JP6137398B1 - blend - Google Patents

Abstract

Provided is a synthesis intermediate for synthesizing monomers necessary for the production of an optical film having good reverse wavelength dispersion. A compound represented by formula (I). [A is an integer of 1 to 3; b is an integer of 1 to 20; c is 0; A1 is a substituted / unsubstituted cyclic aliphatic group or a substituted / unsubstituted aromatic group; Y1 is —O—, — CO-, -CO-O-, -O-CO-, -NR21-CO-, -CO-NR22-, -O-CO-O-, -NR23-CO-O-, -O-CO-NR24- Or -NR25-CO-NR26-; R21 to R26 are each independently H or C1-6 alkyl group; R1 and R2 are each independently H, methyl group or Cl; FG1 is hydroxyl group] ] None

Description

The present invention relates to an optical film and an optical anisotropic body capable of uniform polarization conversion in a wide wavelength range, and a polarizing plate, a flat panel display device, an organic electroluminescence display device and an antireflection using the optical anisotropic material. It relates to film.
The present invention also provides a polymer that can be used for the preparation of the optical film and the optical anisotropic body, a polymerizable compound that can be used for the preparation of the polymer, a mixture containing the polymerizable compound, and a polymerizable liquid crystal composition, In addition, the present invention relates to a compound that can be used for the preparation of the polymerizable compound and a mixture containing the compound.

A retardation plate used in various devices such as a flat panel display device includes a ¼ wavelength plate that converts linearly polarized light into circularly polarized light, a ½ wavelength plate that converts a polarization vibration plane of linearly polarized light by 90 degrees, and the like. There is. These retardation plates can accurately give a phase difference of 1 / 4λ or 1 / 2λ of a light wavelength to a specific monochromatic light.
However, the conventional retardation plate has a problem that polarized light output through the retardation plate is converted into colored polarized light. This is because the material constituting the retardation plate has wavelength dispersion with respect to the retardation, and distribution occurs in the polarization state for each wavelength for white light that is a composite wave in which light rays in the visible light range are mixed. This is because it is impossible to adjust the input light to polarization having a phase difference of 1 / 4λ or 1 / 2λ in all wavelength regions.
In order to solve such a problem, various studies have been made on a broadband retardation plate capable of giving a uniform retardation to light in a wide wavelength range, that is, a so-called reverse wavelength dispersion plate.

On the other hand, with the advancement and widespread use of portable information terminals such as mobile personal computers and mobile phones, it has been required to keep the thickness of flat panel display devices as thin as possible. As a result, it is also required to reduce the thickness of the retardation plate that is a constituent member.
As a method for thinning, a method of producing a retardation plate by applying a polymerizable composition containing a low molecular weight polymerizable compound to a film substrate to form an optical film is the most effective method in recent years. It is said that. Therefore, many developments of a polymerizable compound capable of forming an optical film having excellent reverse wavelength dispersion or a polymerizable composition using the same are carried out.

  For example, in Patent Documents 1 and 2, it is possible to form an optical film having excellent reverse wavelength dispersion, and it is easy to apply to a substrate with a low melting point suitable for processing, and exhibits liquid crystallinity. A polymerizable compound and a polymerizable composition which have a wide temperature range and can be synthesized at low cost have been proposed.

International Publication No. 2014/010325 JP2015-2000877

Here, using a polymerizable composition containing a polymerizable compound, an optical film and an optical anisotropic body (hereinafter, both may be referred to as “optical film or the like”) on an industrial production scale are produced. In some cases, a wide tolerance for manufacturing conditions (process margin) is required.
In particular, when producing an optical film or the like by coating the polymerizable composition in a large area, it is difficult to completely uniform the temperature and time conditions in the drying furnace. The tolerance for manufacturing conditions greatly affects the yield of optical films and the like.

  However, conventional polymerizable compounds and polymerizable compositions cannot provide an optical film or the like that can maintain the liquid crystal phase more stably for a long time, and the process margin is not sufficient. Therefore, a polymerizable liquid crystal composition containing a polymerizable compound capable of forming an optical film or the like that can maintain the liquid crystal phase more stably for a long time has been demanded.

The present invention has been made in view of the above circumstances, has a practically low melting point, can be produced at low cost, and has uniform polarization conversion and stable liquid crystal phase in a wide wavelength range. An object of the present invention is to provide a polymerizable liquid crystal composition capable of forming an optical film or the like that can be maintained for a long time.
The present invention also provides a polymerizable compound useful for the preparation of the polymerizable liquid crystal composition and a mixture containing the polymerizable compound, and a compound useful for the preparation of the polymerizable compound and a mixture containing the compound. For the purpose.

As a result of diligent research to solve the above problems, the present inventors have used a mixture of a predetermined polymerizable compound represented by the following formula (III) and a predetermined polymerizable compound represented by the following formula (IV). For example, the present inventors have found that a polymerizable liquid crystal composition capable of forming an optical film or the like that can maintain a liquid crystal phase more stably for a long period of time, has less coating unevenness, and is excellent in reverse wavelength dispersibility can be obtained at low cost. It came to do.
Thus, according to the present invention, the following compounds, polymerizable compounds, mixtures, polymerizable liquid crystal compositions, polymers, optical films, optical anisotropic bodies, polarizing plates, flat panel display devices, organic electroluminescence display devices, and reflections A prevention film is provided.

[1] The following formula (I):
[In Formula (I), A ¹ and B ¹ each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent, Y ¹ and L ¹ each independently represent a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —, — O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, each independently represents R ^{21 to} R ²⁶ , Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² each independently represent a hydrogen atom, a methyl group or a chlorine atom, and FG ¹ represents a hydroxyl group, a carboxyl group or an amino group; , A represents an integer of 1 to 3, b represents an integer of 1 to 20, and c is 0 or 1 is there. ] The compound shown.

[2] The compound according to [1], wherein the FG ¹ is a hydroxyl group and the c is 0.

[3] The compound according to [1], wherein the FG ¹ is a carboxyl group and the c is 1.

[4] The compound according to any one of [1] to [3] above, and the following formula (II):
[In Formula (II), A ² and B ² each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent, Y ² and L ² are each independently a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —, — O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, each independently represents R ^{21 to} R ²⁶ , Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom, a methyl group or a chlorine atom, FG ² represents a hydroxyl group, a carboxyl group or an amino group, and d is an integer of 1 to 20 E is 0 or 1. ] The compound containing the compound shown by these.

[5] The mixture according to [4], wherein the FG ¹ and FG ² are hydroxyl groups, and the c and e are 0.

[6] The mixture according to [4], wherein FG ¹ and FG ² are carboxyl groups, and c and e are 1.

[7] The mass ratio of the compound represented by the formula (I) to the compound represented by the formula (II) (compound represented by the formula (I): compound represented by the formula (II)) is 1: The mixture according to any one of [4] to [6], which is 1000 to 20: 100.

[8] Formula (III) below:
Wherein (III), Ar ¹ represents a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group having as a substituent ^{D 1} having as a substituent ^{D 1, D 1} Represents an organic group having 1 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Z ¹¹ and Z ¹² each independently represent —CO -O -, - O-CO - , - NR 31 -CO-, or, ^{-CO-NR 32} - ^{represents, R 31} and ^{R 32} are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms A ¹¹ , A ¹² , B ¹¹ and B ¹² each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent. ^{represents, Y 11, Y 12, L} 11 and ^{L 12} are, its Each independently a single bond, -O -, - CO -, - CO-O -, - O-CO -, - NR 21 -CO -, - CO-NR 22 -, - O-CO-O- , —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, wherein each of R ^{21 to} R ²⁶ independently represents a hydrogen atom or a carbon number of 1; Represents an alkyl group of ˜6, R ^{4 to} R ⁷ each independently represents a hydrogen atom, a methyl group or a chlorine atom, and f and k are each an integer of 1 to 3, and the other is 0 to 3 G and j each independently represents an integer of 1 to 20, and h and i are each independently 0 or 1. ] The polymerizable compound shown by this.

[9] Ar ¹ -D ¹ is represented by the following formula (V):
[In the formula (V), Ax represents an organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Ra represents a hydrogen atom or The C1-C20 organic group which may have a substituent is represented. ] The polymerizable compound as described in [8] above, which is a divalent group represented by the formula:

[10] The Ax is represented by the following formula (VI):
[In the formula (VI), R ^X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Or -C (= O) -O-R ^b , where R ^b is an optionally substituted alkyl group having 1 to 20 carbon atoms and an optionally substituted carbon number. An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent. And a plurality of R ^X may be all the same or different, and at least one C—R ^X constituting the ring may be replaced by a nitrogen atom. The polymerizable compound according to [9], which is a group represented by

[11] The Ra has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. The polymerizable compound according to [9] or [10], which may be an alkynyl group having 2 to 20 carbon atoms or an aromatic group having 6 to 18 carbon atoms which may have a substituent.

[12] The polymerizable compound according to any one of [8] to [11], and the following formula (IV):
Wherein (IV), Ar ² represents a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group having as a substituent a D ² having as a substituent D ^2, D ² Represents an organic group having 1 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Z ²¹ and Z ²² each independently represent —CO -O -, - O-CO - , - NR 31 -CO-, or, ^{-CO-NR 32} - ^{represents, R 31} and ^{R 32} are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms Each of A ²¹ , A ²² , B ²¹ and B ²² independently represents a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent. ^{represents, Y 21, Y 22, L} 21 and ^{L 22,} it It is independently a single bond, -O -, - CO -, - CO-O -, - O-CO -, - NR 21 -CO -, - CO-NR 22 -, - O-CO-O-, ^{-NR 23 -CO-O -, -} O-CO-NR 24 -, ^or, -NR 25 ^{-CO-NR 26} - ^represents, R 21 ^{to R 26} each independently represents a hydrogen atom or a carbon number 1 to 6 represents an alkyl group, R ⁸ and R ⁹ each independently represent a hydrogen atom, a methyl group or a chlorine atom, m and q each independently represents an integer of 1 to 20, n and Each p is independently 0 or 1. And a polymerizable compound represented by the formula:

[13] The Ar ¹ -D ¹ is represented by the following formula (V):
[In the formula (V), Ax represents an organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Ra represents a hydrogen atom or The C1-C20 organic group which may have a substituent is represented. And the Ar ² -D ² is represented by the following formula (VII):
[In the formula (VII), Ay represents an organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Rc represents a hydrogen atom or The C1-C20 organic group which may have a substituent is represented. ] The mixture as described in said [12] which is a bivalent group represented by these.

[14] Each of Ax and Ay independently represents the following formula (VI):
[In the formula (VI), R ^X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Or -C (= O) -O-R ^b , where R ^b is an optionally substituted alkyl group having 1 to 20 carbon atoms and an optionally substituted carbon number. An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent. And a plurality of R ^X may be all the same or different, and at least one C—R ^X constituting the ring may be replaced by a nitrogen atom. ] The mixture as described in said [13] which is group represented by these.

[15] The Ra has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. Or an alkynyl group having 2 to 20 carbon atoms or an aromatic group having 6 to 18 carbon atoms which may have a substituent, and Rc may have 1 substituent. Have an alkyl group of -20, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. The mixture according to [13] or [14], which may be an aromatic group having 6 to 18 carbon atoms.

[16] Mass ratio of the polymerizable compound represented by the formula (III) and the polymerizable compound represented by the formula (IV) (polymerizable compound represented by the formula (III): represented by the formula (IV) The mixture according to any one of [12] to [15], wherein the polymerizable compound) is 1: 1000 to 20: 100.

[17] A polymerizable liquid crystal composition comprising the mixture according to any one of [12] to [16] and a polymerization initiator.

[18] A polymer obtained by polymerizing the mixture according to any one of [12] to [16].

[19] A polymer obtained by polymerizing the polymerizable liquid crystal composition according to [17].

[20] An optical film comprising the polymer according to [18] or [19] as a constituent material.

[21] An optical anisotropic body having a layer comprising the polymer according to [18] or [19] as a constituent material.

[22] A polarizing plate comprising the optical anisotropic body according to [21] and a polarizing film.

[23] A flat panel display device comprising the polarizing plate according to [22] and a liquid crystal panel.

[24] An organic electroluminescence display device comprising the polarizing plate according to [22] and an organic electroluminescence panel.

[25] An antireflection film comprising the polarizing plate according to [22].

According to the present invention, an optical film or the like that can maintain a liquid crystal phase more stably for a long time, has a practically low melting point, and is capable of uniform polarization conversion in a wide wavelength range is manufactured at low cost and with a wide process margin. A polymerizable liquid crystal composition that can be produced by the method is provided.
Further, according to the present invention, there are provided a polymerizable compound useful for the preparation of the polymerizable liquid crystal composition and a mixture containing the polymerizable compound, and a compound useful for the preparation of the polymerizable compound and a mixture containing the compound. Provided.
According to the present invention, an optical film and an optical anisotropic body capable of uniform polarization conversion in a wide wavelength range, a polarizing plate, a flat panel display device, and an organic electroluminescence (EL) display device using the same. And an antireflective film is provided.

It is a figure which shows the structure of the laminated body used for the stability evaluation test of the liquid crystal phase, (a) is sectional drawing, (b) is explanatory drawing which shows the relationship between an absorption axis and a slow axis. It is the photograph which image | photographed the laminated body used for the stability evaluation test of a liquid crystal phase from the opposite side to the light box side, (a) is a state of the laminated body in which an optical anisotropic body has no nonuniformity (evaluation index: 5). It is a photograph, (b) is a photograph of the laminate in a state where the optical anisotropic body is uneven (evaluation index: 1).

  Hereinafter, the present invention will be described in detail. In the present invention, “may have a substituent” means “unsubstituted or have a substituent”. In addition, when an organic group such as an alkyl group or aromatic hydrocarbon ring group contained in the general formula has a substituent, the number of carbons of the organic group having the substituent does not include the number of carbons of the substituent And For example, when the aromatic hydrocarbon ring group having 6 to 20 carbon atoms has a substituent, the carbon number of the aromatic hydrocarbon ring group having 6 to 20 carbon atoms does not include the carbon number of such a substituent. Shall.

Here, the compound of the present invention and the mixture containing the compound are not particularly limited, and can be used, for example, when preparing the polymerizable compound of the present invention.
Further, the polymerizable compound of the present invention and the mixture containing the polymerizable compound are not particularly limited, and can be used, for example, when preparing the polymerizable liquid crystal composition of the present invention.
Furthermore, the polymerizable liquid crystal composition of the present invention is not particularly limited, and can be used, for example, when preparing the polymer of the present invention.
The polymer of the present invention is not particularly limited, and can be used as, for example, a constituent material of the optical film of the present invention and a constituent material of a layer of the optical anisotropic body of the present invention. Moreover, the optical anisotropic body of this invention is not specifically limited, For example, it can be used for the polarizing plate of this invention. Furthermore, the polarizing plate of this invention is not specifically limited, For example, it can be used for the flat panel display apparatus of this invention, an organic electroluminescent display apparatus, and an antireflection film.

(1) Compound The compound of the present invention is a compound represented by the following formula (I) (hereinafter sometimes referred to as “compound (I)”), and as a production intermediate of the polymerizable compound (III) described later. Useful.

  Here, in formula (I), a is an integer of 1 to 3, b is an integer of 1 to 20, an integer of 2 to 12 is preferable, an integer of 4 to 8 is more preferable, and c is , 0 or 1.

FG ¹ is a hydroxyl group, a carboxyl group, or an amino group. When c is 0, FG ¹ is preferably a hydroxyl group, and when c is 1, FG ¹ is preferably a carboxyl group.

A ¹ is a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent. Among them, A ¹ is preferably an aromatic group which may have a substituent when c is 0, and a cyclic aliphatic which may have a substituent when c is 1. It is preferably a group.

In addition, the cycloaliphatic group which may have a substituent is an unsubstituted divalent cycloaliphatic group or a divalent cycloaliphatic group having a substituent. The divalent cycloaliphatic group is a divalent aliphatic group having a cyclic structure and usually having 5 to 20 carbon atoms.
Specific examples of the divalent cycloaliphatic group include cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, 1,4-cycloheptane-1,4-diyl, cyclooctane-1,5- Examples thereof include a cycloalkanediyl group having 5 to 20 carbon atoms such as diyl; a bicycloalkanediyl group having 5 to 20 carbon atoms such as decahydronaphthalene-1,5-diyl and decahydronaphthalene-2,6-diyl.

The aromatic group which may have a substituent is an unsubstituted divalent aromatic group or a divalent aromatic group having a substituent. The divalent aromatic group is a divalent aromatic group having an aromatic ring structure and usually having 2 to 20 carbon atoms.
Specific examples of the divalent aromatic group include 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 4,4′-biphenylene group, and the like. A divalent aromatic hydrocarbon ring group having 6 to 20 carbon atoms; such as furan-2,5-diyl, thiophene-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, And a divalent aromatic heterocyclic group having 2 to 20 carbon atoms;

  And as a substituent of the bivalent cycloaliphatic group mentioned above and a bivalent aromatic group, for example, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom; C1-C1 such as a methyl group, an ethyl group, etc. 6 alkyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and isopropoxy group; nitro group; cyano group; and the like. The cycloaliphatic group and the aromatic group may have at least one substituent selected from the above-described substituents. In addition, when it has two or more substituents, each substituent may be the same or different.

When c is 1, L ¹ is a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —, — O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, wherein R ^{21 to} R ²⁶ are each Independently, it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, L ¹ is preferably —O—, —CO—O—, or —O—CO—.

As the alkyl group having 1 to 6 carbon atoms of the ^R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like.

Further, when c is 1, B ¹ is a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent. Among these, B ¹ is preferably an aromatic group that may have a substituent.

Here, the cycloaliphatic group which may have a substituent is an unsubstituted divalent cycloaliphatic group or a divalent cycloaliphatic group having a substituent. The divalent cycloaliphatic group is a divalent aliphatic group having a cyclic structure and usually having 5 to 20 carbon atoms.
Specific examples of the divalent cycloaliphatic group for B ¹ include the same examples as those exemplified as the divalent cycloaliphatic group for A ¹ .

The aromatic group which may have a substituent is an unsubstituted divalent aromatic group or a divalent aromatic group having a substituent. The divalent aromatic group is a divalent aromatic group having an aromatic ring structure and usually having 2 to 20 carbon atoms.
Specific examples of the divalent aromatic group for B ¹ include the same as those exemplified as the divalent aromatic group for A ¹ .

Furthermore, the divalent cyclic aliphatic group and divalent substituents of the aromatic groups of B ^1, those exemplified as the substituent of the divalent cyclic aliphatic group and divalent aromatic groups of the A ¹ The same thing is mentioned.

Y ¹ represents a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —, —O—CO—O—. , —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, wherein each of R ^{21 to} R ²⁶ independently represents a hydrogen atom Or it is a C1-C6 alkyl group. Among these, Y ¹ is preferably —O—, —CO—O—, or —O—CO—.
^As the alkyl group having 1 to 6 carbon atoms R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group.

R ² is a hydrogen atom, a methyl group or a chlorine atom, preferably a hydrogen atom or a methyl group.

R ¹ is a hydrogen atom, a methyl group or a chlorine atom, preferably a hydrogen atom or a methyl group. R ¹ is more preferably the same as R ^2, and both R ¹ and R ² are more preferably hydrogen atoms.

  The compound (I) can be synthesized by combining known synthesis reactions. That is, it can be synthesized by referring to the methods described in various literatures (for example, MARCH'S ADVANCED ORGANIC CHEMISTRY (WILEY), Sandler Caro "Synthesis of Organic Compounds by Functional Group" Naoki Inamoto (Yodogawa Shoten)).

Here, a preferable example of the compound (I) in which c is 0 is not particularly limited, and the following formula (Ia):
[In the formula (Ia), R ¹ , R ² , a and b represent the same meaning as in the formula (I). ] (Referred to below as “compound (Ia)”).

  And there is no restriction | limiting in particular as a manufacturing method of compound (Ia), For example, the method shown below is mentioned.

[In each formula, R ¹ , R ² , a and b represent the same meaning as in formula (I), and L represents a leaving group. ]

  Specifically, first, by the reaction of the hydroquinone represented by the formula (1) and the compound represented by the formula (2) (hereinafter referred to as “compound (2)”), the formula (3) The monoether compound shown (hereinafter referred to as “monoether compound (3)”) is obtained.

  Here, in the formula (2), the leaving group represented by L is not particularly limited, and examples thereof include general leaving groups in the field of organic chemistry. Examples of L include halogen atoms such as a chlorine atom, a bromine atom, and an iodine atom.

Moreover, the usage-amount of hydroquinone and a compound (2) is 1.0-5.0 mol normally with respect to 1 mol of compounds (2), Preferably it is 1.0-5.0 mol, Preferably it is 1.2-1.5 mol.
When the usage rate of hydroquinone is too small, the amount of diether compound produced as a by-product increases, and the yield and purity of the monoether compound (3) tend to decrease. On the other hand, when the usage rate of hydroquinone is too large, it tends to be difficult to efficiently perform the purification treatment after the reaction.

  The reaction of hydroquinone and compound (2) may be carried out in the presence of a base in an inert solvent, or in a two-phase system of an alkaline aqueous solution and a hydrophobic organic solvent. The latter method is preferred because it can be obtained with good yield.

Examples of the inert solvent used in this reaction include amide solvents such as N-methylpyrrolidone and N, N-dimethylformamide; ether solvents such as tetrahydrofuran, 1,3-dimethoxyethane and anisole; and sulfur-containing solvents such as dimethyl sulfoxide. Solvents; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; and a mixed solvent composed of two or more of these solvents; Etc.
Although the usage-amount of a solvent is not specifically limited, Although it can determine suitably considering the kind of compound to be used, reaction scale, etc., it is 1-50 mass parts normally with respect to 1 mass part of compounds (2).

Examples of the base used include pyridine, trimethylamine, triethylamine, aniline, picoline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane, imidazole, N, Organic bases such as N-diisopropylethylamine; metal alcoholates such as sodium methoxide, sodium ethoxide and potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; sodium hydroxide, potassium hydroxide and calcium hydroxide And metal hydroxides such as sodium carbonate, potassium carbonate, and magnesium carbonate.
The usage-amount of a base is 1-5 equivalent normally with respect to a compound (2), Preferably it is 1-2 equivalent.

