WO2019160029A1

WO2019160029A1 - Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device

Info

Publication number: WO2019160029A1
Application number: PCT/JP2019/005316
Authority: WO
Inventors: 渡辺　徹; 愛子吉田; 慶太高橋
Original assignee: 富士フイルム株式会社
Priority date: 2018-02-14
Filing date: 2019-02-14
Publication date: 2019-08-22
Also published as: JP6975308B2; JPWO2019160029A1; KR102426523B1; KR20200105898A

Abstract

The purpose of the present invention is to provide: a polymerizable liquid crystal composition which has excellent stability after dissolution and from which an optically anisotropic film having a good planar shape can be formed; an optically anisotropic film; an optical film; a polarizing plate; and an image display device. This polymerizable liquid crystal composition contains a polymerizable liquid crystal compound represented by formula (1) and a polymerizable liquid crystal compound represented by formula (2). L¹-SP¹-D³-G³-G¹-D¹-Ar-D²-G²-G⁴-D⁴-SP²-L² ··· (1) L¹-SP¹-D³-A³-A¹-D¹-Ar-D²-A²-A⁴-D⁴-SP²-L² ··· (2)

Description

Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device

The present invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.

A polymerizable compound exhibiting reverse wavelength dispersion has features such as being able to accurately convert the light wavelength in a wide wavelength range and being able to reduce the thickness of the retardation film because it has a high refractive index. Therefore, it has been actively researched.
In general, T-type molecular design guidelines have been adopted for polymerizable compounds exhibiting reverse wavelength dispersion, and the wavelength of the major axis is shortened and the wavelength of the minor axis located at the center of the molecule is lengthened. Is required to do.
For this reason, it is known to use a cycloalkylene skeleton having no absorption wavelength for the connection between the short-axis skeleton located in the center of the molecule (hereinafter also referred to as “reverse wavelength dispersion expression part”) and the molecular long axis. (For example, see Patent Documents 1 to 3).

JP 2010-031223 A International Publication No. 2014/010325 JP 2016-081035 A

The inventors of the present invention have studied the polymerizable compound having reverse wavelength dispersion described in Patent Documents 1 to 3, and depending on the type of the polymerizable compound, the stability after dissolution may be inferior, and as a result, It has been clarified that it may be difficult to produce an optically anisotropic film having a good surface shape.

Accordingly, the present invention provides a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display that are excellent in stability after dissolution and can form a good planar optically anisotropic film. It is an object to provide an apparatus.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that two types of polymerizable compounds having different ring structures in the molecular long axis (side chain) as polymerizable compounds exhibiting reverse wavelength dispersion. The present inventors have found that a polymerizable liquid crystal composition in which a liquid crystal compound is used in combination is excellent in stability after dissolution and can form a good planar optical anisotropic film, thereby completing the present invention.
That is, it has been found that the above-described problem can be achieved by the following configuration.

[1] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by formula (1) described later and a polymerizable liquid crystal compound represented by formula (2) described later.
[2] Described in [1], D ¹ and D ² in formulas (1) and (2) described later are both —CO—O— *, and * represents a bonding position with Ar. Polymerizable liquid crystal composition.
[3] D ³ and D ⁴ in formulas (1) and (2) described later are both —CO—O— *, and * represents a bonding position with SP ¹ or SP ^2. [3] The polymerizable liquid crystal composition according to [1] or [2].
[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein L ¹ and L ² in formulas (1) and (2) described later each represents a polymerizable group.
[5] The polymerizable liquid crystal according to any one of [1] to [4], wherein one of A ¹ and A ³ in formula (2) described later represents a cyclohexane ring and the other represents a benzene ring. Composition.
[6] The polymerizable liquid crystal composition according to any one of [1] to [5], wherein A ² and A ⁴ in formula (2) described later each represent a cyclohexane ring.

[7] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [6].
[8] An optical film having the optically anisotropic film according to [7].
[9] A polarizing plate comprising the optical film according to [8] and a polarizer.
[10] An image display device having the optical film according to [8] or the polarizing plate according to [9].

According to the present invention, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display that are excellent in stability after dissolution and can form a good planar optically anisotropic film. An apparatus can be provided.

FIG. 1A is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1B is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1C is a schematic cross-sectional view showing an example of the optical film of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Further, in this specification, the bonding direction of a divalent group (for example, —O—CO—) represented is not particularly limited unless the bonding position is clearly specified. When D ^{1 in} 1) is —CO—O—, assuming that the position bonded to the Ar side is * 1, and the position bonded to the G ¹ side is * 2, D ¹ is * 1- It may be CO-O- * 2 or * 1-O-CO- * 2.

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition of the present invention is represented by a polymerizable liquid crystal compound represented by the following formula (1) (hereinafter also abbreviated as “polymerizable liquid crystal compound (1)”) and the following formula (2). A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (hereinafter also abbreviated as “polymerizable liquid crystal compound (2)”).
L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ¹ -Ar-D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² (1)
L ¹ -SP ¹ -D ³ -A ³ -A ¹ -D ¹ -Ar-D ² -A ² -A ⁴ -D ⁴ -SP ² -L ² (2)

In the present invention, as described above, the polymerizable liquid crystal composition using the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in which a part of the ring structure included in the side chain is different is dissolved. It is excellent in stability and can form a good planar optical anisotropic film.
Although this is not clear in detail, the present inventors presume as follows.
That is, from the results of Comparative Examples 1 to 3 described later, it can be seen that when the polymerizable liquid crystal compound (1) is blended alone, the stability after dissolution is poor. This is considered to be because the polymerizable liquid crystal compound (1) is a compound having a crystal structure having high crystallinity and low solubility by itself.
Therefore, the polymerizable liquid crystal composition in which the polymerizable liquid crystal compound (2) is blended together with the polymerizable liquid crystal compound (1) has similar structures, and the polymerizable liquid crystal compound (1) is packed. In addition, since the polymerizable liquid crystal compound (2) is mixed and packing is inhibited, the stability after dissolution is improved, and as a result, it is considered that a good planar optical anisotropic film can be formed.
Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.

[Polymerizable liquid crystal compound (1)]
The polymerizable liquid crystal compound (1) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (1).
L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ¹ -Ar-D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² (1)

In the above formula (1), G ¹ , G ² , G ³ and G ⁴ each independently represent a cyclohexane ring which may have a substituent.
In the above formula (1), D ¹ , D ² , D ³ and D ⁴ are each independently a single bond, or —CO—, —O—, —S—, —C (═S) —. ^{^{^{, -CR 1 R 2 -, -}}} CR 3 = CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 ~ ^{R 5} are each independently Represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
In the above formula (1), SP ¹ and SP ² are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. Or a divalent linkage in which one or more of —CH ₂ — constituting the branched alkylene group is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—. Represents a group, Q represents a substituent.
In the above formula (1), L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar is an aromatic ring represented by the following formula (Ar-3), at least one of L ¹ and L ² and L ³ and L ^{4 in} the following formula (Ar-3) is a polymerizable group. Represents.

In the above formula (1), the cyclohexane ring represented by G ¹ , G ² , G ³ and G ⁴ is preferably a trans-1,4-cyclohexylene group.
In the above formula (1), the substituent that the cyclohexane ring represented by G ¹ , G ² , G ^3, and G ⁴ may have is Y ¹ in formula (Ar-1) described later. Examples of the substituent which may be used are the same as those described above.

