Polymerizable liquid crystal composition, retardation film, elliptically polarizing plate and optical display

Abstract

To provide a polymerizable liquid crystal composition excellent in solubility in a solvent.SOLUTION: A polymerizable liquid crystal composition having at least two kinds of polymerizable liquid crystalline compounds having the same molecular weight but different molecular structures from each other, and represented by a formula (1): P1-F1-B1-A1-E1-G1-D1-Ar-D2-G2-E2-A2-B2-F2-P2 (1), as the polymerizable liquid crystal compound, G1 and G2 in the formula (1) each contains a polymerizable liquid crystal compound (1-1) which is a 1,4-trans-cyclohexane diyl group and a polymerizable liquid crystal compound (1-2) that is different in a molecular structure only in that at least one of G1 and G2 in the polymerizable liquid crystal compound (1-1) and the formula (1) is 1,4-cis-cyclohexane diyl, and a ratio of a peak area of the polymerizable liquid crystal compound (1-2) relative to a total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), measured by liquid chromatography, is 0.01% or larger and 10% or smaller.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable liquid crystal composition, a retardation film formed from a cured product of the polymerizable liquid crystal composition, and an elliptically polarizing plate and an optical display each including the retardation film. [Background technology]

[0002] Examples of optical films such as retardation films used in flat panel displays (FPDs) include optical films obtained by dissolving a polymerizable liquid crystal compound in a solvent, applying the resulting coating liquid to a supporting substrate, and then polymerizing the resulting coating liquid. Known polymerizable liquid crystal compounds for forming such optical films include nematic liquid crystal compounds having a rod-like structure in which 2 to 4 six-membered rings are linked together.

[0003] On the other hand, one of the characteristics of a retardation film is that it is capable of uniform polarization conversion across the entire wavelength range, and it is known that theoretically uniform polarization conversion is possible in a wavelength range where the value [Re(λ) / Re(550)] obtained by dividing the retardation value Re(λ) at a certain wavelength λ by the retardation value Re(550) at 550 nm is close to 1, or in a wavelength range showing inverse wavelength dispersion of [Re(450) / Re(550)]< 1. Polymerizable liquid crystal compounds that can constitute such retardation films are disclosed, for example, in Patent Documents 1 and 2. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-207765 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-143788 Summary of the Invention [Problem to be solved by the invention]

[0005] Solutions (coating solutions) obtained by dissolving polymerizable liquid crystal compounds in solvents and used in the production of optical films may have poor solubility in various solvents due to the molecular structure of the polymerizable liquid crystal compounds. Such polymerizable liquid crystal compounds with low solubility may precipitate or crystallize and precipitate in the coating solution. Such precipitation or precipitation of polymerizable liquid crystal compounds not only reduces film-forming properties but can also cause alignment defects in the resulting optical film. Therefore, there is a need for the development of polymerizable liquid crystal compositions containing polymerizable liquid crystals that exhibit improved solubility in solvents.

[0006] An object of the present invention is to provide a polymerizable liquid crystal composition that has excellent solubility in a solvent. [Means for solving the problem]

[0007] The present invention provides the following preferred embodiments. [1] Having the same molecular weight but different molecular structures, and having the formula (1): [ka] [In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent; D 1 , D 2 , E 1 , E 2 , B 1 and B 2 are each independently -CR 11 R 12 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 11 -, -NR 11 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, and R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, G1 and G 2 each represents a 1,4-cyclohexanediyl group, A 1 and A 2 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 13 , -OR 13 , optionally substituted with a cyano group or a nitro group, R 13 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, F 1 and F 2 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 14 or may be substituted with a halogen atom, R 14 represents an alkyl group having 1 to 4 carbon atoms, wherein a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and wherein —CH— contained in the alkanediyl group may be substituted with —O— or —CO—; P 1 and P 2 each independently represents a hydrogen atom or a polymerizable group (provided that P 1 and P 2 at least one of which is a polymerizable group)] A polymerizable liquid crystal composition comprising at least two polymerizable liquid crystal compounds represented by the formula: As the polymerizable liquid crystal compound, G in formula (1) 1 and G 2 are 1,4-trans-cyclohexanediyl groups, and the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-1) are G 1 and G 2 and a polymerizable liquid crystal compound (1-2) which has a different molecular structure only in that at least one of the above is a 1,4-cis-cyclohexanediyl group, A polymerizable liquid crystal composition, in which the ratio of the peak area of ​​the polymerizable liquid crystal compound (1-2) to the total peak area of ​​the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is 0.01% or more and 10% or less. [2] The polymerizable liquid crystal compound (1-2) is G in formula (1). 1 and G 2 a polymerizable liquid crystal compound (1-2a) in which either one of G in formula (1) is a 1,4-cis-cyclohexanediyl group; 1 and G 2 and a polymerizable liquid crystal compound (1-2b) in which all of the above are 1,4-cis-cyclohexanediyl groups. [3] The polymerizable liquid crystal composition according to the above [1] or [2], wherein Ar in the formula (1) is a group represented by any one of the formulae (2-1) to (2-5). [ka] [In the formula, *D 1 or D 2 Represents the join with; Q 1 is -S-, -O- or -NR 15 - represents R 15 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 15 - represents R 15 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y 1represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, wherein a hydrogen atom contained in the alkyl group, aromatic hydrocarbon group or aromatic heterocyclic 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—; 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, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, or -NR 15 R 16 or -SR 15 represents Z 1 and Z 2 may be bonded to each other to form an aromatic ring or an aromatic heterocycle, R 15 and R 16 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; 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; Y 3 and Y 4 are each independently represented by the following formula (Y-1): [ka] [In formula (Y-1), M 1represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is 3 and the substituent X 3 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH2- or two or more non-adjacent -CH2- groups each independently represent -O-, -S-, -CO-, - represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or -B 11 -F 11 -P 11 and B 11 , F 11 and P 11 are B in the formula (1), respectively. 1 , F 1 and P 1 are defined in the same manner as above, and 1 , F 1 and P 1 may be the same as or different from; U 1 represents an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group, any carbon atom of which may be substituted with a heteroatom, and the aromatic hydrocarbon group is substituted with one or more of the above-mentioned substituents X 3 may be substituted by; T 1 -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -,-N=CU 2 -,-CO-NU 2 -, -OCO-NU 2-or-O-NU 2 - represents U 2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or (E 11 -A 11 ) q -B 12 -F 12 -P 12 and the alkyl group, the cycloalkyl group, the cycloalkenyl group and the aromatic hydrocarbon group are each unsubstituted or substituted with one or more substituents X 3 the alkyl group is optionally substituted by the cycloalkyl group or cycloalkenyl group, and one -CH2- or two or more non-adjacent -CH2- in the alkyl group are each independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-; one -CH2- or two or more non-adjacent -CH2- in the cycloalkyl group or cycloalkenyl group are each independently replaced by -O-, -CO-, -COO-, -OCO- or -O-CO-O-; E 11 , A 11 , B 12 , F 12 and P 12 are the E in equation (1), respectively. 1 , A 1 , B 1 , F 1 and P 1 are defined in the same manner as above, and 1 , A 1 , B 1 , F 1 and P 1 may be the same as or different from each other, q represents an integer of 0 to 4, and E 11 and / or A11 When there are multiple, they may be the same or different, and U 1 and U 2 and may be bonded to form a ring. represents a group selected from the following: [4] A in Equation (1) 1 and A 2 The polymerizable liquid crystal composition according to any one of [1] to [3] above, wherein each of the is independently a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group. [5] P in Equation (1) 1 and P 2 The polymerizable liquid crystal composition according to any one of the above [1] to [4], wherein each of the is an acryloyl group. [6] The polymerizable liquid crystal composition according to any one of [1] to [5] above, further comprising a photopolymerization initiator. [7] The polymerizable liquid crystal composition according to any one of [1] to [6] above, further comprising an organic solvent. [8] A retardation film comprising a liquid crystal cured film which is a cured product of the polymerizable liquid crystal composition according to any one of [1] to [7] above. [9] The liquid crystal cured film is represented by the formula (i): 0.75≦Re(450) / Re(550)<1.00 (i) [In formula (i), Re(λ) represents the in-plane retardation value of the cured liquid crystal film at a wavelength of λ nm] The retardation film according to [8] above, which satisfies the above.

[10] An elliptically polarizing plate comprising the retardation film according to [8] or [9].

[11] An optical display comprising the elliptically polarizing plate according to

[10] above.

[12] A flexible image display device comprising the elliptically polarizing plate according to

[10] above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a polymerizable liquid crystal composition having excellent solubility in a solvent. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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.

[0010] <Polymerizable liquid crystal composition> The polymerizable liquid crystal composition of the present invention contains at least two polymerizable liquid crystal compounds having the same molecular weight but different molecular structures and represented by formula (1). By containing at least two polymerizable liquid crystal compounds having different molecular structures but the same molecular weight and similar molecular structures represented by formula (1), high solubility in a solvent can be ensured. [ka] [In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent; D 1 , D 2 , E 1 , E 2 , B 1 and B 2 are each independently -CR 11 R 12 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 11 -, -NR 11 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, and R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, G 1 and G 2 each represents a 1,4-cyclohexanediyl group, A 1 and A 2each 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 13 , -OR 13 , optionally substituted with a cyano group or a nitro group, R 13 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, F 1 and F 2 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 14 or may be substituted with a halogen atom, R 14 represents an alkyl group having 1 to 4 carbon atoms, wherein a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and wherein —CH— contained in the alkanediyl group may be substituted with —O— or —CO—; P 1 and P 2 each independently represents a hydrogen atom or a polymerizable group (provided that P 1 and P 2 at least one of which is a polymerizable group).

