Method for producing reactive mixed composition, mixed composition, and method for producing mixed composition

Abstract

The invention relates to a method for producing a reaction mixture composition, a mixture composition, and a method for producing a mixture composition. The present invention addresses the problem of relatively improving the yield of a specific structural isomer for a liquid crystal compound in which a structural isomer is present. The solution of the present invention is a method for producing a reaction mixture composition comprising a step for obtaining a reaction mixture composition containing a compound represented by formula (3) and a compound represented by formula (4) by reacting a compound represented by formula (1) and a compound represented by formula (2) in the presence of a basic compound using an organic solvent having a dielectric constant of 30 or more, in the reaction mixture composition, the value of formula (3) / (formula (3) + formula (4)) is 0.75 or more and less than 0.95, or the value of formula (4) / (formula (3) + formula (4)) is 0.75 or more and less than 0.95, among the area percentage values measured by liquid chromatography of the compound represented by formula (3) and the compound represented by formula (4) in the reaction mixture composition. A-Ar-A (1) HO-Ar-OH (2) A-Ar-OH (3) HO-Ar-A (4)

Description

Technical Field

[0001] This invention relates to a method for manufacturing a reactive mixture, a mixture, and a method for manufacturing a mixture. Background Technology

[0002] Patent Document 1 discloses a liquid crystal compound A-Ar-B obtained by coupling a compound constituting a core portion (Ar) and a compound having a structure that forms side chain portions (A, B). Patent Document 2 also discloses a liquid crystal compound having the same structure.

[0003] Here, when the core compound has an asymmetric structure and the two compounds having structures that form side chains are different from each other, two compounds, as products of the coupling reaction, exist as structural isomers: liquid crystal compounds A-Ar-B and B-Ar-A. It is known that these structural isomers have different solubility and optical properties.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2019 / 160025

[0007] Patent Document 2: Japanese Patent Application Publication No. 2024-30442 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] There is a desire to seek desired properties and utilize a particular one of the structural isomers as described above.

[0010] Methods for solving problems

[0011] This invention includes the following inventions.

[0012] [Invention 1]

[0013] A method for manufacturing a reactive mixture includes the following steps: using an organic solvent with a dielectric constant of 30 or higher, reacting a compound represented by formula (1) with a compound represented by formula (2) in the presence of an alkaline compound to obtain a reactive mixture containing a compound represented by formula (3) and a compound represented by formula (4).

[0014] In the area percentage values ​​determined by liquid chromatography for the compounds represented by formula (3) and formula (4) in the aforementioned reaction mixture, the value of formula (3) / (formula (3)+formula (4)) is 0.75 or more and less than 0.95, or the value of formula (4) / (formula (3)+formula (4)) is 0.75 or more and less than 0.95.

[0015] A-Ar-A(1)

[0016] HO-Ar-OH(2)

[0017] A-Ar-OH(3)

[0018] HO-Ar-A(4)

[0019] A in equations (1), (3), and (4) is represented by the following equation (5):

[0020] *-D 1 -(A 1 -E 1 )m-SP 1 -L 1 (5),

[0021] In equation (5), * indicates the bonding position with Ar in equation (1), equation (3), or equation (4).

[0022] m represents an integer greater than or equal to 1.

[0023] D 1 This represents -C(=O)-O- or -OC(=O)-.

[0024] E 1 This indicates a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linking group formed by a combination of two or more of them, R 1 ~R 5 Each of the following independently represents an alkyl group having 1 to 4 hydrogen atoms, fluorine atoms, or carbon atoms, and when m is an integer of 2 or more, there are multiple E's. 1 They can be the same or different.

[0025] A 1 This indicates that there are multiple A groups, where m is an integer of 2 or more, and the group has 6 or more carbon atoms that can have substituents. 1 They can be the same or different.

[0026] SP 1 This refers to a single bond, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkenyl group having 2 to 20 carbon atoms, a straight-chain or branched ynynyl group having 2 to 20 carbon atoms, or a divalent linking group formed by replacing one or more of the -CH2- groups constituting the aforementioned alkylene group, alkenyl group, or ynynyl group with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent.

[0027] L 1 This indicates a monovalent organic group.

[0028] In formulas (1), (2), (3), and (4), Ar represents any of the groups represented by formulas (Ar-1) to (Ar-6):

[0029] [Chemical Formula 1]

[0030]

[0031] [In formula (Ar-1)~(Ar-6),

[0032] * indicates a relationship with D 1 The bonding part;

[0033] Q 1 Indicates -S-, -O-, or -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents.

[0034] Q 2 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents;

[0035] W 1 and W 2 Each can be represented independently as -O-, -S-, -CO-, -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents;

[0036] Y 1 This refers to alkyl groups having 1 to 6 carbon atoms, aromatic hydrocarbon groups that may have substituents, or aromatic heterocyclic groups.

[0037] Y 2 It represents a CN group or an alkyl group having 1 to 12 carbon atoms that may have substituents, wherein the hydrogen atoms contained in the alkyl group may be replaced by halogen atoms, and the -CH2- contained in the alkyl group may be replaced by -O-, -CO-, -O-CO- or -CO-O-.

[0038] Z1 Z 2 and Z 3 Each of these groups independently represents a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms in the monovalent form, a halogen atom, a cyano group, a nitro group, or -NR. 6 R 7 or -SR 6 Z 1 and Z 2 They can bond with each other to form aromatic rings or aromatic heterocycles, R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms;

[0039] Z 4 This refers to aliphatic hydrocarbon groups or alkoxy groups with 2 to 20 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms in the monovalent form, halogen atoms, cyano groups, nitro groups, and -NR groups. 6 R 7 or -SR 6 R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms;

[0040] Ax represents an organic group having 2 to 30 carbon atoms of 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 that may have substituents, or an organic group having 2 to 30 carbon atoms of at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay can be bonded to form a ring.

[0041] Y 3 and Y 4 Each is independently represented by the following formula (Y) 3 -1) represents the group:

[0042] [Chemical Formula 2]

[0043]

[0044] R Y1 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, which may be substituented by one or more substituents X. 3 Replacement, replacement base X 3This indicates that a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH2- or two or more non-adjacent -CH2- groups can be independently replaced by -O-, -S-, -CO-. A straight-chain or branched alkyl group with 1 to 20 carbon atoms, consisting of -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-, wherein any hydrogen atom in the alkyl group may be replaced by a fluorine atom, or may be -B. 31 -F 31 -P 31 The group represented (where B) 31 Indicates -CR 8 R 9 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 8 -、-NR 8 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, R 8 and R 9 Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms; F 31 This represents an alkane diene with 1 to 12 carbon atoms, where the hydrogen atoms in the alkane diene can be represented by -OR. 10 Or halogen atom substitution, R 10 This refers to an alkyl group having 1 to 4 carbon atoms, where the hydrogen atoms can be replaced by fluorine atoms, and the -CH2- in the alkane diel can be replaced by -O- or -CO-; P 31 (Representing hydrogen atoms or polymeric groups),

[0045] U 1 This refers to an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group, wherein any carbon atom of the aromatic hydrocarbon group can be replaced by a heteroatom, and the aromatic hydrocarbon group can be substituted by one or more of the aforementioned substituents X. 3 replace;

[0046] T 1 This represents -O-, -S-, -COO-, -OCO-, -OCO-O-, and -NU.2 -、-N=CU 2 -、-CO-NU 2 -、-OCO-NU 2 -or-O-NU 2 -, U 2 Representing hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, organic groups having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of which can be replaced by a heteroatom), or (E 31 -A 31 ) q -B 31 -F 31 -P 31 The alkyl, cycloalkyl, cycloalkenyl, and aromatic hydrocarbon groups are either unsubstituted or can be substituted by one or more substituents X. 3 The alkyl group can be substituted by the cycloalkyl or cycloalkenyl group, wherein one -CH2- or two or more non-adjacent -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and one -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl or cycloalkenyl group can be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CO-O-, E 31 Compared with the aforementioned B 31 Similarly defined, A 31 This refers to a divalent alicyclic hydrocarbon group with 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms. The hydrogen atoms contained in this alicyclic hydrocarbon group and the aromatic hydrocarbon group can be halogen atoms, -R... 11 -OR 12 Cyano or nitro substitution, R 11 R represents an alkyl group having 1 to 4 carbon atoms, consisting of hydrogen atoms, fluorine atoms, or carbon atoms. 12 B represents an alkyl group with 1 to 4 carbon atoms, in which the hydrogen atoms can be replaced by fluorine atoms. 31 F 31 and P 31 Each has the same characteristics as the aforementioned B 31 F 31 and P 31 With the same meaning, q represents an integer from 0 to 4, and E 31 and / or A 31In the case of multiple instances, they can be the same or different, U 1 with U 2 They can bond together to form a ring.

[0047] [Invention 2]

[0048] The method for manufacturing the reactive mixture as described in [Invention 1], wherein, based on the total area values ​​of the compounds represented by formula (1), formula (2), formula (3), and formula (4) contained in the aforementioned reactive mixture, the total area percentage values ​​of the compounds represented by formula (3) and formula (4) contained in the aforementioned reactive mixture, as determined by liquid chromatography, are greater than 50% and less than 98%.

[0049] [Invention 3]

[0050] A mixed composition comprising: at least one of the compounds represented by formula (1) and formula (8); the compound represented by formula (7-1); and the compound represented by formula (7-2).

[0051] A-Ar-A(1)

[0052] A-Ar-B(7-1)

[0053] B-Ar-A(7-2)

[0054] B-Ar-B(8)

[0055] In the aforementioned mixed composition, when the sum of the area percentage values ​​of the compound represented by formula (7-1) and the compound represented by formula (7-2) determined by liquid chromatography is set as 100%, the ratio of any one of the structural isomers of the compound represented by formula (7-1) and the compound represented by formula (7-2) contained in the aforementioned mixed composition is greater than 75% and less than 95%.

[0056] A in equations (1), (7-1), and (7-2) is represented by the following equation (5):

[0057] *-D 1 -(A 1 -E 1 )m-SP 1 -L 1 (5),

[0058] In equations (7-1), (7-2), and (8), B is represented by the following equation (6):

[0059] *-D 2 -(A 2-E 2 )n-SP 2 -L 2 (6),

[0060] In equations (5) and (6), * indicates the bonding position with Ar in equations (1), (7-1), (7-2), or (8).

[0061] m and n each independently represent integers greater than 1.

[0062] D 1 and D 2 Each can be represented independently as -C(=O)-O- or -OC(=O)-.

[0063] E 1 and E 2 Each can independently represent a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linking group formed by a combination of two or more of them, R 1 ~R 5 Each of the following independently represents an alkyl group having 1 to 4 hydrogen atoms, fluorine atoms, or carbon atoms, and when m is an integer of 2 or more, there are multiple E's. 1 Each can be the same or different. When n is an integer greater than 2, there exist multiple E. 2 They can be the same or different.

[0064] A 1 and A 2 Each can independently represent a divalent aromatic hydrocarbon group with 6 or more carbon atoms that can have substituents, or a divalent alicyclic hydrocarbon group with 6 or more carbon atoms that can have substituents. When m is an integer of 2 or more, there are multiple A's. 1 Each can be the same or different. When n is an integer greater than 2, there exist multiple A's. 2 They can be the same or different.

[0065] SP 1 and SP 2Each of these groups independently represents a single bond, a straight-chain or branched alkylene group with 1 to 20 carbon atoms, a straight-chain or branched alkenyl group with 2 to 20 carbon atoms, a straight-chain or branched ynynyl group with 2 to 20 carbon atoms, or a divalent linking group formed by replacing one or more of the -CH2- groups constituting the aforementioned alkylene group, alkenyl group, or ynynyl group with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent.

[0066] L 1 and L 2 Each independently represents a monovalent organic group, L 1 and L 2 At least one of them is a polymeric group.

[0067] A and B are different from each other.

[0068] In formulas (1), (7-1), (7-2), and (8), Ar represents any of the groups represented by formulas (Ar-1) to (Ar-6):

[0069] [Chemical Formula 3]

[0070]

[0071] [In formula (Ar-1)~(Ar-6),

[0072] * indicates a relationship with D 1 Or D 2 The bonding part;

[0073] Q 1 Indicates -S-, -O-, or -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents.

[0074] Q 2 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents;

[0075] W 1 and W 2 Each can be represented independently as -O-, -S-, -CO-, -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents;

[0076] Y 1 This refers to alkyl groups having 1 to 6 carbon atoms, aromatic hydrocarbon groups that may have substituents, or aromatic heterocyclic groups.

[0077] Y 2It represents a CN group or an alkyl group having 1 to 12 carbon atoms that may have substituents, wherein the hydrogen atoms contained in the alkyl group may be replaced by halogen atoms, and the -CH2- contained in the alkyl group may be replaced by -O-, -CO-, -O-CO- or -CO-O-.

[0078] Z 1 Z 2 and Z 3 Each of these groups independently represents a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms in the monovalent form, a halogen atom, a cyano group, a nitro group, or -NR. 6 R 7 or -SR 6 Z 1 and Z 2 They can bond with each other to form aromatic rings or aromatic heterocycles, R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms;

[0079] Z 4 This refers to aliphatic hydrocarbon groups or alkoxy groups with 2 to 20 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms in the monovalent form, halogen atoms, cyano groups, nitro groups, and -NR groups. 6 R 7 or -SR 6 R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms;

[0080] Ax represents an organic group having 2 to 30 carbon atoms of 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 that may have substituents, or an organic group having 2 to 30 carbon atoms of at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay can be bonded to form a ring.

[0081] Y 3 and Y 4 Each is independently represented by the following formula (Y) 3 -1) represents the group:

[0082] [Chemical Formula 4]

[0083]

[0084] (Formula (Y 3 In -1),

[0085] R Y1This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, which may be substituented by one or more substituents X. 3 Replacement, replacement base X 3 This refers to a straight-chain or branched alkyl group with 1 to 20 carbon atoms, containing fluorine, chlorine, bromine, iodine, sulfopentafluoride, nitro, cyano, isocyanate, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanate, or one -CH2- or two or more non-adjacent -CH2- groups that can be independently 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 this alkyl group can be replaced by a fluorine atom, or can be -B. 31 -F 31 -P 31 The group represented (where B) 31 Indicates -CR 8 R 9 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 8 -、-NR 8 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, R 8 and R 9 Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms; F 31 This represents an alkane diene with 1 to 12 carbon atoms, where the hydrogen atoms in the alkane diene can be represented by -OR. 10 Or halogen atom substitution, R 10 This refers to an alkyl group having 1 to 4 carbon atoms, where the hydrogen atoms can be replaced by fluorine atoms, and the -CH2- in the alkane diel can be replaced by -O- or -CO-; P 31 (Representing hydrogen atoms or polymeric groups),

[0086] U 1 This refers to an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group, wherein any carbon atom of the aromatic hydrocarbon group can be replaced by a heteroatom, and the aromatic hydrocarbon group can be substituted by one or more of the aforementioned substituents X. 3 replace;

[0087] T1 This represents -O-, -S-, -COO-, -OCO-, -OCO-O-, and -NU. 2 -、-N=CU 2 -、-CO-NU 2 -、-OCO-NU 2 -or-O-NU 2 -, U 2 Representing hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, organic groups having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of which can be replaced by a heteroatom), or (E 31 -A 31 ) q -B 31 -F 31 -P 31 The alkyl, cycloalkyl, cycloalkenyl, and aromatic hydrocarbon groups are either unsubstituted or can be substituted by one or more substituents X. 3 The alkyl group can be substituted by the cycloalkyl or cycloalkenyl group, wherein one -CH2- or two or more non-adjacent -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and one -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl or cycloalkenyl group can be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CO-O-, E 31 Compared with the aforementioned B 31 Similarly defined, A 31 This refers to a divalent alicyclic hydrocarbon group with 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms. The hydrogen atoms contained in this alicyclic hydrocarbon group and the aromatic hydrocarbon group can be halogen atoms, -R... 11 -OR 12 Cyano or nitro substitution, R 11 R represents an alkyl group having 1 to 4 carbon atoms, consisting of hydrogen atoms, fluorine atoms, or carbon atoms. 12 B represents an alkyl group with 1 to 4 carbon atoms, in which the hydrogen atoms can be replaced by fluorine atoms. 31 F 31 and P 31 Each has the same characteristics as the aforementioned B 31 F 31 and P 31With the same meaning, q represents an integer from 0 to 4, and E 31 and / or A 31 In the case of multiple instances, they can be the same or different, U 1 with U 2 They can bond together to form a ring.

[0088] [Invention 4]

[0089] The mixed composition as described in [Invention 3], wherein, based on the total area values ​​of the compounds represented by formula (1), formula (7-1), formula (7-2) and formula (8) contained in the mixed composition, the total area percentage values ​​of the compounds represented by formula (7-1) and formula (7-2) as determined by liquid chromatography are greater than 50% and less than 98%.

[0090] [Invention 5]

[0091] A method for manufacturing a reactive mixture as described in [Invention 1] or [Invention 2], wherein A in formula (5) 1 It is 1,4-cyclohexanediyl or 1,4-phenylenediyl.

