JP6823011B2 - Polymerizable compounds, methods for producing polymerizable compounds, polymerizable compositions, optically anisotropic films, optical films, polarizing plates and image display devices. - Google Patents

Description

The present invention relates to a polymerizable compound, a method for producing a polymerizable compound, a polymerizable composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.

A polymerizable compound exhibiting reverse wavelength dispersibility has features such as being able to accurately convert light wavelengths over a wide wavelength range and being able to thin a retardation film due to its high refractive index. Because of this, it is being actively researched.
Further, as a polymerizable compound exhibiting inverse wavelength dispersibility, a T-type molecular design guideline is generally taken, the wavelength of the major axis of the molecule is shortened, and the wavelength of the minor axis located at the center of the molecule is lengthened. Is required to do.
Therefore, it is known that a cycloalkylene skeleton having no absorption wavelength is used for connecting the short-axis skeleton located in the center of the molecule (hereinafter, also referred to as “reverse wavelength dispersion expression part”) and the long-axis of the molecule. ing.
For example, Patent Document 1 describes a composition containing a polymerizable liquid crystal compound having one inverse wavelength dispersion expressing portion, a polymerizable liquid crystal compound having two or more inverse wavelength dispersion expressing portions, and a solvent. ([Claim 1] [0152], etc.).

Japanese Unexamined Patent Publication No. 2016-121339

When the present inventors have examined a polymerizable liquid crystal compound having two or more inverse wavelength dispersion expressing portions described in Patent Document 1, the solubility may be inferior depending on the structure of the compound, and the reverse used in combination. The birefringence changes when the formed optically anisotropic film is exposed to high temperature and high humidity depending on the type of the polymerizable liquid crystal compound having one wavelength dispersion expressing portion and the polymerization conditions such as the curing temperature. It was clarified that there is a problem of durability that it will be done.

Therefore, the present invention relates to a polymerizable compound having excellent solubility used for forming an optically anisotropic film having excellent durability, a method for producing the same, and a polymerizable composition, an optically anisotropic film, and an optical film. An object of the present invention is to provide a polarizing plate and an image display device.

As a result of diligent studies to achieve the above problems, the present inventors have found that the molecule has two inverse wavelength dispersion expressing portions and the aromatic ring constituting the inverse wavelength dispersion expressing portion has a steric hindrance group. As a result, it has been found that the solubility is improved and the durability of the formed optically anisotropic film is also improved, and the present invention has been completed.
That is, it was found that the above problem can be achieved by the following configuration.

[1] A polymerizable compound represented by the formula (1) described later.
[2] The polymerizable compound according to [1], wherein m in the formula (1) described later is 1.
[3] The description in [1] or [2], wherein Z ¹ in the formulas (Ar-1) to (Ar-8) described later represents a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms. Polymerizable compound.
[4] The polymerizable compound according to any one of [1] to [3], wherein Z ¹ in the formulas (Ar-1) to (Ar-8) described later represents a tert-butyl group.
[5] The polymerizable compound according to any one of [1] to [4], which has a liquid crystallinity.

[6] A method for producing a polymerizable compound for synthesizing the polymerizable compound according to [1].
A first esterification step of reacting a compound represented by the formula (2) described later with a compound represented by the formula (3) described later to produce a first phenol compound.
The first phenol reaction product obtained in the first esterification step is reacted with a compound represented by the formula (4) described later to obtain a polymerizable compound according to [1] in the second esterification step. A method for producing a polymerizable compound.
[7] A method for producing a polymerizable compound for synthesizing the polymerizable compound according to [1].
A first esterification step of reacting a compound represented by the formula (2) described later with a compound represented by the formula (4) described later to produce a second phenol compound.
The second esterification step of reacting the second phenol reaction product obtained in the first esterification step with the compound represented by the formula (3) described later to obtain the polymerizable compound described in [1]. A method for producing a polymerizable compound.

[8] A polymerizable composition containing the polymerizable compound according to any one of [1] to [5].
[9] The polymerizable composition according to [8], further containing a polymerizable compound having two or more polymerizable groups, which is different from the polymerizable compound.
[10] An optically anisotropic film obtained by curing the polymerizable composition according to [8] or [9].
[11] An optical film having the optically anisotropic film according to [10].
[12] A polarizing plate having the optical film according to [11] and a polarizer.
[13] An image display device having the optical film according to [11] or the polarizing plate according to [12].

According to the present invention, a polymerizable compound having excellent solubility used for forming an optically anisotropic film having excellent durability and a method for producing the same, a polymerizable composition, an optically anisotropic film, an optical film, and the like. A polarizing plate and an image display device can be provided.

FIG. 1A is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1B is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1C is a schematic cross-sectional view showing an example of the optical film of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present specification, the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited, and for example, D ¹ in the formula (1) described later is -O-CO-. In the case of, if the position bonded to the G ¹ side is * 1 and the position bonded to the Ar ² side is * 2, D ¹ may be * 1-O-CO- * 2. , * 1-CO-O- * 2.

[Polymerizable compound]
The polymerizable compound of the present invention is a polymerizable compound represented by the following formula (1).

In the present invention, as described above, Ar ¹ and Ar ² in the above formula (1) corresponding to the inverse wavelength dispersion expressing portion are contained in the molecule, and Ar ¹ and Ar ² are steric hindrance groups (3). By using a polymerizable compound having Z ¹ ) in the formulas (Ar-1) to (Ar-8) described later, the solubility is improved and the durability of the formed optically anisotropic film is improved. ..
This is not clear in detail, but the present inventors speculate as follows.
That is, it is presumed that the introduction of the steric hindrance group into the two aromatic rings corresponding to the inverse wavelength dispersion expressing portion lowered the melting point of the polymerizable compound and improved the solubility of the polymerizable compound in the organic solvent.
In addition, the presence of steric hindrance groups introduced into the two aromatic rings corresponding to the inverse wavelength dispersion expressing part suppresses the hydrolysis reaction by inhibiting the approach of water to the central portion of the polymerizable compound, thereby suppressing the hydrolysis reaction. As a result, it is presumed that the durability of the optically anisotropic film is improved.
Hereinafter, the structure of the above formula (1) will be described in detail with respect to the polymerizable compound of the present invention.

As described above, the polymerizable compound of the present invention is a polymerizable compound represented by the following formula (1).

The above equations (1) D ¹ , D ² , D ³ and D ⁴ are independently single-bonded, -O-, -CO-O-, -C (= S) O-, -CR ¹ R ^{2- , -CR 1 R 2 -CR 3 R} 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O- ^{CO-CR 1 R 2 -,} - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 R 3 -, Alternatively, it represents −CO−NR ¹⁻ . R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
Further, in the above formula (1), G ¹ represents ^AG or SP ^G.
Further, in the above formula (1), A ¹ , A ² and ^AG independently represent an aromatic ring having 6 or more carbon atoms or a cycloalkane ring having 6 or more carbon atoms, and constitute the cycloalkane ring. One or more of -CH _2- may be replaced with -O-, -S- or -NH-.
Further, in the above formula (1), SP ¹ , SP ² and SP ^G are independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear chain having 1 to 20 carbon atoms. One or more of -CH _2- which constitutes the above-mentioned alkylene group, the above-mentioned alkenylene group or the above-mentioned alkynylene group, or a linear or branched alkynylene group having 1 to 20 carbon atoms It represents a divalent linking group substituted with O-, -S-, -NH-, -N (Q)-or -CO-, where Q represents a substituent.
Further, in the above formula (1), L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when at least one of Ar ¹ and Ar ² is an aromatic ring represented by the formula (Ar-4) described later, L ¹ and L ² and L ³ and L ³ in the formula (Ar-4) described later At least one of L ⁴ represents a polymerizable group.
Further, in the above equation (1), m represents an integer of 0 to 2, and when m is 2, a plurality of G ^1s may be the same or different, and each of the plurality of D ^1s may be different. It may be the same or different.
Further, the formula (1), l and n each independently represent 0 or an integer of 1 or more, when l is an integer of 2 or more, or different, even a plurality of A ¹ is the same at best, it may be a plurality of D ³ is optionally substituted by one or more identical. When n is an integer of 2 or more, the plurality of D ^4s may be the same or different, and the plurality of A ^2s may be the same or different.

In the above formula (1), examples of the aromatic ring having 6 or more carbon atoms represented by A ¹ , A ² and ^AG include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring. Aromatic heterocycles such as furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, and benzothiazole ring; can be mentioned. Of these, a benzene ring (for example, a 1,4-phenyl group) is preferable.
Further, in the above formula (1), examples of the cycloalkane ring having 6 or more carbon atoms represented by A ¹ , A ² and ^AG include a cyclohexane ring and a cyclohexene ring, and among them, a cyclohexane ring (for example, a cyclohexane ring). Cyclohexane-1,4-diyl group, etc.) is preferred.