[0011] The polymerizable liquid crystal composition of the present invention is characterized in that the at least two polymerizable liquid crystal compounds are 1 and G 2 and a polymerizable liquid crystal compound (1-1) (hereinafter also referred to as "polymerizable liquid crystal compound (1-1")) in which G in the formula (1) is a 1,4-trans-cyclohexanediyl group, respectively. 1 and G 2and a polymerizable liquid crystal compound (1-2) (hereinafter also referred to as "polymerizable liquid crystal compound (1-2)") whose molecular structure differs only in that at least one of them is a 1,4-cis-cyclohexanediyl group. In the present invention, the polymerizable liquid crystal composition may contain only one type of polymerizable liquid crystal compound (1-1), or may contain two or more types. When a plurality of polymerizable liquid crystal compounds (1-1) are contained, the polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound (1-2) corresponding to at least one of the polymerizable liquid crystal compounds (1-1), and may contain a polymerizable liquid crystal compound (1-2) corresponding to each of the plurality of polymerizable liquid crystal compounds (1-1) constituting the polymerizable liquid crystal composition.

[0012] A polymerizable liquid crystal compound (1-1) and G in formula (1) 1 and G 2 By incorporating a polymerizable liquid crystal compound (1-1) in combination with a polymerizable liquid crystal compound (1-2), which is an isomer and has a molecular structure different only in that at least one of the groups is a 1,4-cis-cyclohexanediyl group, the solubility of the polymerizable liquid crystal compound (1-1) in a solvent can be improved. In other words, when the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are incorporated in combination, a larger amount of the polymerizable liquid crystal compound (1-1) can be easily dissolved in the same or a smaller amount of solvent than when the polymerizable liquid crystal compound (1-1) is dissolved alone in a solvent. This reduces the amount of undissolved polymerizable liquid crystal compound remaining in the coating solution and also suppresses precipitation, deposition, and stacking of the polymerizable liquid crystal compound in the coating solution. The improved solubility of the polymerizable liquid crystal compound (1-1) in a solvent leads to the suppression of alignment defects caused by undissolved polymerizable liquid crystal compound and precipitates, and to improved storage stability.

[0013] The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are each represented by the formula (1): [ka] The compound having the structure represented by formula (1) is a polymerizable liquid crystal compound that generally exhibits birefringence with reverse wavelength dispersion when polymerized in a unidirectionally aligned state, and is capable of uniform polarization conversion over a wide wavelength range. Therefore, by using the polymerizable liquid crystal compound represented by formula (1), it is possible to obtain a polymerizable liquid crystal composition that can impart good display characteristics when a retardation film or an elliptically polarizing plate formed from the polymerizable liquid crystal compound is used in an optical display such as a display device.

[0014] In formula (1), G 1 and G 2 Each of the two polymerizable liquid crystal compounds (1-1) and (1-2) constituting the polymerizable liquid crystal composition of the present invention is represented by the formula (1), 1 and G 2 are all 1,4-trans-cyclohexanediyl groups, or G 1 and G 2 are different from each other in that either one or all of them are 1,4-cis-cyclohexanediyl groups.

[0015] In formula (1), D 1 , D 2 , E 1 , E 2 , B 1 and B 2 are each independently -CR 11 R 12 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 11 -, -NR 11 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond. 11 and R 12 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom, a methyl group or an ethyl group.

[0016] In formula (1), D 1 and D 2 are each independently preferably -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -O-CH2-, -CH2-O-, or -CO-NR 11 -or-NR 11 -CO-, and more preferably -CO-O-, -O-CO-, or -CO-NR 11 -or-NR 11 -CO-, and particularly preferably -CO-O- or -O-CO-. 11 is preferably a hydrogen atom, a methyl group, or an ethyl group. 1 and D 2 may be the same or different. 1 and D 2 are identical to each other, D when Ar is the center 1 and D 2 This means that the structures of E 1 and E 2 , A 1 and A 2 , B 1 and B 2 , and ,F 1 and F 2 The same is true for the relationship in

[0017] In formula (1), E 1 , E 2 , B 1 and B 2 are each independently preferably -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, or -CO-NR 11 -, -NR 11 R is —CO— or a single bond, and more preferably —O—, —O—CO— or —CO—O—. 11 is preferably a hydrogen atom, a methyl group, or an ethyl group. 1 and E 2 , and B 1 and B 2 may be the same or different from each other.

[0018] In formula (1), A 1 and A 2 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, wherein a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group can be substituted with a halogen atom, -R 13 , -OR 13 , optionally substituted with a cyano group or a nitro group, R 13 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.

[0019] In formula (1), A 1 and A 2 are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbon atoms, or a 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbon atoms, more preferably a 1,4-phenylenediyl group substituted with a methyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-cyclohexanediyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group. 1 and A 2 may be the same or different from each other.

[0020] In formula (1), F 1 and F 2 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 14 or may be substituted with a halogen atom, R 14represents 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. Furthermore, -CH2- contained in the alkanediyl group may be substituted with -O- or -CO- (however, when there are multiple -O-, they are not adjacent to each other).

[0021] In formula (1), F 1 and F 2 are each independently preferably an optionally substituted alkanediyl group having 4 to 12 carbon atoms. 1 and F 2 may be the same or different from each other.

[0022] P 1 or P 2 Examples of the polymerizable group represented by formula (1) include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyl group, a methacryloyl group, an oxiranyl group, and an oxetanyl group. Among these, an acryloyl group, a methacryloyl group, a vinyl group, and a vinyloxy group are preferred, an acryloyl group and a methacryloyl group are more preferred, and an acryloyl group is even more preferred. In formula (1), P 1 and P 2 may be the same or different as long as either one is a polymerizable group, 1 and P 2 is preferably a polymerizable group, and P 1 and P 2 It is more preferable that all of the groups are acryloyl groups.

[0023] In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, which may have a substituent. In the present invention, the divalent aromatic hydrocarbon group, which may have a substituent, refers to a divalent linking group containing at least one aromatic hydrocarbon ring, and the divalent aromatic heterocyclic group, which may have a substituent, refers to a divalent linking group containing at least one aromatic heterocyclic ring. The aromatic hydrocarbon ring and aromatic heterocyclic ring referred to here refer to ring structures having a π-electron count of [4n+2] (n represents an integer) according to the Hückel rule (in the case of an aromatic heterocyclic ring, the Hückel rule is satisfied, including non-covalent electron pairs on heteroatoms such as -N= and -S-). Ar may contain one aromatic hydrocarbon ring or aromatic heterocyclic ring, or may contain two or more. When Ar contains one aromatic hydrocarbon ring or aromatic heterocyclic ring, it may be a divalent aromatic hydrocarbon group, which may have a substituent, or a divalent aromatic heterocyclic group, which may have a substituent. When two or more aromatic hydrocarbon rings or aromatic heterocyclic rings are contained, the compound may contain only a plurality of aromatic hydrocarbon rings or only a plurality of aromatic heterocyclic rings, or may contain one or more aromatic hydrocarbon rings and one or more aromatic heterocyclic rings. The two or more aromatic hydrocarbon rings and / or aromatic heterocyclic rings may be bonded to each other via a divalent bonding group such as a single bond, -CO-O-, or -O-.

[0024] Examples of aromatic hydrocarbon rings that can be contained in Ar include a benzene ring, a naphthalene ring, and an anthracene ring, with a benzene ring and a naphthalene ring being preferred. Examples of aromatic heterocycles include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. When Ar contains a nitrogen atom, it is preferred that the nitrogen atom has a π electron.

[0025] Among these, Ar preferably has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, more preferably a thiazole ring, a benzothiazole ring, or a benzofuran ring, and even more preferably a benzothiazole ring. When Ar has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, the aromatic heterocycle is preferably a ring represented by D in formula (1). 1 and D 2 may be directly bonded to form a divalent linking group, and D 1 and D 2 However, it is preferable that the entire Ar group including the aromatic heterocycle is sterically configured in a direction approximately perpendicular to the molecular orientation direction.

[0026] In formula (1), the total number N of π electrons contained in the divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group represented by Ar, which may have a substituent, π is preferably 8 or more, more preferably 12 or more, particularly preferably 16 or more, and especially preferably 20 or more. It is also preferably 36 or less, more preferably 32 or less, even more preferably 30 or less, particularly preferably 26 or less, and especially preferably 24 or less.

[0027] Examples of the optionally substituted divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group represented by Ar in formula (1) include groups represented by the following formulae (2-1) to (2-5). [ka]

[0028] In formulas (2-1) to (2-5), * represents D 1 or D 2 Represents the connection part with.

[0029] In formula (2-1), Q 1 is -S-, -O- or -NR 15 - represents R 15represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0030] In formula (2-2), W 1 and W 2 each independently represents -O-, -S-, -CO-, or -NR 15 - represents R 15 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0031] In formula (2-1), 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, and is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, and more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic heterocyclic group having 3 to 12 carbon atoms. 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, aromatic heterocyclic group, or aromatic heterocyclic 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-.