In the above formula (1), examples of the divalent linking group represented by D ¹ , D ² , D ³ and D ⁴ include —CO—O—, —C (═S) O—, —CR ¹ R ² ^{^{^{^{-, - CR 1 R 2 -CR}}}} 1 R 2 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 1 R 2 -, - CO-O-CR 1 R 2 -, - O —CO—CR ¹ R ² —, —CR ¹ R ² —O—CO—CR ¹ R ² —, —CR ¹ R ² —CO—O—CR ¹ R ² —, —NR ⁵ —CR ¹ R ² — And -CO-NR ⁵ -and the like. R ¹ , R ² and R ⁵ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

Among these, it is preferable that both D ¹ and D ² in the above formula (1) are —CO—O— * for easy synthesis and liquid crystallinity. In addition, * represents the coupling | bonding position with Ar.
For the same reason, it is preferable that D ³ and D ⁴ in the above formula (1) are all —O—, —CO—O— *, —CO—NR ⁵ — *, and —CO -O- * is more preferable. Note that * represents a bonding position to SP ¹ or SP ^2.

Examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ¹ and SP ² in the above formula (1) include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and hexylene. Preferred examples include a group, a methylhexylene group, and a heptylene group. SP ¹ and SP ² are as described above, wherein one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms is —O—, —S—, —NH. It may be a divalent linking group substituted with —, —N (Q) —, or —CO—, and examples of the substituent represented by Q include Y in formula (Ar-1) described later. Examples are the same as the substituents ¹ may have.

In the above formula (1), examples of the monovalent organic group represented by L ¹ and L ² include an alkyl group, an aryl group, and a heteroaryl group. The alkyl group may be linear, branched or cyclic, but is preferably linear. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aryl group may be monocyclic or polycyclic but is preferably monocyclic. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms. The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. The alkyl group, aryl group and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents as those which Y ¹ in formula (Ar-1) described later may have.

In the above formula (1), the polymerizable group represented by at least one of L ¹ and L ² is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization.
As the radical polymerizable group, a generally known radical polymerizable group can be used, and preferable examples include an acryloyl group or a methacryloyl group. In this case, it is known that the acryloyl group is generally fast in the polymerization rate, and the acryloyl group is preferable from the viewpoint of improving the productivity. However, the methacryloyl group can be similarly used as the polymerizable group.
As the cationic polymerizable group, generally known cationic polymerizable can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and And vinyloxy groups. Among these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
Examples of particularly preferred polymerizable groups include the following.

In the above formula (1), L ¹ and L ² are each preferably a polymerizable group, and more preferably an acryloyl group or a methacryloyl group, because the film strength after crosslinking is improved.

On the other hand, in the above formula (1), Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5). In the following formulas (Ar-1) to (Ar-5), * represents a bonding position with D ¹ or D ² in the above formula (1).

Here, in the formula (Ar-1), Q ¹ represents N or CH, Q ² represents —S—, —O—, or —N (R ⁶ ) —, and R ⁶ represents Y ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y ¹ may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic complex having 3 to 12 carbon atoms. Represents a cyclic group.
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, n-pentyl group, n-hexyl group and the like.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y ¹ include aryl groups such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y ¹ include heteroaryl groups such as thienyl group, thiazolyl group, furyl group, and pyridyl group.
Examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, and a halogen atom.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group). N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group or an ethyl group. Is particularly preferred.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable. An alkoxy group having a number of 1 to 4 is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom and a chlorine atom are preferable.

In the above formulas (Ar-1) to (Ar-5), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon A monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, —OR ⁷ , —NR ⁸ R ⁹ , or , -SR ¹⁰ , R ⁷ to R ¹⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring. Good.
The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group or an ethyl group. , Isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, methyl group, ethyl group, tert-butyl group The group is particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, and ethylcyclohexyl. Monocyclic saturated hydrocarbon groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, cyclodecadienyl Monocyclic unsaturated hydrocarbon groups such as dienes; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, Tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1. 1 ^3,6 . 0 ^2,7 ] dodecyl group, polycyclic saturated hydrocarbon group such as adamantyl group, and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group, and the like. Of the aryl group (particularly a phenyl group).
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.
On the other hand, the alkyl group having 1 to 6 carbon atoms represented by R ⁷ to R ¹⁰ specifically includes, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. Group, tert-butyl group, n-pentyl group, n-hexyl group and the like.

In the above formulas (Ar-2) and (Ar-3), A ³ and A ⁴ are each independently from —O—, —N (R ¹¹ ) —, —S—, and —CO—. Represents a group selected from the group consisting of R ¹¹ and represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ¹¹ include the same substituents as those which Y ¹ in the above formula (Ar-1) may have.

Further, in the above formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom belonging to Groups 14 to 16 to which a substituent may be bonded.
Examples of the non-metal atoms of Group 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Specific examples of the substituent include Is, for example, an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (eg, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, etc. Is mentioned.

In the formula (Ar-3), D ⁵ and D ⁶ are each independently a single bond, or —CO—, —O—, —S—, —C (═S) —, —CR ^1. R ² —, —CR ³ ═CR ⁴ —, —NR ⁵ —, or a divalent linking group consisting of a combination of two or more thereof, each of R ¹ to R ⁵ independently represents a hydrogen atom, A fluorine atom or an alkyl group having 1 to 4 carbon atoms is represented.
Here, examples of the divalent linking group include the same groups as those described for D ¹ to D ⁴ in the above formula (1).

In the above formula (Ar-3), each of SP ³ and SP ⁴ independently represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. A divalent group in which one or more of —CH ₂ — constituting a chain or branched alkylene group is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—. Q represents a substituent. Examples of the substituent include the same substituents as those which Y ^{1 in} formula (Ar-1) may have.

In the formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group, and L ³ and L ⁴ and at least one of L ¹ and L ^{2 in} the formula (1) Represents a polymerizable group.
Examples of the monovalent organic group include the same as those described for L ¹ and L ² in the above formula (1).
Further, the polymerizable group include the same as those described in L ¹ and L ² in the formula (1).

In the above formulas (Ar-4) to (Ar-5), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and has 2 to 30 carbon atoms. Represents an organic group.
In the above formulas (Ar-4) to (Ar-5), Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon ring and an aromatic group. And an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 2 (International Publication No. 2014/010325).
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by Q ³ include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert, -Butyl group, n-pentyl group, n-hexyl group and the like, and examples of the substituent are the same as those which Y ¹ in the above formula (Ar-1) may have. Can be mentioned.

Specific examples of the polymerizable liquid crystal compound represented by the above formula (1) include, for example, the following formulas (I-1) to (I-8), (II-n), (III-n) and (III) IV-1) to (IV-5) and a side chain represented by any of the following formulas (M-101) to (M-105) L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ^1- *, or * -D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² ) Of these, compounds (1-1) to (1-12) shown in Table 1 below are preferred. In the structure of the core and the side chain, * represents the bonding position between the core and the side chain.
In the following description, the following formula (II-n) refers to a structure represented by the formula (II-2) when n in the formula is 2. The same applies to the following formula (III-n).