The alkaline aqueous solution used in the latter method can be obtained by dissolving an inorganic base in water.
Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; magnesium hydrogen carbonate; Alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate; Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Magnesium hydroxide; Alkaline earth metal hydroxides such as calcium hydroxide;
An inorganic base can be used individually by 1 type or in combination of 2 or more types.

  Content of the inorganic base in alkaline aqueous solution is 1.00-2.00 mol normally with respect to 1 mol of compounds (2), Preferably it is 1.00-1.50 mol. If the content of the inorganic base is too small, the yield of the monoetherified product may be decreased, the reaction rate may be decreased, or a large amount of the compound (2) may remain. On the other hand, when there is too much usage-amount of an inorganic base, the process of neutralizing after reaction will be needed separately.

The amount of the alkaline aqueous solution used is not particularly limited as long as hydroquinone and compound (2) are dissolved.
The usage-amount of alkaline aqueous solution is 1-10 mass parts normally with respect to 1 mass part of compounds (2), Preferably it is 3-6 mass parts. When there is too much usage-amount of alkaline aqueous solution, there exists a possibility that reaction rate may become slow or productivity may fall. On the other hand, if the amount of the alkaline aqueous solution used is too small, the raw material compound or the like may precipitate, or the viscosity of the solution may increase and the reaction rate may decrease.

The hydrophobic organic solvent refers to an organic solvent having a solubility in 100 g of water at 25 ° C. of 10 (g / 100 g-H ₂ O) or less.
Examples of the hydrophobic organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane and cyclohexane; anisole and cyclopentyl methyl ether (CPME), ether solvents such as diethyl ether and diisopropyl ether; alcohol solvents having 4 or more carbon atoms such as 1-butanol and 1-hexanol; halogenated hydrocarbon solvents such as dichloromethane, dichloroethane and chlorobenzene; It is done.
Among these, as the hydrophobic organic solvent, the azeotropic point with water is high, the reaction can be performed at a high temperature, and the desired monoether compound (3) can be easily obtained selectively. An aromatic hydrocarbon solvent, an ether solvent, or an alcohol solvent having 4 or more carbon atoms is preferable, and toluene, xylene, anisole, cyclopentyl methyl ether, or 1-hexanol is more preferable.
In addition, a hydrophobic organic solvent can be used individually by 1 type or in combination of 2 or more types.

  The usage-amount of a hydrophobic organic solvent is 0.2-10 mass parts normally with respect to 1 mass part of compounds (2), Preferably it is 0.5-2 mass parts. If the amount of the hydrophobic organic solvent used is too large, the reaction rate may be slow, or the productivity may be reduced. On the other hand, when the amount of the hydrophobic organic solvent used is too small, it is difficult to obtain the effect of using the hydrophobic organic solvent, and it may be difficult to selectively synthesize the monoetherified product.

The reaction between hydroquinone and compound (2) is performed in an inert gas atmosphere such as nitrogen gas or argon gas.
Although reaction temperature is not specifically limited, Usually, 20-200 degreeC, Preferably it is 60-150 degreeC, More preferably, it is 80-120 degreeC.
The reaction time is usually 1 to 24 hours depending on the reaction temperature and the like.

After completion of the reaction, the target monoether compound (3) can be precipitated as crystals by cooling the reaction solution.
The purity of the monoether compound (3) (the ratio of the monoetherified product to the total of the monoetherified product and the dietherified product) is usually 70% by mass or more, preferably 80% by mass or more.

The crystals of the obtained monoether compound (3) can be directly used in the next step without purification, and further purified by known methods such as column chromatography, recrystallization and reprecipitation as necessary. And it can also use for the next process as a higher purity monoether compound.
The structure of the monoether compound (3) can be determined by measuring an NMR spectrum, an IR spectrum, a mass spectrum, or the like or performing elemental analysis.

  Subsequently, the target compound (Ia) is obtained by a dehydration condensation reaction between the obtained monoether compound (3) and the carboxylic acid compound represented by the formula (4) (hereinafter referred to as “compound (4)”). Can be obtained.

Here, the dehydration condensation reaction is carried out in a suitable solvent in the presence of an acid catalyst.
Although it does not restrict | limit especially as an acid catalyst to be used, Mineral acids, such as hydrochloric acid, a sulfuric acid, phosphoric acid, nitric acid; Heteropoly acids, such as phosphotungstic acid; Organic acids, such as para-toluenesulfonic acid;
The usage-amount of an acid catalyst is 0.01-20 mass% normally with respect to a monoether compound (3), Preferably it is 0.05-10 mass%, More preferably, it is 0.1-5 mass%. Or the usage-amount of an acid catalyst is 0.01-1.0 mol normally with respect to 1 mol of monoether compounds (3), Preferably, it is 0.01-0.5 mol.

Solvents used include ether solvents such as tetrahydrofuran, 1,3-dimethoxyethane and anisole; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane and cyclohexane; benzene, toluene and xylene. Aromatic hydrocarbon solvents; and mixed solvents composed of two or more of these solvents.
Among these, aromatic hydrocarbon solvents are preferable, and toluene is more preferable.

  In the above reaction, it is preferable to carry out a dehydration condensation reaction while removing the produced water out of the system in order to obtain the desired product with good yield. Examples of such a method include a method of performing a reaction while removing water out of the system using an apparatus such as a Dean-Stark tube.

The dehydration condensation reaction may be performed in the presence of an antioxidant in order to stabilize the ether compound. Examples of the antioxidant used include 2,6-di (t-butyl) -4-methylphenol (BHT), 2,2′-methylenebis (6-t-butyl-p-cresol), triphenyl phosphite, and the like. Is mentioned.
When using antioxidant, the usage-amount is 0.1-10 mass parts normally with respect to 100 mass parts of ether compounds, Preferably, it is 0.5-5 mass parts.

Although reaction temperature is not specifically limited, Usually, 20-200 degreeC, Preferably it is 40-150 degreeC, More preferably, it is 60-150 degreeC.
The reaction time is usually 1 to 24 hours depending on the reaction temperature and the like.

After completion of the reaction, conventional post-treatment operations in organic synthetic chemistry are performed, and if desired, the reaction product can be separated and purified by known separation / purification methods such as distillation, column chromatography, recrystallization, and reprecipitation. And the target compound (Ia) can be efficiently isolated.
The structure of the target product can be identified and confirmed by using analytical means such as NMR spectrum, IR spectrum, and mass spectrum.

In addition, a compound (4) can be obtained by dimerizing acrylic acid 2-4. In that case, it is usually obtained as a mixture containing acrylic acid 2-carboxyethyl (dimer), acrylic acid itself, or an oligomer of acrylic acid trimer or higher.
Compound (4) can be used as a single compound by separating and purifying the mixture thus obtained.
Further, as will be described later, when the resulting mixture is a mixture containing acrylic acid and the compound (4), this mixture (hereinafter sometimes referred to as “mixture (D)”) is converted into a compound. It can be used instead of (4). In addition, it is preferable that a mixture (D) contains a compound (4) 0.01-20 mass% in a mixture.
As the compound (4), a commercially available one can be used as it is.

Moreover, as a preferable example of compound (I) whose c is 1, it does not specifically limit but following formula (IIIa):
[In the formula (IIIa), R ¹ , R ² , a and b represent the same meaning as in the formula (I). ] (Hereinafter, sometimes referred to as “compound (IIIa)”).

  And there is no restriction | limiting in particular as a manufacturing method of compound (IIIa), For example, the method shown below (the said compound (Ia) and trans-1, 4- cyclohexane dicarboxylic acid represented by following formula (5) And a method of reacting with the above.

[In each formula, R ¹ , R ² , a and b represent the same meaning as in the formula (I), and R ^d represents a C 1-6 alkyl group such as a methyl group or an ethyl group, or phenyl Represents an aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have a substituent, such as a group, a 4-methylphenyl group, and a 4-methoxyphenyl group. ]

Specifically, first, in a suitable solvent, the sulfonyl chloride compound represented by the formula (6) is reacted with the compound (5) in the presence of the first base.
Subsequently, compound (Ia) and a 2nd base are added to the obtained reaction mixture, and also it reacts.

  Here, the usage-amount of a sulfonyl chloride compound is 0.5-2.1 equivalent normally with respect to 1 equivalent of compound (5), Preferably, it is 0.5-1.1 equivalent.

  Moreover, the usage-amount of compound (Ia) is 0.5-1.0 equivalent normally with respect to 1 equivalent of compound (5).

Furthermore, the usage-amount of a 1st base and a 2nd base is 0.5-2.1 equivalent normally with respect to 1 equivalent of compounds (5), Preferably, it is 0.5-1.1 equivalent. is there.
Examples of the first base and the second base include triethylamine, N, N-diisopropylethylamine, 4- (dimethylamino) pyridine, and the like.

  Further, the reaction temperature can be set to −10 ° C. to 30 ° C., and the reaction time can be set to several minutes to several hours depending on the reaction scale and the like.

  Examples of the solvent used in the above reaction include those exemplified as the solvent that can be used when producing the compound (Ia), and halogen solvents such as methylene chloride and chloroform. Of these, ether solvents are preferred.

  In addition, the usage-amount of a solvent is not specifically limited, Although it can determine suitably considering the kind of compound to be used, reaction scale, etc., it is 1-50 mass parts normally with respect to 1 mass part of compound (Ia). .

After completion of the reaction, normal post-treatment operations in organic synthetic chemistry are performed, and if desired, purification treatment using known separation / purification methods such as column chromatography, recrystallization, distillation, reprecipitation, etc. is performed. Thus, the target product can be isolated.
The structure of the target compound can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.

(2) Mixture containing compound The mixture of the present invention is a mixture containing the compound (I) and a compound represented by the following formula (II) (hereinafter referred to as “compound (II)”). Can be used for the production of the polymerizable compound (III).
In addition, when forming an optical film or the like using a mixture or a polymerizable liquid crystal composition containing the polymerizable compound (III) prepared using the mixture, the reverse wavelength dispersibility of the optical film or the like obtained while expanding the process margin. From the viewpoint of increasing the ratio, the mass ratio of compound (I) to compound (II) in the mixture (compound (I): compound (II)) is preferably 1: 1000 to 20: 100, More preferably, it is 100-20: 100.

  Here, in formula (II), d is an integer of 1-20, an integer of 2-12 is preferable, an integer of 4-8 is more preferable, and e is 0 or 1.

FG ² is a hydroxyl group, a carboxyl group or an amino group. When e is 0, FG ² is preferably a hydroxyl group, and when e is 1, FG ² is preferably a carboxyl group.

A ² is a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent. Among them, A ² is preferably an aromatic group which may have a substituent when e is 0, and a cyclic aliphatic which may have a substituent when e is 1. It is preferably a group.

Here, the cycloaliphatic group which may have a substituent is an unsubstituted divalent cycloaliphatic group or a divalent cycloaliphatic group having a substituent. The divalent cycloaliphatic group is a divalent aliphatic group having a cyclic structure and usually having 5 to 20 carbon atoms.
Specific examples of the bivalent alicyclic group of A ² may include the same ones exemplified as the divalent cyclic aliphatic group of the A ^1.

The aromatic group which may have a substituent is an unsubstituted divalent aromatic group or a divalent aromatic group having a substituent. The divalent aromatic group is a divalent aromatic group having an aromatic ring structure and usually having 2 to 20 carbon atoms.
Specific examples of the divalent aromatic group of A ² may include the same ones exemplified as the divalent aromatic group of the A ^1.

Furthermore, as the substituent of the divalent cyclic aliphatic group and divalent aromatic group A ^2, those exemplified as the substituent of the divalent cyclic aliphatic group and divalent aromatic groups of the A ¹ The same thing is mentioned.

When e is 1, L ² is a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —, — O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, wherein R ^{21 to} R ²⁶ are each Independently, it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among ^{them, L} 2 is, -O -, - CO-O- , or is preferably a -O-CO-.

As the alkyl group having 1 to 6 carbon atoms of the ^R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like.

Further, when c is 1, B ² is a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent. Among these, B ¹ is preferably an aromatic group that may have a substituent.

Here, the cycloaliphatic group which may have a substituent is an unsubstituted divalent cycloaliphatic group or a divalent cycloaliphatic group having a substituent. The divalent cycloaliphatic group is a divalent aliphatic group having a cyclic structure and usually having 5 to 20 carbon atoms.
Specific examples of the divalent cycloaliphatic group for B ² include the same as those exemplified as the divalent cycloaliphatic group for A ¹ .

The aromatic group which may have a substituent is an unsubstituted divalent aromatic group or a divalent aromatic group having a substituent. The divalent aromatic group is a divalent aromatic group having an aromatic ring structure and usually having 2 to 20 carbon atoms.
Specific examples of the divalent aromatic group for B ² include the same as those exemplified as the divalent aromatic group for A ¹ .

Furthermore, the divalent cyclic aliphatic group and divalent substituents of the aromatic group B ^2, those exemplified as the substituent of the divalent cyclic aliphatic group and divalent aromatic groups of the A ¹ The same thing is mentioned.

Y ² represents a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —, —O—CO—O—. , —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, wherein each of R ^{21 to} R ²⁶ independently represents a hydrogen atom Or it is a C1-C6 alkyl group. Among these, Y ² is preferably —O—, —CO—O—, or —O—CO—.
^As the alkyl group having 1 to 6 carbon atoms R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group.

R ³ is a hydrogen atom, a methyl group or a chlorine atom, preferably a hydrogen atom or a methyl group.

  The compound (II) can be synthesized by combining known synthesis reactions. That is, it can be synthesized by referring to the methods described in various literatures (for example, MARCH'S ADVANCED ORGANIC CHEMISTRY (WILEY), Sandler Caro "Synthesis of Organic Compounds by Functional Group" Naoki Inamoto (Yodogawa Shoten)).

From the viewpoint of increasing the reverse wavelength dispersion of an optical film or the like, in the mixture of the present invention, FG ¹ , A ¹ , L ¹ , B ¹ , Y ¹ , R ¹ , b and c of the compound (I) are: Each is preferably the same as FG ² , A ² , L ² , B ² , Y ² , R ³ , d and e of the compound (II). That is, the compound (II) is a compound (except that it does not have “— (CH ₂ CHR ¹ COO) _a —” between “CH ₂ CR ¹ COO—” and “— (CH ₂ ) _b —”). It preferably has the same structure as I).

  The mixture can be prepared, for example, by mixing compound (I) and compound (II) in a desired ratio.

Further, the mixture of the compound (I) in which c is 0 and the compound (II) in which e is 0 is not particularly limited, and the following formula:
[Wherein Y ¹ , A ¹ , FG ¹ and b represent the same meaning as in formula (I). ]
It can also be obtained by reacting the compound represented by the above-mentioned mixture (D).

Furthermore, the mixture of the compound (I) in which c is 1 and the compound (II) in which e is 1 is not particularly limited, and the following formula:
[Wherein L ³ reacts with FG ¹ of compound (I) in which c is 0 and FG ² of compound (II) in which e is 0 to react with —O—, —CO—, —CO—O— ^{, -O-CO -, - NR} 21 -CO -, - CO-NR 22 -, - O-CO-O -, - NR 23 -CO-O -, - O-CO-NR 24 -, or - ^{NR 25} -CO-NR ²⁶ - capable of forming group (provided ^that independently R 21 ^{to R 26} are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) represents, ^{a 1} is the formula It represents the same meaning as (I), and FG ³ represents a hydroxyl group, a carboxyl group or an amino group. ]
And a mixture containing compound (I) in which c is 0 and compound (II) in which e is 0 can also be obtained.

In addition, the mixture of the compound (I) in which c is 1 and the compound (II) in which e is 1 may further contain a compound represented by the following formula (α). In this case, the content of the compound represented by the following formula (α) is 0.05 to 60 with respect to the total amount of the compound (I) in which c is 1 and the compound (II) in which e is 1. It is mass%, Preferably it is 0.05-50 mass%, More preferably, it is 0.05-35 mass%.
[In formula (α), Y ¹ , B ¹ , L ¹ , A ¹ , R ¹ , R ² and b represent the same meaning as in formula (I), and x and y are each independently 0 to 0 An integer of 3 is represented. ]

Here, as a preferable example of the compound (II) in which e is 0, the following formula (IIa):
[In Formula (IIa), R ³ and d represent the same meaning as in Formula (II). ] (Referred to below as “compound (IIa)”).

  Compound (IIa) can be produced by a conventionally known method such as the method described in Patent Document 1, for example.

  Further, for example, a mixture containing compound (Ia) and compound (IIa) can be prepared by mixing compound (Ia) and compound (IIa) described above in a desired ratio.

  Furthermore, the mixture containing the compound (Ia) and the compound (IIa) is obtained by replacing the compound (D) with the compound (D) instead of the compound (4) in the production method for obtaining the compound (Ia) as shown below, for example. It can also be obtained by use.

[In each formula, R ¹ , R ² , a and b represent the same meaning as in the formula (I), and R ³ and d (= b) represent the same meaning as in the formula (II). ]

Moreover, as a preferable example of compound (II) whose e is 1, it does not specifically limit but following formula (IVa):
[In Formula (IVa), R ³ and d represent the same meaning as in Formula (II). ] (It may hereafter be called "compound (IVa)").

  Compound (IVa) can be produced by a conventionally known method such as the method described in Patent Document 1.

  In addition, for example, a mixture containing compound (IIIa) and compound (IVa) can be prepared by mixing compound (IIIa) and compound (IVa) described above in a desired ratio.

Further, the mixture containing compound (IIIa) and compound (IVa) is prepared by, for example, as shown below, in the production method for obtaining compound (IIIa), instead of compound (Ia), It can also be obtained by using a mixture containing compound (IIa).
[In each formula, R ¹ , R ² , a and b represent the same meaning as in formula (I), R ³ and d represent the same meaning as in formula (II), and R ^d represents the formula It represents the same meaning as (6). ]

(3) Polymerizable Compound The polymerizable compound of the present invention is a compound represented by the following formula (III) (hereinafter sometimes referred to as “polymerizable compound (III)”). And can be advantageously used in preparing an optical anisotropic body.

As will be described later, by using a mixture of the polymerizable compound (III) and the polymerizable compound (IV) (compound represented by the formula (IV)), which will be described in detail later, the liquid crystal phase can be made more stable. An optical film that can be maintained for a long time, has a wide process margin, has a practically low melting point, has excellent solubility in general-purpose solvents, and is capable of uniform polarization conversion in a wide wavelength range at low cost. A polymerizable liquid crystal composition that can be produced can be obtained.
The reason for this is not clear, but the polymerizable compound (III) has a structure represented by “— (CH ₂ CHR ⁵ COO) _f —” and / or “— (OCOCHR ⁶ CH ₂ ) _k —”. Therefore, if a mixture of the polymerizable compound (III) and the polymerizable compound (IV) is used, optical characteristics (particularly, reverse wavelength dispersion) are ensured as compared with the case where only the polymerizable compound (IV) is used. However, it is presumed that it is possible to obtain an optical film or the like using a polymer as a constituent material by forming a liquid crystal layer that tends to be in a liquid crystal phase at a lower temperature (that is, easily in a supercooled state at room temperature). Is done.
Incidentally, the polymerizable compound (III) is used alone for the preparation of a polymerizable liquid crystal composition and a polymer, and an optical film using the polymer as a constituent material without being mixed with the polymerizable compound (IV). You can also.

  Here, in formula (III), one of f and k is an integer of 1 to 3, the other is an integer of 0 to 3, and g and j are each independently an integer of 1 to 20. , An integer of 2 to 12 is preferable, and an integer of 4 to 8 is more preferable. H and i are each independently 0 or 1, and 1 is preferable.

Then, Ar ¹ is a divalent aromatic hydrocarbon ring group having as a substituent D ^1, or a divalent aromatic heterocyclic group having as a substituent D ^1. D ¹ is an organic group having 1 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

Here, the divalent aromatic divalent aromatic heterocyclic group having a hydrocarbon ring group or a substituent of D ^1, an aromatic hydrocarbon ring D ¹ is bonded with a substituent D ¹ or two group obtained by removing a hydrogen atom from a ring portion of the aromatic heterocyclic ring D ¹ is bonded is bonded to the carbon other than carbon D ¹ is attached.

As the divalent aromatic hydrocarbon ring group of Ar ¹ , 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 2,6-naphthylene group, 1,5-naphthylene Group, anthracenyl-9,10-diyl group, anthracenyl-1,4-diyl group, anthracenyl-2,6-diyl group and the like.
Among these, 1,4-phenylene group, 1,4-naphthylene group or 2,6-naphthylene group is preferable as the divalent aromatic hydrocarbon ring group.

Examples of the divalent aromatic heterocyclic group for Ar ¹ include benzothiazole-4,7-diyl group, 1,2-benzisothiazole-4,7-diyl group, and benzoxazole-4,7-diyl group. , Indolonyl-4,7-diyl group, benzimidazole-4,7-diyl group, benzopyrazole-4,7-diyl group, 1-benzofuran-4,7-diyl group, 2-benzofuran-4,7-diyl Group, benzo [1,2-d: 4,5-d ′] dithiazolyl-4,8-diyl group, benzo [1,2-d: 5,4-d ′] dithiazolyl-4,8-diyl group, Benzothiophenyl-4,7-diyl group, 1H-isoindole-1,3 (2H) -dione-4,7-diyl group, benzo [1,2-b: 5,4-b ′] dithiophenyl- 4,8-diyl group, benzo [1,2-b: 4, 5-b ′] dithiophenyl-4,8-diyl group, benzo [1,2-b: 5,4-b ′] difuranyl-4,8-diyl group, benzo [1,2-b: 4,5 -B '] difuranyl-4,8-diyl group, benzo [2,1-b: 4,5-b'] dipyrrole-4,8-diyl group, benzo [1,2-b: 5,4-b '] Dipyrrole-4,8-diyl group, benzo [1,2-d: 4,5-d ′] diimidazole-4,8-diyl group and the like.
Among these, as the divalent aromatic heterocyclic group, benzothiazole-4,7-diyl group, benzoxazole-4,7-diyl group, 1-benzofuran-4,7-diyl group, 2-benzofuran- 4,7-diyl group, benzo [1,2-d: 4,5-d ′] dithiazolyl-4,8-diyl group, benzo [1,2-d: 5,4-d ′] dithiazolyl-4, 8-diyl group, benzothiophenyl-4,7-diyl group, 1H-isoindole-1,3 (2H) -dione-4,7-diyl group, benzo [1,2-b: 5,4-b '] Dithiophenyl-4,8-diyl group, benzo [1,2-b: 4,5-b'] dithiophenyl-4,8-diyl group, benzo [1,2-b: 5,4-b '] Difuranyl-4,8-diyl group or benzo [1,2-b: 4,5-b'] difuranyl 4,8-diyl group is preferred.

