Method for producing polymerizable liquid crystal mixture

Abstract

To reduce adhesion of crystalline body to a drying device, when drying crystallization body containing a polymerizable liquid crystal compound, with a producing method of a mixture containing specific polymerizable liquid crystal compound.SOLUTION: A method for producing a polymerizable liquid crystal mixture includes a drying step of the crystalline product containing the polymerizable liquid crystal compound represented by formula (1), which is obtained by a coupling reaction in an organic solvent. The drying step is carried out under conditions satisfying the following equation (A), where the drying temperature of the crystalline product is T [°C] and the solvent content in the crystalline product immediately before the start of the drying step is V [wt%]. V<-0.5T+75, and 30≤V (A)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polymerizable liquid crystal mixture. [Background technology]

[0002] Patent Document 1 describes a method for producing a polymerizable liquid crystal compound, which includes a step of drying the precipitated crystals. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-120659 Summary of the Invention [Problem to be solved by the invention]

[0004] When the polymerizable liquid crystal compound has a complex structure, crystals tend to adhere to the equipment used in the drying process, which can lead to problems such as a decrease in drying efficiency and complicated removal of the adhered crystals from the equipment after the drying process. [Means for solving the problem]

[0005] The present invention includes the following inventions. [Invention 1] A method for producing a polymerizable liquid crystal mixture, comprising a drying step of a crystallized product containing a polymerizable liquid crystal compound represented by formula (1) obtained by a coupling reaction in an organic solvent, The method for producing a polymerizable liquid crystal mixture, wherein the drying step is carried out under conditions that satisfy formula (A), where T [°C] is the drying temperature when drying the crystallized body, and V [wt%] is the liquid content of the organic solvent contained in the crystallized body immediately before the start of the drying step.

[0006] V<-0.5T+75 and 30≦V (A)

[0007] [ka]

[0008] [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 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 R represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond. 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

[0009] E 11 and E 12 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond.

[0010] 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 substituted with a halogen atom, -R 3 , -OR 3 The -CH2- contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. 3represents 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.

[0011] 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.

[0012] 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 Alternatively, it may be substituted with a halogen atom, and -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-.

[0013] P 11 and P 12 each independently represents a hydrogen atom or a polymerizable group. 11 and P 12 At least one of the groups is a polymerizable group. M each independently represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group in which at least two groups selected from the group consisting of divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms are linked via a linking group, and hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are not optionally substituted with halogen atoms, -R 3 , -OR 3 , cyano, or nitro groups.

[0014] Ar 11 and Ar 12each independently represents a divalent aromatic group which may have a substituent. [Invention 2] The method for producing a polymerizable liquid crystal mixture according to [Invention 1], wherein the crystallized product further contains a polymerizable liquid crystal compound represented by formula (2).

[0015] [ka]

[0016] [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 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 R represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond. 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

[0017] E 21 and E 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond.

[0018] G 21 and G 22each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with a halogen atom, -R 3 , -OR 3 The -CH2- contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

[0019] A 21 and A 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , and may be substituted with a cyano group or a nitro group.

[0020] F 21 and F 22 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 Alternatively, it may be substituted with a halogen atom, and -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-.

[0021] P 21 and P 22 each independently represents a hydrogen atom or a polymerizable group. 21 and P 22 At least one of the groups is a polymerizable group. Ar 21 represents a divalent aromatic group which may have a substituent.] [Effects of the Invention]

[0022] According to the present invention, adhesion of crystallized bodies to a drying device can be reduced when drying the crystallized bodies. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 1 is a graph showing the drying temperature and the liquid content in one example of the method for producing a polymerizable liquid crystal mixture. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[0025] <Polymerizable liquid crystal mixture> The polymerizable liquid crystal mixture obtained by the method for producing a polymerizable liquid crystal mixture of the present invention has a structure represented by the formula (1):

[0026] [ka]

[0027] Hereinafter, the polymerizable liquid crystal compound represented by formula (1) may be referred to as "polymerizable liquid crystal compound (1)". In formula (1), k11 and k12 each independently represent an integer of 1 or greater, and may be, for example, an integer of 1 to 5. The sum of k11 and k12 is preferably 2 to 6, more preferably 2 to 4. From the viewpoint of excellent liquid crystal properties, k11 and k12 are preferably each independently 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.

[0028] 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 1 to 6. In formula (1), B 11 and B 12 are each independently -CR 1 R 2-, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, and R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. 11 and B 12 are each independently -CO-O-, -O-CO-, -O-CO-O-, or -CO-NR 1 -, -NR 2 -CO-, -CH2-O-, -O-CH2-, -CH2-S-, -S-CH2- or a single bond is preferred, and -O-CO- or -CO-O- is more preferred. 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), a plurality of B 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.

[0029] R 1 and R 2 Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a tert-butyl group, and are preferably alkyl groups having 1 or 2 carbon atoms, and more preferably a methyl group.

[0030] In formula (1), E 11 and E 12 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR1 -, -NR 2 E represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond. 11 and E 12 are each independently preferably -CO-O-, -O-CO-, -O-CO-O-, or -CO-NR 1 -, -NR 2 E is -CO-, -CH2-O-, -O-CH2-, -CH2-S-, -S-CH2- or a single bond, and more preferably -O-CO- or -CO-O-. 11 and E 12 may be the same or different, but are preferably the same group from the viewpoint of ease of production of the polymerizable liquid crystal compound (1).

