WO2024042834A1

WO2024042834A1 - Mixed composition, retardation film, circularly polarizing plate, production method for mixed composition

Info

Publication number: WO2024042834A1
Application number: PCT/JP2023/023117
Authority: WO
Inventors: 佳祐橋詰; 修治原田; 憲之飛田
Original assignee: 住友化学株式会社
Priority date: 2022-08-24
Filing date: 2023-06-22
Publication date: 2024-02-29
Also published as: JP2024030442A

Abstract

Provided is a mixed composition for a polymerizable liquid crystal compound that has a low phase transition temperature and is preferably suited to production of a retardation film that has excellent optical characteristics.

Description

Mixed composition, retardation film, circularly polarizing plate, method for producing mixed composition

The present invention provides a mixed composition, a retardation film including a cured product of the mixed composition, a circularly polarizing plate including the retardation film, a method for producing the mixed composition, and a method for producing the mixed composition. The present invention relates to a method for producing a reaction mixture composition.

Retardation films used in various image display devices are required to be capable of polarization conversion in the entire wavelength range as one of their characteristics, for example, [Re(450)/Re(550)]<1 It is known that uniform polarization conversion is theoretically possible in a wavelength range exhibiting reverse wavelength dispersion. Many polymerizable liquid crystal compounds that exhibit reverse wavelength dispersion when polymerized and cured are known to have a so-called T-shaped or H-shaped molecular structure. When the structure of the groups (side chains) extending in the long axis direction around the central structure (core structure) of the mold is bilaterally symmetrical, there is a tendency for stronger reverse wavelength dispersion to be exhibited.

On the other hand, depending on the molecular structure of the polymerizable liquid crystal compound, the solubility in solvents may be poor or the optical properties of the optical film may deteriorate. , attempts have been made to solve the above problems (for example, Patent Documents 1 and 2)

International Application Publication No. 2018/123622 International Application Publication No. 2019/160025

A coating solution obtained by dissolving a polymerizable liquid crystal compound in a solvent is applied to a supporting substrate to form a coating film, and then the polymerizable liquid crystal compound contained in the coating film is transferred to a liquid crystal phase state, and the solvent is retained. By removing the film, an optical film such as a retardation film can be obtained. However, conventional liquid crystal mixtures such as those disclosed in the above patent documents have a high phase transition temperature, and heating at high temperatures required during film formation not only deteriorates film formability but also improves the quality of the resulting optical film. This may cause deterioration of optical properties.

An object of the present invention is to provide a mixed composition of polymerizable liquid crystal compounds suitable for producing a retardation film having a low phase transition temperature and preferably excellent optical properties.

The present invention provides the following preferred embodiments.
[1] A mixed composition comprising a compound represented by the following formula (2) and at least one of the compound represented by the formula (1) and the compound represented by the formula (3), The area percentage value measured by liquid chromatography of the compound represented by (2) is the compound represented by formula (1), the compound represented by formula (2), and the formula (3) contained in the mixed composition. The mixed composition is more than 50% and less than 95% based on the sum of the area values of the compounds represented by.
A-Ar-A (1)
A-Ar-B (2)
B-Ar-B (3)
[A in formula (1) and formula (2) is the following formula (4):
*-D ¹ -(A ¹ -E ¹ )m-SP ¹ -L ¹ (4)
It is expressed as
B in formula (2) and formula (3) is the following formula (5):
*-D ² -(A ² -E ² )n-SP ² -L ² (5)
It is expressed as
In formula (4) and formula (5),
* represents the bonding position with Ar in formula (1), formula (2) or formula (3),
m and n each independently represent an integer of 1 or more, and m and n are different from each other,
D ¹ and D ² each independently represent -C(=O)-O- or -O-C(=O)-,
E ¹ and E ² are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ - , -NR ⁵ -, or a combination of two or more thereof, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. If m is an integer greater than or equal to 2, the plurality of ^E1 's may be the same or different, and if n is an integer greater than or equal to 2, the plurality of E2 ^'s may be the same or different. may be different,
A ¹ and A ² are each independently a divalent aromatic hydrocarbon group having 6 or more carbon atoms which may have a substituent, or a divalent aromatic hydrocarbon group having 6 or more carbon atoms which may have a substituent. Represents a divalent alicyclic hydrocarbon group, when m is an integer of 2 or more, the plurality of ^A1s may be the same or different, and when n is an integer of 2 or more, Multiple ^A2s may be the same or different,
SP ¹ and SP ² each independently represent a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, or a linear or branched alkenylene group having 2 to 20 carbon atoms; 20 linear or branched alkynylene groups, or one or more of -CH ₂ - constituting the alkylene group, the alkenylene group, and the alkynylene group is -O-, -S-, -NH-, -N (Q) represents a divalent linking group substituted with - or -CO-, Q represents a substituent,
L ¹ and L ² each independently represent a monovalent organic group, at least one of L ¹ and L ² is a polymerizable group,
Ar in formulas (1) to (3) is a group represented by any of the following formulas (Ar-1) to (Ar-6):

[In formulas (Ar-1) to (Ar-6),
* represents a bond with D ¹ or D ² ;
Q ¹ represents -S-, -O- or -NR ⁶ -, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
^Q2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ⁶ -, and R ⁶ is a hydrogen atom or a carbon number of 1 to 6 which may have a substituent. represents an alkyl group;
Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group,
Y ² represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. -CH ₂ - may be substituted with -O-, -CO-, -O-CO- or -CO-O-;
Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent carbon atom 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR ⁶ R ⁷ or -SR ⁶ , and Z ¹ and Z ² are bonded to each other to form an aromatic ring or an aromatic heterocycle. R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Z ⁴ is an aliphatic hydrocarbon group or alkoxy group having 2 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, represents a cyano group, a nitro group, -NR ⁶ R ⁷ or -SR ⁶ , and R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay may have a hydrogen atom or a substituent. Represents an alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ax and Ay are a bond. may form a ring;
Y ³ and Y ⁴ each independently represent the following formula (Y ³ -1):

[In formula (Y ³ -1),
R ^Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X ³ , and the substituent X ³ is a fluorine atom, a 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, dimethyl A silyl group, a thioisocyano group, or one -CH ₂ - or two or more non-adjacent -CH ₂ -s each independently represent -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-, a linear or It represents a branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or it may be a group represented by -B ³¹ -F ³¹ -P ³¹ (wherein , B ³¹ is -CR ⁸ R ⁹ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C (=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁸ -, -NR ⁸ -CO-, -O-CH ₂ - , -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, and R ⁸ and R ⁹ each independently represent a hydrogen atom, a fluorine atom, or a C 1-4 carbon atom. represents an alkyl group; F ³¹ represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁰ or a halogen atom, and R ¹⁰ is a carbon Represents an alkyl group of numbers 1 to 4, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH ₂ - contained in the alkanediyl group is -O- or -CO- may be substituted with; P ³¹ represents a hydrogen atom or a polymerizable group),
U ¹ represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group is , may be substituted by one or more of the above substituents ^X3 ;
T ¹ is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² - or O-NU ² -, and U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group. (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E ³¹ -A ³¹ ) _q -B ³¹ -F ³¹ - ^P31 , and each of the alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents ^X3 , and the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently substituted with -O -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, - NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or - It may be replaced by C≡C-, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the cycloalkyl group or cycloalkenyl group are each independently -O-, It may be replaced with -CO-, -COO-, -OCO- or O-CO-O-, E ³¹ is defined in the same manner as B ³¹ above, and A ³¹ is a divalent group having 3 to 16 carbon atoms. It represents an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R ¹¹ , -OR ¹² , which may be substituted with a cyano group or a nitro group, R ¹¹ represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents an alkyl group having 1 to 4 carbon atoms. represents a group, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and B ³¹ , F ³¹ and P ³¹ have the same meanings as the above B ³¹ , F ³¹ and P ³¹ , respectively. However, q represents an integer from 0 to 4, and when multiple E ³¹ and/or A ³¹ exist, they may be the same or different, and U ¹ and U ² combine to form a ring. ]
represents a group selected from ]
[2] The mixed composition according to [1] above, wherein one of m in formula (4) and n in formula (5) is 1 and the other is 2.
[3] The above [1] or [2], wherein A ¹ in formula (4) and A ² in formula (5) each independently represent a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group; 2].
[4] The mixed composition according to any one of [1] to [3] above, wherein in formula (4), m is 1 and A ¹ is a 1,4-cyclohexanediyl group.
[5] The mixed composition according to any one of [1] to [4] above, wherein in formula (5), n is 1 and A ² is a 1,4-cyclohexanediyl group.
[6] The mixed composition according to any one of [1] to [5] above, wherein L ¹ in formula (4) and L ² in formula (5) are each an acryloyloxy group.
[7] The above [1], wherein Ar in formulas (1) to (3) is a group represented by any one of formula (Ar-1), formula (Ar-3) and formula (Ar-4). ] to [6]. The mixed composition according to any one of [6].
[8] The mixed composition according to any one of [1] to [7] above, further comprising a photopolymerization initiator.
[9] The mixed composition according to any one of [1] to [8] above, further comprising an organic solvent.
[10] A retardation film comprising a cured product of the mixed composition according to any one of [1] to [9] above.
[11] A circularly polarizing plate comprising the retardation film according to [10] above.
[12] A reaction mixture composition containing a compound represented by formula (7) by reacting a compound represented by formula (1) and a compound represented by formula (6) in the presence of a basic compound The area percentage value measured by liquid chromatography of the compound represented by formula (7) in the reaction mixture is the compound represented by formula (1) contained in the reaction mixture composition, the formula A reaction mixture composition containing the compound represented by formula (7), which is more than 50% and less than 95% based on the sum of the area values of the compound represented by (6) and the compound represented by formula (7). How things are manufactured.
A-Ar-A (1)
HO-Ar-OH (6)
A-Ar-OH (7)
[A in formula (1) and formula (7) is the following formula (4):
*-D ¹ -(A ¹ -E ¹ )m-SP ¹ -L ¹ (4)
It is expressed as
In formula (4), * represents the bonding position with Ar in formula (1) or formula (7),
m represents an integer of 1 or more,
D ¹ represents -C(=O)-O- or -OC(=O)-,
E ¹ is a single bond, -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or , represents a divalent linking group consisting of a combination of two or more of these, R ¹ to R ⁵ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and m is 2 or more. If it is an integer, multiple ^E1s may be the same or different,
A ¹ is a divalent aromatic hydrocarbon group having 6 or more carbon atoms which may have a substituent, or a divalent alicyclic hydrocarbon group having 6 or more carbon atoms which may have a substituent. represents a hydrogen group, and when m is an integer of 2 or more, the plurality of ^A1s may be the same or different,
SP ¹ is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, or a linear or branched alkenylene group having 2 to 20 carbon atoms. or one or more of -CH ₂ - constituting the alkylene group, the alkenylene group, and the alkynylene group is -O-, -S-, -NH-, -N(Q)-, or represents a divalent linking group substituted with -CO-, Q represents a substituent,
L ¹ represents a monovalent organic group,
Ar in formula (1), formula (6) and formula (7) is a group represented by any of the following formulas (Ar-1) to (Ar-6):

[In formula (Y ³ -1),
R ^Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X ³ , and the substituent X ³ is a fluorine atom, a 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, dimethyl A silyl group, a thioisocyano group, or one -CH ₂ - or two or more non-adjacent -CH ₂ -s each independently represent -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-, a linear or It represents a branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or it may be a group represented by -B ³¹ -F ³¹ -P ³¹ (wherein , B ³¹ is -CR ⁸ R ⁹ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C (=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁸ -, -NR ⁸ -CO-, -O-CH ₂ - , -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, and R ⁸ and R ⁹ each independently represent a hydrogen atom, a fluorine atom, or a C 1-4 carbon atom. represents an alkyl group; F ³¹ represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁰ or a halogen atom, and R ¹⁰ is a carbon Represents an alkyl group of numbers 1 to 4, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH ₂ - contained in the alkanediyl group is -O- or -CO- may be substituted with; P ³¹ represents a hydrogen atom or a polymerizable group),
U ¹ represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group is , may be substituted by one or more of the above substituents ^X3 ;
T ¹ is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² - or O-NU ² -, and U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group. (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E ³¹ -A ³¹ ) _q -B ³¹ -F ³¹ - ^P31 , and each of the alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents ^X3 , and the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently substituted with -O -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, - NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or - It may be replaced by C≡C-, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the cycloalkyl group or cycloalkenyl group are each independently -O-, It may be replaced with -CO-, -COO-, -OCO- or O-CO-O-, E ³¹ is defined in the same manner as B ³¹ above, and A ³¹ is a divalent group having 3 to 16 carbon atoms. It represents an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R ¹¹ , -OR ¹² , which may be substituted with a cyano group or a nitro group, R ¹¹ represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents an alkyl group having 1 to 4 carbon atoms. represents a group, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and B ³¹ , F ³¹ and P ³¹ have the same meanings as the above B ³¹ , F ³¹ and P ³¹ , respectively. However, q represents an integer from 0 to 4, and when multiple E ³¹ and/or A ³¹ exist, they may be the same or different, and U ¹ and U ² combine to form a ring. ]
represents a group selected from ]
[13] In the above [12], the compound represented by formula (1) and the compound represented by formula (6) are reacted in the presence of a basic compound having an ionization constant (pKa) of 7 or more. Manufacturing method described.
[14] A reaction mixture composition containing a compound represented by formula (7) obtained by the production method described in [12] or [13] above, and formula (8):
HOOC-(A ² -E ² )n-SP ² -L ² (8)
[In formula (8), A ² , E ² , n, SP ² and L ² each have the same meaning as A ² , E ² , n, SP ² and L ² in formula (5)]
and mixing the compound represented by the formula (7) and the compound represented by the formula (8) to produce the compound represented by the formula (2), The method for producing the mixed composition according to [1] above.

