Coincidence liquid crystal mixture, polymerizable liquid crystal composition

Abstract

To provide a compound capable of lowering the phase transition temperature of a liquid crystal composition without impairing optical characteristics.SOLUTION: A polymerizable liquid crystal compound is represented by formula (1) [where k11, k12 and l each independently represent an integer of 1 or more; B11, B12, E11 and E12 each independently represent a divalent group or a single bond; G11 and G12 each represent a C3-16 divalent alicyclic hydrocarbon group; A11 and A12 each represent a C3-16 divalent alicyclic hydrocarbon group or a C6-20 divalent aromatic hydrocarbon group; F11 and F12 each represent a C1-12 alkanediyl group; Ar11 and Ar12 each represent a divalent aromatic group; M represents a C3-13 divalent aliphatic hydrocarbon group; and P11 and P12 each independently represent H or a polymerizable group (provided that at least one of them represents a polymerizable group)].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, and a retardation film, a polarizing plate, and an optical display formed from the polymerizable liquid crystal composition. [Background technology]

[0002] As an optical film such as a retardation film used in a flat panel display device (FPD), for example, there is an optical film obtained by dissolving a polymerizable liquid crystal compound in a solvent, applying the coating liquid obtained by dissolving the polymerizable liquid crystal compound in a solvent to a supporting substrate, and then polymerizing the coating liquid. Conventionally, as a polymerizable liquid crystal compound, for example, a nematic liquid crystal compound having a rod-like structure in which about 2 to 4 six-membered rings are connected, is known. On the other hand, as one of the characteristics of a retardation film, it is required that the film is capable of polarization conversion in the entire wavelength range. For example, it is known that a uniform polarization conversion is theoretically possible in a wavelength range in which 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 the reverse 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 to 3. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-121339 A [Patent Document 2] JP 2019-156733 A [Patent Document 3] JP 2020-41026 A Summary of the Invention [Problem to be solved by the invention]

[0004] When orienting a polymerizable liquid crystal compound, for example, a coating liquid containing the polymerizable liquid crystal compound is applied to a support substrate, and then the polymerizable liquid crystal compound is heated to a temperature higher than the phase transition temperature to cause a phase transition. If the phase transition temperature of the polymerizable liquid crystal compound is high, it may have an undesirable effect on the support substrate, the usable support substrate may be limited, or the heating temperature may become high, resulting in poor manufacturing efficiency. In addition, when an additive is added to the polymerizable liquid crystal compound for the purpose of lowering the phase transition temperature, the molecular orientation of the liquid crystal compound may be disturbed by the additive, and the desired optical properties may not be obtained. In addition, the additive or the polymerizable liquid crystal compound may precipitate as crystals, which may also prevent the desired optical properties from being obtained.

[0005] An object of the present invention is to provide a compound capable of lowering the phase transition temperature of a liquid crystal composition without impairing the optical properties. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, the present invention provides the following preferred embodiments. [1] A polymerizable liquid crystal compound represented by formula (1). [ka] [In formula (1), k11, k12 and l each independently represent an integer of 1 or more; B 11 and B. 12 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH 2-S- or a single bond, R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms; E 11 and E 12 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or represents a single bond; G 11 and G 12 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , a cyano group or a nitro group, and the -CH 2 - may be replaced by -O-, -S- or -NH-; R 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A 11 and A 12 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , optionally substituted with a cyano group or a nitro group; F 11 and F 12 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3or a halogen atom, and the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-; P 11 and P 12 each independently represents a hydrogen atom or a polymerizable group (provided that P 11 and P 12 at least one of which is a polymerizable group; Each M independently represents a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms which may have a substituent; Ar 11 and Ar 12 each independently represents a divalent aromatic group which may have a substituent. [2] The polymerizable liquid crystal compound according to the above [1], wherein M in formula (1) is a divalent aliphatic hydrocarbon group having 2n carbon atoms (n is an integer of 2 to 4) which may have a substituent. [3] Ar in formula (1) 11 and Ar 12 are each independently a group represented by any one of the following formulae (Ar-1) to (Ar-5): [ka] [In the formulas (Ar-1) to (Ar-5), * denotes a bond; Q 1 is -S-, -O- or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; W 1 and W 2 each independently represents -O-, -S-, -CO-, or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; Y 1represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, 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 replaced by -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 an 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 11 R 12 or -SR 11 and Z 1 and Z 2 may be bonded to each other to form an aromatic ring or an aromatic heterocycle, R 11 and R 12 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, and Ax and Ay may be bonded to form a ring; Y 3 and Y 4 are each independently represented by the following formula (Y 3 -1): [ka] [Formula (Y 3 -1) Medium, R Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is 3 and the substituent X3 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-, any hydrogen atom in the alkyl group may be replaced by a fluorine atom, or -B 31 -F 31 -P 31 and B may be a group represented by 31 , F 31 and P 31 are each the B in the formula (1). 11 , F 11 and P 11 are defined in the same manner as B in formula (1), 11 , F 11 and P 11 may be the same as or different from; U 1 represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group is 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 2is 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 31 -A 31 ) q -B 32 -F 32 -P 32 The alkyl group, the cycloalkyl group, the cycloalkenyl group and the aromatic hydrocarbon group each represent one or more substituents X 3 and the alkyl group is optionally substituted by the cycloalkyl or cycloalkenyl group, and one -CH 2 - or two or more non-adjacent -CH 2 - is independently -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 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-; 31 , A 31 , B 32 , F 32 and P 32 are E in formula (1), 11 , A 11 , B 11 , F 11 and P 11 are defined in the same manner as above, 11 , A 11 , B 11 , F 11 and P 11 may be the same or different, q represents an integer of 0 to 4, and E31 and / or A 31 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 polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of the above [1] to [3] and a polymerizable liquid crystal compound represented by formula (2). [ka] [In formula (2), k21 and k22 each independently represent an integer of 1 or more; B 21 and B. 22 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or a single bond, R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. E 21 and E 22 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH2 -S- or represents a single bond; G 21 and G 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , a cyano group or a nitro group, and the -CH 2 - may be replaced by -O-, -S- or -NH-; R 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A 21 and A 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , optionally substituted with a cyano group or a nitro group; F 21 and F 22 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 or a halogen atom, and the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-; P 21 and P 22 each independently represents a hydrogen atom or a polymerizable group (provided that P 21 and P 22 at least one of which is a polymerizable group; Ar 21 each independently represents a divalent aromatic group which may have a substituent. [5] The polymerizable liquid crystal composition according to [4] above, in which a ratio of a peak area of ​​the polymerizable liquid crystal compound (1) to a total peak area of ​​the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), as measured by liquid chromatography, is 0.1% or more and 50% or less. [6] A in formula (1) 11 , A 12 , B 11 , B 12 , E 11 , E 12 , F 11 , F 12 , G 11 , G 12 , P 11 and P 12 are each represented by A in formula (2). 21 , A 22 , B 21 , B 22 , E 21 , E 22 , F 21 , F 22 , G 21 , G 22 , P 21 and P 22 In formula (1), Ar 11 and Ar 12 are each represented by Ar 21

[0026] (4) or (5), wherein the R is the same as a group represented by the formula: [7] The polymerizable liquid crystal composition according to any one of [4] to [6] above, further comprising a photopolymerization initiator and an organic solvent. [8] A retardation film formed from the polymerizable liquid crystal composition according to any one of the above [4] to [7]. [9] A polarizing plate comprising the retardation film according to [8] above.

[10] An optical display comprising the polarizing plate according to [9] above. Effect of the Invention

[0007] According to the present invention, it is possible to provide a compound capable of lowering the phase transition temperature of a liquid crystal composition without impairing the optical properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, the 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.

[0009] <Polymerizable liquid crystal compound> The polymerizable liquid crystal compound of the present invention has the formula (1): [ka] Hereinafter, the polymerizable liquid crystal compound of the present invention represented by formula (1) will also be referred to as "polymerizable liquid crystal compound (1)".

[0010] In formula (1), k11 and k12 each independently represent an integer of 1 or more, and may be, for example, an integer of 1 to 5. The sum of k11 and k12 is preferably 2 to 6, and more preferably 2 to 4. From the viewpoint of excellent liquid crystal properties, k11 and k12 each independently are preferably 1 or 2, and from the viewpoint of ease of production of the polymerizable liquid crystal compound (1), k11 and k12 are preferably the same number, and in a preferred embodiment of the present invention, k11 and k12 are both 1.

[0011] In formula (1), l represents an integer of 1 or more, and may be, for example, an integer of 1 to 8. From the viewpoint of excellent liquid crystal properties, l is preferably an integer of 1 to 6.

[0012] In formula (1), B 11 and B. 12 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH2 -, -CH 2 -S- or a single bond, R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. 11 and B. 12 each independently represents -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 1 -, -NR 2 -CO-, -CH 2 -O-, -O-CH 2 -, -CH 2 -S-, -S-CH 2 - or a single bond is preferred, and -O-CO- or -CO-O- is more preferred. 11 and B. 12 When a plurality of B are present, they may be the same or different from each other. However, from the viewpoint of ease of production of the polymerizable liquid crystal compound (1), 11 are preferably the same group, and a plurality of B 12 are preferably the same group. 11 and B 12 It is more preferable that all of the above are the same.

[0013] R 1 and R 2 Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a tert-butyl group. Of these, an alkyl group having 1 or 2 carbon atoms is preferred, and a methyl group is more preferred.

[0014] In formula (1), E 11 and E 12 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2 -, -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or a single bond. E 11 and E 12 are each independently preferably -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 1 -, -NR 2 -CO-, -CH 2 -O-, -O-CH 2 -, -CH 2 -S-, -S-CH 2 From the viewpoint of ease of production of the polymerizable liquid crystal compound (1), E 11 and E 12 may be the same or different, but are preferably the same group.

[0015] G 11 and G 12 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms. A hydrogen atom contained in the alicyclic hydrocarbon group may be replaced by a halogen atom, -R 3 , -OR 3 , a cyano group or a nitro group, and the -CH 2 - may be replaced by -O-, -S- or -NH-. 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. 11 and G 12 Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms represented by the formula (g-1) to (g-10) include divalent alicyclic hydrocarbon groups which may contain a heteroatom, and are represented by the formula (g-1) to (g-10). Of these, 5- or 6-membered alicyclic hydrocarbon groups are preferred.

[0016] [ka]

[0017] The groups represented by the above formulas (g-1) to (g-10) may be substituted with an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group; an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group; a cyano group; a nitro group; or a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom.