The divalent aromatic hydrocarbon ring group and divalent aromatic heterocyclic group of Ar ¹ include, in addition to D ¹ , methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tarsha You may have at least 1 substituent chosen from C1-C6 alkyl groups, such as a butyl group. When there are a plurality of substituents, the plurality of substituents may be the same as or different from each other. The substituent other than D ^{1 of the} divalent aromatic hydrocarbon ring group and the divalent aromatic heterocyclic group is at least selected from a methyl group, an ethyl group, a propyl group, a sec-butyl group, and a tertiary butyl group. One substituent is preferred.

In D ¹ "the organic group having 1 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring", the "aromatic ring" A cyclic structure having a broad sense of aromaticity according to the rules, that is, a cyclic conjugated structure having (4n + 2) π electrons, and heteroatoms such as sulfur, oxygen, nitrogen, and the like typified by thiophene, furan, benzothiazole, etc. It means a cyclic structure in which a lone electron pair participates in a π-electron system and exhibits aromaticity.

The aromatic ring D ¹ has may have one or more substituents.
The total number of π electrons contained in Ar ¹ and D ¹ is usually 12 or more, preferably 12 or more and 22 or less, more preferably 12 or more and 20 or less.

Examples of the aromatic hydrocarbon ring represented by D ¹ include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring.
Among these, as the aromatic hydrocarbon ring, a benzene ring and a naphthalene ring are preferable.

Examples of the aromatic heterocycle of D ¹ include 1H-isoindole-1,3 (2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, and indole. Ring, oxadiazole ring, oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, Thiazolopyrazine ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, Pyrimidine ring, pyrrole ring, phenanthridi Ring, phthalazine ring, furan ring, benzo [c] thiophene ring, benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, benzooxadiazole ring, benzoxazole ring, benzothiadiazole ring, benzothiazole ring, benzothiophene And a ring, a benzotriazine ring, a benzotriazole ring, a benzopyrazole ring, a benzopyranone ring, a dihydropyran ring, a tetrahydropyran ring, a dihydrofuran ring, and a tetrahydrofuran ring.
Among these, as the aromatic heterocycle, benzothiazole ring, benzoxazole ring, 1-benzofuran ring, 2-benzofuran ring, benzothiophene ring, 1H-isoindole-1,3 (2H) -dione ring, thiophene ring A furan ring, a benzo [c] thiophene ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a pyran ring, a benzoisoxazole ring, a thiadiazole ring, a benzooxadiazole ring, and a benzothiadiazole ring.

The organic group having 1 to 20 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, which is D ¹ , is not particularly limited. An aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a group represented by the formula: —R ^f C (═N—NR ^g R ^h ) Groups.
In the above formula, R ^f represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or an isopropyl group.
Further, in the above formula, R ^g represents a hydrogen atom or an organic group which may having 1 to 20 carbon atoms which may have a substituent. Here, as a C1-C20 organic group and its substituent, the same thing as what was listed as a specific example of the C1-C20 organic group of Ra mentioned later and its substituent is mentioned.
Further, in the above formula, R ^h represents an organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Here, as a specific example of a C2-C20 organic group and its substituent, the same thing as what was listed as a C2-C20 organic group of Ax mentioned later and a specific example of the substituent is mentioned. .

Specifically, examples of the aromatic hydrocarbon ring group that becomes D ¹ include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a fluorenyl group.
Among these, as the aromatic hydrocarbon ring group, a phenyl group and a naphthyl group are preferable.

Examples of the aromatic heterocyclic group to be D ¹ include phthalimide group, 1-benzofuranyl group, 2-benzofuranyl group, acridinyl group, isoquinolinyl group, imidazolyl group, indolinyl group, furazanyl group, oxazolyl group, oxazolopyrazinyl group Group, oxazolopyridinyl group, oxazolopyridazinyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiadiazolyl group, thiazolyl group, thiazopyrazinyl group, thiazopyridyl group Group, thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group , Phenanthri Dinyl group, phthalazinyl group, furanyl group, benzo [c] thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzimidazolyl group, benzoxazolyl group, benzoxazolyl group, benzothiadiazolyl group, Benzothiazolyl group, benzothienyl group, benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, benzopyranonyl group, dihydropyranyl group, tetrahydropyranyl group, dihydrofuranyl group, tetrahydrofuranyl group, etc. Can be mentioned.
Among these, as the aromatic heterocyclic group, furanyl group, thienyl group, oxazolyl group, thiazolyl group, benzothiazolyl group, benzoxazolyl group, 1-benzofuranyl group, 2-benzofuranyl group, benzothienyl group, thiazopyridyl group Groups are preferred.

The aromatic hydrocarbon ring group and aromatic heterocyclic group to be D ¹ are an aliphatic hydrocarbon group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a sec-butyl group. A halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a substituted amino group such as a dimethylamino group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or an isopropoxy group; a nitro group; a cyclopentyl group or a cyclohexyl group; A cycloalkyl group having 3 to 8 carbon atoms such as a group; a halogenated alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; -C (= O) -R ^{b '} ; -C (= O) -OR ^{b _{'; -SR b'; -SO 2}} R d ';hydroxyl; may have at least one substituent selected from the like. Here, R ^{b ′} has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. Represents an optionally substituted cycloalkyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent, and R ^{d ′} represents the number of carbon atoms such as a methyl group and an ethyl group. An alkyl group having 1 to 6 carbon atoms; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have a substituent, such as a phenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group; When the aromatic hydrocarbon ring group and the aromatic heterocyclic group have a plurality of substituents, the substituents may be the same or different.

R ^{b ′} has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. Examples of the substituent of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms include halogen atoms such as fluorine atom and chlorine atom; cyano group; carbon number of 1 such as methoxy group, ethoxy group, isopropoxy group and butoxy group Nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; aromatic heterocyclic group having 2 to 20 carbon atoms such as furanyl group and thiophenyl group; cyclopropyl substituted trifluoromethyl group, pentafluoroethyl group, such as -CH ₂ CF _3, at least one hydrogen atom with a fluorine atom; group, a cyclopentyl group, a cycloalkyl group having 3 to 8 carbon atoms such as cyclohexyl group The and the like fluoro Achill group having 1 to 12 carbon atoms. The alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, and the aromatic hydrocarbon ring group having 5 to 12 carbon atoms represented by R ^{b ′} are one or more substituents selected from the substituents described above. It may have a group, and when it has a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Moreover, as a substituent of a C3-C12 cycloalkyl group of R < ^{b '} >, C1-C6, such as halogen atoms, such as a fluorine atom and a chlorine atom; Cyano group; Methyl group, an ethyl group, a propyl group, etc. Alkyl groups of 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro groups; and aromatic hydrocarbon groups of 6 to 20 carbon atoms such as phenyl group and naphthyl group. It is done. The cycloalkyl group having 3 to 12 carbon atoms of R ^{b ′} may have one or more substituents selected from the substituents described above, and when having a plurality of substituents, the plurality of substituents are They may be the same or different from each other.

The combination of Ar ¹ and D ¹ described above (Ar ¹ -D ¹ ) includes a phenylene group substituted with a group represented by the formula: —R ^f C (═N—NR ^g R ^h ), 1- A benzothiazol-4,7-diyl group substituted with a benzofuran-2-yl group, a benzothiazol-4,7-diyl group substituted with a 5- (2-butyl) -1-benzofuran-2-yl group, Benzothiazol-4,7-diyl group substituted with 4,6-dimethyl-1-benzofuran-2-yl group, benzothiazol-4,7 substituted with 6-methyl-1-benzofuran-2-yl group -Diyl group, benzothiazol-4,7-diyl group substituted with 4,6,7-trimethyl-1-benzofuran-2-yl group, 4,5,6-trimethyl-1-benzofuran-2-yl group Replaced with Nzothiazol-4,7-diyl group, substituted with 5-methyl-1-benzofuran-2-yl group, substituted with benzothiazol-4,7-diyl group, 5-propyl-1-benzofuran-2-yl group Benzothiazol-4,7-diyl group, benzothiazol-4,7-diyl group substituted with 7-propyl-1-benzofuran-2-yl group, 5-fluoro-1-benzofuran-2-yl group Substituted benzothiazole-4,7-diyl group, benzothiazole-4,7-diyl group substituted with phenyl group, benzothiazole-4,7-diyl group substituted with 4-fluorophenyl group, 4- Benzothiazole-4,7-diyl group substituted with nitrophenyl group, benzothiazole-4,7-diyl group substituted with 4-trifluoromethylphenyl group Benzothiazole-4,7-diyl group substituted with 4-cyanophenyl group, benzothiazole-4,7-diyl group substituted with 4-methanesulfonylphenyl group, substituted with thiophen-2-yl group Benzothiazole-4,7-diyl group, benzothiazole-4,7-diyl group substituted with thiophen-3-yl group, benzothiazole-4,7- substituted with 5-methylthiophen-2-yl group Benzothiazole-4,7 substituted with diyl group, benzothiazole-4,7-diyl group substituted with 5-chlorothiophen-2-yl group, thieno [3,2-b] thiophen-2-yl group -Benzothiazole-4,7-dii substituted with a diyl group, a benzothiazole-4,7-diyl group substituted with a 2-benzothiazolyl group, or a 4-biphenyl group Benzothiazole-4,7-diyl group substituted with 4-propylbiphenyl group, benzothiazole-4,7-diyl group substituted with 4-thiazolyl group, 1-phenylethylene-2-yl group Substituted benzothiazole-4,7-diyl group, benzothiazole-4,7-diyl group substituted with 4-pyridyl group, benzothiazole-4,7-diyl group substituted with 2-furyl group, naphtho [1,2-b] benzothiazole-4,7-diyl group substituted with furan-2-yl group, 1H-isoindole-1,3 (2H) substituted with 5-methoxy-2-benzothiazolyl group -1H-isoindole-1,3 (2H) -dione-4,7-diyl group substituted with a dione-4,7-diyl group, phenyl group, 1H- substituted with a 4-nitrophenyl group Soindole-1,3 (2H) -dione-4,7-diyl group, or 1H-isoindole-1,3 (2H) -dione-4,7-diyl group substituted with 2-thiazolyl group, etc. Is mentioned. Here, R ^f , R ^g , and R ^h represent the same meaning as described above.

Here, as Ar ¹ -D ¹ , a divalent group represented by the following formula (V) is preferable.
[In the formula (V), Ax represents an organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Ra represents a hydrogen atom or The C1-C20 organic group which may have a substituent is represented. ]

In the present specification, the partial structure represented by the following formula (i) means a partial structure represented by the following formula (ia) and / or (iib).

  Here, in Ax, “an organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring”, the “aromatic ring” means Huckel A cyclic structure having a broad sense of aromaticity according to the rules, that is, a cyclic conjugated structure having (4n + 2) π electrons, and heteroatoms such as sulfur, oxygen, nitrogen, and the like typified by thiophene, furan, benzothiazole, etc. It means a cyclic structure in which a lone electron pair participates in a π-electron system and exhibits aromaticity.

  The organic group having 2 to 20 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring may have a plurality of aromatic rings. It may have an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

Examples of the aromatic hydrocarbon ring of Ax include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, and fluorene ring.
Among these, as the aromatic hydrocarbon ring, a benzene ring and a naphthalene ring are preferable.

Examples of the aromatic heterocycle of Ax include 1H-isoindole-1,3 (2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, and indole ring. , Oxadiazole ring, oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazole Zolopyrazine ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine Ring, pyrrole ring, phenanthridi Ring, phthalazine ring, furan ring, benzo [c] thiophene ring, benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, benzooxadiazole ring, benzoxazole ring, benzothiadiazole ring, benzothiazole ring, benzothiophene ring Benzotriazine ring, benzotriazole ring, benzopyrazole ring, benzopyranone ring, dihydropyran ring, tetrahydropyran ring, dihydrofuran ring, tetrahydrofuran ring and the like.
Among these, aromatic heterocycles include monocyclic aromatic heterocycles such as furan ring, thiophene ring, oxazole ring, thiazole ring; benzothiazole ring, benzoxazole ring, quinoline ring, 1-benzofuran ring, 2- A condensed aromatic heterocycle such as a benzofuran ring, a benzothiophene ring, a thiazolopyridine ring and a thiazolopyrazine ring is preferred.

The aromatic ring which Ax has may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and 2 to 6 carbon atoms such as vinyl group and allyl group. An alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; a substituted amino group such as a dimethylamino group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group; Nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group, naphthyl group; -C (= O) -R ^b ; -C (= O) -OR ^b ; -SO ₂ R ^d ; Is mentioned. Here, R ^b may have a C 1-20 alkyl group which may have a substituent, a C 2-20 alkenyl group which may have a substituent, or a substituent. It represents a good cycloalkyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent. R ^d is an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; and a carbon number which may have a substituent such as a phenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group. It represents 6 to 20 aromatic hydrocarbon ring groups. Among these, as a substituent of the aromatic ring which Ax has, a halogen atom, a cyano group, a C1-C6 alkyl group, and a C1-C6 alkoxy group are preferable.
Ax may have a plurality of substituents selected from the above-described substituents. When Ax has a plurality of substituents, the substituents may be the same or different.

Examples of the alkyl group having 1 to 20 carbon atoms of R ^b which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl Group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group Group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like. In addition, it is preferable that carbon number of a C1-C20 alkyl group which may have a substituent is 1-12, and it is still more preferable that it is 4-10.

Examples of the alkenyl group having 2 to 20 carbon atoms of R ^b which may have a substituent include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, and a pentenyl group. Group, hexenyl group, heptenyl group, octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group and the like.
It is preferable that carbon number of the C2-C20 alkenyl group which may have a substituent is 2-12.

Examples of the substituent of the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of R ^b include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a substituted amino group such as a dimethylamino group; a methoxy group Alkoxy having 1 to 20 carbon atoms such as ethoxy group, isopropoxy group, butoxy group; alkoxy having 1 to 12 carbon atoms substituted with alkoxy group having 1 to 12 carbon atoms such as methoxymethoxy group and methoxyethoxy group Group: nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; aromatic heterocyclic group having 2 to 20 carbon atoms such as triazolyl group, pyrrolyl group, furanyl group and thiophenyl group A cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; a cyclopentyloxy group, a cyclohexyloxy group, and the like A cycloalkyloxy group having 3 to 8 carbon atoms; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group, or a dioxanyl group; a carbon number 6 to 14 such as a phenoxy group or a naphthoxy group An aryloxy group of 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, such as a trifluoromethyl group, a pentafluoroethyl group, or —CH ₂ CF ₃ ; a benzofuryl group; a benzopyranyl group Group; benzodioxolyl group; benzodioxanyl group and the like. Among these, as substituents for the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of R ^b , halogen atoms such as fluorine atom and chlorine atom; cyano group; methoxy group, ethoxy group, iso C1-20 alkoxy groups such as propoxy group and butoxy group; nitro groups; aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group; 2 carbon atoms such as furanyl group and thiophenyl group An aromatic heterocyclic group of ˜20; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; at least one of a trifluoromethyl group, a pentafluoroethyl group, —CH ₂ CF _3, etc. A C1-C12 fluoroalkyl group in which one hydrogen atom is substituted with a fluorine atom is preferred.
Note that the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of R ^b may have a plurality of substituents selected from the above-described substituents. When the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms in R ^b have a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Examples of the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent for R ^b include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Groups and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
Examples of the substituent for the cycloalkyl group having 3 to 12 carbon atoms of R ^b include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a substituted amino group such as a dimethylamino group; a methyl group, an ethyl group, a propyl group An alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group; a nitro group; an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; Etc. Among them, examples of the substituent for the cycloalkyl group having 3 to 12 carbon atoms of R ^b include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group. Groups: alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro groups; aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group are preferable.
In addition, the C3-C12 cycloalkyl group of ^Rb may have a some substituent. When the cycloalkyl group having 3 to 12 carbon atoms of R ^b has a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Examples of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent for R ^b include a phenyl group, a 1-naphthyl group, 2 -A naphthyl group etc. are mentioned. Among these, a phenyl group is preferable.
Examples of the substituent of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a substituted amino group such as a dimethylamino group; Group, an ethoxy group, an isopropoxy group, a butoxy group and the like having 1 to 20 carbon atoms; a methoxymethoxy group and a methoxyethoxy group and the like having 1 to 12 carbon atoms substituted by an alkoxy group having 1 to 12 carbon atoms Nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; aromatic heterocycle having 2 to 20 carbon atoms such as triazolyl group, pyrrolyl group, furanyl group and thiophenyl group A group: a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group; a carbon number such as a cyclopentyloxy group or a cyclohexyloxy group A cycloalkyloxy group having 8 to 8 carbon atoms; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group or a dioxanyl group; an aryloxy group having 6 to 14 carbon atoms such as a phenoxy group or a naphthoxy group A fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, such as a trifluoromethyl group, a pentafluoroethyl group, —CH ₂ CF ₃ ; a benzofuryl group; a benzopyranyl group; An oxolyl group; a benzodioxanyl group, and the like. Among them, examples of the substituent of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms include halogen atoms such as fluorine atom and chlorine atom; cyano group; carbon number 1 such as methoxy group, ethoxy group, isopropoxy group, and butoxy group. A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a furanyl group or a thiophenyl group; A cycloalkyl group having 3 to 8 carbon atoms such as a propyl group, a cyclopentyl group and a cyclohexyl group; at least one hydrogen atom such as a trifluoromethyl group, a pentafluoroethyl group or —CH ₂ CF ₃ is substituted with a fluorine atom; In addition, at least one substituent selected from a fluoroalkyl group having 1 to 12 carbon atoms is preferable.
In addition, the C5-C12 aromatic hydrocarbon ring group may have a plurality of substituents. When the aromatic hydrocarbon ring group having 5 to 12 carbon atoms has a plurality of substituents, the substituents may be the same or different.

Here, the aromatic ring of Ax may have a plurality of the same or different substituents, and two adjacent substituents may be bonded together to form a ring. Good. The formed ring may be a monocyclic ring, a condensed polycyclic ring, an unsaturated ring, or a saturated ring.
The “carbon number” of the organic group having 2 to 20 carbon atoms in Ax means the total number of carbon atoms in the whole organic group not including the carbon atom of the substituent.

  The organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle of Ax includes a phenyl group, a naphthyl group, an anthracenyl group, and phenanthrenyl. Group, pyrenyl group, fluorenyl group and the like aromatic hydrocarbon ring group having 6 to 20 carbon atoms; phthalimide group, 1-benzofuranyl group, 2-benzofuranyl group, acridinyl group, isoquinolinyl group, imidazolyl group, indolinyl group, flazanyl group, Oxazolyl group, Oxazolopyrazinyl group, Oxazolopyridinyl group, Oxazolopyridazinyl group, Oxazolopyrimidinyl group, Quinazolinyl group, Quinoxalinyl group, Quinolyl group, Cinnolinyl group, Thiadiazolyl group, Thiazolyl group, Thiazolo group Pyrazinyl group, thiazolopyridinyl group, thiazolo Ridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, phenanthridinyl group, Phthalazinyl group, furanyl group, benzo [c] thienyl group, benzisoxazolyl group, benzoisothiazolyl group, benzoimidazolyl group, benzoxazolyl group, benzoxazolyl group, benzothiadiazolyl group, benzothiazolyl group, Carbon number such as benzothiophenyl group, benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, benzopyranonyl group, dihydropyranyl group, tetrahydropyranyl group, dihydrofuranyl group, tetrahydrofuranyl group 2-20 fragrances A heterocyclic group; a hydrocarbon ring group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; at least one selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring A heterocyclic group having one aromatic ring; an alkyl group having 3 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; an aromatic hydrocarbon ring and an aromatic group An alkenyl group having 4 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of heterocycles; carbon having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles Alkynyl group of several 4-20; etc. are mentioned.

A hydrocarbon ring group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; and at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring A heterocyclic group having; an alkyl group having 3 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring An alkenyl group having 4 to 20 carbon atoms having at least one aromatic ring selected from the group; 4 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring Specific examples of the aromatic hydrocarbon ring and the aromatic heterocyclic ring of the alkynyl group of are listed as specific examples of the aromatic hydrocarbon ring and the aromatic heterocyclic ring of D ¹ above. The same as

  In addition, said organic group may have a 1 or several substituent. When it has a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and carbon number 2 such as vinyl group and allyl group. -6 alkenyl groups; C 1-6 halogenated alkyl groups such as trifluoromethyl groups; substituted amino groups such as dimethylamino groups; C 1-6 alkoxys such as methoxy groups, ethoxy groups, and isopropoxy groups group; a nitro group; a phenyl group, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl or ^{naphthyl; -C (= O) -R b} ; -C (= O) -OR b; -SO 2 R d And the like. Here, R ^b and R ^d represent the same meaning as described above.
Among these, the substituent that the organic group of Ax has is preferably at least one substituent selected from a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. .

  Preferable specific examples of the organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring as Ax are shown below. However, the present invention is not limited to the following. In the following formula, “-” represents a bond with an N atom extending from an arbitrary position of the ring (that is, an N atom bonded to Ax in the formula (V)).

1) Aromatic hydrocarbon ring group

2) Aromatic heterocyclic group

[In each formula, E represents —NR ^z —, an oxygen atom or a sulfur atom, wherein R ^z represents a hydrogen atom; or an alkyl having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group. Represents a group; ]

[In each formula, X and Y each independently represent —NR ^z —, an oxygen atom, a sulfur atom, —SO— or —SO ₂ —. Here, R ^z represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group. ]

[In each formula, X represents the same meaning as described above. ]

3) Hydrocarbon ring group having at least one aromatic ring

4) Heterocyclic group having at least one aromatic ring
[In each formula, X and Y represent the same meaning as described above, Z represents —NR ^z —, an oxygen atom or a sulfur atom, where R ^z represents the same meaning as described above (provided that, in each formula, In which oxygen atom, sulfur atom, —SO—, and —SO ² — are not adjacent to each other). ]

5) An alkyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring

6) An alkenyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring

7) Alkynyl group having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles

In addition, the ring which the preferable specific example of Ax mentioned above has may have one or a plurality of substituents. And when it has a some substituent, a plurality of substituents may mutually be same or different. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and 2 to 6 carbon atoms such as vinyl group and allyl group. An alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; a substituted amino group such as a dimethylamino group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group; Nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group, naphthyl group; -C (= O) -R ^b ; -C (= O) -OR ^b ; -SO ₂ R ^d ; Is mentioned.
Here, R ^b and R ^d represent the same meaning as described above. Among these, as a substituent which the said ring which Ax has, a halogen atom, a cyano group, a C1-C6 alkyl group, and a C1-C6 alkoxy group are preferable.