[Polymerizable liquid crystal compound (2)]
The polymerizable liquid crystal compound (2) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (2).
L ¹ -SP ¹ -D ³ -A ³ -A ¹ -D ¹ -Ar-D ² -A ² -A ⁴ -D ⁴ -SP ² -L ² (2)

In the above formula (2), D ¹ , D ² , D ³ and D ⁴ , SP ¹ and SP ² , L ¹ and L ² , and Ar are the same as those described in the above formula (1). There are also preferred embodiments.
In the above formula (2), A ¹ , A ² , A ³ and A ⁴ each independently have a cyclohexane ring which may have a substituent, or may have a substituent 6 Represents a membered unsaturated ring. However, at least one of A ¹ and A ³ represents a 6-membered unsaturated ring which may have a substituent.

In the above formula (2), the cyclohexane rings represented by A ¹ , A ² , A ³ and A ⁴ are the same as those described as G ¹ , G ² , G ³ and G ^{4 in} the above formula (1). .
In the above formula (2), examples of the 6-membered unsaturated ring represented by A ¹ , A ² , A ³ and A ⁴ include a benzene ring, a cyclohexene ring, and a cyclohexadiene ring.
In addition, examples of the substituent that the cyclohexene ring and the 6-membered unsaturated ring may have include the same substituents that Y ¹ in the above-described formula (Ar-1) may have.

In the above formula (2), among A ¹ , A ² , A ³ and A ⁴ , at least one of A ¹ and A ³ represents an optionally substituted 6-membered unsaturated ring, but the reverse from the viewpoint of enhancing the wavelength dispersion, one of a ¹ and a ³ represents a cyclohexane ring is preferable that the other represents a benzene ring, one of a ¹ and a ³ are trans-1,4- More preferably, it represents a silene group and the other represents a 1,4-phenylene group.
Further, from the viewpoint of enhancing reverse wavelength dispersion, A ² and A ⁴ in the above formula (2) both preferably represent a cyclohexane ring, and more preferably represent a trans-1,4-cyclohexylene group. preferable.

Specific examples of the polymerizable liquid crystal compound represented by the above formula (2) include, for example, the above formulas (I-1) to (I-8), (II-n), (III-n) and A core (* -Ar- *) represented by any one of (IV-1) to (IV-5), the above formulas (M-101) to (M-105) and the following formula (M-1- 1) to (M-1-6), (M-2-1), (M-3-1), (M-4-1), (M-4-2) and (M-5-1) A side chain represented by any one of (L ¹ -SP ¹ -D ³ -A ³ -A ¹ -D ^1- * or * -D ² -A ² -A ⁴ -D ⁴ -SP ² -L ² ), and compounds (2-1-1) to (2-12-2) shown in Table 2 below are preferred. In the structure of the core and the side chain, * represents the bonding position between the core and the side chain.
The following formulas (M-1-5), (M-1-6), (M-2-1), (M-3-1), (M-4-1) and (M-4-2) ) Each represents a side chain in which two structures shown below are mixed.

In the present invention, the content of the polymerizable liquid crystal compound (2) is not particularly limited, but is 0.05 to 15% by mass relative to the total mass of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). Preferably, the content is 0.1 to 10% by mass because the durability is good.

[Other polymerizable compounds]
The polymerizable liquid crystal composition of the present invention contains, in addition to the above-described polymerizable liquid crystal compounds (1) and (2), other polymerizable compounds having one or more polymerizable groups, as long as the solubility is not inhibited. Also good.
Here, the polymerizable group that the other polymerizable compound has is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, an acryloyl group and a methacryloyl group are preferable.

The other polymerizable compound is preferably another polymerizable compound having 1 to 4 polymerizable groups because the wet heat durability of the formed optically anisotropic film is further improved. More preferred is another polymerizable compound having two groups.

Examples of other polymerizable compounds include compounds described in paragraphs [0073] to [0074] of JP-A-2016-053709.
Other polymerizable compounds include compounds represented by the formulas (M1), (M2), and (M3) described in paragraphs [0030] to [0033] of JP2014-077068A. More specifically, specific examples described in paragraphs [0046] to [0055] of the same publication can be given.
As other polymerizable compounds, those having the structures of formulas (1) to (3) described in JP-A-2014-198814 can also be preferably used, and more specifically, [0020] ] To [0035], [0042] to [0050], and specific examples described in paragraphs [0056] to [0057].

The content in the case of containing such other polymerizable compound is less than 60% by mass with respect to the total mass including the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) described above. It is preferably 50% by mass or less, more preferably 2 to 40% by mass.

(Polymerization initiator)
The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics, and the like. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US patent) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970), acylphosphine Oxide compounds (Japanese Patent Publication No. 6) No. 3-40799, JP-B-5-29234, JP-A-10-95788, JP-A-10-29997) and the like.
In the present invention, it is also preferable that the polymerization initiator is an oxime type polymerization initiator. Specific examples thereof include those described in paragraphs [0049] to [0052] of International Publication No. 2017/170443. Agents.

〔solvent〕
The polymerizable liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability for forming an optically anisotropic film.
Specific examples of the solvent include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons. (For example, hexane), alicyclic hydrocarbons (for example, cyclohexane), aromatic hydrocarbons (for example, toluene, xylene, trimethylbenzene), halogenated carbons (for example, dichloromethane, dichloroethane, dichlorobenzene) , Chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cello) Rub etc.), cellosolve acetates, sulfoxides (eg dimethyl sulfoxide etc.), amides (eg dimethylformamide, dimethylacetamide etc.) and the like. These may be used alone or in combination of two or more. You may use together.

(Leveling agent)
The polymerizable liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the optically anisotropic film smooth and facilitating alignment control.
Such a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because of its high leveling effect with respect to the amount added, and from the viewpoint of preventing crying (bloom, bleed), a fluorine-based leveling agent. It is more preferable that
Specific examples of the leveling agent include compounds described in paragraphs [0079] to [0102] of JP 2007-069471, and general formulas described in JP 2013-047204 A ( I) (especially compounds described in paragraphs [0020] to [0032]), a compound represented by general formula (I) described in JP 2012-211306 A (particularly [0022] To the compound described in paragraph [0029], a liquid crystal alignment accelerator represented by the general formula (I) described in JP-A No. 2002-129162 (particularly [0076] to [0078] and [0082] to [0084] Paragraphs), compounds represented by general formulas (I), (II) and (III) described in JP-A-2005-099248 (particularly 0092] ~ [0096] compounds described in Paragraph), and the like. In addition, you may have the function as an orientation control agent mentioned later.

(Orientation control agent)
The polymerizable liquid crystal composition of the present invention can contain an alignment controller as required.
The alignment control agent can form various alignment states such as homeotropic alignment (vertical alignment), inclined alignment, hybrid alignment, cholesteric alignment, etc. in addition to homogeneous alignment, It can be realized with precise control.

As an alignment control agent that promotes homogeneous alignment, for example, a low-molecular alignment control agent or a high-molecular alignment control agent can be used.
Examples of the low molecular orientation control agent include paragraphs [0009] to [0083] of JP-A No. 2002-20363, paragraphs [0111] to [0120] of JP-A No. 2006-106662, and JP-A 2012. The description in paragraphs [0021] to [0029] of Japanese Patent Publication No. 211306 can be referred to, and the contents thereof are incorporated herein.
Further, as the polymer orientation control agent, for example, refer to paragraphs [0021] to [0057] of JP-A No. 2004-198511 and paragraphs [0121] to [0167] of JP-A No. 2006-106662. The contents of which are incorporated herein by reference.