[0018] G 11 and G 12 As each of these, a 5- or 6-membered alicyclic hydrocarbon group represented by any one of formulas (g-1) to (g-4) is more preferable, an alicyclic hydrocarbon group consisting of a 6-membered ring represented by formula (g-1) is even more preferable, a cyclohexane-1,4-diyl group is particularly preferable, and a trans-cyclohexane-1,4-diyl group is particularly preferable. G 11 and G 12 may be the same or different, but being the same is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound (1) and productivity.

[0019] In formula (1), A 11 and A 12 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , and may be substituted with a cyano group or a nitro group.

[0020] A 11 and A 12 Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms and the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (i) include the alicyclic hydrocarbon groups consisting of a 5-membered or 6-membered ring represented by the formula (g-1) to the formula (g-10) above, and the aromatic hydrocarbon groups having about 6 to 20 carbon atoms represented by the formula (a-1) to the formula (a-8).

[0021] [ka]

[0022] In addition, A 11 and A 12 As the above-exemplified groups, some of the hydrogen atoms may be substituted with an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group; an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group; a cyano group; a nitro group; or a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom.

[0023] A 11 and A 12 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group. 11 and A 12 are each preferably a 1,4-phenylene group, and when k11 and k12 are 2 or more, E 11 A binds to 11 and E 12 A binds to 12 are preferably identical to each other, and E 11 A binds to 11 and E 12 A binds to 12 is preferably a 1,4-phenylene group. 11 and A 12 When multiple are present, they may be the same or different.

[0024] In formula (1), F 11 and F 12 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 or a halogen atom, and the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-. 11 and F 12 Each of the alkanediyl groups independently has 3 to 10 carbon atoms, -(CF2 ) 4 -, -(CF 2 ) 6 -, -(CF 2 ) 8 - is preferred, and an alkanediyl group having 4 or 6 carbon atoms [-(CH 2 ) 4 -or-(CH 2 ) 6 - is more preferable. 11 and E 12 may be the same or different, but being the same is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound (1) and productivity.

[0025] P 11 and P 12 Each of P independently represents a hydrogen atom or a polymerizable group. 11 and P 12 At least one of P 11 and P 12 are preferably polymerizable groups from the viewpoint of the film hardness of a liquid crystal cured film obtained by using the polymerizable liquid crystal compound.

[0026] The polymerizable group may be any reactive group capable of polymerizing the polymerizable liquid crystal compound (1), and specific examples thereof include vinyl group, vinyloxy group, styryl group, p-(2-phenylethenyl)phenyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxy group, acetyl group, hydroxy group, carbamoyl group, N-alkylamino group having 1 to 4 carbon atoms, amino group, oxiranyl group, oxetanyl group, formyl group, isocyanato group, isothiocyanato group, etc. Also, the polymerizable group may be a group selected from the above-exemplified groups and F. 11 or F 12 An ether bond or an ester bond may be included to bond P and P, and it is preferable that each of them is bonded via an ether bond. 11 and P 12As the alkyl group, for example, a radically polymerizable group or a cationically polymerizable group suitable for photopolymerization is preferable, and an acryloyloxy group or a methacryloyloxy group is preferable because it is easy to handle and to produce, and an acryloyloxy group is more preferable.

[0027] In formula (1), M each independently represents a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms which may have a substituent. When M in formula (1) is a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms, it is easy to improve the solubility in a solvent of other polymerizable liquid crystal compounds having a structure similar to that of the polymerizable liquid crystal compound (1) in the molecular structure, such as a polymerizable liquid crystal compound represented by formula (2) described later, and is excellent in the effect of lowering the phase transition temperature of the polymerizable liquid crystal compound. Since it is excellent in the effect of lowering the phase transition temperature of the polymerizable liquid crystal compound, a liquid crystal cured film can be obtained from the polymerizable liquid crystal compound at a lower processing temperature, it is advantageous in terms of reducing the influence of heating on the optical properties of the liquid crystal cured film and in terms of production efficiency. Such an effect tends to be significantly higher, particularly compared to when M in formula (1) is a structure having a cyclic structure such as an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The reason for this is not limited, but it is considered that the presence of a divalent aromatic group (Ar 11 and / or Ar 12 It is presumed that because the group M disposed between the two groups does not have a rigid cyclic structure, the flexibility of the molecule is increased, which makes it easier to improve the solubility, resulting in a significant decrease in the phase transition temperature.

[0028] The divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may be linear or branched, and may be a saturated or unsaturated hydrocarbon, but is preferably a saturated hydrocarbon group, and more preferably a linear saturated hydrocarbon group. Specific examples of the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms include alkanediyl groups having 3 to 13 carbon atoms, such as n-propanediyl, i-propanediyl, n-butanediyl, n-pentanediyl, n-hexanediyl, n-heptanediyl, n-octanediyl, n-nonanediyl, and n-decanediyl. When there are multiple Ms, they may be the same or different.

[0029] The hydrogen atoms contained in the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may be replaced by a substituent. When M in formula (1) is a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms and having a substituent, it is preferable that no cyclic structure is present in M ​​including the substituent. In other words, the polymerizable liquid crystal compound (1) of the present invention is a compound represented by -(Ar 11 The structure represented by -O-CO-M-CO-O)- is a group Ar 11 The divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms does not contain a cyclic structure other than an alicyclic hydrocarbon group represented by the formula (1) or an aromatic hydrocarbon group. Examples of the substituent that the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may have include a halogen atom and an alkoxyl group having 1 to 4 carbon atoms. The number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the aliphatic hydrocarbon group represented by M in formula (1).

[0030] Furthermore, when M in formula (1) is a divalent aliphatic hydrocarbon group having 2n carbon atoms (n is an integer of 2 to 4) which may have a substituent, the obtained liquid crystal cured film can exhibit better reverse wavelength dispersion while sufficiently ensuring the effect of lowering the phase transition temperature of the polymerizable liquid crystal compound and the effect of improving the solubility. As the divalent aliphatic hydrocarbon group having 2n carbon atoms, an alkanediyl group having 2n carbon atoms is preferable, and specifically, an n-butanediyl group, an n-hexanediyl group, or an n-octanediyl group.

[0031] M in formula (1) is preferably a divalent alkanediyl group having 3 to 11 carbon atoms which may have a substituent, more preferably a divalent alkanediyl group having 4 to 10 carbon atoms which may have a substituent, even more preferably a divalent alkanediyl group having 4, 6 or 8 carbon atoms which may have a substituent, and particularly preferably an n-butanediyl group, an n-hexanediyl group or an n-octanediyl group.

[0032] In formula (1), Ar 11 and Ar 12 Each independently represents a divalent aromatic group which may have a substituent. The divalent aromatic group which may have a substituent may be a divalent aromatic heterocyclic group and a divalent aromatic heterocyclic group. In the present invention, the divalent aromatic hydrocarbon group which may have a substituent means a divalent linking group containing at least one aromatic hydrocarbon ring, and the divalent aromatic heterocyclic group which may have a substituent means a divalent linking group containing at least one aromatic heterocyclic ring. The aromatic hydrocarbon ring and aromatic heterocyclic ring referred to here are ring structures having a π electron number of [4n+2] (n represents an integer) according to the Huckel rule (in the case of an aromatic heterocyclic ring, the Huckel rule is satisfied, including non-covalent bond electron pairs on heteroatoms such as -N= and -S-). Ar 11 and Ar 12 may contain one aromatic hydrocarbon ring or aromatic heterocycle, or may contain two or more aromatic hydrocarbon rings. When it contains one aromatic hydrocarbon ring or aromatic heterocycle, Ar 11 and Ar 12 may each independently be a divalent aromatic hydrocarbon group which may have a substituent, or a divalent aromatic heterocyclic group which may have a substituent. When the compound contains two or more aromatic hydrocarbon rings or aromatic heterocyclic rings, the compound may contain only a plurality of aromatic hydrocarbon rings, 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-, -O-, etc.

[0033] Ar 11 and Ar12 may be the same or different, but when they are the same, it is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound (1) and productivity. 11 If there are multiple Ar 11 may be the same or different, but are preferably the same group, and 11 and Ar 12 It is more preferable that all are the same.

[0034] Ar 11 and Ar 12 Examples of aromatic hydrocarbon rings that may be included in 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. 11 and Ar 12 When a nitrogen atom is contained, the nitrogen atom preferably has π electrons.

[0035] Among them, Ar 11 and Ar 12 has preferably 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 further preferably a benzothiazole ring. 11 and Ar 12 has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, the aromatic heterocycle is 11 , M or G 12may be directly bonded to the adjacent -CO-O- or -O-CO- to form a divalent linking group constituting the main chain of the compound represented by formula (1); 11 , M or G 12 may be included as a substituent of a divalent linking group directly bonding to the adjacent -CO-O- or -O-CO-, respectively, 11 or Ar 12 It is preferred that the entire group is sterically configured in a direction approximately perpendicular to the molecular orientation direction.

[0036] In formula (1), Ar 11 and Ar 12 The total number N of π electrons contained in the divalent aromatic group which may have a substituent represented by π are each preferably 8 or more, more preferably 12 or more, particularly preferably 16 or more, and especially preferably 20 or more. Also, each is preferably 36 or less, more preferably 32 or less, further preferably 30 or less, particularly preferably 26 or less, and especially preferably 24 or less.

[0037] Ar in formula (1) 11 and Ar 12 Examples of the optionally substituted divalent aromatic group represented by the following formulae (Ar-1) to (Ar-5) include groups represented by the following formulae (Ar-1) to (Ar-5). [ka]

[0038] In the formulas (Ar-1) to (Ar-5), * represents a bond.

[0039] In formula (Ar-1), Q 1 is -S-, -O- or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. In formulae (Ar-3) and (Ar-4), Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0040] In formula (Ar-2), W 1 and W 2 each independently represents -O-, -S-, -CO-, or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0041] In formula (Ar-1), Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group. 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent. Here, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and the -CH 2 - may be substituted by -O-, -CO-, -O-CO- or -CO-O-.

[0042] In formulas (Ar-1) to (Ar-5), Z 1 , Z 2 and Z 3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group or an 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 11 R 12 or -SR 11 represents Z 1 and Z 2 may be bonded to each other to form an aromatic ring or an aromatic heterocycle. 11 and R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0043] In formulae (Ar-3) and (Ar-4), 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.