[0092] [Invention 6]

[0093] A method for manufacturing a reactive mixture as described in [Invention 1] or [Invention 2], wherein L in formula (5) 1 It is an acryloxy group.

[0094] [Invention 7]

[0095] The mixed composition as described in [Invention 3] or [Invention 4], wherein A in formula (5) 1 and A in equation (6) 2 Each is independently 1,4-cyclohexanediyl or 1,4-phenylenediyl.

[0096] [Invention 8]

[0097] The mixed composition as described in [Invention 3] or [Invention 4], wherein L in formula (5) 1 and L in equation (6) 2 All are acryloyloxy groups.

[0098] [Invention 9]

[0099] A method for manufacturing a mixed composition, comprising the steps of: manufacturing a mixed composition using a reactive mixed composition manufactured by any one of the methods for manufacturing a reactive mixed composition according to [Invention 1], [Invention 2], [Invention 5], and [Invention 6], wherein the method for manufacturing the mixed composition includes the following steps:

[0100] The aforementioned reaction mixture is mixed with the compound represented by formula (9), and the compound represented by formula (3) reacts with the compound represented by formula (9) to generate the compound represented by formula (7-1), and the compound represented by formula (4) reacts with the compound represented by formula (9) to generate the compound represented by formula (7-2), thereby obtaining a mixture containing the compound represented by formula (7-1) and the compound represented by formula (7-2).

[0101] HOOC-(A 2 -E 2 )n-SP 2 -L 2 (9)

[0102] A-Ar-B(7-1)

[0103] B-Ar-A(7-2)

[0104] In equation (9),

[0105] n represents an integer greater than or equal to 1.

[0106] E 2 This indicates a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linking group formed by a combination of two or more of them, R 1 ~R 5 Each of the following can independently represent an alkyl group having 1 to 4 hydrogen atoms, fluorine atoms, or carbon atoms, and when n is an integer greater than 2, there are multiple E's. 2 They can be the same or different.

[0107] A 2 This indicates that there are multiple A groups, either divalent aromatic hydrocarbon groups with 6 or more carbon atoms that can have substituents, or divalent alicyclic hydrocarbon groups with 6 or more carbon atoms that can have substituents, when n is an integer of 2 or more. 2 They can be the same or different.

[0108] SP 2This refers to a single bond, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkenyl group having 2 to 20 carbon atoms, a straight-chain or branched ynynyl group having 2 to 20 carbon atoms, or a divalent linking group formed by replacing one or more of the -CH2- groups constituting the aforementioned alkylene group, alkenyl group, or ynynyl group with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent.

[0109] L 2 Represents a monovalent organic group, wherein L 2 and L in equation (5) 1 At least one of them is a polymeric group.

[0110] In equations (7-1) and (7-2), A and Ar have the same meaning as A and Ar in equation (1) (where * in equations (Ar-1) to (Ar-6) indicates the same meaning as D). 1 Or D 2 (bonding part),

[0111] B is represented by the following equation (6):

[0112] *-D 2 -(A 2 -E 2 )n-SP 2 -L 2 (6),

[0113] In equation (6), * represents the bonding position with Ar in equation (7-1) or equation (7-2), and D 2 This represents -C(=O)-O- or -OC(=O)-.

[0114] A 2 E 2 n, SP 2 and L 2 Represent A in equation (9) respectively 2 E 2 n, SP 2 and L 2 They have the same meaning, but A and B are different from each other.

[0115] Invention Effects

[0116] A mixed composition can be obtained that preferentially contains a specific one of the structural isomers of the polymeric liquid crystal compound. Detailed Implementation

[0117] The embodiments of the present invention will now be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the invention.

[0118] <Mixed Composition>

[0119] The mixed composition of the present invention is a mixed composition of liquid crystal compounds, comprising at least one of the compounds represented by formula (1) (hereinafter also referred to as "compound (1)") and the compounds represented by formula (8) (hereinafter also referred to as "compound (8)"); the compound represented by formula (7-1) (hereinafter also referred to as "compound (7-1)"); and the compound represented by formula (7-2) (hereinafter also referred to as "compound (7-2)"). The mixed composition of the present invention, which includes the compound (7-1) having a left-right asymmetric structure centered on the Ar group in formula (7-1) and the compound (7-2) having a left-right asymmetric structure centered on the Ar group in formula (7-2), the compound (1) having a left-right symmetric structure centered on the Ar group in formula (1), and / or the compound (8) having a left-right symmetric structure centered on the Ar group in formula (8) in a specific amount relationship, has a low phase transition temperature to the liquid crystal phase. As a result, film can be formed without exposure to high temperature conditions, and it is expected to impart higher optical properties to the obtained optical film.

[0120] In the method for manufacturing the mixed composition of the present invention, it is possible to manufacture a mixed composition in which the total area percentage values ​​of the compounds represented by formula (7-1) and formula (7-2), as determined by liquid chromatography, are greater than, for example, 50% and less than 98% based on the total area values ​​of the compounds represented by formula (1), formula (7-1), formula (7-2), and formula (8) contained in the mixed composition. That is, it is possible to manufacture a mixed composition containing more of compounds (7-1) and (7-2) as left-right asymmetric structural isomers. Furthermore, in the method for manufacturing the mixed composition of the present invention, by using an organic solvent with a dielectric constant of 30 or more, it is possible to manufacture a mixed composition that selectively contains more of one of the structural isomers, compounds (7-1) and (7-2). Regarding the mixed composition containing the structural isomers described above, depending on which of the structural isomers is contained more, the optical and mechanical properties of the mixed composition may sometimes change. According to the present invention, it is possible to manufacture a mixed composition having unique optical and mechanical properties achieved by selectively containing a greater proportion of a particular one of the structural isomers described above.

[0121] It should be noted that, in this specification, even if the structure of Ar in formula (1) is asymmetrical, the compound is also said to be left-right symmetrical based on the meaning that the structure represented by A in formula (1) bonded to Ar is the same on both sides with Ar as the center. Similarly, even if the structure of Ar in formula (8) is asymmetrical, the compound is also said to be left-right symmetrical based on the meaning that the structure represented by B in formula (8) bonded to Ar is the same on both sides with Ar as the center.

[0122] The compound (7-1) included in the mixed composition of the present invention has a structure represented by formula (7-1). The compound (7-2) included in the mixed composition of the present invention has a structure represented by formula (7-2).

[0123] A-Ar-B(7-1)

[0124] B-Ar-A(7-2)

[0125] Compound (7-1) has a left-right asymmetric structure, that is, the two side chains bonded to Ar (i.e., A and B in formula (7-1)) are different from each other, with the Ar group in formula (7-1) as the center. Similarly, compound (7-2) has a left-right asymmetric structure, that is, the two side chains bonded to Ar are different from each other, with the Ar group in formula (7-2) as the center. Hereinafter, the Ar group in formulas (7-1) and (7-2) will sometimes be referred to as the core part, and the two side chains bonded to the core part will sometimes be referred to as the mesomorphic unit part. More specifically, A in formulas (7-1) and (7-2) has the structure represented by formula (5):

[0126] *-D 1 -(A 1 -E 1 )m-SP 1 -L 1 (5),

[0127] In equations (7-1) and (7-2), B has the structure represented by equation (6):

[0128] *-D 2 -(A 2 -E 2 )n-SP 2 -L 2 (6),

[0129] Equations (7-1) and (7-2) constitute structures that are asymmetrical in at least one of the side chains of A and B.

[0130] In formulas (5) and (6), m and n each independently represent an integer greater than 1. m and n are preferably integers from 1 to 3, more preferably 1 or 2. In formulas (5) and (6), m and n can be the same or different. In compounds (7-1) and (7-2), the ring structure contained in A in formulas (7-1) and (7-2) (i.e., A in formula (5)) 1 The number of groups (represented), and the ring structures contained in B in formulas (7-1) and (7-2) (i.e., A in formula (6)). 2 The difference in the number of groups (represented) is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. In a preferred embodiment of the invention, either m or n is 1, and the other is 2 or 3. In another, more preferred embodiment, either m or n is 1, and the other is 2. Compounds (7-1) and (7-2) having left-right asymmetric structures can effectively reduce the phase transition temperature in mixed compositions with compounds (1) and / or compounds (8) having highly symmetric structures. This is because compounds with left-right symmetric structures can be regularly arranged, thus tending to have excellent crystallinity, and the phase transition temperature tends to be higher, but this is not necessarily the case. It is believed that when compounds with asymmetric structures are added to compounds with such symmetric structures, the compounds with asymmetric structures affect the ease of arrangement of the compounds, acting in the direction of reducing crystallinity, and thus reducing the phase transition temperature. On the other hand, the higher the proportion of asymmetric compounds relative to symmetric compounds, the more difficult it is to ensure the high orientational order achieved by using symmetric compounds, and there is a tendency for reduced optical properties. Therefore, conventionally, asymmetric compounds have been difficult to become the main components constituting the liquid crystal curing layer (e.g., more than 50% by mass relative to the total mass of the (polymeric) liquid crystal compound constituting the liquid crystal curing film, etc.). Although the mechanism is not clear, the mixed composition of the present invention, which has a high proportion of compounds (7-1) and (7-2) with asymmetric structures, can achieve a significant reduction in phase transition temperature and ensure excellent optical properties that are ideal for optical films such as retardation plates. Furthermore, in one embodiment of the present invention, when a compound with a structure having asymmetric structure in terms of the number of ring structures contained in each side chain of A and B is incorporated, this effect is more pronounced than when a compound with a structure having the same number of ring structures in each side chain but still exhibiting asymmetry (e.g., asymmetry due to differences in the length of alkyl chains, etc.) is incorporated.

[0131] In equations (5) and (6), D 1 and D 2 Each can be represented independently as -C(=O)-O- or -OC(=O)-.

[0132] In equations (5) and (6), E 1 and E 2 Each can independently represent a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linking group formed by a combination of two or more of them, R 1 ~R 5 Each of these groups independently represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, a fluorine atom, or a carbon atom. Examples of divalent linking groups formed by combinations of two or more of these groups include -CO-O-, -O-CO-, -C(=S)O-, -O-CO-O-, and -CR. 1 R 2 -CR 1 R 2 -、-O-CR 1 R 2 -、-CR 1 R 2 -O-CR 1 R 2 -、-CO-O-CR 1 R 2 -、-O-CO-CR 1 R 2 -、-CR 1 R 2 -O-CO-CR 1 R 2 -、-CR 1 R 2 -CO-O-CR 1 R 2 -、-NR 5 -CR 1 R 2 -、and -CO-NR 5 - etc. E 1 and E 2 Each is independently preferred to be a single bond, -O-, -CO-O-, -O-CO-, -O-CO-, -O-CO-O-, or -CO-NR. 5 -, more preferably a single bond, -O-, -CO-O-, or -O-CO-. When m is an integer greater than or equal to 2, there exist multiple E... 1 Each can be the same or different. When n is an integer greater than 2, there exist multiple E. 2 They can be the same or different. When m and n are both integers greater than 2, it is similar to SP. 1 or SP 2bonded E 1 and E 2 Each is preferably a single bond, or -O-, -CO-O-, -O-CO-, -C(=S)O-, -O-CO-O-, *-CR 1 R 2 -O-、*-CR 1 R 2 -O-CO- or -NR 5 -(* indicates that A) 1 Or A 2 (the bonding position), more preferably a single bond, -O-, -CO-O- or -O-CO-.

[0133] In equations (5) and (6), A 1 and A 2 Each can independently represent a divalent aromatic hydrocarbon group with 6 or more carbon atoms that may have substituents, or an alicyclic hydrocarbon group with 6 or more carbon atoms that may have substituents. As for the aforementioned A... 1 and A 2 The aromatic hydrocarbon group represented by the number of carbon atoms is 6 or more. Examples of such aromatic hydrocarbon groups are those with 6 to 20 carbon atoms. Specifically, examples of such aromatic hydrocarbon groups are (a-1) to (a-8) shown below.

[0134] [Chemical Formula 5]

[0135]

[0136] As mentioned above, A 1 and A 2 The alicyclic hydrocarbon group with 6 or more carbon atoms is represented by alicyclic hydrocarbon groups with 6 to 16 carbon atoms, specifically alicyclic hydrocarbon groups represented by (a-9) to (a-11) below.

[0137] [Chemical Formula 6]

[0138]

[0139] Substituents that can be present in the aforementioned aromatic hydrocarbon groups and alicyclic hydrocarbon groups include, for example, alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, and tert-butyl; alkoxy groups with 1 to 4 carbon atoms such as methoxy and ethoxy; fluoroalkyl groups with 1 to 4 carbon atoms such as trifluoromethyl; cyano; nitro; halogen atoms such as fluorine, chlorine, and bromine atoms.

[0140] A 1 and A 2Preferably, it is a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms without substituents, or an alicyclic hydrocarbon group with 6 to 16 carbon atoms without substituents; more preferably, it is 1,4-cyclohexanediyl or 1,4-phenylenediyl. When m is an integer of 2 or more, there are multiple A groups. 1 Each can be the same or different. When n is an integer greater than 2, there exist multiple A's. 2 They can be the same or different.

[0141] In this invention, A 1 and A 2 Each is preferably 1,4-cyclohexanediyl or 1,4-phenylenediyl. Additionally, when m is 1, A... 1 Preferably, it is 1,4-cyclohexanediyl, and when n is 1, A 2 Preferably, it is 1,4-cyclohexanediyl. Furthermore, in one embodiment of the invention, it is related to D... 1 and D 2 bonded A 1 and A 2 Preferably, it is 1,4-cyclohexanediyl or 1,4-phenylenediyl, more preferably 1,4-cyclohexanediyl. Furthermore, in a preferred embodiment of the invention, it is related to D... 1 and D 2 bonded A 1 and A 2 In the case of 1,4-cyclohexanediyl, it is bonded to the A 1 and / or A 2 Adjacent E 1 or E 2 A 1 and / or A 2 It is 1,4-phenylenediyl.

[0142] In equations (5) and (6), SP 1 and SP 2 Each of these independently represents a single bond, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkenyl group having 2 to 20 carbon atoms, a straight-chain or branched alynyl group having 2 to 20 carbon atoms, or a divalent linking group obtained by replacing one or more of the -CH2- groups constituting the aforementioned alkylene group, alkenyl group, and alynyl group with -O-, -S-, -NH-, -N(Q)- (Q is a substituent), or -CO-. As SP 1 and SP 2Examples of linear or branched alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, propylene, butylene, amylene, hexylene, methylhexylene, and heptylene. Examples of linear or branched alkenyl groups having 2 to 20 carbon atoms include vinylene, propenylene, and butenylene. Examples of linear or branched ynylene groups having 2 to 20 carbon atoms include ethynylene.

[0143] SP 1 and SP 2 It can also be a divalent linking group obtained by replacing one or more of the -CH2- groups constituting the aforementioned alkylene, alkenylene, and alkyneyl groups with -O-, -S-, -NH-, -N(Q)-, or -CO-. Examples of substituents represented by Q include those represented by A. 1 and A 2 The aromatic hydrocarbon group or alicyclic hydrocarbon group may have substituents as illustrated by the substituents.

[0144] SP 1 and SP 2 Each of the following is preferably a single bond, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkenyl group having 2 to 20 carbon atoms, or a straight-chain or branched alynyl group having 2 to 20 carbon atoms; more preferably a single bond, a straight-chain or branched alkylene group having 1 to 12 carbon atoms, a straight-chain or branched alkenyl group having 2 to 12 carbon atoms, or a straight-chain or branched alynyl group having 2 to 12 carbon atoms; and even more preferably a single bond or a straight-chain or branched alkylene group having 1 to 12 carbon atoms.

[0145] In equations (5) and (6), L 1 and L 2 Each independently represents a monovalent organic group, L 1 and L 2 At least one of them is a polymerizable group. Examples of the aforementioned monovalent organic groups include alkyl, aryl, and heteroaryl groups. Among them, as L... 1 or L 2 The monovalent organic group represented is preferably an alkyl group, more preferably an alkyl group having 1 to 13 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. The aforementioned alkyl group can be linear, branched, or cyclic, preferably linear.

[0146] As L 1 and L 2The polymerizable group referred to is any group capable of polymerizing compounds (7-1) and (7-2). Specifically, examples include vinyl, p-arbutinyl, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, carboxyl, methyl carbonyl, hydroxyl, amide, alkylamino (1-4 carbon atoms), amino, epoxy, oxetyl, aldehyde, isocyanate, isothiocyanate, etc. Furthermore, the polymerizable group may include groups exemplified above combined with SP. 1 or SP 2 Bonded ether or ester bonds. As L 1 and L 2 The polymerizable group indicated is preferably a free radical polymerizable group or a cationic polymerizable group suitable for photopolymerization. In particular, from the perspective of ease of operation and easy manufacture, it is preferred to be acryloyl, methacryloyl, acryloyloxy or methacryloyloxy. From the perspective of high polymerizability, it is more preferred to be acryloyl or acryloyloxy, and even more preferably acryloyloxy.

[0147] Considering that the reactivity (polymerizability) of compounds (7-1) and (7-2) tends to increase, L is preferred. 1 and L 2 All are polymerizable groups, with L being more preferred. 1 and L 2 Each of the following groups is acryloyl, methacryloyl, acryloyloxy, or methacryloyloxy, with L being more preferred. 1 and L 2 All are acryloyloxy groups.