Examples of the alignment control agent that forms or promotes homeotropic alignment include boronic acid compounds and onium salt compounds, and specifically, paragraphs [0023] to [0032] in JP-A-2008-225281. [0052] to [0058] paragraphs of JP2012-208397, paragraphs [0024] to [0055] of JP2008-026730A, and [0043] to [0055] of JP2016-193869A. Reference can be made to compounds described in paragraphs and the like, the contents of which are incorporated herein.

On the other hand, the cholesteric orientation can be realized by adding a chiral agent to the polymerizable composition of the present invention, and the turning direction of the cholesteric orientation can be controlled by the direction of the chirality. The pitch of cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.

When the alignment control agent is contained, the content is preferably 0.01 to 10% by mass, and preferably 0.05 to 5% by mass with respect to the total solid content in the polymerizable liquid crystal composition. More preferred. When the content is within this range, it is possible to obtain a uniform and highly transparent optically anisotropic film without realizing precipitation, phase separation, alignment defects and the like while realizing a desired alignment state.
These alignment control agents can further impart a polymerizable functional group, in particular, a polymerizable functional group that can be polymerized with the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention.

[Other ingredients]
The polymerizable liquid crystal composition of the present invention may contain components other than those described above. For example, liquid crystal compounds other than the above-described polymerizable liquid crystal compounds, surfactants, tilt angle control agents, alignment aids, plasticizers. An agent, a crosslinking agent, etc. are mentioned.

[Optically anisotropic film]
The optically anisotropic film of the present invention is an optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition of the present invention described above.
Examples of the method for forming the optically anisotropic film include a method in which the polymerizable liquid crystal composition of the present invention described above is used to obtain a desired alignment state and then fixed by polymerization.
Here, the polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in polymerization by light irradiation. The irradiation amount is preferably 10 mJ / cm ² to 50 J / cm ² , more preferably 20 mJ / cm ² to 5 J / cm ² , and still more preferably 30 mJ / cm ² to 3 J / cm ^2. 50 to 1000 mJ / cm ² is particularly preferable. Moreover, in order to accelerate | stimulate a polymerization reaction, you may implement on heating conditions.
In the present invention, the optically anisotropic film can be formed on any support in the optical film of the present invention described later or on the polarizer in the polarizing plate of the present invention described later.

The optically anisotropic film of the present invention preferably satisfies the following formula (3).
0.50 <Re (450) / Re (550) <1.00 (3)
In the above formula (3), Re (450) represents in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents in-plane letter of the optically anisotropic film at a wavelength of 550 nm. Represents the foundation. In addition, in this specification, when the measurement wavelength of retardation is not specified, the measurement wavelength is 550 nm.
Further, the values of in-plane retardation and retardation in the thickness direction are values measured using AxoScan OPMF-1 (manufactured by Optoscience) and using light having a measurement wavelength.
Specifically, by inputting an average refractive index ((Nx + Ny + Nz) / 3) and a film thickness (d (μm)) in AxoScan OPMF-1.
Slow axis direction (°)
Re (λ) = R0 (λ)
Rth (λ) = ((nx + ny) / 2−nz) × d
Is calculated.
Note that R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, and means Re (λ).

The optically anisotropic film of the present invention is preferably a positive A plate or a positive C plate, more preferably a positive A plate.

Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
The refractive index in the slow axis direction in the film plane (direction in which the refractive index in the plane is maximum) is nx, the refractive index in the direction perpendicular to the slow axis in the plane is ny, and the refractive index in the thickness direction. When the rate is nz, the positive A plate satisfies the relationship of the formula (A1), and the positive C plate satisfies the relationship of the formula (C1). The positive A plate shows a positive value for Rth, and the positive C plate shows a negative value for Rth.
Formula (A1) nx> ny≈nz
Formula (C1) nz> nx≈ny
The above “≈” includes not only the case where both are completely the same, but also the case where both are substantially the same.
“Substantially the same” means that, for a positive A plate, for example, (ny-nz) × d (where d is the thickness of the film) is −10 to 10 nm, preferably −5 to 5 nm. It is included in “ny≈nz”, and (nx−nz) × d is also included in “nx≈nz” when −10 to 10 nm, preferably −5 to 5 nm. In the positive C plate, for example, (nx−ny) × d (where d is the thickness of the film) includes 0 to 10 nm, preferably 0 to 5 nm, in “nx≈ny”.

When the optically anisotropic film of the present invention is a positive A plate, from the viewpoint of functioning as a λ / 4 plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, More preferably, it is 130 to 150 nm, and particularly preferably 130 to 140 nm.
Here, the “λ / 4 plate” is a plate having a λ / 4 function, and specifically, a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). It is a board which has.

[Optical film]
The optical film of the present invention is an optical film having the optical anisotropic film of the present invention.
FIG. 1A, FIG. 1B, and FIG. 1C (hereinafter, these drawings are abbreviated as “FIG. 1” unless they need to be distinguished in particular) are schematic cross-sectional views showing examples of the optical film of the present invention.
Note that FIG. 1 is a schematic diagram, and the thickness relationship and positional relationship of each layer do not necessarily match the actual ones, and the support, alignment film, and hard coat layer shown in FIG. It is a member.
The optical film 10 shown in FIG. 1 has a support 16, an alignment film 14, and an optical anisotropic film 12 in this order.
1B, the optical film 10 may have a hard coat layer 18 on the side opposite to the side on which the alignment film 14 of the support 16 is provided. As shown in FIG. 1C, The optically anisotropic film 12 may have a hard coat layer 18 on the side opposite to the side where the alignment film 14 is provided.
Hereinafter, various members used in the optical film of the present invention will be described in detail.

(Optically anisotropic film)
The optically anisotropic film included in the optical film of the present invention is the optically anisotropic film of the present invention described above.
In the optical film of the present invention, the thickness of the optically anisotropic film is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[Support]
As described above, the optical film of the present invention may have a support as a base material for forming the optically anisotropic film.
Such a support is preferably transparent, and specifically has a light transmittance of 80% or more.

Examples of such a support include a glass substrate and a polymer film, and examples of the material of the polymer film include a cellulose polymer; an acrylic polymer having an acrylate polymer such as a polymethyl methacrylate and a lactone ring-containing polymer. Polymers; Thermoplastic norbornene polymers; Polycarbonate polymers; Polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; Styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin); Polyethylene, polypropylene, ethylene / propylene copolymer Polyolefin polymers such as polymers; vinyl chloride polymers; amide polymers such as nylon and aromatic polyamide; imide polymers; sulfone polymers; Phon polymers; Polyether ether ketone polymers; Polyphenylene sulfide polymers; Vinylidene chloride polymers; Vinyl alcohol polymers; Vinyl butyral polymers; Arylate polymers; Polyoxymethylene polymers; Epoxy polymers; A mixed polymer may be mentioned.
Moreover, the mode which the polarizer mentioned later serves also as such a support body may be sufficient.