[0031] 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 substituted with a halogen atom, -R 3 , -OR 3 The -CH2- contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. 11 and G 12 Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms and represented by the formula (g-1) include divalent alicyclic hydrocarbon groups which may contain a heteroatom and are represented by the formulas (g-1) to (g-10), and a 5- or 6-membered alicyclic hydrocarbon group is preferred.

[0032] [ka]

[0033] 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.

[0034] 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 preferred, an alicyclic hydrocarbon group consisting of a 6-membered ring represented by formula (g-1) is even more preferred, a cyclohexane-1,4-diyl group is particularly preferred, and a trans-cyclohexane-1,4-diyl group is especially preferred.

[0035] G 11 and G 12 may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound (1) and productivity. 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.

[0036] A 11 and A 12 Examples of the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms and represented by the formula (g-1) to the formula (g-10) or the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include alicyclic hydrocarbon groups consisting of a 5-membered ring or a 6-membered ring, etc., represented by the formula (g-1) to the formula (g-10) above, and aromatic hydrocarbon groups having about 6 to 20 carbon atoms and represented by the formula (a-1) to the formula (a-8).

[0037] [ka]

[0038] In addition, A 11 and A 12 Some of the hydrogen atoms of the groups exemplified above may be substituted with an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group; an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group; a cyano group; a nitro group; or a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom.

[0039] A 11 and A 12 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group. When k11 and k12 are 1, A 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 there are a plurality of groups, they may be the same or different.

[0040] 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 Alternatively, it may be substituted with a halogen atom, and —CH2— contained in the alkanediyl group may be replaced with —O— or —CO—. 11 and F 12are each independently preferably an alkanediyl group having 3 to 10 carbon atoms, -(CF2)4-, -(CF2)6-, or -(CF2)8-, and more preferably an alkanediyl group having 4 or 6 carbon atoms [-(CH2)4- or -(CH2)6-]. 11 and F 12 may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound (1) and productivity.

[0041] P 11 and P 12 each independently represents a hydrogen atom or a polymerizable group. 11 and P 12 At least one of P is a polymerizable group, 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.

[0042] The polymerizable group may be any reactive group capable of polymerizing the polymerizable liquid crystal compound (1), and specific examples thereof include a vinyl group, a vinyloxy group, a styryl group, a p-(2-phenylethenyl)phenyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a carboxy group, an acetyl group, a hydroxy group, a carbamoyl group, an N-alkylamino group having 1 to 4 carbon atoms, an amino group, an oxiranyl group, an oxetanyl group, a formyl group, an isocyanato group, an isothiocyanato group, etc. The polymerizable group may also 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 they are bonded via an ether bond. 11 and P 12 As the alkyl group, for example, a radically polymerizable group or a cationically polymerizable group suitable for photopolymerization is preferred, and an acryloyloxy group or a methacryloyloxy group is particularly preferred because they are easy to handle and to produce, and an acryloyloxy group is more preferred.

[0043] In formula (1), when there are multiple M's, each independently represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group in which at least two groups selected from the group consisting of divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms are linked via a linking group, and hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are not optionally substituted with halogen atoms, -R 3 , -OR 3 , cyano, or nitro groups.

[0044] When there are multiple M's, each independently is preferably a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group in which two or more groups selected from the group consisting of 1 to 5 divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, 1 to 5 divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and 1 to 5 divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms are linked via a linking group. The linking group is preferably -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 1 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S-, or an imide bond is preferred, and -O-, -CO-O-, or -O-CO- is more preferred. A hydrogen atom contained in a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted with a halogen atom, -R 3 , -OR 3 , and may be substituted with a cyano group or a nitro group.

[0045] The total number of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups contained in a group formed by linking two or more groups selected from the group consisting of 1 to 5 divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, 1 to 5 divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and 1 to 5 divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms via a linking group is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less.

[0046] It is particularly preferred that each M 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 solvents of other polymerizable liquid crystal compounds having a molecular structure similar to that of the polymerizable liquid crystal compound (1), such as the polymerizable liquid crystal compound represented by formula (2) described below, and is excellent in the effect of lowering the phase transition temperature of the polymerizable liquid crystal compound. Because of its excellent 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, which 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. This effect tends to be significantly greater, 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, but is not limited to, the presence of a divalent aromatic group (Ar 11 and / or Ar 12 ) does not have a rigid cyclic structure, the flexibility of the molecule is increased, which is thought to facilitate improvement in solubility and result in a significant decrease in the phase transition temperature.

[0047] 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 multiple Ms are present, they may be the same or different.

[0048] The hydrogen atoms contained in the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may be substituted with 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 having -(Ar 11 -O-CO-M-CO-O)- 11 The divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms does not contain a cyclic structure other than an alicyclic hydrocarbon group or an aromatic hydrocarbon group represented by the formula (1). Examples of substituents that the divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may have include halogen atoms and alkoxyl groups having 1 to 4 carbon atoms. The number of carbon atoms contained in the substituent is not included in the number of carbon atoms contained in the aliphatic hydrocarbon group represented by M in formula (1).

[0049] 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 resulting liquid crystal cured film can exhibit better reverse wavelength dispersion while sufficiently ensuring the effects of lowering the phase transition temperature and improving the solubility of the polymerizable liquid crystal compound. As the divalent aliphatic hydrocarbon group having 2n carbon atoms, an alkanediyl group having 2n carbon atoms is preferred, and specific examples thereof include an n-butanediyl group, an n-hexanediyl group, and an n-octanediyl group.

