Polymerizable liquid crystal compound, polymerizable liquid crystal composition, retardation film, circularly polarizing plate, and composition

Abstract

To enhance the solubility of a polymerizable liquid crystal compound in solvents.SOLUTION: A polymerizable liquid crystal compound represented by formula (1), wherein in formula (1), Ar21 represents a group represented by any one of formulas (Ar-1) to (Ar-4), and at least one of Z1 and Z2 is other than a hydrogen atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition, a retardation film, a circularly polarizing plate, and a composition. [Background technology]

[0002] As an optical film such as a retardation film used in a flat panel display device (FPD), for example, there is an optical film obtained by dissolving a polymerizable liquid crystal compound in a solvent, applying the resulting coating liquid to a supporting substrate, and then polymerizing the coating liquid. Such polymerizable liquid crystal compounds are disclosed, for example, in Patent Documents 1 and 2. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-207765 [Patent Document 2] International Publication No. 2019 / 160034 Summary of the Invention [Problem to be solved by the invention]

[0004] There is a demand for polymerizable liquid crystal compounds that have good solubility in solvents. [Means for solving the problem]

[0005] The present invention includes the following inventions. [Invention 1] A polymerizable liquid crystal compound represented by formula (1):

[0006] [ka]

[0007] [In formula (1), k21 and k22 each independently represent an integer of 1 or more; B21 and B 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, and R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

[0008] E 21 and E 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S-; G 21 and G 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with a halogen atom, -R 3 , -OR 3 , a cyano group, or a nitro group, and —CH— contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—, and R 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A 21 and A 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3, optionally substituted with a cyano group or a nitro group; F 21 and F 22 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 or may be substituted by a halogen atom, and —CH2— contained in the alkanediyl group may be replaced by —O— or —CO—; P 21 and P 22 each independently represents a hydrogen atom or a polymerizable group (provided that P 21 and P 22 at least one of which is a polymerizable group; Ar 21 are represented by the following formulas (Ar-1) to (Ar-4):

[0009] [ka]

[0010] [In formulas (Ar-1) to (Ar-4), * denotes binding site; Q 1 is -S-, -O- or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; W 1 and W 2 each independently represents -O-, -S-, -CO-, or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, Y 2represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, wherein a hydrogen atom contained in the alkyl group is optionally substituted with a halogen atom, and wherein —CH— contained in the alkyl group is optionally substituted with —O—, —CO—, —O—CO— or —CO—O—; Z 1 , Z 2 and Z 3 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms; Z 1 and Z 2 At least one of the atoms is other than a hydrogen atom; Ax represents an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, and Ax and Ay may be bonded to form a ring. [Invention 2] A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (1) represented by formula (1) and a polymerizable liquid crystal compound (2) represented by formula (1) and having a structure different from that of the polymerizable liquid crystal compound (1), The polymerizable liquid crystal compound (1) is a compound represented by the formula (Ar-1) to (Ar-4) 1 and Z 2 are different from each other, The polymerizable liquid crystal compound (2) is represented by the formula (1) Ar 21 Among the formulae (Ar-1) to (Ar-4), Ar in the polymerizable liquid crystal compound (1) 21The formula is the same as the formula (Ar-1) to (Ar-4), and Z 1 is Z in the polymerizable liquid crystal compound (1). 2 is identical to Z 2 is Z in the polymerizable liquid crystal compound (1). 1 The polymerizable liquid crystal composition is the same as

[0011] [ka]

[0012] [In formula (1), k21 and k22 each independently represent an integer of 1 or more; B 21 and B 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, and R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

[0013] E 21 and E 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S-; G 21 and G 22each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with a halogen atom, -R 3 , -OR 3 , a cyano group, or a nitro group, and —CH— contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—, and R 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A 21 and A 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , optionally substituted with a cyano group or a nitro group; F 21 and F 22 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 or may be substituted by a halogen atom, and —CH2— contained in the alkanediyl group may be replaced by —O— or —CO—; P 21 and P 22 each independently represents a hydrogen atom or a polymerizable group (provided that P 21 and P 22 at least one of which is a polymerizable group; Ar 21 are represented by the following formulas (Ar-1) to (Ar-4):

[0014] [ka]

[0015] [In formulas (Ar-1) to (Ar-4), * denotes binding site; Q 1 is -S-, -O- or -NR 11- represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; W 1 and W 2 each independently represents -O-, -S-, -CO-, or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, Y 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, wherein a hydrogen atom contained in the alkyl group is optionally substituted with a halogen atom, and wherein —CH— contained in the alkyl group is optionally substituted with —O—, —CO—, —O—CO— or —CO—O—; Z 1 , Z 2 and Z 3 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms; Z 1 and Z 2 At least one of the atoms is other than a hydrogen atom; Ax represents an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, and Ax and Ay may be bonded to form a ring. [Invention 3] Z in formulas (Ar-1) to (Ar-4) 1 and Z 2 The polymerizable liquid crystal compound according to [Invention 1], wherein at least one of the above is an alkyl group having 1 to 6 carbon atoms.

[0016] [Invention 4] Z in formulas (Ar-1) to (Ar-4) 1 and Z 2 The polymerizable liquid crystal compound according to [Invention 1] or [Invention 3], wherein one of

[0017] [Invention 5] Ar in formula (1) 21 teeth, Ar 21 HO-Ar derived from the structure represented by 21 The polymerizable liquid crystal compound according to any one of [Invention 1], [Invention 3] and [Invention 4], wherein the difference between pKa1 and pKa2 of the phenolic hydroxyl group represented by the following formula (K1) and formula (K2) for -OH is 4.00 or more.

[0018] [ka]

[0019] [Invention 6] Ar in formula (1) 21 The polymerizable liquid crystal compound according to any one of [Invention 1] and [Invention 3] to [Invention 5], which has a CLogP value of 5.0 or more.

[0020] [Invention 7] Ar in formula (1) 21is a group represented by formula (Ar-1): The polymerizable liquid crystal compound according to any one of [Invention 1] and [Invention 3] to [Invention 6].

[0021] [Invention 8] P in formula (1) 21 and P 22 The polymerizable liquid crystal compound according to any one of [Invention 1] and [Invention 3] to [Invention 7], wherein each of the is an acryloyloxy group.

[0022] [Invention 9] The polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) each independently represent Z in formulas (Ar-1) to (Ar-4). 1 and Z 2 The polymerizable liquid crystal composition according to [Invention 2], wherein at least one of the above is an alkyl group having 1 to 6 carbon atoms.

[0023] [Invention 10] The polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) each independently represent Z in formulas (Ar-1) to (Ar-4). 1 and Z 2 The polymerizable liquid crystal composition according to [Invention 2] or [Invention 9], wherein one of the groups is a hydrogen atom.

[0024] [Invention 11] Ar in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) 21 teeth, Ar 21 HO-Ar derived from the structure represented by 21 The polymerizable liquid crystal composition according to any one of [Invention 2], [Invention 9] and [Invention 10], wherein the difference between pKa1 and pKa2 of the phenolic hydroxyl groups represented by the following formulae (K1) and (K2) for -OH is 4.00 or more.

[0025] [ka]

[0026] [Invention 12] Ar in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) 21 The polymerizable liquid crystal composition according to any one of [Invention 2] and [Invention 9] to [Invention 11], which has a CLogP value of 5.0 or more.

[0027] [Invention 13] Ar in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) 21 The polymerizable liquid crystal composition according to any one of [Invention 2] and [Invention 9] to [Invention 12], wherein is a group represented by formula (Ar-1):

[0028] [Invention 14] P in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) 21 and P 22 The polymerizable liquid crystal composition according to any one of [Invention 2] and [Invention 9] to [Invention 13], wherein each of the is an acryloyloxy group.

[0029] [Invention 15] A polymerizable liquid crystal composition containing the polymerizable liquid crystal compound according to any one of [Invention 1] and [Invention 3] to [Invention 8].

[0030] [Invention 16] The polymerizable liquid crystal composition according to any one of [Invention 2] and [Invention 9] to [Invention 15], further comprising a photopolymerization initiator.

[0031] [Invention 17] The polymerizable liquid crystal composition according to any one of [Invention 2] and [Invention 9] to [Invention 16], further containing an organic solvent.

[0032] [Invention 18] A retardation film comprising a cured product of the polymerizable liquid crystal composition according to any one of [Invention 2] and [Invention 9] to [Invention 17].

[0033] [Invention 19] A circularly polarizing plate comprising the retardation film according to any one of [Invention 2] and [Invention 9] to [Invention 18].

[0034] [Invention 20] Represented by any one of the formulas (Ar-01) to (Ar-04), and 1 and Z 2 are different from each other, and Among formulae (Ar-01) to (Ar-04), the formula is the same as the formula representing compound (A1), and Z 1 is Z in the compound (A1). 2 is identical to Z 2 is Z in the compound (A1). 1 and a compound (A2) which is identical to

[0035] [ka]

[0036] [In formulas (Ar-01) to (Ar-04), Q 1 is -S-, -O- or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; W 1 and W 2 each independently represents -O-, -S-, -CO-, or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, Y 2represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, wherein a hydrogen atom contained in the alkyl group is optionally substituted with a halogen atom, and wherein —CH— contained in the alkyl group is optionally substituted with —O—, —CO—, —O—CO— or —CO—O—; Z 1 , Z 2 and Z 3 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms; Z 1 and Z 2 At least one of the atoms is other than a hydrogen atom; Ax represents an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; and Ax and Ay may be bonded to form a ring. [Effects of the Invention]

[0037] It is possible to provide a polymerizable liquid crystal compound having good solubility in a solvent, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, a retardation film, and a circularly polarizing plate. DETAILED DESCRIPTION OF THE INVENTION

[0038] Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[0039] <Polymerizable liquid crystal compound> The polymerizable liquid crystal compound of the present invention is represented by formula (1).

[0040] [ka]

[0041] In formula (1), k21 and k22 each independently represent an integer of 1 or greater, and may be, for example, an integer of 1 to 5. The sum of k21 and k22 is preferably 2 to 6, and more preferably 2 to 4. From the viewpoint of excellent liquid crystal properties, k21 and k22 each independently are preferably 1 or 2, and from the viewpoint of ease of production of the polymerizable liquid crystal compound represented by formula (1), k21 and k22 are preferably the same number, and in a preferred embodiment of the present invention, k21 and k22 are both 1.