[0044] In formula (Ar-1), Y 1 is preferably an aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent, and is more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent. The aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent is preferably a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may have a substituent. In this specification, the term "polycyclic aromatic hydrocarbon group" refers to an aromatic hydrocarbon group having at least two aromatic rings, and examples of such groups include a fused aromatic hydrocarbon group formed by condensing two or more aromatic rings and an aromatic hydrocarbon group formed by bonding two or more aromatic rings. The term "polycyclic aromatic heterocyclic group" refers to an aromatic heterocyclic group having at least one heteroaromatic ring and having at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings, and examples of such groups include aromatic heterocyclic groups formed by condensing one or more aromatic heterocyclic rings with one or more rings selected from the group consisting of aromatic rings and heteroaromatic rings, and aromatic heterocyclic groups formed by bonding at least one heteroaromatic ring with at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings.

[0045] Examples of the substituent which the aromatic hydrocarbon group or aromatic heterocyclic group may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 4 carbon atoms, an N,N-dialkylamino group having 2 to 8 carbon atoms, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms.

[0046] Y 1 For example, the following formula (Y 1 -1)~(Y 1 -7). [ka]

[0047] Formula (Y 1 -1) ~ formula (Y 1 -7) In the above, the * part indicates the connecting part.

[0048] Formula (Y 1 -1) ~ formula (Y 1 -7) Medium, Z 4 each independently represents a halogen atom or an organic group having 1 to 20 carbon atoms, and for example, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, a sulfone group, a nitroxy group, a carboxyl group, a trifluoromethyl group, a methoxy group, a thiomethyl group, an N,N-dimethylamino group, or an N-methylamino group is preferable, a halogen atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, or a trifluoromethyl group is more preferable, and a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a pentyl group, or a hexyl group is particularly preferable.

[0049] Formula (Y 1 -1) ~ formula (Y 1 -7) Medium, V 1and V 2 each independently represents -CO-, -S-, or -NR 13 -, -O-, -Se- or -SO 2 -, -S-, -NR 13 - or -O- is preferred. 13 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0050] Formula (Y 1 -1) ~ formula (Y 1 -7) Medium, W 3 ~W 7 each independently represents -C= or -N=.

[0051] Formula (Y 1 -1) ~ formula (Y 1 -7) Medium, V 1 , V 2 and W 3 ~W 7 It is preferred that at least one of the groups represents a group containing S, N or O.

[0052] Formula (Y 1 -1) ~ formula (Y 1 In -7), each a independently represents an integer of 0 to 3, and is preferably 0 or 1. Each b independently represents an integer of 0 to 2, and is preferably 0.

[0053] Formula (Y 1 -1) ~ formula (Y 1 Any of the groups represented by the following formula (Y 1 -8) ~ formula (Y 1 -13), 1 -8) is more preferable. In addition, the * portion represents a linking portion.

[0054] [ka]

[0055] Formula (Y 1 -8) ~ formula (Y 1-13) Medium, Z 4 , a, b, V 1 , V 2 and W 3 is (Y 1 -1) ~ formula (Y 1 -7) Z in 4 , a, b, V 1 , V 2 and W 3 It has the same meaning as:

[0056] Y 1 Specific examples of the formula (ar-1) to (ar-840) described in JP-A-2019-003177 include groups represented by the formulas (ar-1) to (ar-840). Among these, groups represented by the following formulas are preferred.

[0057] [ka]

[0058] In one embodiment of the present invention, the group represented by formula (Ar-1) specifically includes the group represented by the following formula (Ar 1 -1)~(Ar 1 -126), in which the * portion represents a linking portion.

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] In one embodiment of the present invention, the group represented by formula (Ar-2) specifically includes the group represented by the following formula (Ar 2 -1)~(Ar 2 -13) In the formula, the * portion represents a linking portion.

[0066] [ka]

[0067] In one embodiment of the present invention, the group represented by formula (Ar-3) is specifically a group represented by the following formula (Ar 3 -1)~(Ar 3 -23) In the formula, the * portion represents a linking portion.

[0068] [ka]

[0069] [ka]

[0070] The groups represented by formulae (Ar-1) to (Ar-4) may be, in addition to the groups specifically exemplified above, groups described in, for example, JP-A No. 2011-207765, JP-A No. 2008-107767, WO2014 / 010325, etc.

[0071] In formula (Ar-5), Y 3 and Y 4 are each independently represented by the following formula (Y 3 -1): [ka] The group represented by the formula:

[0072] Formula (Y 3 -1) Medium, R Y1 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:

[0073] 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-, any hydrogen atom in the alkyl group may be replaced by a fluorine atom, or -B 31 -F 31 -P 31 and B may be a group represented by 31 , F 31 and P 31 are each the B in the formula (1). 11 , F 11 and P 11 are defined in the same manner as B in formula (1), 11 , F 11 and P 11 may be the same as or different from.

[0074] Substituent X 3 is preferably a fluorine atom, a chlorine atom, or -CF 3 , -OCF3 or a cyano group. Y1 is preferably an unsubstituted, hydrogen atom or an alkyl group having 1 to 6 carbon atoms substituted with one or more fluorine atoms, and more preferably a hydrogen atom.

[0075] Formula (Y 3 -1) Medium, 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 1 is 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. The aromatic hydrocarbon group is a group having one or more of the substituents X 3 may be substituted by:

[0076] U 1 In terms of improving the 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 which is a condensed ring of a 5-membered ring and a 6-membered ring, since this has good wavelength dispersion and shows high birefringence.

[0077] Specifically, U 1 It is preferable that the aryl group has a group represented by the following formula: 1 It has a bond with.

[0078] [ka]

[0079] Formula (Y 3 -1) Medium, 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 31 -A 31 ) q -B 32 -F 32 -P 32 The alkyl group, the cycloalkyl group, the cycloalkenyl group and the aromatic hydrocarbon group are each unsubstituted or have one or more substituents X 3 and the alkyl group may be substituted by the cycloalkyl or cycloalkenyl group. 2 - or two or more non-adjacent -CH 2 - is independently -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 or cycloalkenyl group may be replaced by 2 - or two or more non-adjacent -CH 2 Each - may be independently replaced by -O-, -CO-, -COO-, -OCO- or O-CO-O-. 31 , A 31 , B 32 , F 32 and P 32 are E in formula (1), 11 , A 11 , B 11 , F 11 and P 11 are defined in the same manner as above, 11 , A 11 , B 11 , F 11 and P 11may be the same or different, q represents an integer of 0 to 4, and E 31 and / or A 31 When multiple are present, they may be the same or different.

[0080] T 1 -O-, -S-, -N=CU are the most popular 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 the wavelength dispersion and birefringence. 2 - is more preferable.

[0081] U 2 is one or more of the substituents X 3 and one -CH 2 - or two or more non-adjacent -CH 2 It is preferable that each - may be independently replaced by -O-, -CO-, -COO-, -OCO- or -O-CO-O-, and the alkyl or alkenyl group may be substituted by the cycloalkyl group, cycloalkenyl group or aryl group.

[0082] Among them, U 2 In terms of birefringence and solvent solubility, a hydrogen atom may be substituted with a fluorine atom, and one -CH 2 - or two or more non-adjacent -CH 2 It is more preferable that each - is independently a linear alkyl group having 1 to 20 carbon atoms which may be replaced by -O-, -CO-, -COO- or -OCO-.

[0083] 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 U2 Examples of the cyclic group include those represented by the following formula:

[0084] Y is a popular choice because it is easy to obtain raw materials, has good solubility, and exhibits high birefringence. 3 and Y 4 are expressed by the following formula (Y 3’ -1) ~ formula (Y 3’ -47) is particularly preferred.

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] From the viewpoints of improving the alignment of the polymerizable liquid crystal compound (1), facilitating industrial production, and improving productivity, the group represented by formula (Ar-5) specifically includes the following groups. 5 -1)~(Ar 5 -20) * in the above is G 11 , M or G 12 Each represents a bond to the adjacent -CO-O- or -O-CO-.

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] Among formulae (Ar-1) to (Ar-5), formulae (Ar-1), (Ar-2) and (Ar-5) are preferred, formulae (Ar-1) and (Ar-5) are more preferred, and formula (Ar-1) is even more preferred.

[0093] In formula (1), *-O-CO-G 11 -E 11 -(A 11 -B 11 ) k11 -F 11 -P 11 , and *-O-CO-G 12 -E 12 -(A 12 -B 12 ) k12 -F 12 -P 12 Specific examples of the structure include structures represented by formulae (R-1) to (R-100). In the formula, * represents Ar 11 or Ar 12 represents a bond to, and n represents an integer of 2 to 12. The cyclohexane ring may be in a trans or cis form, but is preferably in a trans form.

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound (1) of the present invention and a compound represented by the formula (2): [ka] [In formula (2), k21 and k22 each independently represent an integer of 1 or more; B 21 and B. 22 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or a single bond, R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. E 21 and E22 are each independently -CR 1 R 2 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH 2 -, -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or represents a single bond; G 21 and G 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , a cyano group or a nitro group, and the -CH 2 - may be replaced by -O-, -S- or -NH-; R 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A 21 and A 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , optionally substituted with a cyano group or a nitro group; F 21 and F 22 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 or a halogen atom, and the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-; P 21 and P 22each independently represents a hydrogen atom or a polymerizable group (provided that P 21 and P 22 at least one of which is a polymerizable group; Ar 21 each independently represents a divalent aromatic group which may have a substituent. The polymerizable liquid crystal compound (hereinafter, also referred to as "polymerizable liquid crystal compound (2)") is represented by the formula (1). By using the polymerizable liquid crystal compound (1) in combination with the polymerizable liquid crystal compound (2), the phase transition temperature of the polymerizable liquid crystal compound (2) can be effectively lowered while suppressing the occurrence of alignment defects. Although the reason for this is unclear, it is considered that when the polymerizable liquid crystal compound (1) of the present invention and the polymerizable liquid crystal compound (2) have structural units similar to each other, M in the formula (1) is an aliphatic hydrocarbon group, and the polymerizable liquid crystal compound (1) has high molecular flexibility, and the compatibility between them is increased, and in this state, the phase transition temperature can be significantly lowered while maintaining the high alignment order of the two polymerizable liquid crystal compounds contained. If the phase transition is possible at a low temperature, a liquid crystal cured film can be prepared from the polymerizable liquid crystal compound at a lower processing temperature, and such a liquid crystal cured film can reduce the influence of heating. In particular, from the viewpoint of suppressing the occurrence of alignment defects and easily lowering the phase transition temperature of the polymerizable liquid crystal compound (as a mixture of the polymerizable liquid crystal compounds (1) and (2)) without impairing the optical properties, the -O-CO-G 11 -E 11 -(A 11 -B 11 ) k11 -F 11 -P 11 , and -O-CO-G 12 -E 12 -(A 12 -B 12 ) k12 -F 12 -P 12 and -O-CO-G of the polymerizable liquid crystal compound (2) 21 -E 21 -(A 21 -B 21 ) k21 -F 21 -P21 , and -O-CO-G 22 -E 22 -(A 22 -B 22 ) k22 -F 22 -P 22 and preferably have similar structural units to each other.