In the present invention, the thickness of the support is not particularly limited, but is preferably 5 to 60 μm, and more preferably 5 to 30 μm.

(Alignment film)
When the optical film of the present invention has the above-mentioned arbitrary support, it is preferable to have an alignment film between the support and the optically anisotropic film. Note that the above-described support may also serve as an alignment film.

The alignment film generally contains a polymer as a main component. The polymer material for alignment film is described in many documents, and many commercially available products can be obtained.
The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred.
With respect to the alignment film that can be used in the present invention, for example, an alignment film described in International Publication No. 01/88574, page 43, line 24 to page 49, line 8; Japanese Patent No. 3907735, paragraphs [0071] to [0095] Modified liquid alcohol described in JP-A-2012-155308, a liquid crystal alignment film formed with a liquid crystal alignment agent described in JP 2012-155308 A, and the like.

In the present invention, it is also preferable to use a photo-alignment film as the alignment film because it is possible to prevent the deterioration of the surface state by not contacting the alignment film surface when forming the alignment film.
The photo-alignment film is not particularly limited, but is a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; described in JP 2012-155308 A A liquid crystal alignment film formed of a liquid crystal aligning agent having a photo-alignable group, such as trade name LPP-JP265CP manufactured by Rollic Technologies, Inc. can be used.

In the present invention, the thickness of the alignment film is not particularly limited. However, from the viewpoint of forming an optically anisotropic film having a uniform thickness by reducing surface irregularities that may exist on the support. The thickness is preferably from 01 to 10 μm, more preferably from 0.01 to 1 μm, still more preferably from 0.01 to 0.5 μm.

[Hard coat layer]
The optical film of the present invention preferably has a hard coat layer in order to impart the physical strength of the film. Specifically, the support may have a hard coat layer on the side opposite to the side on which the alignment film is provided (see FIG. 1B), and the side on which the alignment film of the optical anisotropic film is provided; May have a hard coat layer on the opposite side (see FIG. 1C).
As the hard coat layer, those described in paragraphs [0190] to [0196] of JP-A-2009-98658 can be used.

[Other optically anisotropic films]
The optical film of the present invention may have another optical anisotropic film in addition to the optical anisotropic film of the present invention.
That is, the optical film of the present invention may have a laminated structure of the optical anisotropic film of the present invention and another optical anisotropic film.
Such other optically anisotropic film does not contain any one or both of the above-described polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), and other polymerizable compounds described above (particularly, Any optically anisotropic film obtained by using a liquid crystal compound) is not particularly limited.
Here, in general, liquid crystal compounds can be classified into a rod type and a disk type from the shape. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound (discotic liquid crystal compound) is preferably used. Two or more kinds of rod-like liquid crystal compounds, two or more kinds of disk-like liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a disk-like liquid crystal compound may be used. In order to fix the liquid crystal compound described above, it is more preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound having a polymerizable group, and the liquid crystal compound has two or more polymerizable groups in one molecule. Further preferred. When the liquid crystal compound is a mixture of two or more, it is preferable that at least one liquid crystal compound has two or more polymerizable groups in one molecule.
As the rod-like liquid crystal compound, for example, those described in claim 1 of JP-T-11-53019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used. As the liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 can be preferably used. However, it is not limited to these.

[Ultraviolet absorber]
The optical film of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (particularly ultraviolet rays).
The ultraviolet absorber may be contained in the optically anisotropic film of the present invention, or may be contained in a member other than the optically anisotropic film constituting the optical film of the present invention. As a member other than the optically anisotropic film, for example, a support is preferably mentioned.
As the UV absorber, any conventionally known UV absorber can be used. Of these ultraviolet absorbers, a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber is used from the viewpoint of high ultraviolet absorption and obtaining ultraviolet absorption capability (ultraviolet cut capability) used in an image display device. preferable.
Moreover, in order to widen the absorption width of ultraviolet rays, two or more ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.
Specific examples of the ultraviolet absorber include compounds described in paragraphs [0258] to [0259] of JP2012-18395A, and paragraphs [0055] to [0105] of JP2007-72163A. And the like.
Moreover, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 (all are BASF Corporation) etc. can be used as a commercial item.

[Polarizer]
The polarizing plate of the present invention has the above-described optical film of the present invention and a polarizer.
The polarizing plate of the present invention can be used as a circularly polarizing plate when the above-described optically anisotropic film of the present invention is a λ / 4 plate (positive A plate).
In the polarizing plate of the present invention, when the above-described optically anisotropic film of the present invention is a λ / 4 plate (positive A plate), the slow axis of the λ / 4 plate and the absorption axis of the polarizer described later Is preferably 30 to 60 °, more preferably 40 to 50 °, still more preferably 42 to 48 °, and particularly preferably 45 °.
Here, the “slow axis” of the λ / 4 plate means the direction in which the refractive index is maximum in the plane of the λ / 4 plate, and the “absorption axis” of the polarizer means the direction having the highest absorbance. To do.

[Polarizer]
The polarizer which the polarizing plate of this invention has is not specifically limited if it is a member which has a function which converts light into specific linearly polarized light, A conventionally well-known absorption type polarizer and reflection type polarizer can be utilized. .
As the absorption polarizer, an iodine polarizer, a dye polarizer using a dichroic dye, a polyene polarizer, and the like are used. Iodine polarizers and dye polarizers include coating polarizers and stretchable polarizers, both of which can be applied. Polarized light produced by adsorbing iodine or dichroic dye to polyvinyl alcohol and stretching. A child is preferred.
Further, as a method for obtaining a polarizer by stretching and dyeing in the state of a laminated film in which a polyvinyl alcohol layer is formed on a substrate, Patent No. 5048120, Patent No. 5143918, Patent No. 4691205, Patent No. 4751481 and Japanese Patent No. 4751486 can be cited, and known techniques relating to these polarizers can also be preferably used.
As the reflective polarizer, a polarizer in which thin films having different birefringence are stacked, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate are combined, or the like is used.
Among them, a polyvinyl alcohol resin (a polymer containing —CH ₂ —CHOH— as a repeating unit, particularly at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer, in terms of better adhesion. Are preferably included.

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 30 μm, and even more preferably 5 μm to 15 μm.

(Adhesive layer)
In the polarizing plate of the present invention, an adhesive layer may be disposed between the optically anisotropic film and the polarizer in the optical film of the present invention.
As the pressure-sensitive adhesive layer used for laminating the optically anisotropic film and the polarizer, for example, the ratio of the storage elastic modulus G ′ and the loss elastic modulus G ″ measured with a dynamic viscoelasticity measuring apparatus (tan δ = G ″ / G ′) represents a material having a value of 0.001 to 1.5, and includes a so-called pressure-sensitive adhesive, a substance that easily creeps, and the like. Examples of the adhesive that can be used in the present invention include, but are not limited to, a polyvinyl alcohol-based adhesive.

[Image display device]
The image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, a plasma display panel, and the like.
Among these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and an organic EL display device using an organic EL display panel as a display element, and is a liquid crystal display device. More preferred.

[Liquid Crystal Display]
The liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-described polarizing plate of the present invention and a liquid crystal cell.
In the present invention, among the polarizing plates provided on both sides of the liquid crystal cell, the polarizing plate of the present invention is preferably used as the polarizing plate on the front side, and the polarizing plate of the present invention is used as the polarizing plate on the front side and the rear side. Is more preferable.
Below, the liquid crystal cell which comprises a liquid crystal display device is explained in full detail.