[0042] In formula (1), B 21 and B 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, and R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. 21 and B 22 are each independently -CO-O-, -O-CO-, -O-CO-O-, or -CO-NR 1 -, -NR 2 -CO-, -CH2-O-, -O-CH2-, -CH2-S-, -S-CH2- or a single bond is preferred, and -O-CO- or -CO-O- is more preferred. 21 and B 22When a plurality of B are present, they may be the same or different from each other. However, from the viewpoint of ease of production of the polymerizable liquid crystal compound represented by formula (1), a plurality of B 21 are preferably the same group, and a plurality of B 22 are preferably the same group. 21 and B 22 It is more preferable that all of the above are the same.

[0043] R 1 and R 2 Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a tert-butyl group, and preferably an alkyl group having 1 or 2 carbon atoms, and more preferably a methyl group.

[0044] In formula (1), E 21 and E 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, and -CH2-S-. 21 and E 22 are each independently preferably -CO-O-, -O-CO-, -O-CO-O-, or -CO-NR 1 -, -NR 2 In terms of ease of production of the polymerizable liquid crystal compound represented by formula (1), E 21 and E 22 may be the same or different, but are preferably the same group.

[0045] G 21 and G 22each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms. A hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, -R 3 , -OR 3 The -CH2- contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. 21 and G 22 Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms and represented by the formula (g-1) include divalent alicyclic hydrocarbon groups which may contain a heteroatom and are represented by the formulas (g-1) to (g-10), and a 5- or 6-membered alicyclic hydrocarbon group is preferred.

[0046] [ka]

[0047] The groups represented by the above formulas (g-1) to (g-10) may be substituted with an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group; an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group; a cyano group; a nitro group; or a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom.

[0048] G 21 and G 22 As each of these, a 5- or 6-membered alicyclic hydrocarbon group represented by any one of formulas (g-1) to (g-4) is more preferred, an alicyclic hydrocarbon group consisting of a 6-membered ring represented by formula (g-1) is even more preferred, a cyclohexane-1,4-diyl group is particularly preferred, and a trans-cyclohexane-1,4-diyl group is especially preferred.

[0049] G 21 and G 22may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound represented by formula (1) and productivity. In formula (1), A 21 and A 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , and may be substituted with a cyano group or a nitro group.

[0050] A 21 and A 22 Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms and represented by the formula (g-1) to the formula (g-10) or the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include alicyclic hydrocarbon groups consisting of a 5-membered ring or a 6-membered ring, etc., represented by the formula (g-1) to the formula (g-10) above, and aromatic hydrocarbon groups having about 6 to 20 carbon atoms and represented by the formula (a-1) to the formula (a-8).

[0051] [ka]

[0052] In addition, A 21 and A 22 Some of the hydrogen atoms of the groups exemplified above may be substituted with an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group; an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group; a cyano group; a nitro group; or a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom.

[0053] A 21 and A 22 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group. When k21 and k22 are 1, A 21 and A 22are each preferably a 1,4-phenylene group, and when k21 and k22 are 2 or more, E 21 A binds to 21 and E 22 A binds to 22 are preferably identical to each other, and E 21 A binds to 21 and E 22 A binds to 22 is preferably a 1,4-phenylene group. 21 and A 22 When there are a plurality of groups, they may be the same or different.

[0054] In formula (1), F 21 and F 22 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 Alternatively, it may be substituted with a halogen atom, and —CH— contained in the alkanediyl group may be replaced with —O— or —CO—. 21 and F 22 are each independently preferably an alkanediyl group having 3 to 10 carbon atoms, -(CF2)4-, -(CF2)6-, or -(CF2)8-, and more preferably an alkanediyl group having 4 or 6 carbon atoms [-(CH2)4- or -(CH2)6-]. 21 and E 22 may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound represented by formula (1) and productivity.

[0055] P 21 and P 22 each independently represents a hydrogen atom or a polymerizable group. 21 and P 22 At least one of P is a polymerizable group. 21 and P 22 are preferably polymerizable groups from the viewpoint of the film hardness of a liquid crystal cured film obtained by using the polymerizable liquid crystal compound.

[0056] The polymerizable group may be any reactive group capable of polymerizing the polymerizable liquid crystal compound represented by formula (1), and specific examples thereof include a vinyl group, a vinyloxy group, a styryl group, a p-(2-phenylethenyl)phenyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a carboxy group, an acetyl group, a hydroxy group, a carbamoyl group, an N-alkylamino group having 1 to 4 carbon atoms, an amino group, an oxiranyl group, an oxetanyl group, a formyl group, an isocyanato group, an isothiocyanato group, etc. In addition, the polymerizable group may be a group selected from the above-exemplified groups and F 21 or F 22 An ether bond or an ester bond may be included to bond P and P, and it is preferable that they are bonded via an ether bond. 21 and P 22 As the alkyl group, for example, a radically polymerizable group or a cationically polymerizable group suitable for photopolymerization is preferred, and an acryloyloxy group or a methacryloyloxy group is particularly preferred because they are easy to handle and to produce, and an acryloyloxy group is more preferred.

[0057] Ar in formula (1) 21 is a group represented by any one of the following formulas (Ar-1) to (Ar-4).

[0058] [ka]

[0059] In the formulae (Ar-1) to (Ar-4), * represents a bonding site. In formula (Ar-1), Q 1 is -S-, -O- or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. In formulas (Ar-3) and (Ar-4), Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0060] In formula (Ar-2), W 1 and W2 each independently represents -O-, -S-, -CO-, or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0061] In formula (Ar-1), Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group. 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent. Here, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and -CH2- contained in the alkyl group may be substituted with -O-, -CO-, -O-CO- or -CO-O-.

[0062] In formulas (Ar-1) to (Ar-4), Z 1 , Z 2 and Z 3 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms; Z 1 and Z 2 At least one of these is other than a hydrogen atom.

[0063] Z 1 and Z 2 is Z 1 and Z 2 At least one of Z is preferably an alkyl group having 1 to 6 carbon atoms. 1 and Z 2 are preferably different groups. 1 and Z 2 is Z 1 and Z 2It is preferable that one of Z is a hydrogen atom. 1 and Z 2 is Z 1 and Z 2 It is more preferable that one of them is an alkyl group having 1 to 6 carbon atoms and the other is a hydrogen atom.

[0064] Z 1 and Z 2 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group, and preferred are an isopropyl group and a tert-butyl group.

[0065] In formulas (Ar-3) and (Ar-4), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay may be bonded to form a ring.

[0066] In formula (Ar-1), Y 1is preferably an aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent, and is more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent. The aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent is preferably an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. In this specification, "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and examples thereof include a fused aromatic hydrocarbon group formed by condensing two or more aromatic rings and an aromatic hydrocarbon group formed by bonding two or more aromatic rings. The term "polycyclic aromatic heterocyclic group" refers to an aromatic heterocyclic group having at least one heteroaromatic ring and at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings, and includes aromatic heterocyclic groups formed by condensing one or more aromatic heterocyclic rings with one or more rings selected from the group consisting of aromatic rings and heteroaromatic rings, and aromatic heterocyclic groups formed by bonding at least one heteroaromatic ring with at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings.

[0067] Examples of the substituent that the aromatic hydrocarbon group or aromatic heterocyclic group may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 4 carbon atoms, an N,N-dialkylamino group having 2 to 8 carbon atoms, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms.

[0068] Ar 21 Among the groups represented by formulae (Ar-1) to (Ar-4), the groups represented by formulae (Ar-1) and (Ar-2) are preferred, and the group represented by formula (Ar-1) is more preferred.

[0069] Ar 21Preferred groups represented by the formula are Ar 21 HO-Ar derived from the structure represented by 21 With respect to -OH, examples include those having a ΔpKa value of 4.00 or more, which is the difference between the pKa1 of the phenolic hydroxyl group shown in the following formula (K1) and the pKa2 of the phenolic hydroxyl group shown in the following formula (K2): The ΔpKa value is a value obtained by calculating the negative logarithm of the equilibrium constant Ka in the reaction in which hydrogen ions dissociate from an acid, and can be determined by a known method such as ChemDraw 22.0 (manufactured by Cambridge Software).

[0070] [ka]

[0071] Ar 21 Preferred groups represented by the formula (I) include those having a CLogP value of 5.0 or more. The CLogP value is a value obtained by calculating the logarithm of the partition coefficient of a compound in a water / 1-octanol system, and can be determined by known methods such as MOLINSPIRATION CHEMINFORMATICS (http: / / www.molinspiration.com) or ChemDraw 22.0 (Cambridge Soft). The CLogP value may also be a value listed in a physical property database or literature. 21 A polymerizable liquid crystal compound having a CLogP value of 5.0 or more in the group represented by the formula (I) is more resistant to hydrolysis than a polymerizable liquid crystal compound having a CLogP value of less than 5.0.

[0072] *-O-CO-G in formula (1) 21 -E 21 -(A 21 -B 21 ) k21 -F 21 -P 21 , and *-O-CO-G 22 -E 22 -(A 22 -B 22 ) k22 -F 22-P 22 Specific examples of the structure include structures represented by formulae (R-1) to (R-100).

[0073] In the formula, * represents Ar 21 represents the bonding site to, and n represents an integer of 2 to 12. The cyclohexane ring may be in a trans or cis form, but is preferably in a trans form.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] -O-CO-G in the polymerizable liquid crystal compound represented by formula (1) of the present invention 21 -E 21 -(A 21 -B 21 ) k21 -F 21 -P 21 , and -O-CO-G 22 -E 22 -(A 22 -B 22 ) k22 -F 22 -P 22 and preferably have similar structural units, and more preferably have the same structural units.

[0084] Hereinafter, -O-CO-G in polymerizable liquid crystal compounds 21 -E 21 -(A 21 -B 21 ) k21 -F 21 -P 21 , and -O-CO-G 22 -E 22 -(A 22 -B 22 ) k22 -F 22 -P 22 This is sometimes called a mesogenic structure. 21 The structural unit represented by - is sometimes called the core part.

[0085] <Polymerizable liquid crystal composition> The polymerizable liquid crystal composition of the present invention is, for example, represented by formula (1), 1 and Z 2 and a polymerizable liquid crystal compound (2) represented by formula (1) and having a structure different from that of the polymerizable liquid crystal compound (1).

[0086] The polymerizable liquid crystal compound (2) is represented by the formula (1) Ar 21Among the formulae (Ar-1) to (Ar-4), Ar in the polymerizable liquid crystal compound (1) 21 The formula is the same as the formula (Ar-1) to (Ar-4), and Z 1 is Z in the polymerizable liquid crystal compound (1) 2 is identical to Z 2 is Z in the polymerizable liquid crystal compound (1). 1 is the same as

[0087] The core portion of the polymerizable liquid crystal compound (1) and the core portion of the polymerizable liquid crystal compound (2) are Ar 21 Z in 1 and Z 2 It is preferable that the structures except for the above are the same. It is preferable that both mesogen structures of the polymerizable liquid crystal compound (1) and both mesogen structures of the polymerizable liquid crystal compound (2) are the same. More preferably, the core portion of the polymerizable liquid crystal compound (1) and the core portion of the polymerizable liquid crystal compound (2) are the same as Ar 21 Z in 1 and Z 2 The polymerizable liquid crystal composition contains a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2), in which the structures thereof are identical except for the above, and both mesogenic structures of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) are identical. The polymerizable liquid crystal composition is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2), in which both mesogenic structures of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) are identical except for the above. 21 Z equipped with 1 and Z 2 It can be said that the compound has a structure in which the groups corresponding to the following are interchanged, and contains two types of polymerizable liquid crystal compounds that have the other structures in common.

