KR102438545B1 - Mixed crystal, polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device - Google Patents

Abstract

An object of the present invention is to provide a mixed crystal, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device used for a polymerizable liquid crystal composition having excellent solubility. The mixed crystal of the present invention is a mixed crystal formed of two or more polymerizable liquid crystal compounds represented by the following formula (1) and satisfying predetermined conditions.
L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ¹ -Ar-D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² … (One)

Description

Mixed crystal, polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device

The present invention relates to a mixed crystal, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.

The polymeric compound exhibiting reverse wavelength dispersion has characteristics such as enabling accurate light wavelength conversion in a wide wavelength range, and being able to thin the retardation film because it has a high refractive index. is being studied.

In addition, as a polymeric compound exhibiting reverse wavelength dispersibility, a T-type molecular design guideline is generally adopted, and it is required to shorten the wavelength of the long axis of the molecule and increase the wavelength of the short axis located at the center of the molecule to a longer wavelength. .

For this reason, it is known to use a cycloalkylene skeleton without an absorption wavelength for the connection between a short-axis skeleton (hereinafter also referred to as "reverse wavelength dispersion expression part") located at the center of a molecule and a long-term molecular axis (for example, , see Patent Documents 1 to 3).

Patent Document 1: Japanese Patent Application Laid-Open No. 2010-031223 Patent Document 2: International Publication No. 2014/010325 Patent Document 3: Japanese Patent Laid-Open No. 2016-081035

The present inventors examine the polymeric compound exhibiting reverse wavelength dispersibility described in patent documents 1 - 3, and from a viewpoint of controlling all physical properties, such as a phase transition temperature and crystallinity, 2 or more types of polymeric compound of a similar structure When the blended polymerizable liquid crystal composition was prepared, it was sometimes poor in solubility, and as a result, it was clarified that it was sometimes difficult to produce an optically anisotropic film having a good planar shape.

Accordingly, an object of the present invention is to provide a mixed crystal, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device used for a polymerizable liquid crystal composition excellent in solubility.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination in order to achieve the said subject, the present inventors used 2 or more types of polymerizable liquid crystal compounds which satisfy predetermined conditions as a polymeric compound which shows reverse wavelength dispersion, and formed from these polymerizable liquid crystal compounds. By using the mixed crystal to be used, it was found that the solubility of the polymerizable liquid crystal composition became good, and the present invention was completed.

That is, it discovered that the said subject could be achieved with the following structures.

[1] A mixed crystal formed of two or more polymerizable liquid crystal compounds represented by Formula (1) described later and satisfying any one of Conditions 1 to 5 described later.

[2] The mixed crystal according to [1], wherein D ¹ and D ² in Formula (1) to be described later are both *-CO-O-, and * represents a bonding position with G ¹ or G ² .

[3] The mixed crystal according to [1] or [2], wherein G ¹ , G ² , G ³ , and G ⁴ in Formula (1) to be described later all represent a cyclohexane ring.

[4] Any one of [1] to [3], wherein D ³ and D ⁴ in Formula (1) to be described later are both *-CO-O-, and * represents a bonding position with G ³ or G ⁴ . mixed tablet described in .

[5] The mixed crystal according to any one of [1] to [4], wherein L ¹ and L ² in Formula (1) described later each represent a polymerizable group.

[6] A carboxylic acid compound represented by Formula (1-1) to be described later is reacted with two or more phenolic compounds represented by Formula (1-2) to be described later and satisfying any one of Conditions 6 to 10 described later, A method for producing a mixed crystal, comprising: a reaction step of obtaining a mixed product; and a crystallization step of crystallizing the mixed product to obtain the mixed crystal according to any one of [1] to [5].

[7] A polymerizable liquid crystal composition comprising the mixed crystal according to any one of [1] to [5].

[8] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to [7].

[9] An optical film having the optically anisotropic film according to [8].

[10] A polarizing plate having the optical film according to [9] and a polarizer.

[11] An image display device having the optical film according to [9] or the polarizing plate according to [10].

ADVANTAGE OF THE INVENTION According to this invention, the mixed crystal used for the polymeric liquid crystal composition excellent in solubility, a polymeric liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the optical film of this invention.
1B is a schematic cross-sectional view showing an example of the optical film of the present invention.
1C is a schematic cross-sectional view showing an example of the optical film of the present invention.
FIG. 2A shows the spectrum by X-ray diffraction (XRD) of the mixed crystal (M-1-1) synthesized in Example 1. FIG.
FIG. 2B shows a spectrum by XRD of the polymerizable liquid crystal compound (I-2-4) used in Comparative Example 1. FIG.
FIG. 2C shows a spectrum by XRD of the polymerizable liquid crystal compound (I-4-4) used in Comparative Example 1. FIG.