In the above formula (1), as the linear or branched alkylene group having 1 to 20 carbon atoms represented by SP ¹ , SP ² and SP ^G , an alkylene group having 1 to 12 carbon atoms is preferable, and 1 to 12 carbon atoms are preferable. The alkylene group of 10 is more preferable, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
Further, in the above formula (1), as the linear or branched alkenylene group having 1 to 20 carbon atoms represented by SP ¹ , SP ² and SP ^G , an alkenylene group having 2 to 10 carbon atoms is preferable, and the alkenylene group having 2 to 10 carbon atoms is preferable. 2 to 4 alkenylene groups are more preferable, and for example, an ethenylene group and the like are preferably mentioned.
Further, in the above formula (1), as the linear or branched alkynylene group having 1 to 20 carbon atoms represented by SP ¹ , SP ² and SP ^G , an alkynylene group having 2 to 10 carbon atoms is preferable, and the alkynylene group having 2 to 10 carbon atoms is preferable. 2 to 4 alkynylene groups are more preferable, and for example, ethynylene groups and the like are preferable.

In the above formula (1), examples of the monovalent organic group represented by L ¹ and L ² include an alkyl group, an aryl group, and a heteroaryl group. The alkyl group may be linear, branched or cyclic, but linear is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but monocyclic is preferable. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms. Further, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Further, the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or have a substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.
On the other hand, the polymerizable group represented by at least one of L ¹ and L ² is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and preferred examples thereof include an acryloyl group and a methacryloyl group. In this case, it is known that the acryloyl group is generally faster in terms of polymerization rate, and the acryloyl group is preferable from the viewpoint of improving productivity, but the methacryloyl group is also used as the polymerizable group of the highly birefringent liquid crystal. Can be done.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and , Vinyloxy group and the like. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
The following are examples of particularly preferable polymerizable groups.

In the above equation (1), m represents an integer of 0 to 2, and l and n each independently represent an integer of 0 or 1 or more.
Here, m is preferably 0 or 1, and more preferably 1 from the viewpoint of synthesis.
l and n are preferably integers from 0 to 2 from the viewpoint of solubility and compatibility with other liquid crystal compounds.

On the other hand, in the above formula (1), Ar ¹ and Ar ² are independently selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-8). Represents. In the following formulas (Ar-1) to (Ar-8), * 1 represents the bonding position with D ¹ or D ^3, and * 2 represents the bonding position with D ² or D ⁴ .

Here, in the formula (Ar-1) and (Ar-2), ^{Q 1} represents N or CH, ^{Q 2} is -S -, - O-, or, -N ^{(R 5)} - a Represented, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or 3 carbon atoms which may have a substituent. Represents ~ 12 aromatic heterocyclic groups.
Specific examples of the alkyl group having 1 to 6 carbon atoms indicated by R ⁵ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl. Examples include a group, an n-pentyl group, and an n-hexyl group.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y ¹ include an aryl group such as a phenyl group, a 2,6-diethylphenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y ¹ include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group and a pyridyl group.
Examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, and a halogen atom.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or an isopropyl group) is preferable. , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is used. Is particularly preferable.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and carbon. It is more preferably an alkoxy group of numbers 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.

Further, in the above formulas (Ar-1) to (Ar-8), Z ¹ is a group indicating the above-mentioned steric disorder group, which is a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms and 6 carbon atoms. Represents a monovalent aromatic hydrocarbon group of ~ 20, halogen atom, -OR ⁶ , -NR ⁷ R ⁸ or -SR ⁹ , where R ⁶ ~ R ⁹ independently have 3 to 20 carbon atoms. It represents a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
As the monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms indicated by Z ¹ , an alkyl group having 3 to 15 carbon atoms is preferable, an alkyl group having 3 to 8 carbon atoms is more preferable, and specifically, isopropyl. Groups, tert-pentyl groups (1,1-dimethylpropyl groups), tert-butyl groups, 1,1-dimethyl-3,3-dimethyl-butyl groups are more preferred, and tert-butyl groups are particularly preferred.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms indicated by Z ¹ include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and carbon. Aryl groups of numbers 6-12 (particularly phenyl groups) are preferred.
Examples of the halogen atom indicated by Z ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, as the monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms represented by R ^{6 to} R ⁹ , an alkyl group having 3 to 15 carbon atoms is preferable, and an alkyl group having 3 to 8 carbon atoms is more preferable, specifically. Specifically, an isopropyl group, a tert-pentyl group (1,1-dimethylpropyl group), a tert-butyl group and a 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and a tert-butyl group is particularly preferable. preferable.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^{6 to} R ⁹ include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group. , And an aryl group having 6 to 12 carbon atoms (particularly a phenyl group) is preferable.

Further, in the above formulas (Ar-5) to (Ar-8), Z ² is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic having 3 to 20 carbon atoms. Formula Hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, halogen atom, cyano group, nitro group, -OR ¹⁰ , -NR ¹¹ R ¹² , or -SR ¹³ representing R ¹⁰ to R ¹³ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms indicated by Z ² , an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and more specifically, methyl. Group, ethyl group, isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group and ethyl group. , The tert-butyl group is particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms shown by Z ² include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a methylcyclohexyl. Monocyclic saturated hydrocarbon groups such as groups and ethylcyclohexyl groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl Group, monocyclic unsaturated hydrocarbon group such as cyclodecadien; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] Decyl group, tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms indicated by Z ² include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and carbon. Aryl groups of numbers 6-12 (particularly phenyl groups) are preferred.
Examples of the halogen atom indicated by Z ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, examples of the alkyl group having 1 to 6 carbon atoms shown by R ^{10 to} R ¹³ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl. Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.

Further, in the above formula (Ar-3) and (Ar-4), ^{A 3} and ^{A 4} are each ^{independently, -O -, - N (R} 14) -, - S-, and from -CO- Represents a group selected from the group, where R ¹⁴ represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ¹⁴ include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Further, in the above formula (Ar-3), X represents a non-metal atom of Groups 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Examples of the non-metal atoms of Groups 14 to 16 indicated by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Specific examples of the substituent include a carbon atom having a substituent. Is, for example, an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, etc. Can be mentioned.

Further, in the above formula (Ar-4), D ⁵ and D ⁶ are independently single-bonded, -O-CO-, -C (= S) O-, -CR ¹ R ^2- , -CR ^{1 respectively. R 2 -CR 3 R 4 -,} - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O-CO-CR 1 ^{R 2 -, - CR 1 R} 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 R 3 -, or, -CO Represents −NR ¹ −. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

Further, in the above formula (Ar-4), SP ³ and SP ⁴ are independently single-bonded, linear or branched alkylene groups having 1 to 12 carbon atoms, or directly having 1 to 12 carbon atoms. Divalent in which one or more of -CH _2- constituting the chain or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents the linking group of, and Q represents the substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Further, in the above formula (Ar-4), L ³ and L ⁴ independently represent monovalent organic groups, respectively, and at least 1 of L ³ and L ⁴ and L ¹ and L ^{2 in} the above formula (1). One represents a polymerizable group.
Examples of the monovalent organic group include the same monovalent organic groups represented by L ¹ and L ² in the above formula (1), and examples of the polymerizable group include those in the above formula (1). The same as those described in L ¹ and L ² can be mentioned.

Further, in the above formulas (Ar-5) to (Ar-8), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
Further, in the above formulas (Ar-5) to (Ar-8), Ay is an alkyl group having 1 to 12 (preferably 1 to 6) carbon atoms which may have a hydrogen atom and a substituent, or Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
Here, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms.
Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of International Publication No. 2014/010325.
The alkyl group having 1 to 6 carbon atoms represented by ^{Q 3,} specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert Examples thereof include a-butyl group, an n-pentyl group, an n-hexyl group, and the like, and examples of the substituent include those similar to the substituent that Y ¹ in the above formula (Ar-1) may have. Can be mentioned.

Examples of the polymerizable compound represented by the above formula (1) include compounds represented by the following formulas (I) to (XII), and specifically, D in the following formulas (I) to (VI). ^1, the ^{G 1} and ^{D 2} and K, a compound having a group shown in the following table 1-8 can be mentioned, respectively, ^{D 1,} G 1 in formula (VII) ~ (XII), G 1 and ^{D 2} and Examples of K include compounds having the groups shown in Table 9 below.
In Tables 1 to 8 below, "*" shown in the base such as D ¹ indicates the bonding position.
Further, in the following description, a compound represented by the following formula (I) and having a group represented by 1-1 in Table 1 below is referred to as "compound (I-1-1)" and is described as another compound. Compounds having a structural formula and a group are also described in the same manner. For example, a compound represented by the following formula (II) and having a group shown in 2-3 in Table 2 below can be expressed as "compound (II-2-3)".
Further, in the compound (I-1-1) or the like, the group adjacent to the acryloyloxy group represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and represents a mixture of positional isomers having different methyl group positions. ..