[0104] In formula (2), k21 and k22 each independently represent an integer of 1 or more, and may be, for example, an integer of 1 to 5. The sum of k21 and k22 is preferably 2 to 6, more preferably 2 to 4. From the viewpoint of excellent liquid crystal properties, k21 and k22 each independently are preferably 1 or 2, and from the viewpoint of ease of production of the polymerizable liquid crystal compound (2), k21 and k22 are preferably the same number, and in a preferred embodiment of the present invention, k21 and k22 are both 1. From the viewpoint of excellent liquid crystal properties, k11 and k12 in formula (1) and k21 and k22 in formula (2) are preferably all the same number, and more preferably all 1.

[0105] In formula (2), B 21 , B 22 , E 21 , E 22 , G 21 , G 22 , A 21 , A 22 , F 21 , F 22 , P 21 and P 22 As the group represented by the formula (1), B 11 , B 12 , E 11 , E 12 , G 11 , G 12 , A 11 , A 12 , F 11 , F 12 , P 11 and P 12 The same groups as those exemplified as the group represented by the formula (2) can be mentioned, and the preferred embodiments of each are also the same. 21 As the group represented by the formula (1),11 , Ar 12 The same groups as those exemplified as the group represented by the formula (I) can be mentioned, and the preferred embodiments thereof also apply similarly.

[0106] A in formula (1) 11 , A 12 , B 11 , B 12 , E 11 , E 12 , F 11 , F 12 , G 11 , G 12 , P 11 and P 12 are each represented by A in formula (2). 21 , A 22 , B 21 , B 22 , E 21 , E 22 , F 21 , F 22 , G 21 , G 22 , P 21 and P 22 In formula (1), Ar 11 and Ar 12 are each represented by Ar 21 When the above group in formula (1) and the above group in formula (2) have such a relationship, the compatibility between the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) is likely to be increased, and the phase transition temperature is likely to be significantly decreased while suppressing alignment defects.

[0107] The content of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition of the present invention may be appropriately determined within a range in which the effects of the present invention can be obtained depending on the type of the polymerizable liquid crystal compound (1) and / or the polymerizable liquid crystal compound (2), and the ratio of the peak area of ​​the polymerizable liquid crystal compound (1) to the total peak area of ​​the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) measured by liquid chromatography (hereinafter also referred to as "area percentage value") is preferably 0.1% or more and 50% or less. More preferably, it is 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. When the content of the polymerizable liquid crystal compound (1) is equal to or more than the above lower limit, the solubility of the polymerizable liquid crystal compound in a solvent is easily improved, and the phase transition temperature is easily sufficiently reduced. In addition, when the content of the polymerizable liquid crystal compound (1) is equal to or less than the above upper limit, the alignment state of the liquid crystal can be well maintained when a liquid crystal cured film is produced from the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, so that an optical film having excellent optical properties can be obtained. When a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1) and / or the polymerizable liquid crystal compound (2) are contained, the area percentage value of the polymerizable liquid crystal compound (1) is calculated based on the total peak area of ​​all the polymerizable liquid crystal compounds (1) and all the polymerizable liquid crystal compounds (2). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, it can be measured and calculated by the method described in the examples described later.

[0108] The polymerizable liquid crystal composition of the present invention contains a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), and thus the phase transition temperature can be significantly lowered compared to the case where the polymerizable liquid crystal compound (2) is used alone. For example, the phase transition temperature of a liquid crystal mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition of the present invention is preferably 153° C. or lower, more preferably 150° C. or lower, and even more preferably 145° C. or lower. Furthermore, when the polymerizable liquid crystal compound (1) of the present invention is used in combination with the polymerizable liquid crystal compound (2), the phase transition temperature can be lowered by preferably 8° C. or more, more preferably 10° C. or more, even more preferably 12° C. or more, and particularly preferably 15° C. or more compared to the case where the polymerizable liquid crystal compound (2) is used alone. In the present invention, the phase transition temperature of the polymerizable liquid crystal compound can be measured by the method described in the Examples below. When two or more polymerizable liquid crystal compounds are contained, the phase transition temperature is measured using a polymerizable liquid crystal compound (mixture) having the same composition as the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition.

[0109] Furthermore, the polymerizable liquid crystal composition of the present invention contains a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), and thus has an excellent effect of increasing the solubility of the polymerizable liquid crystal compound in a solvent, compared to the case where the polymerizable liquid crystal compound (2) is used alone.

[0110] The method for producing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition of the present invention is not particularly limited, and each of them 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.

[0111] For example, A in formula (1) 11 and A 12 , B 11 and B 12 , E 11 and E 12 , F 11 and F 12 , G 11 and G 12 , P 11 and P 12 , Ar 11 and Ar 12 The polymerizable liquid crystal compound (1) in which P, F, B, A, E, and G are the same as each other can be produced by esterification reaction of a compound represented by formula (1-1) (hereinafter also referred to as "compound (1-1)"), a compound represented by formula (1-2) (hereinafter also referred to as "compound (1-2)"), and a compound represented by formula (1-3) (hereinafter also referred to as "compound (1-3)"). Note that P, F, B, A, E, and G in formula (1-1) respectively represent P, F, B, A, E, and G in formula (1), 11 and P 12 , F 11 and F 12 , B 11 and B 12 , A 11 and A 12 , E 11 and E 12 , G 11 and G 12In addition, M in the formula (1-2) and Ar in the formula (1-3) are the same as those defined in the formula (1), respectively. 11 , Ar 12 P, F, B, A, E, G and Ar are determined according to the desired polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2).

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] The reaction of the compounds (1-1) to (1-3) is preferably carried out in the presence of a condensing agent. Examples of the condensation agent include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (some of which are commercially available as water-soluble carbodiimide: WSC), bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, carbodiimides such as N,N'-diisopropylcarbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1-(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1 H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxysuccinimide, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 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. In terms of reactivity, cost, and the wide range of solvents available, preferred condensing agents are dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide, and 2,2'-carbonylbis-1H-imidazole.

[0116] The polymerizable liquid crystal compound (2) can be produced, for example, by reacting the compound (1-1) with the compound (1-3).

[0117] In the present invention, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition may be prepared separately and then mixed to be used as a liquid crystal mixture. Alternatively, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) can be obtained as a liquid crystal mixture by reacting the compounds (1-1) to (1-3) in an appropriate ratio. Without isolating each polymerizable liquid crystal compound from the obtained liquid crystal mixture, the liquid crystal mixture can be mixed with the polymerizable liquid crystal compound (1) or with the polymerizable liquid crystal compound (2) as necessary, thereby controlling the contents of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the liquid crystal mixture, thereby preparing a desired polymerizable liquid crystal mixture. When the polymerizable liquid crystal mixture is prepared by the former method, the contents of the polymerizable liquid crystal compounds (1) and (2) can be easily adjusted to a desired range, and the solvent solubility of the polymerizable liquid crystal compounds can be easily controlled. On the other hand, when the polymerizable liquid crystal mixture is prepared by the latter method, the synthesis is simple, and the polymerizable liquid crystal composition can be produced more efficiently.

[0118] When preparing a liquid crystal mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), the amount of the compound (1-2) used in the reaction is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the compound (1-1). The amount of the compound (1-3) used in the reaction is preferably 1 to 70 parts by mass, more preferably 10 to 65 parts by mass, relative to 100 parts by mass of the compound (1-1). By adjusting the amounts of the compound (1-1), the compound (1-2) and the compound (1-3) within the above ranges, it is easy to prepare a liquid crystal mixture containing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in a desired ratio.

[0119] The polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) as long as the effect of the present invention is not affected. Examples of such polymerizable liquid crystal compounds include compounds described in 3.2 Nonchiral rod-like liquid crystal molecules and 3.3 Chiral rod-like liquid crystal molecules in Chapter 3 Molecular structure and liquid crystallinity of Liquid Crystal Handbook (edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), compounds described in JP-A-2010-31223, and polymerizable liquid crystal compounds that can exhibit reverse wavelength dispersion when made into a liquid crystal cured film and polymerizable liquid crystal compounds that can exhibit normal wavelength dispersion, as described in JP-A-2011-207765, JP-A-5962760, etc.

[0120] When the polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, relative to 100 parts by mass of the total of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). In particular, if the content of a liquid crystal compound having a molecular structure significantly different from that of the polymerizable liquid crystal compound (1) or the polymerizable liquid crystal compound (2) is too high, phase separation may occur, which may impair the appearance. Therefore, it is preferable that the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention is substantially composed of a polymerizable liquid crystal compound having a structure similar to that of the polymerizable liquid crystal compound (1). The term "similar" as used herein refers to, for example, the -O-CO-G of the polymerizable liquid crystal compound (1). 11 -E 11 -(A 11 -B 11 ) k11 -F 11 -P 11 , -O-CO-G 12 -E 12 -(A 12 -B 12 ) k12 -F 12 -P 12 The part represented by Ar 11 or Ar 12 The term "substantially constituted" means that the content of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) is 90 mass % or more based on the total mass of the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition of the present invention. In one embodiment of the present invention, the polymerizable liquid crystal composition does not contain any polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2).

[0121] The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition of the present invention (total amount of all polymerizable liquid crystal compounds) is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. If the total mass of the polymerizable liquid crystal compound is within the above range, it is advantageous in terms of the alignment of the obtained liquid crystal cured film. In this specification, the polymerizable liquid crystal compound includes the polymerizable liquid crystal compound (1), the polymerizable liquid crystal compound (2), and other polymerizable liquid crystal compounds different from these, if included (hereinafter, these are also collectively referred to as "polymerizable liquid crystal mixture"). The solid content of the polymerizable liquid crystal composition means all components excluding volatile components such as organic solvents from the polymerizable liquid crystal composition.