[0088] [Content] The contents of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition of the present invention may be appropriately determined depending on the type of polymerizable liquid crystal compound (1) and / or polymerizable liquid crystal compound (2) within a range that achieves the effects of the present invention. However, the ratio of the peak area of ​​polymerizable liquid crystal compound (1) to the total peak area of ​​polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), as measured by liquid chromatography (hereinafter also referred to as "area percentage value"), is preferably 0.1% to 99.9%. It is more preferably 1% by mass or more, even more preferably 10% by mass or more, and particularly preferably 30% by mass or more. When the content of polymerizable liquid crystal compound (1) is within the above range, the solubility of the polymerizable liquid crystal compound in solvents is easily improved, and the phase transition temperature is easily reduced. Furthermore, the alignment state of the liquid crystal can be well maintained when a liquid crystal cured film is prepared from the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, thereby enabling the production of an optical film with excellent optical properties. When a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1) and / or the polymerizable liquid crystal compound (2) are contained, the area percentage value of the polymerizable liquid crystal compound (1) is calculated based on the total peak area of ​​all the polymerizable liquid crystal compounds (1) and all the polymerizable liquid crystal compounds (2). The area percentage value can be calculated based on the peak area measured by liquid chromatography.

[0089] [Phase transition temperature] The polymerizable liquid crystal composition of the present invention, which contains a combination of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), can significantly reduce the phase transition temperature compared to when polymerizable liquid crystal compound (1) or polymerizable liquid crystal compound (2) is used alone. For example, the phase transition temperature of the polymerizable liquid crystal composition of the present invention is preferably 153°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower. Furthermore, when the polymerizable liquid crystal composition of the present invention contains a combination of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), the phase transition temperature can be reduced by preferably 8°C or more, more preferably 10°C or more, even more preferably 12°C or more, and particularly preferably 15°C or more compared to when polymerizable liquid crystal compound (1) or polymerizable liquid crystal compound (2) is used alone. Since a lower phase transition temperature allows a liquid crystal cured film to be obtained from the polymerizable liquid crystal compound at a lower processing temperature, a polymerizable liquid crystal composition containing a combination of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) is advantageous in terms of reducing the effect of heating on the optical properties of the liquid crystal cured film and in terms of production efficiency.

[0090] In the present invention, the phase transition temperature of the polymerizable liquid crystal compound can be measured by the method described in the Examples below. When two or more polymerizable liquid crystal compounds are contained, the phase transition temperature is measured using a polymerizable liquid crystal compound (mixture) having the same composition as the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition.

[0091] <Polymerizable Liquid Crystal Compound Contained in Polymerizable Liquid Crystal Composition> The polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), as long as the effects of the present invention are not adversely affected. Examples of such a polymerizable liquid crystal compound include compounds described in Sections 3.2 Nonchiral Rod-Shaped Liquid Crystal Molecules and 3.3 Chiral Rod-Shaped Liquid Crystal Molecules of Chapter 3, Molecular Structure and Liquid Crystallinity, of "Liquid Crystal Handbook" (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), compounds described in JP 2010-31223 A, and polymerizable liquid crystal compounds that can exhibit reverse wavelength dispersion when formed into a liquid crystal cured film or polymerizable liquid crystal compounds that can exhibit normal wavelength dispersion, as described in JP 2011-207765 A, JP 5962760 A, and the like.

[0092] When the polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound other than polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, relative to 100 parts by mass of the total of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2). In particular, if the content of a liquid crystal compound whose molecular structure is significantly different from that of polymerizable liquid crystal compound (1) or polymerizable liquid crystal compound (2) is too high, phase separation may occur, which may impair the appearance. Therefore, it is preferable that the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention is substantially composed of a polymerizable liquid crystal compound having a structure similar to that of polymerizable liquid crystal compound (1). Note that the term "similar" as used herein refers to, for example, the -O-CO-G of polymerizable liquid crystal compound (1). 21 -E 21 -(A 21 -B 21 ) k21 -F 21 -P 21 , -O-CO-G 22 -E 22 -(A 22 -B 22 ) k22 -F 22 -P 22 The part represented by Ar 21The term "substantially constituted" means that the content of polymerizable liquid crystal compound (1), or polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), is 90 mass % or more relative to the total mass of the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition of the present invention. In one embodiment of the present invention, the polymerizable liquid crystal composition may contain no polymerizable liquid crystal compounds other than polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), or may contain no polymerizable liquid crystal compounds other than polymerizable liquid crystal compound (1).

[0093] The content of the polymerizable liquid crystal compounds in the polymerizable liquid crystal composition of the present invention (total amount of all polymerizable liquid crystal compounds) is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. If the total mass of the polymerizable liquid crystal compounds is within the above range, it is advantageous from the viewpoint of the alignment property of the obtained liquid crystal cured film. The solid content of the polymerizable liquid crystal composition means all components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents.

[0094] <Additives> The polymerizable liquid crystal composition of the present invention may further contain, in addition to the polymerizable liquid crystal compound (1) or a mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), additives such as an organic solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, etc. Each of these components may be used alone or in combination of two or more.

[0095] In the present invention, the polymerizable liquid crystal composition preferably contains a solvent because it is usually applied to a substrate or the like in a state of being dissolved in a solvent. The solvent is preferably a solvent that can dissolve polymerizable liquid crystal compounds such as polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), and is also preferably a solvent that is inactive to the polymerization reaction of the polymerizable liquid crystal compound. Therefore, various solvents can be used. Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; and amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. Among these, organic solvents are preferred, with alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents being more preferred, and from the viewpoint of productivity, at least one solvent selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and N-methylpyrrolidone being even more preferred.

[0096] The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, per 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content per 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass, more preferably 5 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is reduced, resulting in a generally uniform film thickness and reduced unevenness. The solid content can be appropriately determined taking into account the thickness of the liquid crystal cured film to be produced. The polymerizable liquid crystal compound of the present invention has excellent solubility in solvents, which is advantageous in that the amount of organic solvent used during application and storage can be reduced.

[0097] The polymerizable liquid crystal composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that generates reactive species with the aid of light and can initiate a polymerization reaction of the polymerizable liquid crystal or the like. Examples of reactive species include active species such as radicals, cations, or anions. Among these, photopolymerization initiators that generate radicals upon irradiation with light are preferred from the viewpoint of ease of reaction control. As the photopolymerization initiator, only one type may be used, or two or more types may be used in combination.

[0098] Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzil ketal compounds, alkylphenone compounds, acylphosphine oxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts, and sulfonium salts. Specific examples include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 379EG (all manufactured by BASF Japan Ltd.), Seikuol BZ, Seikuol Z, and Seikuol BEE (all manufactured by Seiko Chemical Co., Ltd.), and Kayacure (registered trademark). Examples of suitable anti-aging agents include ADEKA CURE BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Chemical Industries, Ltd.), ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER N-1717, ADEKA OPTOMER N-1919, ADEKA ARCLES NCI-831, ADEKA ARCLES NCI-930 (all manufactured by ADEKA Corporation), TAZ-A, TAZ-PP (all manufactured by Nippon SiberHegner AG), and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

[0099] In the present invention, the polymerizable liquid crystal mixed composition preferably contains at least one type of photopolymerization initiator, and may contain two or more types of photopolymerization initiators. The photopolymerization initiator can fully utilize the energy emitted from the light source and has excellent productivity, so that the maximum absorption wavelength is preferably 300 nm to 400 nm, and more preferably 300 nm to 380 nm, and among these, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

[0100] Examples of α-acetophenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, and more preferably 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. Commercially available α-acetophenone compounds include Irgacure 369, 379EG, and 907 (all manufactured by BASF Japan Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.).

[0101] Oxime photopolymerization initiators generate methyl radicals upon irradiation with light. These methyl radicals facilitate the polymerization of the polymerizable liquid crystal compound deep within the cured liquid crystal film. Furthermore, from the viewpoint of more efficiently promoting the polymerization reaction deep within the cured liquid crystal film, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet light with a wavelength of 350 nm or more. Preferred photopolymerization initiators that can efficiently utilize ultraviolet light with a wavelength of 350 nm or more include triazine compounds and oxime ester carbazole compounds, with oxime ester carbazole compounds being more preferred from the viewpoint of sensitivity. Examples of oxime ester carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime). Commercially available oxime ester carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03 (all manufactured by BASF Japan Ltd.), Adeka Optomer N-1919, and Adeka Arcles NCI-831 (all manufactured by ADEKA Corporation).

[0102] The amount of the photopolymerization initiator added is usually 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is unlikely to be disturbed.

[0103] The use of a sensitizer can increase the sensitivity of the photopolymerization initiator. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0104] The addition of a polymerization inhibitor can control the polymerization reaction of the polymerizable liquid crystal compound. Examples of polymerization inhibitors include hydroquinones having a substituent such as hydroquinone or alkyl ether; catechols having a substituent such as alkyl ether, such as butylcatechol; pyrogallols, radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines, and β-naphthols. To polymerize the polymerizable liquid crystal compound (1) without disturbing the alignment, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0105] Furthermore, the polymerizable liquid crystal composition of the present invention may contain a leveling agent. The leveling agent is an additive that adjusts the fluidity of the polymerizable liquid crystal composition and makes the film obtained by applying the composition flatter, and examples of such leveling agents include silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all manufactured by Momentive Performance Materials Japan LLC), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Limited), Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all manufactured by DIC Corporation), F-top (trade name) EF301, EF303, Examples of suitable leveling agents include EF351 and EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, and SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830 and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all trade names manufactured by BM Chemie). Among these, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

[0106] The content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound. The content of the leveling agent within the above range is preferred because it is easy to align the polymerizable liquid crystal compound and the resulting liquid crystal cured film tends to be smoother. The polymerizable liquid crystal composition may contain two or more types of leveling agents.

[0107] The polymerizable liquid crystal composition of the present invention can be prepared by adding additives such as a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, or a leveling agent to the polymerizable liquid crystal compound (1) or a mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), as needed, and stirring and mixing the mixture at a predetermined temperature.