Hereinafter, the present invention will be described in detail.

Although description of the structural requirements described below may be made based on the typical embodiment of this invention, this invention is not limited to such an embodiment.

In addition, in this specification, the numerical range shown using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in this specification, the bonding direction of the indicated divalent group (for example, -O-CO-) is not particularly limited except for the case where the bonding position is specified, for example, the formula described later When D ¹ in (1) is -CO-O-, if the position bonded to the Ar side is *1 and the position bonded to the G ¹ side is *2, then D ¹ is *1-CO-O -*2 may be sufficient, and *1-O-CO-*2 may be sufficient.

[Orb]

The mixed crystal of the present invention is a mixed crystal formed of two or more polymerizable liquid crystal compounds represented by the following formula (1) and satisfying any one of the following conditions 1 to 5.

L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ¹ -Ar-D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² … (One)

<condition>

Condition 1: Two or more kinds of polymerizable liquid crystal compounds all have an aromatic ring represented by the formula (Ar-1) as Ar in the formula (1), and Z ¹ , Z in the formula (Ar-1) Only any one or more of ² and Y ¹ is a different compound.

Condition 2: Two or more types of polymerizable liquid crystal compounds all have the aromatic ring represented by the said Formula (Ar-2) as Ar in the said Formula (1), and Z< ¹ >, Z in the said Formula (Ar-2) mutually Only at least one of ² and X is a different compound.

Condition 3: Two or more types of polymerizable liquid crystal compounds all have the aromatic ring represented by the said Formula (Ar-3) as Ar in the said Formula (1), and mutually, Z ¹ , Z in the said Formula (Ar-3) Only any one or more of ² , SP ³ , SP ⁴ , L ³ and L ⁴ is a different compound.

Condition 4: Two or more types of polymerizable liquid crystal compounds all have an aromatic ring represented by Formula (Ar-4) as Ar in Formula (1), and Z ¹ , Z in Formula (Ar-4) Only any one or more of ² , Z ³ , Ax and Ay is a different compound.

Condition 5: Two or more types of polymerizable liquid crystal compounds all have an aromatic ring represented by the formula (Ar-5) as Ar in the formula (1), and each other, Z ¹ , Z in the formula (Ar-5) Only any one or more of ² , Z ³ , Ax and Ay is a different compound.

A mixed crystal in the present invention is a state in which one molecule of two or more kinds of heterogeneous compounds is arranged with a predetermined regularity to form a crystal, or two or more kinds of heterogeneous compounds interact at the molecular level. , refers to a state in which a crystal having a predetermined regularity is constituted.

Such a crystal state can be easily confirmed by measuring the X-ray diffraction pattern and observing the change from the X-ray diffraction pattern of each single compound. That is, the X-ray diffraction pattern of the mixed crystal shows a pattern different from the X-ray diffraction pattern of each polymerizable liquid crystal compound constituting the mixed crystal. In addition, as shown in Examples to be described later, such a crystalline state is determined by measuring the transition temperature using differential scanning calorimetry (DSC), the transition temperature of the mixed crystal, and each polymerization constituting the mixed crystal. It can also be easily confirmed by comparing the transition temperatures of the liquid crystal compounds.

In the present invention, the solubility of the polymerizable liquid crystal composition is improved by using a mixed crystal formed of two or more polymerizable liquid crystal compounds satisfying any one of the conditions 1 to 5 described above.

Although this is not clear in detail, the present inventors guess as follows.

That is, the polymerizable liquid crystal compound represented by the above formula (1) is a compound that adopts a crystal structure having high crystallinity and low solubility alone, whereas the polymerizable liquid crystal compound represented by the above formula (1) and the above-mentioned conditions 1 to It is thought that the mixed crystal formed of two or more types of polymerizable liquid crystal compounds satisfying any one of 5 changes from a single crystal structure of a polymeric liquid crystal compound, and, as a result, solubility is improved.

Hereinafter, two or more polymerizable liquid crystal compounds forming the mixed crystal of the present invention will be described in detail.

[Polymerizable Liquid Crystal Compound]

The polymerizable liquid crystal compound forming the mixed crystal of the present invention is represented by the following formula (1) and is two or more polymerizable liquid crystal compounds that satisfy any one of Conditions 1 to 5 described later.

L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ¹ -Ar-D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² … (One)

In the formula (1), D ¹ , D ² , D ³ and D ⁴ are each independently a single bond or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more thereof, R ¹ to R ⁵ are each independently a hydrogen atom, a fluorine atom, Or a C1-C4 alkyl group is represented.