[0122] The polymerizable liquid crystal composition of the present invention may further contain, in addition to the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), additives such as an organic solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, etc. Each of these components may be used alone or in combination of two or more.

[0123] In the present invention, the polymerizable liquid crystal mixture is preferably dissolved in a solvent and applied to a substrate or the like. The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compounds such as the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), and is preferably a solvent inactive to the polymerization reaction of the polymerizable liquid crystal compound. The polymerizable liquid crystal composition of the present invention contains a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), and thus the solvent solubility of the polymerizable liquid crystal compound (2) can be significantly improved compared to the case where the polymerizable liquid crystal compound (2) is dissolved alone in a solvent. Therefore, various solvents can be applied. 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, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are more preferred, and from the viewpoint of productivity, at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and N-methylpyrrolidone is even more preferred.

[0124] The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass, more preferably 5 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is low, so that the thickness of the film becomes approximately uniform and unevenness tends to be less likely to occur. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced. The polymerizable liquid crystal composition of the present invention is advantageous in that it has excellent solubility in a solvent by containing a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), and therefore the amount of organic solvent used during coating and storage can be reduced.

[0125] The polymerizable liquid crystal composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that generates reactive species by the contribution of light and can initiate a polymerization reaction of the polymerizable liquid crystal or the like. Examples of the reactive species include active species such as radicals, cations, and anions. Among them, from the viewpoint of easy reaction control, a photopolymerization initiator that generates radicals by light irradiation is preferred. As the photopolymerization initiator, only one type may be used, or two or more types may be used in combination.

[0126] Examples of photopolymerization initiators include benzoin compounds, benzophenone compounds, benzyl ketal compounds, alkylphenone compounds, acylphosphine oxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts, and sulfonium salts.Specific examples include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (all manufactured by BASF Japan Ltd.), Seikuol BZ, Seikuol Z, Seikuol BEE (all manufactured by Seiko Chemical Co., Ltd.), Kay ... Examples of suitable antibacterial agents include ADEKA CURE BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), 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 mixture composition preferably contains at least one type of photopolymerization initiator, and may contain two or more types of photopolymerization initiators.

[0127] 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 them, an α-acetophenone-based polymerization initiator or an oxime-based photopolymerization initiator is preferable.

[0128] Examples of α-acetophenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, and more preferably 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. Examples of commercially available α-acetophenone compounds include Irgacure 369, 379EG, and 907 (all manufactured by BASF Japan Co., Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.).

[0129] The oxime-based photopolymerization initiator generates methyl radicals by irradiation with light. The methyl radicals allow the polymerization of the polymerizable liquid crystal compound in the deep part of the liquid crystal cured film to proceed favorably. In addition, from the viewpoint of more efficiently proceeding the polymerization reaction in the deep part of the liquid crystal cured film to be formed, it is preferable to use a photopolymerization initiator that can efficiently use ultraviolet light with a wavelength of 350 nm or more. As photopolymerization initiators that can efficiently use ultraviolet light with a wavelength of 350 nm or more, triazine compounds and oxime ester type carbazole compounds are preferable, and from the viewpoint of sensitivity, oxime ester type carbazole compounds are more preferable. Examples of oxime ester type carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like. Commercially available oxime ester carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (all manufactured by BASF Japan Ltd.), ADEKA Optomer N-1919, ADEKA Arcles NCI-831 (all manufactured by ADEKA Corporation), and the like.

[0130] The amount of the photopolymerization initiator added is usually 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is unlikely to be disturbed.

[0131] The photopolymerization initiator can be made highly sensitive by using a sensitizer. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having anthracene and alkyl ether as a substituent; phenothiazine; and rubrene. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having anthracene and alkyl ether as a substituent; 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, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0132] By blending a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone and alkyl ether; catechols having a substituent such as alkyl ether, such as butylcatechol; radical scavengers such as pyrogallols and 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols. In order to polymerize the polymerizable liquid crystal compound (1) without disturbing the alignment, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0133] Furthermore, the polymerizable liquid crystal composition of the present invention may contain a leveling agent. The leveling agent is an additive that has the function of adjusting the fluidity of the polymerizable liquid crystal composition and making the film obtained by applying the composition flatter, and examples of the leveling agent 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 Co., Ltd.) 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, EF351, EF352 (all manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830, 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 Co., Ltd.), etc. Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

[0134] 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, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound is easily aligned, and the obtained liquid crystal cured film tends to be smoother, which is preferable. The polymerizable liquid crystal composition may contain two or more types of leveling agents.

[0135] 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) and the polymerizable liquid crystal compound (2), as necessary, and stirring and mixing them at a predetermined temperature.

[0136] <Retardation film> The polymerizable liquid crystal composition of the present invention has a low phase transition temperature of the polymerizable liquid crystal compound, and can produce a liquid crystal cured film at a lower processing temperature, so that the influence of heating can be reduced to obtain a liquid crystal cured film with excellent optical properties. In addition, the composition has high solubility in solvents and excellent coatability and film-forming properties, so that the occurrence of alignment defects caused by undissolved polymerizable liquid crystal compounds and precipitates and deposits in the composition can be suppressed. 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 originally exhibit, and a liquid crystal cured film with excellent optical properties can be obtained. Therefore, the present invention also relates to a cured product of the polymerizable liquid crystal composition of the present invention, in particular, a retardation film comprising a liquid crystal cured film obtained by curing the polymerizable liquid crystal composition in a state in which the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition are aligned. The retardation film composed of the liquid crystal cured film can fully exhibit the optical properties that the polymerizable liquid crystal compound used can originally exhibit, and can be a retardation film with high optical performance.

[0137] The liquid crystal cured film constituting the retardation film of the present invention may be composed of a homopolymer of polymerizable liquid crystal compound (1) in an oriented state and a homopolymer of polymerizable liquid crystal compound (2), or may be composed of a copolymer in an oriented state of a mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2). Since the polymerization reaction is easy and a uniform liquid crystal cured film is easily obtained, it is preferable that the liquid crystal cured film constituting the retardation film of the present invention is composed of a copolymer in an oriented state of a mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2).

[0138] In one embodiment of the present invention, the retardation film of the present invention is a cured product of the polymerizable liquid crystal composition of the present invention, and includes a liquid crystal cured film having optical properties represented by the following formulas (i), (ii), and (iii). The liquid crystal cured film is usually a cured product obtained by curing a polymerizable liquid crystal compound in a state where the polymerizable liquid crystal compound is aligned in the horizontal direction relative to the plane of the liquid crystal cured film (hereinafter, also referred to as a "horizontally aligned liquid crystal cured film"). Re(450) / Re(550)≦1.00 (i) 1.00≦Re(650) / Re(550) (ii) 100 nm≦Re(550)≦180 nm (iii) (In the formula, Re(λ) represents an in-plane retardation value of the cured liquid crystal film at a wavelength of λ nm, and Re=(nx(λ)-ny(λ))×d (d represents the thickness of the cured liquid crystal film, nx represents the principal refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film in an index ellipsoid formed by the cured liquid crystal film, and ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film and perpendicular to the direction of nx in an index ellipsoid formed by the cured liquid crystal film).)

[0139] When the horizontally aligned liquid crystal cured film satisfies the formulas (i) and (ii), the horizontally aligned liquid crystal cured film exhibits a so-called reverse wavelength dispersion, in which the in-plane retardation value at 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 preferably 0.70 or more, more preferably 0.78 or more, and also preferably 0.90 or less, more preferably 0.88 or less, even more preferably 0.86 or less, particularly preferably 0.85 or less, and particularly preferably 0.84 or less. In addition, Re(650) / Re(550) is preferably 1.00 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

[0140] The in-plane retardation value can be adjusted by the thickness d of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d, the three-dimensional refractive index and the film thickness d can be adjusted to obtain a desired in-plane retardation value (Re(λ): in-plane retardation value of the horizontally aligned liquid crystal cured film at a wavelength λ(nm)).

[0141] In addition, when the horizontally aligned liquid crystal cured film satisfies formula (iii), when an elliptical polarizing plate having a retardation film containing the horizontally aligned liquid crystal cured film is applied to an organic EL display device, the effect of improving the front reflection hue (the effect of suppressing coloration) is excellent. A more preferable range of the in-plane retardation value is 120 nm ≦ Re (550) ≦ 170 nm, and an even more preferable range is 130 nm ≦ Re (550) ≦ 150 nm.

[0142] In one embodiment of the present invention, the retardation film of the present invention is a cured product of the polymerizable liquid crystal composition of the present invention, and includes a liquid crystal cured film having optical properties represented by the following formulas (iv), (v) and (vi). The liquid crystal cured film is usually a cured product obtained by curing a polymerizable liquid crystal compound in a state where the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the liquid crystal cured film (hereinafter, also referred to as a "vertically aligned liquid crystal cured film"). Rth(450) / Rth(550)≦1.00 (iv) 1.00≦Rth(650) / Rth(550) (v) -100nm≦Rth(550)≦-40nm (vi) (In the formula, Rth(λ) represents a retardation value in the thickness direction of the cured liquid crystal film at a wavelength of λ nm, and Rth=((nx(λ)+ny(λ)) / 2-nz)×d (d represents the thickness of the cured liquid crystal film, nx represents the principal refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film in the index ellipsoid formed by the cured liquid crystal film, ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the cured liquid crystal film and perpendicular to the direction of nx in the index ellipsoid formed by the cured liquid crystal film, and nz represents the refractive index at a wavelength of λ nm in a direction perpendicular to the plane of the cured liquid crystal film in the index ellipsoid formed by the cured liquid crystal film).)

[0143] When the vertically aligned liquid crystal cured film satisfies the formulas (iv) and (v), in an elliptical polarizing plate having a retardation film including the vertically aligned liquid crystal cured film, the decrease in ellipticity can be suppressed on the short wavelength side, and the oblique reflection hue can be improved. The value of Rth(450) / Rth(550) in the vertically aligned liquid crystal cured film is preferably 0.70 or more, more preferably 0.78 or more, and also preferably 0.90 or less, more preferably 0.88 or less, even more preferably 0.86 or less, particularly preferably 0.85 or less, and particularly preferably 0.84 or less. In addition, Rth(650) / Rth(550) is preferably 1.0 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

[0144] In addition, when the vertically aligned liquid crystal cured film satisfies formula (vi), the oblique reflection hue can be improved when an elliptical polarizing plate having a retardation film containing the vertically aligned liquid crystal cured film is applied to an organic EL display device. The retardation value Rth(550) in the thickness direction of the vertically aligned liquid crystal cured film is more preferably -90 nm or more, further preferably -80 nm or more, and more preferably -50 nm or less.