[0032] In formulas (2-1) to (2-5), Z 1 , Z 2 and Z 3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, or -NR 15 R 16 or -SR 15 represents Z 1 and Z 2 may be bonded to each other to form an aromatic ring or a heteroaromatic ring. 15 and R 16each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0033] In formulas (2-3) and (2-4), 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.

[0034] The groups represented by formulae (2-1) to (2-4) are not particularly limited, but specific examples include groups described in JP-A Nos. 2011-207765, 2008-107767, WO2014 / 010325, and the like.

[0035] In formula (2-5), Y 3 and Y 4 are each independently represented by the following formula (Y-1): [ka] The group is selected from groups represented by the following formula:

[0036] In formula (Y-1), M 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group may have one or more substituents X 3 may be substituted by

[0037] Substituent X 3represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH2- or two or more non-adjacent -CH2- groups each independently represent -O-, -S-, -CO-, - represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or -B 11 -F 11 -P 11 and B 11 , F 11 and P 11 are B in the formula (1), respectively. 1 , F 1 and P 1 are defined in the same manner as above, and 1 , F 1 and P 1 may be the same as or different from.

[0038] Substituent X 3 is preferably a fluorine atom, a chlorine atom, -CF3, -OCF3 or a cyano group. 1 is preferably an alkyl group having 1 to 6 carbon atoms that is unsubstituted or substituted with a hydrogen atom or one or more fluorine atoms, and more preferably a hydrogen atom.

[0039] U 1 represents an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group. Any carbon atom in the aromatic hydrocarbon group may be substituted with a heteroatom, and U 1is an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. 3 may be substituted by

[0040] U 1 In terms of improving wavelength dispersion, U is preferably an organic group having an aromatic heterocycle in which one or more carbon atoms are substituted with a heteroatom. 1 is more preferably an organic group having an aromatic heterocycle that is a condensed ring of a 5-membered ring and a 6-membered ring, since this has good wavelength dispersion and exhibits high birefringence.

[0041] Specifically, U 1 It is preferable that the group has a group represented by the following formula: In the following formula, these groups may have T at any position. 1 It has a bond with

[0042] [ka]

[0043] T 1 -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -,-N=CU 2 -,-CO-NU 2 -, -OCO-NU 2 -or-O-NU 2 - represents U 2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or (E 11 -A 11 ) q -B 12 -F 12 -P 12The alkyl group, the cycloalkyl group, the cycloalkenyl group and the aromatic hydrocarbon group are each unsubstituted or substituted with one or more substituents X 3 The alkyl group may be substituted with the cycloalkyl group or the cycloalkenyl group. One -CH2- or two or more non-adjacent -CH2- groups in the alkyl group may each independently be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and one -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl group or the cycloalkenyl group may each independently be replaced with -O-, -CO-, -COO-, -OCO-, or O-CO-O-. 11 , A 11 , B 12 , F 12 and P 12 are the E in the above formula (1), respectively. 1 , A 1 , B 1 , F 1 and P 1 are defined in the same manner as above, and 1 , A 1 , B 1 , F 1 and P 1 may be the same as or different from each other, q represents an integer of 0 to 4, and E 11 and / or A 11 When there are a plurality of, they may be the same or different.

[0044] T 1 -O-, -S-, -N=CU are preferred because of their good birefringence and ease of synthesis. 2 -or- NU 2 - is preferable, and -O-, -S- or -NU is preferable because it is easy to improve wavelength dispersion and birefringence. 2 - is more preferable.

[0045] U 2 is one or more of the substituents X 3 and one -CH2- or two or more non-adjacent -CH2- may each independently be replaced by -O-, -CO-, -COO-, -OCO- or -O-CO-O-.

[0046] Among them, U 2 From the viewpoints of birefringence and solvent solubility, it is more preferable that is a linear alkyl group having 1 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and in which one -CH2- or two or more non-adjacent -CH2- groups may each independently be substituted with -O-, -CO-, -COO-, or -OCO-.

[0047] U 1 and U 2 may be bonded to form a ring. In that case, for example, -NU 1 U 2 or -N=CU 1 U 2 Examples of the cyclic group include a cyclic group represented by the following formula:

[0048] Y is a popular choice due to its easy availability, good solubility, and high birefringence. 3 and Y 4 particularly preferably each represents a group selected from the following formulae (Y-1′) to (Y-47′).

[0049] [ka]

[0050] [ka]

[0051] From the viewpoints of improving the alignment of the polymerizable liquid crystal compound (1), facilitating industrial production, and improving productivity, it is preferable that the molecular structure of the polymerizable liquid crystal compound (1) be symmetric. Specific examples of the group represented by formula (2-5) include the following groups. * in the following (2-5a) to (2-5t) represents D 1 or D 2 Represents the connection part with.

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] Among the formulae (2-1) to (2-5), the formulae (2-1), (2-3), (2-4) and (2-5) are preferred, the formulae (2-1) and (2-5) are more preferred, and the formula (2-1) is particularly preferred.

[0056] In the present invention, examples of the polymerizable liquid crystal compound represented by formula (1) include compounds described in JP-A-2019-003177, JP-A-2019-073496, and the like.

[0057] The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention each have a structure represented by the above formula (1), in which G 1 and G 2 The polymerizable liquid crystal compound (1-1) differs from the compound (1) only in the structure of the 1,4-cyclohexanediyl group represented by G 1 and G 2are both 1,4-trans-cyclohexanediyl groups, and the polymerizable liquid crystal compound (1-2) is a compound having a structure similar to that of the polymerizable liquid crystal compound (1-1), and a structure similar to that of the polymerizable liquid crystal compound (1-1). 1 and G 2 The only difference is that at least one of them is a 1,4-cis-cyclohexanediyl group.

[0058] In the present invention, the polymerizable liquid crystal compound (1-2) is a compound represented by the formula (1), 1 and G 2 In the polymerizable liquid crystal compound (1-2a) (hereinafter also referred to as "polymerizable liquid crystal compound (1-2a)"), one of G in formula (1) is a 1,4-trans-cyclohexanediyl group and the other is a 1,4-cis-cyclohexanediyl group, 1 and G 2 and (1-2b) (hereinafter also referred to as "polymerizable liquid crystal compound (1-2b)") may be a polymerizable liquid crystal compound (1-2a) in which all of the above are 1,4-cis-cyclohexanediyl groups. The polymerizable liquid crystal composition of the present invention may contain either the polymerizable liquid crystal compound (1-2a) or the polymerizable liquid crystal compound (1-2b), or may contain both of them.

[0059] The polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal composition (1-1) and the polymerizable liquid crystal compound (1-2) in amounts such that the ratio of the peak area of ​​the polymerizable liquid crystal compound (1-2) to the total peak areas of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) measured by liquid chromatography (hereinafter also referred to as "area percentage value") is 0.01% or more and 10% or less. The polymerizable liquid crystal compound represented by formula (1) having a so-called T-shaped structure in which the constituent molecules are arranged in the long axis direction of the main chain of the compound and in a direction intersecting the long axis direction is represented by G 1 and G 2 When both of G in formula (1) are 1,4-trans-cyclohexanediyl groups (i.e., polymerizable liquid crystal compound (1-1)), 1 and G 2The polymerizable liquid crystal compound (1-1) has a more stable molecular structure than the polymerizable liquid crystal compound (1-2) in which at least one of the groups is a 1,4-cis-cyclohexanediyl group, and is more easily oriented in the desired direction, making it possible to produce an optical film with fewer alignment defects. Therefore, from the viewpoints of alignment and optical properties, the polymerizable liquid crystal compound (1-1) is considered to be advantageous as the polymerizable liquid crystal compound represented by formula (1). In the present invention, by adjusting the amount of the polymerizable liquid crystal compound (1-2) relative to the polymerizable liquid crystal compound (1-1) within a specific range, the solubility of the polymerizable liquid crystal compound (1-1) in a solvent can be sufficiently improved without affecting the alignment of the polymerizable liquid crystal compound (1-1).

[0060] If the area percentage of the polymerizable liquid crystal compound (1-2) is less than the above lower limit, it is difficult to improve the solubility of the polymerizable liquid crystal compound (1-1) in a solvent. However, if the area percentage of the polymerizable liquid crystal compound (1-2) is equal to or greater than the above lower limit, the solubility of the polymerizable liquid crystal compound (1-1) in a solvent tends to be sufficiently improved. Furthermore, if the area percentage of the polymerizable liquid crystal compound (1-2) is equal to or less than the above upper limit, the liquid crystal orientation state can be maintained favorably when preparing an optical film such as a retardation film from a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound. This allows for the production of an optical film with excellent optical properties while suppressing alignment defects. In the present invention, the area percentage of the polymerizable liquid crystal compound (1-2) is more preferably 9% or less, even more preferably 8% or less, particularly preferably 7% or less, and especially preferably 6% or less. In the present invention, the area percentage of the polymerizable liquid crystal compound (1-2) is preferably 0.1% or more, more preferably 0.5%, and even more preferably 2.5% or more. On the other hand, in the present invention, even when the polymerizable liquid crystal compound (1-2) is contained in a small amount, the effect of significantly improving the solubility of the polymerizable liquid crystal compound (1-1) in a solvent is excellent. Therefore, in one embodiment of the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) may be less than 1.0%, and even when it is, for example, 0.5% or less or 0.1% or less, the above-mentioned advantageous effects of the present invention are likely to be sufficiently obtained. When a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1-1) and / or the polymerizable liquid crystal compound (1-2) are contained, the area percentage value of the polymerizable liquid crystal compound (1-2) is calculated based on the total peak area of ​​all the polymerizable liquid crystal compounds (1-2) and all the polymerizable liquid crystal compounds (1-1). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, can be measured and calculated by the method described in the Examples below.