In the present invention, for the reason that the durability of the optically anisotropic film formed with respect to the steric obstacle group of Ar in the above formula (1) is further improved, the above formulas (Ar-1) to (Ar-8) preferably) Z ¹ in is a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms, branched alkyl groups having 3 to 8 carbon atoms ( For example, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc.) are more preferable, and a tert-butyl group is particularly preferable.

Further, the polymerizable compound of the present invention is a polymerizable compound having liquid crystal properties (polymerizable liquid crystal compound) because it can be more easily oriented when used alone or in combination with other liquid crystal compounds. Is preferable.
Here, the liquid crystal property represents a thermotropic liquid crystal property or a riotropic liquid crystal property, and in the thermotropic liquid crystal property, it has one or more intermediate phases between the crystalline phase and the isotropic phase in the process of raising or lowering the temperature. Means. In the lyotropic liquid crystallinity, it means having a phase-separated state with some self-assembling power in water or an organic solvent.

[Method for producing polymerizable compound (1)]
The first production method of the polymerizable compound of the present invention (hereinafter, also abbreviated as "the first production method of the present invention") is a compound represented by the following formula (2) and a compound represented by the following formula (3). In the first esterification step of reacting with and to produce the first phenol compound,
It has a second esterification step of reacting the first phenolic reaction product obtained in the first esterification step with a compound represented by the following formula (4) to obtain a polymerizable compound of the present invention.

Here, Ar in the above formula (2), L, SP, A and D in the above formula (3), and G ¹ and D ¹ in the above formula (4) are the above formula (1), respectively. It is the same as Ar ¹ , L ¹ , SP ¹ , A ¹ , D ³ , G ¹ and D ¹ described in the above. In particular, in the first esterification step of reacting the compound represented by the above formula (2) with the compound represented by the above formula (3), the yield of the phenol compound produced is improved, and thus the above formula ( As for Ar in 2), as in the above formula (1), Z ¹ in the above formulas (Ar-1) to (Ar-8) is a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms. Is preferable.
Further, p in the above equation (3) represents an integer of 0 or 1 or more, and when p is an integer of 2 or more, a plurality of A's may be the same or different, and a plurality of D's may be different. May be the same or different.
Further, q in the above equation (4) represents an integer of 0 to 2, and when q is 2, a plurality of G ^1s may be the same or different, and each of the plurality of D ^1s may be different. It may be the same or different.

[First esterification step]
The first esterification step is a step of reacting the compound represented by the above formula (2) with the compound represented by the above formula (3) to produce a first phenol compound, specifically, the following. This is a step of producing a phenol compound represented by the formula (5).
Here, L, SP, A, D and Ar and l in the above formula (5) are all L ¹ , SP ¹ , A ¹ , D ³ and Ar ¹ and l described in the above formula (1). Is similar to.

The reaction conditions between the compound represented by the above formula (2) and the compound represented by the above formula (3) are not particularly limited, and conventionally known esterification reaction conditions can be appropriately adopted.
For example, the reaction temperature is preferably −10 to 40 ° C., more preferably −5 to 30 ° C., and even more preferably 0 to 20 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 1 to 10 hours, and even more preferably 1 to 8 hours.

[Second esterification step]
The second esterification step is a step of reacting the first phenol compound obtained in the first esterification step with the compound represented by the above formula (4) to obtain the polymerizable compound of the present invention. Specifically, in the step of reacting the first phenol compound represented by the above formula (5) with the compound represented by the above formula (4) to obtain a polymerizable compound represented by the following formula (1A). is there.
Here, L, SP, A, D, Ar, G ¹ and D ¹ and l in the above formula (1A) are all L ¹ , SP ¹ , A ¹ , D described in the above formula (1). ^{3, Ar} 1, is similar to the ^{G 1} and ^{D 1} and l, q in the formula (1A) is an integer of 0 to 2, q is 2, each plurality in ^{G 1} are the same It may be present or different, and the plurality of D ^1s may be the same or different.

The reaction conditions between the first phenol compound represented by the above formula (5) and the compound represented by the above formula (4) are not particularly limited, and conventionally known esterification reaction conditions can be appropriately adopted.
For example, the reaction temperature is preferably −10 to 40 ° C., more preferably −5 to 30 ° C., and even more preferably 0 to 20 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 1 to 10 hours, and even more preferably 1 to 8 hours.

[Method for producing polymerizable compound (Part 2)]
The second method for producing the polymerizable compound of the present invention (hereinafter, also abbreviated as “the second production method of the present invention”) is a compound represented by the following formula (2) and a compound represented by the following formula (4). In the first esterification step of reacting with and to produce a second phenol compound,
It has a second esterification step of reacting a second phenol reactant obtained in the first esterification step with a compound represented by the following formula (3) to obtain a polymerizable compound of the present invention.
Here, Ar in the above formula (2), L, SP, A and D in the above formula (3), and G ¹ and D ¹ in the above formula (4) are the first of the present invention, respectively. It is the same as that described in the manufacturing method.

[First esterification step]
The first esterification step is a step of reacting the compound represented by the above formula (2) with the compound represented by the above formula (4) to produce a second phenol compound. Specifically, the following This is a step of producing a phenol compound represented by the formula (6).
Here, Ar, D ² , G ¹ and D ¹ and m in the above formula (6) are all the same as Ar ¹ , D ² , G ¹ and D ¹ and m described in the above formula (1). Is.

The reaction conditions between the compound represented by the above formula (2) and the compound represented by the above formula (4) are not particularly limited, and conventionally known esterification reaction conditions can be appropriately adopted.
For example, the reaction temperature is preferably −10 to 40 ° C., more preferably −5 to 30 ° C., and even more preferably 0 to 20 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 1 to 10 hours, and even more preferably 1 to 8 hours.

[Second esterification step]
The second esterification step is a step of reacting the second phenol compound obtained in the first esterification step with the compound represented by the above formula (3) to obtain the polymerizable compound of the present invention. Specifically, in the step of reacting the second phenol compound represented by the above formula (6) with the compound represented by the above formula (3) to obtain a polymerizable compound represented by the following formula (1B). is there.
Here, L, SP, A, D, Ar, D ² , G ¹ and D ¹ and m in the above formula (1B) are all L ¹ , SP ¹ , A described in the above formula (1). Similar to ¹ , D ³ , Ar ¹ , D ² , G ¹ and D ¹ and m, and p in the above equation (1B) represents an integer of 0 or 1 or more.

The reaction conditions between the second phenol compound represented by the above formula (6) and the compound represented by the above formula (3) are not particularly limited, and conventionally known esterification reaction conditions can be appropriately adopted.
For example, the reaction temperature is preferably −10 to 40 ° C., more preferably −5 to 30 ° C., and even more preferably 0 to 20 ° C.
The reaction time is preferably 10 minutes to 24 hours, more preferably 1 to 10 hours, and even more preferably 1 to 8 hours.

[Polymerizable composition]
The polymerizable composition of the present invention is a polymerizable composition containing the above-mentioned polymerizable compound of the present invention, and in addition to the polymerizable compound of the present invention, other polymerizable compounds described later, a polymerization initiator, and It can contain a solvent or the like.

[Other polymerizable compounds]
The polymerizable composition of the present invention may contain other polymerizable compounds in addition to the above-mentioned polymerizable compound of the present invention.
Here, the polymerizable group contained in the other polymerizable compound is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, it is preferable to have an acryloyl group or a methacryloyl group.

As the other polymerizable compound, it is preferable that the other polymerizable compound has 2 to 4 polymerizable groups because the durability of the optically anisotropic film to be formed is further improved, and the polymerizable group is used. More preferably, it is another polymerizable compound having two.

Examples of such other polymerizable compounds include compounds represented by the formulas (M1), (M2), and (M3) described in paragraphs [0030] to [0033] of JP-A-2014-0770668. More specifically, the specific examples described in paragraphs [0046] to [0055] of the same publication can be mentioned.

Specific examples of the other polymerizable compound include the liquid crystal compounds described below. The 1,4-cyclohexylene groups in the following formulas are all trans-1,4-cyclohexylene groups.

In the above formula, "*" represents the bonding position.