According to the present invention, it is possible to provide a mixed composition of liquid crystal compounds suitable for producing a retardation film having a low phase transition temperature and preferably excellent optical properties.

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

<Mixed composition>
The mixed composition of the present invention comprises a compound represented by formula (2) (hereinafter also referred to as "compound (2)") and a compound represented by formula (1) (hereinafter also referred to as "compound (1)"). ) and at least one of the compound represented by formula (3) (hereinafter also referred to as "compound (3)"). A compound (2) having a bilaterally asymmetrical structure centered around the group represented by Ar in formula (2) is replaced with a compound (2) having a bilaterally symmetrical structure centered around Ar in formula (1) or formula (3) ( The mixed composition of the present invention containing 1) and/or compound (3) in a specific quantitative relationship has a low phase transition temperature to a liquid crystal phase. This makes it possible to form a film without exposing it to high-temperature conditions, and it is expected that the resulting optical film will have even higher optical properties. In addition, in this specification, even if the structure of Ar in formulas (1) to (3) is left-right asymmetric, a compound represented by A or B in formulas (1) to (3) that is bonded to the Ar If the structure is the same on the left and right sides with Ar as the center, such a compound is considered to be bilaterally symmetrical.

Compound (2) contained in the mixed composition of the present invention has the formula (2):
A-Ar-B (2)
It has the structure represented by . Compound (2) has a group represented by Ar in formula (2), and two side chains bonded to the Ar (i.e., A and B in formula (2)) having different structures. It has an asymmetrical structure. More specifically, A in formula (2) represents formula (4):
*-D ¹ -(A ¹ -E ¹ )m-SP ¹ -L ¹ (4)
It has a structure represented by the following, and B in formula (2) is represented by formula (5):
*-D ² -(A ² -E ² )n-SP ² -L ² (5)
Compound (2) has a structure represented by the following, and the compound (2) has an asymmetric structure in terms of the number of ring structures contained in at least each side chain of A and B.

In formulas (4) and (5), m and n each independently represent an integer of 1 or more. m and n are each independently preferably an integer of 1 to 3, more preferably 1 or 2. In equations (4) and (5), m and n are different numbers. In compound (2), the number of ring structures contained in A in formula (2) (that is, the group represented by A ¹ in formula (4)) and the ring contained in B in formula (2) The difference from the number of structures (that is, the group represented by A ² in formula (5)) is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. . In one preferred embodiment of the invention, one of m and n is 1 and the other is 2 or 3. In a more preferred embodiment, one of m and n is 1 and the other is 2. Compound (2) having a left-right asymmetric structure in the number of ring structures contained in each side chain of A and B is a mixed composition with compound (1) and/or compound (3) having a highly symmetrical structure. can lead to an effective reduction in the phase transition temperature. Although this is not necessarily limited, compounds with a bilaterally symmetrical structure tend to have excellent crystallinity because they can be arranged regularly, and the phase transition temperature tends to be relatively high. When adding a compound with an asymmetric structure to a compound with such a symmetric structure, the compound with an asymmetric structure may affect the ease of arranging the compound, act to reduce crystallinity, and lower the phase transition temperature. it is conceivable that. On the other hand, as the ratio of compounds with a symmetric structure to compounds with a symmetric structure increases, it becomes difficult to secure the high orientational order achieved by compounds with a symmetric structure, and optical properties tend to deteriorate. It was difficult for the compound to become a main component constituting the liquid crystal cured layer (for example, more than 50% by mass with respect to the total mass of the (polymerizable) liquid crystal compound constituting the liquid crystal cured film). Although the mechanism is not clear, the mixed composition of the present invention, which has a high proportion of compound (2) having a left-right asymmetric structure in terms of the number of ring structures contained in each side chain of A and B, has a significantly lower phase transition temperature. It is possible to maintain excellent optical properties, which are ideal for optical films such as retardation plates, while achieving a significant reduction in optical properties. Furthermore, in one embodiment of the present invention, the effect is a structure in which the number of ring structures in each side chain is the same but left-right asymmetrical (for example, in the case where left-right asymmetrical occurs due to a difference in the length of the alkyl chain, etc.) It tends to appear more markedly than when compounding with a compound having .

In formulas (4) and (5), D ¹ and D ² each independently represent -C(=O)-O- or -OC(=O)-.

In formulas (4) and (5), E ¹ and E ² are each independently a single bond, -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of two or more of these, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, Represents an atom or an alkyl group having 1 to 4 carbon atoms. Examples of the divalent linking group consisting of a combination of two or more of the above include -CO-O-, -O-CO-, -C(=S)O-, -O-CO-O-, -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- Examples include NR ⁵ -. E ¹ and E ² are each independently preferably a single bond, -O-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ⁵ -, and more Preferably it is a single bond, -O-, -CO-O- or -O-CO-. When m is an integer of 2 or more, the plural E ¹ 's may be the same or different, and when n is an integer of 2 or more, the plural E ² 's may be the same or different. May be different. When m and n are each an integer of 2 or more, E ¹ and E ² bonded to SP ¹ or SP ² are each 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 the bonding position with A ¹ or A ² ), more preferably a single bond, -O-, -CO-O- or -O-CO-.

In formulas (4) and (5), A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 or more carbon atoms, which may have a substituent, or a substituent. Represents an optional alicyclic hydrocarbon group having 6 or more carbon atoms. Examples of the divalent aromatic hydrocarbon group having 6 or more carbon atoms represented by A ¹ and A ² include aromatic hydrocarbon groups having 6 to 20 carbon atoms, and specifically, the following (a- Examples include aromatic hydrocarbon groups represented by 1) to (a-8).

Examples of the divalent alicyclic hydrocarbon group having 6 or more carbon atoms represented by A ¹ and A ² include alicyclic hydrocarbon groups having 6 to 16 carbon atoms, and specifically, the following ( Examples include alicyclic hydrocarbon groups represented by a-9) to (a-11).

Examples of substituents that the aromatic hydrocarbon group and alicyclic hydrocarbon group may have include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group, and tert-butyl group. ; Alkoxy group having 1 to 4 carbon atoms such as methoxy group and ethoxy group; Fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; Cyano group; Nitro group; Halogen such as fluorine atom, chlorine atom, bromine atom, etc. Examples include atoms.

A ¹ and A ² are an unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted alicyclic hydrocarbon group having 6 to 16 carbon atoms; is preferable, and a 1,4-cyclohexanediyl group or a 1,4-phenylene group is more preferable. When m is an integer of 2 or more, the plural A ¹ 's may be the same or different, and when n is an integer of 2 or more, the plural A ² 's may be the same or different. May be different.

In the present invention, it is preferable that A ¹ and A ² are each independently a 1,4-cyclohexanediyl group or a 1,4-phenylene group. Further, when m is 1, it is preferable that A ¹ is a 1,4-cyclohexanediyl group, and when n is 1, it is preferable that A ² is a 1,4-cyclohexanediyl group. Furthermore, in one embodiment of the present invention, A ¹ and A ² bonded to D ¹ and D ² are preferably 1,4-cyclohexanediyl group or 1,4-phenylene group, and 1,4-cyclohexane More preferably it is a diyl group. Furthermore, in a preferred embodiment of the present invention, when A ¹ and A ² bonded to D ¹ and D ² are 1,4-cyclohexanediyl groups, E adjacent to A ¹ and/or A ² A ¹ and/or A ² bonded to ¹ or E ² are 1,4-phenylene groups.

In formulas (4) and (5), SP ¹ and SP ² each independently represent a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, or a linear or branched alkylene group having 2 to 20 carbon atoms. or a branched alkenylene group, a linear or branched alkynylene group having 2 to 20 carbon atoms, or one or more of -CH ₂ - constituting the alkylene group, the alkenylene group, and the alkynylene group is -O- , -S-, -NH-, -N(Q)- (Q is a substituent), or -CO- represents a divalent linking group substituted. Examples of the linear or branched alkylene group having 1 to 20 carbon atoms represented by SP ¹ and SP ² include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, and methylhexylene group. group, heptylene group, etc. Examples of the linear or branched alkenylene group having 2 to 20 carbon atoms include ethenylene group, propenylene group, and butenylene group. Examples of the linear or branched alkynylene group having 2 to 20 carbon atoms include, for example, an ethynylene group.

SP ¹ and SP ² are such that one or more of -CH ₂ - constituting the alkylene group, alkenylene group, and alkynylene group is -O-, -S-, -NH-, -N(Q)-, or - It may also be a divalent linking group substituted with CO-. Examples of the substituent represented by Q include the same substituents as those exemplified as substituents that the aromatic hydrocarbon group or alicyclic hydrocarbon group represented by A ¹ and A ² may have. .

SP ¹ and SP ² are each independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, or a carbon number It is preferably a linear or branched alkynylene group having 2 to 20 carbon atoms, a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 2 to 12 carbon atoms. or a linear or branched alkynylene group having 2 to 12 carbon atoms, more preferably a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms. More preferred.

In formulas (4) and (5), L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² is a polymerizable group. Examples of the monovalent organic group include an alkyl group, an aryl group, and a heteroaryl group. Among these, the monovalent organic group represented by L ¹ or L ² 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 alkyl group may be linear, branched or cyclic, preferably linear.

The polymerizable groups represented by L ¹ and L ² may be any group that can polymerize compound (2), and specifically include vinyl group, p-stilbene group, acryloyl group, methacryloyl group, Acryloyloxy group, methacroyloxy group, carboxyl group, methylcarbonyl group, hydroxyl group, amide group, alkylamino group having 1 to 4 carbon atoms, amino group, epoxy group, oxetanyl group, aldehyde group, isocyanate group, thioisocyanate group, etc. is exemplified. Moreover, such a polymerizable group may contain an ether bond or an ester bond that connects the above-exemplified group and SP ¹ or SP ² . The polymerizable groups represented by L ¹ and L ² are preferably radically polymerizable groups or cationic polymerizable groups suitable for photopolymerization, especially in that they are easy to handle and easy to manufacture. , an acryloyl group, a methacryloyl group, an acryloyloxy group, or a methacryloyloxy group are preferred, an acryloyl group or an acryloyloxy group is more preferred in terms of high polymerizability, and an acryloyloxy group is even more preferred.

From the viewpoint that the reactivity (polymerizability) of compound (2) is likely to be high, it is preferable that both L ¹ and L ² are polymerizable groups, and L ¹ and L ² are acryloyl group, methacryloyl group, acryloyl group, respectively. It is more preferably an oxy group or a methacryloyloxy group, and even more preferably both L ¹ and L ² are an acryloyloxy group.

Specific examples of the structure represented by formula (4) and the structure represented by formula (5) include structures represented by the following formulas (R-1) to (R-138). . * in the formula represents the bonding position to the group Ar, and n may be an integer from 1 to 20, for example. Note that the cyclohexane ring may be in the trans or cis form, but is preferably in the trans form. Since compound (2) has an asymmetric structure at least in the number of ring structures around the group Ar, for example, as the structure represented by formula (4) (i.e., A in formula (2)), one ring It has a structure represented by any of the following formulas (R-1) to (R-31) having a structure, and as a structure represented by formula (5) (i.e., B in formula (2)), A structure represented by any of the following formulas (R-32) to (R-73) having two ring structures, or a structure represented by any of the following formulas (R-74) to (R-138) having three ring structures. It can have a structure represented by any of the following. Alternatively, for example, the structure represented by formula (4) has a structure represented by any of the following formulas (R-32) to (R-73) having two ring structures, and the structure represented by formula (5) The structure represented by may have a structure represented by any of the following formulas (R-74) to (R-138) having three ring structures.

Furthermore, the terminal portion in each of the above structures (for example, the portion corresponding to -SP ¹ -L ¹ in formula (4)) may have any of the following structures.

In a preferred embodiment of the present invention, each structure represented by D ¹ , SP ¹ and L ¹ in formula (4) constituting compound (2) is each represented by formula (5 ) is the same as each structure represented by D ² , SP ² and L ² . That is, structure A represented by formula (4) and structure B represented by formula (5) are the structure represented by -(A ¹ -E ¹ )m- in formula (4), It is preferable that the structure differs only from the structure represented by -(A ² -E ² )n- in formula (5). When compound (2) has such a structure, the molecular structures of compound (2) and compound (1) and/or compound (3) contained in the liquid crystal mixture are similar or similar to each other, and the liquid crystal mixture is The phase transition temperature tends to be effectively lowered. In addition, in a liquid crystal mixture in which the molecular structures of the contained compounds are similar or similar to each other, the liquid crystal compounds have less influence on each other when aligning, and are easily aligned with a high degree of alignment order, so the optical properties of the resulting cured liquid crystal film are improved. Easy to improve.