[0148] As for the structures represented by formula (5) and formula (6), specifically, for example, the structures represented by formulas (R-1) to (R-138) can be cited below. In the formula, * indicates the bonding position to the Ar group, and n can be an integer from 1 to 20, for example. It should be noted that the cyclohexane ring can be trans or cis, but trans is preferred. Compounds (7-1) and (7-2) have an asymmetric structure centered on the Ar group. Therefore, for example, as the structure represented by formula (5) (i.e., A in formulas (7-1) and (7-2), it may have a structure represented by any of the following formulas (R-1) to (R-31) containing one ring structure. As the structure represented by formula (6) (i.e., B in formulas (7-1) and (7-2), it may have a structure represented by any of the following formulas (R-32) to (R-73) containing two ring structures, or a structure represented by any of the following formulas (R-74) to (R-138) containing three ring structures. Alternatively, for example, as the structure represented by formula (5), it may have a structure represented by any of the following formulas (R-32) to (R-73) containing two ring structures. As the structure represented by formula (6), it may have a structure represented by any of the following formulas (R-74) to (R-138) containing three ring structures.

[0149] [Chemical Formula 7]

[0150]

[0151] [Chemical Formula 8]

[0152]

[0153] [Chemical Formula 9]

[0154]

[0155] [Chemical Formula 10]

[0156]

[0157] [Chemical Formula 11]

[0158]

[0159] [Chemical Formula 12]

[0160]

[0161] [Chemical Formula 13]

[0162]

[0163] [Chemical Formula 14]

[0164]

[0165] [Chemical Formula 15]

[0166]

[0167] [Chemical Formula 16]

[0168]

[0169] [Chemical Formula 17]

[0170]

[0171] [Chemical Formula 18]

[0172]

[0173] [Chemical Formula 19]

[0174]

[0175] [Chemical Formula 20]

[0176]

[0177] In addition, the end portions in each of the above structures (for example, equivalent to -SP in equation (5)) 1 -L 1 (a portion thereof) can be a structure having any of the following structures.

[0178] [Chemical Formula 21]

[0179]

[0180] In a preferred embodiment of the present invention, D in formula (5) constituting compounds (7-1) and (7-2) 1 SP 1 and L 1 The structures represented are respectively related to D in formula (6) that constitutes compounds (7-1) and (7-2). 2 SP 2 and L 2 The structures represented are identical. That is, the preferred structure A represented by equation (5) and the structure B represented by equation (6) are identical only in equation (5) in the form of -(A 1 -E 1 The structure represented by )m- is similar to -(A) in equation (6). 2 -E 2The difference in structure is indicated by )n-. When compounds (7-1) and (7-2) have such structures, the molecular structures of compounds (7-1) and (7-2) contained in the liquid crystal mixture are similar or approximate to those of compounds (1) and / or (8), making it easier to effectively reduce the phase transition temperature of the liquid crystal mixture. In addition, in liquid crystal mixtures where the molecular structures of the contained compounds are similar or approximate, there is less influence on each other when aligning the liquid crystal compounds, and they are easier to align with a high degree of orientation order, thus making it easier to further improve the optical properties of the obtained liquid crystal cured film.

[0181] In formulas (5) and (6), the group represents any one of the following formulas (Ar-1) to (Ar-6). Regarding the groups represented by formulas (Ar-1) to (Ar-5), in the polymeric liquid crystal compounds represented by formulas (7-1) and (7-2), a large molecular structure is imparted in the direction intersecting the long axis, resulting in a long absorption wavelength in the short axis direction. Therefore, they generally exhibit reverse wavelength dispersion in the phase difference generated by the oriented liquid crystal molecules. Regarding the groups represented by formula (Ar-6), the phase difference generated by the oriented liquid crystal molecules is more often positive wavelength dispersion.

[0182] [Chemical Formula 22]

[0183]

[0184] The total number of π electrons N contained in the divalent linking group of an aromatic hydrocarbon ring or aromatic heterocycle, as represented by formulas (Ar-1) to (Ar-6). π Preferably, the value is 12 or more, more preferably 16 or more, even more preferably 18 or more, and particularly preferably 20 or more. Furthermore, it is preferably less than 36, more preferably 32 or less, even more preferably 30 or less, and particularly preferably 26 or less.

[0185] In equations (Ar-1) to (Ar-6), * indicates D in equation (5) or equation (6). 1 Or D 2 The bonding part.

[0186] In equation (Ar-1), Q 1 Indicates -S-, -O-, or -NR 6 -, R 6 This represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents. In formulas (Ar-3) and (Ar-4), Q... 2 It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that may have substituents.

[0187] In equation (Ar-2), W 1and W 2 Each can be represented independently as -O-, -S-, -CO-, -NR 6 -, R 6 It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that may have substituents.

[0188] In equation (Ar-1), Y 1 This refers to an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have substituents, or an aromatic heterocyclic group. In formula (Ar-2), Y 2 This indicates a CN group or an alkyl group having 1 to 12 carbon atoms that may have substituents. Here, the hydrogen atoms contained in the alkyl group may be replaced by halogen atoms, and the -CH2- contained in the alkyl group may be replaced by -O-, -CO-, -O-CO-, or -CO-O-.

[0189] In formula (Ar-1)~(Ar-6), Z 1 Z 2 and Z 3 Each of these groups independently represents a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms in the monovalent form, a halogen atom, a cyano group, a nitro group, or -NR. 6 R 7 or -SR 6 Z 1 and Z 2 They can bond with each other to form aromatic rings or aromatic heterocycles. R 6 and R 7 Each can be independently represented as an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0190] In equation (Ar-6), Z 4 This refers to aliphatic hydrocarbon groups or alkoxy groups with 2 to 20 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms in the monovalent form, halogen atoms, cyano groups, nitro groups, and -NR groups. 6 R 7 or -SR 6 R 6 and R 7 Each can be independently represented as an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0191] In formulas (Ar-3) and (Ar-4), Ax represents an organic group having 2 to 30 carbon atoms of at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, and Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have substituents, or an organic group having 2 to 30 carbon atoms of at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Ax and Ay can be bonded to form a ring.

[0192] In equation (Ar-1), Y 1 Preferably, the aromatic hydrocarbon group or aromatic heterocyclic group may have substituents; more preferably, it is an aromatic hydrocarbon group with 6 to 12 carbon atoms or an aromatic heterocyclic group with 3 to 12 carbon atoms that may have substituents. The aromatic hydrocarbon group or aromatic heterocyclic group that may have substituents is preferably a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. In this specification, "polycyclic aromatic hydrocarbon group" refers to an aromatic hydrocarbon group having at least two aromatic rings, including fused aromatic hydrocarbon groups formed by the fusion of two or more aromatic rings and aromatic hydrocarbon groups formed by the bonding of two or more aromatic rings. "Polycyclic aromatic heterocyclic group" refers to an aromatic heterocyclic group having at least one heterocyclic ring and having at least one ring selected from the group consisting of aromatic rings and heterocyclic rings. Examples include aromatic heterocyclic groups formed by fusion of one or more aromatic heterocyclic rings with one or more rings selected from the group consisting of aromatic rings and heterocyclic rings, and aromatic heterocyclic groups formed by bonding at least one heterocyclic ring with at least one ring selected from the group consisting of aromatic rings and heterocyclic rings.

[0193] Examples of substituents that may be present in the aforementioned aromatic hydrocarbon group or aromatic heterocyclic group include halogen atoms, alkyl groups with 1 to 6 carbon atoms, cyano groups, nitro groups, nitroso groups, alkyl sulfinyl groups with 1 to 6 carbon atoms, alkyl sulfonyl groups with 1 to 6 carbon atoms, carboxyl groups, fluoroalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, alkyl thioalkyl groups with 1 to 6 carbon atoms, N-alkylamino groups with 1 to 4 carbon atoms, N,N-dialkylamino groups with 2 to 8 carbon atoms, aminosulfonyl groups, N-alkyl aminosulfonyl groups with 1 to 6 carbon atoms, and N,N-dialkyl aminosulfonyl groups with 2 to 12 carbon atoms.

[0194] The groups represented by formulas (Ar-1) to (Ar-4) can be, for example, the groups described in Japanese Patent Application Publication No. 2011-207765, Japanese Patent Application Publication No. 2008-107767, and International Publication No. 2014 / 010325.

[0195] In formula (Ar-5), Y 3 and Y 4 Each is independently selected from the following formula (Y) 3 -1) represents the group.

[0196] [Chemical Formula 23]

[0197]

[0198] Formula (Y 3 In -1), R Y1 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. This alkyl group may be substituented by one or more substituents X. 3 replace.

[0199] Substitute base X 3 This refers to a straight-chain or branched alkyl group with 1 to 20 carbon atoms, containing fluorine, chlorine, bromine, iodine, sulfopentafluoride, nitro, cyano, isocyanate, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanate, or one -CH2- or two or more non-adjacent -CH2- groups that can be independently 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 this alkyl group can be replaced by a fluorine atom, or can be -B. 31 -F 31 -P 31 The group indicated. B 31 Indicates -CR 8 R 9 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 8 -、-NR 8 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, R 8 and R 9 Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms; F 31 This represents an alkane diene with 1 to 12 carbon atoms, where the hydrogen atoms in the alkane diene can be represented by -OR. 10 Or halogen atom substitution, R 10 This refers to an alkyl group having 1 to 4 carbon atoms, where the hydrogen atoms can be replaced by fluorine atoms, and the -CH2- in the alkane diel can be replaced by -O- or -CO-; P 31 It represents a hydrogen atom or a polymeric group.

[0200] As a replacement for base X 3 Preferably, it is a fluorine atom, a chlorine atom, -CF3, -OCF3, or a cyano group. Y1 Preferably, the alkyl group having 1 to 6 carbon atoms is unsubstituted, or has hydrogen atoms or is substituted by one or more fluorine atoms, and more preferably has hydrogen atoms.

[0201] Formula (Y 3 -1) in, U1 This refers to an organic group with 2 to 30 carbon atoms, containing an aromatic hydrocarbon group. Any carbon atom of this aromatic hydrocarbon group can be replaced by a heteroatom. 1 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. This aromatic hydrocarbon group may be substituted by one or more of the aforementioned substituents X. 3 replace.

[0202] Considering the improved wavelength dispersion, U 1 Preferably, it is an organic group having an aromatic heterocycle in which one or more carbon atoms are replaced by heteroatoms. Considering the good wavelength dispersion and high birefringence resulting from the oriented liquid crystal molecules, U 1 More preferably, it is an organic group having an aromatic heterocyclic ring that is a fused ring of a 5-membered ring and a 6-membered ring.

[0203] Formula (Y 3 In -1), T 1 This represents -O-, -S-, -COO-, -OCO-, -OCO-O-, and -NU. 2 -、-N=CU 2 -、-CO-NU 2 -、-OCO-NU 2 -or-O-NU 2 -, U 2 Representing hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, organic groups having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of which can be replaced by a heteroatom), or (E 31 -A 31 ) q -B 31 -F 31 -P 31 The alkyl, cycloalkyl, cycloalkenyl, and aromatic hydrocarbon groups are either unsubstituted or can be substituted by one or more substituents X. 3The alkyl group can be substituted by the cycloalkyl or cycloalkenyl group. One -CH2- or two or more non-adjacent -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-. Similarly, one -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl or cycloalkenyl group can be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CO-O-. 31 Compared with the aforementioned B 31 Similarly defined, A 31 This refers to a divalent alicyclic hydrocarbon group with 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms. The hydrogen atoms contained in this alicyclic hydrocarbon group and the aromatic hydrocarbon group can be halogen atoms, -R... 11 -OR 12 Cyano or nitro substitution. 11 R represents an alkyl group having 1 to 4 carbon atoms, consisting of hydrogen atoms, fluorine atoms, or carbon atoms. 12 This refers to an alkyl group having 1 to 4 carbon atoms, where the hydrogen atoms can be replaced by fluorine atoms. (B) 31 F 31 and P 31 Each has the same characteristics as the aforementioned B 31 F 31 and P 31 With the same meaning, q represents an integer from 0 to 4. E 31 and / or A 31 When multiple instances exist, they can be the same or different.

[0204] T 1 From the perspective of good birefringence and ease of synthesis, -O-, -S-, and -N=CU are preferred. 2 -or-NU 2 From the perspective of easily improving wavelength dispersion and birefringence in oriented liquid crystal molecules, -O-, -S-, or -NU- are more preferred. 2 -

[0205] U 2 Preferably, it can be substituted by one or more of the aforementioned substituents X. 3The alkyl or alkenyl group having 1 to 20 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, or the cycloalkenyl group having 3 to 12 carbon atoms, or the aforementioned alkyl or alkenyl group that can be replaced by the cycloalkyl, cycloalkenyl or aryl group, and each of the two or more non-adjacent -CH2- can be independently replaced by -O-, -CO-, -COO-, -OCO- or -O-CO-O-.

[0206] Among them, considering birefringence and solvent solubility, U 2 More preferably, the hydrogen atom can be replaced by a fluorine atom and one -CH2- or two or more non-adjacent -CH2- can each be independently replaced by a straight-chain alkyl group having 1 to 20 carbon atoms of -O-, -CO-, -COO- or -OCO-.

[0207] U 1 with U 2 They can be bonded to form a ring. In this case, for example, -NU can be cited. 1 U 2 The cyclic group, or -N=CU, represents a cyclic group. 1 U 2 The cyclic group is represented.

[0208] Among the formulas (Ar-1) to (Ar-6), the group represented by any one of the formulas (Ar-1) to (Ar-5) is preferred, the group represented by any one of the formulas (Ar-1), (Ar-3) and (Ar-4) is more preferred, and the group represented by formula (Ar-1) is even more preferred.

[0209] Compounds (7-1) and (7-2) are generally polymerizable liquid crystal compounds, preferably polymerizable liquid crystal compounds that exhibit so-called reverse wavelength dispersion, obtained by individually orienting and polymerizing compound (7-1) to form a liquid crystal cured film and obtained by individually orienting and polymerizing compound (7-2) to form a liquid crystal cured film.

[0210] The mixed composition of the present invention comprises, in addition to compounds (7-1) and (7-2), at least one of compounds (1) and (8). Compound (1) is a compound having a structure represented by A in formula (7-1) or formula (7-2) constituting compound (7-1) or compound (7-2) on both sides of Ar, which is a symmetrical structure centered on Ar. Similarly, compound (8) is a compound having a structure represented by B in formula (7-1) or formula (7-2) constituting compound (7-1) or compound (7-2) on both sides of Ar, which is a symmetrical structure centered on Ar. Compound (1) and compound (8) are each preferably polymerizable compounds. Compound (1) and compound (8) may each be a liquid crystal compound or a non-liquid crystal compound. However, from the viewpoint of improving optical properties, it is preferable that at least one of compounds (1) and compound (8) included other than compounds (7-1) and (7-2) is a liquid crystal compound. More preferably, all compounds corresponding to compounds (1), (7-1), (7-2), and (8) included in the mixed composition are liquid crystal compounds. Even more preferably, all compounds corresponding to compounds (1), (7-1), (7-2), and (8) are polymeric liquid crystal compounds. The mixed composition of the present invention may include multiple polymeric liquid crystal compounds corresponding to compounds (1), (7-1), (7-2), and / or (8).

[0211] In the mixed composition of the present invention, the total area percentage values ​​of compounds (7-1) and (7-2) determined by liquid chromatography are, for example, greater than 50% and less than 98% based on the total area values ​​of compounds (1), (7-1), (7-2), and (8) contained in the mixed composition. Here, in this specification, "area percentage value" refers to the ratio of the peak area of ​​the target compound to the total peak area of ​​compounds (1), (7-1), (7-2), and (8). If the total area percentage values ​​of compounds (7-1) and (7-2) are greater than 50%, the phase transition temperature of the mixed composition can be sufficiently reduced, and film formation can be performed at a lower processing temperature when producing a liquid crystal curable film. As a result, damage and orientation defects caused by heating at high temperatures can be suppressed, film formation can be performed without reducing the optical properties that the polymeric liquid crystal compound used can originally exhibit, and a liquid crystal curable film with excellent optical properties can be obtained. Compared to symmetrical liquid crystal compounds, asymmetrical liquid crystal compounds may be disadvantageous in terms of wavelength dispersion (especially reverse wavelength dispersion) of the resulting liquid crystal cured film. However, by including asymmetrical compounds (7-1) and (7-2) in a specific balance as described above, comprising more than 50% by area percentage of asymmetrical compounds (7-1) and (7-2), and a smaller amount of symmetrical compounds (1) and / or (8) than compounds (7-1) and (7-2), superior optical properties can be imparted to the liquid crystal cured film obtained by individually orienting and polymerizing symmetrical compounds, which are generally considered to have a stronger tendency to exhibit reverse wavelength dispersion. From the viewpoint of easily further improving such effects, in this invention, the total area percentage of compounds (7-1) and (7-2) is preferably 55% or more, more preferably 60% or more, further preferably 65% ​​or more, particularly preferably 70% or more, and for example, may also be 75% or more. The upper limit of the combined area percentage values ​​of compounds (7-1) and (7-2) may be, for example, 90% or less, or 85% or less. Furthermore, it is particularly preferred that the area percentage value of either compound (7-1) or (7-2) is greater than 50% and less than 98%, and the lower limit of this range may be 55% or more, more preferably 60% or more, further preferably 65% ​​or more, particularly preferably 70% or more, and for example, 75% or more.