[0061] The method for producing the polymerizable liquid crystal compounds represented by formula (1), such as the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention, is not particularly limited, and the polymerizable liquid crystal compounds 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 compounds.

[0062] For example, D in Equation (1) 1 and D 2 is *-O-CO- (* represents the bond with Ar), and G 1 and G 2 is a 1,4-trans-cyclohexanediyl group, and has a symmetric structure with Ar as the center (i.e., E 1 and E 2 , A 1 and A 2 , B 1 and B 2 , F 1 and F 2 , P 1 and P 2 and are the same) the following formula (A-1): [ka] The polymerizable liquid crystal compound (1-1) represented by Formula (B): HO-Ar-OH (B) and an alcohol compound (B) represented by the formula: Formula (C): [ka] The compound (A-1) can be produced by esterifying a carboxylic acid compound (C) represented by the following formula: 1 , E 2 , A 1 , A 2 , B 1 , B 2 , F 1 , F 2 , P 1 and P 2 is the same as that defined in the above formula (1), and is determined according to the structure of the polymerizable liquid crystal compound (1-1) represented by formula (A-1).

[0063] The alcohol compound (B) may be any compound in which two hydroxyl groups are bonded to an aromatic group Ar corresponding to the aromatic group Ar in formula (1) in the desired polymerizable liquid crystal compound (1-1). The aromatic group Ar is the same as defined above, and examples thereof include compounds in which the two * moieties in formulas (2-1) to (2-5) are hydroxyl groups.

[0064] The carboxylic acid compound (C) may be a compound represented by the formula (1) of the desired polymerizable liquid crystal compound (1-1). 1 -F 1 -B 1 -A 1 -E 1 -G 1 - the corresponding structure of G 1 Any compound having a carboxyl group bonded to a 1,4-trans-cyclohexanediyl group bonded as the aryl group may be used.

[0065] G in formula (1)1 and G 2 The polymerizable liquid crystal compound (1-2a) in which either one of the above is a 1,4-cis-cyclohexanediyl group can be obtained by reacting the alcohol compound (B) with the carboxylic acid compound (C) to obtain a polymerizable liquid crystal compound represented by the following formula (D): [ka] and reacting the compound represented by the following formula (C'): [ka] The compound (C') can be produced by reacting the compound (C') with a carboxylic acid compound (C') represented by the formula (C') and (D). 1 , E 2 , A 1 , A 2 , B 1 , B 2 , F 1 , F 2 , P 1 and P 2 is the same as that defined in the above formula (1), and is determined according to the structure of the polymerizable liquid crystal compound (1-1) represented by formula (A-1).

[0066] Also, G in formula (1) 1 and G 2 The polymerizable liquid crystal compound (1-2b) in which each of the above is a 1,4-cis-cyclohexanediyl group can be produced, for example, by using a carboxylic acid compound (C') instead of the carboxylic acid compound (C) in the method exemplified as the production method for the polymerizable liquid crystal compound (1-1).

[0067] The esterification reaction between the alcohol compound (B) and the carboxylic acid compound (C) and / or the carboxylic acid compound (C') is preferably carried out in the presence of a condensing agent, which allows the esterification reaction to be carried out efficiently and quickly.

[0068] Examples of the condensing agent include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide, Imides and carbodiimide compounds such as bis(trimethylsilyl)carbodiimide, 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, 1H-benzyloxytrimethylsilyl ... N-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 fluoroborate, 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 para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, trichloroacetic acid pentachlorophenyl ester, and the like.

[0069] The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention can be prepared separately and then mixed to form a liquid crystal mixture. 2 and a reactive group R of the compound represented by formula (II). 2 and R of the compound represented by formula (III) 1 A liquid crystal mixture containing the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2a) and / or the polymerizable liquid crystal compound (1-2b) can also be prepared by a method comprising reacting the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2a) and / or the polymerizable liquid crystal compound (1-2b). [ka] [In the formula, R 1 and R 2 are each independently a reactive group, Ar, E 1 , E 2 , A 1 , A 2 , B 1 , B 2 , F 1 , F 2 , P 1 and P 2 represents Ar and E in formula (1). 1 , E 2 , A 1 , A 2 , B 1 , B 2 , F 1 , F 2 , P 1 and P 2 It has the same meaning as The former method has the advantage that the contents of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) in the polymerizable liquid crystal composition can be easily controlled, while the latter method has the advantage that the synthesis is simple and the polymerizable liquid crystal composition can be produced more efficiently.

[0070] Ar, E in formula (I), formula (II) and formula (III) 1 , E 2 , A 1 , A 2 , B 1, B 2 , F 1 , F 2 , P 1 and P 2 is determined depending on the corresponding molecular structures of the desired polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2).

[0071] R in formula (III) 1 and R in formula (I) and formula (II) 2 represents D in formula (1) which reacts with each other to form the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2). 1 and D 2 Any compound capable of forming a structure represented by the formula: 1 and / or R 2 Examples of the reactive group represented by R include a hydroxyl group, a carboxyl group, and an amino group. 1 and R 2 The reactive groups represented by the following formula (1) may be selected.

[0072] From the viewpoint of ease of reaction, ease of handling of materials, availability, etc., a compound represented by formula (III) is typically selected from the group consisting of R 1 is a hydroxyl group, and the compounds represented by formula (I) and formula (II) are represented by the formula (I) and formula (II). 2 and a carboxylic acid compound in which each of the groups is a carboxyl group, to produce a polymerizable liquid crystal compound (liquid crystal mixture) constituting the polymerizable liquid crystal composition of the present invention. The esterification reaction can be carried out according to the same method as the esterification reaction that can be used to produce the polymerizable liquid crystal compound represented by formula (I), and for example, the method described above or the method and conditions described in JP 2019-003177 A can be used.

[0073] The content ratios of the polymerizable liquid crystal compound (1-1), the polymerizable liquid crystal compound (1-2a), and the polymerizable liquid crystal compound (1-2b) in the liquid crystal mixture obtained can be controlled by adjusting the amounts of the compound represented by formula (I) and the compound represented by formula (II) used in the preparation. 1 and R 2 By using a plurality of carboxylic acid compounds in the method of reacting with a compound, a large number of compounds can be synthesized simultaneously.

[0074] The polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), as long as the effect of the present invention is not adversely affected. Examples of the polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) include polymerizable liquid crystal compounds that do not have the molecular structure represented by formula (1), such as polymerizable liquid crystal compounds that generally exhibit positive wavelength dispersion when aligned and polymerized, such as compounds having a polymerizable group among those described in "3.8.6 Network (Completely Crosslinked)" and "6.5.1 Liquid Crystal Materials b. Polymerizable Nematic Liquid Crystal Materials" in "Liquid Crystal Handbook" (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000).

[0075] When the polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), from the viewpoint of obtaining a liquid crystal cured film having a high degree of orientational order, the proportion of the polymerizable liquid crystal compound (1) relative to the total mass of all polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition is preferably 51 mass% or more, more preferably 70 mass% or more, even more preferably 90 mass% or more, and may be 100 mass%.

[0076] When two or more types of polymerizable liquid crystal compounds (1-1) are contained, it is sufficient to contain a polymerizable liquid crystal compound (1-2) corresponding to at least one of the polymerizable liquid crystal compounds (1-1), and the content of the polymerizable liquid crystal compound (1-1) having the corresponding polymerizable liquid crystal compound (1-2) and the corresponding polymerizable liquid crystal compound (1-2) is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more, based on the total mass of all polymerizable liquid crystal compounds.

[0077] The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition (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. A content of the polymerizable liquid crystal compound within the above range is advantageous from the viewpoint of the alignment of the resulting cured liquid crystal film. In this specification, the solid content of the polymerizable liquid crystal composition refers to all components excluding volatile components such as organic solvents from the polymerizable liquid crystal mixture.

[0078] In addition to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), the polymerizable liquid crystal composition of the present invention may further contain additives such as a photopolymerization initiator, an organic solvent, a polymerization inhibitor, a photosensitizer, a leveling agent, etc. Each of these components may be used alone or in combination of two or more.

[0079] The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator. The polymerization initiator is a compound that generates reactive species with the aid of heat or 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, and anions. Among these, a photopolymerization initiator that generates radicals upon irradiation with light is preferred from the viewpoint of easy reaction control.

[0080] Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzil ketal 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.). In the present invention, the polymerizable liquid crystal composition preferably contains at least one type of photopolymerization initiator, and may contain two or more types of photopolymerization initiators.

[0081] 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.

[0082] Examples of α-acetophenone-based polymerization initiators 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.).

[0083] 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).