In formula (4) and formula (5), it is a group represented by any of the following formulas (Ar-1) to (Ar-6). The groups represented by formulas (Ar-1) to (Ar-5) give a bulky molecular structure in the direction crossing the long axis direction in the polymerizable liquid crystal compound represented by formula (2), They have a common feature in that the absorption wavelength in the short axis direction is a long wavelength, and the retardation generated by oriented liquid crystal molecules usually has reverse wavelength dispersion. In the group represented by formula (Ar-6), the retardation generated by aligned liquid crystal molecules often has positive wavelength dispersion.

The total number N _π of π electrons contained in the divalent linking group containing an aromatic hydrocarbon ring or an aromatic heterocycle represented by formulas (Ar-1) to (Ar-6) is preferably 12 or more. , more preferably 16 or more, still more preferably 18 or more, particularly preferably 20 or more. Further, it is preferably less than 36, more preferably 32 or less, even more preferably 30 or less, particularly preferably 26 or less.

In formulas (Ar-1) to (Ar-6), * represents a bond with D ¹ or D ² in formula (4) or formula (5).

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

In formula (Ar-2), W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ⁶ -, and R ⁶ has a hydrogen atom or a substituent. represents an alkyl group having 1 to 6 carbon atoms.

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

In formulas (Ar-1) to (Ar-6), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 3 to 20 carbon atoms; 20 alicyclic hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, halogen atom, cyano group, nitro group, -NR ⁶ R ⁷ or -SR ⁶ , Z ¹ and Z ² may be combined with each other to form an aromatic ring or an aromatic heterocycle. R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formula (Ar-6), Z ⁴ is an aliphatic hydrocarbon group or alkoxy group having 2 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic group having 6 to 20 carbon atoms. represents a group hydrocarbon group, a halogen atom, a cyano group, a nitro group, -NR ⁶ R ⁷ or -SR ⁶ . R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms

In formulas (Ar-3) and (Ar-4), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , Ay is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon number having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. It represents 2 to 30 organic groups, and Ax and Ay may be combined to form a ring.

In formula (Ar-1), Y ¹ is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and has 6 to 6 carbon atoms and may have a substituent. A 12 aromatic hydrocarbon group or an aromatic heterocyclic group having 3 to 12 carbon atoms is more preferred. The aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent is preferably an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. As used herein, "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and a fused aromatic hydrocarbon group formed by condensing two or more aromatic rings. Examples include aromatic hydrocarbon groups formed by bonding a hydrocarbon group and two or more aromatic rings. "Polycyclic aromatic heterocyclic group" means an aromatic heterocyclic group having at least one heteroaromatic ring and at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring. , an aromatic heterocyclic group formed by the condensation of one or more aromatic heterocycles and one or more rings selected from the group consisting of aromatic rings and heteroaromatic rings, and at least one heteroaromatic ring and aromatic Examples include an aromatic heterocyclic group formed by bonding a ring and at least one ring selected from the group consisting of a heteroaromatic ring.

Examples of substituents that the aromatic hydrocarbon group or aromatic heterocyclic group may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, and an alkylsulfinyl group having 1 to 6 carbon atoms. group, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, N-alkylamino group, N,N-dialkylamino group having 2 to 8 carbon atoms, sulfamoyl group, N-alkylsulfamoyl group having 1 to 6 carbon atoms and N,N-dialkylsulfa having 2 to 12 carbon atoms A moyl group is mentioned.

Examples of Y ¹ include groups represented by the following formulas (Y ¹ -1) to (Y ¹ -7).

In formulas (Y ¹ -1) to (Y ¹ -7), the * part represents a connecting part.

In formulas (Y ¹ -1) to (Y ¹ -7), Z ⁵ each independently represents a halogen atom or an organic group having 1 to 20 carbon atoms, such as a fluorine atom, a chlorine atom, a bromine atom , methyl group, ethyl group, isopropyl group, sec-butyl group, cyano group, nitro group, sulfone group, nitroxydo group, carboxyl group, trifluoromethyl group, methoxy group, thiomethyl group, N,N-dimethylamino group, N - Methylamino group is preferred, halogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, cyano group, nitro group, trifluoromethyl group is more preferred, methyl group, ethyl group, isopropyl group, sec-butyl group A pentyl group and a hexyl group are particularly preferred.

In formulas (Y ¹ -1) to (Y ¹ -7), V ¹ and V ² are each independently -CO-, -S-, -NR ¹³ -, -O-, -Se- or - It represents SO ₂ -, and is preferably -S-, -NR ¹³ - or -O-. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In formulas (Y ¹ -1) to (Y ¹ -7), W ³ to W ⁷ each independently represent -C= or -N=.

In formulas (Y ¹ -1) to (Y ¹ -7), at least one of V ¹ , V ² and W ³ to W ⁷ preferably represents a group containing S, N or O.

In formulas (Y ¹ -1) to (Y ¹ -7), a each independently represents an integer of 0 to 3, preferably 0 or 1. b each independently represents an integer of 0 to 2, preferably 0.

Any group represented by formula (Y ¹ -1) to formula (Y ¹ -7) is any group represented by formula (Y ¹ -8) to formula (Y ¹ -13) below. A group represented by formula (Y ^{1 -8) is preferable, and a group represented by formula (Y 1} -8) is more preferable. Note that the * part represents a connecting part.

In formulas (Y ¹ -8) to (Y ¹ -13), Z ⁵ , a, b, V ¹ , V ² and W ³ are the same as those in (Y ¹ -1) to (Y ¹ -7) It has the same meaning as Z ⁵ , a, b, V ¹ , V ² and W ³ .

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

In one embodiment of the present invention, the group represented by formula (Ar-1) specifically includes groups represented by the following formulas (Ar ¹ -1) to (Ar ¹ -126). The * part in the formula represents a connecting part with D ¹ or D ² in formula (4) or formula (5).

In one embodiment of the present invention, the group represented by formula (Ar-2) specifically includes groups represented by the following formulas (Ar ² -1) to (Ar ² -13). The * part in the formula represents a connecting part with D ¹ or D ² in formula (4) or formula (5).

In one embodiment of the present invention, the group represented by formula (Ar-3) specifically includes groups represented by the following formulas (Ar ³ -1) to (Ar ³ -23). The * part in the formula represents a connecting part with D ¹ or D ² in formula (4) or formula (5).

In addition to the groups specifically exemplified above, the groups represented by formulas (Ar-1) to (Ar-4) include, for example, JP-A No. 2011-207765, JP-A No. 2008-107767, WO2014/ The groups described in JP 010325 and the like may also be used.

In formula (Ar-5), Y ³ and Y ⁴ each independently represent the following formula (Y ³ -1):

selected from the groups represented by

In formula (Y ³ -1), R ^Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group may be substituted with one or more substituents ^X3 .

Substituent X ³ is 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 -CH ₂ - or two or more non-adjacent -CH ₂ -s each independently -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- represents a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or -B ³¹ -F ³¹ -P ³¹ It may be a group represented by B ³¹ is -CR ⁸ R ⁹ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C( =S) -O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁸ -, -NR ⁸ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond, and R ⁸ and R ⁹ are each independently a hydrogen atom, a fluorine atom, or an alkyl having 1 to 4 carbon atoms. represents a group; F ³¹ represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with -OR ¹⁰ or a halogen atom, and R ¹⁰ represents a carbon number Represents an alkyl group of 1 to 4, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH ₂ - contained in the alkanediyl group is -O- or -CO-. It may be substituted; P ³¹ represents a hydrogen atom or a polymerizable group.

The substituent X ³ is preferably a fluorine atom, a chlorine atom, -CF ₃ , -OCF ₃ or a cyano group. R ^Y1 is preferably an alkyl group having 1 to 6 carbon atoms that is unsubstituted or substituted with a hydrogen atom or one or more fluorine atoms, and more preferably a hydrogen atom.

In formula (Y ³ -1), U ¹ represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and U ¹ has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , is an organic group having 2 to 30 carbon atoms. The aromatic hydrocarbon group may be substituted with one or more of the above substituents ^X3 .

U ¹ is preferably an organic group having an aromatic heterocycle in which one or more carbon atoms are substituted with a hetero atom, from the viewpoint of good wavelength dispersion. ^U1 is an organic group having an aromatic heterocycle which is a condensed ring of a 5-membered ring and a 6-membered ring, since it has good wavelength dispersion due to aligned liquid crystal molecules and exhibits high birefringence. It is more preferable.

Specifically, U ¹ preferably has a group represented by the following formula. In addition, in the following formula, these groups have a bond with T ¹ at an arbitrary position.

In formula (Y ³ -1), T ¹ is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO- NU ² -, -OCO-NU ² - or O-NU ² -, where U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. A cycloalkenyl group, an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E ³¹ -A ³¹ ) _q -B ³¹ -F ³¹ -P ³¹ . Each of the alkyl group, cycloalkyl group, cycloalkenyl group, and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents ^X3 , and the alkyl group is the cycloalkyl group. Alternatively, it may be substituted with a cycloalkenyl group. One -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO- , -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH -OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and the cycloalkyl group or cyclo One -CH ₂ - or two or more non-adjacent -CH ₂ -s in an alkenyl group are each independently -O-, -CO-, -COO-, -OCO- or O-CO-O - may be replaced. E ³¹ is defined in the same manner as B ³¹ above, and A ³¹ represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms; The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹¹ , -OR ¹² , a cyano group, or a nitro group. R ¹¹ represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, R ¹² represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a fluorine atom. You can leave it there. B ³¹ , F ³¹ and P ³¹ have the same meanings as B ³¹ , F ³¹ and P ³¹ , respectively, and q represents an integer of 0 to 4. When a plurality of E ³¹ and/or A ³¹ are present, they may be the same or different.

T ¹ is preferably -O-, -S-, -N=CU ² - or -NU ² - from the viewpoint of good birefringence and easy synthesis, and has a good effect on wavelength dispersion in aligned liquid crystal molecules. From the viewpoint of easily improving birefringence, -O-, -S-, or -NU ² - is more preferable.

U ² may be substituted by one or more of the above substituents X ³ , and one -CH ₂ - or two or more non-adjacent -CH ₂ -s each independently represent -O-, An alkyl group or alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, which may be substituted with -CO-, -COO-, -OCO- or -O-CO-O-, or It is preferably a cycloalkenyl group having 3 to 12 carbon atoms, or the above-mentioned alkyl group or alkenyl group which may be substituted with the cycloalkyl group, cycloalkenyl group, or aryl group.

Among them, in U ² , from the viewpoint of birefringence and solvent solubility, the hydrogen atom may be substituted with a fluorine atom, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s are each independently More preferably, it is a linear alkyl group having 1 to 20 carbon atoms which may be replaced with -O-, -CO-, -COO- or -OCO-.

U ¹ and U ² may be combined to form a ring. In that case, examples include a cyclic group represented by -NU ¹ U ² or a cyclic group represented by -N=CU ¹ U ² .

Y ³ and Y ⁴ are each selected from the following formulas (Y ^3' -1) to (Y ^3' -47) in view of easy availability of raw materials, good solubility, and high birefringence. It is particularly preferred to represent a group.

From the viewpoint of improving the orientation of compound (2) and facilitating industrial production and improving productivity, the group represented by formula (Ar-5) is specifically the following group. can be mentioned. * in (Ar ⁵ -1) to (Ar ⁵ -20) below represents a bond with D ¹ or D ² in formula (4) or formula (5).

In one embodiment of the present invention, the group represented by formula (Ar-6) specifically includes groups represented by the following formulas (Ar ⁶ -1) to (Ar ⁶ -5). The * part in the formula represents a connecting part with D ¹ or D ² in formula (4) or formula (5). Note that Cl in formula (Ar ⁶ -3) may be another halogen atom.

Among formulas (Ar-1) to (Ar-6), groups represented by any of formulas (Ar-1) to (Ar-5) are preferable, and groups represented by formulas (Ar-1) and (Ar-3) are preferable. ) and the group represented by formula (Ar-4) are more preferred, and the group represented by formula (Ar-1) is even more preferred.

Compound (2) is usually a polymerizable liquid crystal compound, and it is preferable that the cured liquid crystal film obtained by aligning and polymerizing compound (2) alone is a polymerizable liquid crystal compound that exhibits so-called reverse wavelength dispersion. .