The group adjacent to the acryloyloxy group in the above formulas II-2-8 and II-2-9 represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and the positions of the methyl groups are different. Represents a mixture of bodies.

[Polymerization initiator]
The polymerizable composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670), acidoin ether (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrance. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents). 35493667 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 4,212,970), acylphosphine. Examples thereof include oxide compounds (described in JP-A-63-40799, JP-A-5-29234, JP-A-10-95788, JP-A-10-29997).

〔solvent〕
The polymerizable composition of the present invention preferably contains a solvent from the viewpoint of workability for forming an optically anisotropic film.
Specific examples of the solvent include ketones (for example, acetone, 2-butanone, methylisobutylketone, cyclohexanone, cyclopentanone, etc.), ethers (for example, dioxane, tetrahydrofuran, etc.), and aliphatic hydrocarbons. (Eg, hexane, etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatic hydrocarbons (eg, toluene, xylene, trimethylbenzene, etc.), carbon halides (eg, dichloromethane, dichloroethane, dichlorobenzene, etc.) , Chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, etc.) , Etc.), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), etc., and these may be used alone or in combination of two or more. You may.

[Optical anisotropic film]
The optically anisotropic film of the present invention is an optically anisotropic film obtained by curing the above-mentioned polymerizable composition of the present invention.
Examples of the method for forming the optically anisotropic film include a method in which the above-mentioned polymerizable composition of the present invention is used to obtain a desired orientation state and then immobilized by polymerization.
Here, the polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation. Irradiation amount ^is preferably ^{10mJ / cm 2 ~50J / cm 2} , more preferably ^{20mJ / cm 2 ~5J / cm 2} , more preferably 30mJ ^/ cm ² ~3J ^/ cm 2 , 50 to 1000 mJ / cm ² is particularly preferable. Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.
In the present invention, the optically anisotropic film can be formed on an arbitrary support in the optical film of the present invention described later or on a polarizer in the polarizing plate of the present invention described later.

In the present invention, for the reason that the contrast ratio in the image display device, particularly the liquid crystal display device is improved, the optically anisotropic film is polymerized (orientation) after the above-mentioned polymerizable liquid crystal composition of the present invention is oriented in the smectic phase. It is preferably a film obtained by immobilization).
It is considered that this is because the smectic phase has a higher order than the nematic phase, and scattering due to the misalignment of the optically anisotropic layer is suppressed. Whether or not the optically anisotropic film exhibits a smectic phase can be determined by whether or not it has a periodic structure by X-ray diffraction. For example, the presence or absence of a periodic structure can be confirmed by analyzing the diffraction pattern with a thin film X-ray diffractometer ATXG (manufactured by Rigaku Corporation).

The optically anisotropic film of the present invention is preferably a positive A plate or a positive C plate, and more preferably a positive A plate.

Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
The refractive index in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized) is nx, the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny, and the refraction in the thickness direction. When the rate is nz, the positive A plate satisfies the relation of the formula (A1), and the positive C plate satisfies the relation of the formula (C1). The positive A plate shows a positive value for Rth, and the positive C plate shows a negative value for Rth.
Equation (A1) nx> ny≈nz
Equation (C1) nz> nx≈ny
The above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same.
“Substantially the same” means that in a positive A plate, for example, (ny-nz) × d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in "ny≈nz", and when (nx-nz) xd is -10 to 10 nm, preferably -5 to 5 nm, it is also included in "nx≈nz". Further, in the positive C plate, for example, when (nx−ny) × d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, it is also included in “nx≈ny”.

When the optically anisotropic film of the present invention is a positive A plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, from the viewpoint of functioning as a λ / 4 plate. It is more preferably 130 to 150 nm, and particularly preferably 130 to 140 nm.
Here, the "λ / 4 plate" is a plate having a λ / 4 function, and specifically, a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light). It is a plate having.

[Optical film]
The optical film of the present invention is an optical film having the optically anisotropic film of the present invention.
1A, 1B and 1C (hereinafter, these drawings are abbreviated as "FIG. 1" when no particular distinction is required) are schematic cross-sectional views showing an example of the optical film of the present invention, respectively.
Note that FIG. 1 is a schematic view, and the thickness relationship and positional relationship of each layer do not always match the actual ones, and the support, alignment film, and hard coat layer shown in FIG. 1 all have an arbitrary configuration. It is a member.
The optical film 10 shown in FIG. 1 has a support 16, an alignment film 14, and an optically anisotropic film 12 in this order.
Further, as shown in FIG. 1B, the optical film 10 may have a hard coat layer 18 on the side opposite to the side where the alignment film 14 of the support 16 is provided, and as shown in FIG. 1C, the optical film 10 may have a hard coat layer 18. The hard coat layer 18 may be provided on the side of the optically anisotropic film 12 opposite to the side on which the alignment film 14 is provided.
Hereinafter, various members used in the optical film of the present invention will be described in detail.

[Optically anisotropic film]
The optically anisotropic film of the optical film of the present invention is the above-mentioned optically anisotropic film of the present invention.
In the optical film of the present invention, the thickness of the optically anisotropic film is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[Support]
As described above, the optical film of the present invention may have a support as a base material for forming an optically anisotropic film.
Such a support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.

Examples of such a support include a glass substrate and a polymer film, and examples of the polymer film material are cellulose-based polymers; acrylic-based polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers. Polymers; Thermoplastic norbornene-based polymers; Polycarbonate-based polymers; Polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; Stylized polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); Polyethylene, polypropylene, ethylene and propylene Polyolefin-based polymers such as polymers; Vinyl chloride-based polymers; Amid-based polymers such as nylon and aromatic polyamides; Imid-based polymers; Sulfon-based polymers; Polyether sulfone-based polymers; Polyether ether ketone-based polymers; Polyphenylene sulfide-based polymers Examples thereof include vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; allylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; or polymers obtained by mixing these polymers.
Further, the polarizer described later may also serve as such a support.

In the present invention, the thickness of the support is not particularly limited, but is preferably 5 to 60 μm, and more preferably 5 to 30 μm.

[Alignment film]
When the optical film of the present invention has any of the above-mentioned supports, it is preferable that the optical film has an alignment film between the support and the optically anisotropic film. The support described above may also serve as an alignment film.

The alignment film generally contains a polymer as a main component. The polymer material for the alignment film has been described in many documents, and many commercially available products are available.
The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, or a derivative thereof. Particularly modified or unmodified polyvinyl alcohol is preferable.
Regarding the alignment film that can be used in the present invention, for example, the alignment film described in International Publication No. 01/88574, p. 43, line 24 to p. 49, line 8; paragraphs [0071] to [0995] of Japanese Patent No. 3907735. ], And the like; a liquid crystal alignment film formed by the liquid crystal alignment agent described in Japanese Patent Application Laid-Open No. 2012-155308; and the like.

In the present invention, it is also preferable to use a photoalignment film as the alignment film because it is possible to prevent surface deterioration by not contacting the surface of the alignment film when the alignment film is formed.
The photoalignment film is not particularly limited, but is a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; A liquid crystal alignment film formed by a liquid crystal alignment agent having a photo-oriented group; a trade name LPP-JP265CP manufactured by Polyimide, Inc. can be used.

Further, in the present invention, the thickness of the alignment film is not particularly limited, but from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic film having a uniform film thickness, It is preferably 01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[Hard coat layer]
The optical film of the present invention preferably has a hard coat layer in order to impart physical strength to the film. Specifically, the hard coat layer may be provided on the side opposite to the side where the alignment film of the support is provided (see FIG. 1B), and the side where the alignment film of the optically anisotropic film is provided. May have a hard coat layer on the opposite side (see FIG. 1C).
As the hard coat layer, those described in paragraphs [0190] to [0196] of JP2009-98658A can be used.

[Other optically anisotropic films]
The optical film of the present invention may have another optically anisotropic film in addition to the optically anisotropic film of the present invention.
That is, the optical film of the present invention may have a laminated structure of the optically anisotropic film of the present invention and another optically anisotropic film.
Such other optically anisotropic films are optically anisotropic obtained by using the above-mentioned other polymerizable compounds (particularly liquid crystal compounds) without blending the polymerizable compound represented by the above formula (1). It is not particularly limited as long as it is a sex membrane.
Here, in general, liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shapes. Furthermore, there are low molecular weight and high molecular weight types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (polymer physics / phase transition dynamics, by Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound). Two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of disk-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound may be used. For the immobilization of the above-mentioned liquid crystal compound, it is more preferable to form a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound having a polymerizable group, and the liquid crystal compound may have two or more polymerizable groups in one molecule. More preferred. When the liquid crystal compound is a mixture of two or more kinds, it is preferable that at least one kind of liquid crystal compound has two or more polymerizable groups in one molecule.
As the rod-shaped liquid crystal compound, for example, those described in claim 1 of JP-A No. 11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and discotics can be used. As the liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP2007-108732 and paragraphs [0013] to [0108] of JP2010-2404038 can be preferably used. However, it is not limited to these.