[0145] The retardation film of the present invention is, 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. The composition can be produced by a method comprising the steps of:

[0146] 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 described below. Examples of the substrate include glass substrates and film substrates, but resin film substrates are preferred from the viewpoint of processability. Examples of the resin 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; polyether sulfone; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene oxide. Such resins can be formed into a film by known means such as solvent casting and melt extrusion to form a 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.

[0147] 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; cellulose ester substrates manufactured by Konica Minolta Opto Co., Ltd., 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 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 Inc., such as "ZEONORFILM (registered trademark)"; and cyclic olefin resin substrates manufactured by JSR Corporation, such as "ARTONFILM (registered trademark)."

[0148] From the viewpoints of thinning the retardation film, ease of peeling the substrate, handleability of the substrate, and the like, the thickness of the substrate is usually from 5 to 300 μm, and preferably from 10 to 150 μm.

[0149] 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.

[0150] Next, the solvent is removed by drying or the like to form a dried coating film. Examples of drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. In this case, the coating film obtained from the polymerizable liquid crystal composition is heated to dry and remove the solvent from the coating film, and the polymerizable liquid crystal compound can be aligned in a desired direction (for example, horizontal or vertical) relative to the coating film plane. The heating temperature of the coating film can be appropriately determined in consideration of the materials of the polymerizable liquid crystal compound used and the substrate on which the coating film is formed, but in order to phase-transition the polymerizable liquid crystal compound to a liquid crystal phase state, it is usually necessary that the temperature is equal to or higher than the liquid crystal phase transition temperature. In order to make the polymerizable liquid crystal compound have a desired alignment state while removing the solvent contained in the polymerizable liquid crystal composition, the composition can be heated to a temperature equal to or higher than the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.

[0151] The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2), and can usually undergo liquid crystal phase transition at a temperature lower than the temperature at which each of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) transitions to a liquid crystal phase. In one embodiment of the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture constituting the polymerizable liquid crystal composition of the present invention is preferably 25°C or higher and 153°C or lower. When the phase transition temperature to the liquid crystal phase is within the above range, a liquid crystal cured film can be produced at a lower processing temperature, and a liquid crystal cured film having high optical properties that the polymerizable liquid crystal compound can inherently exhibit can be obtained while suppressing deterioration of optical properties due to heating. In addition, 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. Furthermore, since the liquid crystal phase transition can be performed by heating at a relatively low temperature, there is also an advantage that the options for the support substrate to which the polymerizable liquid crystal composition is applied are expanded. In the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture is usually 40° C. or higher, more preferably 50° C. or higher, and even more preferably 60° C. or higher, from the viewpoint of enabling the resulting liquid crystal cured film to exhibit reverse wavelength dispersion characteristics, and is more preferably 150° C. or lower, even more preferably 145° C. or lower, and particularly preferably 144° C. or lower, from the viewpoint of achieving more significant effects of the present invention. 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), etc. The phase transition temperature in the polymerizable liquid crystal mixture of the present invention containing at least two polymerizable liquid crystal compounds means a temperature measured using a mixture of polymerizable liquid crystal compounds in which all polymerizable liquid crystal compounds constituting the polymerizable liquid crystal mixture are mixed in the same ratio as the composition in the polymerizable liquid crystal mixture.

[0152] 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, and preferably 0.5 to 5 minutes.

[0153] The removal of the solvent from the coating film may be performed simultaneously with or separately from the heating of the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, but is preferably performed simultaneously from the viewpoint of improving productivity. 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 provided to adequately remove the solvent in the coating film obtained from the polymerizable liquid crystal composition under conditions in which the polymerizable liquid crystal compound contained in the coating film is not polymerized. Examples of the drying method in the pre-drying step include natural drying, ventilation drying, heat drying, and reduced pressure drying, and 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 of solvent, its boiling point, and its amount, etc.

[0154] Next, in the obtained dried coating film, the polymerizable liquid crystal compound is polymerized by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, thereby forming a liquid crystal cured film that is a polymer of the polymerizable liquid crystal compound existing in a desired orientation state. Since the polymerizable liquid crystal composition of the present invention can be highly polymerized by light irradiation such as high-intensity ultraviolet light while suppressing damage to the polymerizable liquid crystal compound, a photopolymerization method is usually used as a polymerization method. In photopolymerization, the light irradiated to the dried coating film is appropriately selected according to the type of polymerization initiator contained in the dried coating film, the type and amount of the polymerizable liquid crystal compound. Specific examples thereof 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 active electron beams. Among them, ultraviolet light is preferred in terms of ease of controlling the progress of the polymerization reaction and the ability to use photopolymerization devices that are widely used in this field, and 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. In addition, during polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dried coating film with an appropriate cooling means. By adopting such a cooling means, the polymerization of the polymerizable liquid crystal compound can be carried out at a lower temperature, and even if a substrate having a relatively low heat resistance is used, a liquid crystal cured film can be appropriately formed. In addition, it is also possible to promote the polymerization reaction by increasing the polymerization temperature within a range in which no problems due to heat during light irradiation (such as deformation of the substrate due to heat) occur. During photopolymerization, a patterned cured film can also be obtained by performing masking or development.

[0155] Examples of the light source of the active 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 the wavelength range of 380 to 440 nm, a chemical lamp, a black light lamp, a microwave excited mercury lamp, and a metal halide lamp.

[0156] 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 time for light irradiation is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and further preferably 0.1 seconds to 1 minute. When irradiating once or multiple times with such ultraviolet irradiation intensity, the integrated 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 It is.

[0157] The thickness of the liquid crystal cured film can be appropriately selected depending on the display device to which it is applied, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

[0158] The coating film of the polymerizable liquid crystal composition may be formed on an alignment film. The alignment film has an alignment regulating force that aligns the polymerizable liquid crystal compound in a desired direction. For example, there is a horizontal alignment film that has an alignment regulating force that aligns the polymerizable liquid crystal compound in the horizontal direction, and a vertical alignment film that has an alignment regulating force that aligns the polymerizable liquid crystal compound in the vertical direction. The alignment regulating force can be arbitrarily adjusted by the type of alignment film, the surface state, the rubbing conditions, etc., and when the alignment film is formed of a photoalignable polymer, it can be arbitrarily adjusted by the polarized light irradiation conditions, etc.

[0159] The alignment film is preferably one that has solvent resistance such that the polymerizable liquid crystal composition is not dissolved by coating, etc., and also has heat resistance in the heat treatment for removing the solvent and for orienting the polymerizable liquid crystal compound described below. Examples of the alignment film include an alignment film containing an alignment polymer, a photoalignment film, a groove alignment film having a concave-convex pattern or a plurality of grooves on the surface, and a stretched film stretched in the alignment direction, and the like, and a photoalignment film is preferred from the viewpoint of the accuracy of the alignment angle and quality.

[0160] Examples of the oriented polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acids, which are hydrolyzates thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Among them, polyvinyl alcohol is preferred. The oriented polymers can be used alone or in combination of two or more kinds.

[0161] 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 removing the solvent, or by applying an alignment polymer composition to a substrate, removing the solvent, and rubbing (rubbing method). Examples of the solvent include the same solvents as those exemplified above as solvents that can be used in the polymerizable liquid crystal composition.

[0162] 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, and more preferably about 0.1 to 10%.

[0163] As the oriented polymer composition, a commercially available alignment film material may be used as it is. 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).

[0164] The method for applying the alignable polymer composition to the substrate may be the same as the method exemplified for applying the polymerizable liquid crystal composition to the substrate.

[0165] Methods for removing the solvent contained in the orientable polymer composition include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0166] In order to impart an orientation control force to the orientation film, a rubbing treatment can be performed as necessary (rubbing method). A method for imparting an orientation control force by the rubbing method includes a method in which an orientation polymer composition is applied to a substrate and annealed to bring an orientation 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 orientation directions can also be formed on the orientation film.

[0167] 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). Photo-alignment films are also advantageous in that the direction of the alignment control force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

[0168] The photoreactive group refers to a group that generates liquid crystal alignment ability by irradiation with light. Specifically, it includes groups involved in photoreactions that induce molecular alignment or are the origin of liquid crystal alignment ability, such as isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction, caused by irradiation with light. Among them, groups involved in dimerization reaction or photocrosslinking reaction are preferred in terms of excellent alignment ability. As the photoreactive group, a group having an unsaturated bond, particularly a double bond, is preferred, and a group having at least one 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) is particularly preferred.

[0169] Examples of photoreactive groups having a C=C bond include vinyl groups, polyene groups, stilbene groups, stilbazole groups, stilbazolium groups, chalcone groups, and cinnamoyl groups. Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of 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. Examples of 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.

[0170] Among them, photoreactive groups involved in photodimerization are preferred, and cinnamoyl and chalcone groups are preferred because the amount of polarized light irradiation required for photoalignment is relatively small and a photoalignment film having excellent thermal stability and stability over time is easily obtained. As the 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.

[0171] A photo-alignment layer can be formed on a substrate by applying the photo-alignment film-forming composition on the substrate. The solvent contained in the composition can be the same as the solvents exemplified above as the solvents usable for the polymerizable liquid crystal composition, and can be appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group.

[0172] The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of polymer or monomer and the thickness of the intended photo-alignment film, but is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass, based on the mass of the composition for forming a photo-alignment film. The composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer, within a range that does not significantly impair the properties of the photo-alignment film.

[0173] The method of applying the composition for forming a photo-alignment film to a substrate may be the same as the method of applying the oriented polymer composition to a substrate. Examples of the method of removing the solvent from the applied composition for forming a photo-alignment film include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0174] The polarized light may be irradiated by directly irradiating the polarized UV light onto the composition for forming a photo-aligned film coated on the substrate after removing the solvent, or by irradiating the polarized light from the substrate side and transmitting the polarized light. In addition, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in 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) having a wavelength of 250 to 400 nm is particularly preferable. Examples of light sources used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and 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 preferable because they have a high emission intensity of ultraviolet light with a wavelength of 313 nm. The light from the light source can be irradiated by passing through an appropriate polarizer to irradiate the polarized UV light. As such a polarizer, a polarizing filter, a polarizing prism such as a Glan-Thompson or Glan-Taylor type polarizer, or a wire grid type polarizer can be used.