[0084] The amount of the photopolymerization initiator added is usually 0.1 to 30 parts by mass, preferably 0.5 to 100 parts by mass of the polymerizable liquid crystal compound, more preferably 1 to 20 parts by mass, and more preferably 15 to 20 parts by mass. 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.

[0085] 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 the polymerizable liquid crystal compounds that constitute the polymerizable liquid crystal composition, such as the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), and is also preferably a solvent that is inactive to the polymerization reaction of the polymerizable liquid crystal compounds. 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, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are more preferred.

[0086] The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 70 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 30 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition tends to be low, the film thickness tends to be approximately uniform, and unevenness tends to be less likely to occur. The solid content can be determined appropriately taking into account the thickness of the liquid crystal cured film to be produced.

[0087] 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 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 polymerizable liquid crystal compound.

[0088] Furthermore, 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 polymerizable liquid crystal compound.

[0089] 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.

[0090] 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 polymerizable liquid crystal compound. The content of the leveling agent within the above range is preferred because it facilitates alignment of the polymerizable liquid crystal compound and tends to result in a smoother liquid crystal cured film. The polymerizable liquid crystal composition may contain two or more types of leveling agents.

[0091] 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 (1-1) and the polymerizable liquid crystal compound (1-2), as needed, and stirring and mixing them at a predetermined temperature.

[0092] <Retardation film> The polymerizable liquid crystal composition of the present invention has high solubility of the polymerizable liquid crystal compound in a solvent, and is therefore effective in suppressing the occurrence of alignment defects due to undissolved polymerizable liquid crystal compounds or precipitation or deposition of the polymerizable liquid crystal compound during storage. Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to form a film without reducing the optical properties that the polymerizable liquid crystal compound can inherently exhibit, and a cured liquid crystal film with excellent optical properties can be obtained. Therefore, the present invention also relates to a retardation film comprising a cured product (cured liquid crystal film) of the polymerizable liquid crystal composition of the present invention, which is a liquid crystal cured film obtained by curing the polymerizable liquid crystal compound in an aligned state. A retardation film composed of the cured liquid crystal film can fully exhibit the optical properties that the polymerizable liquid crystal compound used inherently exhibits, and can be a retardation film with high optical performance.

[0093] The liquid crystal cured film constituting the retardation film of the present invention may be composed of a homopolymer of polymerizable liquid crystal compound (1-1) in an aligned state and a homopolymer of polymerizable liquid crystal compound (1-2), or may be composed of a copolymer of a mixture of polymerizable liquid crystal compound (1-1) and polymerizable liquid crystal compound (1-2) 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 (1-1) and polymerizable liquid crystal compound (1-2) in an aligned state.

[0094] In one embodiment of the present invention, the retardation film of the present invention is configured to include a liquid crystal cured film that is a cured product of the polymerizable liquid crystal composition of the present invention, and the liquid crystal cured film is represented by the following formula (i): 0.75≦Re(450) / Re(550)<1.0 (i) [In formula (i), Re(λ) represents the in-plane retardation value of the liquid crystal cured film at a wavelength of λ nm] It is preferable that the optical property be expressed by the following formula: When the liquid crystal cured film satisfies formula (i), the liquid crystal cured film exhibits so-called reverse wavelength dispersion, in which the in-plane retardation value at a short wavelength is smaller than the in-plane retardation value at a long wavelength. Since the reverse wavelength dispersion is improved and the optical properties of the retardation film are further improved, Re(450) / Re(550) is more preferably 0.76 or more, even more preferably 0.78 or more, and more preferably 0.92 or less, even more preferably 0.90 or less, particularly preferably 0.87 or less, even more particularly preferably 0.86 or less, and particularly preferably 0.85 or less.

[0095] In one embodiment of the present invention, the retardation film of the present invention has the following formula (ii): 1.00≦Re(650) / Re(550) (ii) [In formula (ii), Re(λ) represents the in-plane retardation value of the retardation film at a wavelength of λ nm] In view of the optical properties of the retardation film, Re(650) / Re(550) is more preferably 1.01 or more, and further preferably 1.02 or more.

[0096] In one embodiment of the present invention, the retardation film of the present invention is represented by the following formula (iii): 100 nm ≦ Re(550) ≦ 180 nm (iii) [In formula (iii), Re(λ) represents the in-plane retardation value of the retardation film at a wavelength of λ nm] The cured liquid crystal film preferably contains a liquid crystal cured film having optical properties represented by the formula (iii). The cured liquid crystal film satisfying the formula (iii) functions as a λ / 4 plate, and when an elliptically polarizing plate having a retardation film containing the cured liquid crystal film is applied to an optical display or the like, it is excellent in improving the front reflection hue (inhibiting coloration). The in-plane retardation value is more preferably in the range of 120 nm≦Re(550)≦170 nm, and even more preferably in the range of 130 nm≦Re(550)≦150 nm.

[0097] The in-plane retardation value can be adjusted by the thickness d of the cured liquid crystal film. The in-plane retardation value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d. Therefore, a desired in-plane retardation value (Re(λ): in-plane retardation value of the cured liquid crystal film at wavelength λ (nm)) can be obtained by adjusting the three-dimensional refractive index and film thickness d. In the formula, d represents the thickness of the target cured liquid crystal film, nx represents the principal refractive index at a wavelength 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, and ny represents the refractive index at a wavelength 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.

[0098] The retardation film of the present invention may be, for example, a step 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 A process in which the polymerizable liquid crystal compound is polymerized by light irradiation while maintaining the alignment state, forming a liquid crystal cured film. It can be produced by a method comprising:

[0099] 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.

[0100] 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)."

[0101] 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.

[0102] 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.

[0103] The solvent is then removed by drying or other methods to form a dried coating film. Examples of drying methods include natural drying, forced air drying, heat drying, and reduced-pressure drying. In this process, heating the coating film obtained from the polymerizable liquid crystal composition not only dries and removes the solvent from the coating film, but also aligns the polymerizable liquid crystal compound in a desired direction (e.g., horizontal or vertical) relative to the coating film plane. The heating temperature for 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 cause the polymerizable liquid crystal compound to undergo a phase transition to a liquid crystal phase state, a temperature above the liquid crystal phase transition temperature is generally required. To achieve the desired alignment state while removing the solvent contained in the polymerizable liquid crystal composition, the composition can be heated to a temperature above 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. The liquid crystal phase transition temperature can be measured, for example, using a polarizing microscope equipped with a temperature-control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. The phase transition temperature in the polymerizable liquid crystal composition 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 composition are mixed in the same ratio as the composition in the polymerizable liquid crystal composition.

[0104] The polymerizable liquid crystal composition of the present invention contains at least two types of polymerizable liquid crystal compounds (1-1) and (1-2), and can usually undergo liquid crystal phase transition at a temperature lower than the temperature at which each of the polymerizable liquid crystal compounds (1-1) and (1-2) transitions to a liquid crystal phase alone. Therefore, 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, and production efficiency can be improved. In addition, since the liquid crystal phase transition can be achieved by heating at a relatively low temperature, there is also the advantage that the options for support substrates on which the polymerizable liquid crystal composition is applied are broadened.

[0105] 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.

[0106] 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.

[0107] 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, allowing a liquid crystal cured film to be appropriately formed even when a substrate with relatively low heat resistance is used. 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.

[0108] 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.

[0109] 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.

[0110] The thickness of the liquid crystal cured film can be appropriately selected depending on the optical display to which it is applied, etc. It is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

[0111] A 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, an alignment film that has an alignment regulating force that aligns the polymerizable liquid crystal compound in the horizontal direction is called a horizontal alignment film, and an alignment film that has an alignment regulating force that aligns the polymerizable liquid crystal compound in the vertical direction is called a vertical alignment film. The alignment regulating force can be adjusted as desired 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 as desired by the polarized light irradiation conditions, etc.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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%.

[0116] 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).

[0117] 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.

[0118] Methods for removing the solvent contained in the oriented polymer composition include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] If masking is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) with different liquid crystal alignment directions can be formed.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] <Elliptical polarizing plate> The present invention includes an elliptically polarizing plate comprising the retardation film of the present invention. The elliptically polarizing plate of the present invention comprises the retardation film of the present invention and a polarizing film. 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 having as a polarizer a film coated with a dye having absorption anisotropy, etc. Examples of the dye having absorption anisotropy include a dichroic dye.

[0133] A film including, as a polarizer, a stretched film having adsorbed thereon a dye having absorption anisotropy is typically produced by uniaxially stretching a polyvinyl alcohol-based resin film, dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, treating the polyvinyl alcohol-based resin film having adsorbed thereon with an aqueous boric acid solution, and washing the film with water after the treatment with the aqueous boric acid solution, and then sandwiching the resulting polarizer between transparent protective films via an adhesive on at least one surface thereof.

[0134] Polyvinyl alcohol resins are obtained by saponifying polyvinyl acetate resins. Examples of polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate with other monomers copolymerizable with vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

[0135] The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified; for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The polymerization degree of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.