[0108] <Method for producing polymerizable liquid crystal compound> The method for producing the polymerizable liquid crystal compound represented by formula (1) constituting the polymerizable liquid crystal composition of the present invention is not particularly limited, and the compound can be produced by appropriately combining known organic synthesis reactions (e.g., condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel-Crafts reaction, Heck reaction, aldol reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lectures, etc., depending on the structure of the compound.

[0109] For example, A in formula (1) 21 and A 22 , B 21 and B 22 , E 21 and E 22 , F 21 and F 22 , G 21 and G 22 , P 21 and P 22The polymerizable liquid crystal compound (1) in which k21 and k22 are the same can be produced by esterifying a compound represented by formula (1-1) (hereinafter also referred to as "compound (1-1)") with a compound represented by formula (1-3) (hereinafter also referred to as "compound (1-3)"). P, F, B, A, E, and G in formula (1-1) respectively represent P in formula (1). 21 and P 22 , F 21 and F 22 , B 21 and B 22 , A 21 and A 22 , E 21 and E 22 , G 21 and G 22 In addition, m in formula (1-1) is the same as that defined as k21 and k22 in formula (1). In addition, Ar in formula (1-3) is the same as that defined as Ar in formula (1). 21 P, F, B, A, E, G and Ar are determined depending on the desired polymerizable liquid crystal compound (1) and the desired polymerizable liquid crystal compound (2).

[0110] [ka]

[0111] [ka]

[0112] The compound (1-3) is represented by any one of the following formulae (Ar-01) to (Ar-04): In the formulae (Ar-01) to (Ar-04), all symbols have the same meanings as above.

[0113] [ka]

[0114] The reaction of the compounds (1-1) and (1-3) is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (some of which are commercially available as water-soluble carbodiimide: WSC), bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bis(trimethylsilyl)carbodiimide), ... carbodiimides such as N,N'-diisopropylcarbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1-(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1 H-Benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N′,N′-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxysuccinimide, O-(6-chlorobenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium tetrafluoroborate parafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium paratoluenesulfonate, 2-fluoro-1-methylpyridinium paratoluenesulfonate, trichloroacetic acid pentachlorophenyl ester, and the like.

[0115] In terms of reactivity, cost, and the wide range of solvents available, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide, and 2,2'-carbonylbis-1H-imidazole are preferred as condensing agents.

[0116] In the present invention, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition may be prepared separately and then mixed together to form a liquid crystal mixture. 21 and Ar in polymerizable liquid crystal compounds (2) 21 A mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) can also be obtained by using a composition containing two compounds corresponding to the above and reacting compound (1-1) and the above composition in an appropriate ratio.

[0117] The compound (1-3) used in the production of the polymerizable liquid crystal compound represented by formula (1) is preferably a compound represented by any one of formulas (Ar-01) to (Ar-04), 1 and Z 2 These compounds are represented by the same formula as the compound (A1) among formulas (Ar-01) to (Ar-04), and Z 1 is Z in the compound (A1). 2 is identical to Z 2 is Z in the compound (A1). 1 The compound identical to the compound (A2) is used as the composition used to prepare a mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). A composition containing the compound (A1) and the compound (A2) is preferred. In the compound (A1) and the compound (A2) contained in the composition, Ar 21 Z in 1 and Z2 The structure is the same except for Ar 21 Z in 1 and Z 2 The polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) having the same structure except for the above can be produced as a mixture.

[0118] <Retardation film> The polymerizable liquid crystal composition of the present invention has a low phase transition temperature of the polymerizable liquid crystal compound, allowing for the preparation of a cured liquid crystal film at a lower processing temperature. This reduces the effects of heating and allows for the production of a cured liquid crystal film with excellent optical properties. Furthermore, the composition has high solubility in solvents and excellent coatability and film-forming properties, thereby suppressing the occurrence of alignment defects due to undissolved polymerizable liquid crystal compounds or precipitates or deposits in the composition. Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to form a film without reducing the inherent optical properties of the polymerizable liquid crystal compound, thereby producing a cured liquid crystal film with excellent optical properties. Therefore, the present invention also relates to a cured product of the polymerizable liquid crystal composition of the present invention, particularly a retardation film comprising a cured product of the polymerizable liquid crystal composition, which is a cured product of the polymerizable liquid crystal composition, and which is obtained by curing the polymerizable liquid crystal composition in an aligned state. A retardation film composed of the cured liquid crystal film can fully exhibit the inherent optical properties of the polymerizable liquid crystal compound used, resulting in a retardation film with high optical performance.

[0119] The liquid crystal cured film constituting the retardation film of the present invention may be composed of a homopolymer of polymerizable liquid crystal compound (1) in an aligned state and a homopolymer of polymerizable liquid crystal compound (2), or may be composed of a copolymer of a mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) in an aligned state. Because the polymerization reaction is easy and a uniform liquid crystal cured film is easily obtained, the liquid crystal cured film constituting the retardation film of the present invention is preferably composed of a copolymer of a mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) in an aligned state.

[0120] In one embodiment of the present invention, the retardation film of the present invention is a cured product of the polymerizable liquid crystal composition of the present invention, and includes a liquid crystal cured film having optical properties represented by the following formulas (i), (ii), and (iii): The liquid crystal cured film is usually a cured product obtained by curing the polymerizable liquid crystal compound in a state where it is aligned horizontally relative to the plane of the liquid crystal cured film (hereinafter, also referred to as a "horizontally aligned liquid crystal cured film").

[0121] Re(450) / Re(550)≦1.00 (i) 1.00≦Re(650) / Re(550) (ii) 100 nm ≦ Re(550) ≦ 180 nm (iii) (In the formula, Re(λ) represents the in-plane retardation value of the cured liquid crystal film at a wavelength of λ nm, and Re=(nx(λ)-ny(λ))×d (d represents the thickness of the cured liquid crystal film, nx represents the principal refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film in an index ellipsoid formed by the cured liquid crystal film, and ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film and perpendicular to the direction of nx in an index ellipsoid formed by the cured liquid crystal film).) When the horizontally aligned liquid crystal cured film satisfies formulas (i) and (ii), the horizontally aligned liquid crystal cured film exhibits a so-called reverse wavelength dispersion, in which the in-plane retardation value at short wavelengths is smaller than the in-plane retardation value at long wavelengths. To improve the reverse wavelength dispersion and further improve the optical properties of the retardation film, Re(450) / Re(550) is preferably 0.70 or more, more preferably 0.78 or more, and also preferably 0.90 or less, more preferably 0.88 or less, even more preferably 0.86 or less, particularly preferably 0.85 or less, and particularly preferably 0.84 or less. Furthermore, Re(650) / Re(550) is preferably 1.00 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

[0122] The in-plane retardation value can be adjusted by the thickness d of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d, a desired in-plane retardation value (Re(λ): in-plane retardation value of the horizontally aligned liquid crystal cured film at a wavelength λ (nm)) can be obtained by adjusting the three-dimensional refractive index and the film thickness d.

[0123] Furthermore, when the horizontally aligned liquid crystal cured film satisfies formula (iii), an elliptically polarizing plate having a retardation film containing the horizontally aligned liquid crystal cured film is applied to an organic EL display device, and the effect of improving the front reflection hue (the effect of suppressing coloration) is excellent. A more preferable range of the in-plane retardation value is 120 nm≦Re(550)≦170 nm, and an even more preferable range is 130 nm≦Re(550)≦150 nm.

[0124] In one embodiment of the present invention, the retardation film of the present invention is a cured product of the polymerizable liquid crystal composition of the present invention, and includes a liquid crystal cured film having optical properties represented by the following formulas (iv), (v), and (vi): The liquid crystal cured film is usually a cured product obtained by curing the polymerizable liquid crystal compound in a state where it is aligned in a direction perpendicular to the plane of the liquid crystal cured film (hereinafter, also referred to as a "vertically aligned liquid crystal cured film").

[0125] Rth(450) / Rth(550)≦1.00 (iv) 1.00≦Rth(650) / Rth(550) (v) -100nm≦Rth(550)≦-40nm (vi) [In the formula, Rth(λ) represents a retardation value of the cured liquid crystal film in the thickness direction at a wavelength of λ nm, and Rth=((nx(λ)+ny(λ)) / 2-nz)×d (d represents the thickness of the cured liquid crystal film, nx represents the principal refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film in the index ellipsoid formed by the cured liquid crystal film, ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film and perpendicular to the direction of nx in the index ellipsoid formed by the cured liquid crystal film, and nz represents the refractive index at a wavelength of λ nm in a direction perpendicular to the plane of the cured liquid crystal film in the index ellipsoid formed by the cured liquid crystal film).] When the vertically aligned liquid crystal cured film satisfies formulas (iv) and (v), an elliptical polarizer equipped with a retardation film containing the vertically aligned liquid crystal cured film can suppress a decrease in ellipticity at short wavelengths and improve the oblique reflection hue. The value of Rth(450) / Rth(550) in the vertically aligned liquid crystal cured film is preferably 0.70 or more, more preferably 0.78 or more, and also preferably 0.90 or less, more preferably 0.88 or less, even more preferably 0.86 or less, particularly preferably 0.85 or less, and especially preferably 0.84 or less. Furthermore, Rth(650) / Rth(550) is preferably 1.0 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

[0126] Furthermore, when the vertically aligned liquid crystal cured film satisfies formula (vi), the oblique reflection hue can be improved when an elliptically polarizing plate equipped with a retardation film containing the vertically aligned liquid crystal cured film is applied to an organic EL display device. The retardation value Rth(550) in the film thickness direction of the vertically aligned liquid crystal cured film is more preferably −90 nm or more, even more preferably −80 nm or more, and more preferably −50 nm or less.

[0127] The retardation film of the present invention can be produced, for example, by a method including the steps of forming a coating film of the polymerizable liquid crystal composition of the present invention, drying the coating film, and aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal composition, and polymerizing the polymerizable liquid crystal compound by light irradiation while maintaining the aligned state, to form a liquid crystal cured film.

[0128] The coating film of the polymerizable liquid crystal composition can be formed by applying the polymerizable liquid crystal composition onto a substrate or onto an alignment film, which will be described later. Examples of substrates include glass substrates and film substrates, with resin film substrates being preferred from the viewpoint of processability. Examples of resins constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. These resins can be formed into a film by known means such as solvent casting or melt extrusion to form the substrate. The substrate surface may have a protective layer formed from an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like, and may be subjected to a surface treatment such as a release treatment such as silicone treatment, a corona treatment, or a plasma treatment.