<Liquid crystal cell>
The liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic). It is not limited to.
In a TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °. The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. The VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening the viewing angle. ), (3) A liquid crystal cell (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98). Further, any of a PVA (Patterned Vertical Alignment) type, a photo-alignment type (Optical Alignment), and a PSA (Polymer-Stained Alignment) may be used. Details of these modes are described in JP-A-2006-215326 and JP-T 2008-538819.
In an IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. The IPS mode displays black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal. JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light during black display in an oblique direction and improving the viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.

[Organic EL display device]
As an organic EL display device which is an example of the image display device of the present invention, for example, from the viewing side, a polarizer, a λ / 4 plate (positive A plate) made of the optically anisotropic film of the present invention, and an organic EL device. An embodiment having the display panel in this order is preferable.
The organic EL display panel is a display panel configured using an organic EL element in which an organic light emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

<Synthesis of Compound (I-1)>
The synthesis of the compound (I-1) represented by the following formula (I-1) was performed with reference to the method described in Justus Liebigs Analder der Chemie, 726, 103-109 (1969).

<Synthesis of Compound (I-4)>
Compound (I-4) represented by the following formula (I-4) was synthesized in the same manner as compound (I-1) except that benzoquinone was changed to 2-t-butylbenzoquinone.

As shown in the above scheme, 125 g (0.462 mol) of dimethyl 4,4-biphenyldicarboxylate (S-1-a) was added to 1000 mL of acetic acid, and 12.5 g of palladium carbon catalyst (wet product) was added. The catalytic hydrogenation reaction was carried out in an autoclave at 130 ° C. and 2 MPa.
After completion of the reaction, the reaction mixture was cooled to room temperature (23 ° C.), and then the catalyst was removed by filtration.
Then, after acetic acid was distilled off under reduced pressure, ethyl acetate and an aqueous sodium hydrogen carbonate solution were added. Thereafter, the mixture was stirred and separated to remove the aqueous layer, and the organic layer was washed with 10% brine. Sodium sulfate was added to this solution for drying, and the solvent was concentrated to obtain dimethyl 4,4′-dicyclohexanedicarboxylate (S-1-b) (130 g).
Without further purification, dimethyl 4,4′-dicyclohexanedicarboxylate (130 g), potassium hydroxide pellets (manufactured by Aldrich, purity 90%) 86.3 g, cumene 1300 mL, and polyethylene glycol 2000 (Tokyo) (Made by Kasei Kogyo Co., Ltd.) 10 mL was mixed, a Dean-Stark tube was attached, and it heated and stirred at 120 degreeC. After the methanol was distilled off, the external temperature was set to 180 ° C., and heating and refluxing were continued for 20 hours while the solvent was distilled off. The progress of the reaction was confirmed by NMR (Nuclear Magnetic Resonance). After completion of the reaction, the reaction mixture was cooled, 1300 mL of ethanol was added to the reaction solution, and the precipitated potassium salt was collected by filtration.
Next, this potassium salt was dissolved in 1300 ml of water, concentrated hydrochloric acid was added under ice cooling until the pH of the system became 3, and the precipitated carboxylic acid was collected by filtration to recover a crude product.
The recovered crude product was suspended in 500 mL of acetone, stirred at 50 ° C. for 30 minutes, cooled to room temperature, and collected by filtration to obtain 93.9 g of a crystal of dicyclohexanedicarboxylic acid (S-1-c) (yield: 80 %)Obtained.

As shown in the above scheme, 10.0 g (39.3 mmol) of the compound (S-1-c), 50 mL of N, N-dimethylacetamide (DMAc), 8.0 ml (78.6 mmol) of triethylamine, and 2,6 -433 mg of di-t-butyl-4-methylphenol was mixed at room temperature (23 ° C).
To the mixture, 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 30 ml of 1N hydrochloric acid and 50 ml of toluene were added, and the mixture was stirred at 40 ° C. and then separated. The organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution, 1% aqueous sodium hydrogen carbonate solution and 1% aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. After adding 40 mL of hexane to the residue to precipitate crystals, the mixture was cooled to 5 ° C. and stirred for 30 minutes under ice water, and then the crude product was collected by filtration. The obtained crude product was suspended in 40 mL of hexane, stirred for 30 minutes, filtered, and dried by blowing to obtain 5.39 g of compound (S-1-d) (yield 36%). .

[Synthesis of Polymerizable Liquid Crystal Compound (1-1)]

As shown in the above scheme, 12.90 g (33.9 mmol) of the compound (S-1-d), 40 mL of toluene, 2.82 g of N, N-dimethylformamide (DMF), and 2,6-di-t- 15 mg of butyl-4-methylphenol was mixed at room temperature, and the internal temperature was cooled to 5 ° C. To the mixture, 3.94 g (33.1 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 20 ° C. for 30 minutes, the separated lower layer was removed. The internal temperature was cooled to 5 ° C., and a solution of compound (I-1) 3.83 g (15.4 mmol) in tetrahydrofuran (THF) (100 ml) was added. N, N-diisopropylethylamine (DIPEA) 8.57 g (66.3 mmol) was added dropwise so that the internal temperature did not rise above 10 ° C., and the mixture was stirred at room temperature for 2 hours. After stirring, 100 mL of isopropyl alcohol and 50 mL of water were added dropwise in this order to stop the reaction, and the precipitated crystals were separated by furnace. The obtained crude product was dissolved in 90 mL of THF, and then recrystallized by adding 200 mL of isopropyl alcohol to obtain 13.5 g (13.9 mmol) of a polymerizable liquid crystal compound (1-1) (yield 90%). .

[Synthesis of polymerizable liquid crystal compound (1-3)]

As shown in the above scheme, 2.53 g (6.65 mmol) of compound (S-1-d), 8 mL of toluene, 0.5 mL of N, N-dimethylformamide (DMF), 2,6-di-t-butyl- 4-methylphenol 33 mg was mixed at room temperature, and the internal temperature was cooled to 5 ° C. To the mixture, 0.58 ml (7.98 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 20 ° C. for 30 minutes, the separated lower layer was removed. The internal temperature was cooled to 5 ° C., and a solution of compound (I-4) 0.92 g (3.02 mmol) in tetrahydrofuran (THF) (10 ml) was added. 2.90 ml (16.6 mmol) of N, N-diisopropylethylamine (DIPEA) was added dropwise so that the internal temperature did not rise above 10 ° C., and the mixture was stirred at 30 ° C. for 2 hours. After stirring, 15 ml of 1N hydrochloric acid and 15 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was concentrated under reduced pressure. To the obtained concentrated liquid, 30 mL of isopropyl alcohol was added dropwise at an internal temperature of 40 ° C., and then the crystals were precipitated by cooling to an internal temperature of 5 ° C., followed by filtration. The obtained crude product was dissolved in 10 mL of ethyl acetate, and then recrystallized by adding 35 mL of isopropyl alcohol to obtain 2.65 g (2.58 mmol) of a polymerizable liquid crystal compound (I-3) (yield) 85%).