[0212] It should be noted that, in the case where the mixed composition of the present invention contains multiple compounds equivalent to compound (1), compound (7-1), compound (7-2), and / or compound (8), the total area percentage value of compound (7-1) and compound (7-2) can be calculated based on the peak area of ​​all compounds (7-1) and all compounds (7-2) relative to the total peak area of ​​all compounds (1), all compounds (7-1), all compounds (7-2), and all compounds (8). The area percentage value can be calculated based on the peak area determined by liquid chromatography, and more specifically, it can be determined and calculated using the methods described in the examples described later.

[0213] The mixed composition of the present invention comprises compounds (7-1) and (7-2), and compounds (1) and / or (8), and the total area percentage of compounds (7-1) and (7-2) is greater than 50%. Therefore, compared to the case of using compounds (1) and (8) alone, which have highly symmetrical structures, and to the case of a mixed composition where the area percentage of compounds with highly symmetrical structures is greater than 50%, the phase transition temperature to the liquid crystal phase can be significantly reduced. For example, regarding the liquid crystal phase transition temperature (nematic phase transition temperature) of compounds (7-1) and (7-2) constituting the mixed composition of the present invention, and the mixed composition of compounds (1) and / or (8), in the case of a liquid crystal mixture from which the liquid crystal cured film exhibits reverse wavelength dispersion, it is preferably 120°C or less, more preferably 115°C or less, and sometimes 110°C or less, and even more preferably 105°C or less. In addition, the phase transition temperature (nematic phase transition temperature) of the mixed composition is generally 25°C or higher, preferably 40°C or higher, and more preferably 50°C or higher.

[0214] In one embodiment of the present invention, the mixed composition of the present invention can reduce the phase transition temperature (nematic phase transition temperature) by preferably 5°C or more, more preferably 10°C or more, further preferably 15°C or more, particularly preferably 20°C or more, compared to the phase transition temperature (nematic phase transition temperature) of compound (1) or compound (8) alone. For example, it can sometimes reduce it by 30°C or more, and even more than 35°C. In addition, compared to a mixed composition that contains both compound (7-1) and compound (7-2) and compound (1) and / or compound (8), but the total area percentage of compound (7-1) and compound (7-2) is 50% or less, the phase transition temperature can be reduced by preferably 5°C or more, more preferably 10°C or more, and for example, it can sometimes reduce it by 15°C or more, and even more than 20°C.

[0215] In this invention, the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), or a thermogravimetric differential calorimeter (TG-DTA). When multiple liquid crystal compounds are included, the aforementioned phase transition temperature refers to the temperature measured using a mixture of the liquid crystal compounds described below, which is obtained by mixing compounds corresponding to compounds (1), (7-1), (7-2), and (8) constituting the mixed composition with all other liquid crystal compounds except those corresponding to compounds (1), (7-1), (7-2), and (8) at the same ratio as the composition in the mixed composition.

[0216] Regarding the mixed composition of the present invention, as long as the total area percentage of compounds (7-1) and (7-2) is greater than 50% and the effects of the present invention can be obtained, liquid crystal compounds other than compounds (1), (7-1), (7-2), and (8) (hereinafter also referred to as "other liquid crystal compounds") may also be included. Examples of such liquid crystal compounds include, for example, compounds described in Chapter 3, Molecular Structure and Liquidity, 3.2 Chiral Rod-shaped Liquid Crystal Molecules, and 3.3 Chiral Rod-shaped Liquid Crystal Molecules of the Liquid Crystal Compendium (edited by the Liquid Crystal Compendium Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2012), compounds described in Japanese Patent Application Publication No. 2010-31223, Japanese Patent Application Publication No. 2011-207765, and Japanese Patent No. 5962760, which exhibit reverse wavelength dispersion when formed into a liquid crystal curable film, and polymeric liquid crystal compounds that exhibit positive wavelength dispersion, etc.

[0217] When the mixed composition of the present invention contains other liquid crystal compounds, the content of the other liquid crystal compounds is preferably 15 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 a total of 100 parts by mass of compounds (1), (7-1), (7-2), and (8). In particular, if the content of liquid crystal compounds with molecular structures that are significantly different from those of compounds (1), (7-1), (7-2), and / or (8) becomes too high, phase separation is likely to occur, which may damage the appearance or make it difficult to ensure high optical properties. Therefore, the liquid crystal compounds constituting the mixed composition of the present invention are preferably composed of liquid crystal compounds having a structure similar to that of compounds (7-1) and (7-2).

[0218] It should be noted that the aforementioned "similar" refers to, for example, having a structure that is partially common to side chain A (i.e., the structure represented by formula (5)), side chain B (i.e., the structure represented by formula (6)), and Ar in compound (7-1). Furthermore, the aforementioned "substantially composed of..." means that, relative to the total mass of the compounds corresponding to compounds (1), (7-1), (7-2), and (8) contained in the mixed composition and all other liquid crystal compounds, the content of the compounds corresponding to compounds (1), (7-1), (7-2), and (8) is 90% by mass or more. In one aspect of the present invention, the mixed composition does not contain any liquid crystal compounds other than those corresponding to compounds (1), (7-1), (7-2), and / or (8).

[0219] The mixed composition of the present invention may consist only of compounds (7-1), (7-2), (1), and / or (8). From the viewpoint of improving reactivity and operability when polymerizing compounds (7-1), (7-2), (1), and / or (8) to obtain a liquid crystal curable film, the mixed composition of the present invention may contain, in addition to compounds (1), (7-1), (7-2), and (8), components such as a photopolymerization initiator, an organic solvent, a polymerization inhibitor, a photosensitizer, and a leveling agent.

[0220] In the case where the mixed composition of the present invention contains other components as described above besides compounds (1), (7-1), (7-2), and (8), the total mass of compounds (1), (7-1), (7-2), and (8) in the mixed composition of the present invention can be, 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 component of the mixed composition. When the total mass of compounds (1), (7-1), (7-2), and (8) is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal curable film. It should be noted that the so-called solid component of the mixed composition refers to the amount of all components obtained after removing volatile components such as organic solvents from the mixed composition.

[0221] The mixed composition of the present invention may contain a polymerization initiator. A polymerization initiator is a compound capable of initiating a polymerization reaction of polymerizable compounds, etc. From the viewpoint that it is independent of the phase state of thermotropic liquid crystals, a photopolymerization initiator that generates active free radicals through the action of light is preferred.

[0222] Photopolymerization initiators can be any compound capable of initiating the polymerization reaction of polymerizable compounds, and known photopolymerization initiators can be used. Specifically, photopolymerization initiators capable of generating active free radicals or acids through the action of light can be used, with photopolymerization initiators that generate free radicals through the action of light being preferred. Photopolymerization initiators can be used alone or in combination of two or more.

[0223] As photopolymerization initiators, known photopolymerization initiators can be used. For example, as photopolymerization initiators that generate active free radicals, self-cracking benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc., can be used. Hydrogen-abstracting compounds such as benzophenone compounds, alkylacetophenone compounds, benzoin ether compounds, benzoin ketal compounds, dibenzocycloheptanone compounds, anthraquinone compounds, xanthonesone compounds, thioxanthonesone compounds, haloacetophenone compounds, dialkoxyacetophenone compounds, halodiimidazole compounds, halotriazine compounds, triazine compounds, etc., can be used. As photopolymerization initiators that generate acids, iodonium salts and sulfonium salts, etc., can be used. Considering the excellent reaction efficiency at low temperatures, self-destructive photopolymerization initiators are preferred, especially acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, and oxime ester compounds.

[0224] The content of the photopolymerization initiator is typically 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 1 to 10 parts by mass, relative to the total amount of polymerizable compounds contained in the mixed composition (100 parts by mass). Within the above range, the reaction of the polymerizable groups proceeds sufficiently and the orientation of the liquid crystal compound is not easily disturbed. It should be noted that, in this specification, "polymerizable compound" refers to a compound having at least one polymerizable group.

[0225] In this invention, the mixed composition is typically applied to a substrate or the like in a state dissolved in an organic solvent, and therefore preferably contains an organic solvent. As an organic solvent, it is preferred to be a solvent capable of dissolving compounds (7-1) and (7-2), as well as compounds (1) and / or compounds (8), and further preferably a solvent that is inactive for the polymerization reaction of these compounds. Examples of organic solvents include methanol, ethanol, ethylene glycol, isopropanol, 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-imidazolinone. These organic solvents can be used alone or in combination of two or more. Among them, alcohol solvents, ester solvents, ketone solvents, chlorinated solvents, amide solvents, and aromatic hydrocarbon solvents are preferred.

[0226] The content of organic solvent in the mixed composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, relative to 100 parts by mass of the mixed composition. Therefore, the solid component preferably accounts for 2 to 50 parts by mass, more preferably 5 to 50 parts by mass, in 100 parts by mass of the mixed composition. If the solid component is 50 parts by mass or less, the viscosity of the mixed composition becomes lower, and therefore the thickness of the film during coating becomes approximately uniform, and the tendency for unevenness is less likely to occur. The above-mentioned solid component can be appropriately determined with consideration of the thickness of the cured film to be manufactured.

[0227] From the viewpoint of stabilizing the polymerization reaction, the mixture may contain a polymerization inhibitor. The extent to which the polymerization reaction of the polymerizable compound proceeds can be controlled using a polymerization inhibitor.

[0228] Examples of the aforementioned polymerization inhibitors include hydroquinone, alkoxylated hydroquinone, alkoxylated catechol (e.g., butylated catechol), pyrogallol, free radical scavengers such as 2,2,6,6-tetramethylpiperidine-1-oxy radical; thiophenols; β-naphthylamines and β-naphthols.

[0229] The amount of inhibitor is typically 0.01 to 10 parts by mass relative to 100 parts by mass of the polymerizable compound, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass. If the content of the polymerization inhibitor is within the above range, polymerization can be carried out without disturbing the orientation of the polymerizable liquid crystal compound.

[0230] The mixture may contain a sensitizer. A photosensitizer is preferred as the sensitizer. Examples of such sensitizers include, for example, xanthonone compounds such as xanthonone and thioxanthonone (e.g., 2,4-diethylthioxanthonone, 2-isopropylthioxanthonone); anthracene compounds such as anthracene and alkoxy-containing anthracene (e.g., dibutoxyanthracene); phenothiazine and rubrene.

[0231] When the mixed composition contains a sensitizer, the polymerization reaction of the polymerizable compounds contained in the mixed composition can be further promoted. The content of the photosensitizer is typically 0.01 to 10 parts by mass relative to 100 parts by mass of the total polymerizable compounds, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.

[0232] The mixture may contain a leveling agent. A leveling agent is an additive that adjusts the flowability of the composition and makes the film obtained by coating the composition smoother. Examples of leveling agents include organic modified silicone oils, polyacrylates, and perfluoroalkyl groups. Polyacrylate leveling agents and perfluoroalkyl groups are preferred.

[0233] The leveling agent content in the mixed 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 polymerizable compound. If the leveling agent content is within the above range, there is a tendency for compounds (7-1) and (7-2) to achieve horizontal orientation, and for the resulting cured film to become smoother. If the leveling agent content exceeds the above range relative to the polymerizable compound, there is a tendency for unevenness to occur in the resulting cured film. It should be noted that the mixed composition may contain two or more leveling agents.

[0234] <Method for manufacturing the mixed composition>

[0235] The mixed composition of the present invention can be prepared by adding additives such as solvents, photopolymerization initiators, polymerization inhibitors, photosensitizers or leveling agents to compounds (7-1) and (7-2), as well as compounds (1) and / or compounds (8) as needed, and stirring and mixing at a specified temperature.

[0236] The compounds (1), (7-1), (7-2), and (8) constituting the mixed composition of the present invention can be manufactured by appropriately combining known organic synthesis reactions (e.g., condensation reactions, esterification reactions, Williamson etherification reactions, Ullmann reactions, Wittig reactions, Schiff base synthesis reactions, benzylation reactions, sage reactions, Suzuki-Miyaura reactions, Negishi reactions, Kumada reactions, Hiyama reactions, Buchwald-Hartwig reactions, Fred-Cleifurc reactions, Heck reactions, aldol condensation reactions, etc.) according to their structures. Specifically, polymerizable liquid crystal compounds can be prepared independently by esterification reactions of alcohol compounds having structures corresponding to the structures of desired compounds (1), (7-1), (7-2), or (8) with carboxylic acid compounds, according to methods for manufacturing polymerizable liquid crystal compounds as described in, for example, Japanese Patent Application Publication No. 2010-31223.

[0237] The mixed composition of the present invention, which contains compounds (7-1) and (7-2) with an area percentage value greater than 50%, can also be prepared by mixing compounds (7-1) and (7-2), which are prepared independently by the method described above, with compounds (1) and / or compounds (8) at a desired ratio in which the area percentage value of compounds (7-1) and (7-2) is greater than 50%. However, the mixed composition of the present invention, which has a combined area percentage value of compounds (7-1) and (7-2) having a left-right asymmetric structure centered on Ar, greater than 50%, can be prepared, for example, by a method comprising reacting compound (1) with a compound represented by formula (2) (hereinafter also referred to as "compound (2)") in the presence of a basic compound to obtain a reaction mixture containing a compound represented by formula (3) (hereinafter also referred to as "compound (3)") and a compound represented by formula (4) (hereinafter also referred to as "compound (4)"), using the aforementioned reaction mixture as an intermediate material.

[0238] HO-Ar-OH(2)

[0239] [In equation (2), Ar has the same meaning as Ar in equation (1) above.]

[0240] A-Ar-OH(3)

[0241] HO-Ar-A(4)

[0242] [In equations (3) and (4), A and Ar have the same meanings as A and Ar in equation (1) above.]

[0243] In the case of preparation by mixing separately prepared compounds (7-1) and (7-2) with compound (1) and / or compound (8), compounds (7-1) and (7-2) need to be temporarily removed. For example, when compounds (7-1) and (7-2) are generated by conventional manufacturing methods as described below, theoretically, they can only be obtained in amounts of less than 50%. Therefore, when removing compounds (7-1) and (7-2) from them, a more cumbersome purification process is required. With the aforementioned method of the present invention, such a cumbersome purification process is not required, and therefore, the desired mixed composition can be manufactured more efficiently. Furthermore, in the case of preparing an alcoholic compound (2) which can constitute the core part of compound (7-1) and compound (7-2) (equivalent to the Ar structure in formula (7-1) and formula (7-2)) by esterification reaction, and bonding it with two or more carboxylic acid compounds having structures that are different from each other and which are the side chain parts (mesocrystalline unit parts) of compound (7-1) and compound (7-2), theoretically it is impossible to obtain a mixed composition in which the total area percentage of compound (7-1) and compound (7-2) is greater than 50%. However, if the aforementioned method includes the step of obtaining a reaction mixture containing compound (3) and compound (4) from compound (1) and compound (2), it is easy, simple and more efficient to prepare a mixed preparation containing compound (7-1) and compound (7-2) in a high proportion of greater than 50%.

[0244] The present invention includes a step (hereinafter also referred to as "step (i)") of reacting a compound represented by formula (1) with a compound represented by formula (2) in the presence of an alkaline compound to obtain a reactive mixture comprising a compound represented by formula (3) and a compound represented by formula (4). Step (i) may also be referred to as a method for manufacturing the reactive mixture.

[0245] In the method for manufacturing the reactive mixture of the present invention, the area percentage values ​​of compounds (3) and (4) in the reactive mixture, determined by liquid chromatography, are such that the value of compound (3) / (compound (3) + compound (4)) is 0.75 or more and less than 0.95, or the value of compound (4) / (compound (3) + compound (4)) is 0.75 or more and less than 0.95. The content of which compound (3) or compound (4) is more abundant in the reactive mixture can be adjusted by the structure of the core portion of compounds (1) and (2) used in step (i) (corresponding to the structure of Ar in formulas (1) and (2)), the reaction conditions in step (i), the solvent used in step (i), the selection of additives, etc. Since a reactive mixture containing a greater proportion of either compound (3) or compound (4) can be obtained, as described later, a mixture containing a specific one of the structural isomers of compound (7-1) and compound (7-2) can be manufactured.

[0246] In the method for manufacturing the reactive mixture, for example, the compound represented by formula (3) and the compound represented by formula (4) are included, wherein, based on the total area values ​​of the compound represented by formula (1), the compound represented by formula (2), the compound represented by formula (3) and the compound represented by formula (4) included in the reactive mixture, the total area percentage values ​​of the compound represented by formula (3) and the compound represented by formula (4) in the aforementioned reactive mixture, as determined by liquid chromatography, are greater than 50% and less than 98%.

[0247] Provide a detailed description of process (i).