Moreover, ⁱⁿ said Formula ( ¹ ), G1, G2, ^G3 , and G4 ^respectively independently represent the C6 or more cycloalkane ring which may have a substituent.

Moreover, in said Formula ( ¹ ), SP1 and ^SP2 are each independently a single bond, a C1-C12 linear or branched alkylene group, or a C1-C12 linear or branched alkylene group. One or more of constituting -CH ₂ - represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent.

Moreover, in said Formula (1), L< ¹ > and L< ² > respectively independently represent a monovalent organic group, ^and at least one of L< ¹ > and L2 represents a polymeric group. However, when Ar is an aromatic ring represented by a following formula (Ar-3), at least 1 of L< ³ > and L< ⁴ > in L< ¹ > and L< ² > and following formula (Ar-3) represents a polymeric group.

Examples of the divalent linking group represented by D ¹ , D ² , D ³ and D ⁴ in the formula (1) include -O-, -CO-O-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ¹ R ² -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ¹ R ² -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ¹ R ² -, -CR ¹ R ² -CO-O-CR ¹ R ² -, -NR ⁵ -CR ¹ R ² -, and -CO-NR ⁵ -; and the like. R ¹ , R ² and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

Among these, it is preferable that ^both D1 and D2 in said Formula ( ¹ ) are *-CO-O- from the reason that it is easy to synthesize|combine and liquid crystallinity is easy to express. In addition, * represents a bonding position with G ¹ or G ² .

Moreover, for the same reason, it is preferable that both D ³ and D ⁴ in the formula (1) are -O-, *-CO-O-, *-CO-NR ⁵ -, and *-CO-O- more preferably. In addition, * represents a bonding position with G ³ or G ⁴ .

Examples of the cycloalkane ring having 6 or more carbon atoms represented by G ¹ , G ² , G ³ and G ⁴ in the formula (1) include a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a cyclododecaine ring. a ring, a cyclodocosein ring, etc. are mentioned.

Among these, it is preferable that all ^of G1, G2, G3, and G4 ⁱⁿ said Formula ( ¹ ) are a cyclohexane ring ( ¹ , 4- cyclohexylene group) from the reason liquid crystallinity is easy to express, , a trans-1,4-cyclohexylene group is more preferable.

Moreover, as a substituent which the C6 or more cycloalkane ring may have, the thing similar to the substituent which Y< ¹ > in Formula (Ar-1) mentioned later may have is mentioned.

In said formula ( ¹ ), as a C1 ^- C12 linear or branched alkylene group which SP1 and SP2 represent, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, A methylhexylene group, a heptylene group, etc. are mentioned suitably. In addition, SP ¹ and SP ² are, as described above, at least one of -CH ₂ - constituting a linear or branched alkylene group having 1 to 12 carbon atoms -O-, -S-, -NH-, It may be a divalent linking group substituted with -N(Q)- or -CO-, and examples of the substituent represented by Q include the same substituents as the substituents Y ¹ in Formula (Ar-1) described later may have.

In the 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. Although linear, branched, or cyclic|annular form may be sufficient as an alkyl group, linear is preferable. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are still more preferable. Moreover, although monocyclic or polycyclic may be sufficient as an aryl group, monocyclic is preferable. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable. Moreover, the heteroaryl group may be monocyclic or polycyclic may be sufficient as it. The number of heteroatoms constituting the heteroaryl group is preferably 1-3. As for the hetero atom which comprises a heteroaryl group, a nitrogen atom, a sulfur atom, and an oxygen atom are preferable. 6-18 are preferable and, as for carbon number of a heteroaryl group, 6-12 are more preferable. Moreover, unsubstituted may be sufficient as an alkyl group, an aryl group, and a heteroaryl group may have a substituent. As a substituent, the thing similar to the substituent which Y< ¹ > in Formula (Ar-1) mentioned later may have is mentioned.

Although the polymeric group which at least one of L< ¹ > and L< ² > represents in said Formula (1) is not specifically limited, The polymeric group which can radically polymerize or cationic polymerize is preferable.

As a radically polymerizable group, a generally known radically polymerizable group can be used, As a suitable thing, an acryloyl group or a methacryloyl group is mentioned. In this case, as for the polymerization rate, it is known that an acryloyl group is generally fast, and although an acryloyl group is preferable from a viewpoint of productivity improvement, methacryloyl group can also be used similarly as a polymeric group.

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 spirothoester group, a vinyloxy group, etc. can be heard Especially, an alicyclic ether group or a vinyloxy group is suitable, and an epoxy group, an oxetanyl group, or a vinyloxy group is especially preferable.