Here, more preferable specific examples of Ax are shown below. However, Ax is not limited to the following.
[In each formula, X represents the same meaning as described above. ]

As described above, the ring may have one or more substituents. When it has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; cyano group; carbon numbers such as vinyl group and allyl group. 2-6 alkenyl groups; C1-C6 halogenated alkyl groups such as trifluoromethyl groups and pentafluoroethyl groups; substituted amino groups such as dimethylamino groups; carbons such as methoxy groups, ethoxy groups and isopropoxy groups An alkoxy group having 1 to 6 carbon atoms; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; -C (= O) -R ^b ; -C (= O) -OR ^b ; _-SO 2 ^{R d;} and the like. Here, R ^b and R ^d represent the same meaning as described above.
Among these, as a substituent which the said ring has, a halogen atom, a cyano group, a C1-C6 alkyl group, and a C1-C6 alkoxy group are preferable.

Ax is more preferably a group represented by the following formula (VI).

In the above formula (VI), R ^X represents a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group or a propyl group; A nitro group; a fluoroalkyl group having 1 to 6 carbon atoms such as trifluoromethyl group and pentafluoroethyl group; an alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; or -C (═O) —O—R ^b , where R ^b is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent, as described above. Represents an -20 alkenyl group, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, or an optionally substituted aromatic hydrocarbon ring group having 5 to 12 carbon atoms. .

The plurality of R ^X may be the same or different from each other, and any C—R ^X constituting the ring may be replaced with a nitrogen atom.

Here, specific examples of the group in which C—R ^{X of the} group represented by the above formula (VI) is replaced with a nitrogen atom are shown below. However, the group in which C—R ^X is replaced with a nitrogen atom is not limited thereto.
[In each formula, R ^X represents the same meaning as described above. ]

Among these, as Ax, those in which R ^{X of the} group represented by the formula (VI) are all hydrogen atoms are preferable.

Moreover, as a C1-C20 organic group which may have a substituent of Ra of the bivalent group represented by the said Formula (V), it does not restrict | limit in particular, For example, a substituent An optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and an optionally substituted alkynyl having 2 to 20 carbon atoms. group, a cycloalkyl group having 3 to 12 carbon atoms which may have a _{^{substituent, -C (= O) -R b}} , -SO 2 -R d, -C (= S) NH-R i, substituted Examples thereof include an aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have a group, or an aromatic heterocyclic group having 2 to 20 carbon atoms which may have a substituent.

Here, R ^b and R ^d represent the same meaning as described above, and R ⁱ is an optionally substituted alkyl group having 1 to 20 carbon atoms and an optionally substituted carbon number. An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group having 5 to 20 carbon atoms which may have a substituent, or The C5-C20 aromatic heterocyclic group which may have a substituent is represented.
Then, the R ^i, alkyl groups and substituents thereof having 1 to 20 carbon atoms an alkyl group of carbon atoms which may 20 have a substituent, the number of carbon atoms which may have a substituent group 2 The alkenyl group having 2 to 20 carbon atoms of the alkenyl group of 20 and its substituent, and the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, and Examples of the substituent include R 1 ^b alkyl groups having 1 to 20 carbon atoms and substituents thereof, alkenyl groups having 2 to 20 carbon atoms and substituents thereof, and cycloalkyl groups having 3 to 12 carbon atoms and substituents thereof. Specific examples are the same as those listed. Further, the R ^i, as the aromatic hydrocarbon ring group of 5 to 20 carbon atoms which may have a substituent, a phenyl group, 1-naphthyl, 2-naphthyl and the like, the substituent Examples of the aromatic heterocyclic group having 5 to 20 carbon atoms that may have include a pyridinyl group and a quinolyl group. Furthermore, examples of the substituent for the aromatic hydrocarbon ring group and the aromatic heterocyclic group include the same ones as those exemplified as the substituent for the organic group having 2 to 20 carbon atoms of Ax.

  In addition, as a C1-C20 alkyl group of the C1-C20 alkyl group which may have a substituent of Ra, a methyl group, an ethyl group, n-propyl group, isopropyl group, n- Butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n- Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n- Examples include heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like. And the carbon number of the C1-C20 alkyl group which may have a substituent is preferably 1-12, and more preferably 1-10.

In addition, as the alkenyl group having 2 to 20 carbon atoms of the alkenyl group having 2 to 20 carbon atoms which may have a substituent, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, Examples include a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, and the like.
It is preferable that carbon number of the C2-C20 alkenyl group which may have a substituent is 2-12.

  Furthermore, as the alkynyl group having 2 to 20 carbon atoms of the alkynyl group having 2 to 20 carbon atoms which may have a substituent, Ra includes ethynyl group, propynyl group, 2-propynyl group (propargyl group), butynyl. Group, 2-butynyl group, 3-butynyl group, pentynyl group, 2-pentynyl group, hexynyl group, 5-hexynyl group, heptynyl group, octynyl group, 2-octynyl group, nonanyl group, decanyl group, 7-decanyl group, etc. Is mentioned.

  Examples of the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo group. An octyl group etc. are mentioned.

And as a substituent of a C1-C20 alkyl group, a C2-C20 alkenyl group, and a C2-C20 alkynyl group of Ra, halogen atoms, such as a fluorine atom and a chlorine atom; A substituted amino group such as a dimethylamino group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group; an alkoxy group having 1 to 12 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group; An alkoxy group having 1 to 12 carbon atoms substituted with a group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group or a thiophenyl group; An aromatic heterocyclic group having 2 to 20 carbon atoms; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; A cycloalkyloxy group having 3 to 8 carbon atoms such as a nyloxy group and a cyclohexyloxy group; a cyclic ether group having 2 to 12 carbon atoms such as a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group and a dioxanyl group; a phenoxy group and a naphthoxy group An aryloxy group having 6 to 14 carbon atoms such as trifluoromethyl group, pentafluoroethyl group, —CH ₂ CF _3, etc., wherein at least one hydrogen atom is substituted with a fluorine atom, Achill group; benzofuryl group; a benzopyranyl group; benzodioxolyl group; benzodioxanyl ^{group; -C (= O) -R b} ; -C (= O) -OR b; -SO 2 R d; -SR b ; substituted with -SR ^b an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group, and the like. Here, R ^b and R ^d represent the same meaning as described above.
Note that the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, and the alkynyl group having 2 to 20 carbon atoms in Ra may have a plurality of the substituents described above, In the case of having a group, the plurality of substituents may be the same as or different from each other.

Examples of the substituent of the cycloalkyl group having 3 to 12 carbon atoms of Ra include halogen atoms such as fluorine atom and chlorine atom; cyano group; substituted amino group such as dimethylamino group; methyl group, ethyl group, propyl group and the like An alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and an isopropoxy group; a nitro group; an aromatic hydrocarbon having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group ring group; a cyclopropyl group, a cyclopentyl group, a cycloalkyl group having 3 to 8 carbon atoms such as a cyclohexyl ^{group; -C (= O) -R b} ; -C (= O) -OR b; -SO 2 R d; Hydroxyl group; and the like. Here, R ^b and R ^d represent the same meaning as described above.
In addition, the C3-C12 cycloalkyl group of Ra may have a plurality of the above-described substituents, and when it has a plurality of substituents, the plurality of substituents may be the same or different from each other. Good.

  In addition, as Ra, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 2 to 20 carbon atoms, and substituents thereof, the aromatic hydrocarbon ring group and aromatic Group heterocyclic groups and the same groups as those listed as substituents thereof.

  Among the above, Ra includes a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and a substituent. C2-C20 alkynyl group which may have, C5-C20 cycloalkyl group which may have a substituent, C6-C18 aroma which may have a substituent An aromatic hydrocarbon group having 5 to 18 carbon atoms which may have a substituent, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, C2-C10 alkenyl group which may have a substituent, C2-C10 alkynyl group which may have a substituent, C5-C10 which may have a substituent More preferred are cycloalkyl groups and aromatic hydrocarbon ring groups having 6 to 12 carbon atoms.

In Formula (III) described above, Z ¹¹ and Z ¹² are each independently —CO—O—, —O—CO—, —NR ³¹ —CO—, or —CO—NR ³² —. In the formula, R ³¹ and R ³² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, Z ¹¹ is preferably —CO—O—. Z ¹² is preferably —O—CO—.

Further, A ¹¹ and A ¹² are each independently a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent. Among them, A ¹¹ and A ¹² are preferably have a substituent is also optionally cyclic aliphatic group.

In addition, the cycloaliphatic group which may have a substituent is an unsubstituted divalent cycloaliphatic group or a divalent cycloaliphatic group having a substituent. The divalent cycloaliphatic group is a divalent aliphatic group having a cyclic structure and usually having 5 to 20 carbon atoms.
Specific examples of the divalent cycloaliphatic group represented by A ¹¹ and A ¹² include the same groups as those exemplified as the divalent cycloaliphatic group represented by A ^{1 in} the formula (I).

The aromatic group which may have a substituent is an unsubstituted divalent aromatic group or a divalent aromatic group having a substituent. The divalent aromatic group is a divalent aromatic group having an aromatic ring structure and usually having 2 to 20 carbon atoms.
Specific examples of the divalent aromatic group represented by A ¹¹ and A ¹² include the same ones as exemplified as the divalent aromatic group represented by A ^{1 in} the formula (I).

Furthermore, examples of the substituent for the divalent cycloaliphatic group and the divalent aromatic group of A ¹¹ and A ¹² include the divalent cycloaliphatic group and the divalent aromatic group of A ^{1 in} the formula (I). The same thing as what was illustrated as a substituent of group is mentioned.

When h and / or i is 1, L ¹¹ and L ¹² are each independently a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ^21. —CO—, —CO—NR ²² —, —O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —. Here, R ^{21 to} R ²⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among ^{them, L 11} and ^{L 12} are each independently, -O -, - CO-O- , or is preferably a -O-CO-.
As the alkyl group having 1 to 6 carbon atoms of the ^R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like.

When h and / or i is 1, B ¹¹ and B ¹² are each independently a cyclic aliphatic group which may have a substituent, or an aromatic which may have a substituent. It is a family group. Among them, B ¹¹ and B ¹² is preferably an aromatic group which may have a substituent.

Here, the cycloaliphatic group which may have a substituent is an unsubstituted divalent cycloaliphatic group or a divalent cycloaliphatic group having a substituent. The divalent cycloaliphatic group is a divalent aliphatic group having a cyclic structure and usually having 5 to 20 carbon atoms.
Specific examples of the divalent cycloaliphatic group represented by B ¹¹ and B ¹² include the same groups as those exemplified as the divalent cycloaliphatic group represented by A ^{1 in} the formula (I).

The aromatic group which may have a substituent is an unsubstituted divalent aromatic group or a divalent aromatic group having a substituent. The divalent aromatic group is a divalent aromatic group having an aromatic ring structure and usually having 2 to 20 carbon atoms.
Specific examples of the divalent aromatic group of B ¹¹ and B ¹² include the same ones as exemplified as the divalent aromatic group of A ^{1 in} the formula (I).

Further, the divalent cycloaliphatic group and the divalent aromatic group of B ¹¹ and B ¹² may be substituted with the divalent cycloaliphatic group and divalent aromatic group of A ^{1 in} the formula (I). The same thing as what was illustrated as a substituent of group is mentioned.

Y ¹¹ and Y ¹² are each independently a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —. , —O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, wherein R ^{21 to} R ²⁶ are And each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among ^{them, Y 11} and ^{Y 12} each independently, -O -, - CO-O- , or is preferably a -O-CO-.
^As the alkyl group having 1 to 6 carbon atoms R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group.

R ^{4 to} R ⁷ are each independently a hydrogen atom, a methyl group or a chlorine atom, preferably a hydrogen atom or a methyl group. R ^{4 to} R ⁷ are all preferably the same, and R ^{4 to} R ⁷ are more preferably all hydrogen atoms.

In addition, from the viewpoint of obtaining an optical film or the like excellent in reverse wavelength dispersion, the polymerizable compound (III) preferably has a structure in which left and right are generally symmetrical about Ar ¹ -D ¹ . Specifically, the polymerizable compound ^{(III), R 4,} g and h are each ^the same as ^R 7, j and ^{i, -Y 11 - [B 11} -L 11] h -A 11 - and a symmetry structure with a symmetry around the side (*) which binds to Ar ¹ - Z ¹¹ - and ^{(*), (*) -} Z 12 -A 12 - [L 12 -B 12] i -Y 12 It is preferable.
Note that “having a symmetric structure with (*) as the center of symmetry” means, for example, —CO—O — (*) and (*) — O—CO— or —O — (*) and (*). It means having a structure such as —O— or —O—CO — (*) and (*) — CO—O—.

  The polymerizable compound (III) can be synthesized by combining known synthetic reactions. That is, it can be synthesized by referring to the methods described in various literatures (for example, MARCH'S ADVANCED ORGANIC CHEMISTRY (WILEY), Sandler Caro "Synthesis of Organic Compounds by Functional Group" Naoki Inamoto (Yodogawa Shoten)).

Here, a preferable example of the polymerizable compound (III) in which h and i are 1 is not particularly limited, and the following formula (Va):
[In Formula (Va), R ^{4 to} R ⁷ , Ra, R ^x , f, g, j, and k represent the same meaning as described above. ] (Referred to below as “polymerizable compound (Va)”).

The production method of the polymerizable compound (Va) is not particularly limited. For example, 2,5-dihydroxybenzaldehyde represented by the following formula (7) and a compound represented by the following formula (b) ( Hereinafter, a compound represented by the following formula (9)) and a compound represented by the following formula (c) (hereinafter, referred to as “compound (c)”) are reacted sequentially, and a compound represented by the following formula (9) ( Hereinafter, a method of obtaining a polymerizable compound (Va) by obtaining “compound (9)” and reacting the obtained compound (9) with a hydrazine compound represented by the following formula (10). Is mentioned.
[In each formula, R ^{4 to} R ⁷ , f, g, j, k, Ra, and R ^X represent the same meaning as described above, and L represents a leaving group as in Formula (2). ]

  In addition, in the compound (b) and the compound (c) (hereinafter sometimes referred to as “compound (b) and the like”), the compound (acid halide) in which L is a halogen atom is converted into the above-described compound (IIIa). It can be obtained by reacting a halogenating agent such as thionyl chloride in the presence of an activator.

Examples of the activator used here include quaternary ammonium salts such as N, N-dimethylformamide, benzyltriethylammonium chloride, and benzyltrimethylammonium chloride.
And the usage-amount of an activator is 0.1-3 mol normally with respect to 1 mol of compounds (b).

In the compound (b) and the like, the compound (mixed acid anhydride) in which L is a methanesulfonyloxy group or an alkyl (aryl) sulfonyloxy group such as a p-toluenesulfonyloxy group is mixed with the above-mentioned compound in an appropriate solvent. In the compound (IIIa), R ^d SO ₂ Cl [wherein R ^d represents the same meaning as in the formula (6). ] Is obtained by reacting in the presence of a base.
As the base, triethylamine, N, N-diisopropylethylamine, 4- (dimethylamino) pyridine and the like can be used.
Examples of the suitable solvent include those exemplified as the solvent that can be used for producing the compound (Ia), and halogen solvents such as methylene chloride and chloroform. Of these, ether solvents are preferred.

Examples of the solvent used in the reaction of 2,5-dihydroxybenzaldehyde represented by the above formula (7) with compound (b) and the like include chlorinated solvents such as chloroform and methylene chloride; N-methylpyrrolidone, N, N-dimethyl Amide solvents such as formamide, N, N-dimethylacetamide, hexamethylphosphoric triamide; ethers such as 1,4-dioxane, cyclopentylmethyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane; dimethyl sulfoxide, sulfolane, etc. Sulfur-containing solvents of: aromatic hydrocarbon solvents such as benzene, toluene, xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-octane, cyclopentane, cyclohexane; and these solvents Or a mixed solvent composed of two or more thereof.
The amount of the solvent used is not particularly limited and can be appropriately determined in consideration of the type of compound used, reaction scale, and the like, but is usually 1 to 50 g with respect to 1 g of compound (b) and the like.

  In addition, the target polymeric compound (Va) is 1: 2-2 in a molar ratio (compound (9): hydrazine compound (10)) of the obtained compound (9) and hydrazine compound (10). : 1, preferably by reaction at a ratio of 1: 1.5 to 1.5: 1, can be produced with high selectivity and high yield.

  In this case, the reaction can be carried out by adding an acid catalyst such as an organic acid such as (±) -10-camphorsulfonic acid and paratoluenesulfonic acid; an inorganic acid such as hydrochloric acid and sulfuric acid; By adding an acid catalyst, the reaction time may be shortened and the yield may be improved. The addition amount of the acid catalyst is usually 0.001 to 1 mol with respect to 1 mol of the compound (9). Further, the acid catalyst may be added as it is, or may be added as a solution dissolved in an appropriate solution.

The solvent used for the reaction between the compound (9) and the hydrazine compound (10) is not particularly limited as long as it is inert to the reaction. For example, alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether; acetic acid Ester solvents such as ethyl and propyl acetate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; N, N-dimethylformamide Amide solvents such as N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; chlorinated solvents such as chloroform and methylene chloride; and mixed solvents composed of two or more of these solvents.
Among these, alcohol solvents, chlorine solvents, ether solvents, and mixed solvents composed of two or more of these are preferable.

  In addition, the usage-amount of a solvent is not specifically limited, Although it can determine suitably considering the kind of compound to be used, reaction scale, etc., it is 1-100g normally with respect to 1g of hydrazine compounds (10).

  The reaction proceeds smoothly in a temperature range from −10 ° C. to the boiling point of the solvent used. The reaction time for each reaction is usually from several minutes to several hours depending on the reaction scale.

(4) Mixture containing polymerizable compound The mixture of the present invention is a mixture containing the polymerizable compound (III) and a polymerizable compound represented by the following formula (IV) (polymerizable compound (IV)), For example, it can be used for the production of a polymerizable liquid crystal composition and a polymer described later.
From the viewpoint of enhancing the reverse wavelength dispersibility of the optical film obtained while widening the process margin when forming an optical film or the like using the polymerizable liquid crystal composition prepared using the mixture or the mixture, The mass ratio of the polymerizable compound (III) to the polymerizable compound (IV) (polymerizable compound (III): polymerizable compound (IV)) is preferably 1: 1000 to 20: 100, and 1: 100 More preferably, it is -20: 100.

If a mixture of the polymerizable compound (III) and the polymerizable compound (IV) is used, the liquid crystal phase can be maintained more stably for a long time, has a wide process margin, has a practically low melting point, An optical film having excellent solubility in a general-purpose solvent and capable of uniform polarization conversion in a wide wavelength range can be produced at low cost.
The reason for this is not clear, but the polymerizable compound (III) has a structure represented by “— (CH ₂ CHR ⁵ COO) _f —” and / or “— (OCOCHR ⁶ CH ₂ ) _k —”. Therefore, if a mixture of the polymerizable compound (III) and the polymerizable compound (IV) is used, optical characteristics (particularly, reverse wavelength dispersion) are ensured as compared with the case where only the polymerizable compound (IV) is used. However, it is presumed that it is possible to obtain an optical film or the like using a polymer as a constituent material by forming a liquid crystal layer that tends to be in a liquid crystal phase at a lower temperature (that is, easily in a supercooled state at room temperature). Is done.

  Here, in formula (IV), m and q are each independently an integer of 1 to 20, preferably an integer of 2 to 12, more preferably an integer of 4 to 8, and n and p are each Independently, 0 or 1, with 1 being preferred.

Then, Ar ² represents a divalent aromatic hydrocarbon ring group having as a substituent D ^2, or a divalent aromatic heterocyclic group having as a substituent D ^2. D ² is an organic group having 1 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

Here, the divalent aromatic divalent aromatic heterocyclic group having a hydrocarbon ring group or D ² substituents, an aromatic hydrocarbon ring D ² is bonded with a substituent D ² or two group obtained by removing a hydrogen atom from a ring portion of the aromatic heterocyclic ring D ² is bonded is bonded to the carbon other than carbon D ² is bonded.

And, examples of the divalent aromatic hydrocarbon ring group Ar ^2, may be the same as those noted examples of the divalent aromatic hydrocarbon ring group Ar ¹ of the polymerizable compound (III).
The divalent aromatic heterocyclic group of Ar ^2, may be the same as those noted examples of the divalent aromatic heterocyclic group of Ar ¹ in the polymerizable compound (III).

Incidentally, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group of Ar ^2, the polymerizable compound and Ar ¹ in (III) also has at least one substituent in addition to the D ² It may be. The substituents of the divalent aromatic hydrocarbon ring group and divalent aromatic heterocyclic group of Ar ² include the divalent aromatic hydrocarbon ring group and divalent aromatic heterocyclic ring of Ar ^1. The same thing as what was illustrated as a substituent in case a group has a substituent is mentioned.