[0175] If masking is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) in which the liquid crystal alignment directions are different can be formed.

[0176] A groove alignment film is a film that has a concave-convex pattern or multiple grooves on the film surface. When a polymerizable liquid crystal compound is applied to a film with multiple equally spaced linear grooves, the liquid crystal molecules are aligned in the direction along the grooves.

[0177] Methods for obtaining a groove 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 a pattern shape, followed by development and rinsing to form an uneven pattern; a method in which a layer of uncured UV-curable resin is formed on a plate-shaped master having grooves on its surface, 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 unevenness, followed by curing.

[0178] Furthermore, as a material that exhibits an alignment control force that aligns a polymerizable liquid crystal compound in a direction perpendicular to the plane of the liquid crystal cured film, in addition to the above-mentioned alignment polymers, a fluorine-based polymer such as a perfluoroalkyl, a silane compound, and a polysiloxane compound obtained by a condensation reaction thereof may be used.

[0179] When a silane compound is used as a material for forming the alignment film, a compound containing Si and C elements as constituent elements is preferable from the viewpoint of easily reducing surface tension and easily increasing adhesion with a layer adjacent to the alignment film, and a silane compound can be suitably used. As the silane compound, a silane-containing ionic compound or the like can be used, and the vertical alignment regulating force can be increased by using such a silane compound. As the silane compound, one type may be used alone, two or more types may be used in combination, or it may be used by mixing with other materials. When the silane compound is a non-ionic silane compound, a silane compound having an alkyl group at the molecular end is preferable from the viewpoint of easily increasing the vertical alignment regulating force, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable.

[0180] 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 1000 nm, more preferably 10 to 500 nm or less, even more preferably 10 to 300 nm, and particularly preferably 50 to 250 nm.

[0181] The present invention includes a polarizing plate (elliptical polarizing plate) including the retardation film of the present invention. The polarizing plate of the present invention usually includes the retardation film of the present invention and a polarizing film. The polarizing film is a film having a polarizing function, and examples of the polarizing film include a stretched film having a dye having anisotropy adsorbed thereon, a film coated with a dye having anisotropy, and the like, which includes a polarizer, etc. Examples of the dye having anisotropy include a dichroic dye.

[0182] A film including, as a polarizer, a stretched film having adsorbed thereon a dye having absorption anisotropy is usually 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 the adsorbed dichroic dye 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 film between a transparent protective film via an adhesive on at least one surface of the polarizer produced through these steps.

[0183] Polyvinyl alcohol resins are obtained by saponifying polyvinyl acetate resins. As polyvinyl acetate resins, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith are used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

[0184] The degree of saponification of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.

[0185] Such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film. The method for forming a film of the polyvinyl alcohol-based resin 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.

[0186] The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. When the uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before or during the boric acid treatment. It is also possible to perform the uniaxial stretching at these multiple stages. In the uniaxial stretching, the film may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially stretched using a heated roll. The uniaxial stretching may be dry stretching in which stretching is performed in the atmosphere, or wet stretching in which stretching is performed in a state where the polyvinyl alcohol-based resin film is swollen using a solvent. The stretching ratio is usually about 3 to 8 times.

[0187] Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is carried out, for example, by a method of immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

[0188] 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 trisazo or tetrakisazo. It is preferable that the polyvinyl alcohol resin film is immersed in water before the dyeing process.

[0189] When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol resin film by immersing it in an aqueous solution containing iodine and potassium iodide is usually adopted. The content of iodine in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide 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.

[0190] 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 -4 ~10 parts by mass, preferably 1 × 10 -3 ~1 part by mass, more preferably 1 × 10 -3 ~1×10 -2 The amount of the dye in the aqueous solution is expressed by 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 the aqueous solution (dyeing time) is usually about 10 to 1,800 seconds.

[0191] The boric acid treatment after dyeing with a dichroic dye can usually be carried out by immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The content of boric acid in this aqueous boric acid 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 aqueous boric acid 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 aqueous boric acid solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually 50°C or higher, preferably 50 to 85°C, and more preferably 60 to 80°C.

[0192] The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The washing can be performed, 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.

[0193] After washing with water, a drying treatment is carried out to obtain a polarizer. The drying treatment can be carried out using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30 to 100°C, and preferably 50 to 80°C. The time of the drying treatment 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 treatment. The moisture content is usually about 5 to 20 mass%, and preferably 8 to 15 mass%. When the moisture content is within the above range, a polarizer having appropriate flexibility and excellent thermal stability can be easily obtained.

[0194] The polyvinyl alcohol-based resin film is then uniaxially stretched, dyed with a dichroic dye, treated with boric acid, washed with water and dried to obtain a polarizer having a thickness of preferably 5 to 40 μm.

[0195] Examples of the film coated with a dye having absorption anisotropy include a film obtained by coating a composition containing a dichroic dye having liquid crystal properties or a composition containing a dichroic dye and a polymerizable liquid crystal. The film preferably has a protective film on one or both sides. Examples of the protective film include the same resin film as the above-mentioned example of the substrate usable for producing the liquid crystal cured film.

[0196] The film coated with the dye having absorption anisotropy is preferably thin, but if it is too thin, the strength decreases and the processability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

[0197] Specific examples of the film coated with a dye having absorption anisotropy include the films described in JP-A-2012-33249 and the like.

[0198] The polarizing film may have a transparent protective film laminated on at least one surface of the polarizer thus obtained via an adhesive. As the transparent protective film, a transparent film similar to the resin film exemplified above as the substrate usable for producing the liquid crystal cured film can be preferably used.

[0199] The polarizing plate of the present invention is composed of the retardation film of the present invention and a polarizing film. For example, the retardation film of the present invention and the polarizing film are laminated via an adhesive layer or a pressure-sensitive adhesive layer, etc., to obtain the elliptical polarizing plate of the present invention.

[0200] In one aspect of the present invention, when the retardation film of the present invention containing a horizontally aligned liquid crystal cured film and a polarizing film are laminated, it is preferable to laminate them so that the angle between the slow axis (optical axis) of the horizontally aligned liquid crystal cured film constituting the retardation film and the absorption axis of the polarizing film is 45±5°.

[0201] The polarizing plate of the present invention may have a structure similar to that of a conventional elliptical polarizing plate, or a polarizing film and a retardation film, for example, a pressure-sensitive adhesive layer (sheet) for attaching the elliptical polarizing plate to a display element such as an organic EL display, a protective film for protecting the surface of the polarizing film or retardation film from scratches or dirt, etc.

[0202] The polarizing plate of the present invention can be used in various 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 the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (e.g., a field emission display device (FED) and a surface field emission display device (SED)), an electronic paper (a display device using electronic ink or an electrophoretic element, a plasma display device, a projection display device (e.g., a grating light valve (GLV) display device, a display device having a digital micromirror device (DMD)), and a piezoelectric ceramic display. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. These display devices may be display devices 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 for an organic electroluminescence (EL) display device and an inorganic electroluminescence (EL) display device. These display devices (optical displays) can exhibit good image display characteristics by being provided with the polarizing plate of the present invention, which has excellent optical properties. EXAMPLES

[0203] The present invention will now be described in more detail with reference to the following examples. In the examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified.

[0204] [HPLC measurement] The HPLC measurement may be performed under any conditions as long as the peaks derived from the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) can be separated. An example of the HPLC measurement conditions is 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

[0205] <Preparation of polymerizable liquid crystal compound> Synthesis Example 1: Preparation of polymerizable liquid crystal compound (2) A polymerizable liquid crystal compound represented by the following formula (2-1-1) (hereinafter referred to as "polymerizable liquid crystal compound (2-1-1)") was synthesized according to the following scheme. [ka]

[0206] A 100mL-four-neck flask equipped with a Dimroth condenser and a thermometer was filled with nitrogen, and 11.02g of compound (E-1) synthesized with reference to patent document (JP 2010-31223), 4.22g of compound (D-2) synthesized with reference to patent document (JP 2011-207765), 0.02g of DMAP (manufactured by Wako Pure Chemical Industries, Ltd.), 0.20g of BHT (manufactured by Wako Pure Chemical Industries, Ltd.), and 58g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed, and then 4.05g of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and these were reacted at 0°C overnight. After the reaction was completed, insoluble components were removed by filtration. The obtained chloroform solution was dropped into acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) of a mass three times the mass of chloroform contained in the solution, and a solid was precipitated. 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 11.75 g of polymerizable liquid crystal compound (2-1-1). The yield of polymerizable liquid crystal compound (2-1-1) was 81% based on compound (D-2).

[0207] Synthesis Example 2: Preparation of a mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) [ka]

[0208] A 100mL four-neck flask equipped with a Dimroth condenser and a thermometer was filled with nitrogen, and 10.91g of compound (E-1), 4.22g of compound (D-2), 0.06g of compound (F-3) (manufactured by Wako Pure Chemical Industries, Ltd.), 0.02g of DMAP (manufactured by Wako Pure Chemical Industries, Ltd.), 0.20g of BHT (manufactured by Wako Pure Chemical Industries, Ltd.), and 58g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed, and then 4.05g of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and these were reacted at 0°C overnight. After the reaction was completed, insoluble components were removed by filtration. The obtained chloroform solution was dropped into acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) of a mass three times the mass of chloroform contained in the solution, and a solid was precipitated. The precipitated solid was then filtered off, washed three times with 20 g of acetonitrile, and dried under reduced pressure at 30°C to obtain 12.34 g of a mixture of polymerizable liquid crystal compound (2-1-1) and polymerizable liquid crystal compound (1-1-1). The mixture thus obtained contained 5.0% of polymerizable liquid crystal compound (1-1-1) based on the total mass of the mixture. The yield of the mixture was 85.0% based on compound (D-2). Note that n in the above formula (1-1-1) is 2.

[0209] Synthesis Examples 3-13 Liquid crystal mixtures (1) to (12) containing the polymerizable liquid crystal compound (2-1-1) and any one of the polymerizable liquid crystal compounds (1-1-2) to (1-1-10) were prepared in the same manner as in Synthesis Example 2, except that the compound (F-3) was replaced with the compounds (F-4) to (F-10), (F-1) or (F-2) shown in Table 1. The polymerizable liquid crystal compounds (1-1-2) to (1-1-10) each represent -O-CO-(C 3 H 6)-CO-O- structure, in which the propylene group is replaced with an aliphatic hydrocarbon group or alicyclic group derived from compound (F-4) to (F-10), (F-1) or (F-2).