[0050] 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.

[0051] 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 or 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 count 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 heterocyclic ring, or may contain two or more aromatic hydrocarbon rings. When Ar contains one aromatic hydrocarbon ring or aromatic heterocyclic ring, 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 two or more aromatic hydrocarbon rings or aromatic heterocyclic rings are contained, the group 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-, or -O-.

[0052] Ar 11 and Ar12 may be the same or different, but if they are the same, it is advantageous in terms of ease of industrial production of the polymerizable liquid crystal compound (1) and productivity. 11 If there are multiple Ar 11 may be the same or different, but are preferably the same group. 11 and Ar 12 It is more preferable that all of are the same.

[0053] Ar 11 and Ar 12 Examples of aromatic hydrocarbon rings that can be contained in include a benzene ring, a naphthalene ring, an anthracene ring, etc., 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 in the group, the nitrogen atom preferably has π electrons.

[0054] Among them, Ar 11 and Ar 12 Preferably, Ar has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, more preferably a thiazole ring, a benzothiazole ring, or a benzofuran ring, and even more 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 that constitutes the main chain of the compound represented by formula (1); 11 , M or G 12 may be contained 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 preferable that the entire group is sterically arranged in a direction approximately perpendicular to the molecular orientation direction.

[0055] 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. They are also preferably 36 or less, more preferably 32 or less, even more preferably 30 or less, particularly preferably 26 or less, and especially preferably 24 or less.

[0056] 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).

[0057] [ka]

[0058] In the formulae (Ar-1) to (Ar-5), * represents a bond. In formula (Ar-1), Q 1 is -S-, -O- or -NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. In formulas (Ar-3) and (Ar-4), Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0059] 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.

[0060] In formula (Ar-1), Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group. 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent. Here, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and -CH2- contained in the alkyl group may be substituted with -O-, -CO-, -O-CO- or -CO-O-.

[0061] 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 alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, or -NR 11 R 12 or -SR 11 represents Z 1 and Z 2 may be bonded to each other to form an aromatic ring or a heteroaromatic ring. 11 and R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0062] In formulas (Ar-3) and (Ar-4), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay may be bonded to form a ring.

[0063] 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 an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. In this specification, "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and examples thereof include a fused aromatic hydrocarbon group formed by condensing two or more aromatic rings and an aromatic hydrocarbon group formed by bonding two or more aromatic rings. The term "polycyclic aromatic heterocyclic group" refers to an aromatic heterocyclic group having at least one heteroaromatic ring and at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings, and includes aromatic heterocyclic groups formed by condensing one or more aromatic heterocyclic rings with one or more rings selected from the group consisting of aromatic rings and heteroaromatic rings, and aromatic heterocyclic groups formed by bonding at least one heteroaromatic ring with at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings.

[0064] Examples of the substituent that the aromatic hydrocarbon group or aromatic heterocyclic group may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 4 carbon atoms, an N,N-dialkylamino group having 2 to 8 carbon atoms, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms.

[0065] The groups represented by formulae (Ar-1) to (Ar-4) may be groups described in, for example, JP-A Nos. 2011-207765, 2008-107767, and WO2014 / 010325.

[0066] In formula (Ar-5), Y 3 and Y 4 are each independently represented by the following formula (Y 3 -1):

[0067] [ka]

[0068] The group is selected from groups represented by the following formula: 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

[0069] Substituent X 3represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH2- or two or more non-adjacent -CH2- groups each independently represent -O-, -S-, -CO-, - represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or -B 31 -F 31 -P 31 and B 31 , F 31 and P 31 are B in the formula (1), respectively. 11 , F 11 and P 11 are defined in the same way as B in formula (1), 11 , F 11 and P 11 may be the same as or different from.

[0070] Substituent X 3 is preferably a fluorine atom, a chlorine atom, —CF3, —OCF3 or a cyano group. Y1 is preferably an alkyl group having 1 to 6 carbon atoms that is unsubstituted or substituted with a hydrogen atom or one or more fluorine atoms, and more preferably a hydrogen atom.

[0071] 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 1is an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. 3 may be substituted by

[0072] U 1 In terms of improving wavelength dispersion, U is preferably an organic group having an aromatic heterocycle in which one or more carbon atoms are substituted with a heteroatom. 1 is more preferably an organic group having an aromatic heterocycle that is a condensed ring of a 5-membered ring and a 6-membered ring, since this has good wavelength dispersion and exhibits high birefringence.

[0073] 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 substituted with one or more substituents X 3The alkyl group may be substituted with the cycloalkyl group or cycloalkenyl group. One -CH2- or two or more non-adjacent -CH2- groups in the alkyl group may each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and one -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl group or cycloalkenyl group may each independently be replaced by -O-, -CO-, -COO-, -OCO-, or O-CO-O-. 31 , A 31 , B 32 , F 32 and P 32 are the E in Equation (1), respectively. 11 , A 11 , B 11 , F 11 and P 11 are defined in the same manner as above, and 11 , A 11 , B 11 , F 11 and P 11 may be the same as or different from each other, q represents an integer of 0 to 4, and E 31 and / or A 31 When there are a plurality of, they may be the same or different.

