) film thickness: 1.0 ⁇ m) was obtained.
• HTP before exposure 1 / ⁇ (360 / twist angle (°)) ⁇ film thickness ( ⁇ m) ⁇ (total addition concentration (mass%) of compound CD-1 in the liquid crystal layer ) / 100) ⁇
• the obtained pre-exposure HTP was evaluated according to the following evaluation criteria.
• C HTP before exposure is less than 30 ⁇ m -1
• HTP change amount ( ⁇ m -1 )
• the obtained amount of change in HTP was evaluated according to the following evaluation criteria.
• ⁇ HTP saturation rate> The liquid crystal layer 1 after being exposed for 1 second with the above ⁇ HTP change amount> is further exposed to light having a wavelength of 365 nm for 4 seconds with an illuminance of 30 mW / cm 2 (exposure for a total of 5 seconds), and then the formula (1). ) was used to calculate the HTP after exposure for 5 seconds, and the HTP saturation rate was calculated according to the following formula (3).
• HTP saturation rate (%) ⁇
• the obtained HTP saturation rate was evaluated according to the following evaluation criteria.
• Liquid crystal layers 2 to 10 were prepared and evaluated in various ways in the same procedure as in Example 1 except that the chiral compounds shown in Table 1 were used instead of the compound CD-1.
• Example 8 to 13 and Comparative Examples 4 to 5 The liquid crystal layer 11 to the liquid crystal layer 11 to the same procedure as in Example 1 except that the chiral compound shown in Table 2 was used instead of the compound CD-1 and the light having a wavelength of 315 nm was exposed instead of the light having a wavelength of 360 nm. 18 was prepared and evaluated in various ways.
• Liquid crystal layers 19 to 22 were prepared and evaluated in various ways in the same procedure as in Example 1 except that the chiral compounds shown in Table 3 were used instead of the compound CD-1.
• Examples 16 to 17 and Comparative Examples 8 to 9 The liquid crystal layer 23 to the liquid crystal layer 23 to the same procedure as in Example 1 except that the chiral compound shown in Table 3 was used instead of the compound CD-1 and the light was exposed to light having a wavelength of 315 nm instead of light having a wavelength of 360 nm. 26 was prepared and evaluated in various ways.
• Liquid crystal layers 27 to 28 were prepared and evaluated in various ways in the same procedure as in Example 1 except that the chiral compounds shown in Table 4 were used instead of the compound CD-1.
• R in Tables 1 to 4 represents a coupling position.
• the “Y” column in Table 1 indicates whether Y represents a group represented by the general formula (C-1) or a group represented by the general formula (C-2).
• the columns “L 1 “, “R 1 “, “Z”, and “A 2 " represent the groups corresponding to each group in the general formula (C-1).
• the columns “L 1 or L 2 ", “R 1 “, “Z”, and “A 2 or R 3 " correspond to each group in the general formula (C-1) or the general formula (C-2). Represents a group to do.

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