[0129] Commercially available products may be used as the substrate. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd., such as Fujitac Film; and cellulose ester substrates manufactured by Konica Minolta Opto, Inc., such as "KC8UX2M," "KC8UY," and "KC4UY." Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona (Germany), such as "Topas (registered trademark)," cyclic olefin resins manufactured by JSR Corporation, such as "Arton (registered trademark)," cyclic olefin resins manufactured by Nippon Zeon Corporation, such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)," and cyclic olefin resins manufactured by Mitsui Chemicals, Inc., such as "Apel (registered trademark)." Commercially available cyclic olefin resin substrates may also be used. Commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd., such as "S-Cina (registered trademark)" and "SCA40 (registered trademark)"; cyclic olefin resin substrates manufactured by Optes Co., Ltd., such as "ZEONORFILM (registered trademark)"; and cyclic olefin resin substrates manufactured by JSR Corporation, such as "ARTONFILM (registered trademark)."

[0130] From the viewpoints of thinning the retardation film, ease of peeling the substrate, ease of handling the substrate, etc., the thickness of the substrate is usually 5 to 300 μm, and preferably 10 to 150 μm. Examples of a method for applying the polymerizable liquid crystal composition to a substrate or the like include known methods such as application methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography.

[0131] The solvent is then removed by drying or the like to form a dried coating film. Examples of drying methods include natural drying, forced air drying, heat drying, and reduced-pressure drying. In this case, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent can be dried and removed from the coating film, and the polymerizable liquid crystal compound can be aligned in a desired direction (e.g., horizontal or vertical) relative to the coating film plane. The heating temperature of the coating film can be determined appropriately taking into account the materials of the polymerizable liquid crystal compound used and the substrate on which the coating film is formed. However, in order to transition the polymerizable liquid crystal compound to a liquid crystal phase state, a temperature equal to or higher than the liquid crystal phase transition temperature is usually required. To achieve the desired alignment state while removing the solvent contained in the polymerizable liquid crystal composition, the composition can be heated, for example, to a temperature equal to or higher than the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.

[0132] The polymerizable liquid crystal composition of the present invention contains polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2). The composition typically undergoes a liquid crystal phase transition at a temperature lower than the temperature at which each of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) undergoes a liquid crystal phase transition. In one embodiment of the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture constituting the polymerizable liquid crystal composition of the present invention is preferably 25°C or higher and 153°C or lower. When the phase transition temperature to the liquid crystal phase is within this range, a liquid crystal cured film can be produced at a lower processing temperature, and a liquid crystal cured film having the high optical properties inherently exhibited by the polymerizable liquid crystal compound can be obtained while suppressing deterioration of optical properties due to heating. Furthermore, in the production of a retardation film using the polymerizable liquid crystal composition of the present invention, excessive consumption of thermal energy can be suppressed, thereby improving production efficiency. Furthermore, the ability to undergo a liquid crystal phase transition by heating at a relatively low temperature also has the advantage of broadening the options for supporting substrates onto which the polymerizable liquid crystal composition is applied. In the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture is usually 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher, from the viewpoint that the resulting liquid crystal cured film can exhibit reverse wavelength dispersion characteristics, and is more preferably 150°C or lower, even more preferably 145°C or lower, and particularly preferably 144°C or lower, from the viewpoint of achieving more significant effects of the present invention.

[0133] The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), etc. The phase transition temperature of the polymerizable liquid crystal mixture of the present invention containing at least two polymerizable liquid crystal compounds means a temperature measured using a mixture of polymerizable liquid crystal compounds in which all polymerizable liquid crystal compounds constituting the polymerizable liquid crystal mixture are mixed in the same ratio as the composition of the polymerizable liquid crystal mixture.

[0134] The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type and boiling point of the solvent, and the amount thereof, but is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

[0135] The removal of the solvent from the coating film may be carried out simultaneously with or separately from heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature. However, from the viewpoint of improving productivity, the removal of the solvent is preferably carried out simultaneously. Before heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, a pre-drying step may be carried out to adequately remove the solvent from the coating film obtained from the polymerizable liquid crystal composition under conditions that do not polymerize the polymerizable liquid crystal compound contained in the coating film. Examples of drying methods in the pre-drying step include natural drying, forced air drying, heat drying, and reduced pressure drying. The drying temperature (heating temperature) in the drying step can be appropriately determined depending on the type of polymerizable liquid crystal compound used, the type and boiling point of the solvent, and the amount thereof.

[0136] Next, the resulting dried coating film is polymerized by light irradiation while maintaining the orientation of the polymerizable liquid crystal compound, thereby forming a liquid crystal cured film, which is a polymer of the polymerizable liquid crystal compound present in a desired orientation. The polymerizable liquid crystal composition of the present invention can be highly polymerized by irradiation with high-intensity light such as ultraviolet light while minimizing damage to the polymerizable liquid crystal compound. Therefore, photopolymerization is typically used as the polymerization method. In photopolymerization, the light irradiated onto the dried coating film is appropriately selected depending on the type of polymerization initiator contained in the dried coating film and the type and amount of the polymerizable liquid crystal compound. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, and actinic electron beams. Among these, ultraviolet light is preferred because it allows for easy control of the polymerization reaction and allows the use of photopolymerization equipment widely used in the field. It is preferable to select the types of polymerizable liquid crystal compound and polymerization initiator contained in the polymerizable liquid crystal composition so that they can be photopolymerized by ultraviolet light. Furthermore, during polymerization, the polymerization temperature can be controlled by irradiating the dried coating film with light while cooling it with an appropriate cooling means. By employing such a cooling means, polymerization of the polymerizable liquid crystal compound can be carried out at a lower temperature, and even if a substrate with relatively low heat resistance is used, a liquid crystal cured film can be appropriately formed. Furthermore, the polymerization reaction can be accelerated by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (such as deformation of the substrate due to heat). During photopolymerization, a patterned cured film can also be obtained by performing masking or development.

[0137] Examples of the light source for the actinic energy rays include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source emitting light in a wavelength range of 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

[0138] The UV irradiation intensity is usually 10 to 3,000 mW / cm2 The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating a photopolymerization initiator. The light irradiation time is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and even more preferably 0.1 seconds to 1 minute. When irradiating once or multiple times with such ultraviolet irradiation intensity, the cumulative light amount is 10 to 3,000 mJ / cm. 2 , preferably 50 to 2,000 mJ / cm 2 , more preferably 100 to 1,000 mJ / cm 2 is.

[0139] The thickness of the liquid crystal cured film can be appropriately selected depending on the display device to which it is applied, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm. The coating film of the polymerizable liquid crystal composition may be formed on an alignment film. The alignment film has an alignment regulating force that aligns the polymerizable liquid crystal compound in a desired direction. For example, there is a horizontal alignment film that has an alignment regulating force that aligns the polymerizable liquid crystal compound in the horizontal direction, and a vertical alignment film that has an alignment regulating force that aligns the polymerizable liquid crystal compound in the vertical direction. The alignment regulating force can be adjusted arbitrarily by the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed from a photoalignable polymer, it can be adjusted arbitrarily by the polarized light irradiation conditions, etc.

[0140] The alignment film preferably has solvent resistance so that the polymerizable liquid crystal composition does not dissolve when applied, and also has heat resistance in the heat treatment for removing the solvent and for orienting the polymerizable liquid crystal compound, which will be described later. Examples of the alignment film include an alignment film containing an alignment polymer, a photo-alignment film, a groove alignment film having a concavo-convex pattern or a plurality of grooves on the surface, and a stretched film stretched in the alignment direction, and from the viewpoint of the precision of the alignment angle and quality, a photo-alignment film is preferred.

[0141] Examples of orienting polymers include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and their hydrolyzed products such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Among these, polyvinyl alcohol is preferred. Orienting polymers can be used alone or in combination of two or more.

[0142] An alignment film containing an alignment polymer is usually obtained by applying a composition in which an alignment polymer is dissolved in a solvent (hereinafter, sometimes referred to as an "alignment polymer composition") to a substrate and then removing the solvent, or by applying the alignment polymer composition to a substrate, removing the solvent, and then rubbing the substrate (rubbing method). Examples of the solvent include the same solvents as those exemplified above as solvents that can be used for the polymerizable liquid crystal composition.

[0143] The concentration of the orienting polymer in the orienting polymer composition may be within a range in which the orienting polymer material can be completely dissolved in the solvent, and is preferably 0.1 to 20% in terms of solid content relative to the solution, more preferably about 0.1 to 10%.

[0144] As the oriented polymer composition, commercially available alignment film materials may be used as they are. Examples of commercially available alignment film materials include SUNEVER (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and OPTOMER (registered trademark, manufactured by JSR Corporation).

[0145] The method for applying the alignment polymer composition to the substrate may be the same as the method exemplified as the method for applying the polymerizable liquid crystal composition to the substrate. Methods for removing the solvent contained in the oriented polymer composition include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0146] In order to impart an alignment control force to the alignment film, a rubbing treatment can be performed as needed (rubbing method). A method for imparting an alignment control force by the rubbing method includes a method in which an alignment polymer composition is applied to a substrate and annealed to bring the alignment polymer film formed on the substrate surface into contact with a rotating rubbing roll wrapped with a rubbing cloth. If masking is performed during the rubbing treatment, multiple regions (patterns) with different alignment directions can also be formed on the alignment film.

[0147] A photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "photo-alignment film-forming composition") to a substrate, removing the solvent, and then irradiating the substrate with polarized light (preferably polarized UV). Another advantage of a photo-alignment film is that the direction of the alignment control force can be freely controlled by selecting the polarization direction of the polarized light to be irradiated.

[0148] The photoreactive group refers to a group that exhibits liquid crystal alignment ability upon irradiation with light. Specific examples include groups involved in photoreactions that induce molecular alignment upon irradiation with light or that are the origin of liquid crystal alignment ability, such as isomerization, dimerization, photocrosslinking, or photodecomposition. Among these, groups involved in dimerization or photocrosslinking are preferred because of their excellent alignment properties. As the photoreactive group, groups having an unsaturated bond, particularly a double bond, are preferred, and groups having at least one bond selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond) are particularly preferred.

[0149] Photoreactive groups having a C=C bond include vinyl groups, polyene groups, stilbene groups, stilbazole groups, stilbazolium groups, chalcone groups, and cinnamoyl groups. Photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Photoreactive groups having an N=N bond include azobenzene groups, azonaphthalene groups, aromatic heterocyclic azo groups, bisazo groups, formazan groups, and groups having an azoxybenzene structure. Photoreactive groups having a C=O bond include benzophenone groups, coumarin groups, anthraquinone groups, and maleimide groups. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

[0150] Among these, photoreactive groups involved in photodimerization reactions are preferred, and cinnamoyl and chalcone groups are preferred because they require a relatively small amount of polarized light irradiation for photoalignment and are likely to produce a photoalignment film with excellent thermal stability and stability over time. As a polymer having a photoreactive group, one having a cinnamoyl group such that the terminal of the polymer side chain has a cinnamic acid structure is particularly preferred.