[0248] A-Ar-A(1)

[0249] HO-Ar-OH(2)

[0250] A-Ar-OH(3)

[0251] HO-Ar-A(4)

[0252] In formulas (1), (2), (3) and (4), A and Ar respectively represent the same meaning as A and Ar in formula (1) above, and can be determined based on the structure of the final desired compound (7-1) and compound (7-2).

[0253] Compound (1) can be synthesized or bonded by appropriately combining known organic synthesis reactions according to its structure. Specifically, it can be prepared from a compound having a structure corresponding to that of the desired compound (1) by means of a method described, for example, in Japanese Patent Application Publication No. 2010-31223.

[0254] Regarding compound (2) as an alcohol compound, it is a compound having two hydroxyl groups bonded to Ar corresponding to the Ar group in the desired compounds (3) and (4).

[0255] In step (i), the reaction of compound (1) with compound (2) takes place in the presence of a basic compound. Although not necessarily limited to the following reaction, it is inferred that in the presence of a basic compound, the hydrogen atom of the hydroxyl group (-OH) of compound (2) bonded to Ar is abstracted, thereby changing to a transition state, and one molecule of OH-Ar-O - Nucleophilic attack on one molecule of compound (1) is performed based on a side chain A [i.e., *-D] bonded to Ar in compound (1). 1 -(A 1 -E 1 )m-SP 1 -L 1 〕of (for -OCO- or -COO-)D 1 A nucleophilic substitution reaction occurs due to the relationship between the two molecules, resulting in two molecules of compound (3). It is inferred that the hydrogen atom of a hydroxyl group (-OH) bonded to Ar in compound (2) is abstracted, thus entering a transition state. One molecule of -O-Ar-OH performs a nucleophilic attack on one molecule of compound (1), based on the side chain A (i.e., *-D) bonded to Ar in compound (1). 1 -(A 1 -E 1 )m-SP 1 -L 1 〕of (for -OCO- or -COO-)D 1 The nucleophilic substitution reaction occurs due to the relationship between the two molecules, thereby generating a compound with 2 molecules (4).

[0256] Through the aforementioned reaction, two molecules of compound (3), two molecules of compound (4), or one molecule of compound (3) and one molecule of compound (4) can be obtained from one molecule of compound (1) which is left-right symmetrical. Compound (3) and compound (4) are suitable as intermediates for the manufacture of compounds (7-1) and (7-2). By reacting a reaction mixture containing compounds (3) and (4) with a compound having a structure corresponding to a side chain B that is different from the side chain A structure in compound (1), the mixed composition of the present invention containing compounds (7-1) and (7-2) having left-right asymmetric structures can be easily and efficiently manufactured with an area percentage value greater than 50%.

[0257] In step (i), the basic compound can be any basic compound that can abstract hydrogen from a hydroxyl group of compound (2) bonded to Ar, thereby initiating the above-mentioned nucleophilic substitution reaction between compound (1) and compound (2). It can be appropriately selected and used from known basic compounds. The basic compound can be an inorganic basic compound or an organic basic compound. Only one type can be used, or two or more types can be used in combination. From the viewpoint of being able to carry out the reaction between compound (1) and compound (2) more efficiently and to easily obtain a reaction mixture composition containing compound (3) and compound (4) in a high proportion, the basic compound in step (i) is preferably a basic compound with a dissociation constant (pKa) of 7 or more.

[0258] The dissociation constant (pKa), also known as the acid dissociation constant, is obtained by expressing the equilibrium constant Ka in a dissociation reaction that releases hydrogen ions from an acid using a negative common logarithm. The dissociation constant of a base is the dissociation constant of its conjugate acid (acid dissociation constant). It should be noted that, in this specification, the dissociation constant of basic compounds can be determined using the pH characteristic solubility method.

[0259] The pKa of the basic compound used in step (i) is preferably 7.5 or higher, more preferably 8 or higher, and even more preferably 9 or higher. There is no particular upper limit, but it is usually 17 or lower, preferably 15 or lower, and more preferably 13.5 or lower. If the pKa of the basic compound is within the above range, the reaction between compound (1) and compound (2) can be carried out easily and efficiently, and a reaction mixture composition containing compound (3) and compound (4) in a high proportion can be easily obtained.

[0260] Specifically, examples of the basic compound used in step (i) include N,N-dimethylaminopyridine (pKa: 9.7), diazabicycloundecene (pKa: 13.5), triethanolamine (pKa: 10.75), N-methylmorpholine (pKa: 7.38), 1,4-diazabicyclo[2.2.2]octane (pKa: 8.7), N,N-diisopropylethylamine (pKa: 10.98), and potassium tert-butoxide (pKa: 17). Among these, N,N-dimethylaminopyridine, diazabicycloundecene, and triethanolamine are preferred, and N,N-dimethylaminopyridine and diazabicycloundecene are more preferred.

[0261] The amount of alkaline compound used in step (i) can be appropriately determined based on the type of alkaline compound used and the desired ratio of compound (3) and compound (4) in the reaction mixture. For example, relative to 1 mole of compound (2), it is preferably 0.01 moles or more, more preferably 0.05 moles or more, even more preferably 0.1 moles or more, and preferably 10 moles or less, more preferably 5 moles or less, even more preferably 3 moles or less, and particularly preferably 1 mole or less. If the amount of alkaline compound is within the above range, the reaction between compound (1) and compound (2) can be carried out efficiently, and a reaction mixture containing compound (3) and compound (4) in a high proportion can be easily obtained. It should be noted that when multiple alkaline compounds are contained, it is preferable that the total content of alkaline compounds with a pKa of 7 or more is within the above range.

[0262] In step (i), the reaction between compound (1) and compound (2) is carried out in the presence of an organic solvent with a dielectric constant of 30 or higher. The solvent used in step (i) only needs to have a dielectric constant of 30 or higher, and can be the same as or different from the organic solvent constituting the mixed composition of the present invention. Examples of organic solvents with a dielectric constant of 30 or higher include N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethyl sulfoxide, sulfolane, and acetonitrile. From the viewpoint of the solubility of compound (1), compound (2), the generated compound (3), and compound (4), N-methyl-2-pyrrolidone (NMP) and dimethylacetamide (DMAc) are preferred as the solvent used in step (i). The above solvents can be used alone or in combination.

[0263] The amount of solvent used is not particularly limited. In order to fully dissolve each compound and enable efficient reaction, for example, it is 1 part by mass or more relative to 1 part by mass of compound (1), preferably 1.2 parts by mass or more. In order to avoid using excessive solvent, it is usually 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 20 parts by mass or less.

[0264] In the reaction of compound (1) and compound (2), additives may be used as needed. For example, to prevent polymerization, the reaction may be carried out in the presence of a polymerization inhibitor. Examples of polymerization inhibitors include 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylenebis(6-tert-butyl-p-cresol), triphenyl phosphite, tri(nonylphenyl) phosphite, phenothiazine, etc. When using a polymerization inhibitor, the amount added relative to 1 mole of compound (1) is preferably 0.01 moles or more, more preferably 0.05 moles or more, and preferably 1.0 molar equivalent or less.

[0265] The reaction between compound (1) and compound (2) can be carried out in a mixture of compound (1), compound (2) and basic compound, solvent and additives as needed.

[0266] The conditions in the aforementioned reactions can be appropriately determined based on the types of compounds used, the scale of the reaction, etc.

[0267] In one embodiment of the manufacturing method of the present invention, the reaction temperature of compound (1) and compound (2) is preferably 0°C to 80°C, more preferably 20°C to 60°C. If the reaction temperature is within the aforementioned range, the reaction of compound (1) and compound (2) is easily carried out, and the target compound is easily and more safely obtained under mild conditions.

[0268] The reaction time is determined based on the type of compound used, the proportion of compounds, and the reaction temperature. While it also depends on the scale of the reaction, it is preferably 10 minutes to 48 hours, and more preferably 10 minutes to 24 hours. In this invention, the reaction time of compound (1) and compound (2) begins at the point when compound (1), compound (2), and the basic compound begin to coexist, and ends at the point when the reaction of compound (1) and compound (2) stops / ends. The extent of the reaction can be confirmed by analytical methods such as high-performance liquid chromatography, thin-layer chromatography, and gas chromatography.

[0269] The structure of the obtained compound can be identified by NMR spectroscopy, IR spectroscopy, mass spectrometry, elemental analysis, etc.

[0270] The sum of the area percentage values ​​of compounds (3) and (4) in the reactive mixture containing compounds (3) and (4) obtained in step (i) is preferably greater than 50% and less than 98% based on the sum of the area values ​​of compounds (1), (2), (3), and (4) contained in the reactive mixture. If compounds (3) and (4) are contained in the reactive mixture in an amount greater than 50% based on the sum of their area percentage values, the reactive mixture can be used as an intermediate material to obtain the mixed composition of the present invention containing compounds (7-1) and (7-2) in an amount greater than 50% based on their area percentage values. By controlling the reaction of compound (1) and compound (2) in step (i), in addition to adjusting the amount of compound (3) and compound (4) in the resulting reaction mixture, the amounts of compound (1) and compound (2) are also pre-adjusted, thereby enabling the mixture composition of the present invention, which simultaneously contains high proportions of compound (7-1) and compound (7-2) and the necessary amount of compound (1) and / or compound (8), to be obtained via step (ii) described later. The amount of compound (3) and compound (4) contained in the reaction mixture composition can be appropriately determined according to the proportion of compound (7-1) and compound (7-2) in the mixture composition of the present invention containing the ultimately desired compound (7-1) and compound (7-2), for example, it can be 55% or more, 60% or more, 65% or more, or 70% or more, for example, it can be 90% or less or 85% or less. Furthermore, for example, the area percentage value of either compound (3) or compound (4) can be greater than 50% and less than 98%, and the lower limit of this range can be 55% or more, more preferably 60% or more, further preferably 65% ​​or more, particularly preferably 70% or more, and for example, 75% or more. For example, in a reactive mixture that can be used as an intermediate in a mixed composition in which the total area percentage value of compounds (7-1) and (7-2) is 75%, the content of compounds (3) and (4) is preferably 75% or more based on the total area percentage value. A reactive mixture containing compounds (3) and (4) in such a proportion is suitable as an intermediate material for obtaining the mixed composition of the present invention with a low phase transition temperature. It should be noted that the area percentage value can be calculated based on the peak area determined by liquid chromatography, as previously described in the mixed composition of the present invention.

[0271] The reaction mixture containing compounds (3) and (4) obtained by step (i) is mixed with a compound represented by formula (9) (hereinafter also referred to as "compound (9)"), so that compounds (3) and (4) react with compound (9) (hereinafter also referred to as "step (ii)"), thereby enabling the production of the mixture composition of the present invention containing compounds (7-1) and (7-2).

[0272] HOOC-(A 2 -E 2 )n-SP 2 -L 2 (9)

[0273] Processes (i) and (ii) can be performed continuously, or, for example, after temporarily storing the reaction mixture obtained in process (i), process (ii) can be performed discontinuously (intermittently). When processes (i) and (ii) are performed continuously, there is no need for operations such as purification or removal; therefore, this is preferable from the viewpoint of manufacturing efficiency and workability. Furthermore, when processes (i) and (ii) are performed discontinuously, for example, the amount of impurities generated in process (i) that can be carried into process (ii) can be reduced; therefore, this is preferable from the viewpoint of obtaining products with high purity.

[0274] A in equation (9) 2 E 2 n, SP 2 and L 2 They respectively represent A in the above formula (6) 2 E 2 n, SP 2 and L 2 The same meaning can be determined based on the structures of the final desired compounds (7-1) and (7-2).

[0275] Compound (9) can be synthesized or bonded by appropriately combining known organic synthesis reactions according to its structure. Specifically, it can be prepared from a compound having a structure corresponding to that of the desired compound (9) by means of a method described, for example, in Japanese Patent Application Publication No. 2010-31223.

[0276] The reaction of compound (3) and compound (4) with compound (9) in the reaction mixture is an esterification reaction, preferably carried out in the presence of a condensing agent. By carrying out the esterification reaction in the presence of a condensing agent, the esterification reaction can be carried out efficiently and rapidly.

[0277] Examples of condensing agents used in step (ii) include, for example, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide methyl p-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis(2,6) Carbodiimide compounds such as diisopropylphenyl)carbodiimide and bis(trimethylsilyl)carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazolium, 1,1'-oxodiimidazolium, diphenyl azidophosphate, 1-(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinylphosphonium hexafluorophosphate, 1H-benzotriazolium Azoxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimino)ureon tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-benzyloxycarbonylsuccinimide, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethylureon tetrafluoroborate, O-(6-chlorobenzotriazolium) (-1-yl)-N,N,N',N'-tetramethylureon hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolineon chloride, 2-chloro-1,3-dimethylimidazolineon hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium p-toluenesulfonate, 2-fluoro-1-methylpyridinium p-toluenesulfonate, and pentachlorophenyl trichloroacetate, etc. From the viewpoints of reactivity, cost, and available solvents, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, diisopropylcarbodiimide, and 2,2'-carbonylbis-1H-imidazole are preferred as condensing agents.

[0278] The amount of condensing agent used in the esterification reaction of compounds (3) and (4) with compound (9) can be appropriately determined according to the types of compounds (3), (4), and (9), the type of condensing agent, etc. For example, it is usually 1.0 to 1.5 moles relative to 1 mole of the mixture of compounds (3) and (4).

[0279] Furthermore, the aforementioned esterification reaction can be carried out in the presence of a catalyst. Examples of catalysts include N,N-dimethylaminopyridine, N,N-dimethylaniline, and dimethyltrimethylammonium pentafluorobenzenesulfonic acid. For example, the amount of catalyst used is preferably 0.01 to 0.5 moles relative to 1 mole of the mixture of compounds (3) and (4).

[0280] The esterification reactions of compounds (3) and (4) with compound (9) in step (ii) are typically carried out in a solvent. The solvent may be the same as or different from the solvent used in step (i). From the viewpoint of reaction yield and productivity, the solvent in step (ii) is preferably a nonpolar organic solvent such as pentane, hexane, heptane, toluene, xylene, benzene, chlorobenzene, chloroform, or dichloromethane. These solvents may be used alone or in combination.

[0281] Regarding the amount of compound (9) used, from the viewpoint that the desired amount of compounds (7-1) and (7-2) can be obtained in good yield, it is preferably 0.5 to 2.5 moles, more preferably 0.75 to 2.0 moles, and even more preferably 1.0 to 1.3 moles, relative to 1 mole of the mixture of compounds (3) and (4).

[0282] The amount of solvent used is not particularly limited, but is preferably 1 to 100 parts by mass relative to the total of 1 part by mass of compound (3) and compound (4) and compound (9), more preferably 5 to 70 parts by mass, and even more preferably 10 to 50 parts by mass.

[0283] From the viewpoint of reaction yield and productivity, the temperature of the esterification reaction in step (ii) is preferably -20 to 120°C, more preferably -20 to 60°C, and even more preferably -10 to 20°C. Furthermore, from the viewpoint of reaction yield and productivity, the reaction time is preferably 1 minute to 72 hours, more preferably 1 to 48 hours, and even more preferably 1 to 24 hours. In this invention, the reaction time of compounds (3) and (4) with compound (9) is defined as the starting point when compounds (3) and (4) begin to coexist with compound (9), and as the ending point when the reaction of compounds (3) and (4) with compound (9) stops / ends. The extent of the reaction can be confirmed by analytical methods such as high-performance liquid chromatography, thin-layer chromatography, and gas chromatography.

[0284] The structure of the obtained compound can be identified by NMR spectroscopy, IR spectroscopy, mass spectrometry, elemental analysis, etc. After the reaction is completed, as needed, post-treatments such as filtration, neutralization, extraction, and washing, separation treatments such as distillation and crystallization, and other processes applicable in organic synthesis chemistry can be performed to obtain the mixed composition of the present invention containing compounds (7-1) and (7-2) in the form of a mixture of liquid crystal compounds. The product obtained by adding the necessary components such as organic solvents and photopolymerization initiators as previously described to the mixed composition obtained in this way can be used as a mixed composition for forming a phase difference film.

[0285] In the method for manufacturing the mixed composition of the present invention, by adjusting the amount of compound (9) used in step (ii), the total amount of compound (3) contained in the mixed composition can react with compound (9). Similarly, the total amount of compound (4) contained in the mixed composition can react with compound (9). In the case where the total amounts of compound (3) and compound (4) react with compound (9), in the method for manufacturing the mixed composition of the present invention, for example, in the area percentage values ​​of compounds (7-1) and (7-2) in the mixed composition determined by liquid chromatography, the value of compound (7-1) / (compound (7-1) + compound (7-2)) is 0.75 or more and less than 0.95, or the value of compound (7-2) / (compound (7-1) + compound (7-2)) is 0.75 or more and less than 0.95.

[0286] That is, in the mixed composition of the present invention, when the sum of the area percentage values ​​of compound (7-1) determined by liquid chromatography and compound (7-2) determined by liquid chromatography is set as 100%, the ratio of any one of the structural isomers of compound (7-1) and compound (7-2) contained in the aforementioned mixed composition is greater than 75% and less than 95%. Thus, according to the method for manufacturing the mixed composition of the present invention, it is possible to manufacture a mixed composition that preferentially contains a greater proportion of a specific one of the structural isomers of compound (7-1) and compound (7-2). The ratio of any one of the structural isomers of compound (7-1) and compound (7-2) is preferably 80% or more. The upper limit of the ratio of any one of the structural isomers of compound (7-1) and compound (7-2) may, for example, be 90% or less, or 85% or less.