[0136] Such a polyvinyl alcohol-based resin is formed into a film and used as a raw film for a polarizing film. The method for forming the polyvinyl alcohol-based resin into a film is not particularly limited, and the film can be formed by a known method. The thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

[0137] The uniaxial stretching of the polyvinyl alcohol-based resin film can be carried out before, simultaneously with, or after dyeing with a dichroic dye. When uniaxial stretching is carried out after dyeing, this uniaxial stretching may be carried out before or during the boric acid treatment. It is also possible to carry out uniaxial stretching in these multiple stages. In uniaxial stretching, the film may be uniaxially stretched between rolls with different peripheral speeds, or may be uniaxially stretched using a heated roll. The uniaxial stretching may be dry stretching in which stretching is carried out in the air, or wet stretching in which the polyvinyl alcohol-based resin film is stretched in a swollen state using a solvent. The stretching ratio is usually about 3 to 8 times.

[0138] Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is carried out, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

[0139] Specifically, iodine or a dichroic organic dye is used as the dichroic pigment. Examples of the dichroic organic dye include a dichroic direct dye made of a disazo compound such as CIDIRECT RED 39, and a dichroic direct dye made of a compound such as a trisazo or tetrakisazo. The polyvinyl alcohol resin film is preferably immersed in water before the dyeing process.

[0140] When iodine is used as the dichroic dye, a dyeing method is usually employed in which a polyvinyl alcohol resin film is immersed in an aqueous solution containing iodine and potassium iodide. The iodine content in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The potassium iodide content is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40°C. The immersion time in this aqueous solution (dyeing time) is usually about 20 to 1,800 seconds.

[0141] On the other hand, when a dichroic organic dye is used as the dichroic pigment, a method of dyeing a polyvinyl alcohol resin film by immersing it in an aqueous solution containing a water-soluble dichroic dye is usually adopted. The content of the dichroic organic dye in this aqueous solution is usually 1 × 10 per 100 parts by mass of water. -4 about 10 parts by mass, preferably 1×10 -3 to 1 part by mass, and more preferably 1×10 -3 ~1×10 -2 The total weight of the aqueous solution is expressed as parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the aqueous dichroic dye solution used for dyeing is usually about 20 to 80°C. The immersion time in this aqueous solution (dyeing time) is usually about 10 to 1,800 seconds.

[0142] The boric acid treatment after dyeing with a dichroic dye can usually be carried out by immersing the dyed polyvinyl alcohol-based resin film in a boric acid aqueous solution. The content of boric acid in this boric acid aqueous solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichroic dye, this boric acid aqueous solution preferably contains potassium iodide, and in this case, the content of potassium iodide is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature for the boric acid treatment is usually 50°C or higher, preferably 50 to 85°C, and more preferably 60 to 80°C.

[0143] The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The washing can be carried out, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of the water used in the washing is usually about 5 to 40°C. The immersion time is usually about 1 to 120 seconds.

[0144] After washing with water, the film is dried to obtain a polarizer. The drying can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature for the drying is usually about 30 to 100°C, and preferably 50 to 80°C. The drying time is usually about 60 to 600 seconds, and preferably 120 to 600 seconds. The moisture content of the polarizer is reduced to a practical level by the drying. The moisture content is usually about 5 to 20% by mass, and preferably 8 to 15% by mass. When the moisture content is within the above range, a polarizer having appropriate flexibility and excellent thermal stability is likely to be obtained.

[0145] The thickness of the polarizer obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing with a dichroic dye, treating with boric acid, washing with water and drying is preferably 5 to 40 μm.

[0146] Examples of films coated with a dye having absorption anisotropy include films obtained by coating a composition containing a dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal compound. The film preferably has a protective film on one or both sides. Examples of the protective film include the same resin films as those exemplified above as substrates that can be used in producing a liquid crystal cured film.

[0147] The thinner the film coated with the dye having absorption anisotropy, the better. From the viewpoint of strength and processability, the thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

[0148] Specific examples of the film coated with a dye having absorption anisotropy include the films described in JP-A-2013-33249.

[0149] A polarizing film can be obtained by laminating a transparent protective film on at least one surface of the polarizer obtained in this way via an adhesive. As the transparent protective film, a transparent film similar to the resin film exemplified above as a substrate usable for producing a liquid crystal cured film constituting a retardation film can be preferably used.

[0150] The elliptically polarizing plate of the present invention is composed of 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 the polarizing film via an adhesive layer or a pressure-sensitive adhesive layer or the like.

[0151] In one aspect of the present invention, when the retardation film of the present invention containing a liquid crystal cured film and a polarizing film are laminated, it is preferable to laminate them 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°.

[0152] The elliptically polarizing plate of the present invention may have a structure similar to that of a conventional general elliptically polarizing plate, or a polarizing film and a retardation film, such as a pressure-sensitive adhesive layer (sheet) for attaching the elliptically polarizing plate to a display element or the like constituting an optical display, or a protective film used for protecting the surface of the polarizing film or retardation film from scratches and dirt.

[0153] The elliptically polarizing plate of the present invention can be used in a variety of display devices, particularly optical displays. 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 electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, flexible image displays, touch panel display devices, electron emission display devices (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 any of 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 be displays that display two-dimensional images or stereoscopic display devices that display three-dimensional images. In particular, the elliptical polarizing plate of the present invention can be suitably used in organic electroluminescence (EL) display devices and inorganic electroluminescence (EL) display devices. These display devices (optical displays) can exhibit good image display characteristics by comprising the elliptical polarizing plate of the present invention, which has excellent optical properties.

[0154] The flexible image display device having the elliptically polarizing plate of the present invention preferably further has a window and a touch panel touch sensor. A flexible image display device comprises, for example, a laminate for a flexible image display device and an organic EL display panel, and is configured to be foldable with the laminate for a flexible image display device disposed on the viewing side of the organic EL display panel. The laminate for a flexible image display device may include, in addition to the above-described elliptically polarizing plate of the present invention, a window, a touch panel touch sensor, etc. The order of lamination of these components is arbitrary, but it is preferable that they are laminated in the order of window, elliptically polarizing plate, and touch panel touch sensor from the viewing side, or in the order of window, touch panel touch sensor, and elliptically polarizing plate.

[0155] The presence of an elliptically polarizing plate on the viewing side of the touch panel touch sensor is preferable because it makes the pattern of the touch panel touch sensor less visible, improving the visibility of the displayed image. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, etc. Furthermore, the laminate for a flexible image display device can include a light-shielding pattern formed on at least one surface of any one of the window, the elliptically polarizing plate, and the touch panel touch sensor.

[0156] The window is disposed on the viewing side of the flexible image display device and serves to protect other components from external impacts and environmental changes such as temperature and humidity. While glass has traditionally been used as such a protective layer, the window in a flexible image display device is not rigid like glass but has flexible properties. The window may be made of a flexible transparent substrate and may include a hard coat layer on at least one surface.

[0157] The transparent substrate preferably has a visible light transmittance of 70% or more, more preferably 80% or more. Any transparent polymer film can be used as the transparent substrate. Among them, polyamide film, polyamideimide film or polyimide film, polyester film, olefin film, acrylic film, and cellulose film, which have excellent transparency and heat resistance, are preferred. It is also preferred to disperse inorganic particles such as silica, organic fine particles, rubber particles, etc. in the polymer film.

[0158] The thickness of the transparent substrate is preferably 5 to 200 μm, and more preferably 20 to 100 μm.

[0159] A hard coat layer may be provided on at least one surface of the transparent substrate constituting the window. The thickness of the hard coat layer is not particularly limited and may be, for example, 2 to 100 μm. When the thickness of the hard coat layer is within the above range, sufficient impact resistance, scratch resistance, and flex resistance are easily ensured.

[0160] The hard coat layer can be formed by curing a hard coat-forming composition containing a reactive material that forms a crosslinked structure upon irradiation with active energy rays or thermal energy. Active energy rays are preferred. Active energy rays are defined as energy rays that can decompose a compound that generates active species to generate active species. Examples of active energy rays include visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, gamma rays, and electron beams, with ultraviolet light being particularly preferred. The hard coat-forming composition typically contains at least one radically polymerizable compound and one cationically polymerizable compound, as well as a polymerization initiator. The radically polymerizable compound, the cationically polymerizable compound, and the polymerization initiator are not particularly limited and include conventionally known compounds. The hard coat composition may further contain one or more selected from the group consisting of solvents and additives. As long as the solvent can dissolve or disperse the polymerizable compound and polymerization initiator, any solvent known in the field of optical films for forming hard coats can be used without limitation. Examples of additives include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, and antifouling agents.

[0161] A touch panel touch sensor is used as an input device. Various types of touch panel touch sensors have been proposed, including resistive, surface acoustic wave, infrared, electromagnetic induction, and capacitive types, and any of these types may be used. Among these, capacitive types are preferred. A capacitive touch panel touch sensor is divided into an active area and an inactive area located on the periphery of the active area. The active area corresponds to the area where a screen is displayed on a display panel (display area) and is an area where a user's touch is sensed. The inactive area corresponds to the area where no screen is displayed on a display device (non-display area). A touch panel touch sensor includes a flexible substrate; a sensing pattern formed in the active area of ​​the substrate; and sensing lines formed in the inactive area of ​​the substrate for connection to an external driving circuit via the sensing pattern and pad area.

[0162] The flexible substrate, the sensing pattern, and each sensing line are not particularly limited, and materials available in the art can be selected.

[0163] The substrate having flexibility can be, for example, a substrate made of the same material as the transparent substrate of the window. The substrate for the touch panel touch sensor preferably has a toughness of 2,000 MPa% or more to prevent cracking of the touch panel touch sensor, and more preferably has a toughness of 2,000 MPa% to 30,000 MPa%. Here, toughness is defined as the area under the stress (MPa)-strain (%) curve up to the breaking point, obtained through a tensile test of the polymer material.