[0151] The composition for forming a photo-alignment film can be applied to a substrate to form a photo-alignment-inducing layer on the substrate. The solvent contained in the composition can be the same as the solvents exemplified above as solvents that can be used in the polymerizable liquid crystal composition, and can be appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group.

[0152] The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be adjusted appropriately depending on the type of polymer or monomer and the desired thickness of the photo-alignment film, but is preferably at least 0.2 mass % relative to the mass of the composition for forming a photo-alignment film, and more preferably in the range of 0.3 to 10 mass %. The composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer, as long as the properties of the photo-alignment film are not significantly impaired.

[0153] The method for applying the composition for forming a photo-alignment film to a substrate may be the same as the method for applying the alignment polymer composition to a substrate. Methods for removing the solvent from the applied composition for forming a photo-alignment film may include, for example, natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0154] The polarized light irradiation can be performed by directly irradiating the substrate with polarized UV light after removing the solvent from the composition for forming a photo-alignment film coated thereon, or by irradiating the substrate with polarized light and then transmitting the polarized light. It is particularly preferable that the polarized light be substantially parallel. The wavelength of the polarized light to be irradiated should be within a wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) with a wavelength of 250 to 400 nm is particularly preferable. Examples of light sources used for polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF. High-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are more preferable. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred due to their high emission intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV light can be irradiated by passing light from the light source through an appropriate polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as a Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.

[0155] If masking is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) with different liquid crystal alignment directions can be formed. A groove alignment film is a film with a concave-convex pattern or multiple grooves on its surface. When a polymerizable liquid crystal compound is applied to a film with multiple equally spaced linear grooves, the liquid crystal molecules are oriented in the direction along the grooves.

[0156] Methods for obtaining a grooved alignment film include a method in which the surface of a photosensitive polyimide film is exposed to light through an exposure mask having slits in the shape of a pattern, followed by development and rinsing to form a concave-convex pattern; a method in which a layer of uncured UV-curable resin is formed on a plate-shaped master having grooves on its surface, and the formed resin layer is transferred to a substrate and then cured; and a method in which a roll-shaped master having multiple grooves is pressed against an uncured UV-curable resin film formed on a substrate to form concave-convex patterns, followed by curing.

[0157] Furthermore, as a material that exhibits an alignment control force that aligns the polymerizable liquid crystal compound in a direction perpendicular to the plane of the liquid crystal cured film, in addition to the above-mentioned alignment polymers, fluorine-based polymers such as perfluoroalkyl, silane compounds, and polysiloxane compounds obtained by a condensation reaction thereof may also be used.

[0158] When a silane compound is used as a material for forming the alignment film, a compound containing Si and C as constituent elements is preferred, and a silane compound can be suitably used, from the viewpoint of easily reducing surface tension and easily increasing adhesion to layers adjacent to the alignment film. Silane-containing ionic compounds can be used as the silane compound, and the use of such silane compounds can increase the vertical alignment regulating force. The silane compound may be used alone or in combination with two or more types, or may be mixed with other materials. When the silane compound is a nonionic silane compound, a silane compound having an alkyl group at the molecular end is preferred, from the viewpoint of easily increasing the vertical alignment regulating force, and a silane compound having an alkyl group with 3 to 30 carbon atoms is more preferred.

[0159] The thickness of the alignment film (alignment film containing an alignment polymer or photoalignment film) is usually in the range of 10 to 10,000 nm, preferably in the range of 10 to 1,000 nm, more preferably 10 to 500 nm or less, even more preferably 10 to 300 nm, and particularly preferably 50 to 250 nm.

[0160] <Circular polarizer> The present invention includes a circular polarizing plate comprising the retardation film of the present invention. The circular polarizing plate of the present invention usually comprises a polarizing film.

[0161] The polarizing film is a film having a polarizing function, and examples thereof include a stretched film having adsorbed thereon a dye having absorption anisotropy, a film containing a film coated with a dye having absorption anisotropy as a polarizer, etc. As such a polarizing film, for example, known polarizing films used in circular polarizing plates, such as those described in JP-A-2013-33249 and JP-A-2013-200445, can be used.

[0162] The circular polarizing plate of the present invention is configured to include the retardation film of the present invention and a polarizing film, and can be obtained, for example, by laminating the retardation film of the present invention and a polarizing film via an adhesive layer, a pressure-sensitive adhesive layer, etc. In one embodiment of the present invention, when the retardation film of the present invention and a polarizing film are laminated, they are preferably laminated so that the angle formed between the slow axis (optical axis) of the liquid crystal cured film constituting the retardation film and the absorption axis of the polarizing film is 45±5°.

[0163] The circular polarizing plate of the present invention may have a structure similar to that of a conventional general circular polarizing plate, or a polarizing film and a retardation film, such as a pressure-sensitive adhesive layer (sheet) for attaching the circular polarizing plate to a display element or the like constituting an image display device, or a protective film used for protecting the surface of a polarizing film or a retardation film from scratches or dirt.

[0164] The circularly polarizing plate of the present invention can be used in various display devices. A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal display devices, organic electroluminescent (EL) display devices, inorganic electroluminescent (EL) display devices, flexible image displays, touch panel display devices, electron emission displays (e.g., field emission displays (FEDs) and surface field emission displays (SEDs)), electronic paper (display devices using electronic ink or electrophoretic elements), plasma display devices, projection display devices (e.g., grating light valve (GLV) displays and displays having digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal display devices include transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection liquid crystal display devices. These display devices may display two-dimensional images or three-dimensional images. In particular, the circular polarizer of the present invention is suitable for use in organic electroluminescent (EL) display devices and inorganic electroluminescent (EL) display devices. These display devices (optical displays) can exhibit good image display characteristics by being equipped with the circular polarizing plate of the present invention, which has excellent optical properties. [Example]

[0165] The present invention will be explained in more detail below with reference to examples. In the examples, "%" and "parts" mean mass % and mass parts, respectively, unless otherwise specified. Hereinafter, a compound represented by formula (#) may be referred to as compound (#) according to its formula number. "#" indicates the formula number.

[0166] [Solubility evaluation] At 25°C, 0.50 g of toluene (TEP) and a stir bar were placed in a vial, and the synthesized compounds or mixtures were added while stirring with a magnetic stirrer (HS-30DN, AS ONE Corporation) until residual dissolution was visually confirmed. Once residual dissolution was confirmed, the solubility of each polymerizable liquid crystal compound or mixture was calculated as a weight percent concentration using the formula (total weight of each polymerizable liquid crystal compound) / (total weight of each polymerizable liquid crystal compound + weight of TEP). Evaluation was based on the following criteria. A (Excellent): 5wt% or more, B (Acceptable): 1wt% or more but less than 5wt%, C (Unacceptable): Less than 1wt% Furthermore, the same solubility evaluation as above was carried out using cyclopentanone (CYP) instead of the solvent, and the results were evaluated according to the following criteria. A (Excellent): 30wt% or more, B (Acceptable): 15wt% or more and less than 30wt%, C (Unacceptable): Less than 15wt% [Evaluation of phase transition temperature] The phase transition temperature can be measured using a polarizing microscope equipped with a temperature-controlling stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. Specifically, using a polarizing microscope equipped with a temperature-controlling stage (LEXT, manufactured by Olympus Corporation), the temperature was raised from room temperature, and the temperature at which the phase transition from a crystal or other liquid crystal phase to a nematic phase was determined from the texture observation by polarizing microscope observation. The determined phase transition temperatures were evaluated according to the following criteria. A (Excellent): Less than 120°C, B (Acceptable): 120°C to 140°C, C (Unacceptable): 140°C or more [Evaluation of the hydrolysis resistance of monomers] The compounds were purified by silica gel column chromatography using chloroform and methanol as developing solvents, yielding compounds with a purity of 95% or higher. Next, for hydrolysis, 100 mg of the compound was dissolved in a 10 v / v% water / dimethylacetamide solution and heated and stirred at 90°C for 48 hours. After the reaction was completed, the residual percentage of each component was calculated by HPLC. The hydrolysis resistance of the monomer was evaluated according to the following criteria, based on the ratio of the peak area of ​​the polymerizable liquid crystal compound after hydrolysis to the peak area of ​​the polymerizable liquid crystal compound before hydrolysis. A (Excellent): 90% or more, B (Acceptable): 80% to less than 90%, C (Unacceptable): Less than 80% The HPLC measurement used for analyzing each compound may be performed under any conditions as long as the peaks derived from each polymerizable liquid crystal compound can be separated. An example of the HPLC measurement conditions is shown below.

[0167] (Measurement conditions) Measurement equipment: HPLC LC-10AT (Shimadzu Corporation) Column: L-Column ODS (inner diameter 3.0 mm, length 150 mm, particle size 3 μm) Temperature: 40℃ Mobile phase A: 0.1%(v / v)-TFA / water Mobile phase B: 0.1% (v / v)-TFA / acetonitrile Gradient: 0min 50%-B 30min 100%-B 60min 100%-B 60.01min 50%-B 75min 50%-B Flow rate: 0.5mL / min Injection volume: 5μL Detection wavelength: 350 nm [Raw material synthesis] <Synthesis Example 1> The quinone compound represented by formula (I-2) was synthesized according to the following scheme.

[0168] [ka]

[0169] A suspension obtained by mixing 100.2 g (305 mmol) of the compound represented by formula (I-1) above with 1.8 kg of acetonitrile was cooled to 0 °C. Compound (I-1) was synthesized with reference to a prior art document (JP 2019-3177 A). An aqueous solution of 350.9 g of diammonium cerium (IV) nitrate (640 mmol, 2.1 mol per 1 mol of compound (I-1)) and 700 g of pure water was added dropwise to the suspension over 4 hours, and the mixture was then heated to room temperature and stirred for 4 hours to carry out the reaction. After the reaction, the suspension was filtered under reduced pressure, and the resulting crude product was washed three times with pure water and dried, yielding 96.7 g of the desired quinone represented by formula (I-2) (yield 97%).

[0170] <Synthesis Example 2> A mixture of compounds (I-3a) and (I-3b) was synthesized according to the following scheme.