The mixed composition of the present invention contains at least one of compound (1) and compound (3) in addition to compound (2). Compound (1) has a structure represented by A in formula (2) constituting compound (2) (i.e., a structure represented by formula (4)) on both sides of Ar, and has left and right structures centered on Ar. is a compound with a symmetric structure. Similarly, compound (3) has the structure represented by B in formula (2) constituting compound (2) (that is, the structure represented by formula (5)) on both sides of Ar. It is a compound that has a symmetrical structure left and right at the center. Compound (1) and compound (3) are each preferably a polymerizable compound. Compound (1) and compound (3) may each be a liquid crystal compound or a non-liquid crystal compound, but from the viewpoint of improving optical properties, compound (1) contained in addition to compound (2) may be used. ) and compound (3) is preferably a liquid crystal compound, and all compounds corresponding to compound (1), compound (2), and compound (3) contained in the mixed composition are liquid crystal compounds. More preferably, all of the compounds corresponding to compound (1), compound (2), and compound (3) are polymerizable liquid crystal compounds. The mixed composition of the present invention may contain a plurality of polymerizable liquid crystal compounds corresponding to compound (1), compound (2) and/or compound (3), respectively.

In the mixed composition of the present invention, the area percentage value of compound (2) measured by liquid chromatography is the sum of the area values of compound (1), compound (2), and compound (3) contained in the mixed composition. more than 50% and less than 95% based on Here, in this specification, "area percentage value" means the ratio of the peak area of the target compound to the total peak area of compound (1), compound (2), and compound (3). When the area percentage value of compound (2) exceeds 50%, the phase transition temperature in the mixed composition tends to be sufficiently lowered, and a cured liquid crystal film can be formed at a lower processing temperature. This makes it possible to suppress the occurrence of damage and orientation defects caused by heating at high temperatures, and it becomes possible to form films without deteriorating the optical properties that can originally be expressed by the polymerizable liquid crystal compound used, resulting in excellent optical properties. A cured liquid crystal film having characteristics can be obtained. Asymmetrical liquid crystal compounds may be disadvantageous compared to symmetrical liquid crystal compounds, for example, in terms of wavelength dispersion (especially reverse wavelength dispersion) of the resulting cured liquid crystal film; In general, by containing a more bilaterally asymmetrical compound (2) and a less bilaterally symmetrical compound (1) and/or (3) than compound (2) in a specific balance as described above, Optical properties superior to those of a cured liquid crystal film obtained by aligning and polymerizing a left-right symmetrical compound alone, which is said to tend to exhibit reverse wavelength dispersion, can be imparted. From the viewpoint of further enhancing such effects, in the present invention, the area percentage value of compound (2) is preferably 55% or more, more preferably 60% or more, still more preferably 65% or more, particularly preferably 70% or more. % or more, and may be, for example, 75% or more. The upper limit of the area percentage value of compound (2) may be, for example, 90% or less, or 85% or less.
In addition, in the mixed composition of the present invention, when a plurality of compounds corresponding to compound (1), compound (2) and/or compound (3) are included, the area percentage value of compound (2) is ), calculated based on the peak area of all compounds (2) relative to the total peak area of all compounds (2) and all compounds (3). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, it can be measured and calculated by the method described in the Examples below.

The mixed composition of the present invention contains compound (2) in combination with compound (1) and/or compound (3), and the area percentage value of compound (2) exceeds 50%, so that, for example, , when a compound having a highly symmetrical structure such as compound (1) or compound (3) is used alone, and a mixed composition in which the area percentage value of the compound having a highly symmetrical structure exceeds 50%. The phase transition temperature to the liquid crystal phase can be significantly lowered compared to the case of solids. For example, the liquid crystal phase transition temperature (nematic phase transition temperature) of the mixed composition of compound (2) and compound (1) and/or compound (3) constituting the mixed composition of the present invention is When the cured liquid crystal film obtained from is a liquid crystal mixture capable of exhibiting reverse wavelength dispersion, the temperature is preferably 120°C or lower, more preferably 115°C or lower, and may be, for example, 110°C or lower, or even 105°C or lower. . Further, the phase transition temperature (nematic phase transition temperature) of the mixed composition is usually 25°C or higher, preferably 40°C or higher, and more preferably 50°C or higher.

In one embodiment of the present invention, the mixed composition of the present invention preferably has a phase transition temperature of 5% compared to the phase transition temperature (nematic phase transition temperature) of compound (1) or compound (3) alone. The temperature can be lowered by 10°C or more, more preferably 15°C or more, particularly preferably 20°C or more, for example, 30°C or more, and even 35°C or more. In addition, compared to a mixed composition that contains compound (1) and/or compound (3) together with compound (2), but in which the area percentage value of compound (2) is 50% or less, the phase transition temperature is preferably lowered. The temperature can be lowered by 5°C or more, more preferably by 10°C or more, for example by 15°C or more, and even by 20°C or more.

In the present 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), a thermogravimetric differential thermal analyzer (TG-DTA), etc. . When a plurality of liquid crystal compounds are included, the above phase transition temperature is the same as that of the compounds corresponding to compounds (1) to (3) constituting the mixed composition and all other compounds other than the compounds corresponding to compounds (1) to (3). It means the temperature measured using a mixture of liquid crystal compounds in which the liquid crystal compounds are mixed in the same ratio as the composition in the mixed composition.

The mixed composition of the present invention may contain liquid crystal compounds other than compounds (1) to (3) (hereinafter referred to as " (also referred to as "other liquid crystal compounds"). Examples of such liquid crystal compounds include 3.2 Non-chiral rod-like liquid crystal molecules in Chapter 3, Molecular Structure and Liquid Crystal Properties, of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000). , 3.3 Compounds described in chiral rod-like liquid crystal molecules, compounds described in JP-A No. 2010-31223, cured liquid crystal films such as those described in JP-A No. 2011-207765, Patent No. 5962760, etc. Examples include a polymerizable liquid crystal compound that can exhibit reverse wavelength dispersion when used as a polymer, a polymerizable liquid crystal compound that can exhibit forward wavelength dispersion, and the like.

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 based on a total of 100 parts by mass of compound (1), compound (2), and compound (3). The amount is not more than 10 parts by mass, more preferably not more than 10 parts by mass, even more preferably not more than 5 parts by mass. In particular, if the content of a liquid crystal compound whose molecular structure is significantly different from that of Compound (1), Compound (2) and/or Compound (3) is too high, phase separation is likely to occur, resulting in poor appearance and high optical properties. Therefore, it is preferable that the liquid crystal compound constituting the mixed composition of the present invention is substantially composed of a liquid crystal compound having a structure similar to that of compound (2).
Note that the above-mentioned "similar" refers to, for example, side chain A (i.e., the structure represented by formula (4)) and side chain B (i.e., the structure represented by formula (5)) in compound (2). , Ar has a common structure. In addition, the above-mentioned "substantially constitutes" refers to compounds (1) to (3) in which the content of compounds corresponding to compound (1), compound (2), and compound (3) is included in the mixed composition. This means that the amount is 90% by mass or more based on the total mass of the compound corresponding to and all other liquid crystal compounds. In one embodiment of the present invention, the mixed composition does not contain any liquid crystal compounds other than compounds corresponding to compound (1), compound (2) and/or compound (3).

The mixed composition of the present invention may be composed only of compound (2) and compound (1) and/or compound (3). From the viewpoint of improving reactivity, handling properties, etc. when compound (2) and compound (1) and/or compound (3) are polymerized to obtain a cured liquid crystal film, the mixed composition of the present invention contains compound ( In addition to 1), compound (2), and compound (3), the composition may further contain components such as a photopolymerization initiator, an organic solvent, a polymerization inhibitor, a photosensitizer, and a leveling agent.

When the mixed composition of the present invention contains the above-mentioned further components in addition to Compound (1), Compound (2) and Compound (3), Compound (1), Compound (3) in the mixed composition of the present invention The total mass of (2) and compound (3) may be, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, and more preferably It is 85 to 98 parts by weight, more preferably 90 to 95 parts by weight. If the total mass of compound (1), compound (2) and compound (3) is within the above range, it is advantageous from the viewpoint of orientation of the obtained cured liquid crystal film. Note that the solid content of the mixed composition means the amount of all components excluding volatile components such as organic solvents from the mixed composition.

The mixed composition of the present invention may contain a polymerization initiator. The polymerization initiator is a compound capable of initiating a polymerization reaction such as a polymerizable compound, and from the viewpoint of not depending on the phase state of the thermotropic liquid crystal, a photopolymerization initiator that generates active radicals by the action of light is preferable.

As the photopolymerization initiator, any known photopolymerization initiator can be used as long as it is a compound that can initiate the polymerization reaction of the polymerizable compound. Specifically, photopolymerization initiators that can generate active radicals or acids by the action of light can be mentioned, and among them, photopolymerization initiators that can generate radicals by the action of light are preferred. The photopolymerization initiators can be used alone or in combination of two or more.

As the photopolymerization initiator, a known photopolymerization initiator can be used. For example, as a photopolymerization initiator that generates active radicals, self-cleavable benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-Aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc. can be used, and hydrogen abstraction type benzophenone compounds, alkylphenone compounds, benzoin ether compounds, benzyl ketal compounds, dibenzo Suberone-based compounds, anthraquinone-based compounds, xanthone-based compounds, thioxanthone-based compounds, halogenoacetophenone-based compounds, dialkoxyacetophenone-based compounds, halogenobisimidazole-based compounds, halogenotriazine-based compounds, triazine-based compounds, etc. can be used. As the photopolymerization initiator that generates acid, iodonium salts, sulfonium salts, and the like can be used. From the viewpoint of excellent reaction efficiency at low temperatures, self-cleavable photopolymerization initiators are preferred, and acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, and oxime ester compounds are particularly preferred.

The content of the photopolymerization initiator is usually 0.1 parts by mass or more and 20 parts by mass or less, preferably 1 part by mass or more and 15 parts by mass, based on 100 parts by mass of the total amount of polymerizable compounds contained in the mixed composition. part or less, more preferably 1 part by mass or more and 10 parts by mass or less. Within the above range, the reaction of the polymerizable group will proceed sufficiently and the orientation of the liquid crystal compound will not be easily disturbed. In this specification, the term "polymerizable compound" means a compound having at least one polymerizable group.

In the present invention, the mixed composition preferably contains an organic solvent because it is usually applied to a substrate etc. in a state dissolved in an organic solvent. The organic solvent is preferably a solvent that can dissolve compound (2), compound (1) and/or compound (3), etc., and is preferably a solvent that is inert to the polymerization reaction of these compounds. Examples of organic solvents include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether. ; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone Solvents; 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; ethers such as tetrahydrofuran and dimethoxyethane Solvents: Chlorine-containing solvents such as chloroform and chlorobenzene; Amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. . These organic solvents can be used alone or in combination of two or more. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are more preferred.

The content of the organic solvent in the mixed composition is preferably 50 to 98 parts by weight, more preferably 50 to 95 parts by weight, based on 100 parts by weight of the mixed composition. Therefore, the solid content in 100 parts by mass of the mixed composition is preferably 2 to 50 parts by mass, more preferably 5 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the mixed composition becomes low, so that the thickness of the film upon application becomes approximately uniform, and unevenness tends to occur less easily. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the cured film to be produced.

From the viewpoint of stably proceeding the polymerization reaction, the mixed composition may contain a polymerization inhibitor. The degree of progress of the polymerization reaction of the polymerizable compound can be controlled by the polymerization inhibitor.

Examples of the polymerization inhibitor include radicals such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (such as butylcatechol), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical. Scavengers; thiophenols; β-naphthylamines, β-naphthols, and the like.

The amount is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of polymerizable compounds. When 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.

The mixed composition may contain a sensitizer. As the sensitizer, a photosensitizer is preferred. Examples of the sensitizer include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene such as anthracene and anthracene containing an alkoxy group (for example, dibutoxyanthracene, etc.); Compounds include phenothiazine and rubrene.

When the mixed composition contains a sensitizer, the polymerization reaction of the polymerizable compound contained in the mixed composition can be further promoted. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 parts by mass, based on 100 parts by mass of the total amount of polymerizable compounds. ~3 parts by mass.

The mixed composition may contain a leveling agent. A leveling agent is an additive that has the function of adjusting the fluidity of the composition and making the film obtained by applying the composition more flat, and examples include organically modified silicone oil, polyacrylate, and perfluorinated silicone oil. Examples include alkyl leveling agents. Among these, polyacrylate leveling agents and perfluoroalkyl leveling agents are preferred.

The content of the leveling agent in the mixed composition is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total amount of polymerizable compounds. When the content of the leveling agent is within the above range, it becomes easier to horizontally align the compound (2) and the like, and the resulting cured film tends to be smoother. When the content of the leveling agent relative to the polymerizable compound exceeds the above range, the resulting cured film tends to be uneven. Note that the mixed composition may contain two or more types of leveling agents.

<Method for producing mixed composition>
The mixed composition of the present invention contains compound (2), compound (1) and/or compound (3), and optionally a solvent, a photoinitiator, a polymerization inhibitor, a photosensitizer or a leveling agent. It can be prepared by adding additives such as agents and stirring and mixing at a predetermined temperature.

Compounds (1) to (3) constituting the mixed composition of the present invention are manufactured by Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic, respectively. Known organic synthesis described in Synthesis, New Experimental Chemistry Course, etc. Reactions (e.g. condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald reaction) Hartwig reaction, Friedel-Crafts reaction, Heck reaction, aldol reaction, etc.) can be produced by appropriately combining them depending on the structure. Specifically, for example, according to the method for producing a polymerizable liquid crystal compound described in JP-A No. 2010-31223, etc., a compound having a structure corresponding to the structure of the desired compound (1), compound (2), or compound (3) is used. They can be prepared separately by esterification reaction between an alcohol compound and a carboxylic acid compound.