[0164] Each layer (window, elliptical polarizer, touch panel touch sensor) constituting the laminate for a flexible image display device, as well as the film members (polarizing film, retardation film, etc.) constituting each layer, can be formed using a pressure-sensitive adhesive. Examples of commonly used pressure-sensitive adhesives include aqueous adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent-volatile adhesives, moisture-curable adhesives, heat-curable adhesives, anaerobic-curable adhesives, active energy ray-curable adhesives, curing agent-mixed adhesives, hot-melt adhesives, pressure-sensitive adhesives (adhesives), and remoistening adhesives. Among these, aqueous solvent-volatile adhesives, active energy ray-curable adhesives, and pressure-sensitive adhesives are preferred. The thickness of the pressure-sensitive adhesive layer can be adjusted appropriately depending on the required adhesive strength, but is typically 0.01 μm to 500 μm, preferably 0.1 μm to 300 μm. When the laminate for a flexible image display device contains multiple pressure-sensitive adhesive layers, the types and thicknesses of the pressure-sensitive adhesives constituting each pressure-sensitive adhesive layer may be the same or different. [Example]

[0165] The present invention will be described in more detail below with reference to the following examples. In the examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified.

[0166] 1. Preparation of polymerizable liquid crystal compounds and liquid crystal mixtures Production Example 1: Production of polymerizable liquid crystal compound represented by formula (A-1) A polymerizable liquid crystal compound represented by the following formula (A-1) (hereinafter referred to as "polymerizable liquid crystal compound (A-1)") was synthesized according to the following scheme. [ka]

[0167] A 100 mL four-neck flask equipped with a Dimroth condenser and a thermometer was conditioned under a nitrogen atmosphere. 11.02 g of compound (E-1) synthesized with reference to Patent Document (JP 2010-31223 A), 4.00 g of compound (D-1) synthesized with reference to Patent Document (JP 2011-207765 A), 0.02 g of DMAP (Wako Pure Chemical Industries, Ltd.), 0.20 g of BHT (Wako Pure Chemical Industries, Ltd.), and 58 g of chloroform (Kanto Chemical Co., Ltd.) were added and mixed. Then, 4.05 g of IPC (Wako Pure Chemical Industries, Ltd.) was added using a dropping funnel, 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 acetonitrile (Wako Pure Chemical Industries, Ltd.) in an amount three 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 20 g of acetonitrile, and then dried under reduced pressure at 30° C. to obtain 11.43 g of polymerizable liquid crystal compound (A-1). The yield of polymerizable liquid crystal compound (A-1) was 80% based on compound (D-1).

[0168] Preparation Example 2: Preparation of Liquid Crystal Mixture (A') A liquid crystal mixture containing polymerizable liquid crystal compounds represented by the following formulae (A-1) to (A-3) (hereinafter also referred to as "liquid crystal mixture (A')") was synthesized according to the following scheme. [ka] [ka] Referring to Patent Document (JP 2010-31223 A), 27.02 g of a mixture represented by compound (E-2) was synthesized by replacing trans-1,4-cyclohexanedicarboxylic acid with cis-1,4-cyclohexanedicarboxylic acid. Using a 10 / 90 mixture of the resulting compound (E-2) and compound (E-1), compound (E-1) in Preparation Example 1 was replaced with the mixture of compound (E-2) and compound (E-1), and synthesis was performed to obtain 10.57 g of liquid crystal mixture (A'). Analysis of the resulting liquid crystal mixture (A') by HPLC revealed that the liquid crystal mixture contained the above compounds (A-1), (A-2), and (A-3), and the sum of the peak areas of compound (A-2) and compound (A-3) was 3.00% of the total peak area of ​​compound (A-1), compound (A-2), and compound (A-3).

[0169] [HLPC measurement] The HPLC measurement may be carried out under any conditions as long as the peak derived from the polymerizable liquid crystal compound can be separated. The HPLC measurement conditions used for the analysis in the examples and comparative examples of the present invention are shown below. (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 70%-B 30min 100%-B 60min 100%-B 60.01min 70%-B 75min 70%-B Flow rate: 0.5mL / min Injection volume: 5μL Detection wavelength: 254 nm

[0170] Production Example 3: Production of polymerizable liquid crystal compound represented by formula (B-1) A polymerizable liquid crystal compound represented by the following formula (B-1) (hereinafter referred to as "polymerizable liquid crystal compound (B-1)") was synthesized according to the following scheme. [ka]

[0171] The reaction was carried out in the same manner as in Production Example 1, except that the amount of compound (D-2) was changed to 4.22 g, to obtain 11.75 g of polymerizable liquid crystal compound (B-1). The yield of polymerizable liquid crystal compound (B-1) was 81% based on compound (D-2).

[0172] Preparation Example 4: Preparation of Liquid Crystal Mixture (B') A liquid crystal mixture containing polymerizable liquid crystal compounds represented by the following formulae (B-1) to (B-3) (hereinafter also referred to as "liquid crystal mixture (B')") was synthesized according to the following scheme. [ka]

[0173] A reaction was carried out in the same manner as in Production Example 2, except that the amount of compound (D-2) was changed to 4.22 g, to obtain 10.88 g of liquid crystal mixture (B'). Analysis of the obtained liquid crystal mixture (B') under the above HPLC measurement conditions revealed that the liquid crystal mixture contained the above compounds (B-1), (B-2), and (B-3), and the total peak area of ​​the above compounds (B-2) and (B-3) was 5.23% relative to the total peak area of ​​the compounds (B-1), (B-2), and (B-3), which was 100%.

[0174] Preparation Example 5: Preparation of Liquid Crystal Mixture (C') The reaction was carried out in the same manner as in Production Example 4, except that the mixing ratio of compound (E-2) and compound (E-1) used in Production Example 4 was changed to 20 / 80, to obtain 10.44 g of liquid crystal mixture (C'). Analysis of the obtained liquid crystal mixture (C') under the above HPLC measurement conditions revealed that the liquid crystal mixture contained the above compounds (B-1), (B-2), and (B-3), and the total peak area of ​​the above compounds (B-2) and (B-3) was 12.3% of the total peak area of ​​the compounds (B-1), (B-2), and (B-3), which was 100%. In the above Production Examples 1 to 5, the compound (A-1) and the compound (B-1) each correspond to the polymerizable liquid crystal compound (1-1) of the present invention, the compound (A-2) and the compound (B-2) each correspond to the polymerizable liquid crystal compound (1-2a) of the present invention, and the compound (A-3) and the compound (B-3) each correspond to the polymerizable liquid crystal compound (1-2b) of the present invention.

[0175] 2. Polymerizable Liquid Crystal Compounds / Mixtures of Examples and Comparative Examples (1) Example 1: Preparation of Liquid Crystal Mixture (1) The liquid crystal mixture (A') obtained in the above Production Example 2 and the polymerizable liquid crystal compound (A-1) obtained in the above Production Example 1 were mixed under the above HPLC measurement conditions so that the peak areas of the compounds (A-2) and (A-3) were 0.1% relative to the total peak area of ​​the compounds (A-1), (A-2) and (A-3) being 100%, to obtain a liquid crystal mixture (1).

[0176] (2) Example 2: The liquid crystal mixture (A') obtained in the above Production Example 2 was used as a liquid crystal mixture (2).

[0177] (3) Example 3: Preparation of Liquid Crystal Mixture (4) The liquid crystal mixture (B') obtained in Production Example 4 and the polymerizable liquid crystal compound (B-1) obtained in Production Example 3 were mixed under the above HPLC measurement conditions so that the peak areas of compounds (B-2) and (B-3) were 0.4% relative to the total peak area of ​​compounds (B-1), (B-2) and (B-3) being 100%, to obtain liquid crystal mixture (3).

[0178] (4) Example 4: The liquid crystal mixture (B') obtained in the above Production Example 4 was used as a liquid crystal mixture (4).

[0179] (5) Comparative Example 1: The polymerizable liquid crystal compound (A-1) obtained in Production Example 1 was used as liquid crystal compound (1).

[0180] (6) Comparative Example 2: The polymerizable liquid crystal compound (B-1) obtained in Production Example 3 was used as liquid crystal compound (2).

[0181] (7) Comparative Example 3: The liquid crystal mixture (C') obtained in Production Example 5 was used as liquid crystal mixture (5).

[0182] 3.Solubility evaluation N-methylpyrrolidone (NMP) and a stir bar were placed in a vial, and while stirring with a magnetic stirrer (HS-30DN, AS ONE), the liquid crystal mixtures (1) to (5) and liquid crystal compounds (1) and (2) prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were added until residual liquid crystal compounds were visually confirmed. Once residual liquid crystal compounds were confirmed, the solubility of each liquid crystal mixture and polymerizable liquid crystal compound in NMP was calculated as a weight percent concentration using the formula (weight of each liquid crystal mixture and polymerizable liquid crystal compound) / (weight of each liquid crystal mixture and polymerizable liquid crystal compound + weight of NMP). The results are shown in Table 2.