[0171] [ka]

[0172] A 500 mL four-neck flask equipped with a Dimroth condenser and a thermometer was placed under a nitrogen atmosphere. 10.0 g (30.6 mmol) of the quinone represented by formula (I-2) was mixed with 0.629 g (3.70 mmol) of silver nitrate (I), 7.87 g (77.1 mmol) of pivalic acid, 90 g of acetonitrile, and 7.5 g of purified water. The resulting suspension was heated to 60 °C. A separately prepared aqueous solution of 21.0 g (91.9 mmol) of ammonium persulfate and 30 g of purified water was added dropwise to the suspension over 20 minutes, followed by stirring at 60 °C for 20 hours. The suspension was cooled to room temperature and filtered under reduced pressure. The resulting crude product was washed with purified water and acetone and dried to obtain 10.3 g of a crude mixture of compounds (I-3a) and (I-3b). 513 g of tetrahydrofuran was added to 10.3 g of the above mixture, the temperature was raised to 55 °C, and insoluble components were removed by filtration. The filtrate was concentrated to dryness to obtain 8.81 g of the target compound (75% yield based on the quinone compound represented by formula (I-2)). The mixture ratio, (I-3a) / (I-3b)=49 / 51 based on the area ratio of HPLC.

[0173] <Synthesis Example 3> A mixture of compounds (I-4a) and (I-4b) was synthesized according to the following scheme.

[0174] [ka]

[0175] A 300 mL four-neck flask equipped with a Dimroth condenser and thermometer was conditioned under a nitrogen atmosphere. 8.81 g (23.0 mmol) of a mixture of compounds (I-3a) and (I-3b) was mixed with 44 g of tetrahydrofuran to obtain a suspension. A separately prepared solution of 12.1 g (69.1 mmol) of sodium dithionite and 50 g of purified water was added to the suspension, and the reaction was initiated by adding one drop of 20% aqueous sodium hydroxide solution with a Pasteur pipette. After stirring for 4 hours at 25 °C, the suspension was filtered, washed with purified water, and dried to obtain 8.28 g of the target mixture (93% yield). The mixture ratio (I-4a) / (I-4b) was 48 / 52 based on the area ratio of HPLC. 2.65 g of the resulting mixture was used for separation and purification. Silica gel column chromatography and recrystallization and washing using chloroform yielded 0.67 g of compound (I-4a) and 0.62 g of compound (I-4b). The purity of the obtained crystals was 87.1% for compound (I-4a) and 81.8% for compound (I-4b) by HPLC. However, since neither crystal contained any isomers, they were used in the next step.

[0176] [Example 1] A 100 mL four-neck flask equipped with a Dimroth condenser and a thermometer was conditioned under a nitrogen atmosphere, and 0.80 g (2.08 mmol) of the compound represented by formula (I-4b) obtained according to Synthesis Example 3 above and 2.19 g (4.58 mmol) of the compound represented by formula (M-1) below, synthesized according to a prior art document (JP 2010-31223 A), 21 mg (0.10 mmol) of N,N-dimethylaminopyridine, and 50 mg of 2,6-di-t-butyl-4-methylphenol were dissolved in 13 g of chloroform (Kanto Chemical Co., Ltd.). The internal temperature was cooled to 0 ° C., and then 0.66 g (5.22 mmol) of N,N'-diisopropylcarbodiimide (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise. The mixture was allowed to react overnight at 0 ° C. After completion of the reaction, insoluble components were removed by filtration. The resulting chloroform solution was added dropwise to methanol in an amount 10 times the weight of the chloroform contained in the solution, resulting in the precipitation of a solid. The precipitated solid was then filtered, washed three times with 25 g of methanol, and dried under reduced pressure at 30°C, yielding 2.17 g (88% yield) of a polymerizable liquid crystal compound represented by formula (1-A). The core of the polymerizable liquid crystal compound represented by formula (1-A) is derived from compound (I-4b), and both mesogenic structures are derived from compound (M-1). The polymerizable liquid crystal compound represented by formula (1-A) is also referred to as polymerizable liquid crystal compound (1-A). Various evaluations were performed on the polymerizable liquid crystal compound (1-A). The results are shown in Table 1.

[0177] [ka]

[0178] [Example 2] Polymerizable liquid crystal compound (1-B) was obtained by synthesizing in the same manner as in Example 1, except that the compound represented by formula (I-4b) was changed to the compound represented by formula (I-4a). Polymerizable liquid crystal compound (1-B) is a polymerizable liquid crystal compound whose core portion is derived from compound (I-4a) and whose both mesogenic structures are derived from compound (M-1). Various evaluations of polymerizable liquid crystal compound (1-B) were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0179] [Example 3] Polymerizable liquid crystal compound (1-C) was obtained by synthesis in the same manner as in Example 1, except that the mesogen was changed from the compound represented by formula (M-1) to the following compound (M-2). Polymerizable liquid crystal compound (1-C) is a polymerizable liquid crystal compound in which the core portion is derived from compound (I-4b) and both mesogen structures are derived from compound (M-2). Various evaluations of polymerizable liquid crystal compound (1-C) were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0180] [Synthesis of Compound (M-2)]

[0181] [ka]

[0182] (1st step) 50.0 g (257.4 mmol) of the compound represented by formula (AI), 0.65 g (5 mmol) of N,N-dimethylaminopyridine, 58.4 g (270.3 mmol) of succinic acid (2-ethyloxyacrylate), 100 mg of 2,6-di-t-butyl-4-methylphenol, and 400 mL of tetrahydrofuran were mixed. The resulting solution was ice-cooled and stirred under a nitrogen atmosphere, and 35.7 g (283.2 mmol) of N,N'-diisopropylcarbodiimide was added dropwise to the solution. After stirring at room temperature for 5 hours, an aqueous solution of 14.7 g (77 mmol) of p-toluenesulfonic acid monohydrate dissolved in 150 g of purified water was added and further stirred. The reaction solution was concentrated using an evaporator, and 400 mL of toluene was added. Insoluble components were filtered, and the filtrate was recovered and washed with saturated sodium bicarbonate water and saturated brine. After drying over anhydrous sodium sulfate and filtration, the solvent was removed and the residue was dried under reduced pressure at 30° C. to obtain 91 g of the compound represented by formula (BI).

[0183] (2nd process) A solution was obtained by mixing 91 g of the compound represented by formula (BI), 96.9 g (463 mmol) of trans-cyclohexanedicarboxylic acid dichloride, 2.8 g of 2,6-di-t-butyl-4-methylphenol, and 218 g of tetrahydrofuran. The resulting solution was cooled to 0°C, and 31.3 g (309 mmol) of triethylamine was added dropwise over 2 hours and stirred for 1 hour. 100 g of water was added to the reaction mixture, and the mixture was heated to 25°C and stirred for 1 hour. Meanwhile, 80.0 g (579 mmol) of potassium carbonate and 120 g of pure water were mixed. The resulting aqueous solution was added dropwise to the reaction mixture. After the reaction was completed, the lower layer was removed and the organic layer was recovered. 400 mL of toluene was added to the recovered organic layer, which was then washed with 2N aqueous hydrochloric acid and saturated saline. The organic layer was recovered, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by evaporation. The obtained crude product was purified by silica gel column chromatography to obtain 26.3 g (yield 22%, based on the compound represented by formula (AI)) of the compound represented by formula (M-2).

[0184] [Example 4] Polymerizable liquid crystal compound (1-D) was obtained by synthesis in the same manner as in Example 3, except that the compound represented by formula (I-4b) was changed to the compound represented by formula (I-4a). Polymerizable liquid crystal compound (1-D) is a polymerizable liquid crystal compound whose core portion is derived from compound (I-4a) and whose both mesogenic structures are derived from compound (M-2). Various evaluations of polymerizable liquid crystal compound (1-D) were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0185] [Example 5] A mixture of compounds (I-5a) and (I-5b) shown below was obtained in the same manner as in Synthesis Example 2, except that pivalic acid was replaced with isobutyric acid. A mixture of compounds (I-6a) and (I-6b) shown below was obtained in the same manner as in Synthesis Example 3, except that the mixture of compounds (I-3a) and (I-3b) in Synthesis Example 3 was replaced with a mixture of compounds (I-5a) and (I-5b). Polymerizable liquid crystal compound (1-E) was obtained by synthesis in the same manner as in Example 1, except that the compound represented by formula (I-4b) was replaced with compound (I-6b). Polymerizable liquid crystal compound (1-E) is a polymerizable liquid crystal compound whose core portion is derived from compound (I-6b) and whose both mesogenic structures are derived from compound (M-1). Various evaluations of polymerizable liquid crystal compound (1-E) were performed in the same manner as in Example 1. The results are shown in Table 1.

[0186] [ka]

[0187] [ka]

[0188] [Example 6] Polymerizable liquid crystal compound (1-F) was obtained by synthesis in the same manner as in Example 1 above, except that the compound represented by formula (I-4b) was replaced with a compound represented by formula (I-7), which was synthesized with reference to JP 2016-081035 A. Polymerizable liquid crystal compound (1-F) is a polymerizable liquid crystal compound whose core portion is derived from compound (I-7) and whose both mesogenic structures are derived from compound (M-1). Various evaluations of polymerizable liquid crystal compound (1-F) were performed in the same manner as in Example 1. The results are shown in Table 1.

[0189] [ka]

[0190] [Example 7] A polymerizable liquid crystal composition containing polymerizable liquid crystal compound (1-A) and polymerizable liquid crystal compound (1-B) was obtained by synthesizing in the same manner as in Example 1, except that compound (I-4b) was changed to a mixture of compound (I-4b) and compound (I-4a). The obtained polymerizable liquid crystal composition was subjected to various evaluations in the same manner as in Example 1. The results are shown in Table 1.

[0191] [Example 8] A polymerizable liquid crystal composition containing polymerizable liquid crystal compound (1-E) and polymerizable liquid crystal compound (1-G) was obtained by synthesis in the same manner as in Example 5, except that compound (I-6b) was changed to a mixture of compound (I-6b) and compound (I-6a). The obtained polymerizable liquid crystal composition was subjected to various evaluations in the same manner as in Example 1. The results are shown in Table 1. Polymerizable liquid crystal compound (1-G) is a polymerizable liquid crystal compound in which the core portion is derived from compound (I-6a) and both mesogenic structures are derived from compound (M-1).

[0192] [Comparative Example 1] Comparative compound 1 was obtained by synthesis in the same manner as in Example 1, except that compound (I-4b) was changed to compound (IX1) shown below. Comparative compound 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1. Comparative compound 1 is a polymerizable liquid crystal compound whose core portion is derived from compound (IX1) and whose both mesogenic structures are derived from compound (M-1).

[0193] Compound (IX1): Compound represented by formula (IX1); synthesized with reference to JP 2019-3177 A

[0194] [ka]

[0195] Comparative Example 2 Comparative compound 2 was obtained by synthesis in the same manner as in Example 1, except that compound (I-4b) was changed to compound (IX2) shown below. Comparative compound 2 was evaluated in the same manner as in Example 1. The results are shown in Table 1. Comparative compound 2 is a polymerizable liquid crystal compound whose core portion is derived from compound (IX2) and whose both mesogenic structures are derived from compound (M-1).