The following are mentioned as an example of a especially preferable polymeric group.

[Formula 1]

In said Formula (1), it is preferable that it is a polymeric group, and, as for L< ¹ > and L< ² > in said Formula (1), it is more preferable that it is an acryloyl group or a methacryloyl group from the reason that heat-resistant durability becomes favorable.

In addition, in said Formula (1), Ar represents any one aromatic ring selected from the group which consists of groups represented by following formula (Ar-1) - (Ar-5). In addition, in the following formulas (Ar-1) to (Ar-5), * represents a bonding position with D ¹ or D ² in the formula (1).

[Formula 2]

Here, in the formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N(R ⁶ )-, and R ⁶ is hydrogen An atom or a C1-C6 alkyl group is represented, Y< ¹ > represents a C6-C12 aromatic hydrocarbon group which may have a substituent, or a C3-C12 aromatic heterocyclic group.

Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -pentyl group, n-hexyl group, etc. are mentioned.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y ¹ include aryl groups such as phenyl group, 2,6-diethylphenyl group and naphthyl group.

Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y ¹ include heteroaryl groups such as thienyl group, thiazolyl group, furyl group and pyridyl group.

Moreover, as a substituent which Y< ¹ > may have, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned, for example.

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 (eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group) , isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

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 (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) is more preferable. and more preferably an alkoxy group having 1 to 4 carbon atoms, particularly preferably a methoxy group or an ethoxy group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that they are a fluorine atom and a chlorine atom.

In addition, in the formulas (Ar-1) to (Ar-5), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. represents a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁷ , -NR ⁸ R ⁹ , or -SR ¹⁰ ; R ⁷ to R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.

The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, an isopropyl group, and a tert-pentyl group. (1,1-dimethylpropyl group), tert-butyl group and 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, ethyl group and tert-butyl group are particularly preferable.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, monocyclic saturated hydrocarbon groups such as an ethylcyclohexyl group; Monocyclic groups such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodesenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodecadiene unsaturated hydrocarbon group; 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;

Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, 2,6-diethylphenyl group, naphthyl group, and biphenyl group, and an aryl group having 6 to 12 carbon atoms (especially phenyl group) is preferred.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that they are a fluorine atom, a chlorine atom, and a bromine atom.

On the other hand, specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁷ to R ¹⁰ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. -butyl group, n-pentyl group, n-hexyl group, etc. are mentioned.

In addition, in the formulas (Ar-2) and (Ar-3), A ³ and A ⁴ each independently represent -O-, -N(R ¹¹ )-, -S-, and -CO- A group selected from the group is represented, and R ¹¹ represents a hydrogen atom or a substituent.

Examples of the substituent represented by R ¹¹ include the same substituents as the substituents Y ¹ in the formula (Ar-1) may have.

In addition, in the formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded.

Moreover, as a nonmetallic atom of Group 14-16 represented by X, an oxygen atom, a sulfur atom, the nitrogen atom which has a substituent, and the carbon atom which has a substituent are mentioned, for example, As a substituent, specifically, for example, An alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (eg, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkyl carbonyl group, a sulfo group, a hydroxyl group, etc. are mentioned. .

In addition, in the formula (Ar-3), D ⁵ and D ⁶ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more thereof, R ¹ to R ⁵ are each independently a hydrogen atom, a fluorine atom, or a carbon number An alkyl group of 1-4 is shown.

Here, as a divalent coupling group, the thing similar to what was demonstrated for D1- ^D4 in said Formula ( ¹ ) is mentioned.

In the formula (Ar-3), SP ³ and SP ⁴ are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkyl having 1 to 12 carbon atoms. One or more of -CH ₂ - constituting the ren group represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent indicates. As a substituent, the thing similar to the substituent which Y< ¹ > in said Formula (Ar-1) may have is mentioned.

In addition, in the formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ and L ² in the formula (1) is a polymerizable group. indicates

Examples of the monovalent organic group include the same as those described for L ¹ and L ² in the formula (1).

Moreover, as a polymeric group, the thing similar to what was demonstrated in L< ¹ > and L< ² > in said Formula (1) is mentioned.

In addition, in the formulas (Ar-4) to (Ar-5), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. .

Further, in the formulas (Ar-4) to (Ar-5), Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic heterocycle selected from the group consisting of An organic group having 2 to 30 carbon atoms and having at least one aromatic ring is shown.

Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may couple|bond together, and may form the ring.

Moreover, Q< ³ > represents a C1-C6 alkyl group which may have a hydrogen atom or a substituent.

Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 2 (International Publication No. 2014/010325).