[Synthesis of Polymerizable Liquid Crystal Compound (1-9)]
A polymerizable liquid crystal compound (1-9) represented by the following formula was synthesized according to the method described in paragraphs [0161] to [0163] of JP 2010-084032 A.

As shown in the above scheme, a suspension of 60.0 g of aluminum chloride and 30.0 g of acetyl chloride in 120 mL of carbon disulfide was cooled to −50 ° C., and 30.0 g of cyclohexene was added dropwise. After stirring at −20 ° C. or lower for 15 minutes, the solution portion was removed, and 300 mL of benzene was added, followed by stirring at 45 ° C. for 3 hours. The reaction solution was ice-cooled, quenched with 100 mL of 1N hydrochloric acid, and the organic layer was washed with 1N hydrochloric acid and 10% aqueous NaOH. The reaction mixture was dried over magnesium sulfate and purified by silica gel column chromatography to obtain 32.0 g of compound (S-2-a).
17.3 g of aluminum chloride and 100 mL of dichloroethane were cooled to 5 to 10 ° C., and 12.9 g of compound (S-2-a) was added. 5.1 g of acetyl chloride was added dropwise at 5-10 ° C., and the mixture was stirred at 5-10 ° C. for 1 hour. 100 mL of water was added to stop the reaction, and the organic layer was dried over magnesium sulfate. Purification by silica gel column chromatography gave 9.3 g (yield 60%) of compound (S-2-b).
After adding 0.28 g of tetrabutylammonium chloride and 2.8 g of sodium sulfate to a solution of 75.0 g of sodium hypochlorite and 13.9 g of sodium hydroxide, 8.6 g of compound (S-2-b) was added. , And stirred at 60 ° C. for 3 hours. After cooling to room temperature, the pH was adjusted to 2 with 30% sulfuric acid, the precipitated carboxylic acid was collected by filtration, and the crude product was recovered. The recovered crude product was suspended in 50 mL of acetone and stirred at 50 ° C. for 30 minutes, then cooled to room temperature and collected by filtration to obtain 7.8 g of compound (S-2-c) (yield 90%).

Next, as shown in the above scheme, 5.0 g (20 mmol) of the compound (S-2-c), 50 mL of N, N-dimethylacetamide (DMAc), 5.6 ml (40 mmol) of triethylamine, and 2,6-di 43 mg of tert-butyl-4-methylphenol was mixed at room temperature. To the mixture, 4.9 g (22 mmol) of 4-methylsulfonyloxybutyl acrylate was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 12.5 ml of 1N hydrochloric acid and 25 ml of toluene were added, and the mixture was stirred at 40 ° C. and separated. The organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution, 1% aqueous sodium hydrogen carbonate solution and 1% aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography gave 2.6 g of compound (S-2-d) (yield 35%).

[Synthesis of polymerizable liquid crystal compound (2-1-7)]

Compound (S-2-d) 1.0 g (2.7 mmol), ethyl acetate (EA) 10 mL, N, N-dimethylacetamide (DMAc) 3 mL, 2,6-di-t-butyl-4-methylphenol 5 mg Were mixed at room temperature, and the internal temperature was cooled to 5 ° C. To the mixture, 0.24 mL (3.2 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, a solution of compound (I-1) 0.30 g (1.2 mmol) in tetrahydrofuran (THF) (5 ml) was added. N, N-diisopropylethylamine (DIPEA) (0.94 ml, 5.4 mmol) was added dropwise, and the mixture was stirred at room temperature for 6 hours. After stirring, 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 1.0 g (1.1 mmol) of a polymerizable liquid crystal compound (2-1-7) (yield 88%).

Compound (S-1-d) 30.0 g (79 mmol), Compound (I-1) 39.2 g (158 mmol), tetrahydrofuran 525 mL, chloroform 175 mL, 2,6-di-t-butyl-4-methylphenol 44 g was mixed at room temperature, and 22.7 g (119 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added. 1.44 g of dimethylaminopyridine was added and stirred at room temperature for 3 hours. The reaction was stopped by adding 220 ml of 1N hydrochloric acid and 220 ml of ethyl acetate, and liquid separation was performed. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain 25.0 g (41 mmol) of compound (S-1-e) (yield 52%).

[Synthesis of polymerizable liquid crystal compound (2-1-5)]

1.63 g (2.7 mmol) of compound (S-1-e), 1.0 g (2.7 mmol) of compound (S-2-d), tetrahydrofuran 20 mL, chloroform 6 mL, 2,6-di-t-butyl- 15 mg of 4-methylphenol was mixed at room temperature, and 0.61 g (3.2 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added. 0.05 g of dimethylaminopyridine was added and stirred at room temperature for 3 hours. The reaction was stopped by adding 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate, and liquid separation was performed. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain 2.2 g (2.3 mmol) of a polymerizable liquid crystal compound (2-1-5) (yield 85%).

[Synthesis of polymerizable liquid crystal compound (2-3-1)]
Except that the compound (I-1) used for the synthesis of the compound (S-1-e) was replaced with the compound (I-4), the same method as in the polymerizable liquid crystal compound (2-1-5) was used. A polymerizable liquid crystal compound represented by the formula (2-3-1) was synthesized.

[Synthesis of Polymerizable Liquid Crystal Compound (2-9-2)]
In the same manner as the polymerizable liquid crystal compound (2-1-7) except that the compound I described in paragraph [0161] of JP 2010-084032 A was used instead of the compound (I-1), A polymerizable liquid crystal compound (2-9-2) represented by the following formula was synthesized.

[Solubility]
The solubility of the synthesized polymerizable liquid crystal compound was measured by the following method. The results are shown in Table 3 and Table 4 below. In the following 3 and Table 4, the evaluation of the solubility of Examples 1 to 8 was carried out by mixing the polymerizable liquid crystal compounds described in Table 3 and Table 4 in the ratios described in Table 3 and Table 4 below. The mixture was evaluated.
First, 1.0 g of the total amount of the polymerizable liquid crystal compound was weighed in a 10 mL sample bottle, and 1.5 g of a solvent was added until the solid content became 40% by mass. Thereafter, the mixture was shaken well by hand at 50 ° C., and allowed to stand at room temperature (23 ° C.) for 10 minutes.
On the other hand, if there was any undissolved residue, the solvent was added so that the solid content was 35% by mass (+0.36 g). Thereafter, the mixture was shaken well by hand at 50 ° C., left at room temperature (23 ° C.) for 10 minutes, and then visually observed to finish if it was clear, and determined to be 35% by mass.
Further, if there was any undissolved residue, a solvent was added so that it would be 30% by mass. The same operation was performed in increments of 5% by mass, and repeated until 5% by mass. If there was undissolved, it was determined that the solubility was less than 5% by mass (<5% by mass), and the process was completed. CPN (cyclopentanone) was used as a solvent for solubility measurement.
A: Solubility in CPN is 20% or more B: Solubility in CPN is 10% or more and less than 20% C: Solubility in CPN is 5% or more and less than 10% D: Solubility in CPN is 5% or less

[Solution stability]
The dissolution stability of the polymerizable liquid crystal compounds synthesized in Examples and Comparative Examples was measured by the following method. The results are shown in Table 3 and Table 4 below. In the following 3 and Table 4, the dissolution stability of Examples 1 to 8 was evaluated by mixing the polymerizable liquid crystal compounds described in Table 3 and Table 4 in the ratios described in Table 3 and Table 4 below. The mixture was evaluated.
Specifically, after weighing 1.0 g of the polymerizable liquid crystal compound as a total amount in a 10 mL sample bottle and adding a solvent until a predetermined solid content (15% by mass in Table 3, 30% by mass in Table 4) is obtained. The mixture was shaken well by hand at 50 ° C., allowed to stand at room temperature (23 ° C.) for 10 minutes, and then visually observed.
Thereafter, the sample bottle containing the dissolved solution was aged at 23 ° C. for 28 days. The presence or absence of precipitation was visually confirmed 14 days and 28 days after the liquid was prepared.
CPN (cyclopentanone) was used as a solvent for dissolution stability measurement.
A: No precipitation is observed, and the liquid is clear.
B: Although no precipitate is observed, the liquid is slightly turbid.
C: Slight deposits are observed.
D: A large amount of precipitate is observed.
E: The whole liquid is solidified.