[0074] T 1 -O-, -S-, -N=CU are preferred because of their good birefringence and ease of synthesis. 2 -or- NU 2 - is preferable, and -O-, -S- or -NU is preferable because it is easy to improve wavelength dispersion and birefringence. 2 - is more preferable.

[0075] U 2 is one or more of the substituents X 3and one -CH2- or two or more non-adjacent -CH2- may each independently be replaced by -O-, -CO-, -COO-, -OCO- or -O-CO-O-.

[0076] Among them, U 2 From the viewpoints of birefringence and solvent solubility, it is more preferable that is a linear alkyl group having 1 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and in which one -CH2- or two or more non-adjacent -CH2- groups may each independently be substituted with -O-, -CO-, -COO-, or -OCO-.

[0077] U 1 and U 2 may be bonded to form a ring. In that case, for example, -NU 1 U 2 or -N=CU 1 U 2 Examples of the cyclic group include a cyclic group represented by the following formula: Among the formulae (Ar-1) to (Ar-5), the formulae (Ar-1), (Ar-2) and (Ar-5) are preferred, the formulae (Ar-1) and (Ar-5) are more preferred, and the formula (Ar-1) is even more preferred.

[0078] *-O-CO-G in formula (1) 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 12Specific 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.

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] In one embodiment of the present invention, the polymerizable liquid crystal mixture may contain two or more polymerizable liquid crystal compounds having different l in formula (1). In one embodiment of the present invention, the polymerizable liquid crystal mixture may contain two or more polymerizable liquid crystal compounds having different M in formula (1).

[0089] The polymerizable liquid crystal mixture of the present invention may contain, in addition to the polymerizable liquid crystal compound (1), a polymerizable liquid crystal compound represented by formula (2) (hereinafter also referred to as "polymerizable liquid crystal compound (2)").

[0090] [ka]

[0091] [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 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, and R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

[0092] E 21 and E 22 are each independently -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2represents -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-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 substituted with a halogen atom, -R 3 , -OR 3 , a cyano group, or a nitro group, and —CH— contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—, and R 3 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom; A 21 and A 22 each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, -R 3 , -OR 3 , optionally substituted with a cyano group or a nitro group; F 21 and F 22 each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR 3 or may be substituted by a halogen atom, and —CH2— contained in the alkanediyl group may be replaced by —O— or —CO—; P 21 and P 22 each independently represents a hydrogen atom or a polymerizable group (provided that P 21 and P 22 at least one of which is a polymerizable group; Ar 21 represents a divalent aromatic group which may have a substituent.] By using a combination of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), the phase transition temperature of polymerizable liquid crystal compound (2) can be effectively lowered while suppressing the occurrence of alignment defects. Although the reason for this is unclear, when polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) of the present invention have similar structural units, M in formula (1) is an aliphatic hydrocarbon group, and polymerizable liquid crystal compound (1) has high molecular flexibility, which is thought to enhance their compatibility. This state is believed to significantly lower the phase transition temperature while maintaining the high alignment order of the two polymerizable liquid crystal compounds contained therein. If the phase transition can be performed 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 be less affected by 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 polymerizable liquid crystal compounds (1) and (2)) without impairing the optical properties, the -O-CO-G of polymerizable liquid crystal compound (1) of the present invention is preferred. 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 polymerizable liquid crystal compound (2) 21 -E 21 -(A 21 -B 21 ) k21 -F 21 -P 21 , and -O-CO-G 22 -E 22 -(A 22 -B 22 ) k22 -F 22 -P 22 and preferably have similar structural units to each other.

[0093] In formula (2), k21 and k22 each independently represent an integer of 1 or greater, and may be, for example, an integer of 1 to 5. The sum of k21 and k22 is preferably 2 to 6, more preferably 2 to 4. From the viewpoint of excellent liquid crystal properties, k21 and k22 each independently represent 1 or 2. 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. Furthermore, 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.

[0094] 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), Ar 11 , Ar 12 The same groups as those exemplified as the group represented by the formula (I) can be mentioned, and the same applies to the preferred embodiments thereof.

[0095] A in formula (1) 11 , A 12 , B 11 , B 12 , E11 , 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 and Ar in formula (1) is the same as the group represented by 11 and Ar 12 are each represented by Ar in formula (2). 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 enhanced, and the phase transition temperature is likely to be significantly reduced while suppressing alignment defects.

[0096] The contents of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition containing the polymerizable liquid crystal mixture of the present invention may be appropriately determined within a range that achieves the effects of the present invention, depending on the type of polymerizable liquid crystal compound (1) and / or polymerizable liquid crystal compound (2). However, the ratio of the peak area of ​​polymerizable liquid crystal compound (1) to the total peak area of ​​polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), as measured by liquid chromatography (hereinafter also referred to as "area percentage"), is preferably 0.1% to 70%. It is more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more. When the content of polymerizable liquid crystal compound (1) is equal to or greater than the above-mentioned lower limit, the solubility of the polymerizable liquid crystal compound in solvents is easily improved, and the phase transition temperature is easily reduced. Furthermore, when the content of polymerizable liquid crystal compound (1) is equal to or less than the above-mentioned upper limit, the alignment state of the liquid crystal can be well maintained when preparing a liquid crystal cured film from the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, thereby enabling the production of an optical film with excellent optical properties. When a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1) and / or the polymerizable liquid crystal compound (2) are contained, the area percentage value of the polymerizable liquid crystal compound (1) is calculated based on the total peak area of ​​all the polymerizable liquid crystal compounds (1) and all the polymerizable liquid crystal compounds (2). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, can be measured and calculated by the method described in the examples below.