Also, the D ^2, D ¹ as the organic group having 1 to 20 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic ring, the polymerizable compound (III) Are the same as those exemplified as the organic group having 1 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

As a combination of Ar ² and D ² (Ar ² -D ² ), a phenylene group substituted with a group represented by the formula: —R ^f C (═N—NR ^g R ^h ), 1-benzofuran- A benzothiazole-4,7-diyl group substituted with a 2-yl group, a benzothiazole-4,7-diyl group substituted with a 5- (2-butyl) -1-benzofuran-2-yl group, 4, Benzothiazol-4,7-diyl group substituted with 6-dimethyl-1-benzofuran-2-yl group, benzothiazol-4,7-diyl group substituted with 6-methyl-1-benzofuran-2-yl group Substituted with 4,6,7-trimethyl-1-benzofuran-2-yl group, benzothiazol-4,7-diyl group, 4,5,6-trimethyl-1-benzofuran-2-yl group Benzoti Zol-4,7-diyl, benzothiazol-4,7-diyl substituted with 5-methyl-1-benzofuran-2-yl, 5-propyl-1-benzofuran-2-yl Benzothiazol-4,7-diyl group, benzothiazol-4,7-diyl group substituted with 7-propyl-1-benzofuran-2-yl group, 5-fluoro-1-benzofuran-2-yl group Substituted benzothiazole-4,7-diyl group, benzothiazole-4,7-diyl group substituted with phenyl group, benzothiazole-4,7-diyl group substituted with 4-fluorophenyl group, 4- A benzothiazole-4,7-diyl group substituted with a nitrophenyl group, a benzothiazole-4,7-diyl group substituted with a 4-trifluoromethylphenyl group, 4- Benzothiazole-4,7-diyl group substituted with an anophenyl group, benzothiazole-4,7-diyl group substituted with 4-methanesulfonylphenyl group, benzothiazole-4 substituted with thiophen-2-yl group , 7-diyl group, benzothiazol-4,7-diyl group substituted with thiophen-3-yl group, benzothiazole-4,7-diyl group substituted with 5-methylthiophen-2-yl group, 5 A benzothiazol-4,7-diyl group substituted with a chlorothiophen-2-yl group, a benzothiazol-4,7-diyl group substituted with a thieno [3,2-b] thiophen-2-yl group, Benzothiazole-4,7-diyl group substituted with 2-benzothiazolyl group, benzothiazole-4,7-diyl group substituted with 4-biphenyl group, 4 -Benzothiazole-4,7-diyl group substituted with propylbiphenyl group, benzothiazole-4,7-diyl group substituted with 4-thiazolyl group, benzoate substituted with 1-phenylethylene-2-yl group Thiazole-4,7-diyl group, benzothiazole-4,7-diyl group substituted with 4-pyridyl group, benzothiazole-4,7-diyl group substituted with 2-furyl group, naphtho [1,2, -B] benzothiazole-4,7-diyl group substituted with a furan-2-yl group, 1H-isoindole-1,3 (2H) -dione-4 substituted with a 5-methoxy-2-benzothiazolyl group , 7-Diyl group, 1H-isoindole-1,3 (2H) -dione-4,7-diyl group substituted with phenyl group, 1H-isoin substituted with 4-nitrophenyl group 1,3- (2H) -dione-4,7-diyl group, or 1H-isoindole-1,3 (2H) -dione-4,7-diyl group substituted with 2-thiazolyl group, etc. Is mentioned. Here, R ^f , R ^g , and R ^h represent the same meaning as described above.

Among these, as Ar ² -D ² , a group represented by the following formula (VII) is more preferable.
[In the formula (VII), Ay represents an organic group having 2 to 20 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Rc represents a hydrogen atom or The C1-C20 organic group which may have a substituent is represented. ]

  Here, as the organic group having 2 to 20 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of Ay, the aromatic group of Ax in the above formula (V) is used. The same thing as what was illustrated as a C2-C20 organic group which has at least 1 aromatic ring chosen from the group which consists of a hydrocarbon ring and an aromatic heterocyclic ring is mentioned.

Among them, as Ay, a group represented by the following formula (VI) is preferable, as in Ax of the above formula (V), and all of R ^{X of the} group represented by the following formula (VI) are hydrogen atoms. Further preferred.
[In formula (VI), R ^X represents the same meaning as described above. ]

  Moreover, as a C1-C20 organic group which may have a substituent of Rc, as a C1-C20 organic group which may have a substituent of Ra of the said Formula (V), The same thing as illustrated may be mentioned.

In the above formula (IV), Z ²¹ and Z ²² are each independently —CO—O—, —O—CO—, —NR ³¹ —CO—, or —CO—NR ³² —. In the formula, R ³¹ and R ³² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, Z ²¹ is preferably —CO—O—. Z ²² is preferably —O—CO—.

Further, A ²¹ and A ²² are each independently a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent. Among them, A ²¹ and A ²² is preferably a good cyclic aliphatic group which may have a substituent.
In addition, as the cyclic aliphatic group which may have a substituent of A ²¹ and A ²² or the aromatic group which may have a substituent, A ^{11 of the} polymerizable compound (III) may be used. and have a substituent a ¹² they also have a good cyclic aliphatic group or a substituent same as the like and also aromatic groups.

When n and / or p is 1, L ²¹ and L ²² are each independently a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ^21. —CO—, —CO—NR ²² —, —O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —. Here, R ^{21 to} R ²⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among ^{them, L 21} and ^{L 22} are each independently, -O -, - CO-O- , or is preferably a -O-CO-.
As the alkyl group having 1 to 6 carbon atoms of the ^R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like.

When n and / or p is 1, B ²¹ and B ²² are each independently a cyclic aliphatic group which may have a substituent, or an aromatic which may have a substituent. It is a family group. In particular, it is preferable B ²¹ and B ²² are aromatic group which may have a substituent.
The cyclic aliphatic group which may have a substituent or the aromatic group which may have a substituent of B ²¹ and B ²² may be B ^{11 of the} polymerizable compound (III). And the same as the cyclic aliphatic group which may have a substituent of B ¹² or the aromatic group which may have a substituent.

Y ²¹ and Y ²² are each independently a single bond, —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —. , —O—CO—O—, —NR ²³ —CO—O—, —O—CO—NR ²⁴ —, or —NR ²⁵ —CO—NR ²⁶ —, wherein R ^{21 to} R ²⁶ are And each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among these, Y ²¹ and Y ²² are preferably each independently —O—, —CO—O—, or —O—CO—.
^As the alkyl group having 1 to 6 carbon atoms R 21 ^{to R 26,} for example a methyl group, an ethyl group, a propyl group, an isopropyl group.

R ⁸ and R ⁹ are each independently a hydrogen atom, a methyl group or a chlorine atom, preferably a hydrogen atom or a methyl group. R ⁸ is more preferably the same as R ^9, and both R ⁸ and R ⁹ are more preferably hydrogen atoms.

From the viewpoint of obtaining an optical film having excellent reverse wavelength dispersion, the polymerizable compound (IV) preferably has a symmetrical structure with Ar ² -D ² as the center. Specifically, the polymerizable compound in ^{(IV), R 8,} m and n are each ^the same as ^R 9, q and ^{p, -Y 21 - [B 21} -L 21] n -A 21 - and a symmetry structure with a symmetry around the side (*) which binds to Ar ² - Z ²¹ - and ^{(*), (*) -} Z 22 -A 22 - [L 22 -B 22] p -Y 22 It is preferable.
Note that “having a symmetric structure with (*) as the center of symmetry” means, for example, —CO—O — (*) and (*) — O—CO— or —O — (*) and (*). It means having a structure such as —O— or —O—CO — (*) and (*) — CO—O—.

  The polymerizable compound (IV) can be produced by combining known synthetic reactions. That is, it can be synthesized by referring to the methods described in various literatures (for example, MARCH'S ADVANCED ORGANIC CHEMISTRY (WILEY), Sandler Caro "Synthesis of Organic Compounds by Functional Group" Naoki Inamoto (Yodogawa Shoten)).

In addition, although not particularly limited, from the viewpoint of enhancing the reverse wavelength dispersion of an optical film or the like, the mixture of the present invention is composed of Ar ¹ , Z ¹¹ , Z ¹² , A ¹¹ , and the polymerizable compound (III). A ¹² , B ¹¹ , B ¹² , Y ¹¹ , Y ¹² , L ¹¹ , L ¹² , R ⁴ , R ⁷ , g, j, h and i are respectively Ar ² and Z ^{21 of the} polymerizable compound (IV). , Z ²² , A ²¹ , A ²² , B ²¹ , B ²² , Y ²¹ , Y ²² , L ²¹ , L ²² , R ⁸ , R ⁹ , m, q, n and p are preferably the same. D ¹ and D ² may be the same as or different from each other.
That is, the portion other than D ^{1 of} the polymerizable compound (III) is “-(CH ₂ CHR ⁵ COO) _f −” between “CH ₂ CR ⁴ COO—” and “— (CH ₂ ) _g —”. Of the polymerizable compound (IV) except that “— (OCOCHR ⁶ CH ₂ ) _k —” is not present between “—OCOCR ⁷ CH ₂ ” and “— (CH ₂ ) _j —”. preferably it has the same structure as the D ² other portions.

  And a mixture can be prepared by mixing polymeric compound (III) and polymeric compound (IV) in a desired ratio, for example.

Further, the mixture is not particularly limited, and the following formula:
[Wherein L ⁴ reacts with FG ¹ of compound (I) or FG ² of compound (II) described above to react with —CO—O—, —O—CO—, —NR ³¹ —CO—, or Represents a group capable of forming —CO—NR ³² — (wherein R ³¹ and R ³² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and L ⁵ is converted to D ¹ Represents a possible group, Ar ¹ represents the same meaning as in formula (III). ]
And a mixture containing the compound (I) and the compound (II) described above can be reacted, and then L ⁵ can be converted to D ¹ .

Here, a preferable example of the polymerizable compound (IV) in which n and p are 1 is not particularly limited, and the following formula (VIa):
[In the formula (VIa), R ⁸ , R ⁹ , Rc, R ^x , m and q have the same meaning as described above, and R ^X is preferably a hydrogen atom. ] (Hereinafter, sometimes referred to as “compound (VIa)”).

  Compound (VIa) can be produced by a conventionally known method such as the method described in Patent Document 1.

  Further, for example, a mixture containing the compound (Va) and the compound (VIa) can be prepared by mixing the compound (Va) and the compound (VIa) described above in a desired ratio.

  Further, the mixture containing the compound (Va) and the compound (VIa) is obtained by, for example, replacing the compound (b) and the compound (c) with the compound (IIIa) and the compound (Va) in the production method for obtaining the compound (Va). It can also be obtained by using a mixture comprising (IVa).

(5) Polymerizable liquid crystal composition The polymerizable liquid crystal composition of the present invention includes a mixture containing the above-described polymerizable compound (a mixture containing the polymerizable compound (III) and the polymerizable compound (IV)), a polymerization initiator, Containing.
The polymerizable liquid crystal composition of the present invention is useful as a raw material for producing the polymer, optical film, and optical anisotropic body of the present invention, as will be described later. According to the polymerizable liquid crystal composition of the present invention, the liquid crystal phase can be maintained more stably for a long time, has a wide process margin, has a practically low melting point, has excellent solubility in general-purpose solvents, and Thus, an optical film or the like capable of uniform polarization conversion in a wide wavelength range can be produced at a low cost.

Here, a polymerization initiator is mix | blended from a viewpoint of performing the polymerization reaction of the polymeric compound contained in the polymeric liquid crystal composition more efficiently.
And as a polymerization initiator to be used, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, etc. are mentioned.

  As the radical polymerization initiator, a thermal radical generator which is a compound that generates an active species capable of initiating polymerization of a polymerizable compound by heating; visible light, ultraviolet rays (i-rays, etc.), far ultraviolet rays, electrons Any of photoradical generators, which are compounds that generate active species capable of initiating polymerization of polymerizable compounds upon exposure to exposure light such as X-rays and X-rays, can be used, but photoradical generators are used. Is preferred.

  Photo radical generators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds , Xanthone compounds, diazo compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure. A photoradical generator can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, Examples include 1,2-octanedione and 2-benzyl-2-dimethylamino-4′-morpholinobylophenone.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1 2,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2-bromophenyl) -4,4 ′, , 5′-Tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator (photo radical generator), it is preferable to use a hydrogen donor in terms of further improving sensitivity.
Here, the “hydrogen donor” means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. As the hydrogen donor, mercaptan compounds, amine compounds and the like defined below are preferable.

  Examples of mercaptan compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine and the like. Can be mentioned. Examples of amine compounds include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, Examples include 4-dimethylaminobenzoic acid and 4-dimethylaminobenzonitrile.

  Examples of triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran). -2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl)- 3,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, and other triazine compounds having a halomethyl group. it can.

  Specific examples of O-acyloxime compounds include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio) phenyl]- Octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl- 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole-3- Yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetyloxime), Non-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl- 6- (2-Methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5) -Tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxy) Ranyl) benzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9H-carbazol-3-yl] -1 -(O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9- And ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime). it can.

  Moreover, a commercial item can also be used as it is as a photoradical generator. As specific examples, trade names: Irgacure 907, trade names: Irgacure 184, trade names: Irgacure 369, trade names: Irgacure 651, trade names: Irgacure 819, trade names: Irgacure 907, and trade names: Irgacure AX Product name: Adeka optomer N1919, etc. manufactured by the company.

  Examples of the anionic polymerization initiator include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene, and pyrene; polyfunctional initiators such as dilithium salts and trilithium salts;

  Examples of the cationic polymerization initiator include proton acids such as sulfuric acid, phosphoric acid, perchloric acid and trifluoromethanesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride and tin tetrachloride; A combined system of a group onium salt or an aromatic onium salt and a reducing agent.

  These polymerization initiators can be used alone or in combination of two or more.

  In the polymerizable liquid crystal composition of the present invention, the blending ratio of the polymerization initiator is usually 0.1 to 30 parts by mass, preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the mixture containing the polymerizable compound described above. 10 parts by mass.

The polymerizable liquid crystal composition of the present invention preferably contains a surfactant in order to adjust the surface tension. The surfactant is not particularly limited, but a nonionic surfactant is usually preferable. A commercially available product may be used as the nonionic surfactant, and examples thereof include a nonionic surfactant which is an oligomer having a molecular weight of about several thousand, for example, trade name: “Factent 208G” manufactured by Neos.
Here, in the polymerizable liquid crystal composition of the present invention, the blending ratio of the surfactant is usually 0.01 to 10 parts by mass, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total polymerizable compound. It is.

Furthermore, the polymerizable liquid crystal composition of the present invention further contains other components as long as the effects of the present invention are not affected, in addition to a mixture containing a polymerizable compound, a polymerization initiator, and a surfactant. May be. Other components include metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, Examples thereof include metal oxides such as titanium oxide.
In addition, other components include other copolymerizable monomers. Specifically, it is not particularly limited. For example, 4- (2-methacryloyloxyethyloxy) benzoic acid-4′-methoxyphenyl, 4- (6-methacryloyloxyhexyloxy) benzoic acid biphenyl, 4- (2-acryloyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2-methacrylolyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2-methacrylolyloxyethyloxy) Benzoic acid-3 ′, 4′-difluorophenyl, 4- (2-methacryloyloxyethyloxy) benzoic acid naphthyl, 4-acryloyloxy-4′-decylbiphenyl, 4-acryloyloxy-4′-cyanobiphenyl, 4- (2-acryloyloxyethyloxy) -4′-cyanobiphenyl, 4- (2-methacrylic) Yloxyethyloxy) -4′-methoxybiphenyl, 4- (2-methacryloyloxyethyloxy) -4 ′-(4 ″ -fluorobenzyloxy) -biphenyl, 4-acryloyloxy-4′-propylcyclohexylphenyl, 4 -Methacryloyl-4'-butylbicyclohexyl, 4-acryloyl-4'-amyltran, 4-acryloyl-4 '-(3,4-difluorophenyl) bicyclohexyl, 4- (2-acryloyloxyethyl) benzoic acid (4 -Amylphenyl), 4- (2-acryloyloxyethyl) benzoic acid (4- (4′-propylcyclohexyl) phenyl), trade name “LC-242” (manufactured by BASF), and JP-A-2007-002208 Gazette, JP2009-173893, JP2009-27498 Copolymerizable monomers such as the compounds disclosed in JP-A No. 2010-0309779, JP-A 2010-031223, JP-A 2011-006360 and JP-A 2010-24438. Can be mentioned.
The blending ratio of these other components is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the total polymerizable compound.

The polymerizable liquid crystal composition of the present invention is usually prepared by mixing and dissolving a predetermined amount of a mixture containing a polymerizable compound, a polymerization initiator, and other components blended as required in a suitable organic solvent. Can be prepared.
In this case, the polymerizable compound (III) and the polymerizable compound (IV) as a mixture may be added in a premixed state or may be added separately.

  Organic solvents to be used include ketones such as cyclopentanone, cyclohexanone and methyl ethyl ketone; acetate esters such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; 1,4-dioxane and cyclopentylmethyl And ethers such as ether, tetrahydrofuran, tetrahydropyran and 1,3-dioxolane;

(6) Polymer The polymer of the present invention polymerizes a mixture containing the above-described polymerizable compound (a mixture containing the polymerizable compound (III) and the polymerizable compound (IV)) or the above-described polymerizable liquid crystal composition. Is obtained.
Here, “polymerization” means a chemical reaction in a broad sense including a crosslinking reaction in addition to a normal polymerization reaction.
The polymer of the present invention usually comprises the following monomer units derived from the polymerizable compound (III) (repeating unit (III) ′) and the following monomers derived from the polymerizable compound (IV). Unit (repeating unit (IV) ′).
[Ar ¹ , D ¹ , Z ¹¹ , Z ¹² , A ¹¹ , A ¹² , B ¹¹ , B ¹² , Y ¹¹ , Y ¹² , L ¹¹ , L ¹² , R ^{4 to} R ⁷ in Formula (III) ′ f, g, h, i, j and k have the same meaning as in formula (III), and Ar ² , D ² , Z ²¹ , Z ²² , A ²¹ , A ²² , B ^{21 in} formula (IV) ′. , B ²² , Y ²¹ , Y ²² , L ²¹ , L ²² , R ⁸ , R ⁹ , m, n, p and q have the same meaning as in formula (IV). ]

  In addition, since the polymer of this invention is prepared using the mixture containing polymeric compound (III) and polymeric compound (IV), it can be used suitably as structural materials, such as an optical film.

In addition, the polymer of the present invention is not particularly limited, and can be used in any shape depending on the application such as a film shape, a powder shape, or a layer shape in which powders are aggregated.
Specifically, the polymer film can be used favorably as a constituent material of the optical film and optical anisotropic body described later, and the polymer powder can be used for paints, anti-counterfeit articles, security articles, etc. The layer made of polymer powder can be used favorably as a constituent material of the optical anisotropic body.

  Specifically, the polymer of the present invention specifically comprises (α) a mixture containing a polymerizable compound or a polymerizable liquid crystal composition in a suitable organic solvent, and then a target high molecular weight. By isolating the molecules, dissolving the resulting polymer in an appropriate organic solvent to prepare a solution, coating the solution on an appropriate substrate, drying the resulting coating, and optionally heating (Β) A mixture containing a polymerizable compound or a polymerizable liquid crystal composition is dissolved in an organic solvent, and this solution is applied onto a substrate by a known coating method, and then the solvent is removed, followed by heating or It can be suitably produced by a method of performing a polymerization reaction by irradiating active energy rays.

The organic solvent used for the polymerization reaction in the method (α) is not particularly limited as long as it is inactive. For example, aromatic hydrocarbons such as toluene, xylene and mesitylene; ketones such as cyclohexanone, cyclopentanone and methyl ethyl ketone; acetate esters such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; And ethers such as cyclopentyl methyl ether, tetrahydrofuran and tetrahydropyran;
Among these, from the viewpoint of excellent handleability, those having a boiling point of 60 to 250 ° C are preferable, and those having a boiling point of 60 to 150 ° C are more preferable.

  In the method (α), an organic solvent for dissolving the isolated polymer and an organic solvent used in the method (β) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, Ketone solvents such as cyclohexanone; ester solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as dichloromethane, chloroform and dichloroethane; tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, Ether solvents such as cyclopentyl methyl ether and 1,3-dioxolane; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and N-methylpyrrolidone; Can be mentioned. Among these, a solvent having a boiling point of 60 to 200 ° C. is preferable from the viewpoint of easy handling. These solvents may be used alone or in combination of two or more.

As the substrate used in the methods (α) and (β), a known and commonly used material can be used regardless of organic or inorganic. For example, examples of the organic material include polycycloolefins (for example, ZEONEX, ZEONOR (registered trademark; manufactured by ZEON CORPORATION), ARTON (registered trademark; manufactured by JSR), and APPEL (registered trademark; manufactured by Mitsui Chemicals)), Examples include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose, cellulose triacetate, polyethersulfone, etc., and inorganic materials include silicon, glass, calcite, etc. Is mentioned.
The substrate used may be a single layer or a laminate.
As the substrate, a substrate made of an organic material is preferable, and a resin film obtained by forming an organic material into a film is more preferable.
In addition, as a board | substrate, the board | substrate etc. which are used for preparation of the optical anisotropic body mentioned later are mentioned.

  In addition, a known method can be used as a method of applying the polymer solution to the substrate in the method (α) and a method of applying the polymerization reaction solution to the substrate in the method (β). Specifically, for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, gravure coating method, die coating method A cap coating method or the like can be used.

  Furthermore, as a method of drying or solvent removal in the methods (α) and (β), natural drying, heat drying, reduced pressure drying, reduced pressure heat drying and the like can be used.

  Examples of a method for polymerizing the mixture and the polymerizable liquid crystal composition include a method of irradiating active energy rays and a thermal polymerization method. However, since the reaction proceeds at room temperature without requiring heating, active energy rays are used. The method of irradiating is preferable. Among these, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.

Here, the temperature at the time of light irradiation is preferably 30 ° C. or less. The light irradiation intensity is usually in the range of 1 W / m ^{2 to} 10 kW / m ² , preferably in the range of 5 W / m ^{2 to 2} kW / m ² .

The polymer obtained as described above can be used by being transferred from the substrate, peeled off from the substrate and used alone or as a constituent material of an optical film without being peeled off from the substrate. You can also
The polymer peeled from the substrate can be used after being pulverized by a known method to form a powder.

  The number average molecular weight of the polymer of the present invention obtained as described above is preferably 500 to 500,000, more preferably 5,000 to 300,000. If the number average molecular weight is in such a range, it is desirable because high hardness can be obtained and handleability is excellent. The number average molecular weight of the polymer can be measured by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard sample and tetrahydrofuran as an eluent.

  According to the polymer of the present invention, the liquid crystal phase can be maintained more stably for a long time, has a wide process margin, has a practically low melting point, has excellent solubility in general-purpose solvents, and has a wide wavelength range. It is possible to obtain an optical film or the like that can perform uniform polarization conversion in the region and is satisfactory in terms of performance at a low cost.

(7) Optical film The optical film of this invention is formed using the polymer of this invention, and contains the layer which has an optical function. The optical function means simple transmission, reflection, refraction, birefringence and the like.

Here, the optical film of the present invention is in the form (alignment substrate / (alignment film) / optical film) formed on the alignment substrate which may have an alignment film, and a transparent substrate film different from the alignment substrate. The optical film may be transferred in any form (transparent substrate film / optical film), or in the case where the optical film is self-supporting, it may be in any form of an optical film single layer (optical film).
As the alignment film and the alignment substrate, the same substrate and alignment film as those of the optical anisotropic body described later can be used.