[Examples 1 to 8 and Comparative Examples 1 to 3]
[Production of optical film]
A polymerizable composition (coating solution for optically anisotropic film) having the following composition was prepared and applied by spin coating to a glass substrate with a rubbed polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.). did. The coating film was aligned at 200 ° C. to form a liquid crystal layer. Then, it cooled to 135 degreeC, the orientation fixation by 1000 mJ / cm < ² > ultraviolet irradiation was performed, the optically anisotropic film was formed, and the optical film for wavelength dispersion measurement was obtained.

―――――――――――――――――――――――――――――――――
Coating liquid for optically anisotropic film ―――――――――――――――――――――――――――――――――
Polymerizable liquid crystal compound (1) (compound described in Table 3 or Table 4 below)
Polymerizable liquid crystal compound (2) (compound described in Table 3 or Table 4 below)
Photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass The following fluorine-containing compound A 0.12 parts by mass Cyclopentanone 85.00 parts by mass ―――――――――――――――――――――
Here, content of the said polymeric liquid crystalline compound (1) and (2) is 15 mass parts in total, and each was mix | blended by the ratio (%) shown in following Table 3 and following Table 4. FIG.
In Table 4 below, the mixing ratio of the polymerizable liquid crystal compounds (1-1) and (1-3) as the polymerizable liquid crystal compound (1) is 1: 1, and the polymerizable liquid crystal compound (2 The mixing ratio of the polymerizable liquid crystal compound (2-1-5) and (2-3-1) as 1) is 1: 1.

[Surface]
About the produced optical film, planar shape was confirmed with the polarizing microscope and visual observation, and the following references | standards evaluated.
A: No bright spots or streak-like defects are observed B: Some bright spots or streak-like defects are observed C: Many bright spots or streak-like defects are present D: Defects are not generated or oriented on the entire surface

From the results shown in Table 3 and Table 4 above, it was found that when the polymerizable liquid crystal compound (2) was not blended, that is, the single product of the polymerizable liquid crystal compound (1) was inferior in dissolution stability (Comparative Examples 1 to 3).
On the other hand, it was found that the mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) has good dissolution stability, and the surface shape of an optical film formed using the mixture is also good ( Examples 1 to 8).

Claims

A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by the following formula (1) and a polymerizable liquid crystal compound represented by the following formula (2).
L 1 -SP 1 -D 3 -G 3 -G 1 -D 1 -Ar-D 2 -G 2 -G 4 -D 4 -SP 2 -L 2 (1)
L 1 -SP 1 -D 3 -A 3 -A 1 -D 1 -Ar-D 2 -A 2 -A 4 -D 4 -SP 2 -L 2 (2)
In the formula (1), G 1 , G 2 , G 3 and G 4 each independently represent a cyclohexane ring which may have a substituent.
In the formula (2), A 1 , A 2 , A 3 and A 4 are each independently a cyclohexane ring which may have a substituent, or a 6-membered group which may have a substituent. Represents a saturated ring. However, at least one of A 1 and A 3 represents a 6-membered unsaturated ring which may have a substituent.
In the formulas (1) and (2), D 1 , D 2 , D 3 and D 4 are each independently a single bond, or —CO—, —O—, —S—, —C (═S ) —, —CR 1 R 2 —, —CR 3 ═CR 4 —, —NR 5 —, or a divalent linking group consisting of two or more thereof, wherein R 1 to R 5 are each Independently, it represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
SP 1 and SP 2 each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. A divalent linking group in which one or more of —CH 2 — constituting is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—; Represents a substituent.
L 1 and L 2 each independently represent a monovalent organic group, and at least one of L 1 and L 2 represents a polymerizable group. However, when Ar is an aromatic ring represented by the following formula (Ar-3), at least one of L 1 and L 2 and L 3 and L 4 in the following formula (Ar-3) is a polymerizable group. Represents.
Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).

Here, in the formulas (Ar-1) to (Ar-5), * represents a bonding position with D 1 or D 2 .
Q 1 represents N or CH.
Q 2 represents —S—, —O—, or —N (R 6 ) —, and R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y 1 represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms.
Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, Represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, —OR 7 , —NR 8 R 9 , or —SR 10 , wherein R 7 to R 10 each represents Independently, it represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may combine with each other to form an aromatic ring.
A 3 and A 4 each independently represents a group selected from the group consisting of —O—, —N (R 11 ) —, —S—, and —CO—, and R 11 represents hydrogen Represents an atom or substituent.
X represents a hydrogen atom or a non-metal atom of Groups 14 to 16 to which a substituent may be bonded.
D 5 and D 6 are each independently a single bond, or —CO—, —O—, —S—, —C (═S) —, —CR 1 R 2 —, —CR 3 ═CR. 4 -, - NR 5 -, or a divalent linking group formed from these two or more thereof, R 1 - R 5 are each independently a hydrogen atom, a fluorine atom or a C 1 - 4 represents an alkyl group.
SP 3 and SP 4 each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. A divalent linking group in which one or more of —CH 2 — constituting is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—; Represents a substituent.
L 3 and L 4 each independently represent a monovalent organic group, and at least one of L 3 and L 4 and L 1 and L 2 in the formula (1) or (2) represents a polymerizable group. Represent.
Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. And an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring.
Q 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
The polymerizable liquid crystal according to claim 1, wherein D 1 and D 2 in the formulas (1) and (2) are both —CO—O— *, and * represents a bonding position with Ar. Composition.
Formula (1) and (2) D 3 and D 4 in the are both a -CO-O- *, * represents a bonding position to SP 1 or SP 2, claim 1 or 2 The polymerizable liquid crystal composition described in 1.
The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein L 1 and L 2 in the formulas (1) and (2) both represent a polymerizable group.
The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein one of A 1 and A 3 in the formula (2) represents a cyclohexane ring and the other represents a benzene ring.
The polymerizable liquid crystal composition according to any one of claims 1 to 5, wherein A 2 and A 4 in the formula (2) each represent a cyclohexane ring.
An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 6.
An optical film having the optically anisotropic film according to claim 7.
A polarizing plate comprising the optical film according to claim 8 and a polarizer.
An image display device comprising the optical film according to claim 8 or the polarizing plate according to claim 9.