[0183] 4. Evaluation of alignment defects (1) Preparation of optical film (phase difference film) An optical film (retardation film) was produced according to the following procedure. (i) Preparation of composition for forming photo-alignment film The following components were mixed, and the resulting mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a photo-alignment film. Photoalignment material (5 parts) represented by the following formula (number average molecular weight approximately 28,000): [ka] Solvent (95 parts): Cyclopentanone

[0184] (ii) Preparation of polymerizable liquid crystal composition A cycloolefin polymer film (COP) (ZF-14, manufactured by Zeon Corporation) was treated once using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) under conditions of an output of 0.3 kW and a treatment speed of 3 m / min. The composition for forming a photoalignment film was applied to the corona-treated surface using a bar coater, dried at 80°C for 1 minute, and then irradiated with 100 mJ / cm using a polarized UV irradiation device (SPOT CURE SP-7, manufactured by Ushio Inc.). 2 The polarized UV exposure was carried out with an integrated light amount of 100 nm. The thickness of the obtained photo-alignment film was measured with a laser microscope (LEXT, manufactured by Olympus Corporation). Next, the liquid crystal mixture (1) prepared in Example 1 above was placed in a vial tube, and a photopolymerization initiator, a leveling agent, a polymerization inhibitor, and a solvent were added according to the composition shown in Table 1, followed by stirring using a carousel at 80°C for 30 minutes to obtain a polymerizable liquid crystal composition. The blending amount of the solvent was set so that the mass % of the liquid crystal mixture was 13% with respect to the total amount of the polymerizable liquid crystal composition (solution).

[0185] [Table 1]

[0186] Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan) Leveling agent: Polyacrylate compound (BYK-361N; manufactured by BYK Japan) Polymerization inhibitor: BHT (Wako Pure Chemical Industries, Ltd.) Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Chemical Co., Ltd.)

[0187] (iii) Preparation of optical films The obtained polymerizable liquid crystal composition was applied onto the alignment film using a bar coater, dried at 120°C for 1 minute, and then irradiated with ultraviolet light (under a nitrogen atmosphere, wavelength: 365 nm, cumulative light intensity at wavelength 365 nm: 1000 mJ / cm) using a high-pressure mercury lamp (Uniquer VB-15201BY-A, manufactured by Ushio Inc.). 2 ) to prepare an optical film. In addition, polymerizable liquid crystal compositions and optical films were prepared in the same manner as above, except that the liquid crystal mixtures (2) to (5) and liquid crystal compounds (1) and (2) prepared in Examples 2 to 5 and Comparative Examples 1 to 3 were used instead of the liquid crystal mixture (1), and a photopolymerization initiator, a leveling agent, a polymerization inhibitor, and a solvent were added according to the compositions shown in Table 1.

[0188] (2) Evaluation of alignment defects The obtained optical film was cut into a 10 cm square, and the number of alignment defects on the screen was visually confirmed using a polarizing microscope (LEXT, manufactured by Olympus Corporation), and evaluated according to the following evaluation criteria. The results are shown in Table 1. (Evaluation criteria for orientation defects) 1: Alignment defects occur over the entire surface (>100 defects) 2:11~100 pieces 3:1~10 pieces 4: No defects

[0189] [Table 2]

[0190] As shown in Table 1, it was confirmed that the polymerizable liquid crystal compositions according to the present invention (Examples 1 to 4) contain a specific amount of polymerizable liquid crystal compound (1-2) relative to the polymerizable liquid crystal compound (1-1), thereby suppressing alignment defects and improving the solubility of the polymerizable liquid crystal compound (1-1) in a solvent.

Claims

1. They have the same molecular weight but different molecular structures, and are represented by the formula (1): 【Chemistry 1】 [In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent; D １ , D ２ , E １ , E ２ , B １ and B ２ are each independently -CR １１ R １２ -, -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 １１ -, -NR １１ -CO-, -O-CH ２ -, -CH ２ —O—, —S—CH ２ -, -CH ２ represents —S— or a single bond, and R １１ and R １２ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, G １ and G ２ each represents a 1,4-cyclohexanediyl group, A １ and A ２ 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 １３ , -OR １３ , optionally substituted with a cyano group or a nitro group, R １３ 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, F １ and F ２ each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR １４ or may be substituted with a halogen atom, R １４ represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and —CH ２ - may be replaced by -O- or -CO-; P １ and P ２ each independently represents a hydrogen atom or a polymerizable group (provided that P １ and P ２ at least one of which is a polymerizable group] A polymerizable liquid crystal composition comprising at least two polymerizable liquid crystal compounds represented by As the polymerizable liquid crystal compound, G in formula (1) １ and G ２ are 1,4-trans-cyclohexanediyl groups, and the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-1) are １ and G ２ and a polymerizable liquid crystal compound (1-2) which has a different molecular structure only in that at least one of the above is a 1,4-cis-cyclohexanediyl group, the ratio of the peak area of ​​the polymerizable liquid crystal compound (1-2) to the total peak area of ​​the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), as measured by liquid chromatography, is 0.1% or more and 10% or less; A polymerizable liquid crystal composition, wherein Ar in formula (1) is a group represented by any one of formulas (2-1) to (2-5). 【Chemistry 2】 [In the formula, * is D １ or D ２ Represents the bond with; Q １ is —S—, —O— or —NR １５ represents -, and R １５ 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 １５ represents -, and R １５ 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 or an aromatic heterocyclic group which may have a substituent, a hydrogen atom contained in the alkyl group, the aromatic hydrocarbon group or the aromatic heterocyclic group may be substituted with a halogen atom, and a —CH ２ - may be substituted by -O-, -CO-, -O-CO- or -CO-O-; 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 and Z ２ are each a hydrogen atom, and Z ３ represents a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR １５ R １６ or -SR １５ represents R １５ and R １６ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; 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; Y ３ and Y ４ are each independently represented by the following formula (Y-1): 【Transformation 3】 [In formula (Y-1), M １ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is ３ and the substituent X ３ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one —CH ２ - or two or more non-adjacent -CH ２ each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be replaced by —O—, —S—, —CO—, —COO—, —OCO—, —CO-S—, —S-CO—, —O-CO-O—, —CO-NH—, —NH-CO—, —CH═CH-COO—, —CH═CH-OCO—, —COO-CH═CH—, —OCO-CH═CH—, —CH═CH—, —CF═CF- or —C≡C—, and any hydrogen atom in the alkyl group may be replaced by a fluorine atom, or —B １１ -F １１ -P １１ and B may be a group represented by １１ , F １１ and P １１ are B in the formula (1), respectively. １ , F １ and P １ are defined in the same manner as above, and １ , F １ and P １ may be the same as or different from; U １ represents an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group, any carbon atom of which may be substituted with a heteroatom, and the aromatic hydrocarbon group is substituted with one or more of the above-mentioned substituents X ３ may be substituted by T １ is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ２ -, -N=CU ２ --, --CO-NU ２ --, --OCO-NU ２ -or-O-NU ２ - represents U ２ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or (E １１ -A １１ ) ｑ -B １２ -F １２ -P １２ and the alkyl group, the cycloalkyl group, the cycloalkenyl group and the aromatic hydrocarbon group are each unsubstituted or substituted with one or more substituents X ３ and the alkyl group may be substituted by the cycloalkyl group or the cycloalkenyl group, and one —CH ２ - or two or more non-adjacent -CH ２ - each independently represents -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, or -SO ２ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and one -CH in the cycloalkyl group or cycloalkenyl group may be replaced by ２ - or two or more non-adjacent -CH ２ - may be independently replaced by -O-, -CO-, -COO-, -OCO- or -O-CO-O-; １１ , A １１ , B １２ , F １２ and P １２ are E in formula (1), respectively. １ , A １ , B １ , F １ and P １ are defined in the same manner as above, and １ , A １ , B １ , F １ and P １ may be the same as or different from each other, q represents an integer of 0 to 4, and E １１ and / or A １１ When there are a plurality of U, they may be the same or different. １ and U ２ and may be bonded to form a ring. represents a group selected from the following.

2. The polymerizable liquid crystal compound (1-2) is G １ and G ２ and a polymerizable liquid crystal compound (1-2a) in which either one of G in formula (1) is a 1,4-cis-cyclohexanediyl group. １ and G ２ and a polymerizable liquid crystal compound (1-2b) in which all of the above are 1,4-cis-cyclohexanediyl groups.

3. P in formula (1) １ and P ２ The polymerizable liquid crystal composition according to claim 1 or 2, wherein each of the groups is an acryloyl group.

4. The polymerizable liquid crystal composition according to any one of claims 1 to 3, further comprising a photopolymerization initiator.

5. The polymerizable liquid crystal composition according to any one of claims 1 to 4, further comprising an organic solvent.

6. A retardation film comprising a liquid crystal cured film which is a cured product of the polymerizable liquid crystal composition according to any one of claims 1 to 5.

7. The liquid crystal cured film has the formula (i): 0.75≦Re(450) / Re(550)<1.00 (i) [In formula (i), Re(λ) represents the in-plane retardation value of the liquid crystal cured film at a wavelength of λ nm] The retardation film according to claim 6 , which satisfies the above.

8. An elliptically polarizing plate comprising the retardation film according to claim 6 or 7.

9. An optical display comprising the elliptically polarizing plate of claim 8.

10. A flexible image display device comprising the elliptically polarizing plate according to claim 8.

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