  And the optical film of this invention apply | coats the solution of the mixture containing a (A) polymeric compound, or the solution of a polymeric liquid crystal composition on an orientation board | substrate, the obtained coating film is dried, and heat processing (liquid crystal) Orientation), a method of performing light irradiation and / or heat treatment (polymerization), and (B) a liquid crystal polymer solution obtained by polymerizing a mixture or a liquid crystal composition containing a polymerizable compound. It can manufacture by the method of apply | coating on and drying the coating film obtained arbitrarily.

  The optical film of the present invention can be used for optical anisotropic bodies, alignment films for liquid crystal display elements, color filters, low-pass filters, light polarizing prisms, various optical filters, and the like.

In addition, it is preferable that the following alpha value and beta value calculated | required from the phase difference in the wavelength 449.9nm, 548.5nm, and 650.2nm which were measured for the optical film of this invention by the ellipsometer are in a predetermined range. Specifically, the α value is preferably 0.70 to 0.99, and more preferably 0.75 to 0.90. Further, the β value is preferably 1.00 to 1.25, more preferably 1.01 to 1.20.
α = (phase difference at 449.9 nm) / (phase difference at 548.5 nm)
β = (phase difference at 650.2 nm) / (phase difference at 548.5 nm)

(8) Optical anisotropic body The optical anisotropic body of this invention has a layer which uses the polymer of this invention as a constituent material.
The optical anisotropic body of the present invention can be obtained, for example, by forming an alignment film on a substrate and further forming a layer (liquid crystal layer) made of the polymer of the present invention on the alignment film. . The optically anisotropic body of the present invention may be one in which a layer made of the polymer of the present invention (liquid crystal layer) is directly formed on a substrate, or a layer made of the polymer of the present invention (liquid crystal layer). It may consist of only.
The polymer layer may be a film polymer or a powder polymer aggregate.

Here, the alignment film is formed on the surface of the substrate in order to regulate the alignment of the polymerizable liquid crystal compound in one direction in the plane.
The alignment film is formed by applying a solution (composition for alignment film) containing a polymer such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamideimide, or polyetherimide onto the substrate in a film shape, drying, and unidirectional It can be obtained by rubbing.
The thickness of the alignment film is preferably 0.001 to 5 μm, and more preferably 0.001 to 1 μm.

The rubbing treatment method is not particularly limited, and examples thereof include a method of rubbing the alignment film in a certain direction with a roll made of a synthetic fiber such as nylon or a natural fiber such as cotton or a felt. In order to remove the fine powder (foreign matter) generated during the rubbing treatment and clean the surface of the alignment film, it is preferable to clean the alignment film with isopropyl alcohol or the like after the rubbing treatment.
In addition to the method of rubbing, a function of regulating the alignment in one direction within the plane can also be provided by a method of irradiating the surface of the alignment film with polarized ultraviolet rays.

  Examples of the substrate on which the alignment film is formed include a glass substrate and a substrate made of a synthetic resin film. Examples of the synthetic resin include acrylic resin, polycarbonate resin, polyethersulfone resin, polyethylene terephthalate resin, polyimide resin, polymethyl methacrylate resin, polysulfone resin, polyarylate resin, polyethylene resin, polystyrene resin, polyvinyl chloride resin, and cellulose diacetate. , Cellulose triacetate, and thermoplastic resins such as alicyclic olefin polymers.

  Examples of alicyclic olefin polymers include cyclic olefin random multi-component copolymers described in JP-A No. 05-310845, US Pat. No. 5,179,171, JP-A No. 05-97978, and US Pat. No. 5,202,388. And hydrogenated polymers described in Japanese Patent Application Laid-Open No. 11-124429 (International Publication No. 99/20676), and thermoplastic dicyclopentadiene ring-opening polymers and hydrogenated products thereof. .

In the present invention, as a method for forming the liquid crystal layer comprising the polymer of the present invention on the alignment film, the same method as described in the section of the polymer of the present invention (the above (α) and (β)) can be used. Can be mentioned.
The thickness of the obtained liquid crystal layer is not particularly limited, but is usually 1 to 10 μm.

  In addition, as a kind of optical anisotropic body of this invention, a phase difference plate, a viewing angle expansion plate, etc. are mentioned, without being specifically limited.

In the optical anisotropic body of the present invention, the following α value and β value obtained from the phase differences at wavelengths of 449.9 nm, 548.5 nm, and 650.2 nm measured with an ellipsometer may be within a predetermined range. preferable. Specifically, the α value is preferably 0.70 to 0.99, and more preferably 0.75 to 0.90. Further, the β value is preferably 1.00 to 1.25, more preferably 1.01 to 1.20.
α = (phase difference at 449.9 nm) / (phase difference at 548.5 nm)
β = (phase difference at 650.2 nm) / (phase difference at 548.5 nm)

(9) Polarizing plate, etc. The polarizing plate of the present invention comprises the optical anisotropic body of the present invention and a polarizing film.
Specific examples of the polarizing plate of the present invention include those obtained by laminating the optical anisotropic body of the present invention on a polarizing film directly or via another layer (glass plate or the like).

  The manufacturing method of a polarizing film is not specifically limited. As a method for producing a PVA-based polarizing film, a method of stretching uniaxially after iodine ions are adsorbed on a PVA-based film, a method of adsorbing iodine ions after stretching a uniaxially stretched PVA-based film, A method of simultaneously performing iodine ion adsorption and uniaxial stretching, a method of stretching a uniaxial film after dyeing a PVA film with a dichroic dye, a method of dyeing a dichroic dye after stretching a PVA film uniaxially, a PVA system The method of performing simultaneously dyeing | staining with a dichroic dye and uniaxial stretching to a film is mentioned. In addition, as a method for producing a polyene polarizing film, a method of heating and dehydrating in the presence of a dehydration catalyst after stretching a PVA film uniaxially, a method of stretching a polyvinyl chloride film uniaxially and then in the presence of a dehydrochlorination catalyst And a known method such as heating and dehydrating.

  In the polarizing plate of the present invention, the polarizing film and the optical anisotropic body of the present invention may be in contact with each other through an adhesive layer made of an adhesive (including an adhesive). The average thickness of the adhesive layer is usually 0.01 μm to 30 μm, preferably 0.1 μm to 15 μm. The adhesive layer is preferably a layer having a tensile fracture strength according to JIS K7113 of 40 MPa or less.

  Adhesives constituting the adhesive layer include acrylic adhesives, urethane adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, polyvinyl alkyl ether adhesives, rubber adhesives, vinyl chloride Vinyl acetate adhesive, styrene / butadiene / styrene copolymer (SBS copolymer) adhesive, hydrogenated product (SEBS copolymer) adhesive, ethylene / vinyl acetate copolymer, ethylene-styrene copolymer, etc. Ethylene adhesives, and acrylic ester adhesives such as ethylene / methyl methacrylate copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl methacrylate copolymers and ethylene / ethyl acrylate copolymers, etc. Is mentioned.

  Since the polarizing plate of the present invention uses the optical anisotropic body of the present invention, it can be manufactured at low cost, has low reflection luminance, and can perform uniform polarization conversion in a wide wavelength range. But it is excellent.

  Moreover, by using the polarizing plate of this invention, the flat panel display apparatus using a liquid crystal panel, the organic electroluminescent display apparatus using an organic electroluminescent panel, and an antireflection film can be manufactured suitably.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

Synthesis Example 1 Synthesis of Compound 1

Step 1: Synthesis of Intermediate A

In a nitrogen stream, 17.98 g (104.42 mmol) of trans-1,4-cyclohexanedicarboxylic acid and 180 ml of tetrahydrofuran (THF) were added to a three-necked reactor equipped with a thermometer. To this, 6.58 g (57.43 mmol) of methanesulfonyl chloride was added, and the reactor was immersed in a water bath to adjust the internal temperature of the reaction solution to 20 ° C. Next, 6.34 g (62.65 mmol) of triethylamine was added dropwise over 10 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C. After completion of the dropwise addition, the whole volume was further stirred at 25 ° C. for 2 hours.
To the resulting reaction solution, 0.64 g (5.22 mmol) of 4- (dimethylamino) pyridine and 13.80 g of 4- (6-acryloyloxy-hex-1-yloxy) phenol (manufactured by DKSH) (52 .21 mmol) was added, and the reactor was immersed again in a water bath to adjust the internal temperature of the reaction solution to 15 ° C. Thereto, 6.34 g (62.65 mmol) of triethylamine was added dropwise over 10 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C. After completion of the dropwise addition, the whole volume was further stirred at 25 ° C. for 2 hours. After completion of the reaction, 1000 ml of distilled water and 100 ml of saturated brine were added to the reaction solution, and extracted twice with 400 ml of ethyl acetate. The organic layer was collected, dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After evaporating and removing the solvent from the filtrate using a rotary evaporator, the obtained residue was purified by silica gel column chromatography (THF: toluene = 1: 9 (volume ratio, the same applies hereinafter)). Analysis was performed by high performance liquid chromatography, and purification by silica gel column chromatography was repeated until the purity reached 99.5% or higher. As a result, 14.11 g of intermediate A was obtained as a white solid (yield: 65 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 12.12 (s, 1 H), 6.99 (d, 2 H, J = 9.0 Hz), 6.92 (d, 2 H, J = 9.0 Hz), 6.32 (dd, 1 H, J = 1.5 Hz, 17.5 Hz), 6.17 (dd, 1 H, J = 10.0 Hz, 17.5 Hz), 5.93 (dd, 1H, J = 1.5 Hz, 10.0 Hz), 4.11 (t, 2H, J = 6.5 Hz), 3.94 (t, 2H, J = 6.5 Hz), 2.48-2.56 (M, 1H), 2.18-2.26 (m, 1H), 2.04-2.10 (m, 2H), 1.93-2.00 (m, 2H), 1.59-1 .75 (m, 4H), 1.35 to 1.52 (m, 8H)

Step 2: Synthesis of Intermediate B

In a three-necked reactor equipped with a thermometer, 4.00 g (9.56 mmol) of the intermediate A synthesized in Step 1 and 60 ml of THF were placed in a nitrogen stream to obtain a uniform solution. Thereto, 1.12 g (9.78 mmol) of methanesulfonyl chloride was added, and the reactor was immersed in a water bath to adjust the internal temperature of the reaction solution to 20 ° C. Subsequently, 1.01 g (9.99 mmol) of triethylamine was added dropwise over 5 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C., and the whole volume was further stirred at 25 ° C. for 2 hours. To the obtained reaction solution, 0.11 g (0.87 mmol) of 4- (dimethylamino) pyridine and 0.60 g (4.35 mmol) of 2,5-dihydroxybenzaldehyde were added, and the reactor was immersed again in a water bath. The internal temperature of the reaction solution was 15 ° C. Thereto, 1.10 g (10.87 mmol) of triethylamine was added dropwise over 5 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C., and the whole volume was further stirred at 25 ° C. for 2 hours. After completion of the reaction, 400 ml of distilled water and 50 ml of saturated brine were added to the reaction solution, and extracted twice with 750 ml of ethyl acetate. The organic layer was collected, dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After the solvent was removed from the filtrate by a rotary evaporator, the obtained residue was dissolved in 100 ml of THF. 500 ml of methanol was added to the solution to precipitate crystals, and the precipitated crystals were collected by filtration. The obtained crystal was washed with methanol and then vacuum-dried to obtain 2.51 g of intermediate B as a white solid (yield: 62 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 10.02 (s, 1 H), 7.67 (d, 1 H, J = 3.0 Hz), 7.55 (dd, 1 H, J = 3.0 Hz, 8.5 Hz), 7.38 (d, 1H, J = 8.5 Hz), 6.99-7.04 (m, 4H), 6.91-6.96 (m, 4H) 6.32 (dd, 2H, J = 1.5 Hz, 17.5 Hz), 6.17 (dd, 2H, J = 10.0 Hz, 17.5 Hz), 5.93 (dd, 2H, J = 1) .5 Hz, 10.0 Hz), 4.11 (t, 4H, J = 6.5 Hz), 3.95 (t, 4H, J = 6.5 Hz), 2.56-2.81 (m, 4H) 2.10-2.26 (m, 8H), 1.50-1.76 (m, 16H), 1.33-1.49 (m, 8H)

Step 3: Synthesis of Compound 1 In a three-necked reactor equipped with a thermometer, 2.30 g (2.45 mmol) of the intermediate B synthesized in Step 2 above and 25 ml of THF were placed in a nitrogen stream to obtain a uniform solution. To the solution, 0.49 ml (0.25 mmol) of concentrated hydrochloric acid was added. To this solution, a solution of 0.40 g (2.45 mmol) of 2-hydrazinobenzothiazole in 5 ml of THF was added dropwise over 15 minutes. After completion of the addition, the whole volume was further stirred at 25 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into 400 ml of methanol, and the precipitated solid was collected by filtration. The solid collected by filtration was dried with a vacuum dryer to obtain 2.4 g of Compound 1 as a pale yellow solid (yield: 90 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 12.63 (s, 1H), 8.10 (s, 1H), 7.80 (d, 1H, J = 5.0 Hz), 7.60 (d, 1H, J = 3.0 Hz), 7.48 (s, 1H), 7.21-7.35 (m, 3H), 7.14 (t, 1H, J = 7.5 Hz) ), 6.98-7.05 (m, 4H), 6.91-6.97 (m, 4H), 6.32 (dd, 2H, J = 1.5 Hz, 17.5 Hz), 6.18. (Dd, 2H, J = 10.0 Hz, 17.5 Hz), 5.93 (dd, 2H, J = 1.5 Hz, 10.0 Hz), 4.12 (t, 4H, J = 6.5 Hz), 3.95 (t, 4H, J = 6.5 Hz), 2.56-2.83 (m, 4H), 2.11-2.30 (m, 8H), 1.52-1.80 m, 16H), 1.33-1.49 (m, 8H)

Synthesis Example 2 Synthesis of Compound 2

Step 1: Synthesis of Intermediate C

In a four-necked reactor equipped with a thermometer, 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole was placed in a nitrogen stream and dissolved in 20 ml of N, N-dimethylformamide (DMF). To this solution, 8.36 g (60.5 mmol) of potassium carbonate and 3.08 g (14.5 mmol) of 1-iodohexane were added and stirred at 50 ° C. for 7 hours. After completion of the reaction, the reaction solution was cooled to 20 ° C., poured into 200 mL of water, and extracted with 300 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (hexane: ethyl acetate = 75: 25) to obtain 2.10 g of Intermediate C as a white solid (yield: 69.6 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.60 (dd, 1 H, J = 1.0 Hz, 8.0 Hz), 7.53 (dd, 1 H, J = 1.0 Hz, 8. 0 Hz), 7.27 (ddd, 1 H, J = 1.0 Hz, 8.0 Hz, 8.0 Hz), 7.06 (ddd, 1 H, J = 1.0 Hz, 8.0 Hz, 8.0 Hz), 4 .22 (s, 2H), 3.74 (t, 2H, J = 7.5 Hz), 1.69-1.76 (m, 2H), 1.29-1.42 (m, 6H), 0 .89 (t, 3H, J = 7.0Hz)

Step 2: Synthesis of Compound 2 In a four-necked reactor equipped with a thermometer, 697 mg (2.37 mmol) of the intermediate C synthesized in Step 1 and an intermediate synthesized in Step 2 of Synthesis Example 1 in a nitrogen stream Body B (2.00 g, 2.13 mmol) was added and dissolved in a mixed solvent of 3 ml of ethanol and 20 ml of THF. To this solution, 55.1 mg (0.237 mmol) of (±) -10-camphorsulfonic acid was added and stirred at 40 ° C. for 5 hours. After completion of the reaction, the reaction solution was poured into 150 ml of water and extracted with 300 ml of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a white solid. This white solid was purified by silica gel column chromatography (toluene: ethyl acetate = 90: 10) to obtain 2.24 g of compound 2 as a white solid (yield: 86.4 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 7.75 (d, 1H, J = 2.5 Hz), 7.67-7.70 (m, 3H), 7.34 (ddd, 1H , J = 1.0 Hz, 7.0 Hz, 7.5 Hz), 7.17 (ddd, 1 H, J = 1.0 Hz, 7.5 Hz, 7.5 Hz), 7.12 (d, 1 H, J = 9) 0.0 Hz), 7.10 (dd, 1H, J = 2.5 Hz, 9.0 Hz), 6.99 (d, 2H, J = 9.0 Hz), 6.98 (d, 2H, J = 9. 0 Hz), 6.88 (d, 4H, J = 9.0 Hz), 6.40 (dd, 2H, J = 1.5 Hz, 17.0 Hz), 6.13 (dd, 2H, J = 10.5 Hz) 17.5 Hz), 5.82 (dd, 2H, J = 1.5 Hz, 10.5 Hz), 4.30 (t, 2H, J = 8.0 Hz) 4.18 (t, 4H, J = 6.5 Hz), 3.95 (t, 4H, J = 6.5 Hz), 2.58-2.70 (m, 4H), 2.31-2. 35 (m, 8H), 1.66-1.82 (m, 18H), 1.31-1.54 (m, 14H), 0.90 (t, 3H, J = 7.0 Hz)

(Synthesis Example 3) Synthesis of Compound 3

Step 1: Synthesis of Intermediate D

In a three-necked reactor equipped with a thermometer, in a nitrogen stream, 3.00 g (17.69 mmol) of 2-chlorobenzothiazole and 7.65 g (70.74 mmol) of phenylhydrazine were dissolved in 30 ml of ethylene glycol. . This solution was heated to 140 ° C. and reacted for 5 hours. Thereafter, 300 ml of distilled water was added to the reaction solution, and extracted twice with 100 ml of ethyl acetate. The organic layer was dried over sodium sulfate, concentrated with a rotary evaporator, dissolved by adding 15 ml of THF, and the solution was put into 300 ml of distilled water. The precipitated solid was filtered, washed with distilled water, and then vacuum dried to obtain a yellow solid. The obtained yellow solid was put in a flask, 50 ml of toluene was added and stirred for 30 minutes, and then the solid component insoluble in toluene was removed by filtration. The filtrate was concentrated with a rotary evaporator and purified by silica gel column chromatography (THF: toluene = 2: 50) to obtain 0.94 g of Intermediate D as a yellow oil (yield: 22 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 8.01 (dd, 2H, J = 1.0 Hz, 9.0 Hz), 7.78 (dd, 1H, J = 1.0 Hz, 8.0 Hz), 7.51 (dd, 1 H, J = 1.0 Hz, 8.0 Hz), 7.43 (dd, 2 H, J = 7.5 Hz, 8.5 Hz), 7.28 (dt, 1 H) , J = 1.0 Hz, 7.5 Hz), 7.08-7.16 (m, 2H), 6.26 (s, 2H)

Step 2: Synthesis of Compound 3 In a three-necked reactor equipped with a thermometer, 1.00 g (1.06 mmol) of the intermediate B synthesized in Step 2 of synthesis of Compound 1 of Synthesis Example 1 was placed in a nitrogen stream. Dissolved in 30 ml of THF. To this solution, 0.22 ml (0.22 mmol) of 1N hydrochloric acid and 0.38 g (1.60 mmol) of the intermediate D synthesized in Step 1 were added and reacted at 40 ° C. for 2 hours. Thereafter, the reaction solution was concentrated with a rotary evaporator and purified by silica gel column chromatography (chloroform: THF = 40: 1) to obtain 1.14 g of Compound 3 as a pale yellow solid (yield: 95 mol%). ).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.82 (d, 1 H, J = 2.5 Hz), 7.73 (dd, 1 H, J = 1.0 Hz, 8.0 Hz), 7 .64-7.70 (m, 2H), 7.60 (d, 2H, J = 7.5 Hz), 7.35-7.42 (m, 3H), 7.30 (dt, 1H, J = 1.0 Hz, 7.5 Hz), 7.18 (dt, 1H, J = 1.0 Hz, 7.5 Hz), 7.03-7.12 (m, 2H), 7.00 (d, 2H, J = 9.0 Hz), 6.99 (d, 2H, J = 9.0 Hz), 6.90 (d, 2H, J = 9.0 Hz), 6.89 (d, 2H, J = 9.0 Hz) 6.41 (dd, 1H, J = 1.5 Hz, 17.5 Hz), 6.41 (dd, 1H, J = 1.5 Hz, 17.5 Hz), 6.13 (dd, H, J = 10.5 Hz, 17.5 Hz), 6.13 (dd, 1 H, J = 10.5 Hz, 17.5 Hz), 5.82 (dd, 1 H, J = 1.5 Hz, 10.5 Hz) 5.82 (dd, 1H, J = 1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J = 6.5 Hz), 4.18 (t, 2H, J = 6.5 Hz), 3.92-3.98 (m, 4H), 2.56-2.71 (m, 2H), 2.41-2.50 (m, 1H), 2.27-2.40 (m, 5H) ), 2.12-2.22 (m, 2H), 1.64-1.91 (m, 14H), 1.41-1.56 (m, 10H), 1.19-1.31 (m) , 2H)

(Synthesis Example 4) Synthesis of Compound 4

Step 1: Synthesis of Intermediate E

In a four-necked reactor equipped with a thermometer, 2.50 g (16.6 mmol) of cyclohexylhydrazine hydrochloride was placed in a nitrogen stream and dissolved in 8 ml of triethylamine. To this solution was added 5.63 g (33.2 mmol) of 2-chlorobenzothiazole, and the mixture was stirred at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to 20 ° C., and the reaction solution was poured into 150 ml of saturated aqueous sodium hydrogen carbonate solution and extracted with 300 ml of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (hexane: ethyl acetate = 75: 25) to obtain 1.02 g of intermediate E as a white solid (yield: 22.3 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 7.58 (d, 1H, J = 7.8 Hz), 7.52 (d, 1H, J = 8.2 Hz), 7.26 (dd , 1H, J = 7.4 Hz, 8.2 Hz), 7.05 (dd, 1H, J = 7.4 Hz, 7.8 Hz), 4.25-4.32 (m, 1H), 4.04 ( s, 2H), 1.84-1.88 (m, 4H), 1.68-1.73 (m, 1H), 1.43-1.59 (m, 4H), 1.08-1. 19 (m, 1H)