Mixed compositions of the invention comprising compound (2) in an area percentage value of greater than 50% are compound (2) prepared separately by a method as described above, and compound (1) and/or compound (3). It can also be prepared by mixing the compound (2) in a desired ratio such that the area percentage value exceeds 50%. However, the mixed composition of the present invention in which the area percentage value of compound (2) having a left-right asymmetric structure centering on Ar exceeds 50% is, for example, compound (1) and formula (6):
HO-Ar-OH (6)
[Ar in formula (6) has the same meaning as Ar in formula (1) above]
A compound represented by formula (7) (hereinafter also referred to as "compound (6)") is reacted in the presence of a basic compound:
A-Ar-OH (7)
[A and Ar in formula (7) each represent the same meaning as A and Ar in formula (1) above]
The reaction mixture composition can be prepared as an intermediate material by a method including a step of obtaining a reaction mixture composition containing the compound represented by (hereinafter also referred to as "compound (7)"). When compound (2) prepared separately is mixed with compound (1) and/or compound (3), it is necessary to take out compound (2). When compound (2) is produced by the production method, it can be obtained in an amount that is less than 50% of the theoretical amount, so when compound (2) is extracted from it, a more complicated purification step is required. According to the method of the present invention, there is no need to go through such extremely complicated purification steps, so that a desired mixed composition can be produced more efficiently. In addition, an alcohol compound that can constitute the core part (structure corresponding to Ar in formula (2)) of compound (2) such as compound (6), and a side chain part (mesogen part) of compound (2) When prepared by combining two or more carboxylic acid compounds with different structures by esterification reaction, a mixed composition in which the area percentage value of compound (2) theoretically exceeds 50%. However, if the method includes the step of obtaining a reaction mixture composition containing compound (7) from compound (1) and compound (6), compound (2) will be obtained at a high rate of over 50%. It is easy to easily and more efficiently prepare a mixed preparation containing the following.

The present invention provides a reaction mixture containing a compound represented by formula (7) by reacting a compound represented by formula (1) and a compound represented by formula (6) in the presence of a basic compound. The area percentage value measured by liquid chromatography of the compound represented by formula (7) in the reaction mixture includes the step of obtaining a composition (hereinafter also referred to as "step (i)"). The formula is more than 50% and less than 95% based on the total area value of the compound represented by formula (1), the compound represented by formula (6), and the compound represented by formula (7) included. The present invention is directed to a method for producing a reaction mixture composition containing the compound represented by (7).
A-Ar-A (1)
HO-Ar-OH (6)
A-Ar-OH (7)
A and Ar in formula (1), formula (6), and formula (7) respectively represent the same meanings as A and Ar in the above formula (1), and ultimately form the desired structure of compound (2). Determined accordingly.

Compound (1) can be produced by appropriately combining and bonding known organic synthesis reactions depending on its structure. Specifically, it can be prepared from a compound having a structure corresponding to the structure of the desired compound (1), for example, according to the method described in JP-A No. 2010-31223 and the like.

The compound (6) which is an alcohol compound may be a compound in which two hydroxy groups are bonded to Ar corresponding to the group Ar in the desired compound (7). Examples of the compound (6) include compounds in which two * moieties in each group Ar exemplified as specific examples of the formulas (Ar-1) to (Ar-6) above are hydroxyl groups.

In step (1), the reaction between compound (1) and compound (6) is carried out in the presence of a basic compound. Although not necessarily limited to the following reaction, in the presence of a basic compound, the hydrogen of one of the hydroxy groups (-OH) bonded to Ar of compound (6) is extracted, resulting in a transition state. The molecule OH-Ar-O ^- makes a nucleophilic attack on one molecule of compound (1), and one side chain A [i.e., *-D ¹ -(A ¹ - E ¹ ) m-SP ¹ -L ¹ ] that generates two molecules of compound (7) by causing a nucleophilic substitution reaction in the relationship with D ¹ (-OCO- or -COO-) It is estimated to be.

Through the above reaction, two molecules of compound (7) are obtained from one molecule of compound (1) which is bilaterally symmetrical. Compound (7) is suitable as an intermediate for producing compound (2), and a side chain B having a structure different from side chain A in compound (1) is added to the reaction mixture composition containing compound (7). By reacting a compound represented by the below-mentioned formula (8) having a structure corresponding to the above, the mixture composition of the present invention containing the compound (2) having a left-right asymmetric structure with a high area percentage value exceeding 50% You can easily and efficiently manufacture things.

In step (i), the basic compound extracts hydrogen from one of the hydroxy groups bonded to Ar of compound (6) to initiate and proceed the nucleophilic substitution reaction between compound (1) and compound (6). If possible, it may be appropriately selected from known basic compounds. The basic compound may be an inorganic basic compound or an organic basic compound, and may be used alone or in combination of two or more. From the viewpoint that the reaction between compound (1) and compound (6) can proceed more efficiently and it is easier to obtain a reaction mixture composition containing a high proportion of compound (7), the basic compound in step (i) is , a basic compound having an ionization constant (pKa) of 7 or more is preferred.

The ionization constant (pKa) is also called the acid dissociation constant, and is the equilibrium constant Ka in a dissociation reaction in which hydrogen ions are released from an acid, expressed as a negative common logarithm. The ionization constant of a base is the ionization constant (acid dissociation constant) of the conjugate acid of the base. In addition, in this specification, the ionization constant of a basic compound is calculated|required by the pH characteristic solubility method.

The basic compound used in step (i) preferably has a pKa of 7.5 or more, more preferably 8 or more, and even more preferably 9 or more, and the upper limit is not particularly limited, but is usually 17 or less. Yes, preferably 15 or less, more preferably 13.5 or less. When the pKa of the basic compound is within the above range, the reaction between compound (1) and compound (6) tends to proceed efficiently, and a reaction mixture composition containing a high proportion of compound (7) is easily obtained.

Specific examples of the basic compound used in step (i) include N,N-dimethylaminopyridine (pKa: 9.7), diazabicycloundecene (pKa: 13.5), and triethanolamine (pKa: 13.5). : 10.75), N-methylmorpholine (pKa: 7.38), 1,4-diazabicyclo[2.2.2]octane (pKa: 8.7), N,N-diisopropylethylamine (pKa: 10. 98), potassium tert-butoxide (pKa: 17), and the like. Among them, N,N-dimethylaminopyridine, diazabicycloundecene, and triethanolamine are preferred, and N,N-dimethylaminopyridine and diazabicycloundecene are more preferred.

The amount of the basic compound used in step (i) may be appropriately determined depending on the type of basic compound used, the desired proportion of compound (7) in the reaction mixture composition, etc. For example, the amount is preferably 0.01 mol or more, more preferably 0.05 mol or more, even more preferably 0.1 mol or more, and preferably 10 mol or less, more preferably 1 mol or more of compound (6). is 5 mol or less, more preferably 3 mol or less, particularly preferably 1 mol or less. When the amount of the basic compound is within the above range, the reaction between compound (1) and compound (6) tends to proceed efficiently, and a reaction mixture composition containing a high proportion of compound (7) is easily obtained. In addition, when a plurality of types of basic compounds are included, it is preferable that the total content of basic compounds having a pKa of 7 or more is within the above range.

In step (i), the reaction between compound (1) and compound (6) is preferably carried out in the presence of a solvent. Examples of the solvent include the same organic solvents as exemplified as those that can be included in the mixed composition of the present invention. These solvents can be used alone or in combination of two or more. Further, the organic solvent may be the same as or different from the organic solvent constituting the mixed composition of the present invention. As the solvent used in step (i), from the viewpoint of solubility of compound (1), compound (6), and compound (7) to be produced, ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), etc. ), amide solvents such as cyclopentanone, ketone solvents such as cyclopentanone, etc. are preferred.

The amount of the solvent used is not particularly limited, but it is usually 1 part by mass per 1 part by mass of compound (1) and compound (6) in order to sufficiently dissolve each compound and allow the reaction to proceed efficiently. As mentioned above, the amount is preferably 1.2 parts by mass or more, and in order to avoid using an excessive amount of 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.

Additives may be used in the reaction between compound (1) and compound (6) as necessary. For example, it may be carried out in the presence of a polymerization inhibitor to prevent polymerization. Examples of the polymerization inhibitor include 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylenebis(6-tert-butyl-p-cresol), triphenyl phosphite, and Examples include tris(nonylphenyl) phosphate, phenothiazine, and the like. When using a polymerization inhibitor, the amount added is preferably 0.01 mol or more, more preferably 0.05 mol or more, and preferably 1.0 mol equivalent per 1 mol of compound (1). It is as follows.

The reaction between compound (1) and compound (6) can be carried out in a state in which compound (1), compound (6), a basic compound, and, if necessary, a solvent, additives, etc. are mixed.

Conditions for the reaction can be appropriately determined depending on the type of each compound used, the scale of the reaction, and the like.
In one embodiment of the production method of the present invention, the reaction temperature between compound (1) and compound (6) is preferably 0°C to 80°C, more preferably 20°C to 60°C. When the reaction temperature is within the above range, the reaction between compound (1) and compound (6) tends to proceed, and the mild conditions make it easier to obtain the target compound more safely.

The reaction time may be determined depending on the type of compound used, blending ratio, reaction temperature, etc. Depending on the reaction scale, etc., the time is preferably 10 minutes to 48 hours, more preferably 10 minutes to 24 hours. In the present invention, the reaction time between compound (1) and compound (6) starts from the time when compound (1), compound (6), and the basic compound begin to coexist; ) The end point is the point at which the reaction with the reaction mixture stops/completes. The degree of progress of the reaction can be confirmed by analytical means such as high performance liquid chromatography, thin layer chromatography, and gas chromatography.

The structure of the obtained compound can be identified by measurements such as NMR spectrum, IR spectrum, mass spectrum, elemental analysis, etc.

The area percentage value measured by liquid chromatography of compound (7) in the reaction mixture composition containing compound (7) obtained in step (i) is the area percentage value of compound (1) and compound (6) contained in the reaction mixture composition. It is preferably more than 50% and less than 95% based on the total area value of compound (7). When the reaction mixture composition contains compound (7) in an amount exceeding 50% in terms of area percentage, the reaction mixture composition, as an intermediate material, contains compound (2) in an amount exceeding 50% in terms of area percentage. A mixed composition of the invention can be obtained. The progress of the reaction between compound (1) and compound (6) in step (i) is controlled to increase the amount of compound (1) and compound (6) in addition to the amount of compound (7) in the resulting reaction mixture composition. ), the mixture of the present invention containing a high proportion of compound (2) and the required amount of compound (1) and/or compound (3) can be prepared through step (ii) described below. A composition can be obtained. The amount of compound (7) contained in the reaction mixture composition can be appropriately determined depending on the blending ratio of compound (2) in the mixture composition of the present invention finally containing the desired compound (2), For example, it may be 55% or more, 60% or more, 65% or more, or 70% or more, and may be, for example, 90% or less, or 85% or less. For example, in a reaction mixture composition that can be used as an intermediate for a mixed composition in which the area percentage value of compound (2) is 75%, the content of compound (7) is 75% or more in area percentage value. It is preferable. A reaction mixture composition containing compound (7) in such a proportion is suitable as an intermediate material for obtaining the mixture composition of the present invention having a low phase transition temperature. Note that the area percentage value can be calculated based on the peak area measured by liquid chromatography in the same manner as described above for the mixed composition of the present invention.

A reaction mixture composition containing compound (7) obtained by step (i) and formula (8):
HOOC-(A ² -E ² )n-SP ² -L ² (8)
(hereinafter also referred to as "compound (8)") and reacting compound (7) with compound (8) (hereinafter, this step is also referred to as "step (ii)"). ) can produce the mixed composition of the present invention containing compound (2). Even if step (i) and step (ii) are carried out continuously, for example, after the reaction mixture obtained in step (i) is once stored, step (i) is discontinuously carried out and step (ii) is carried out. (batch method). When step (i) and step (ii) are performed continuously, for example, there is no need to perform purification or extraction operations, which is preferable from the viewpoint of production efficiency and workability. In addition, when performing step (i) and step (ii) discontinuously, for example, the amount of impurities generated in step (i) carried into step (ii) can be reduced, resulting in high purity. This is preferable from the viewpoint that it is possible to obtain the following products.

A ² , E ² , n, SP ² and L ² in formula (8) have the same meanings as A ² , E ² , n, SP ² and L ² in formula (5) above, respectively, and the final is determined depending on the desired structure of compound (2).

Compound (8) can be produced by appropriately combining and bonding known organic synthesis reactions depending on its structure. Specifically, it can be prepared from a compound having a structure corresponding to the structure of the desired compound (8), for example, according to the method described in JP-A No. 2010-31223 and the like.

The reaction between compound (7) and compound (8) in the reaction mixture is an esterification reaction, and is preferably carried out in the presence of a condensing agent. By performing the esterification reaction in the presence of a condensing agent, the esterification reaction can be performed efficiently and quickly.