[0196] Compound (IX2): A compound represented by formula (IX2); synthesized with reference to JP 2011-207765 A

[0197] [ka]

[0198] Comparative Example 3 Compound (I-4b) was changed to a compound represented by formula (IX3) shown below, and a liquid crystal was synthesized as follows to obtain comparative compound 3. Comparative compound 3 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0199] Compound (IX3): Compound represented by formula (IX3); synthesized with reference to "Journal of Chemical Crystallography" (1997); 27(9); pp. 515-526.

[0200] [ka]

[0201] [Synthesis of comparative compound 3] 5.0 g (20.1 mmol) of the compound represented by formula (IX3), 17.7 g (42.3 mmol) of the compound represented by formula (M-1), 49 mg (0.40 mmol) of N,N-dimethylaminopyridine, and 310 mg of 2,6-di-t-butyl-4-methylphenol were dissolved in 90 g of chloroform (Kanto Chemical Co., Ltd.). After cooling to 0°C, 5.59 g (44.3 mmol) of N,N'-diisopropylcarbodiimide (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise and the mixture was allowed to react overnight at 0°C. After completion of the reaction, insoluble components were removed by filtration. The resulting chloroform solution was added dropwise to methanol in an amount 10 times the weight of the chloroform contained in the solution, resulting in precipitation of a solid. Subsequently, the precipitated solid was filtered off, washed three times with 100 g of methanol, and then dried under reduced pressure at 30°C to obtain 17.1 g (yield 83%) of comparative compound 3. Comparative compound 3 is a polymerizable liquid crystal compound whose core is derived from compound (IX3) and whose both mesogenic structures are derived from compound (M-1).

[0202] [Table 1]

[0203] As shown in Table 1, Examples 1 to 8 have better TEP solubility than Comparative Examples 1 to 3. Examples 1 to 5, 7 and 8 have better CYP solubility than Comparative Examples 1 to 3. Ar in formula (1) 21 Z equipped with 1 and Z 2 According to Examples 7 and 8, which contain two polymerizable liquid crystal compounds having a structure in which the groups corresponding to the following are interchanged and other structures are common, the phase transition temperature becomes lower.

[0204] In Examples 1, 2 and 7, which contain polymerizable liquid crystal compounds having a core derived from a compound having a CLogP value of 5 or more, the polymerizable liquid crystal compounds are less susceptible to hydrolysis.

Claims

1. A polymerizable liquid crystal compound represented by formula (1): 【Chemical 1】 [In formula (1), k21 and k22 each independently represent an integer of 1 or more; B ２１ and B ２２ are each independently -CR １ R ２ -, -CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ -, -NR ２ -CO-, -O-CH ２ -, -CH ２ —O—, —S—CH ２ -, -CH ２ represents —S— or a single bond, and R １ and R ２ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. E ２１ and E ２２ are each independently -CR １ R ２ -, -CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ -, -NR ２ -CO-, -O-CH ２ -, -CH ２ —O—, —S—CH ２ -, -CH ２ represents -S-; G ２１ and G ２２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is not substituted with a halogen atom, —R ３ , -OR ３ , a cyano group or a nitro group, and the —CH ２ - may be substituted with -O-, -S- or -NH-; R ３ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A ２１ and A ２２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R ３ , -OR ３ , optionally substituted with a cyano group or a nitro group; F ２１ and F ２２ each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR ３ or may be substituted with a halogen atom, and —CH contained in the alkanediyl group ２ - may be replaced by -O- or -CO-; P ２１ and P ２２ each independently represents a hydrogen atom or a polymerizable group (provided that P ２１ and P ２２ at least one of which is a polymerizable group; Ar ２１ are represented by the following formulas (Ar-1) to (Ar-4): 【Chemistry 2】 [In formulas (Ar-1) to (Ar-4), * denotes a binding site; Q １ is —S—, —O— or —NR １１ represents -, and R １１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, Q ２ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; W １ and W ２ each independently represents —O—, —S—, —CO—, or —NR １１ represents -, and R １１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y １ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, Y ２ represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and a —CH ２ - may be substituted by -O-, -CO-, -O-CO- or -CO-O-; Z １ , Z ２ and Z ３ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms; Z １ and Z ２ at least one of which is other than a hydrogen atom; Ax represents an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay may be bonded to form a ring. is a group represented by any one of the following:

2. A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (1) represented by formula (1) and a polymerizable liquid crystal compound (2) represented by formula (1) and having a structure different from that of the polymerizable liquid crystal compound (1), The polymerizable liquid crystal compound (1) is represented by the formula (Ar-1) to (Ar-4) １ and Z ２ are different from each other, The polymerizable liquid crystal compound (2) is represented by the formula (1) ２１ is Ar in the polymerizable liquid crystal compound (1) among the formulas (Ar-1) to (Ar-4). ２１ and Z in formulas (Ar-1) to (Ar-4) is represented by the same formula as １ is Z in the polymerizable liquid crystal compound (1). ２ is identical to Z ２ is Z in the polymerizable liquid crystal compound (1). １ The polymerizable liquid crystal composition is the same as 【Chemistry 3】 [In formula (1), k21 and k22 each independently represent an integer of 1 or more; B ２１ and B ２２ are each independently -CR １ R ２ -, -CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ -, -NR ２ -CO-, -O-CH ２ -, -CH ２ —O—, —S—CH ２ -, -CH ２ represents —S— or a single bond, and R １ and R ２ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. E ２１ and E ２２ are each independently -CR １ R ２ -, -CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ -, -NR ２ -CO-, -O-CH ２ -, -CH ２ —O—, —S—CH ２ -, -CH ２ represents -S-; G ２１ and G ２２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is not substituted with a halogen atom, —R ３ , -OR ３ , a cyano group or a nitro group, and the —CH ２ - may be substituted with -O-, -S- or -NH-; R ３ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A ２１ and A ２２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R ３ , -OR ３ , optionally substituted with a cyano group or a nitro group; F ２１ and F ２２ each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR ３ or may be substituted with a halogen atom, and —CH contained in the alkanediyl group ２ - may be replaced by -O- or -CO-; P ２１ and P ２２ each independently represents a hydrogen atom or a polymerizable group (provided that P ２１ and P ２２ at least one of which is a polymerizable group; Ar ２１ are represented by the following formulas (Ar-1) to (Ar-4): 【Chemistry 4】 [In formulas (Ar-1) to (Ar-4), * denotes a binding site; Q １ is —S—, —O— or —NR １１ represents -, and R １１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, Q ２ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; W １ and W ２ each independently represents —O—, —S—, —CO—, or —NR １１ represents -, and R １１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y １ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, Y ２ represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and a —CH ２ - may be substituted by -O-, -CO-, -O-CO- or -CO-O-; Z １ , Z ２ and Z ３ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms; Z １ and Z ２ at least one of which is other than a hydrogen atom; Ax represents an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay may be bonded to form a ring. is a group represented by any one of the following:

3. Z in formulas (Ar-1) to (Ar-4) １ and Z ２ 2. The polymerizable liquid crystal compound according to claim 1, wherein at least one of the following is an alkyl group having 1 to 6 carbon atoms:

4. Z in formulas (Ar-1) to (Ar-4) １ and Z ２ The polymerizable liquid crystal compound according to claim 1 , wherein one of the groups is a hydrogen atom.

5. Ar in formula (1) ２１ teeth, Ar ２１ HO-Ar derived from the structure represented by ２１ 2. The polymerizable liquid crystal compound according to claim 1, wherein the difference between pKa1 and pKa2 of the phenolic hydroxyl groups represented by the following formulae (K1) and (K2) for —OH is 4.00 or more. 【Chemistry 5】

6. Ar in formula (1) ２１ The polymerizable liquid crystal compound according to claim 1 , wherein the CLogP value is 5.0 or more.

7. Ar in formula (1) ２１ The polymerizable liquid crystal compound according to claim 1, wherein is a group represented by formula (Ar-1):

8. P in formula (1) ２１ and P ２２ The polymerizable liquid crystal compound according to claim 1 , wherein each of the groups is an acryloyloxy group.

9. The polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) each independently represent Z in formulas (Ar-1) to (Ar-4). １ and Z ２ 3. The polymerizable liquid crystal composition according to claim 2, wherein at least one of the following is an alkyl group having 1 to 6 carbon atoms:

10. The polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) each independently represent Z in formulas (Ar-1) to (Ar-4). １ and Z ２ The polymerizable liquid crystal composition according to claim 2 , wherein one of the groups is a hydrogen atom.

11. Ar in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) ２１ teeth, Ar ２１ HO-Ar derived from the structure represented by ２１ 3. The polymerizable liquid crystal composition according to claim 2, wherein the difference between pKa1 and pKa2 of the phenolic hydroxyl groups represented by the following formulae (K1) and (K2) for —OH is 4.00 or more. 【Chemistry 6】

12. Ar in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) ２１ The polymerizable liquid crystal composition according to claim 2 , wherein the CLogP value is 5.0 or more.

13. Ar in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) ２１ The polymerizable liquid crystal composition according to claim 2, wherein is a group represented by formula (Ar-1).

14. P in formula (1) in the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) ２１ and P ２２ The polymerizable liquid crystal composition according to claim 2 , wherein each of the groups is an acryloyloxy group.

15. A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1 .

16. The polymerizable liquid crystal composition according to claim 2 or 15, further comprising a photopolymerization initiator.

17. The polymerizable liquid crystal composition according to claim 2 or 15, further comprising an organic solvent.

18. A retardation film comprising a cured product of the polymerizable liquid crystal composition according to claim 2 or 15.

19. A circularly polarizing plate comprising the retardation film according to claim 18.

20. Represented by any one of formulas (Ar-01) to (Ar-04), １ and Z ２ are different from each other, and Among formulas (Ar-01) to (Ar-04), the formula is the same as the formula representing compound (A1), and Z １ is Z in the compound (A1). ２ is identical to Z ２ is Z in the compound (A1). １ and a compound (A2) which is identical to 【Chemistry 7】 [In formulas (Ar-01) to (Ar-04), Q １ is —S—, —O— or —NR １１ represents -, and R １１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, Q ２ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; W １ and W ２ each independently represents —O—, —S—, —CO—, or —NR １１ represents -, and R １１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y １ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group, Y ２ represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and a —CH ２ - may be substituted by -O-, -CO-, -O-CO- or -CO-O-; Z １ , Z ２ and Z ３ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms; Z １ and Z ２ at least one of which is other than a hydrogen atom; Ax represents an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay may be bonded to form a ring.

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