[Polarizer]
The polarizing plate of the present invention has the above-mentioned optical film of the present invention and a polarizer.
Further, the polarizing plate of the present invention can be used as a circular polarizing plate when the above-mentioned optically anisotropic film of the present invention is a λ / 4 plate (positive A plate).
Further, in the polarizing plate of the present invention, when the above-mentioned optically anisotropic film of the present invention is a λ / 4 plate (positive A plate), the slow-phase axis of the λ / 4 plate and the absorption axis of the polarizer described later are used. The angle formed by the light is preferably 30 to 60 °, more preferably 40 to 50 °, further preferably 42 to 48 °, and particularly preferably 45 °.
Here, the "slow phase axis" of the λ / 4 plate means the direction in which the refractive index becomes maximum in the plane of the λ / 4 plate, and the "absorption axis" of the polarizer means the direction in which the absorbance is highest. To do.

[Polarizer]
The polarizer of the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorption-type polarizers and reflection-type polarizers can be used. ..
As the absorption type polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a polyene-based polarizer, and the like are used. Iodine-based polarized light and dye-based polarized light include coated and stretched polarized light, and both can be applied. However, polarized light produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching it. Children are preferred.
Further, as a method for obtaining a polarizer by stretching and dyeing a laminated film having a polyvinyl alcohol layer formed on a substrate, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 46910205, and Japanese Patent No. No. 4751481 and No. 4751486 can be mentioned, and known techniques for these polarizers can also be preferably used.
As the reflective polarizer, a polarizer in which thin films having different birefringences are laminated, a wire grid type polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined, and the like are used.
Among them, a polymer containing a polyvinyl alcohol-based resin (-CH _2- CHOH- as a repeating unit. In particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers, in that the adhesion is more excellent. It is preferable that the polymer contains one).

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 30 μm, and even more preferably 5 μm to 15 μm.

[Adhesive layer]
In the polarizing plate of the present invention, an adhesive layer may be arranged between the optically anisotropic film in the optical film of the present invention and the polarizer.
The pressure-sensitive adhesive layer used for laminating the optically anisotropic film and the polarizer includes, for example, the ratio of the storage elastic modulus G'measured by a dynamic viscoelasticity measuring device to the loss elastic modulus G'(tan δ =). It represents a substance having a G "/ G') of 0.001 to 1.5, and includes so-called adhesives, substances that easily creep, and the like. Examples of the pressure-sensitive adhesive that can be used in the present invention include, but are not limited to, a polyvinyl alcohol-based pressure-sensitive adhesive.

[Image display device]
The image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
Of these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element, and the liquid crystal display device is preferable. More preferred.

[Liquid crystal display device]
The liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-mentioned polarizing plate of the present invention and a liquid crystal cell.
In the present invention, among the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the polarizing plate of the present invention as the polarizing plate on the front side, and the polarizing plate of the present invention as the polarizing plate on the front side and the rear side. Is more preferable to use.
The liquid crystal cells constituting the liquid crystal display device will be described in detail below.

<LCD cell>
The liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to.
In the TN mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °. The TN mode liquid crystal cell is most often used as a color TFT liquid crystal display device, and has been described in many documents.
In the VA mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied. In the VA mode liquid crystal cell, (1) a VA mode liquid crystal cell in a narrow sense in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. 2-). In addition to (described in Japanese Patent Application Laid-Open No. 176625), (2) a liquid crystal cell (SID97, Digital of technique. Papers (Proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for expanding the viewing angle ), (3) Liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied (Proceedings of the Japan Liquid Crystal Discussion Group 58-59). (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98) are included. Further, it may be any of PVA (Patternized Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment). Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819.
In the liquid crystal cell in the IPS mode, the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane by applying an electric field parallel to the substrate surface. In the IPS mode, the display is black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other. Methods for reducing leakage light during black display in an oblique direction and improving the viewing angle by using an optical compensation sheet are described in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. It is disclosed in JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.

[Organic EL display device]
Examples of the organic EL display device which is an example of the image display device of the present invention include, for example, from the visual side, a λ / 4 plate (positive A plate) made of a polarizer, an optically anisotropic film of the present invention, and an organic EL. A mode having a display panel in this order is preferably mentioned.
Further, the organic EL display panel is a display panel configured by using an organic EL element having an organic light emitting layer (organic electroluminescence layer) sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

[Example 1]
<Synthesis of compound (Ic)>

As shown in the above scheme, compound (Ic) was synthesized according to the method described in paragraph [0175] (Example 17) of JP-A-2016-081035.

<Synthesis of compound (I-1c)>

Then, as shown in the above scheme, 1.72 g (8.21 mmol) of compound (I-1b) and 5.0 g (16.4 mmol) of compound (Ic) were placed in tetrahydrofuran (THF) (50 mL). , 0 ° C., and 2.65 g (20.5 mmol) of N, N-diisopropylethylamine (DIPEA) was added dropwise thereto. After stirring at 0 ° C. for 1 hour, ethyl acetate (60 mL) and 1N hydrochloric acid aqueous solution (100 mL) were added at 0 ° C. Then, the aqueous layer was removed and the organic layer was washed with saline. The organic layer was dried over sodium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. Methanol was added and the precipitated solid was filtered to obtain 4.03 g of compound (I-1c) (yield 65%).

<Synthesis of compound (I-1-1)>

Then, as shown in the above scheme, 1.15 g (2.27 mmol) of compound (I-1-1a), 7.5 mL of ethyl acetate (EA), 2.3 mL of N, N-dimethylacetamide (DMAc), and 30 mg of 2,6-di-t-butyl-4-methylphenol was mixed at room temperature (23 ° C.), and the internal temperature was cooled to 5 ° C. To the mixture, 0.19 ml (2.66 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 0.7 g (0.95 mmol) of compound (I-1c) was added. 0.73 g (5.68 mmol) of N, N-diisopropylethylamine (DIPEA) was added dropwise so that the internal temperature did not exceed 5 ° C., and then the mixture was stirred at room temperature for 3 hours. After stirring, methanol and water were added, and the precipitated solid was filtered to obtain 0.99 g of compound (I-1-1) (yield 60%).
¹ H-NMR (Nuclear Magnetic Resonance) of the obtained compound (I-1-1) is shown below.
^{1 1} H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 (m, 6H), 1.4 (s, 18H), 1.7-1.8 (m, 12H), 2.4 ( m, 14H), 2.6-2.7 (m, 12H), 2.9 (t, 4H), 4.1-4.3 (m, 8H), 5.2 (m, 2H), 5 .8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.0 (d, 4H), 7.2 (d, 4H), 7.4 (s, 2H)

[Example 4]
<Synthesis of compound (I-2-10)>

In the above scheme, compound (I-1-10a) was synthesized by a conventional method using 4-acrylicoxybutanol and phosgene.
Then, as shown in the above scheme, 0.5 g (0.669 mmol) of compound (I-2c), 0.82 g (4.01 mmol) of compound (I-1-10a), and 2,6-di-t. 7 mg of −butyl-4-methylphenol was stirred in dichloromethane (15 mL) at 0 ° C., and 8 mg (0.0629 mmol) of DMAP and 0.32 ml (4.01 mmol) of pyridine were added dropwise thereto. After stirring at room temperature for 2 hours, 10 ml of water and 15 ml of ethyl acetate were added, and the mixture was extracted with ethyl acetate. The organic layer was washed with 1N hydrochloric acid water, saturated sodium bicarbonate water, and 10% saline solution in this order, the organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 0.44 g (0.402 mmol) of compound (I-2-10) (yield 60%).
^{1 1} H-NMR of the obtained compound (I-2-10) is shown below.
^{1 1} H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 (s, 18H), 1.8-2.0 (m, 8H), 3.7-3.9 (m, 8H), 4.2 (t, 4H), 4.4 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.3 (s) , 2H)

[Example 5]
<Synthesis of compound (I-4c)>

As shown in the scheme above, 5.0 g (16.4 mmol) of compound (I-c) was stirred in THF (50 mL) at 0 ° C. and DIPEA and 1.26 g (I-4b) of compound (I-4b) were added. It was added dropwise in the order of 8.21 mmol).
Then, after stirring at 0 ° C. for 1 hour, ethyl acetate (60 mL) and 1N hydrochloric acid aqueous solution (100 mL) were added at 0 ° C. The aqueous layer was removed and the organic layer was washed with saline. The organic layer was dried over sodium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography, and then acetonitrile was added and the precipitated solid was filtered to obtain 2.5 g of compound (I-4c) (yield 45%).