Step 2: Synthesis of Compound 4 In a three-necked reactor equipped with a thermometer, 1.40 g (1.49 mmol) of the intermediate B synthesized in Step 2 of Synthesis of Compound 1 of Synthesis Example 1 in a nitrogen stream, the above step Intermediate E456 synthesized in 1 (456 mg, 1.84 mmol), (±) -10-camphorsulfonic acid 38.6 mg (0.166 mmol), THF 16 ml, and ethanol 4 ml were added to obtain a uniform solution. Then, it was made to react at 40 degreeC for 5 hours. After completion of the reaction, the reaction solution was poured into 100 ml of water and extracted with 200 ml of ethyl acetate. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. Using a rotary evaporator, ethyl acetate was distilled off from the filtrate under reduced pressure to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (chloroform: THF = 97: 3) to obtain 1.24 g of compound 4 as a pale yellow solid (yield: 71.4 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 8.15 (s, 1H), 7.72 (d, 1H, J = 1.5 Hz), 7.68 (dd, 1H, J = 1) .5Hz, 8.0Hz), 7.66 (dd, 1H, J = 1.5Hz, 8.0Hz), 7.31-7.35 (m, 1H), 7.14-7.18 (m, 1H), 7.13 (d, 1H, J = 9.0 Hz), 7.10 (dd, 1H, J = 1.5 Hz, 9.0 Hz), 6.96-7.00 (m, 4H), 6.86-6.90 (m, 4H), 6.40 (dd, 2H, J = 1.5 Hz, 17.0 Hz), 6.13 (dd, 2H, J = 10.0 Hz, 17.0 Hz) 5.82 (dd, 2H, J = 1.5 Hz, 10.0 Hz), 4.62-4.70 (m, 1H), 4.17 (t, 4H, J = 6) 5 Hz), 3.94 (t, 4H, J = 6.5 Hz), 2.55-2.74 (m, 4H), 2.27-2.47 (m, 10H), 1.90-2. 00 (m, 4H), 1.65-1.85 (m, 16H), 1.42-1.55 (m, 10H), 1.24-1.33 (m, 2H)

Synthesis Example 5 Synthesis of Compound 5

Step 1: Synthesis of intermediate F

To a three-necked reactor equipped with a thermometer, 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole was placed in a nitrogen stream and dissolved in 30 ml of DMF. 7.88 g (24.2 mol) of cesium carbonate was added to this solution and cooled to 0 ° C., 1.98 g (14.5 mmol) of butyl 2-chloroethyl ether was added dropwise over 5 minutes, and then the reaction solution was cooled to room temperature ( The mixture was returned to 23 ° C. and the same below and stirred for 3 hours. After completion of the reaction, 200 ml of water was added to the reaction solution and extracted twice with 100 ml of ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration with a rotary evaporator, purification by silica gel column chromatography (n-hexane: ethyl acetate = 75: 25) gave 1.70 g of intermediate F as a white solid (yield 53.0 mol%). .
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.61 (dd, 1 H, J = 1.0 Hz, 8.0 Hz), 7.50 (dd, 1 H, J = 1.0 Hz, 8. 0 Hz), 7.27-7.29 (m, 1H), 7.04-7.08 (m, 1H), 4.70 (s, 2H), 4.01 (t, 2H, J = 5. 0 Hz), 3.82 (t, 2H, J = 5.0 Hz), 3.44 (t, 2H, J = 7.0 Hz), 1.52-1.57 (m, 2H), 1.31- 1.39 (m, 2H), 0.90 (t, 3H, J = 7.0 Hz)

Step 2: Synthesis of Compound 5 In a three-necked reactor equipped with a thermometer, 1.50 g (1.60 mmol) of the intermediate B synthesized in Step 2 of Synthesis Example 1 in the nitrogen stream, Form F 396 mg (1.78 mmol), (±) -10-camphorsulfonic acid 41.4 mg (0.178 mmol), THF 16 ml, and ethanol 4 ml were added to obtain a homogeneous solution. Then, it was made to react at 40 degreeC for 5 hours. After completion of the reaction, the reaction solution was poured into 100 ml of water and extracted with 200 ml of ethyl acetate. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. Using a rotary evaporator, ethyl acetate was distilled off from the filtrate under reduced pressure to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (toluene: ethyl acetate = 9: 1) to obtain 1.31 g of compound 5 as a pale yellow solid (yield: 69.4 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 8.03 (s, 1H), 7.76 (d, 1H, J = 1.5 Hz), 7.65-7.71 (m, 2H) ), 7.34 (ddd, 1H, J = 1.5 Hz, 8.0 Hz, 8.0 Hz), 7.17 (ddd, 1H, J = 1.5 Hz, 8.0 Hz, 8.0 Hz), 7. 09-7.12 (m, 2H), 6.96-7.00 (m, 4H), 6.87-6.90 (m, 4H), 6.40 (dd, 2H, J = 1.5 Hz) , 17.5 Hz), 6.13 (dd, 2H, J = 10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J = 1.5 Hz, 10.5 Hz), 4.45 (t, 2H, J = 5.5 Hz), 4.18 (t, 4H, J = 7.0 Hz), 3.95 (t, 4H, J = 7.0 Hz), 3.7 (T, 2H, J = 5.5 Hz), 3.44 (t, 2H, J = 7.0 Hz), 2.55-2.74 (m, 4H), 2.28-2.40 (m, 8H), 1.65-1.83 (m, 16H), 1.42-1.55 (m, 10H), 1.25-1.34 (m, 2H), 0.85 (t, 3H, J = 7.0Hz)

Synthesis Example 6 Synthesis of Compound 6

Step 1: Synthesis of Intermediate G

In a four-necked reactor equipped with a thermometer, 5.04 g (30.5 mmol) of 2-hydrazinobenzothiazole was placed in a nitrogen stream and dissolved in 50 ml of DMF. To this solution were added 14.9 g (45.8 mmol) of cesium carbonate and 4.94 g (36.6 mmol) of 4-bromo-1-butene, and the mixture was stirred at room temperature for 7 hours. After completion of the reaction, the reaction solution was poured into 200 mL of water and extracted with 300 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (n-hexane: ethyl acetate = 70: 30) to obtain 4.40 g of Intermediate G as a white solid (yield: 49.5 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.60 (dd, 1 H, J = 1.0 Hz, 8.0 Hz), 7.54 (dd, 1 H, J = 1.0 Hz, 8. 0 Hz), 7.28 (ddd, 1H, J = 1.0 Hz, 7.5 Hz, 8.0 Hz), 7.06 (ddd, 1H, J = 1.0 Hz, 7.5 Hz, 8.0 Hz), 5 .89 (ddt, 1H, J = 7.0 Hz, 10.5 Hz, 17.0 Hz), 5.17 (ddt, 1H, J = 1.5 Hz, 3.0 Hz, 17.0 Hz), 5.09 (ddt , 1H, J = 1.0 Hz, 3.0 Hz, 10.5 Hz), 4.26 (s, 2H), 3.85 (t, 2H, J = 7.0 Hz), 2.52 (dddt, 2H, J = 1.0Hz, 1.5Hz, 7.0Hz, 7.0Hz)

Step 2: Synthesis of Compound 6 In a four-necked reactor equipped with a thermometer, 195 mg (1.77 mmol) of the intermediate G synthesized in Step 1 and a compound 1 of Synthesis Example 1 were synthesized in a nitrogen stream. Intermediate B synthesized in 2: 1.50 g (1.60 mmol) was added and dissolved in a mixed solvent of 3 ml of ethanol and 15 ml of THF. To this solution, 41.2 mg (0.177 mmol) of (±) -10-camphorsulfonic acid was added and stirred at 40 ° C. for 8 hours. After completion of the reaction, the reaction solution was poured into 150 ml of water and extracted with 300 ml of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (toluene: ethyl acetate = 90: 10) to obtain 1.26 g of compound 6 as a white solid (yield: 69.3 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.76 (d, 1H, J = 2.5 Hz), 7.67-7.70 (m, 3H), 7.35 (ddd, 1H , J = 1.5 Hz, 7.5 Hz, 8.0 Hz), 7.18 (ddd, 1H, J = 1.5 Hz, 7.5 Hz, 8.0 Hz), 7.10-7.14 (m, 2H) ), 6.99 (d, 2H, J = 9.5 Hz), 6.98 (d, 2H, J = 9.5 Hz), 6.88 (d, 4H, J = 9.5 Hz), 6.40. (Dd, 2H, J = 1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J = 10.5 Hz, 17.5 Hz), 5.89 (ddt, 1H, J = 6.5 Hz, 10 .5 Hz, 17.0 Hz), 5.82 (dd, 2H, J = 1.5 Hz, 10.5 Hz), 5.18 (dd, 1H, = 1.5 Hz, 17.0 Hz), 5.15 (dd, 1H, J = 1.5 Hz, 10.5 Hz), 4.38 (t, 2H, J = 7.0 Hz), 4.18 (t, 4H, J = 6.5 Hz), 3.95 (t, 4H, J = 6.5 Hz), 2.58-2.68 (m, 4H), 2.51 (dt, 2H, J = 6.5 Hz) 7.0 Hz), 2.31-2.35 (m, 8H), 1.76-1.85 (m, 4H), 1.65-1.74 (m, 12H), 1.41-1 .54 (m, 8H)

(Synthesis Example 7) Synthesis of Compound 7

Step 1: Synthesis of intermediate H

To a three-necked reactor equipped with a thermometer, 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole was placed in a nitrogen stream and dissolved in 30 ml of DMF. 7.88 g (24.2 mol) of cesium carbonate was added to this solution and cooled to 0 ° C., 2.39 g (14.5 mmol) of 2-bromohexane was added dropwise over 5 minutes, and then the reaction solution was returned to room temperature. Stir for 3 hours. After completion of the reaction, 200 ml of water was added to the reaction solution and extracted twice with 100 ml of ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration with a rotary evaporator, purification by silica gel column chromatography (n-hexane: ethyl acetate = 93: 7) yielded 1.61 g of intermediate H as a white solid (yield 53.4 mol%). .
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 7.59 (dd, 1 H, J = 1.0 Hz, 8.0 Hz), 7.52 (dd, 1 H, J = 1.0 Hz, 8. 0 Hz), 7.24-7.30 (m, 1H), 7.05 (ddd, 1H, J = 1.0 Hz, 8.0 Hz, 8.0 Hz), 3.97 (s, 2H), 1. 47-1.74 (m, 3H), 1.20-1.41 (m, 7H), 0.89 (t, 3H, J = 5.5 Hz)

Step 2: Synthesis of Compound 7 In a three-necked reactor equipped with a thermometer, 1.50 g (1.60 mmol) of the intermediate B synthesized in Step 2 of Synthesis of Compound 1 of Synthesis Example 1 in a nitrogen stream, the above Step Intermediate H444 synthesized in 1 (444 mg, 1.78 mmol), (±) -10-camphorsulfonic acid 41.4 mg (0.178 mmol), THF 16 ml, and ethanol 4 ml were added to obtain a uniform solution. Then, it was made to react at 40 degreeC for 5 hours. After completion of the reaction, the reaction solution was poured into 100 ml of water and extracted with 200 ml of chloroform. The obtained organic layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration with a rotary evaporator, purification was performed by silica gel column chromatography (toluene: ethyl acetate = 92: 8) to obtain 1.35 g of Compound 7 as a pale yellow solid (yield: 72.4 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 8.04 (s, 1H), 7.73 (d, 1H, J = 1.5 Hz), 7.69 (dd, 1H, J = 1) .5 Hz, 7.8 Hz), 7.65 (dd, 1 H, J = 1.5 Hz, 7.8 Hz), 7.33 (ddd, 1 H, J = 1.5 Hz, 7.8 Hz, 7.8 Hz), 7.07-7.19 (m, 3H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J = 1) .5 Hz, 17.5 Hz), 6.13 (dd, 2H, J = 10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J = 1.5 Hz, 10.5 Hz), 4.18 ( t, 4H, J = 6.5 Hz), 3.95 (t, 4H, J = 6.5 Hz), 2.54-2.73 (m, 4H), 2.2 -2.40 (m, 8H), 1.65-1.83 (m, 16H), 1.60-1.62 (m, 2H), 1.57 (d, 3H, J = 7.5 Hz) 1.24-1.55 (m, 13H), 0.87 (t, 3H, J = 7.5 Hz)

Synthesis Example 8 Synthesis of Compound 8

Step 1: Synthesis of Intermediate I

In a four-necked reactor equipped with a thermometer, 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole was placed in a nitrogen stream and dissolved in 30 ml of DMF. To this solution, 7.88 g (24.2 mmol) of cesium carbonate and 1.93 g (14.5 mmol) of 1-bromo-2-butyne were added and stirred at room temperature for 20 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water, extracted with 300 ml of ethyl acetate, and the ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a brown solid. This brown solid was purified by silica gel column chromatography (n-hexane: ethyl acetate = 85: 15) to obtain 1.25 g of Intermediate I as a white solid (yield: 47.5 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.63 (dd, 1 H, J = 1.3 Hz, 7.8 Hz), 7.58 (dd, 1 H, J = 1.3 Hz, 7. 8 Hz), 7.29 (ddd, 1 H, J = 1.3 Hz, 7.8 Hz, 7.8 Hz), 7.10 (ddd, 1 H, J = 1.3 Hz, 7.8 Hz, 7.8 Hz), 4 .56 (q, 2H, J = 2.5 Hz), 4.36 (s, 2H), 1.84 (t, 3H, J = 2.5 Hz)

Step 2: Synthesis of Compound 8 In a three-necked reactor equipped with a thermometer, 1.50 g (1.60 mmol) of the intermediate B synthesized in Step 2 of Synthesis of Compound 1 of Synthesis Example 1 in a nitrogen stream, the above Step Intermediate I synthesized in 1) 387 mg (1.78 mmol), (±) -10-camphorsulfonic acid 41.4 mg (0.178 mmol), THF 16 ml, and ethanol 4 ml were added to obtain a homogeneous solution. Then, it was made to react at 40 degreeC for 5 hours. After completion of the reaction, the reaction solution was poured into 100 ml of water and extracted with 200 ml of chloroform. The obtained organic layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration with a rotary evaporator, purification was performed by silica gel column chromatography (toluene: ethyl acetate = 9: 1) to obtain 1.54 g of compound 8 as a pale yellow solid (yield: 84.9 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.90 (s, 1H), 7.78 (d, 1H, J = 1.3 Hz), 7.67-7.73 (m, 2H) ), 7.35 (ddd, 1H, J = 1.3 Hz, 7.5 Hz, 7.5 Hz), 7.18 (ddd, 1H, J = 1.3 Hz, 7.5 Hz, 7.5 Hz), 7. 09-7.15 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J = 1.5 Hz) , 17.0 Hz), 6.13 (dd, 2H, J = 10.5 Hz, 17.0 Hz), 5.82 (dd, 2H, J = 1.5 Hz, 10.5 Hz), 5.06 (d, 2H, J = 2.0 Hz), 4.18 (t, 4H, J = 6.0 Hz), 3.95 (t, 4H, J = 6.0 Hz), 2.5 -2.76 (m, 4H), 2.26-2.43 (m, 8H), 1.64-1.83 (m, 19H), 1.41-1.55 (m, 8H)

Synthesis Example 9 Synthesis of Compound 9

Step 1: Synthesis of Intermediate J

In a four-necked reactor equipped with a thermometer, 5.00 g (30.3 mmol) of 2-hydrazinobenzothiazole was placed in a nitrogen stream and dissolved in 100 ml of DMF. To this solution, 20.9 g (152 mmol) of potassium carbonate and 5.17 g (30.3 mmol) of 5-bromovaleronitrile were added and stirred at 60 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to 20 ° C., and the reaction solution was poured into 500 mL of water and extracted with 500 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (n-hexane: ethyl acetate = 60: 40) to obtain 3.41 g of Intermediate J as a white solid (yield: 45.7 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 7.60 (d, 1H, J = 7.8 Hz), 7.51 (d, 1H, J = 8.1 Hz), 7.28 (dd , 1H, J = 7.3, 8.1 Hz), 7.07 (dd, 1H, J = 7.3 Hz, 7.8 Hz), 4.23 (s, 2H), 3.81 (t, 2H, J = 6.9 Hz), 2.46 (t, 2H, J = 7.1 Hz), 1.88-1.95 (m, 2H), 1.71-1.79 (m, 2H)

Step 2: Synthesis of Compound 9 In a three-necked reactor equipped with a thermometer, 1.50 g (1.60 mmol) of the intermediate B synthesized in Step 2 of synthesis of Compound 1 of Synthesis Example 1 in a nitrogen stream, the above Step Intermediate J 438 mg (1.78 mmol) synthesized in Step 1, (±) -10-camphorsulfonic acid 41.4 mg (0.178 mmol), THF 16 ml, and ethanol 4 ml were added to obtain a uniform solution. Then, it was made to react at 40 degreeC for 5 hours. After completion of the reaction, the reaction solution was poured into 100 ml of water and extracted with 200 ml of ethyl acetate. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. Using a rotary evaporator, ethyl acetate was distilled off from the filtrate under reduced pressure to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (toluene: ethyl acetate = 85: 15) to obtain 1.31 g of compound 9 as a pale yellow solid (yield: 70.2 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.74 (d, 1H, J = 1.5 Hz), 7.64-7.72 (m, 3H), 7.35 (ddd, 1H) , J = 1.5 Hz, 8.0 Hz, 8.0 Hz), 7.19 (ddd, 1H, J = 1.5 Hz, 8.0 Hz, 8.0 Hz), 7.10-7.14 (m, 2H) ), 6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J = 1.5 Hz, 17.0 Hz), 6.12 (Dd, 2H, J = 10.5 Hz, 17.0 Hz), 5.82 (dd, 2H, J = 1.5 Hz, 10.5 Hz), 4.22 (t, 2H, J = 6.5 Hz), 4.18 (t, 4H, J = 6.5 Hz), 3.95 (t, 4H, J = 6.5 Hz), 2.58-2.75 (m, 4H) 2.55 (t, 2H, J = 6.5 Hz), 2.26-2.40 (m, 8H), 1.96 (tt, 2H, J = 6.5 Hz, 6.5 Hz), 1. 66-1.83 (m, 18H), 1.42-1.55 (m, 8H)

Example 1 Synthesis of Compound X

Step 1: Synthesis of Intermediate K

To a three-necked reactor equipped with a cooler and a thermometer, 104.77 g (0.9515 mol) of hydroquinone, 100 g (0.7320 mol) of 6-chlorohexanol, 500 g of distilled water and 100 g of o-xylene were added in a nitrogen stream. It was. While stirring the whole volume, 35.15 g (0.8784 mol) of sodium hydroxide was further added in small portions over 20 minutes so that the temperature of the contents did not exceed 40 ° C. After completion of the addition of sodium hydroxide, the contents were heated and reacted for another 12 hours under reflux conditions (96 ° C.).
After completion of the reaction, the temperature of the reaction solution was lowered to 80 ° C., 200 g of distilled water was added, and then the reaction solution was cooled to 10 ° C. to precipitate crystals. The precipitated crystals were separated into solid and liquid by filtration, and the obtained crystals were washed with 500 g of distilled water and vacuum-dried to obtain 123.3 g of brown crystals.
As a result of analyzing the brown crystals by high performance liquid chromatography, the content ratio (molar ratio) of the compounds contained in the brown crystals was (hydroquinone / intermediate K / byproduct K = 1.3 / 90.1 / 8. 1). This mixture was used directly in Step 2 without purification.