[0210] [Table 1]

[0211] <Solubility evaluation> At 25°C, 1.00g of N-methylpyrrolidone (NMP) and a stirrer were placed in a vial, and while stirring with a magnetic stirrer (HS-30DN, AS ONE), the above synthetic compounds were added until residual dissolution was visually confirmed. When residual dissolution was confirmed, the solubility of each liquid crystal mixture and polymerizable liquid crystal compound in NMP was calculated as a weight percent concentration from (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 3.

[0212] <Preparation of polymerizable liquid crystal composition> Example 1 The liquid crystal mixture (1) of the polymerizable liquid crystal compound (1-1-1) and the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis Example 2 was placed in a vial, and a polymerization initiator, a leveling agent, a polymerization inhibitor, and a solvent were added according to the composition shown in Table 2. The mixture was stirred at 80°C for 30 minutes using a carousel to obtain a polymerizable liquid crystal composition (1). The amounts of the polymerization initiator, leveling agent, and polymerization inhibitor shown in Table 2 are amounts charged relative to 100 parts by mass of the liquid crystal mixture (1). The blending amount of the solvent was set so that the mass % of the solid content was 13% with respect to the total amount of the polymerizable liquid crystal composition.

[0213] [Table 2]

[0214] 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.)

[0215] Example 2 A polymerizable liquid crystal composition (2) was obtained in the same manner as in Example 1, except that 510 mg of the liquid crystal mixture (2) of the polymerizable liquid crystal compound (1-1-2) and the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis Example 3 and 490 mg of the compound (2-1-1) obtained in Synthesis Example 1 were mixed and used as the polymerizable liquid crystal compound. Using the obtained polymerizable liquid crystal composition (2), HPLC analysis was performed under the above-mentioned measurement conditions, and the area percentage value of the polymerizable liquid crystal compound (1-1-2) based on the total amount of the polymerizable liquid crystal compound (2-1-1) and the polymerizable liquid crystal compound (1-1-2) was calculated.

[0216] Examples 3 to 8 and 10 to 12 Polymerizable liquid crystal compositions (3) to (8) and (10) to (12) were obtained in the same manner as in Example 1, except that the liquid crystal mixture (1) was replaced with the liquid crystal mixtures (2) to (10), respectively.

[0217] Example 9 A polymerizable liquid crystal composition (9) was obtained in the same manner as in Example 1, except that 500 mg of the liquid crystal mixture (8) of the polymerizable liquid crystal compound (1-1-6) and the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis Example 9 and 500 mg of the compound (2-1-1) obtained in Synthesis Example 1 were mixed and used as the polymerizable liquid crystal compound. HPLC analysis was performed under the above-mentioned measurement conditions using the obtained polymerizable liquid crystal composition (9), and the area percentage value of the polymerizable liquid crystal compound (1-1-6) based on the total amount of the polymerizable liquid crystal compound (2-1-1) and the polymerizable liquid crystal compound (1-1-6) was measured.

[0218] Comparative Example 1 A polymerizable liquid crystal composition (13) was obtained in the same manner as in Example 1, except that the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis example 1 was used instead of the liquid crystal mixture (1).

[0219] Comparative Examples 2 and 3 Polymerizable liquid crystal compositions (14) and (15) were obtained in the same manner as in Example 1, except that the liquid crystal mixture (1) was replaced with the liquid crystal mixture (11) or (12) obtained in Synthesis Example 12 or 13, respectively, according to Table 3.

[0220] <Measurement of phase transition temperature> 1000 mg of the liquid crystal mixture used in the polymerizable liquid crystal compositions (1) to (15) was weighed out in a vial, and 2 g of chloroform was added to dissolve the mixture. The obtained solution was applied to a glass substrate with a PVA alignment film that had been subjected to a rubbing treatment, and then dried. The substrate was placed on a cooling and heating device (Japan High Tech Corporation's "LNP94-2") and heated from room temperature to 180°C, and then cooled to room temperature. The state during the temperature change was observed with a polarizing microscope (LEXT, Olympus Corporation), and the temperature at which the nematic phase was reached was measured and defined as the nematic phase transition temperature. The results are shown in Table 3.

[0221] [Table 3]

[0222] <Measurement of optical properties (α value)> For the polymerizable liquid crystal compositions (1), (3), (4), (6), (8), (10) to (12) and (15) in which M in formula (1) is an aliphatic hydrocarbon group, optical films (retardation films) were prepared and the optical properties were evaluated. The results are shown in Table 4. [Preparation of composition for forming photoalignment 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 photoalignment film. Photoalignment material (5 parts) represented by the following formula: [ka] (Number average molecular weight: approx. 28000) Solvent (95 parts): Cyclopentanone

[0223] [Production of optical film (retardation film)] An optical film was produced as follows. A cycloolefin polymer film (COP) (ZF-14, Zeon Corporation) was treated once using a corona treatment device (AGF-B10, Kasuga Electric Co., Ltd.) under conditions of an output of 0.3 kW and a treatment speed of 3 m / min. The photoalignment film-forming composition was applied to the corona-treated surface with a bar coater, dried at 80°C for 1 minute, and irradiated with 100 mJ / cm using a polarized UV irradiation device (SPOT CURE SP-7, Ushio Inc.). 2 The film thickness of the resulting alignment film was measured with a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 100 nm.

[0224] Each of the polymerizable liquid crystal compositions (1), (3), (4), (6), (8), (10) to (12), and (15) was applied onto an 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, accumulated light amount at a wavelength of 365 nm: 1000 mJ / cm) using a high-pressure mercury lamp (Unicur VB-15201BY-A, manufactured by Ushio Inc.). 2 ) to prepare an optical film.

[0225] The optical film prepared above was used as a measurement sample, and the front retardation values ​​for light with wavelengths of 450 nm and 550 nm were measured using a measuring device (Oji Scientific Instruments' "KOBRA-WR"), and the α value = Re(450) / Re(550) was calculated.

[0226] [Table 4]

Claims

1. A polymerizable liquid crystal compound represented by formula (1): 【Chemistry 1】 [In formula (1), k11, k12 and l each independently represent an integer of 1 or more; B １１ and B １２ Each independently represents -CR １ R ２ --, --CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ --, --NR ２ -CO-, -O-CH ２ --, --CH ２ -O-, -S-CH ２ --, --CH ２ represents —S— or a single bond; R １ and R ２ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms; E １１ and E １２ Each independently represents -CR １ R ２ --, --CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ --, --NR ２ -CO-, -O-CH ２ --, --CH ２ -O-, -S-CH ２ --, --CH ２ represents -S- or a single bond; G １１ and G １２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is not substituted with a halogen atom, -R ３ , -OR ３ , a cyano group or a nitro group, and the —CH ２ - may be replaced by -O-, -S- or -NH-; R ３ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A １１ and A １２ 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 particularly limited, and ３ , -OR ３ , optionally substituted with a cyano group or a nitro group; F １１ and F １２ each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR ３ or a halogen atom, and the —CH ２ - may be replaced by -O- or -CO-; P １１ and P １２ each independently represents a hydrogen atom or a polymerizable group (provided that P １１ and P １２ at least one of which is a polymerizable group; Each M independently represents a divalent aliphatic hydrocarbon group having 2n carbon atoms (n is an integer of 2 to 4) which may have a substituent; Ar １１ and Ar １２ each independently represents the following formula (Ar-1): 【change】 [In formula (Ar-1), * represents a bond; Q 1 represents -S-; 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 which may have a substituent; Z 1 and Z 2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an 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 11 R 12 or -SR 11 , Z 1 and Z 2 may bond together to form an aromatic ring or an aromatic heterocycle, and R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It represents a group represented by the following formula:

2. A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1 and a polymerizable liquid crystal compound represented by formula (2). 【Chemistry 4】 [In formula (2), k21 and k22 each independently represent an integer of 1 or more; B ２１ and B ２２ Each independently represents -CR １ R ２ --, --CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ --, --NR ２ -CO-, -O-CH ２ --, --CH ２ -O-, -S-CH ２ --, --CH ２ represents —S— or a single bond; R １ and R ２ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. E ２１ and E ２２ Each independently represents -CR １ R ２ --, --CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ --, --NR ２ -CO-, -O-CH ２ --, --CH ２ -O-, -S-CH ２ --, --CH ２ represents -S- or a single bond; G ２１ and G ２２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is not substituted with a halogen atom, -R ３ , -OR ３ , a cyano group or a nitro group, and the —CH ２ - may be replaced by -O-, -S- or -NH-; R ３ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A ２１ and A ２２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not particularly limited, and ３ , -OR ３ , optionally substituted with a cyano group or a nitro group; F ２１ and F ２２ each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR ３ or a halogen atom, and the —CH ２ - may be replaced by -O- or -CO-; P ２１ and P ２２ each independently represents a hydrogen atom or a polymerizable group (provided that P ２１ and P ２２ at least one of which is a polymerizable group; Ar ２１ is represented by the following formula (Ar-1): 【change】 [In formula (Ar-1), * represents a bond; Q 1 represents -S-; 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 which may have a substituent; Z 1 and Z 2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an 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 11 R 12 or -SR 11 , Z 1 and Z 2 may bond together to form an aromatic ring or an aromatic heterocycle, and R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It represents a group represented by the following formula:

3. 3. The polymerizable liquid crystal composition according to claim 2, wherein a ratio of a peak area of ​​the polymerizable liquid crystal compound (1) to a total peak area of ​​the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), as measured by liquid chromatography, is 0.1% or more and 50% or less.

4. A in formula (1) １１ , A １２ , B １１ , B １２ , E １１ , E １２ , F １１ , F １２ , G １１ , G １２ , P １１ and P １２ Each of the groups represented by the formula (2) is A ２１ , A ２２ , B ２１ , B ２２ , E ２１ , E ２２ , F ２１ , F ２２ , G ２１ , G ２２ , P ２１ and P ２２ Ar in formula (1) is the same as the group represented by １１ and Ar １２ Each of the groups represented by the formula (2) is ２１ The polymerizable liquid crystal composition according to claim 2 or 3, wherein the group is the same as a group represented by the following formula:

5. The polymerizable liquid crystal composition according to any one of claims 2 to 4, further comprising a photopolymerization initiator and an organic solvent.

6. A retardation film formed from the polymerizable liquid crystal composition according to any one of claims 2 to 5.

7. A polarizing plate comprising the retardation film according to claim 6 .

8. An optical display comprising the polarizer of claim 7.

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