<Synthesis of compound (I-4-1)>

As shown in the above scheme, in the method for synthesizing compound (I-1-1), the same method as compound (I-1-1) except that compound (I-1c) was changed to compound (I-4c). , The compound (I-4-1) was synthesized.
^{1 1} H-NMR of the obtained compound (I-4-1) is shown below.
^{1 1} H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 (m, 6H), 1.4 (s, 18H), 1.7-1.8 (m, 8H), 2.4 ( m, 8H), 2.6-2.7 (m, 12H), 2.9 (t, 4H), 4.1-4.3 (m, 8H), 5.2 (m, 2H), 5 .8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.0 (d, 4H), 7.2 (d, 4H), 7.4 (m, 4H)

[Example 6]
<Synthesis of compound (I-6c)>

As shown in the scheme above, 5.0 g (16.4 mmol) of compound (I-c) was stirred in THF (50 mL) under a nitrogen atmosphere at 0 ° C. and 2.55 g (19.7 mmol) of DIPEA. , And 1.04 g (8.21 mmol) of compound (I-6b) were added dropwise in this order. After stirring at room temperature for 1 hour, ethyl acetate (60 mL) and 1N hydrochloric acid solution (100 mL) were added at 0 ° C. The aqueous layer was removed and the organic layer was washed with saline. The organic layer was dried over sodium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. Acetonitrile was added and the precipitated solid was filtered to obtain 2.7 g of compound (I-6c) (yield 50%).

<Synthesis of compound (I-6-1)>

As shown in the above scheme, in the method for synthesizing compound (I-1-1), the same method as compound (I-1-1) except that compound (I-1c) was changed to compound (I-6c). In, the compound (I-6-1) was synthesized.
^{1 1} H-NMR of the obtained compound (I-6-1) is shown below.
^{1 1} H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 (m, 6H), 1.4 (s, 18H), 1.7-1.8 (m, 8H), 2.4 ( m, 8H), 2.6-2.7 (m, 12H), 2.9 (t, 4H), 4.1-4.3 (m, 8H), 5.2 (m, 2H), 5 .8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.0 (d, 4H), 7.2 (d, 4H), 7.4 (s, 2H)

[Example 7]
<Synthesis of compound (I-7c)>

As shown in the above scheme, 2.0 g (6.57 mmol) of compound (I-c) and 0.78 g (3.29 mmol) of compound (I-7b) are stirred in DMAc (20 mL) at room temperature under a nitrogen atmosphere. Then, 1.2 g (8.21 mmol) of K ₂ CO ₃ was added thereto. After stirring at 70 ° C. for 3 hours, ethyl acetate (60 mL) and 1N hydrochloric acid water (50 mL) were added at room temperature. The aqueous layer was removed, and the organic layer was washed with 1N hydrochloric acid and saline in that order. The organic layer was dried over sodium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography, and then acetonitrile was added and the precipitated solid was filtered to obtain 0.63 g (0.628 mmol) of compound (I-7c) (yield 30%). ).

<Synthesis of compound (I-7-1)>

As shown in the above scheme, in the method for synthesizing compound (I-2-1), the same method as compound (I-2-1) except that compound (I-2c) was changed to compound (I-7c). The compound (I-7-1) was synthesized in.
^{1 1} H-NMR of the obtained compound (I-7-1) is shown below.
^{1 1} H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 (m, 6H), 1.4 (s, 18H), 1.7-1.8 (m, 8H), 2.4 ( m, 8H), 2.6-2.7 (m, 12H), 2.9 (t, 4H), 4.1-4.3 (m, 8H), 4.5 (m, 4H), 5 .2 (m, 2H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.0 (d, 4H), 7.2 (d, 4H), 7.3 (s, 2H)

[Example 9]
<Synthesis of compound (I-8-10)>

As shown in the above scheme, in the method for synthesizing compound (I-2-10), the same method as compound (I-2-10) except that compound (I-2c) was changed to compound (I-8c). The compound (I-8-10) was synthesized (yield 59%).
^{1 1} H-NMR of the obtained compound (I-8-10) is shown below.
^{1 1} H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 (s, 18H), 1.4 (m, 3H), 1.8-2.0 (m, 8H), 3.2- 3.6 (m, 3H), 4.1 (m, 2H), 4.2 (m, 5H), 4.4 (t, 4H), 4.5 (m, 1H), 5.8 (dd) , 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.3 (s, 2H)

[Example 10]
<Synthesis of compound (I-1-1b)>

As shown in the scheme above, 3.01 g (5.97 mmol) of compound (I-1-1a), 15 mL of ethyl acetate, 4.5 mL of N, N-dimethylacetamide, and 2,6-di-t-butyl-. 65 mg of 4-methylphenol was mixed at room temperature, and the internal temperature was cooled to 5 ° C. 0.52 ml (7.17 mmol) of thionyl chloride was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 2.0 g (6.57 mmol) of compound (Ic) in THF (8 ml) was added dropwise. After adding 2.6 ml (14.9 mmol) of N, N-diisopropylethylamine so that the internal temperature did not exceed −5 ° C., the mixture was stirred at −5 ° C. or lower for 30 minutes. After stirring, 10 ml of 1N hydrochloric acid water and 10 ml of ethyl acetate were added to stop the reaction, and the liquid was separated. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. As a result of measuring the ratio of (I-1-1b): (I-1-1c) of the obtained crude material by high performance liquid chromatography, (I-1-1b) :( I-1-1c) = 97. : It was 3. The obtained crude product was purified by silica gel column chromatography to obtain 2.83 g (3.58 mmol) of compound (I-1-1b) (yield 65%).

<Synthesis of compound (II-1-1)>

Then, as shown in the above scheme, 1.0 g (1.26 mmol) of compound (I-1-1b) was stirred in ethyl acetate (15 mL) and DMAc (7 mL) at 0 ° C. and there was compound (I). -1b) 0.12 g (0.57 mmol) was added. After dropping 0.25 ml (1.47 mmol) of DIPEA, 3.5 mg of DMAP was added. After stirring at room temperature for 2 hours, ethyl acetate (20 mL) and 1N hydrochloric acid solution (50 mL) were added at 0 ° C. The aqueous layer was removed and the organic layer was washed with saline. The organic layer was dried over sodium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. A crude product was obtained by adding methanol and filtering the precipitated solid. The obtained crude product was purified by column chromatography to obtain 0.3 g of compound (II-1-1) (yield 30%).
^{1 1} H-NMR of the obtained compound (II-1-1) is shown below.
^{1 1} H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.3 (m, 6H), 1.4 (s, 18H), 1.7-1.8 (m, 12H), 2.4 ( m, 14H), 2.6-2.7 (m, 12H), 2.9 (t, 4H), 4.1-4.3 (m, 8H), 5.2 (m, 2H), 5 .8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.0 (d, 4H), 7.2 (d, 4H), 7.4 (s, 2H)

[Example 11]
<Synthesis of compound (I-9c)>

As shown in the above scheme, the compound (I-9c) is prepared in the same manner as the compound (I-1c) except that the compound (I-1b) in the synthesis of the compound (I-1c) is changed to the compound (I-9b). Synthesized (yield 65%).

<Synthesis of compound (VII-9-6)>

In the above scheme, the synthesis of compound (I-1-6a) was carried out by the method described in paragraphs [0091] to [0092] of JP-A-2018-25770.
Then, as shown in the above scheme, in the synthesis of compound (I-1-1), compound (I-1-1a) is changed to compound (I-1--6a), and compound (I-1c) is changed to compound. Compound (VII-9-6) was synthesized (yield 65%) in the same manner as compound (I-1-1) except that it was changed to (I-9c).

[Comparative Example 1]
<Synthesis of compound (VII-1-1)>
Compound (XIII-1-1) was obtained in the same manner as in Example 1 except that p-benzoquinone, which is compound (Ia), was used as a starting material and the following scheme was followed.

[Comparative Example 2]
Compound (XIII-1-2) was obtained in the same manner as in Example 1 except that the scheme below was followed.

<Synthetic aptitude>
The synthetic suitability of the polymerizable compounds synthesized in Examples 1 to 11 and Comparative Examples 1 and 2 was evaluated according to the following criteria. The results are shown in Tables 10 and 11 below.
A: Phenol intermediate [Refers to any compound of compound (Ic) and compound (If). The same shall apply hereinafter in this paragraph. ] Is 50% or more in any of the steps, and column purification is not required.
B: When the yield from the phenol intermediate is 50% or more in any step, but column purification is required.
C: When the yield from the phenol intermediate is less than 50% in any step.