[0287] In the method for manufacturing the mixed composition of the present invention, the following steps (ib) and (ii-b) may be performed instead of the above steps (i) and (ii).

[0288] Step (ib) is the same as step (i) except that the compound represented by formula (8) is used instead of the compound represented by formula (1). That is, step (ib) is the following step: using an organic solvent with a dielectric constant of 30 or higher, the compound represented by formula (8) is reacted with the compound represented by formula (2) in the presence of a basic compound.

[0289] In step (ib), the compound represented by formula (8) is reacted with the compound represented by formula (2) to obtain a reaction mixture comprising the compound represented by formula (3-b) and the compound represented by formula (4-b).

[0290] B-Ar-OH (3-b)

[0291] HO-Ar-B (4-b)

[0292] [In equations (3-b) and (4-b), Ar and B have the same meanings as described above.]

[0293] In step (ib), the area percentage values ​​of the compounds represented by formula (3-b) and formula (4-b) in the aforementioned reaction mixture, as determined by liquid chromatography, are such that the value of formula (3-b) / (formula (3-b) + formula (4-b)) is 0.75 or more and less than 0.95, or the value of formula (4-b) / (formula (3-b) + formula (4-b)) is 0.75 or more and less than 0.95.

[0294] In step (ii-b), the compound represented by formula (3-b) is used instead of the compound represented by formula (3), the compound represented by formula (4-b) is used instead of the compound represented by formula (4), and the compound represented by formula (10) is used instead of the compound represented by formula (9). Otherwise, it is common to step (ii). That is, step (ii-b) is the following step: reacting the compound represented by formula (3-b) with the compound represented by formula (10) to generate the compound represented by formula (7-2), and reacting the compound represented by formula (4-b) with the compound represented by formula (10) to generate the compound represented by formula (7-1), thereby obtaining a mixed composition comprising the compound represented by formula (7-1) and the compound represented by formula (7-2). The mixed composition obtained by performing step (ii-b) may contain at least one of the compounds represented by formula (1) and formula (8) in addition to the compounds represented by formula (7-1) and formula (7-2).

[0295] HOOC-(A 1 -E 1 )m-SP 1 -L 1 (10)

[0296] [In equation (10), all symbols represent the same meanings as above.]

[0297] Similar to the cases of performing steps (i) and (ii) above, steps (ib) and (ii-b) can be performed continuously or discontinuously.

[0298] It should be noted that the above steps (ib) and (ii-b) can also be described as the same as replacing the structures represented by A and B in the compounds of steps (i) and (ii). Alternatively, step (ib) can also be described as the same as replacing the structure represented by A in the compounds of step (i) with the structure represented by B in the compounds of step (ii).

[0299] <Phase difference film>

[0300] The phase transition temperature of the hybrid composition of the present invention is low. Therefore, by using the hybrid composition of the present invention, film formation can be performed at low temperatures without reducing the optical properties that the liquid crystal compound can originally exhibit, and a liquid crystal cured film with excellent optical properties can be easily obtained. Therefore, the present invention also relates to a retardation film comprising a liquid crystal cured film, which is a cured product of the hybrid composition of the present invention, and is formed by curing the liquid crystal compound in the hybrid composition in an oriented state. The retardation film composed of the cured product of the aforementioned hybrid composition can fully exhibit the optical properties that the liquid crystal compound used can originally exhibit, and can become a retardation film with high optical performance.

[0301] The liquid crystal curable film constituting the phase retardation film of the present invention can be composed of homopolymers of compounds (7-1) and (7-2) in an oriented state, and homopolymers of compounds (1) and / or (8). Alternatively, it can be composed of copolymers in an oriented state of a mixture of compounds (7-1), (7-2), and (1) and / or (8). In order to facilitate polymerization and obtain a uniform liquid crystal curable film, the liquid crystal curable film constituting the phase retardation film of the present invention is preferably composed of copolymers in an oriented state of a mixture of compounds (7-1), (7-2), and (1) and / or (8).

[0302] In one embodiment of the invention, the phase retardation film of the invention is preferably a cured product of the mixed composition of the invention, and satisfies the optical properties represented by the following formulas (a), (b) and (c). Such a liquid crystal cured film is typically a cured product formed by curing compounds (7-1) and (7-2) and compounds (1) and / or compound (8) in a horizontally oriented state relative to the plane of the liquid crystal cured film (hereinafter also referred to as "horizontally oriented liquid crystal cured film").

[0303] Re(450) / Re(550)≤1.00 (a)

[0304] 1.00≤Re(650) / Re(550) (b)

[0305] 100nm≤Re(550)≤180nm (c)

[0306] [In the formula, Re(λ) represents the in-plane phase difference at wavelength λnm of the liquid crystal curing film, Re=(nx(λ)-ny(λ))×d (d represents the thickness of the liquid crystal curing film, nx represents the principal refractive index at wavelength λnm in the direction parallel to the plane of the liquid crystal curing film within the refractive index ellipsoid formed by the liquid crystal curing film, and ny represents the refractive index at wavelength λnm in the direction parallel to the plane of the liquid crystal curing film and orthogonal to the aforementioned nx direction within the refractive index ellipsoid formed by the liquid crystal curing film).]

[0307] When a horizontally oriented liquid crystal curing film satisfies formulas (a) and (b), the horizontally oriented liquid crystal curing film exhibits so-called inverse wavelength dispersibility, that is, the in-plane phase difference value at short wavelengths is smaller than the in-plane phase difference value at long wavelengths. From the perspective of improving inverse wavelength dispersibility and further improving the optical properties of the phase difference film, Re(450) / Re(550) is preferably 0.70 or more, more preferably 0.72 or more, even more preferably 0.75 or more, and preferably 0.90 or less, more preferably 0.87 or less, even more preferably 0.85 or less, and particularly preferably 0.83 or less. Furthermore, Re(650) / Re(550) is preferably 1.00 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

[0308] The aforementioned in-plane phase difference value can be adjusted by the thickness d of the horizontally oriented liquid crystal curing film. The in-plane phase difference value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d. Therefore, in order to obtain the desired in-plane phase difference value (Re(λ): the in-plane phase difference value of the horizontally oriented liquid crystal curing film at wavelength λ (nm), the three-dimensional refractive index and film thickness d can be adjusted.

[0309] Furthermore, when the horizontally oriented liquid crystal curing film satisfies formula (c), the retardation film including this horizontally oriented liquid crystal curing film functions as a λ / 4 plate, resulting in excellent improvement in the frontal reflection hue (suppression of coloring effect) when the elliptical polarizing plate with the retardation film including this liquid crystal curing film is applied to optical displays, etc. A more preferred range for the in-plane phase difference value is 120nm ≤ Re(550) ≤ 170nm, and a further preferred range is 130nm ≤ Re(550) ≤ 150nm.

[0310] The phase retardation film of the present invention can be manufactured, for example, by a method comprising the following steps: forming a coating film of the mixed composition of the present invention, drying the coating film, and orienting the polymeric liquid crystal compound (hereinafter, the compounds contained in the mixed composition that can form a liquid crystal curable film are collectively referred to as "polymeric liquid crystal compound") comprising compounds (7-1) and (7-2); and, while maintaining the orientation state, polymerizing the aforementioned polymeric liquid crystal compound by light irradiation to form a liquid crystal curable film.

[0311] A coating film of the mixed composition can be formed by coating the mixed composition onto a substrate or an alignment film. As the substrate, substrates known in the art, such as glass substrates and resin film substrates, can be appropriately selected and used. Furthermore, as the alignment film, alignment films commonly used for manufacturing optical films (especially retardation films), such as alignment films containing orientation polymers, photo-aligned films, grooved alignment films with raised or recessed patterns or multiple grooves on the surface, and stretched films stretched along the alignment direction, can be appropriately selected and used.

[0312] Examples of methods for coating a mixed composition onto a substrate include known methods such as spin coating, extrusion coating, gravure coating, die coating, squeegee coating, applicator coating, and printing methods such as flexographic printing.

[0313] Next, the solvent is removed by drying or the like, thereby forming a dried coating film. Examples of drying methods include natural drying, ventilation drying, heating drying, and reduced pressure drying. At this time, by heating the coating film obtained from the mixed composition, the solvent can be dried and removed from the coating film, and the polymeric liquid crystal compound is oriented in a desired direction (e.g., horizontal or vertical) relative to the plane of the coating film. The heating temperature of the coating film can be appropriately determined considering the material of the polymeric liquid crystal compound used and the substrate to which the coating film is to be formed. Generally, a temperature above the liquid crystal phase transition temperature is required to transform the polymeric liquid crystal compound into a liquid crystal phase state. To remove the solvent contained in the mixed composition while simultaneously achieving the desired orientation of the polymeric liquid crystal compound, for example, the temperature can be heated to around or above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymeric liquid crystal compound contained in the aforementioned mixed composition.

[0314] The hybrid composition of the present invention comprises at least compounds (7-1) and (7-2), and compound (1) and / or compound (8), which are generally capable of transforming into a liquid crystal phase at a temperature lower than the temperature at which each individual compound transforms into a liquid crystal phase. Therefore, in the manufacture of a retardation film using the hybrid composition of the present invention, not only can a retardation film with excellent optical properties be obtained, but excessive heat consumption can also be suppressed, thereby improving production efficiency. Furthermore, by enabling liquid crystal phase transformation at a lower heating temperature, it also has the advantage of a wider range of selectable support substrates for coating the hybrid composition.

[0315] The heating time can be appropriately determined according to the heating temperature, the type of polymeric liquid crystal compound contained, the type of solvent, its boiling point and amount, etc., and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

[0316] Solvent removal from the coating film can be performed simultaneously with heating to a temperature above the liquid crystal phase transition temperature of the liquid crystal compound contained in the mixed composition, or it can be performed separately. However, from the viewpoint of improving productivity, simultaneous removal is preferred. Before heating to a temperature above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, a pre-drying step can be provided to moderately remove the solvent from the coating film under conditions where the polymerizable liquid crystal compound contained in the coating film obtained from the mixed composition will not polymerize. Examples of drying methods in the pre-drying step include natural drying, ventilation drying, heating drying, and reduced pressure drying. The drying temperature (heating temperature) in this drying step can be appropriately determined according to the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point, and its amount.

[0317] Next, in the obtained dried coating film, while maintaining the orientation state of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized by light irradiation, thereby forming a liquid crystal cured film as a polymer of the polymerizable liquid crystal compound existing in the desired orientation state. Regarding the mixed composition of the present invention, since it is possible to highly polymerize by irradiation with high-intensity ultraviolet light or the like while suppressing damage to the polymerizable liquid crystal compound, photopolymerization is generally used as the polymerization method. In photopolymerization, the light irradiating the dried coating film can be appropriately selected according to the type of polymerization initiator, the type of polymerizable liquid crystal compound contained in the dried coating film, and their amount. Specific examples include light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, and active electron beams. From the perspective of easily controlling the polymerization reaction and using devices widely used in the art as photopolymerization devices, ultraviolet light is preferred, and it is preferable to select the type of polymerizable liquid crystal compound and polymerization initiator contained in the mixed composition in advance in a manner that allows photopolymerization using ultraviolet light. Furthermore, during polymerization, the polymerization temperature can be controlled by simultaneously cooling the dried coating film using appropriate cooling methods and then irradiating it with light. If the polymerization of the polymerizable liquid crystal compound is carried out at a lower temperature using such cooling methods, a liquid crystal cured film can be appropriately formed even when using a substrate with low heat resistance. Additionally, the polymerization reaction can be promoted by increasing the polymerization temperature within a range that does not cause adverse effects due to heat during light irradiation (such as substrate deformation due to heat). During photopolymerization, a patterned cured film can also be obtained through masking, development, and other processes.

[0318] The thickness of the liquid crystal curing film can be appropriately selected according to the display device to which it is applied. Preferably, it is 0.2 to 3 μm, more preferably 0.2 to 2 μm.

[0319] Examples of light sources for the aforementioned active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED light sources that emit light in the wavelength range of 380–440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

[0320] Ultraviolet radiation intensity is typically 10–3,000 mW / cm². 2The intensity of ultraviolet irradiation is preferably within the wavelength range effective for activating the photopolymerization initiator. The irradiation time is typically 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and even more preferably 0.1 seconds to 1 minute. When irradiated once or multiple times at such an intensity, the cumulative light intensity is 10 to 3,000 mJ / cm². 2 Preferably, it is 50–2,000 mJ / cm². 2 More preferably 100–1,000 mJ / cm 2 .

[0321] <Circular polarizing plate>

[0322] This invention includes a circular polarizer containing the phase retardation film of this invention. The circular polarizer of this invention typically contains a polarizing film.

[0323] A polarizing film is a film that has a polarizing function. Examples include a stretched film that adsorbs pigments with anisotropic absorption properties, and a film that includes a polarizing sheet coated with pigments with anisotropic absorption properties. As such a polarizing film, known polarizing films that can be used in circular polarizing plates, as described in Japanese Patent Application Publication Nos. 2013-33249 and 2013-200445, can be used.

[0324] The circular polarizer of the present invention is constructed by including the retardation film and the polarizing film of the present invention. For example, the circular polarizer of the present invention can be obtained by laminating the retardation film and the polarizing film of the present invention through an adhesive layer or a bonding agent layer. In one embodiment of the present invention, when the retardation film and the polarizing film of the present invention are laminated, it is preferable that the laminations are arranged such that the angle between the slow axis (optical axis) of the liquid crystal curable film constituting the retardation film and the absorption axis of the polarizing film is 45 ± 5°.

[0325] The circular polarizer of the present invention can have the same configuration as conventional circular polarizers, or polarizing films and retardation films. Examples of such configurations include, for instance, an adhesive layer (sheet) for attaching the circular polarizer to a display element constituting an image display device, and a protective film used to protect the surfaces of the polarizing film and retardation film from damage or contamination.

[0326] The circular polarizing plate of the present invention can be used in various display devices.

[0327] A display device is a device having display elements, including light-emitting elements or light-emitting devices as light sources. Examples of display devices include liquid crystal displays, organic electroluminescent (EL) displays, inorganic electroluminescent (EL) displays, flexible image displays, touch panel displays, electron emission displays (e.g., field emission displays (FED), surface field emission displays (SED)), electronic paper (display devices using electronic inks and electrophoretic elements), plasma displays, projection displays (e.g., grating light valve (GLV) displays, displays with digital micromirror devices (DMD)), and piezoelectric ceramic displays. Liquid crystal displays include any one of transmissive liquid crystal displays, semi-transmissive liquid crystal displays, reflective liquid crystal displays, direct-viewing liquid crystal displays, and projection liquid crystal displays. These display devices can be displays for two-dimensional images or stereoscopic displays for three-dimensional images. In particular, the circular polarizer of the present invention can be suitably used in organic electroluminescent (EL) displays and inorganic electroluminescent (EL) displays. These display devices (optical displays) are able to present excellent image display characteristics through the circular polarizer of the present invention, which has excellent optical properties.

[0328] The present invention will be described in more detail below using examples. It should be noted that, unless otherwise specified, "%" and "parts" in the examples refer to mass percentage and mass parts, respectively.

[0329] The HPLC determination used for the analysis of each compound can be performed under any conditions, as long as the peaks from each polymerizable liquid crystal compound can be separated. An example of HPLC determination conditions is shown below.

[0330] (Measurement conditions)

[0331] Apparatus used for measurement: HPLC LC-10AT (manufactured by Shimadzu Corporation)

[0332] Column: L-Column ODS (inner diameter 3.0mm, length 150mm, particle size 3μm)

[0333] Temperature: 40℃

[0334] Mobile phase A: 0.1% (v / v)-TFA / water

[0335] Mobile phase B: 0.1% (v / v)-TFA / acetonitrile

[0336] Gradient: 0 min 50% - B

[0337] 30min 100%-B

[0338] 60min 100%-B

[0339] 60.01min 50%-B

[0340] 75min 50%-B

[0341] Flow rate: 0.5 mL / min

[0342] Injection volume: 5μL

[0343] Detection wavelength: 350nm

[0344] Synthesis of Compound (P3-1)

[0345] Compound (1-1a) was synthesized with reference to patent document (Japanese Patent Application Publication No. 2019-3177). Compound (1-2a) was synthesized with reference to patent document (Japanese Patent Application Publication No. 2010-31223), and compound (P3-1) was synthesized from compound (1-1a) and compound (1-2a).

[0346] [Chemical Formula 24]

[0347]

[0348] Synthesis of Compound (P1-1)

[0349] Compound (1-3a) was synthesized with reference to Patent Document (International Publication No. 2022 / 181518). Compound (P1-1) was synthesized from compound (1-1a) and compound (1-3a) with reference to Patent Document (Japanese Patent Application Publication No. 2010-31223).