[0097] The polymerizable liquid crystal composition containing the polymerizable liquid crystal mixture of the present invention contains a combination of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), which can significantly reduce the phase transition temperature compared to when polymerizable liquid crystal compound (2) is used alone. For example, the phase transition temperature of the liquid crystal mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition is preferably 153°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower. Furthermore, when polymerizable liquid crystal compound (1) is used in combination with polymerizable liquid crystal compound (2), the phase transition temperature can be reduced by preferably 8°C or more, more preferably 10°C or more, even more preferably 12°C or more, and particularly preferably 15°C or more compared to when polymerizable liquid crystal compound (2) is used alone.

[0098] In the present invention, the phase transition temperature of the polymerizable liquid crystal compound can be measured by the method described in the Examples below. When two or more polymerizable liquid crystal compounds are contained, the phase transition temperature is measured using a polymerizable liquid crystal compound (mixture) having the same composition as the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition.

[0099] Furthermore, the polymerizable liquid crystal composition containing the polymerizable liquid crystal mixture of the present invention contains a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), and is therefore excellent in the 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.

[0100] <Method for producing polymerizable liquid crystal mixture> The method for producing a polymerizable liquid crystal mixture of the present invention includes a synthesis step of obtaining a polymerizable liquid crystal compound by a coupling reaction in an organic solvent, a crystallization step of precipitating a crystallized substance containing the polymerizable liquid crystal compound, a filtration step of filtering a suspension containing the crystallized substance, and a drying step of drying the filtered crystallized substance.

[0101] In the method for producing a polymerizable liquid crystal mixture of the present invention, the method for synthesizing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) that constitute the polymerizable liquid crystal mixture is not particularly limited, and they 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.) that are described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lectures, etc., depending on their structures.

[0102] 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 esterifying 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 above. 11 , Ar 12 P, F, B, A, E, G and Ar are determined depending on the desired polymerizable liquid crystal compound (1) and the desired polymerizable liquid crystal compound (2).

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] The reaction of the compounds (1-1) to (1-3) is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (some of which are commercially available as water-soluble carbodiimide: WSC), bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bis(trimethylsilyl)carbodiimide), ... carbodiimides such as N,N'-diisopropylcarbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1-(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1 H-Benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxysuccinimide, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate parafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, trichloroacetic acid pentachlorophenyl ester, and the like.

[0107] In terms of reactivity, cost, and the wide range of solvents available, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide, and 2,2'-carbonylbis-1H-imidazole are preferred as condensing agents.

[0108] The polymerizable liquid crystal compound (2) can be produced, for example, by reacting the compound (1-1) with the compound (1-3). In the present invention, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal mixture may be prepared separately and then mixed to form 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.

[0109] The former method allows easy adjustment of the contents of the polymerizable liquid crystal compounds (1) and (2) to the desired ranges, and easy control of the solvent solubility of the polymerizable liquid crystal compounds, while the latter method allows easy synthesis and more efficient production of the polymerizable liquid crystal composition.

[0110] When polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) are prepared as a liquid crystal mixture, the amount of 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, per 100 parts by mass of compound (1-1). The amount of compound (1-3) used in the reaction is preferably 1 to 70 parts by mass, more preferably 10 to 65 parts by mass, per 100 parts by mass of compound (1-1). By adjusting the amounts of compound (1-1), compound (1-2), and compound (1-3) within the above ranges, a liquid crystal mixture containing polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) in the desired ratio can be easily prepared.

[0111] The crystallization step in the method for producing a polymerizable liquid crystal mixture is not particularly limited, and can be carried out by a known method, as long as a crystallized product containing the polymerizable liquid crystal compound (1) or a crystallized product containing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) can be obtained.

[0112] The filtration step in the method for producing a polymerizable liquid crystal mixture is not particularly limited, but for example, suction filtration can be employed. The drying step in the method for producing a polymerizable liquid crystal mixture is carried out under conditions that satisfy formula (A), where T [°C] is the drying temperature when drying the crystallized body, and V [wt%] is the liquid content of the organic solvent contained in the crystallized body immediately before the start of the drying step.

[0113] V<-0.5T+75 and 30≦V (A) The drying device used in the drying step is not particularly limited, and examples thereof include vacuum, heating, and air-blowing dryers, and may be a rotary dryer or a vibration dryer.

[0114] When the structure of the polymerizable liquid crystal compound is complicated, the crystallized substance may easily adhere to the apparatus used in the drying process. 12 and one or more groups represented by Ar 11When drying a crystallized mass containing a polymerizable liquid crystal compound (1) having a group represented by the formula (I), the crystallized mass is likely to adhere to the drying apparatus. Furthermore, when drying a crystallized mass of a polymerizable liquid crystal mixture containing, in addition to the polymerizable liquid crystal compound (1), a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1), such as the polymerizable liquid crystal compound (2), the crystallized mass is more likely to adhere to the drying apparatus. In this regard, a method for producing a polymerizable liquid crystal mixture in which the drying step is performed under conditions satisfying the above formula (A) can reduce adhesion of the crystallized mass to the drying apparatus when drying a crystallized mass containing the polymerizable liquid crystal compound (1). This can prevent a decrease in drying efficiency due to adhesion of the crystallized mass during the drying step. Furthermore, the complicated process of removing the adhered crystallized mass from the apparatus after the drying step can be prevented.