Examples of the condensing agent used in step (ii) include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimidemeth-para-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylamino Carbodiimides such as propyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (commercially available as water-soluble carbodiimide: WSC), bis(2,6-diisopropylphenyl)carbodiimide, and bis(trimethylsilyl)carbodiimide Compound, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1-(4-nitrobenzenesulfonyl)- 1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N, N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxysuccinimide, O- (6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N' , N'-tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium Examples include hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, and trichloroacetic acid pentachlorophenyl ester. . From the viewpoint of reactivity, cost, usable solvent, etc., dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide are used as condensing agents. Preferred are hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bisisopropylcarbodiimide, and 2,2'-carbonylbis-1H-imidazole.

The amount of the condensing agent used in the esterification reaction between compound (7) and compound (8) can be appropriately determined depending on the types of compound (7) and compound (8), the type of condensing agent, etc. For example, the amount is usually 1.0 to 1.5 mol per 1 mol of compound (7).

Additionally, the esterification reaction may be performed in the presence of a catalyst. Examples of the catalyst include N,N-dimethylaminopyridine, N,N-dimethylaniline, dimethylammonium pentafluorobenzenesulfonate, and the like. The amount of the catalyst used is, for example, preferably 0.01 to 0.5 mol per 1 mol of compound (7).

The esterification reaction between compound (7) and compound (8) in step (ii) is usually carried out in a solvent. Examples of the solvent include the same solvents as those exemplified as those that can be used in the reaction between compound (1) and compound (6) in step (i). The solvent used in step (ii) may be the same as or different from step (i). From the viewpoint of reaction yield and productivity, nonpolar organic solvents such as pentane, hexane, heptane, toluene, xylene, benzene, chlorobenzene, chloroform, and dichloromethane are preferred. These solvents may be used alone or in combination.

The amount of compound (8) to be used is preferably 0.5 to 2.5 mol, more preferably 0.5 to 2.5 mol, per 1 mol of compound (7), from the viewpoint of easily obtaining the desired amount of compound (2) in good yield. is 0.75 to 2.0 mol, more preferably 1.0 to 1.3 mol.

The amount of the solvent used is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, based on 1 part by mass of compound (7) and compound (8). Parts by weight, more preferably 10 to 50 parts by weight.

The temperature of the esterification reaction in step (ii) is preferably -20 to 120°C, more preferably -20 to 60°C, still more preferably -10 to 20°C, from the viewpoint of reaction yield and productivity. It is ℃. Further, from the viewpoint of reaction yield and productivity, the esterification reaction time is preferably 1 minute to 72 hours, more preferably 1 to 48 hours, and still more preferably 1 to 24 hours. In the present invention, the reaction time between compound (7) and compound (8) is determined from the time when compound (7) and compound (8) begin to coexist. The end point is when the reaction has stopped/completed. The degree of progress of the reaction can be confirmed by analytical means such as high performance liquid chromatography, thin layer chromatography, and gas chromatography.

The structure of the obtained compound can be identified by measurements such as NMR spectrum, IR spectrum, mass spectrum, elemental analysis, etc. After the reaction is completed, as necessary, for example, by performing treatments and operations that can be adopted in organic synthetic chemistry, such as post-treatments such as filtration, neutralization, extraction, and water washing, and isolation treatments such as distillation and crystallization. The mixed composition of the present invention containing compound (2) can be obtained as a mixture of liquid crystal compounds. A mixed composition obtained in this way, to which necessary components such as an organic solvent and a photopolymerization initiator as described above are added, can be used as a mixed composition for forming a retardation film.

<Retardation film>
Since the mixed composition of the present invention has a low phase transition temperature, by using the mixed composition of the present invention, it is possible to form a film at low temperatures without reducing the optical properties that a liquid crystal compound can originally exhibit. Therefore, it is easy to obtain a cured liquid crystal film having excellent optical properties. Therefore, the present invention also relates to a retardation film that is a cured product of the mixed composition of the present invention and includes a cured liquid crystal film formed by curing the liquid crystal compound in the mixed composition in an oriented state. A retardation film composed of a cured product of the mixed composition can sufficiently exhibit the optical properties that the liquid crystal compound used can originally exhibit, and can be a retardation film having high optical performance.

The cured liquid crystal film constituting the retardation film of the present invention may be composed of a homopolymer of compound (2) in an oriented state and a homopolymer of compound (1) and/or compound (3), or , compound (2), and a copolymer of a mixture of compound (1) and/or compound (3) in an oriented state. Since the polymerization reaction is easy and it is easy to obtain a uniform liquid crystal cured film, the liquid crystal cured film constituting the retardation film of the present invention can be prepared using compound (2) and a mixture of compound (1) and/or compound (3). Preferably, it is composed of a copolymer in an oriented state.

In one aspect of the present invention, the retardation film of the present invention is a cured product of the mixed composition of the present invention, and satisfies the optical properties represented by the following formulas (a), (b), and (c). preferable. Such a cured liquid crystal film is usually a cured product (hereinafter referred to as a cured product) obtained by curing compound (2) and compound (1) and/or compound (3) in a state in which they are oriented horizontally with respect to the plane of the cured liquid crystal film. (also referred to as "horizontal alignment liquid crystal cured film").
Re(450)/Re(550)≦1.00 (a)
1.00≦Re(650)/Re(550) (b)
100nm≦Re(550)≦180nm (c)
[In the formula, Re (λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm, and Re = (nx (λ) - ny (λ)) × d (d is the thickness of the liquid crystal cured film. In the refractive index ellipsoid formed by the liquid crystal cured film, nx represents the principal refractive index at a wavelength λ nm in a direction parallel to the plane of the liquid crystal cured film, and ny represents the refractive index ellipsoid formed by the liquid crystal cured film. , represents the refractive index at a wavelength λnm in a direction parallel to the plane of the cured liquid crystal film and perpendicular to the direction of nx). ]

When the horizontally aligned liquid crystal cured film satisfies formulas (a) and (b), the horizontally aligned liquid crystal cured film has an in-plane retardation value at a short wavelength that is smaller than an in-plane retardation value at a long wavelength. It exhibits so-called reverse wavelength dispersion. Re(450)/Re(550) is preferably 0.70 or more, more preferably 0.72 or more, and even more preferably It is 0.75 or more, and preferably 0.90 or less, more preferably 0.87 or less, even more preferably 0.85 or less, particularly preferably 0.83 or less. Moreover, Re(650)/Re(550) is preferably 1.00 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

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

Further, when the horizontally aligned liquid crystal cured film satisfies formula (3), the retardation film including the horizontally aligned liquid crystal cured film functions as a λ/4 plate, and the elliptically polarizing plate includes the retardation film including the liquid crystal cured film. It has an excellent effect of improving the hue of frontal reflection (effect of suppressing coloring) when applied to optical displays and the like. A more preferable range of the in-plane retardation value is 120 nm≦Re(550)≦170 nm, and an even more preferable range is 130 nm≦Re(550)≦150 nm.

The retardation film of the present invention includes, for example,
A coating film of the mixed composition of the present invention is formed, the coating film is dried, and a polymerizable liquid crystal compound containing the compound (2) in the mixed composition (hereinafter, liquid crystal curing contained in the mixed composition) is dried. A step of orienting compounds that can constitute a film (also simply referred to as a "polymerizable liquid crystal compound"), and
It can be produced by a method including a step of polymerizing the polymerizable liquid crystal compound by light irradiation while maintaining the alignment state to form a cured liquid crystal film.

A coating film of the mixed composition can be formed by applying the mixed composition onto a substrate or an alignment film. As the base material, any base material known in the art, such as a glass base material or a resin film base material, may be appropriately selected and used. In addition, as alignment films, optical films (especially alignment films) such as alignment films containing alignment polymers, optical alignment films, groove alignment films having uneven patterns or a plurality of grooves on the surface, and stretched films stretched in the alignment direction are used. An alignment film generally used for producing a retardation film) can be appropriately selected and used.

Methods for applying the mixed composition to the substrate include coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography. Known methods may be used.

Next, by removing the solvent by drying or the like, a dry coating film is formed. Examples of the drying method 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 is dried and removed from the coating film, and the polymerizable liquid crystal compound is directed in a desired direction (for example, horizontally or vertically) with respect to the plane of the coating film. It can be oriented to The heating temperature of the coating film can be determined as appropriate by considering the polymerizable liquid crystal compound used and the material of the base material forming the coating film, etc., but it is usually , the temperature must be higher than the liquid crystal phase transition temperature. In order to bring the polymerizable liquid crystal compound into a desired alignment state while removing the solvent contained in the mixed composition, for example, the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the mixed composition is adjusted. (phase transition temperature) or higher.

The mixed composition of the present invention contains at least compound (2), compound (1) and/or compound (3), and usually produces liquid crystals at a temperature lower than the temperature at which each individual compound transitions to a liquid crystal phase. can transition to a phase. Therefore, in manufacturing a retardation film using the mixed composition of the present invention, not only can a retardation film with excellent optical properties be obtained, but also excessive consumption of thermal energy can be suppressed, resulting in production efficiency. can be improved. Furthermore, since the liquid crystal phase transition can be effected by heating at a relatively low temperature, there is an advantage that the choice of supporting substrates to which the mixed composition is applied is expanded.

The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound contained, the type of solvent, its boiling point, its amount, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 ~5 minutes.

Removal of the solvent from the coating film may be performed simultaneously with heating the liquid crystal compound contained in the mixed composition to a temperature equal to or higher than the liquid crystal phase transition temperature, or may be performed separately, but from the viewpoint of improving productivity, it may be performed simultaneously. It is preferable. Before heating the polymerizable liquid crystal compound to a temperature higher than the liquid crystal phase transition temperature, the solvent in the coating film obtained from the mixed composition is appropriately removed under conditions such that the polymerizable liquid crystal compound contained in the coating film obtained from the mixed composition does not polymerize. A preliminary drying step may be provided for this purpose. Drying methods in this pre-drying step include natural drying, ventilation drying, heating drying, and vacuum drying, and the drying temperature (heating temperature) in this drying step depends on the type of polymerizable liquid crystal compound used and the solvent used. It can be determined as appropriate depending on the type, boiling point, amount, etc.

Next, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, thereby forming a polymer of the polymerizable liquid crystal compound existing in the desired orientation state. A certain liquid crystal cured film is formed. Since the mixed composition of the present invention can be highly polymerized by irradiation with light such as high-intensity ultraviolet rays while suppressing damage to the polymerizable liquid crystal compound, a photopolymerization method is usually used as the polymerization method. It will be done. In photopolymerization, the light irradiated onto the dry coating film is appropriately selected depending on the type of polymerization initiator, the type of polymerizable liquid crystal compound, and the amount thereof contained in the dry coating film. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, and active electron beams. Among these, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use photopolymerization equipment that is widely used in the field. It is preferable to select the types of polymerizable liquid crystal compound and polymerization initiator contained in the mixed composition in advance. Moreover, during polymerization, the polymerization temperature can also be controlled by irradiating the dry coating film with light while cooling it with an appropriate cooling means. By employing such a cooling means and polymerizing the polymerizable liquid crystal compound at a lower temperature, a cured liquid crystal film can be appropriately formed even if a substrate with relatively low heat resistance is used. It is also possible to promote the polymerization reaction by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (such as deformation of the base material due to heat). A patterned cured film can also be obtained by performing masking or development during photopolymerization.

Examples of the light source of the active energy ray include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, and a wavelength range. Examples include an LED light source that emits light in the range of 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

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

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

<Circular polarizing plate>
The present invention includes a circularly polarizing plate containing the retardation film of the present invention. The circularly polarizing plate of the present invention usually includes a polarizing film.
The polarizing film is a film having a polarizing function, and includes a stretched film on which a dye having absorption anisotropy is adsorbed, a film containing a film coated with a dye having absorption anisotropy as a polarizer, and the like. As such a polarizing film, for example, a known polarizing film used for a circularly polarizing plate as described in JP-A-2013-33249, JP-A-2013-200445, etc. can be used.

The circularly polarizing plate of the present invention includes the retardation film of the present invention and the polarizing film. For example, the retardation film of the present invention and the polarizing film are combined with an adhesive layer or a pressure-sensitive adhesive layer. The circularly polarizing plate of the present invention can be obtained by laminating the two layers with each other. In one embodiment of the present invention, when the retardation film of the present invention and a polarizing film are laminated, the angle between the slow axis (optical axis) of the liquid crystal cured film constituting the retardation film and the absorption axis of the polarizing film is It is preferable to stack the layers so that the angle is 45±5°.

The circularly polarizing plate of the present invention may have a configuration similar to that of a conventional general circularly polarizing plate, or a polarizing film and a retardation film. Such structures include, for example, adhesive layers (sheets) for bonding circularly polarizing plates to display elements, etc. that constitute image display devices, and adhesive layers (sheets) for protecting the surfaces of polarizing films and retardation films from scratches and dirt. Examples include a protective film used for this purpose.