[0350] [Chemical Formula 25]

[0351]

[0352] Synthesis of Compound (P1-2)

[0353] Compound (1-4a) was synthesized with reference to Patent Document (International Publication No. 2022 / 181518). Compound (P1-2) was synthesized from compound (1-1a) and compound (1-4a) with reference to Patent Document (Japanese Patent Application Publication No. 2010-31223).

[0354] [Chemical Formula 26]

[0355]

[0356] <Synthesis of Compounds (1-5a)>

[0357] 43.0 g of compound (1-3a), 0.5 g of DMF, and 57.0 g of toluene were added and mixed. 24.2 g of thionyl chloride was added dropwise over 1 hour. Then, a solution obtained by mixing 16.9 g of 4-hydroxybenzoic acid and 21.5 g of pyridine in 200 g of THF was added dropwise, and the mixture was kept at room temperature for 2 hours. The resulting reaction solution was diluted with toluene, washed separately with 20% sulfuric acid aqueous solution, water, and saturated sodium bicarbonate aqueous solution, and then purified by column chromatography to obtain 24.5 g of compound (1-5a).

[0358] [Chemical Formula 27]

[0359]

[0360] Synthesis of Compound (P1-3)

[0361] Referring to the patent document (Japanese Patent Application Publication No. 2010-31223), compound (P1-3) is synthesized from compound (1-1a) and compound (1-5a).

[0362] [Chemical Formula 28]

[0363]

[0364] [Example 1]

[0365] <Synthesis of the Mixture Composition (1)>

[0366] A nitrogen atmosphere was created in a 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer. 5.0 g of compound (1-1a) synthesized according to patent document (Japanese Patent Application Publication No. 2019-3177), 17.2 g of compound (P3-1) synthesized according to patent document (Japanese Patent Application Publication No. 2010-31223), 0.4 g of DMAP (N,N-dimethylaminopyridine, manufactured by FUJIFILM Wako Pure Chemical Corporation) (approximately 0.2 mol relative to 1 mol of compound (1-1a), 0.2 g of BHT (butylated hydroxytoluene, manufactured by FUJIFILM Wako Pure Chemical Corporation), and 70 g of N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) (approximately 4 parts by mass relative to 1 part by mass of compound (P3-1)) were added and mixed. The mixture was then reacted at 50°C for 4 hours. After the reaction was complete, 100 g of toluene (prepared by Nacalai Tesque) was added, followed by the addition of three times the amount of water to N-methylpyrrolidone and extraction to obtain a toluene solution. 6.8 g of compound (1-3a) synthesized according to patent document (International Publication No. 2022 / 181518) was added to this toluene solution, and 2.9 g of IPC (diisopropylcarbodiimide, prepared by FUJIFILM Wako Pure Chemical Corporation) was further added using a dropping funnel, allowing them to react overnight at 0°C. After the reaction was complete, insoluble components were removed by filtration. 300 g of methanol (prepared by FUJIFILM Wako Pure Chemical Corporation) was added dropwise to three times the mass of toluene contained in the solution, causing a solid to precipitate. The precipitated solid was then removed by filtration, washed three times with 10 g of methanol, and dried under reduced pressure at 30°C to obtain 26.3 g of the mixed composition (1).

[0367] The ratio of polymeric liquid crystal compound (P1-1), polymeric liquid crystal compound (P2-1a), polymeric liquid crystal compound (P2-1b), and polymeric liquid crystal compound (P3-1) in the mixture (1) was determined by high performance liquid chromatography. The results showed that (P1-1):(P2-1a):(P2-1b):(P3-1) = 3.7:65.6:20.2:10.5.

[0368] It should be noted that in Example 1, compound (P3-1) corresponds to compound (1) in step (i), compound (1-1a) corresponds to compound (2) in step (i), and compound (1-3a) corresponds to compound (9) in step (ii). In addition, compound (P1-1) corresponds to compound (8), and compounds (P2-1a) and (P2-1b) correspond to compounds (7-1) and (7-2), respectively.

[0369] [Chemical Formula 29]

[0370]

[0371] [Example 2]

[0372] <Synthesis of Mixture Composition (2)>

[0373] The N-methylpyrrolidone was replaced with N,N-dimethylacetamide (manufactured by FUJIFILM Wako Pure Chemical Corporation), and the reaction was carried out using the same method as in Example 1 to obtain a mixed composition (2) of 26.3 g.

[0374] The ratio of polymeric liquid crystal compound (P1-1), polymeric liquid crystal compound (P2-1a), polymeric liquid crystal compound (P2-1b), and polymeric liquid crystal compound (P3-1) in the mixture (2) was determined by high performance liquid chromatography. The results showed that (P1-1):(P2-1a):(P2-1b):(P3-1)=3.5:64.8:20.1:11.6.

[0375] [Example 3]

[0376] <Synthesis of Mixed Composition (3)>

[0377] DMAP 0.4g was replaced with DBU (diazabicycloundecene, manufactured by Tokyo Chemical Co., Ltd.) 1.2g (approximately 0.5 moles relative to 1 mole of compound (1-1a)), and the mixture was reacted using the same method as in Example 1 to obtain 26.2g of the mixed composition (3).

[0378] The ratio of polymeric liquid crystal compound (P1-1), polymeric liquid crystal compound (P2-1a), polymeric liquid crystal compound (P2-1b), and polymeric liquid crystal compound (P3-1) in the mixture (3) was determined by high performance liquid chromatography. The results showed that (P1-1):(P2-1a):(P2-1b):(P3-1)=0.0:79.4:17.6:3.0.

[0379] [Example 3]

[0380] <Synthesis of the Mixed Composition (3')>

[0381] A 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer was filled with a nitrogen atmosphere. 5.0 g of compound (1-1a) synthesized according to patent document (Japanese Patent Application Publication No. 2019-3177), 13.5 g of compound (P1-1), 1.2 g of DBU (approximately 0.5 mol relative to 1 mol of compound (1-1a), 0.2 g of BHT, and 70 g of N-methylpyrrolidone (approximately 5 parts by mass relative to 1 part by mass of compound (P1-1)) were added and mixed. The mixture was then reacted at 50°C for 4 hours. After the reaction was complete, 100 g of toluene (prepared by Nacalai Tesque) was added, followed by the addition of three times the amount of water to N-methylpyrrolidone and extraction to obtain a toluene solution. 9.6 g of compound (1-2a) was added to this toluene solution, and 2.9 g of IPC was further added using a dropping funnel. The mixture was then reacted at 0°C overnight. After the reaction was complete, insoluble components were removed by filtration. 300 g of methanol (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise to the solution at a mass equal to three times the mass of toluene contained in the solution, causing a solid to precipitate. The precipitated solid was then removed by filtration, washed three times with 10 g of methanol, and dried under reduced pressure at 30 °C to obtain 26.3 g of the mixed composition (3').

[0382] The ratio of polymeric liquid crystal compound (P1-1), polymeric liquid crystal compound (P2-1a), polymeric liquid crystal compound (P2-1b), and polymeric liquid crystal compound (P3-1) in the mixture (3') was determined by high performance liquid chromatography. The results showed that (P1-1):(P2-1a):(P2-1b):(P3-1) = 3.0:17.6:79.4:0.0.

[0383] It should be noted that in Example 3', compound (P1-1) corresponds to compound (8) in step (ib), compound (1-1a) corresponds to compound (2) in step (ib), and compound (1-2a) corresponds to compound (10) in step (ii-b). Additionally, compound (P3-1) corresponds to compound (1), and compounds (P2-1a) and (P2-1b) correspond to compounds (7-1) and (7-2), respectively.

[0384] [Chemical Formula 30]

[0385]

[0386] [Example 4]

[0387] <Synthesis of the Mixture Composition (4)>

[0388] Compound (1-3a) was replaced with compound (1-4a), and otherwise the reaction was carried out using the same method as in Example 1 to obtain a mixed composition (4).

[0389] The ratio of polymeric liquid crystal compound (P1-2), polymeric liquid crystal compound (P2-2a), polymeric liquid crystal compound (P2-2b), and polymeric liquid crystal compound (P3-1) in the mixture (4) was determined by high performance liquid chromatography. The results showed that (P1-2):(P2-2a):(P2-2b):(P3-1) = 3.6:65.6:20.2:10.6.

[0390] It should be noted that in Example 4, compound (P3-1) corresponds to compound (1) in step (i), compound (1-1a) corresponds to compound (2) in step (i), and compound (1-4a) corresponds to compound (9) in step (ii). Additionally, compound (P1-2) corresponds to compound (8), and compounds (P2-2a) and (P2-2b) correspond to compounds (7-1) and (7-2), respectively.

[0391] [Chemical Formula 31]

[0392]

[0393] [Example 5]

[0394] <Synthesis of the Mixed Composition (5)>

[0395] Compound (1-3a) was replaced with compound (1-4a), and otherwise the reaction was carried out using the same method as in Example 2 to obtain a mixed composition (5).

[0396] The ratio of polymeric liquid crystal compound (P1-2), polymeric liquid crystal compound (P2-2a), polymeric liquid crystal compound (P2-2b), and polymeric liquid crystal compound (P3-1) in the mixture (5) was determined by high performance liquid chromatography. The results showed that (P1-2):(P2-2a):(P2-2b):(P3-1) = 3.4:64.8:20.1:11.7.

[0397] [Example 6]

[0398] <Synthesis of the Mixed Composition (6)>

[0399] Compound (1-3a) was replaced with compound (1-4a), and otherwise the reaction was carried out using the same method as in Example 3 to obtain a mixed composition (6).

[0400] The ratio of polymeric liquid crystal compound (P1-2), polymeric liquid crystal compound (P2-2a), polymeric liquid crystal compound (P2-2b), and polymeric liquid crystal compound (P3-1) in the mixture (6) was determined by high performance liquid chromatography. The results showed that (P1-2):(P2-2a):(P2-2b):(P3-1)=0.0:79.4:17.6:3.0.

[0401] [Example 6]

[0402] <Synthesis of the Mixed Composition (6')>

[0403] The compound (P1-1) was replaced with compound (P1-2), and otherwise the reaction was carried out using the same method as in Example 3' to obtain a mixed composition (6').

[0404] The ratio of polymeric liquid crystal compound (P1-2), polymeric liquid crystal compound (P2-2a), polymeric liquid crystal compound (P2-2b), and polymeric liquid crystal compound (P3-1) in the mixture (6) was determined by high performance liquid chromatography. The results showed that (P1-2):(P2-2a):(P2-2b):(P3-1) = 3.0:17.6:79.4:0.0.

[0405] It should be noted that in Example 6', compound (P1-2) corresponds to compound (8) in step (ib), compound (1-1a) corresponds to compound (2) in step (ib), and compound (1-2a) corresponds to compound (10) in step (ii-b). Additionally, compound (P3-1) corresponds to compound (1), and compounds (P2-2a) and (P2-2b) correspond to compounds (7-1) and (7-2), respectively.

[0406] [Example 7]

[0407] <Synthesis of the Mixture Composition (7)>

[0408] Compounds (1-3a) were replaced with compounds (1-5a), and otherwise the reaction was carried out using the same method as in Example 1 to obtain a mixed composition (7).

[0409] The ratio of polymeric liquid crystal compound (P1-3), polymeric liquid crystal compound (P2-3a), polymeric liquid crystal compound (P2-3b), and polymeric liquid crystal compound (P3-1) in the mixture (7) was determined by high performance liquid chromatography. The results showed that (P1-3):(P2-3a):(P2-3b):(P3-1) = 4.2:66.0:20.3:9.5.

[0410] It should be noted that in Example 7, compound (P3-1) corresponds to compound (1) in step (i), compound (1-1a) corresponds to compound (2) in step (i), and compound (1-5a) corresponds to compound (9) in step (ii). Additionally, compound (P1-3) corresponds to compound (8), and compounds (P2-3a) and (P2-3b) correspond to compounds (7-1) and (7-2), respectively.

[0411] [Chemical Formula 32]

[0412]

[0413] [Example 8]

[0414] <Synthesis of the Mixture Composition (8)>

[0415] Compound (1-3a) was replaced with compound (1-5a), and otherwise the reaction was carried out using the same method as in Example 2 to obtain a mixed composition (8).

[0416] The ratio of polymeric liquid crystal compound (P1-3), polymeric liquid crystal compound (P2-3a), polymeric liquid crystal compound (P2-3b), and polymeric liquid crystal compound (P3-1) in the mixture (8) was determined by high performance liquid chromatography. The results showed that (P1-3):(P2-3a):(P2-3b):(P3-1) = 4.0:65.3:20.2:10.5.

[0417] [Example 9]

[0418] <Synthesis of the Mixture Composition (9)>

[0419] Compound (1-3a) was replaced with compound (1-5a), and otherwise the reaction was carried out using the same method as in Example 3 to obtain a mixed composition (9).

[0420] The ratio of polymeric liquid crystal compound (P1-3), polymeric liquid crystal compound (P2-3a), polymeric liquid crystal compound (P2-3b), and polymeric liquid crystal compound (P3-1) in the mixture (9) was determined by high performance liquid chromatography. The results showed that (P1-3):(P2-3a):(P2-3b):(P3-1) = 0.0:79.7:17.7:2.7.

[0421] [Example 9]

[0422] <Synthesis of the Mixed Composition (9')>

[0423] The compound (P1-1) was replaced with compound (P1-3), and the reaction was carried out using the same method as in Example 3' to obtain a mixed composition (9').

[0424] The ratio of polymeric liquid crystal compound (P1-3), polymeric liquid crystal compound (P2-3a), polymeric liquid crystal compound (P2-3b), and polymeric liquid crystal compound (P3-1) in the mixed composition (9') was determined by high performance liquid chromatography. The results showed that (P1-3):(P2-3a):(P2-3b):(P3-1) = 2.7:17.7:79.7:0.0.

[0425] It should be noted that in Example 9', compound (P1-3) corresponds to compound (8) in step (ib), compound (1-1a) corresponds to compound (2) in step (ib), and compound (1-2a) corresponds to compound (10) in step (ii-b). Additionally, compound (P3-1) corresponds to compound (1), and compounds (P2-3a) and (P2-3b) correspond to compounds (7-1) and (7-2), respectively.

[0426] [Comparative Examples 1-5]

[0427] The solvents used were changed as shown in Table 1, and the reactions were carried out using the same method as in Example 1 to obtain the various mixed compositions. The compositional ratios of the polymerizable liquid crystal compounds in the mixed compositions are shown in Table 2.

[0428] [Comparative Example 6]

[0429] The solvents used were changed as shown in Table 1, and the reactions were carried out using the same method as in Example 3 to obtain the various mixed compositions. The compositional composition of each polymerizable liquid crystal compound is shown in Table 2.

[0430] [Comparative Example 7]

[0431] The solvent used was changed as shown in Table 3, and the reaction was carried out using the same method as in Example 4 to obtain the mixed composition. The composition of each polymerizable liquid crystal compound in the mixed composition is shown in Table 4.

[0432] [Comparative Example 8]

[0433] The solvent used was changed as shown in Table 3, and the reaction was carried out using the same method as in Example 6 to obtain the mixed composition. The composition of each polymerizable liquid crystal compound in the mixed composition is shown in Table 4.

[0434] [Comparative Examples 9-12]

[0435] The solvents used were changed as shown in Table 5, and the reactions were carried out using the same method as in Example 7 to obtain the various mixed compositions. The compositional composition of each polymerizable liquid crystal compound is shown in Table 6.

[0436] [Comparative Example 13]

[0437] The solvent used was changed as shown in Table 5, and the reaction was carried out using the same method as in Example 9 to obtain the mixed composition. The composition of each polymerizable liquid crystal compound in the mixed composition is shown in Table 6.

[0438] [Hydrolysis Resistance Test]

[0439] For the mixed composition (1), chloroform and methanol were used as developing solvents, and the mixture was purified by silica gel column chromatography to obtain compounds (P1-1), (P2-1a), (P2-1b), and (P3-1), respectively. Similarly, the mixed compositions (4) and (7) were also purified to obtain compounds (P1-2), (P1-3), (P2-2a), (P2-2b), (P2-3a), (P2-3b), and (P3-1).

[0440] 100 mg of each compound (P1-1), (P1-2), (P1-3), (P2-1a), (P2-1b), (P2-2a), (P2-2b), (P2-3a), (P2-3b), and (P3-1) were dissolved in 10 v / v water / dimethylacetamide solution and heated and stirred at 90 °C and 68 hr. After the reaction was completed, the residual rate of each component was calculated using HPLC. Then, the residual rate of each composition was calculated by using the residual rates of the above components and the ratios of the components in the compositions listed in Tables 2, 4, and 6. A higher residual rate indicates higher hydrolysis resistance.

[0441] [Table 1]

[0442]

[0443] [Table 2]

[0444]

[0445] [Table 3]

[0446]

[0447] [Table 4]

[0448]

[0449] [Table 5]

[0450]

[0451] [Table 6]

[0452]

[0453] It should be noted that the upward arrow "↑" in the table refers to the same as above. The input sequence "A→B" indicates a manufacturing method that includes step (i) of reacting compound (1) with compound (2) having a structure represented by A, i.e., a manufacturing method that performs steps (i) and (ii). The input sequence "B→A" indicates a manufacturing method that includes step (ib) of reacting compound (8) with compound (2) having a structure represented by B, i.e., a manufacturing method that performs steps (ib) and (ii-b).