<Phase transition temperature>
The phase transition temperature of the polymerizable compounds synthesized in Examples 1 to 11 and Comparative Examples 1 and 2 was measured using a polarizing microscope. The results are shown in Tables 10 and 11 below. From the results shown in Tables 10 and 11 below, it was confirmed that only compound (I-6-1) had liquid crystallinity.

<Solubility>
The solubility of the polymerizable compound synthesized in Examples 1 to 11 and Comparative Examples 1 and 2 was measured by the method shown below. The results are shown in Tables 10 and 11 below.
Specifically, 50 mg of the compound was weighed in a 1.5 mL sample bottle, and the solvent was added until the solid content became 40 wt% (75 mg).
After shaking well by hand at room temperature (23 ° C.), it was visually observed and if it was clear, the process was terminated, and the solubility was determined to be 40 wt%. If there was any undissolved residue, a solvent was added so that the solid content was 35 wt% (+ 18 mg). After shaking well by hand at room temperature (23 ° C.), it was visually observed and if it was clear, it was terminated, and it was determined to be 35 wt%. If there was any undissolved residue, the solvent was added so as to be 30 wt%. The same operation was performed in increments of 5 wt%, and the process was repeated until it reached 5 wt%. MEK (methyl ethyl ketone) and CPN (cyclopentanone) were used as solvents for the solubility measurement.
A: Solubility of any of MEK and CPN is 30% or more B: Solubility of any of MEK and CPN is 15% or more and less than 30% C: Solubility of any of MEK and CPN is 15% or more

[Examples 1 , 4 to 7 , 9 to 11 and Comparative Examples 1 and 2]
<Formation of photoalignment film P-1>
Example of JP2012-155308A on one surface of a polarizer 1 having a film thickness of 20 μm produced by adsorbing iodine on a stretched polyvinyl alcohol film according to Example 1 of JP-A-2001-141926 The photo-alignment coating liquid 1 prepared with reference to the description of No. 3 was applied using a second bar.
After coating, the solvent was removed by drying to form the photoisomerization composition layer 1.
The obtained photoisomerization composition layer 1 was irradiated with polarized ultraviolet rays (500 mJ / cm ² , using a 750 W ultrahigh pressure mercury lamp) to form a photoalignment film P-1.

<Manufacturing of optical film>
A coating liquid for an optically anisotropic film having the following composition was applied onto the photoalignment film P-1 by a spin coating method to form a liquid crystal composition layer.
The formed liquid crystal composition layer was heated on a hot plate and then cooled to 60 ° C. to stabilize the orientation.
Then, the orientation was fixed by irradiation with ultraviolet rays at 60 ° C. to form an optically anisotropic film, and an optical film was produced.
―――――――――――――――――――――――――――――――――
Coating liquid for optically anisotropic membrane ――――――――――――――――――――――――――――――――――
-The following liquid crystal compound L-1 33.17 parts by mass-The following liquid crystal compound L-2 33.17 parts by mass-Polymer compound (compounds shown in Tables 10 and 11 below)
33.17 parts by mass ・ The following polymerization initiator S-1 (oxime type) 3.00 parts by mass ・ Leveling agent (the following compound T-1) 0.20 parts by mass ・ Chloroform 219.30 parts by mass ―――――― ―――――――――――――――――――――――――――

[Comparative Example 3]
The same method as in Example 1 was used except that the polymerizable compound (I-1-1) was not used and the amounts of the liquid crystal compound L-1 and the liquid crystal compound L-2 used were changed to 50.0 parts by mass. , An optical film was prepared.

[Comparative Example 4]
An optical film was produced in the same manner as in Example 1 except that the following polymerizable compound (G-1) was used instead of the polymerizable compound (I-1-1).

Each of the optical films prepared in the above-mentioned Examples and Comparative Examples was immersed in warm water at 50 ° C. for 30 minutes or more to remove the softened polarizer 1 and isolate an optically anisotropic film.

<Reverse wavelength dispersibility>
For each optically anisotropic film, in-plane retardation at wavelengths of 450 nm and 550 nm was measured using Axo Scan (0PMF-1, manufactured by Axometrics), and Re (450) / Re (550) was used as the following index. evaluated. The results are shown in Tables 10 and 11 below. Since the optically anisotropic films isolated from the optical films prepared in Comparative Examples 1 and 2 were not oriented, they were not evaluated and are indicated by "-" in Table 11 below.
A: Improved inverse wavelength dispersibility compared to when no polymerizable compound is added (Comparative Example 2) B: Equivalent to no addition of a polymerizable compound (Comparative Example 2) C: No polymerizable compound added (Comparative Example 2) ) Worse reverse wavelength dispersibility than when

<Durability>
Each of the optical films produced in the above-mentioned Examples and Comparative Examples was bonded onto a glass plate with the optically anisotropic film side on the glass side via an adhesive.
Then, using Axo Scan (0PMF-1, manufactured by Axometrics), the durability of the retardation value was evaluated by the following index. The results are shown in Tables 10 and 11 below. Since the optically anisotropic films isolated from the optical films prepared in Comparative Examples 1 and 2 were not oriented, they were not evaluated and are indicated by "-" in Table 11 below.
If the test condition is evaluated as "A" in the test of leaving the product in an environment of 100 ° C. and 95% relative humidity for 120 hours, it can be judged that the durability is good.
A: The amount of change in the value after the test with respect to the initial phase difference value is less than 10% of the initial value B: The amount of change in the value after the test with respect to the initial phase difference value is 10% or more and less than 20% of the initial value C : The amount of change in the value after the test with respect to the initial phase difference value is 20% or more of the initial value.

From the results shown in Tables 10 and 11, even when the molecule has two inverse wavelength dispersion expressing portions, when the aromatic ring constituting the inverse wavelength dispersion expressing portion does not have a steric hindrance group, It was found that the solubility was poor and the polymerizable composition was not oriented (Comparative Examples 1 and 2).
On the other hand, it was found that the polymerizable compound having two inverse wavelength dispersion expressing portions in the molecule and the aromatic ring constituting the inverse wavelength dispersion expressing portion has a steric hindrance group is excellent in solubility (implementation). From the comparison between Examples 1 , 4 to 7 , 9 to 11), and Examples 1 , 4 to 7 , 9 to 11 and Comparative Example 3, it was found that the durability of the optically anisotropic film was improved.
Further, from the comparison of Examples 1 , 4 to 7 , 9 to 11, in consideration of synthetic suitability, solubility, reverse wavelength dispersibility and durability comprehensively, Example 6 using a polymerizable compound having liquid crystallinity was used. Turned out to be superior.

10 Optical film 12 Optical anisotropic film 14 Alignment film 16 Support 18 Hard coat layer

Claims (13)

A polymerizable compound represented by the following formula (1).
Here, in the above equation (1), D ¹ , D ² , D ³ and D ⁴ are independently single-bonded, −O−, −CO—O−, −C (= S) O−, −. ^{CR 1 R 2 -, - CR} 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 ^{-, - O-CO-CR} 1 R 2 -, - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR ² Represents R ³ − or −CO −NR ¹ −. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ represents ^AG or SP ^G.
A ¹ , A ² and ^AG each independently represent an aromatic ring having 6 or more carbon atoms or a cycloalkane ring having 6 or more carbon atoms, and one or more of −CH ₂ − constituting the cycloalkane ring. May be replaced with -O-, -S- or -NH-.
SP ¹ , SP ² and SP ^G are independently single-bonded, linear or branched alkylene groups having 1 to 20 carbon atoms, linear or branched alkenylene groups having 1 to 20 carbon atoms, and carbons. One or more of the linear or branched alkynylene groups of numbers 1 to 20, or the alkylene group, the alkenylene group, or -CH _2- constituting the alkynylene group are -O-, -S-, -NH. Represents a divalent linking group substituted with −, −N (Q) − or −CO−, where Q represents a substituent.
L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when at least one of Ar ¹ and Ar ² is an aromatic ring represented by the following formula (Ar-4), L ¹ and L ² and L ³ and L ^{4 in the following} formula (Ar-4) At least one of represents a polymerizable group.
m represents an integer of 0 to 2, and when m is 2, the plurality of G ^1s may be the same or different, and the plurality of D ^1s may be the same or different. Good.
l and n each independently represent 0 or an integer of 1 or more, when l is an integer of 2 or more, each of the plurality of A ¹ may be the same or different and a plurality of D ³ is They may be the same or different. When n is an integer of 2 or more, the plurality of D ^4s may be the same or different, and the plurality of A ^2s may be the same or different.
Ar ¹ and Ar ² are independently selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8). Represents the aromatic ring of.