[0115] <Polymerizable liquid crystal composition> The polymerizable liquid crystal composition containing the polymerizable liquid crystal mixture 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). Examples of such polymerizable liquid crystal compounds include those described in Sections 3.2 Nonchiral Rod-Shaped Liquid Crystal Molecules and 3.3 Chiral Rod-Shaped Liquid Crystal Molecules of Chapter 3, Molecular Structure and Liquid Crystallinity, of "Liquid Crystal Handbook" (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), as well as those described in JP 2010-31223 A, JP 2011-207765 A, and Japanese Patent No. 5,962,760 A, which are capable of exhibiting reverse wavelength dispersion when formed into a cured liquid crystal film, and those capable of exhibiting normal wavelength dispersion.

[0116] When the polymerizable liquid crystal composition contains a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, relative to 100 parts by mass of the total of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). In particular, if the content of a liquid crystal compound whose molecular structure is 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 is substantially composed of a polymerizable liquid crystal compound having a structure similar to that of the polymerizable liquid crystal compound (1). Note that 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 by" means that the content of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) is 90 mass % or more of the total mass of the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition. In one aspect of this embodiment, 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).

[0117] The content of the polymerizable liquid crystal compounds in the polymerizable liquid crystal composition (total amount of all polymerizable liquid crystal compounds) is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. A total mass of the polymerizable liquid crystal compounds within the above range is advantageous in terms of the alignment of the resulting cured liquid crystal film. In this specification, the polymerizable liquid crystal composition may contain polymerizable liquid crystal compound (1), polymerizable liquid crystal compound (2), and other polymerizable liquid crystal compounds different from these as a polymerizable liquid crystal mixture. The solid content of the polymerizable liquid crystal composition refers to all components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents.

[0118] In addition to the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), the polymerizable liquid crystal composition may further contain 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.

[0119] The polymerizable liquid crystal composition preferably contains a solvent because it is usually applied to a substrate or the like in a dissolved state in a solvent. The solvent is preferably a solvent capable of dissolving polymerizable liquid crystal compounds such as polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), and is preferably a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound. By containing a combination of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), the polymerizable liquid crystal composition can significantly improve the solvent solubility of polymerizable liquid crystal compound (2) compared to when polymerizable liquid crystal compound (2) is dissolved alone in a solvent. This makes it possible to use a variety of solvents. Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; and amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. Among these, organic solvents are preferred, with alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents being more preferred, and from the viewpoint of productivity, at least one solvent selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and N-methylpyrrolidone being even more preferred.

[0120] The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, per 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content per 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass, more preferably 5 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is reduced, resulting in a generally uniform film thickness and reduced unevenness. The solid content can be appropriately determined taking into account the thickness of the liquid crystal cured film to be produced. The polymerizable liquid crystal composition containing a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) has excellent solubility in solvents, which is advantageous in that the amount of organic solvent used during application and storage can be reduced.

[0121] The polymerizable liquid crystal composition preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that generates reactive species with the aid of light and can initiate a polymerization reaction of the polymerizable liquid crystal or the like. Examples of reactive species include active species such as radicals, cations, or anions. Among these, photopolymerization initiators that generate radicals upon irradiation with light are preferred from the viewpoint of ease of reaction control. As the photopolymerization initiator, only one type may be used, or two or more types may be used in combination.

[0122] Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzil ketal compounds, alkylphenone compounds, acylphosphine oxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts, and sulfonium salts. Specific examples include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 379EG (all manufactured by BASF Japan Ltd.), Seikuol BZ, Seikuol Z, and Seikuol BEE (all manufactured by Seiko Chemical Co., Ltd.), and Kayacure (registered trademark). Examples of suitable anti-aging agents include ADEKA CURE BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Chemical Industries, Ltd.), ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER N-1717, ADEKA OPTOMER N-1919, ADEKA ARCLES NCI-831, ADEKA ARCLES NCI-930 (all manufactured by ADEKA Corporation), TAZ-A, TAZ-PP (all manufactured by Nippon SiberHegner AG), and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

[0123] The polymerizable liquid crystal composition preferably contains at least one type of photopolymerization initiator, and may contain two or more types of photopolymerization initiators. The photopolymerization initiator can fully utilize the energy emitted from the light source and has excellent productivity, so that the maximum absorption wavelength is preferably 300 nm to 400 nm, and more preferably 300 nm to 380 nm, and among these, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

[0124] Examples of α-acetophenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, and more preferably 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. Commercially available α-acetophenone compounds include Irgacure 369, 379EG, and 907 (all manufactured by BASF Japan Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.).

[0125] Oxime photopolymerization initiators generate methyl radicals upon irradiation with light. These methyl radicals facilitate the polymerization of the polymerizable liquid crystal compound deep within the cured liquid crystal film. Furthermore, from the viewpoint of more efficiently promoting the polymerization reaction deep within the cured liquid crystal film, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet light with a wavelength of 350 nm or more. Preferred photopolymerization initiators that can efficiently utilize ultraviolet light with a wavelength of 350 nm or more include triazine compounds and oxime ester carbazole compounds, with oxime ester carbazole compounds being more preferred from the viewpoint of sensitivity. Examples of oxime ester carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime). Commercially available oxime ester carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03 (all manufactured by BASF Japan Ltd.), Adeka Optomer N-1919, and Adeka Arcles NCI-831 (all manufactured by ADEKA Corporation).