Step 2: Synthesis of intermediate L

In a three-necked reactor equipped with a condenser with a Dean-Stark tube and a thermometer, 10.00 g of brown crystals containing intermediate K synthesized in Step 1 above in a nitrogen stream, 100 g of toluene, 2,6-di-t -Butyl-p-cresol 0.105 g (0.476 mmol) was added and the whole volume was stirred. The solution was heated to 80 ° C., 20.56 g (0.1427 mol) of 2-carboxyethyl acrylate and 1.37 g (14.3 mmol) of methanesulfonic acid were added, and the water produced was removed under reflux conditions (110 ° C.). The dehydration reaction was performed for 2 hours. Next, the reaction solution was cooled to 30 ° C., 500 g of distilled water was added, and the whole volume was stirred and allowed to stand. The organic layer was separated, and 500 g of 5% brine was added to the obtained organic layer for liquid separation. The organic layer was separated and dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentrating with a rotary evaporator, purification by silica gel column chromatography (toluene: ethyl acetate = 8: 1) yielded 7.93 g of intermediate L as a white solid in a total of steps 1-2 (yield) : 40 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 6.77 (d, 2H, J = 9.0 Hz), 6.76 (d, 2H, J = 9.0 Hz), 6.41 (dd , 1H, J = 1.5 Hz, 17.5 Hz), 6.11 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 5.83 (dd, 1H, J = 1.5 Hz, 10.5 Hz) ), 4.83 (s, 1H), 4.44 (t, 2H, J = 6.5 Hz), 4.13 (t, 2H, J = 6.5 Hz), 3.89 (t, 2H, J = 6.5 Hz), 2.69 (t, 2H, J = 6.5 Hz), 1.71-1.80 (m, 2H), 1.62-1.70 (m, 2H), 1.36 -1.52 (m, 4H)

Step 3: Synthesis of Intermediate M

In a nitrogen stream, 3.58 g (0.0208 mol) of trans-1,4-cyclohexanedicarboxylic acid and 25 ml of THF were added to a three-necked reactor equipped with a thermometer. Next, 1.25 g (0.0109 mol) of methanesulfonyl chloride was added, and the reactor was immersed in a water bath to adjust the internal temperature of the reaction solution to 5 ° C. Then, 1.15 g (0.0114 mol) of triethylamine was added dropwise over 15 minutes so that the internal temperature of the reaction solution was 15 ° C. or lower. After stirring the reaction solution at 5 ° C. for 1 hour, 0.127 g (1.04 mmol) of 4- (dimethylamino) pyridine and 3.51 g (0.0104 mol) of intermediate L were added, and 1.15 g (0.0114 mol) of triethylamine was added. Was added dropwise over 15 minutes so that the internal temperature of the reaction solution was 15 ° C. or lower. Thereafter, the reaction solution was reacted at 25 ° C. for 2 hours. After completion of the reaction, 300 ml of distilled water and 30 ml of saturated saline were added to the reaction solution, and extracted twice with 200 ml of chloroform. The obtained organic layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration with a rotary evaporator, purification by silica gel column chromatography (chloroform: THF = 95: 5) yielded 2.41 g of Intermediate M as a white solid (yield: 47 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 6.96 (d, 2H, J = 9.0 Hz), 6.86 (d, 2H, J = 9.0 Hz), 6.41 (dd , 1H, J = 1.5 Hz, 17.5 Hz), 6.11 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 5.83 (dd, 1H, J = 1.5 Hz, 10.5 Hz) ), 4.44 (t, 2H, J = 6.5 Hz), 4.13 (t, 2H, J = 6.5 Hz), 3.93 (t, 2H, J = 6.5 Hz), 2.69 (T, 2H, J = 6.5 Hz), 2.47-1.57 (m, 1H), 2.34-2.43 (m, 1H), 2.12-2.28 (m, 4H) 1.73-1.82 (m, 2H), 1.36-1.71 (m, 10H)

Step 4: Synthesis of intermediate N

In a three-necked reactor equipped with a thermometer, in a nitrogen stream, Intermediate A synthesized in Step 1 of Synthesis Example 1: 3.90 g (8.85 mmol), DMF 0.52 g (7.1 mmol), and toluene 39 g were added. added. The solution was cooled to 5 ° C., and 1.10 g (9.3 mmol) of thionyl chloride was added dropwise over 10 minutes, followed by reaction at 5 ° C. for 1 hour. Then, after concentrating a reaction liquid with a rotary evaporator, white solid was obtained by making it vacuum-dry.
Further, in a three-necked reactor equipped with a thermometer, 6.10 g (0.0443 mol) of 2,5-dihydroxybenzaldehyde and 0.985 g (9.7 mmol) of triethylamine were put in a nitrogen stream and dissolved in 35 g of THF. . The solution was cooled to 5 ° C., and the white solid obtained above was added and reacted for 30 minutes. Thereafter, 200 ml of distilled water and 10 ml of saturated brine were added to the reaction solution, and extracted twice with 100 ml of ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration with a rotary evaporator, purification by silica gel column chromatography (toluene: THF = 95: 5) yielded 1.53 g of intermediate N as a white solid (yield: 32 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 10.91 (s, 1 H), 9.86 (s, 1 H), 7.32 (d, 1 H, J = 3.0 Hz), 7. 24 (dd, 1H, J = 3.0 Hz, 9.0 Hz), 7.01 (d, 1H, J = 9.0 Hz), 6.97 (d, 2H, J = 9.0 Hz), 6.87 (D, 2H, J = 9.0 Hz), 6.40 (dd, 1H, J = 1.5 Hz, 17.5 Hz), 6.12 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 5.82 (dd, 1H, J = 1.5 Hz, 10.5 Hz), 4.17 (t, 2H, J = 6.5 Hz), 3.94 (t, 2H, J = 6.5 Hz), 2 51-2.65 (m, 2H), 2.20-2.35 (m, 4H), 1.75-1.83 (m, 2H), 1.63-1.75 m, 6H), 1.36-1.55 (m, 4H)

Step 6: Synthesis of intermediate P

In a three-necked reactor equipped with a thermometer, the intermediate M synthesized in Step 3: 1.00 g (2.04 mmol) was placed in a nitrogen stream and dissolved in 15 ml of THF. Next, 0.234 g (2.04 mmol) of methanesulfonyl chloride was added, the reaction solution was cooled to 5 ° C., and 0.236 g (2.33 mmol) of triethylamine was added dropwise over 10 minutes. After the reaction solution was reacted at 5 ° C. for 1 hour, 0.018 g (0.15 mmol) of 4-dimethylaminopyridine and 0.786 g (1.46 mmol) of the intermediate N synthesized in Step 4 were added, and 0.177 g of triethylamine was added. (1.75 mmol) was added dropwise over 10 minutes. Thereafter, the reaction solution was reacted at 25 ° C. for 2 hours, and then 200 ml of distilled water and 20 ml of saturated brine were added to the reaction solution, followed by extraction twice with 100 ml of chloroform. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration by a rotary evaporator, purification by silica gel column chromatography (chloroform: THF = 99: 1) gave 1.15 g of intermediate P as a white solid (yield: 78 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 10.08 (s, 1 H), 7.61 (d, 1 H, J = 3.0 Hz), 7.37 (dd, 1 H, J = 3.0 Hz, 9.0 Hz), 7.20 (d, 1 H, J = 9.0 Hz), 6.98 (d, 2 H, J = 9.0 Hz), 6.97 (d, 2 H, J = 9.0 Hz), 6.88 (d, 2H, J = 9.0 Hz), 6.88 (d, 2H, J = 9.0 Hz), 6.41 (dd, 1H, J = 1.5 Hz, 17 .5 Hz), 6.40 (dd, 1H, J = 1.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 6.11 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 5.83 (dd, 1 H, J = 1.5 Hz, 10.5 Hz), 5.82 (dd, 1 H, = 1.5 Hz, 10.5 Hz), 4.44 (t, 2H, J = 6.5 Hz), 4.17 (t, 2H, J = 6.5 Hz), 4.13 (t, 2H, J = 6.5 Hz), 3.94 (t, 2H, J = 6.5 Hz), 3.94 (t, 2H, J = 6.5 Hz), 2.53-2.74 (m, 6H), 2. 20-2.39 (m, 8H), 1.60-1.83 (m, 16H), 1.34-1.56 (m, 8H)

Step 7: Synthesis of Compound X In a three-necked reactor equipped with a thermometer, intermediate P synthesized in Step 6 above: 0.944 g (0.934 mmol) in a nitrogen stream, synthesized in Step 1 of Synthesis Example 2 Intermediate C: 0.279 g (1.12 mmol) and 2,6-di-t-butyl-p-cresol 0.02 g were dissolved in 15 ml of THF. 44 mg (0.189 mmol) of (+)-10-camphorsulfonic acid and 2 ml of ethanol were added to the solution, and the mixture was heated to 40 ° C. and reacted for 5 hours. After completion of the reaction, 100 ml of distilled water and 15 ml of saturated brine were added to the reaction solution, and extracted twice with 100 ml of ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration with a rotary evaporator, the obtained solid was dissolved in 10 ml of chloroform. 150 ml of methanol was added to the solution to precipitate crystals, followed by filtration. The crystals were washed with methanol and dried in vacuo to obtain 0.986 g of Compound X as a pale yellow solid (yield: 80 mol%).
The structure of the target product was identified by ¹ H-NMR. The results are shown below.

¹ H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 7.75 (d, 1H, J = 2.5 Hz), 7.65-7.71 (m, 3H), 7.34 (dd , 1H, J = 1.0 Hz, 7.5 Hz), 7.17 (dd, 1H, J = 1.0 Hz, 7.5 Hz), 7.07-7.14 (m, 2H), 6.99 ( d, 2H, J = 9.0 Hz), 6.98 (d, 2H, J = 9.0 Hz), 6.88 (d, 2H, J = 9.0 Hz), 6.88 (d, 2H, J = 9.0 Hz), 6.41 (dd, 1 H, J = 1.5 Hz, 17.5 Hz), 6.40 (dd, 1 H, J = 1.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 6.11 (dd, 1H, J = 10.5 Hz, 17.5 Hz), 5.83 (dd, 1H, = 1.5 Hz, 10.5 Hz), 5.82 (dd, 1H, J = 1.5 Hz, 10.5 Hz), 4.44 (t, 2H, J = 6.5 Hz), 4.30 (t, 2H, J = 7.5 Hz), 4.18 (t, 2H, J = 6.5 Hz), 4.13 (t, 2H, J = 6.5 Hz), 3.95 (t, 2H, J = 6) .5 Hz), 3.94 (t, 2H, J = 6.5 Hz), 2.54-2.74 (m, 6H), 2.25-2.40 (m, 8H), 1.62-1 .84 (m, 18H), 1.28-1.56 (m, 14H), 0.90 (t, 3H, J = 7.0 Hz)

Example 2 Synthesis of Mixture X

Step 1: Synthesis of intermediate mixture Q

In a three-necked reactor equipped with a condenser with a Dean-Stark tube and a thermometer, 10.00 g of brown crystals containing intermediate K synthesized in Step 1 of Example 1 in a nitrogen stream, 100 g of toluene, 2, 6 -Di-t-butyl-p-cresol 0.105 g (0.476 mmol) was added and the whole volume was stirred. The solution was heated to 80 ° C., 5.14 g (71.3 mmol) of acrylic acid and 0.91 g (9.51 mmol) of methanesulfonic acid were added, and dehydration reaction was performed under reflux conditions (110 ° C.) while removing generated water. For 3 hours. Next, the reaction solution was cooled to 30 ° C., 500 g of distilled water was added, and the whole volume was stirred and allowed to stand. The organic layer was separated, and 500 g of 5% brine was added to the obtained organic layer for liquid separation. The organic layer was separated and dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After concentration by a rotary evaporator, purification by silica gel column chromatography (toluene: ethyl acetate = 8: 1) gave 8.2 g of the mixture Q as a white solid. As a result of analyzing the white solid by high performance liquid chromatography, the content ratio (molar ratio) of the compounds contained in the white solid was as follows. This mixture was used directly in Step 2 without purification.

Step 2: Synthesis of intermediate mixture R

In a nitrogen stream, 10.68 g (62.0 mmol) of trans-1,4-cyclohexanedicarboxylic acid and 90 ml of THF were added to a three-necked reactor equipped with a thermometer. Thereto, 3.9 g (34.1 mmol) of methanesulfonyl chloride was added, and the reactor was immersed in a water bath to adjust the internal temperature of the reaction solution to 20 ° C. Next, 3.79 g (37.5 mmol) of triethylamine was added dropwise over 10 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C. After completion of the dropwise addition, the whole volume was further stirred at 25 ° C. for 2 hours.
To the obtained reaction solution, 0.38 g (3.12 mmol) of 4- (dimethylamino) pyridine and 8.2 g of the mixture Q synthesized in the previous step 1 are added, and the reactor is immersed in a water bath again to immerse the reaction solution in the reaction solution. The temperature was 15 ° C. Thereto, 3.79 g (37.5 mmol) of triethylamine was added dropwise over 10 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C. After completion of the addition, the whole volume was further stirred at 25 ° C. for 2 hours. After completion of the reaction, 1000 ml of distilled water and 100 ml of saturated brine were added to the reaction solution, and extracted twice with 400 ml of ethyl acetate. The organic layer was collected, dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After evaporating and removing the solvent from the filtrate with a rotary evaporator, the obtained residue was purified by silica gel column chromatography (THF: toluene = 1: 9) to obtain 7.1 g of a mixture R as a white solid. As a result of analyzing the white solid by high performance liquid chromatography, the content ratio (molar ratio) of the compounds contained in the white solid was as follows. This mixture was used directly in Step 3 without purification.

Step 3: Synthesis of mixture S

A three-necked reactor equipped with a thermometer was charged with 7.1 g of the mixture R synthesized in Step 2 and 100 ml of THF in a nitrogen stream to obtain a uniform solution. Thereto, 2.39 g (20.9 mmol) of methanesulfonyl chloride was added, and the reactor was immersed in a water bath to adjust the internal temperature of the reaction solution to 20 ° C. Next, 2.16 g (21.3 mmol) of triethylamine was added dropwise over 5 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C. After completion of the dropwise addition, the whole volume was further stirred at 25 ° C. for 2 hours. To the obtained reaction solution, 0.19 g (1.54 mmol) of 4- (dimethylamino) pyridine and 1.07 g (7.72 mmol) of 2,5-dihydroxybenzaldehyde were added, and the reactor was immersed again in a water bath. The internal temperature of the reaction solution was 15 ° C. Thereto, 1.95 g (19.3 mmol) of triethylamine was added dropwise over 5 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C. After completion of the dropwise addition, the whole volume was further stirred at 25 ° C. for 2 hours. After completion of the reaction, 400 ml of distilled water and 50 ml of saturated brine were added to the reaction solution, and extracted twice with 750 ml of ethyl acetate. The organic layer was collected, dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. After removing the solvent from the filtrate by evaporation using a rotary evaporator, the obtained residue was dissolved in 150 ml of THF. 750 ml of methanol was added to the solution to precipitate crystals, and the precipitated crystals were collected by filtration. The obtained crystals were washed with methanol and vacuum-dried to obtain 4.5 g of a mixture S as a white solid. As a result of analyzing the white solid by high performance liquid chromatography, the content ratio (molar ratio) of the compounds contained in the white solid was as follows. This mixture was used directly in Step 4 without purification.

Step 4: Synthesis of Mixture X In a three-necked reactor equipped with a thermometer, 4.5 g of the mixture S synthesized in Step 3 above and 50 ml of THF were placed in a nitrogen stream to obtain a homogeneous solution. 93 ml (0.48 mmol) was added. To this solution, a THF 10 ml solution of the intermediate C 1.25 g (5.0 mmol) synthesized in Step 1 of Synthesis Example 2 was added dropwise over 15 minutes. After completion of the dropwise addition, the whole volume was further stirred at 25 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into 800 ml of methanol, and the precipitated solid was collected by filtration. The solid collected by filtration was dried with a vacuum dryer to obtain 4.2 g of a mixture X as a pale yellow solid. As a result of analyzing the white solid by high performance liquid chromatography, the content ratio (molar ratio) of the compounds contained in the white solid was as follows.

<Measurement of phase transition temperature>
10 mg of each of Compounds 1 to 9 and Compound X are weighed, and in a solid state, a glass substrate with a polyimide alignment film subjected to rubbing treatment (manufactured by EHC Co., Ltd., trade name: orientation treated glass) Substrate) sandwiched between two sheets. This substrate was placed on a hot plate, heated from 40 ° C. to 200 ° C., and then cooled again to 40 ° C. Changes in the structure of the structure when the temperature was raised or lowered were observed with a deflection optical microscope (Nikon Corporation, ECLIPSELV100POL type) to determine the phase transition temperature.

The measured phase transition temperatures are shown in Table 1 below.
In Table 1, “C” represents Crystal, “N” represents Nematic, and “I” represents Isotropic. Here, “Crystal” means that the test compound is in a solid phase, “Nematic” means that the test compound is in a nematic liquid crystal phase, and “Isotropic” means that the test compound is in an isotropic liquid phase. Show.

(Examples 3 to 11)
0.99 g of each of Compounds 1 to 9 obtained in Synthesis Examples 1 to 9, 10 mg of Compound X obtained in Example 1, 30 mg of photopolymerization initiator (BASF, trade name: Irgacure OXE02), interface 100 mg of a 1% cyclopentanone solution of an activator (manufactured by Neos, trade name: Footage 208G) was dissolved in a mixed solvent of 0.3 g of 1,3-dioxolane and 2.0 g of cyclopentanone. This solution was filtered through a disposable filter having a pore diameter of 0.45 μm to obtain polymerizable compositions (polymerizable liquid crystal compositions) 1 to 9, respectively.

(Examples 12 to 20)
0.90 g of each of Compounds 1 to 9 obtained in Synthesis Examples 1 to 9, 100 mg of Compound X obtained in Example 1, 30 mg of photopolymerization initiator (trade name: Irgacure OXE02 manufactured by BASF), interface 100 mg of a 1% cyclopentanone solution of an activator (manufactured by Neos, trade name: Footage 208G) was dissolved in a mixed solvent of 0.3 g of 1,3-dioxolane and 2.0 g of cyclopentanone. This solution was filtered through a disposable filter having a pore diameter of 0.45 μm to obtain a polymerizable composition (polymerizable liquid crystal composition 10 to 18).

(Example 21)
1.0 g of the mixture X obtained in Example 2, 30 mg of a photopolymerization initiator (manufactured by BASF, trade name: Irgacure OXE02), 1% of a surfactant (manufactured by Neos, trade name: Footage 208G) 100 mg of the cyclopentanone solution was dissolved in a mixed solvent of 0.3 g of 1,3-dioxolane and 2.0 g of cyclopentanone. This solution was filtered through a disposable filter having a pore diameter of 0.45 μm to obtain a polymerizable liquid crystal composition 19.

(Comparative Examples 1-9)
1.0 g of each of the compounds 1 to 9 obtained in Synthesis Examples 1 to 9, 30 mg of a photopolymerization initiator (BASF, trade name: Irgacure OXE02), surfactant (manufactured by Neos, trade name: footer) 100 mg of a 1% cyclopentanone solution of Gent 208G) was dissolved in a mixed solvent of 0.3 g of 1,3-dioxolane and 2.0 g of cyclopentanone. This solution was filtered through a disposable filter having a pore diameter of 0.45 μm to obtain polymerizable liquid crystal compositions 1r to 9r, respectively.

<Stability evaluation of liquid crystal phase>
(I) Formation of liquid crystal layer by polymerizable liquid crystal composition To transparent glass substrate (trade name: orientation treated glass substrate manufactured by EHC Co., Ltd.) provided with a rubbed polyimide alignment film. Each of the polymerizable liquid crystal compositions 1-19 and 1r-9r was applied using a # 4 wire bar. The coating film was dried at a temperature shown in Table 2 for 1 minute, and then subjected to an alignment treatment at a temperature shown in Table 2 for 1 minute to form a liquid crystal layer (thickness: about 2.5 μm).
(Ii) Formation of optical anisotropic body After the liquid crystal layer prepared in (i) is left at the temperature shown in Table 2 for 1 minute or 15 minutes, 1500 mJ at the temperature shown in Table 2 from the coated surface side of each liquid crystal layer. Polymerization was performed by irradiating with / cm ² of ultraviolet rays to obtain optical anisotropic bodies with transparent glass substrates, respectively.
(Iii) Determination of liquid crystal phase stability The optically anisotropic body with a transparent glass substrate obtained in the above (ii) was disposed as shown in FIG. 1 to obtain a laminate, and the surface state was visually observed. . A state without unevenness is a good state. The state with little unevenness was set to 5, the state where unevenness was generated was set to 1, and the degree was evaluated in five steps. The evaluation results are summarized in Table 2.
In FIG. 1, as the polarizing film, a PVA polarizing film (manufactured by Sumitomo Chemical Co., Ltd.) was used. In addition, photographs of a state without unevenness (evaluation index: 5) and a state where unevenness occurs (evaluation index: 1) are shown in FIGS. 2A and 2B, respectively.

<Measurement of optical properties>
About the optically anisotropic body with a transparent glass substrate obtained by said (ii), the phase difference between 245.9 nm and 998.4 nm was measured using the ellipsometer (JA Woollam company make, M2000U type | mold). . Further, wavelength dispersion was evaluated from α and β values calculated as follows using the measured phase difference. The results are shown in Table 3.
α = (phase difference at 449.9 nm) / (phase difference at 548.5 nm)
β = (phase difference at 650.2 nm) / (phase difference at 548.5 nm)
In addition, in the case of ideal chromatic dispersion exhibiting broadband characteristics, that is, inverse chromatic dispersion, the α value is smaller than 1 and the β value is larger than 1. In the case of flat wavelength dispersion, the α and β values are comparable. In the case of general (normal) wavelength dispersion, the α value is larger than 1 and the β value is smaller than 1. That is, a flat wavelength dispersion in which the α value and the β value are approximately the same is preferable, and an inverse wavelength dispersion in which α is smaller than 1 and β is larger than 1 is particularly preferable.
Here, the film thickness of the optical anisotropic body is measured with a surface shape measuring device DEKTAK150 (manufactured by ULVAC, Inc.) by scratching the optical anisotropic body of the optical anisotropic body with a transparent glass substrate with a needle. Measured.

  From Table 2, it can be seen that in the polymerizable liquid crystal composition containing the compound X, the liquid crystal phase can be maintained more stably for a long time, and a coating film with less coating unevenness can be obtained. It can also be seen that when the amount of compound X added is 10% (Examples 12 to 20), the drying temperature can be lowered and a liquid crystal composition that is easier to handle can be obtained.

  From Table 3, it can be seen that also in Examples 1 to 21, α is smaller than 1 and β is larger than 1. Therefore, it can be seen that even when the compound X is added, the ideal wavelength dispersion exhibiting the broadband property, that is, the reverse wavelength dispersion is maintained.

According to the present invention, an optical film or the like that can maintain a liquid crystal phase more stably for a long time, has a practically low melting point, and is capable of uniform polarization conversion in a wide wavelength range is manufactured at low cost and with a wide process margin. A polymerizable liquid crystal composition that can be produced by the method is provided.
Further, according to the present invention, there are provided a polymerizable compound useful for the preparation of the polymerizable liquid crystal composition and a mixture containing the polymerizable compound, and a compound useful for the preparation of the polymerizable compound and a mixture containing the compound. Provided.
According to the present invention, an optical film and an optical anisotropic body capable of uniform polarization conversion in a wide wavelength range, a polarizing plate, a flat panel display device, and an organic electroluminescence (EL) display device using the same. And an antireflective film is provided.

Claims (4)

The following formula (I):
[In formula (I), a represents an integer of 1 to 3, b represents an integer of 1 to 20, c is 0,
A ¹ represents a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent,
Y ¹ represents —O—, —CO—, —CO—O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² —, —O—CO—O—, —NR ²³ —. CO-O -, - O- CO-NR 24 -, ^or, -NR 25 ^{-CO-NR 26} - ^represents, R 21 ^{to R 26} each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms Represents
R ¹ and R ² each independently represents a hydrogen atom, a methyl group or a chlorine atom,
FG ¹ represents a hydroxyl group. And a compound represented by
Formula (II) below:
[In formula (II), d represents an integer of 1 to 20, e is 0,
A ² represents a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent,
Y ² represents —O—, —CO—, —CO —O—, —O—CO—, —NR ²¹ —CO—, —CO—NR ²² — , —O —CO—O—, —NR ²³ —. CO-O -, - O- CO-NR 24 -, ^or, -NR 25 ^{-CO-NR 26} - ^represents, R 21 ^{to R 26} each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms Represents
R ³ represents a hydrogen atom, a methyl group or a chlorine atom,
FG ² represents a hydroxyl group. And a compound represented by
Containing mixture. A ¹ is a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent, or an aromatic group having carbon atoms of 2-20 that may have a substituent, claim 1 The mixture described in 1 . A ¹ and A ² are each independently a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent, or an aromatic having 2 to 20 carbon atoms which may have a substituent. The mixture according to claim 1 or 2 , which represents a group. The mass ratio of the compound represented by the formula (I) and the compound represented by the formula (II) (the compound represented by the formula (I): the compound represented by the formula (II)) is 1: 1000-20 : The mixture according to any one of claims 1 to 3 , which is 100.