The circularly polarizing plate of the present invention can be used in various display devices.
A display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a flexible image display device, a touch panel display device, an electron emission display device (for example, a field emission display (FED)), surface field emission display (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection type display device (e.g. grating light valve (GLV) display device, digital micromirror device (DMD) ) and piezoelectric ceramic displays.Liquid crystal display devices include transmissive liquid crystal display devices, transflective liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection type liquid crystal display devices. These display devices may be display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images.In particular, the circularly polarizing plate of the present invention can be suitably used for organic electroluminescent (EL) display devices and inorganic electroluminescent (EL) display devices.These display devices (optical displays) can be used by providing the circularly polarizing plate of the present invention with excellent optical properties. , it is possible to exhibit good image display characteristics.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, "%" and "parts" in the examples mean % by mass and parts by mass, respectively, unless otherwise specified.

HPLC measurement used for analysis of each compound may be performed under any conditions as long as peaks derived from each compound can be separated. An example of HPLC measurement conditions is shown below.
(Measurement condition)
Measuring device: HPLC LC-10AT (manufactured by Shimadzu Corporation)
Column: L-Column ODS (inner diameter 3.0 mm, length 150 mm, particle size 3 μm)
Temperature: 40℃
Mobile phase A: 0.1% (v/v)-TFA/water Mobile phase B: 0.1% (v/v)-TFA/acetonitrile Gradient: 0 min 50%-B
30min 100%-B
60min 100%-B
60.01min 50%-B
75min 50%-B
Flow rate: 0.5mL/min
Injection volume: 5μL
Detection wavelength: 350nm

The ionization constant (pKa) of the basic compound used in the examples was measured by a pH characteristic solubility method.

1. Preparation of mixed composition (1) Example 1
Mixed composition 1 containing compound (P1-1), compound (P2-1) and compound (P3-1) was obtained according to the following method.

A nitrogen atmosphere was placed in a 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer, and 5.0 g of compound (6a) synthesized with reference to patent document (JP 2010-031223), patent document (JP 2010-031223). 31223), 28.7 g of compound (1a), 0.5 g of DMAP (N,N-dimethylaminopyridine, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) (approx. 0.3 mol), 0.2 g of BHT (dibutylhydroxytoluene, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 50 g of tetrahydrofuran (manufactured by Hayashi Pure Chemical Industries, Ltd.) were added and mixed, and these were mixed at 50 °C. The reaction was allowed to proceed for 4 hours. After the reaction was completed, the tetrahydrofuran solution was concentrated to dryness, and then 50 g of toluene (manufactured by Nacalai Tesque) was added to obtain a reaction mixture composition 1 containing compound (7a).
As a result of measuring the area ratio of compound (6a), compound (1a) and compound (7a) in the obtained reaction mixture composition 1 by high performance liquid chromatography, it was found that compound (6a): compound (1a): compound (7a) )=9.5:29.7:61.2.

Next, 6.8 g of compound (8a) synthesized with reference to patent document (Unexamined Japanese Patent Publication No. 2016-53149) was added, and IPC (diisopropylcarbodiimide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 2. An additional 9 g was added and these were allowed to react at 0° C. overnight. After the reaction was completed, insoluble components were removed by filtration. The solution was added dropwise to 150 g of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), which was three times the mass of toluene contained in the solution, to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 10 g of methanol, and then dried under reduced pressure at 30°C to obtain Compound (P1-1), Compound (P2-1), and Compound (P3-1). 15.0 g of Mixed Composition 1 containing:
As a result of measuring the ratio of compound (P1-1), compound (P2-1), and compound (P3-1) in the obtained mixed composition 1 by high performance liquid chromatography, it was found that compound (P1-1): compound ( P2-1): Compound (P3-1) = 9.5:61.2:29.4. Note that Compound (P1-1) and Compound (P2-1) were liquid crystal compounds, and Compound (P3-1) was a non-liquid crystal compound.

(2) Example 2
Mixed composition 2 containing compound (P2-1) and compound (P3-1) was obtained according to the following method.
A nitrogen atmosphere was placed in a 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer, and 5.0 g of compound (6a) synthesized with reference to patent document (JP 2010-031223), patent document (JP 2010-031223). 28.7 g of compound (1a) synthesized with reference to No. 31223), 0.5 g of DBU (diazabicycloundecene, manufactured by Tokyo Kasei Co., Ltd.) (about 0.2 mol per 1 mol of compound (6a)) , 0.2 g of BHT (dibutylhydroxytoluene, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 50 g of tetrahydrofuran (manufactured by Hayashi Pure Chemical Industries, Ltd.) were added and mixed, and these were reacted at 50° C. for 24 hours. . After the reaction was completed, the tetrahydrofuran solution was concentrated to dryness, and then 50 g of toluene (manufactured by Nacalai Tesque) was added to obtain a reaction mixture composition 2 containing compound (7a).
As a result of measuring the area ratio of compound (6a), compound (1a) and compound (7a) in the obtained reaction mixture composition 2 by high performance liquid chromatography, it was found that compound (6a): compound (1a): compound (7a) )=0.0:21.8:78.2.

Next, 6.8 g of compound (8a) synthesized with reference to patent document (JP 2016-53149) was added, and IPC (diisopropylcarbodiimide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 2. An additional 9 g was added and these were allowed to react at 0° C. overnight. After the reaction was completed, insoluble components were removed by filtration. The solution was added dropwise to 150 g of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), which was three times the mass of toluene contained in the solution, to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 10 g of methanol, and then dried under reduced pressure at 30°C to obtain mixed composition 2 containing compound (P2-1) and compound (P3-1). 15.0g was obtained.
As a result of measuring the ratio of compound (P1-1), compound (P2-1), and compound (P3-1) in the obtained mixed composition 2 by high performance liquid chromatography, it was found that (P1-1):(P2- 1):(P3-1)=0.0:78.2:21.8.

(3) Example 3
Mixed composition 3 containing compound (P1-1) and compound (P2-1) was obtained according to the following method.
A nitrogen atmosphere was placed in a 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer, and 5.0 g of compound (6a) synthesized with reference to patent document (JP 2010-031223), patent document (JP 2010-031223). 10.3 g of compound (1a) synthesized with reference to No. 31223), 0.5 g of DBU (diazabicycloundecene, manufactured by Tokyo Kasei Co., Ltd.) (about 0.2 mol per 1 mol of compound (6a)) , 0.2 g of BHT (dibutylhydroxytoluene, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 50 g of tetrahydrofuran (manufactured by Hayashi Pure Chemical Industries, Ltd.) were added and mixed, and these were reacted at 50° C. for 24 hours. . After the reaction was completed, the tetrahydrofuran solution was concentrated to dryness, and then 50 g of toluene (manufactured by Nacalai Tesque) was added to obtain a reaction mixture composition 3 containing compound (7a).
As a result of measuring the area ratio of compound (6a), compound (1a) and compound (7a) in the obtained reaction mixture composition 3 by high performance liquid chromatography, it was found that compound (6a): compound (1a): compound (7a) )=22.4:0.0:77.6.

Next, 6.8 g of compound (8a) synthesized with reference to patent document (Unexamined Japanese Patent Publication No. 2016-53149) was added, and IPC (diisopropylcarbodiimide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 2. An additional 9 g was added and these were allowed to react at 0° C. overnight. After the reaction was completed, insoluble components were removed by filtration. The solution was added dropwise to 150 g of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), which was three times the mass of toluene contained in the solution, to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 10 g of methanol, and then dried under reduced pressure at 30°C to obtain mixed composition 3 containing compound (P1-1) and compound (P2-1). 15.0g was obtained.
As a result of measuring the ratio of compound (P1-1), compound (P2-1), and compound (P3-1) in the obtained mixed composition 3 by high performance liquid chromatography, it was found that compound (P1-1): compound ( P2-1): Compound (P3-1) = 22.4:77.6:0.0.

(4) Comparative example 1
A nitrogen atmosphere was placed in a 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer, and 5.0 g of compound (6a) synthesized with reference to patent document (JP 2010-031223), patent document (JP 2016-2016) 9.5 g of compound (8a) synthesized with reference to No. 53149), 0.2 g of DMAP (N,N-dimethylaminopyridine, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and BHT (dibutylhydroxytoluene, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). 0.2 g (manufactured by Yakuza Co., Ltd.) and 50 g of chloroform (manufactured by Nacalai Tesque) were added. Using a dropping funnel, 4.0 g of IPC (diisopropylcarbodiimide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was further added, and the mixture was reacted at 0° C. overnight. After the reaction was completed, insoluble components were removed by filtration. The solution was added dropwise to 150 g of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), which was three times the mass of toluene contained in the solution, to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 10 g of methanol, and then dried under reduced pressure at 30° C. to obtain 15.0 g of Composition 4 containing Compound (P3-1).
The resulting composition 4 did not contain a compound corresponding to compound (2).

(5) Comparative example 2
Mixed composition 5 containing compound (P1-1), compound (P2-1) and compound (P3-1) was obtained according to the following method.

A nitrogen atmosphere was placed in a 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer, and 5.0 g of compound (6a) synthesized with reference to the patent document (JP 2010-031223) and the patent document (JP 2016-2016) 2.5 g of compound (8a) synthesized with reference to Patent Document No. 53149), 7.3 g of compound (8b) synthesized with reference to patent document (JP 2010-031223), DMAP (N,N-dimethylaminopyridine, Fuji Film 0.2 g of BHT (dibutylhydroxytoluene, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 50 g of chloroform (manufactured by Nacalai Tesque) were added. Using a dropping funnel, 4.0 g of IPC (diisopropylcarbodiimide, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was further added, and the mixture was reacted at 0° C. overnight. After the reaction was completed, insoluble components were removed by filtration. The solution was added dropwise to 150 g of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) three times the mass of chloroform contained in the solution to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed three times with 10 g of methanol, and then dried under reduced pressure at 30° C. to form Compound (P1-1), Compound (P2-1), and Compound (P3-1). 15.0g of Mixed Composition 5 containing the following was obtained.
As a result of measuring the ratio of compound (P1-1), compound (P2-1), and compound (P3-1) in the obtained mixed composition 5 by high performance liquid chromatography, it was found that (P1-1):(P2- 1):(P3-1)=3.1:36.4:60.4.

2. Evaluation of mixed composition (1) Measurement of phase transition temperature The phase transition temperature is measured using a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), etc. can be measured. Specifically, the measurement was performed using a polarizing microscope (LEXT, manufactured by Olympus Corporation) equipped with a temperature control stage in accordance with the following.
1 g of each of the mixed compositions 1 to 5 obtained above was weighed into a vial, and 2 g of chloroform was added and dissolved. The obtained solution was applied to a rubbed glass substrate with a PVA alignment film and dried. This substrate was placed on a cooling/heating device ("LNP94-2" manufactured by Japan Hitech), heated from room temperature to 180° C., and then cooled to room temperature. The changes in temperature were observed using a polarizing microscope (LEXT, manufactured by Olympus), and the temperature at which the nematic phase occurred was measured, which was defined as the nematic phase transition temperature. The results are shown in Table 2.

(2) Evaluation of optical properties (i) Preparation of polymerizable liquid crystal composition Put mixed compositions 1 to 5 into a vial tube, add photopolymerization initiator, leveling agent, and polymerization inhibitor according to the compositions listed in Table 1. and a solvent were charged and stirred for 30 minutes at 80° C. using a carousel to obtain polymerizable liquid crystal composition 1.
The amounts of the photopolymerization initiator, leveling agent, and polymerization inhibitor shown in Table 1 are the amounts added to 100 parts by mass of the mixed composition obtained in Example 1. Further, the amount of the solvent blended was set so that the mass % of the composition was 13% with respect to the total amount of the solution.

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

(ii) Preparation of optical film [Preparation of composition for forming photoalignment film]
A composition for forming a photo-alignment film was obtained by mixing the following components and stirring the resulting mixture at 80° C. for 1 hour.
Photoalignable material (5 parts) represented by the following formula:

(Number average molecular weight: approx. 28,000)
Solvent (95 parts): cyclopentanone

[Manufacture of optical film (retardation film)]
An optical film was manufactured as follows. Cycloolefin polymer film (COP) (ZF-14, manufactured by Zeon Corporation) was processed using a corona treatment device (AGF-B10, manufactured by Kasuga Denki Co., Ltd.) at an output of 0.3 kW and a processing speed of 3 m/min. Treated once. The photo-alignment film forming composition was applied to the corona-treated surface using a bar coater. It was dried at 80° C. for 1 minute, and exposed to polarized UV light using a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.) at an integrated light intensity of 100 mJ/cm ² . The thickness of the obtained alignment film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation) and was found to be 100 nm.

Polymerizable liquid crystal composition 1 was applied onto the alignment film using a spin coater, dried at 120°C for 1 minute, and then exposed to ultraviolet light using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.). An optical film was produced by irradiating (under nitrogen atmosphere, wavelength: 365 nm, integrated light amount at wavelength 365 nm: 1000 mJ/cm ² ). Using the optical film produced above as a measurement sample, the front retardation value for light with a wavelength of 450 nm and a wavelength of 550 nm was measured using a measuring device ("KOBRA-WR" manufactured by Oji Scientific Instruments Co., Ltd.), and Re(450) was measured. /Re(550) was calculated. The results are shown in Table 2.