[0126] 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.

[0127] The use of a sensitizer can increase the sensitivity of the photopolymerization initiator. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0128] The addition of a polymerization inhibitor can control the polymerization reaction of the polymerizable liquid crystal compound. Examples of polymerization inhibitors include hydroquinones having a substituent such as hydroquinone or alkyl ether; catechols having a substituent such as alkyl ether, such as butylcatechol; pyrogallols, radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines, and β-naphthols. To polymerize the polymerizable liquid crystal compound (1) without disturbing the alignment, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0129] Furthermore, the polymerizable liquid crystal composition may contain a leveling agent, which is an additive that adjusts the fluidity of the polymerizable liquid crystal composition and makes the film obtained by applying the composition flatter, and examples of such leveling agents include silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all manufactured by Momentive Performance Materials) Japan LLC), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Limited), Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all manufactured by DIC Corporation), F-top (trade name) EF301, EF303, Examples of suitable leveling agents include EF351 and EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, and SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830 and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all trade names manufactured by BM Chemie). Among these, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

[0130] The content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound. The content of the leveling agent within the above range is preferred because it is easy to align the polymerizable liquid crystal compound and the resulting liquid crystal cured film tends to be smoother. The polymerizable liquid crystal composition may contain two or more types of leveling agents.

[0131] The polymerizable liquid crystal composition 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 needed, and stirring and mixing them at a predetermined temperature.

[0132] <Retardation film> The polymerizable liquid crystal composition of this embodiment has a low phase transition temperature of the polymerizable liquid crystal compound, allowing a liquid crystal cured film to be produced at a lower processing temperature, thereby reducing the effects of heating and producing a liquid crystal cured film with excellent optical properties. Furthermore, the composition has high solubility in solvents and excellent coatability and film-forming properties, thereby suppressing the occurrence of alignment defects caused by undissolved polymerizable liquid crystal compound or precipitates or deposits in the composition. A retardation film composed of a liquid crystal cured film can fully exhibit the optical properties inherently exhibited by the polymerizable liquid crystal compound used, and can become a retardation film with high optical performance.

[0133] The retardation film can be produced, for example, by a method including the steps of forming a coating film of a polymerizable liquid crystal composition, drying the coating film, and aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal composition, and polymerizing the polymerizable liquid crystal compound by light irradiation while maintaining the aligned state, to form a liquid crystal cured film.

[0134] <Polarizing plate> The retardation film can be used in a polarizing plate (elliptically polarizing plate). A polarizing plate usually includes a retardation film and a polarizing film.

[0135] The polarizing film is a film having a polarizing function, and examples thereof include a stretched film having adsorbed thereon a dye having absorption anisotropy, a film having as a polarizer a film coated with a dye having absorption anisotropy, etc. Examples of the dye having absorption anisotropy include a dichroic dye.

[0136] Polarizers can be used in a variety of display devices, particularly optical displays. A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (e.g., field emission display devices (FEDs) and surface field emission display devices (SEDs)), electronic paper (display devices using electronic ink or electrophoretic elements), plasma display devices, projection display devices (e.g., grating light valve (GLV) display devices and displays having digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal display devices include transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection liquid crystal display devices. These display devices may 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 is suitable for use in organic electroluminescence (EL) display devices and inorganic electroluminescence (EL) display devices. These display devices (optical displays) can exhibit excellent image display characteristics by incorporating the polarizing plate of the present invention, which has excellent optical properties. [Example]

[0137] The present invention will be described in more detail below with reference to the following examples. In the examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified. [HPLC measurement conditions] The HPLC measurement may be carried out under any conditions as long as the peaks derived from each polymerizable liquid crystal compound can be separated. An example of the HPLC measurement conditions is shown below.

[0138] (Example of 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 [Example 1] A mixture (hereinafter referred to as mixture (B)) of a polymerizable liquid crystal compound represented by the following formula (2-1) (hereinafter referred to as "polymerizable liquid crystal compound (2-1)") and a polymerizable liquid crystal compound represented by the following formula (1-1) (hereinafter referred to as "polymerizable liquid crystal compound (1-1)") was synthesized according to the following scheme. The obtained mixture (B) is also referred to as a polymerizable liquid crystal composition.

[0139] [ka]