Here, in the formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8), * 1 represents the bonding position with D ³ or D ^4, and * 2 is. Represents the connection position with D ¹ or D ² . However, when l is 0, the coupling position with D ³ represents the coupling position with SP ^1, and when m is 0, the coupling position with D ¹ represents the coupling position with D ² . When n is 0, the coupling position with D ⁴ represents the coupling position with SP ² .
Further, Q ¹ represents N or CH.
Further, Q ² represents -S-, -O-, or -N (R ⁵ )-, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Further, Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
In addition, Z ¹ is a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms , −OR ⁶ , −NR ⁷ R ⁸ or −SR. It represents ^9, R 6 to R ⁹ each independently represent a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms having 3 to 20 carbon atoms. However, the monovalent aliphatic hydrocarbon group having 3 carbon atoms is limited to the isopropyl group.
Further, Z ² is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic group having 6 to 20 carbon atoms. Group Hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -OR ¹⁰ , -NR ¹¹ R ¹² or -SR ¹³ , and R ^{10 to} R ¹³ independently represent hydrogen atoms or 1 to 1 carbon atoms. Represents an alkyl group of 6.
Further, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹⁴ )-, -S-, and -CO-, and R ¹⁴ is hydrogen. Represents an atom or substituent.
Further, X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded .
Also, Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocycle represents an organic group having 2 to 30 carbon atoms.
Further, Ay is an alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom and a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Represents an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms. The polymerizable compound according to claim 1, wherein m in the formula (1) is 1. Claim that Z ¹ in the formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8) represents a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms. The polymerizable compound according to 1 or 2. The invention according to any one of claims 1 to 3, wherein Z ¹ in the formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8) represents a tert-butyl group. Polymerizable compound. The polymerizable compound according to any one of claims 1 to 4, which has a liquid crystallinity. A method for producing a polymerizable compound for synthesizing the polymerizable compound according to claim 1.
A first esterification step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) to produce a first phenol compound.
The second esterification step of reacting the first phenol reaction product obtained in the first esterification step with the compound represented by the following formula (4) to obtain the polymerizable compound according to claim 1. A method for producing a polymerizable compound.

Here, in the above formula (2), Ar is selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8). Represents one of the aromatic rings.


Here, in the formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8), * 1 and * 2 represent the bonding positions with the hydroxyl groups, respectively.
Further, Q ¹ represents N or CH.
Further, Q ² represents -S-, -O-, or -N (R ⁵ )-, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Further, Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
In addition, Z ¹ is a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms , −OR ⁶ , −NR ⁷ R ⁸ or −SR. It represents ^9, R 6 to R ⁹ each independently represent a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms having 3 to 20 carbon atoms. However, the monovalent aliphatic hydrocarbon group having 3 carbon atoms is limited to the isopropyl group.
Further, Z ² is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic group having 6 to 20 carbon atoms. Group Hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -OR ¹⁰ , -NR ¹¹ R ¹² or -SR ¹³ , and R ^{10 to} R ¹³ independently represent hydrogen atoms or 1 to 1 carbon atoms. Represents an alkyl group of 6.
Further, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹⁴ )-, -S-, and -CO-, and R ¹⁴ is hydrogen. Represents an atom or substituent.
Further, X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded .
Also, Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocycle represents an organic group having 2 to 30 carbon atoms.
Further, Ay is an alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom and a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Represents an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms.
On the other hand, in the formulas (3) and (4), D and D ¹ are independently single-bonded, -O-, -CO-O-, -C (= S) O-, and -CR ¹ R ^{2 respectively. -, - CR 1 R 2 -CR} 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O ^{-CO-CR 1 R 2 -,} - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 R 3 - , Or -CO-NR ^1- . R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ represents ^AG or SP ^G.
A and ^AG each independently represent an aromatic ring having 6 or more carbon atoms or a cycloalkane ring having 6 or more carbon atoms, and one or more of −CH ₂₋ constituting the cycloalkane ring is −O−. , -S- or -NH- may be substituted.
SP and SP ^G are independently single-bonded, linear or branched alkylene groups having 1 to 20 carbon atoms, linear or branched alkenylene groups having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. One or more of the linear or branched alkynylene group, or the alkylene group, the alkenylene group, or -CH _2- constituting the alkynylene group is -O-, -S-, -NH-, -N. (Q) represents a divalent linking group substituted with − or −CO−, where Q represents a substituent.
L represents a polymerizable group. However, when Ar in the formula (2) is an aromatic ring represented by the formula (Ar-4), at least one of L ³ and L ^{4 in} the formula (Ar-4) is polymerizable. When it is a group, L represents a monovalent organic group.
q represents an integer of 0 to 2, and when q is 2, the plurality of G ^1s may be the same or different, and the plurality of D ^1s may be the same or different. Good.
p represents an integer of 0 or 1 or more, and when p is an integer of 2 or more, a plurality of A's may be the same or different, and a plurality of D's may be the same or different. You may. A method for producing a polymerizable compound for synthesizing the polymerizable compound according to claim 1.
The first esterification step of reacting the compound represented by the following formula (2) with the compound represented by the following formula (4) to produce a second phenol compound,
The second esterification step of reacting the second phenol reaction product obtained in the first esterification step with the compound represented by the following formula (3) to obtain the polymerizable compound according to claim 1. A method for producing a polymerizable compound.

Here, in the above formula (2), Ar is selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8). Represents one of the aromatic rings.


Here, in the formulas (Ar-1) to (Ar-3) and (Ar-5) to (Ar-8), * 1 and * 2 represent the bonding positions with the hydroxyl groups, respectively.
Further, Q ¹ represents N or CH.
Further, Q ² represents -S-, -O-, or -N (R ⁵ )-, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Further, Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
In addition, Z ¹ is a monovalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms , −OR ⁶ , −NR ⁷ R ⁸ or −SR. It represents ^9, R 6 to R ⁹ each independently represent a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms having 3 to 20 carbon atoms. However, the monovalent aliphatic hydrocarbon group having 3 carbon atoms is limited to the isopropyl group.
Further, Z ² is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic group having 6 to 20 carbon atoms. Group Hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -OR ¹⁰ , -NR ¹¹ R ¹² or -SR ¹³ , and R ^{10 to} R ¹³ independently represent hydrogen atoms or 1 to 1 carbon atoms. Represents an alkyl group of 6.
Further, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹⁴ )-, -S-, and -CO-, and R ¹⁴ is hydrogen. Represents an atom or substituent.
Further, X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded .
Also, Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocycle represents an organic group having 2 to 30 carbon atoms.
Further, Ay is an alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom and a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Represents an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms.
On the other hand, in the formulas (3) and (4), D and D ¹ are independently single-bonded, -O-, -CO-O-, -C (= S) O-, and -CR ¹ R ^{2 respectively. -, - CR 1 R 2 -CR} 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O ^{-CO-CR 1 R 2 -,} - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 R 3 - , Or -CO-NR ^1- . R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ represents ^AG or SP ^G.
A and ^AG each independently represent an aromatic ring having 6 or more carbon atoms or a cycloalkane ring having 6 or more carbon atoms, and one or more of −CH ₂₋ constituting the cycloalkane ring is −O−. , -S- or -NH- may be substituted.
SP and SP ^G are independently single-bonded, linear or branched alkylene groups having 1 to 20 carbon atoms, linear or branched alkenylene groups having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. One or more of the linear or branched alkynylene group, or the alkylene group, the alkenylene group, or -CH _2- constituting the alkynylene group is -O-, -S-, -NH-, -N. (Q) represents a divalent linking group substituted with − or −CO−, where Q represents a substituent.
L represents a polymerizable group. However, when Ar in the formula (2) is an aromatic ring represented by the formula (Ar-4), at least one of L ³ and L ^{4 in} the formula (Ar-4) is polymerizable. When it is a group, L represents a monovalent organic group.
q represents an integer of 0 to 2, and when q is 2, the plurality of G ^1s may be the same or different, and the plurality of D ^1s may be the same or different. Good.
p represents an integer of 0 or 1 or more, and when p is an integer of 2 or more, a plurality of A's may be the same or different, and a plurality of D's may be the same or different. You may. A polymerizable composition containing the polymerizable compound according to any one of claims 1 to 5. The polymerizable composition according to claim 8, further comprising a polymerizable compound having two or more polymerizable groups, which is different from the polymerizable compound. An optically anisotropic film obtained by curing the polymerizable composition according to claim 8 or 9. The optical film having the optically anisotropic film according to claim 10. A polarizing plate having the optical film according to claim 11 and a polarizer. An image display device having the optical film according to claim 11 or the polarizing plate according to claim 12.