Claims

1. A method for manufacturing a reactive mixture, comprising the steps of: reacting a compound represented by formula (1) with a compound represented by formula (2) in the presence of an organic solvent having a dielectric constant of 30 or greater, thereby obtaining a reactive mixture comprising a compound represented by formula (3) and a compound represented by formula (4). In the area percentage values ​​determined by liquid chromatography for the compounds represented by formula (3) and formula (4) in the reaction mixture, the value of formula (3) / (formula (3) + formula (4)) is 0.75 or more and less than 0.95, or the value of formula (4) / (formula (3) + formula (4)) is 0.75 or more and less than 0.

95. A-Ar-A(1) HO-Ar-OH(2) A-Ar-OH(3) HO-Ar-A(4) In equations (1), (3), and (4), A is represented by the following equation (5): *-D 1 -(A 1 -E 1 )m-SP 1 -L 1 (5), In equation (5), * indicates the bonding position with Ar in equation (1), equation (3), or equation (4). m represents an integer greater than or equal to 1. D 1 This represents -C(=O)-O- or -OC(=O)-. E 1 This indicates a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linking group formed by a combination of two or more of them, R 1 ~R 5 Each of the following independently represents an alkyl group having 1 to 4 hydrogen atoms, fluorine atoms, or carbon atoms, and when m is an integer of 2 or more, there are multiple E's. 1 They can be the same or different. A 1 This indicates that there are multiple A groups, where m is an integer of 2 or more, and the group has 6 or more carbon atoms that can have substituents. 1 They can be the same or different. SP 1 This refers to a single bond, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkenyl group having 2 to 20 carbon atoms, a straight-chain or branched ynynyl group having 2 to 20 carbon atoms, or a divalent linking group formed by replacing one or more of the -CH2- groups constituting the alkylene group, the alkenyl group, or the ynynyl group with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent. L 1 Indicates a monovalent organic group. In formulas (1), (2), (3), and (4), Ar represents any of the groups represented by formulas (Ar-1) to (Ar-6): [Chemical Formula 1] In formula (Ar-1)~(Ar-6), * indicates a relationship with D 1 The bonding portion; Q 1 Indicates -S-, -O-, or -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents. Q 2 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents; W 1 and W 2 Each can be represented independently as -O-, -S-, -CO-, -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents; Y 1 This refers to alkyl groups having 1 to 6 carbon atoms, aromatic hydrocarbon groups that may have substituents, or aromatic heterocyclic groups. Y 2 It represents a CN group or an alkyl group having 1 to 12 carbon atoms that may have substituents, wherein the hydrogen atoms contained in the alkyl group may be replaced by halogen atoms, and the -CH2- contained in the alkyl group may be replaced by -O-, -CO-, -O-CO- or -CO-O-. Z 1 Z 2 and Z 3 Each of these groups independently represents a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms in the monovalent form, a halogen atom, a cyano group, a nitro group, or -NR. 6 R 7 or -SR 6 Z 1 and Z 2 They can bond with each other to form aromatic rings or aromatic heterocycles, R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms; Z 4 This refers to aliphatic hydrocarbon groups or alkoxy groups with 2 to 20 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms in the monovalent form, halogen atoms, cyano groups, nitro groups, and -NR groups. 6 R 7 or -SR 6 R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms; Ax represents an organic group having 2 to 30 carbon atoms of 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 that may have substituents, or an organic group having 2 to 30 carbon atoms of at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay can be bonded to form a ring. Y 3 and Y 4 Each is independently represented by the following formula (Y) 3 -1) represents the group: [Chemical Formula 2] Formula (Y 3 In -1), R Y1 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, which may be substituented by one or more substituents X. 3 Replacement, replacement base X 3 This refers to a straight-chain or branched alkyl group with 1 to 20 carbon atoms, containing fluorine, chlorine, bromine, iodine, sulfopentafluoride, nitro, cyano, isocyanate, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanate, or one -CH2- or two or more non-adjacent -CH2- groups that can be independently 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 this alkyl group can be replaced by a fluorine atom, or can be -B. 31 -F 31 -P 31 The group represented (where, B 31 Indicates -CR 8 R 9 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 8 -、-NR 8 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, R 8 and R 9 Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms; F 31 This represents an alkane diene with 1 to 12 carbon atoms, where the hydrogen atoms in the alkane diene can be represented by -OR. 10 Or halogen atom substitution, R 10 This refers to an alkyl group having 1 to 4 carbon atoms, where the hydrogen atoms can be replaced by fluorine atoms, and the -CH2- in the alkane diel can be replaced by -O- or -CO-; P 31 (Representing hydrogen atoms or polymeric groups), U 1 This refers to an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group, wherein any carbon atom of the aromatic hydrocarbon group can be replaced by a heteroatom, and the aromatic hydrocarbon group can be substituted by one or more of the aforementioned substituents X. 3 replace; T 1 represents -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -, -N=CU 2 -, -CO-NU 2 -、-OCO-NU 2 -or-O-NU 2 -, U 2 Representing hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, organic groups having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of which can be replaced by a heteroatom), or (E 31 -A 31 ) q -B 31 -F 31 -P 31 The alkyl, cycloalkyl, cycloalkenyl, and aromatic hydrocarbon groups are either unsubstituted or can be substituted by one or more substituents X. 3 The alkyl group can be substituted by the cycloalkyl or cycloalkenyl group, wherein one -CH2- or two or more non-adjacent -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and one -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl or cycloalkenyl group can be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CO-O-, E 31 With the aforementioned B 31 Similarly defined, A 31 This refers to a divalent alicyclic hydrocarbon group with 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms. The hydrogen atoms contained in this alicyclic hydrocarbon group and the aromatic hydrocarbon group can be halogen atoms, -R... 11 -OR 12 Cyano or nitro substitution, R 11 R represents an alkyl group having 1 to 4 carbon atoms, consisting of hydrogen atoms, fluorine atoms, or carbon atoms. 12 B represents an alkyl group with 1 to 4 carbon atoms, in which the hydrogen atoms can be replaced by fluorine atoms. 31 F 31 and P 31 Each has the same characteristics as B 31 F 31 and P 31 With the same meaning, q represents an integer from 0 to 4, and E 31 and / or A 31 In the case of multiple instances, they can be the same or different, U 1 with U 2 They can bond together to form a ring.

2. The method for manufacturing the reactive mixture as described in claim 1, wherein, Based on the total area values ​​of the compounds represented by formula (1), formula (2), formula (3) and formula (4) contained in the reactive mixture, the total area percentage values ​​of the compounds represented by formula (3) and formula (4) contained in the reactive mixture, as determined by liquid chromatography, are greater than 50% and less than 98%.

3. A mixed composition comprising: at least one of the compounds represented by formula (1) and formula (8); the compound represented by formula (7-1); and the compound represented by formula (7-2). A-Ar-A(1) A-Ar-B(7-1) B-Ar-A(7-2) B-Ar-B(8) In the mixed composition, when the sum of the area percentage values ​​of the compound represented by formula (7-1) and the compound represented by formula (7-2) determined by liquid chromatography is set as 100%, the ratio of any one structural isomer of the compound represented by formula (7-1) and the compound represented by formula (7-2) contained in the mixed composition is greater than 75% and less than 95%. In equations (1), (7-1), and (7-2), A is represented by the following equation (5): *-D 1 -(A 1 -E 1 )m-SP 1 -L 1 (5), In equations (7-1), (7-2), and (8), B is represented by the following equation (6): *-D 2 -(A 2 -E 2 )n-SP 2 -L 2 (6), In equations (5) and (6), * indicates the bonding position with Ar in equations (1), (7-1), (7-2), or (8). m and n each independently represent integers greater than 1. D 1 and D 2 Each can be represented independently as -C(=O)-O- or -OC(=O)-. E 1 and E 2 Each can independently represent a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linking group formed by a combination of two or more of them, R 1 ~R 5 Each of the following independently represents an alkyl group having 1 to 4 hydrogen atoms, fluorine atoms, or carbon atoms, and when m is an integer of 2 or more, there are multiple E's. 1 Each can be the same or different. When n is an integer greater than 2, there exist multiple E. 2 They can be the same or different. A 1 and A 2 Each can independently represent a divalent aromatic hydrocarbon group with 6 or more carbon atoms that can have substituents, or a divalent alicyclic hydrocarbon group with 6 or more carbon atoms that can have substituents. When m is an integer of 2 or more, there are multiple A's. 1 Each can be the same or different. When n is an integer greater than 2, there exist multiple A's. 2 They can be the same or different. SP 1 and SP 2 Each of these groups independently represents a single bond, a straight-chain or branched alkylene group with 1 to 20 carbon atoms, a straight-chain or branched alkenyl group with 2 to 20 carbon atoms, a straight-chain or branched ynynyl group with 2 to 20 carbon atoms, or a divalent linking group formed by replacing one or more of the -CH2- groups constituting the alkylene group, the alkenyl group, or the ynynyl group with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent. L 1 and L 2 Each independently represents a monovalent organic group, L 1 and L 2 At least one of them is a polymeric group. A and B are different from each other. In formulas (1), (7-1), (7-2), and (8), Ar represents any of the groups represented by formulas (Ar-1) to (Ar-6): [Chemical Formula 3] In formula (Ar-1)~(Ar-6), * indicates a relationship with D 1 Or D 2 The bonding portion; Q 1 Indicates -S-, -O-, or -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents. Q 2 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents; W 1 and W 2 Each can be represented independently as -O-, -S-, -CO-, -NR 6 -, R 6 Represents an alkyl group having 1 to 6 carbon atoms, which may contain hydrogen atoms or substituents; Y 1 This refers to alkyl groups having 1 to 6 carbon atoms, aromatic hydrocarbon groups that may have substituents, or aromatic heterocyclic groups. Y 2 It represents a CN group or an alkyl group having 1 to 12 carbon atoms that may have substituents, wherein the hydrogen atoms contained in the alkyl group may be replaced by halogen atoms, and the -CH2- contained in the alkyl group may be replaced by -O-, -CO-, -O-CO- or -CO-O-. Z 1 Z 2 and Z 3 Each of these groups independently represents a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms in the monovalent form, a halogen atom, a cyano group, a nitro group, or -NR. 6 R 7 or -SR 6 Z 1 and Z 2 They can bond with each other to form aromatic rings or aromatic heterocycles, R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms; Z 4 This refers to aliphatic hydrocarbon groups or alkoxy groups with 2 to 20 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms in the monovalent form, halogen atoms, cyano groups, nitro groups, and -NR groups. 6 R 7 or -SR 6 R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms; Ax represents an organic group having 2 to 30 carbon atoms of 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 that may have substituents, or an organic group having 2 to 30 carbon atoms of at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles; Ax and Ay can be bonded to form a ring. Y 3 and Y 4 Each is independently represented by the following formula (Y) 3 -1) represents the group: [Chemical Formula 4] Formula (Y 3 In -1), R Y1 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, which may be substituented by one or more substituents X. 3 Replacement, replacement base X 3 This refers to a straight-chain or branched alkyl group with 1 to 20 carbon atoms, containing fluorine, chlorine, bromine, iodine, sulfopentafluoride, nitro, cyano, isocyanate, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanate, or one -CH2- or two or more non-adjacent -CH2- groups that can be independently 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 this alkyl group can be replaced by a fluorine atom, or can be -B. 31 -F 31 -P 31 The group represented (where, B 31 Indicates -CR 8 R 9 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 8 -、-NR 8 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or a single bond, R 8 and R 9 Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms; F 31 This represents an alkane diene with 1 to 12 carbon atoms, where the hydrogen atoms in the alkane diene can be represented by -OR. 10 Or halogen atom substitution, R 10 This refers to an alkyl group having 1 to 4 carbon atoms, where the hydrogen atoms can be replaced by fluorine atoms, and the -CH2- in the alkane diel can be replaced by -O- or -CO-; P 31 (Representing hydrogen atoms or polymeric groups), U 1 This refers to an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group, wherein any carbon atom of the aromatic hydrocarbon group can be replaced by a heteroatom, and the aromatic hydrocarbon group can be substituted by one or more of the aforementioned substituents X. 3 replace; T 1 represents -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -, -N=CU 2 -, -CO-NU 2 -、-OCO-NU 2 -or-O-NU 2 -, U 2 Representing hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, organic groups having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of which can be replaced by a heteroatom), or (E 31 -A 31 ) q -B 31 -F 31 -P 31 The alkyl, cycloalkyl, cycloalkenyl, and aromatic hydrocarbon groups are either unsubstituted or can be substituted by one or more substituents X. 3 The alkyl group can be substituted by the cycloalkyl or cycloalkenyl group, wherein one -CH2- or two or more non-adjacent -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, and one -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl or cycloalkenyl group can be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CO-O-, E 31 With the aforementioned B 31 Similarly defined, A 31 This refers to a divalent alicyclic hydrocarbon group with 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms. The hydrogen atoms contained in this alicyclic hydrocarbon group and the aromatic hydrocarbon group can be halogen atoms, -R... 11 -OR 12 Cyano or nitro substitution, R 11 R represents an alkyl group having 1 to 4 carbon atoms, consisting of hydrogen atoms, fluorine atoms, or carbon atoms. 12 B represents an alkyl group with 1 to 4 carbon atoms, in which the hydrogen atoms can be replaced by fluorine atoms. 31 F 31 and P 31 Each has the same characteristics as B 31 F 31 and P 31 With the same meaning, q represents an integer from 0 to 4, and E 31 and / or A 31 In the case of multiple instances, they can be the same or different, U 1 with U 2 They can bond together to form a ring.

4. The mixture of claim 3, wherein, Based on the total area values ​​of the compounds represented by formula (1), formula (7-1), formula (7-2) and formula (8) contained in the mixed composition, the total area percentage values ​​of the compounds represented by formula (7-1) and formula (7-2) as determined by liquid chromatography are greater than 50% and less than 98%.

5. The method for manufacturing the reactive mixture as described in claim 1 or 2, wherein, A in equation (5) 1 It is 1,4-cyclohexanediyl or 1,4-phenylenediyl.

6. The method for manufacturing the reactive mixture as described in claim 1 or 2, wherein, L in equation (5) 1 It is an acryloxy group.

7. The mixture as claimed in claim 3 or 4, wherein, A in equation (5) 1 and A in equation (6) 2 Each is independently 1,4-cyclohexanediyl or 1,4-phenylenediyl.

8. The mixture composition as described in claim 3 or 4, wherein, L in equation (5) 1 and L in equation (6) 2 All are acryloyloxy groups.

9. A method for manufacturing a mixed composition, comprising using a reactive mixed composition manufactured by the method for manufacturing a reactive mixed composition according to claim 1 or 2, the method comprising the following steps: The reaction mixture is mixed with the compound represented by formula (9), and the compound represented by formula (3) reacts with the compound represented by formula (9) to generate the compound represented by formula (7-1), and the compound represented by formula (4) reacts with the compound represented by formula (9) to generate the compound represented by formula (7-2), thereby obtaining a mixture comprising the compound represented by formula (7-1) and the compound represented by formula (7-2). HOOC-(A 2 -E 2 )n-SP 2 -L 2 (9) A-Ar-B(7-1) B-Ar-A(7-2) In equation (9), n represents an integer greater than or equal to 1. E 2 This indicates a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -、-CR 3 =CR 4 -、-NR 5 - or a divalent linking group formed by a combination of two or more of them, R 1 ~R 5 Each of the following can independently represent an alkyl group having 1 to 4 hydrogen atoms, fluorine atoms, or carbon atoms, and when n is an integer greater than 2, there are multiple E's. 2 They can be the same or different. A 2 This indicates that there are multiple A groups, either divalent aromatic hydrocarbon groups with 6 or more carbon atoms that can have substituents, or divalent alicyclic hydrocarbon groups with 6 or more carbon atoms that can have substituents, when n is an integer of 2 or more. 2 They can be the same or different. SP 2 This refers to a single bond, a straight-chain or branched alkylene group having 1 to 20 carbon atoms, a straight-chain or branched alkenyl group having 2 to 20 carbon atoms, a straight-chain or branched ynynyl group having 2 to 20 carbon atoms, or a divalent linking group formed by replacing one or more of the -CH2- groups constituting the alkylene group, the alkenyl group, or the ynynyl group with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent. L 2 Represents a monovalent organic group, wherein, L 2 and L in equation (5) 1 At least one of them is a polymeric group. In equations (7-1) and (7-2), A and Ar have the same meaning as A and Ar in equation (1) (where * in equations (Ar-1) to (Ar-6) indicates the same meaning as D). 1 Or D 2 (bonding part), B is represented by the following equation (6): *-D 2 -(A 2 -E 2 )n-SP 2 -L 2 (6), In equation (6), * represents the bonding position with Ar in equation (7-1) or equation (7-2), and D 2 This represents -C(=O)-O- or -OC(=O)-. A 2 E 2 n, SP 2 and L 2 Represent A in equation (9) respectively 2 E 2 n, SP 2 and L 2 They have the same meaning, but A and B are different from each other.

Images