[0140] A 500 mL four-neck flask equipped with a Dimroth condenser and a thermometer was filled with nitrogen. 17.60 g of compound (E-1), 10.00 g of compound (D-1), 0.80 g of compound (F-1) (Fujifilm Wako Pure Chemical Industries, Ltd.), 0.95 g of compound (F-2), 0.07 g of DMAP (Fujifilm Wako Pure Chemical Industries, Ltd.), 0.20 g of BHT (Fujifilm Wako Pure Chemical Industries, Ltd.), and 464 g of chloroform (Kanto Chemical Co., Ltd.) were added and mixed. 9.61 g of IPC (Fujifilm Wako Pure Chemical Industries, Ltd.) was then added using a dropping funnel, and the mixture was allowed to react at 0 °C overnight. After the reaction, 3.45 g of carboraffin and 3.45 g of Radiolite #900 (registered trademark) (Showa Chemical Industry Co., Ltd.) were added and stirred for 1 hour to obtain a suspension. A filter paper (No. 5A) was placed in a Buchner funnel, and 1.72 g of Radiolite #900 (registered trademark) (Showa Chemical Industry Co., Ltd.), 3.45 g of silica gel, and 1.72 g of Radiolite #900 (registered trademark) (Showa Chemical Industry Co., Ltd.) were layered in this order. The suspension was poured into the Buchner funnel and subjected to suction filtration. After washing twice with 146 g of chloroform (Kanto Chemical Co., Ltd.), the resulting filtrate was concentrated to 220 g using an evaporator. The concentrated solution was transferred to a 1000 mL four-neck flask equipped with a Dimroth condenser and a thermometer and placed under a nitrogen atmosphere. After heating the four-neck flask to 60°C, 524 g of normal heptane (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise over 1.5 hours. After adding 33 g of denatured alcohol (Imazu Pharmaceutical Co., Ltd.), the mixture was kept at room temperature for 1 hour and then cooled to 25°C. A filter paper (No. 5A) was placed in a Buchner funnel, and the resulting suspension was poured into it and suction filtered to obtain a wet cake (filtration step). 10 g of the resulting wet cake was added to a 100 mL flask, which was then attached to an evaporator and immersed in a water bath. While rotating the flask, the temperature of the water bath was raised to 50°C, and the flask was kept at room temperature for 1 hour without reducing the pressure inside the flask. The rotation of the flask was stopped, and the condition of the flask wall was observed to evaluate adhesion.

[0141] [Adhesion evaluation] The state of the flask wall was observed and evaluated according to the following criteria. The results are shown in Table 1. A (Excellent): No wet cake adhesion B (Good): Some wet cake is attached, but can be removed by tapping. C (Unacceptable): Wet cake is attached and does not come off even when tapped. After evaluating the adhesiveness, the flask was rotated while immersed in the water bath, and the pressure inside the flask was reduced to distill off the solvent, yielding a dry cake (drying step). The liquid content V of the wet cake was calculated from the weight of the obtained dry cake and the weight of the wet cake, and was found to be 45 wt%. The temperature of the water bath corresponds to the drying time T in the drying step. The liquid content V corresponds to the liquid content of the organic solvent contained in the crystallized mass immediately before the start of the drying step. Furthermore, when the obtained mixture (B) was analyzed by HPLC, it was found that l in the above formula (1-1) was 1 to 4.

[0142] [Examples 2 to 9 and Comparative Examples 1 to 3] In each of the examples and comparative examples, synthesis and evaluation were carried out in the same manner as in Example 1, except that the drying temperature T and liquid content V were changed to the values ​​shown in Table 1. The results are shown in Table 1.

[0143] The liquid content V was adjusted by the suction filtration time when obtaining the wet cake.

[0144] [Table 1]

[0145] As shown in Table 1, Examples 1 to 9 were evaluated as having better adhesion than Comparative Examples 1 to 3. The better the evaluation of adhesion, the more likely it is that adhesion of crystallized bodies to a drying device will be reduced in the drying step when producing a polymerizable liquid crystal mixture.

[0146] Figure 1 is a graph plotting the results of each example and each comparative example, with the drying temperature T on the horizontal axis and the liquid content V on the vertical axis. Also in Figure 1, the first line L1 (V = -0.5T + 75) is shown as a dashed line, and the second line L2 (V = 30) is shown as a dashed line. Examples 1 to 9 satisfy V < -0.5T + 75 and V ≥ 30.

Claims

1. A method for producing a polymerizable liquid crystal mixture, comprising a drying step of a crystallized product containing a polymerizable liquid crystal compound represented by formula (1) obtained by a coupling reaction in an organic solvent, a drying temperature when drying the crystallized body is T [°C], and a liquid content of the organic solvent contained in the crystallized body immediately before the start of the drying step is V [wt %], the drying step is performed under conditions that satisfy formula (A). V<-0.5T+75 and 30≦V (A) 【Chemistry 1】 [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-, -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. 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-, -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 substituted with -O-, -S- or -NH-. ３ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. 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. 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 may be substituted with a halogen atom, and —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. １１ and P １２ At least one of the groups is a polymerizable group. M each independently represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group in which at least two groups selected from the group consisting of divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms are linked via a linking group, and hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are not optionally substituted with halogen atoms, -R ３ , -OR ３ , cyano, or nitro groups. Ar １１ and Ar １２ each independently represents a divalent aromatic group which may have a substituent.

2. The method for producing a polymerizable liquid crystal mixture according to claim 1 , wherein the crystallized product further contains a polymerizable liquid crystal compound represented by formula (2): 【Chemistry 2】 [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-, -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. １ and R ２ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. E ２１ and E ２２ are each independently -CR １ R ２ -, -CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １ -, -NR ２ -CO-, -O-CH ２ -, -CH ２ —O—, —S—CH ２ -, -CH ２ represents —S— 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 substituted with -O-, -S- or -NH-. ３ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. A ２１ and A ２２ each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group or the aromatic hydrocarbon group is not substituted with a halogen atom, —R ３ , -OR ３ , and may be substituted with a cyano group or a nitro group. F ２１ and F ２２ each independently represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is -OR ３ or may be substituted with a halogen atom, and —CH contained in the alkanediyl group ２ - may be replaced by -O- or -CO-. P ２１ and P ２２ each independently represents a hydrogen atom or a polymerizable group. ２１ and P ２２ At least one of the groups is a polymerizable group. Ar ２１ represents a divalent aromatic group which may have a substituent.

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