In the same manner as above, polymerizable liquid crystal compositions 2 to 5 were prepared for mixed compositions 2 to 5, optical films were produced, and the optical properties of each were evaluated. The results are shown in Table 2.

Claims

A mixed composition comprising a compound represented by the following formula (2) and at least one of a compound represented by the formula (1) and a compound represented by the formula (3), the composition comprising the compound represented by the formula (2) The area percentage value measured by liquid chromatography of the compound represented by is the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) contained in the mixed composition. more than 50% and less than 95%, based on the sum of the area values of the compounds.
A-Ar-A (1)
A-Ar-B (2)
B-Ar-B (3)
[A in formula (1) and formula (2) is the following formula (4):
*-D 1 -(A 1 -E 1 )m-SP 1 -L 1 (4)
It is expressed as
B in formula (2) and formula (3) is the following formula (5):
*-D 2 -(A 2 -E 2 )n-SP 2 -L 2 (5)
It is expressed as
In formula (4) and formula (5),
* represents the bonding position with Ar in formula (1), formula (2) or formula (3),
m and n each independently represent an integer of 1 or more, and m and n are different from each other,
D 1 and D 2 each independently represent -C(=O)-O- or -O-C(=O)-,
E 1 and E 2 are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -, -CR 3 =CR 4 - , -NR 5 -, or a combination of two or more thereof, and R 1 to R 5 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. If m is an integer greater than or equal to 2, the plurality of E1 's may be the same or different, and if n is an integer greater than or equal to 2, the plurality of E2 's may be the same or different. may be different,
A 1 and A 2 are each independently a divalent aromatic hydrocarbon group having 6 or more carbon atoms which may have a substituent, or a divalent aromatic hydrocarbon group having 6 or more carbon atoms which may have a substituent. Represents a divalent alicyclic hydrocarbon group, when m is an integer of 2 or more, the plurality of A1s may be the same or different, and when n is an integer of 2 or more, Multiple A2s may be the same or different,
SP 1 and SP 2 each independently represent a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, or a linear or branched alkenylene group having 2 to 20 carbon atoms; 20 linear or branched alkynylene groups, or one or more of -CH 2 - constituting the alkylene group, the alkenylene group, and the alkynylene group is -O-, -S-, -NH-, -N (Q) represents a divalent linking group substituted with - or -CO-, Q represents a substituent,
L 1 and L 2 each independently represent a monovalent organic group, at least one of L 1 and L 2 is a polymerizable group,
Ar in formulas (1) to (3) is a group represented by any of the following formulas (Ar-1) to (Ar-6):

[In formulas (Ar-1) to (Ar-6),
* represents a bond with D 1 or D 2 ;
Q 1 represents -S-, -O- or -NR 6 -, R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
Q2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W 1 and W 2 each independently represent -O-, -S-, -CO-, -NR 6 -, and R 6 is a hydrogen atom or a carbon number of 1 to 6 which may have a substituent. represents an alkyl group;
Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group,
Y 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. -CH 2 - may be substituted with -O-, -CO-, -O-CO- or -CO-O-;
Z 1 , Z 2 and Z 3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent carbon atom 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR 6 R 7 or -SR 6 , and Z 1 and Z 2 are bonded to each other to form an aromatic ring or an aromatic heterocycle. R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Z 4 is an aliphatic hydrocarbon group or alkoxy group having 2 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, represents a cyano group, a nitro group, -NR 6 R 7 or -SR 6 , and R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay may have a hydrogen atom or a substituent. Represents an alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ax and Ay are a bond. may form a ring;
Y 3 and Y 4 each independently represent the following formula (Y 3 -1):

[In formula (Y 3 -1),
R Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X 3 , and the substituent X 3 is a fluorine atom, a 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, dimethyl A silyl group, a thioisocyano group, or one -CH 2 - or two or more non-adjacent -CH 2 -s each independently represent -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-, a linear or It represents a branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or it may be a group represented by -B 31 -F 31 -P 31 (wherein , B 31 is -CR 8 R 9 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C (=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 8 -, -NR 8 -CO-, -O-CH 2 - , -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or a single bond, and R 8 and R 9 each independently represent a hydrogen atom, a fluorine atom, or a C 1-4 carbon atom. represents an alkyl group; F 31 represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with -OR 10 or a halogen atom, and R 10 is a carbon Represents an alkyl group of numbers 1 to 4, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH 2 - contained in the alkanediyl group is -O- or -CO- may be substituted with; P 31 represents a hydrogen atom or a polymerizable group),
U 1 represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group is , may be substituted by one or more of the above substituents X3 ;
T 1 is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -, -N=CU 2 -, -CO-NU 2 -, -OCO-NU 2 - or O-NU 2 -, and U 2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group. (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E 31 -A 31 ) q -B 31 -F 31 - P31 , and each of the alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents X3 , and the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one -CH 2 - or two or more non-adjacent -CH 2 -s in the alkyl group are each independently substituted with -O -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO 2 -, -O-CO-O-, -CO-NH-, - NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or - It may be replaced by C≡C-, and one -CH 2 - or two or more non-adjacent -CH 2 -s in the cycloalkyl group or cycloalkenyl group are each independently -O-, It may be replaced with -CO-, -COO-, -OCO- or O-CO-O-, E 31 is defined in the same manner as B 31 above, and A 31 is a divalent group having 3 to 16 carbon atoms. It represents an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 11 , -OR 12 , which may be substituted with a cyano group or a nitro group, R 11 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R 12 represents an alkyl group having 1 to 4 carbon atoms. represents a group, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and B 31 , F 31 and P 31 have the same meanings as the above B 31 , F 31 and P 31 , respectively. However, q represents an integer from 0 to 4, and when multiple E 31 and/or A 31 exist, they may be the same or different, and U 1 and U 2 combine to form a ring. ]
represents a group selected from ]
The mixed composition according to claim 1, wherein one of m in formula (4) and n in formula (5) is 1 and the other is 2.
The mixture according to claim 1 or 2, wherein A 1 in formula (4) and A 2 in formula (5) are each independently a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group. Composition.
The mixed composition according to claim 1 or 2, wherein in formula (4), m is 1 and A 1 is a 1,4-cyclohexanediyl group.
The mixed composition according to claim 1 or 2, wherein in formula (5), n is 1 and A 2 is a 1,4-cyclohexanediyl group.
The mixed composition according to claim 1 or 2, wherein L 1 in formula (4) and L 2 in formula (5) are each an acryloyloxy group.
Claim 1 or 2, wherein Ar in formulas (1) to (3) is a group represented by any one of formula (Ar-1), formula (Ar-3) and formula (Ar-4). Mixture composition as described.
The mixed composition according to claim 1 or 2, further comprising a photopolymerization initiator.
The mixed composition according to claim 1 or 2, further comprising an organic solvent.
A retardation film comprising a cured product of the mixed composition according to claim 1.
A circularly polarizing plate comprising the retardation film according to claim 10.
A compound represented by formula (1) and a compound represented by formula (6) are reacted in the presence of a basic compound to obtain a reaction mixture composition containing a compound represented by formula (7). The area percentage value measured by liquid chromatography of the compound represented by formula (7) in the reaction mixture is the compound represented by formula (1), formula (6) contained in the reaction mixture composition. Production of a reaction mixture composition containing a compound represented by formula (7) that is more than 50% and less than 95% based on the sum of the area values of the compound represented by and the compound represented by formula (7) Method.
A-Ar-A (1)
HO-Ar-OH (6)
A-Ar-OH (7)
[A in formula (1) and formula (7) is the following formula (4):
*-D 1 -(A 1 -E 1 )m-SP 1 -L 1 (4)
It is expressed as
In formula (4), * represents the bonding position with Ar in formula (1) or formula (7),
m represents an integer of 1 or more,
D 1 represents -C(=O)-O- or -OC(=O)-,
E 1 is a single bond, -CO-, -O-, -S-, -C(=S)-, -CR 1 R 2 -, -CR 3 =CR 4 -, -NR 5 -, or , represents a divalent linking group consisting of a combination of two or more of these, R 1 to R 5 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and m is 2 or more. If it is an integer, multiple E1s may be the same or different,
A 1 is a divalent aromatic hydrocarbon group having 6 or more carbon atoms which may have a substituent, or a divalent alicyclic hydrocarbon group having 6 or more carbon atoms which may have a substituent. represents a hydrogen group, and when m is an integer of 2 or more, the plurality of A1s may be the same or different,
SP 1 is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, or a linear or branched alkenylene group having 2 to 20 carbon atoms. or one or more of -CH 2 - constituting the alkylene group, the alkenylene group, and the alkynylene group is -O-, -S-, -NH-, -N(Q)-, or represents a divalent linking group substituted with -CO-, Q represents a substituent,
L 1 represents a monovalent organic group,
Ar in formula (1), formula (6) and formula (7) is a group represented by any of the following formulas (Ar-1) to (Ar-6):

[In formulas (Ar-1) to (Ar-6),
* represents a bond with D 1 or D 2 ;
Q 1 represents -S-, -O- or -NR 6 -, R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
Q2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W 1 and W 2 each independently represent -O-, -S-, -CO-, -NR 6 -, and R 6 is a hydrogen atom or a carbon number of 1 to 6 which may have a substituent. represents an alkyl group;
Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group,
Y 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. -CH 2 - may be substituted with -O-, -CO-, -O-CO- or -CO-O-;
Z 1 , Z 2 and Z 3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent carbon atom 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR 6 R 7 or -SR 6 , and Z 1 and Z 2 are bonded to each other to form an aromatic ring or an aromatic heterocycle. R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Z 4 is an aliphatic hydrocarbon group or alkoxy group having 2 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, represents a cyano group, a nitro group, -NR 6 R 7 or -SR 6 , and R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay may have a hydrogen atom or a substituent. Represents an alkyl group having 1 to 6 carbon atoms, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ax and Ay are a bond. may form a ring;
Y 3 and Y 4 each independently represent the following formula (Y 3 -1):

[In formula (Y 3 -1),
R Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X 3 , and the substituent X 3 is a fluorine atom, a 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, dimethyl A silyl group, a thioisocyano group, or one -CH 2 - or two or more non-adjacent -CH 2 -s each independently represent -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-, a linear or It represents a branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or it may be a group represented by -B 31 -F 31 -P 31 (wherein , B 31 is -CR 8 R 9 -, -CH 2 -CH 2 -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C (=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 8 -, -NR 8 -CO-, -O-CH 2 - , -CH 2 -O-, -S-CH 2 -, -CH 2 -S- or a single bond, and R 8 and R 9 each independently represent a hydrogen atom, a fluorine atom, or a C 1-4 carbon atom. represents an alkyl group; F 31 represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with -OR 10 or a halogen atom, and R 10 is a carbon Represents an alkyl group of numbers 1 to 4, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and -CH 2 - contained in the alkanediyl group is -O- or -CO- may be substituted with; P 31 represents a hydrogen atom or a polymerizable group),
U 1 represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom, and the aromatic hydrocarbon group is , may be substituted by one or more of the above substituents X3 ;
T 1 is -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -, -N=CU 2 -, -CO-NU 2 -, -OCO-NU 2 - or O-NU 2 -, and U 2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group. (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E 31 -A 31 ) q -B 31 -F 31 - P31 , and each of the alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be unsubstituted or substituted with one or more substituents X3 , and the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one -CH 2 - or two or more non-adjacent -CH 2 -s in the alkyl group are each independently substituted with -O -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO 2 -, -O-CO-O-, -CO-NH-, - NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or - It may be replaced by C≡C-, and one -CH 2 - or two or more non-adjacent -CH 2 -s in the cycloalkyl group or cycloalkenyl group are each independently -O-, It may be replaced with -CO-, -COO-, -OCO- or O-CO-O-, E 31 is defined in the same manner as B 31 above, and A 31 is a divalent group having 3 to 16 carbon atoms. It represents an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 11 , -OR 12 , which may be substituted with a cyano group or a nitro group, R 11 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R 12 represents an alkyl group having 1 to 4 carbon atoms. represents a group, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and B 31 , F 31 and P 31 have the same meanings as the above B 31 , F 31 and P 31 , respectively. However, q represents an integer from 0 to 4, and when multiple E 31 and/or A 31 exist, they may be the same or different, and U 1 and U 2 combine to form a ring. ]
represents a group selected from ]
The manufacturing method according to claim 12, wherein the compound represented by formula (1) and the compound represented by formula (6) are reacted in the presence of a basic compound having an ionization constant (pKa) of 7 or more. .
A reaction mixture composition containing a compound represented by formula (7) obtained by the production method according to claim 12, and formula (8):
HOOC-(A 2 -E 2 )n-SP 2 -L 2 (8)
[In formula (8), A 2 , E 2 , n, SP 2 and L 2 each have the same meaning as A 2 , E 2 , n, SP 2 and L 2 in formula (5)]
and mixing the compound represented by the formula (7) and the compound represented by the formula (8) to produce the compound represented by the formula (2), A method for producing the mixed composition according to claim 1.