Moreover, as a C1-C6 alkyl group which Q< ³ > represents, specifically, for example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group , n-pentyl group, n-hexyl group, etc. are mentioned, As a substituent, the thing similar to the substituent which Y< ¹ > in said Formula (Ar-1) may have is mentioned.

<Conditions 1 to 5>

In the present invention, the polymerizable liquid crystal compound forming the mixed crystal is two or more polymerizable liquid crystal compounds represented by the above formula (1) and satisfying any one of the following conditions 1 to 5.

Condition 1: Two or more kinds of polymerizable liquid crystal compounds all have an aromatic ring represented by the formula (Ar-1) as Ar in the formula (1), and Z ¹ , Z in the formula (Ar-1) Only any one or more of ² and Y ¹ is a different compound.

Condition 2: Two or more types of polymerizable liquid crystal compounds all have the aromatic ring represented by the said Formula (Ar-2) as Ar in the said Formula (1), and Z< ¹ >, Z in the said Formula (Ar-2) mutually Only at least one of ² and X is a different compound.

Condition 3: Two or more types of polymerizable liquid crystal compounds all have the aromatic ring represented by the said Formula (Ar-3) as Ar in the said Formula (1), and mutually, Z ¹ , Z in the said Formula (Ar-3) Only any one or more of ² , SP ³ , SP ⁴ , L ³ and L ⁴ is a different compound.

Condition 4: Two or more types of polymerizable liquid crystal compounds all have an aromatic ring represented by Formula (Ar-4) as Ar in Formula (1), and Z ¹ , Z in Formula (Ar-4) Only any one or more of ² , Z ³ , Ax and Ay is a different compound.

Condition 5: Two or more types of polymerizable liquid crystal compounds all have an aromatic ring represented by the formula (Ar-5) as Ar in the formula (1), and each other, Z ¹ , Z in the formula (Ar-5) Only any one or more of ² , Z ³ , Ax and Ay is a different compound.

Here, with respect to Condition 1, "two or more types of polymerizable liquid crystal compounds all have an aromatic ring represented by Formula (Ar-1) as Ar in Formula (1)" means two or more types of forming a mixed crystal. All of the polymerizable liquid crystal compounds refer to those having an aromatic ring represented by the formula (Ar-1) as Ar in the formula (1), for example, as Ar in the formula (1), in the formula (Ar-1) Intent to exclude two types of polymerizable liquid crystal compounds comprising a polymerizable liquid crystal compound having an aromatic ring represented by the above formula (1) and a polymerizable liquid crystal compound having an aromatic ring represented by the formula (Ar-2) as Ar in the formula (1). to be.

In addition, regarding condition 1, "a compound differing from each other only in at least any one of Z ¹ , Z ² and Y ¹ in the formula (Ar-1)" means that two or more polymerizable liquid crystal compounds forming a mixed crystal are Any one or more of Z ¹ , Z ² , and Y ¹ in the formula (Ar-1) is different, and the other structures in the formula (Ar-1) are not different.

In addition, the above-mentioned analysis is the same also in the analysis in other conditions.

As the polymerizable liquid crystal compound represented by the formula (1), for example, compounds (I-1) to (I) represented by the following formula (I), wherein Z ¹ and Z ² in the following formula (I) are represented by the following Table 1 -8) is suitably mentioned. In addition, K in following formula (I) shows the side chain structure mentioned later.

[Formula 3]

[Table 1]

Moreover, as a polymeric liquid crystal compound represented by the said Formula (1), it is represented by following formula (II), for example, and Z< ¹ >, Z< ² > and n in following formula (II) are represented by following Table 2 (II-1) ) to (II-20) are preferably mentioned. In addition, K in following formula (II) shows the side chain structure mentioned later.

[Formula 4]

[Table 2]

Moreover, as a polymeric liquid crystal compound represented by said Formula ( ¹ ), it is represented by following formula (III), for example, ^Z1 , Z2, ^Z4 , ^Z5 , ^Z6 , and ^Z7 in following formula (III) are Compounds (III-1) to (III-9) shown in Table 3 below are preferably exemplified. In addition, K in following formula (III) shows the side chain structure mentioned later.

[Formula 5]

[Table 3]

Moreover, as a polymeric liquid crystal compound represented by said Formula ( ¹ ), it is represented by following formula ( ^IV ), for example, and Z1, Z2, ^Z4 , ^Z5 , ^Z6 , and ^Z7 in following formula (IV) are Compounds (IV-1) to (IV-5) shown in Table 4 below are preferably exemplified. In addition, K in following formula (IV) shows the side chain structure mentioned later.

[Formula 6]

[Table 4]

In addition, as K (side chain structure) in said Formula (I) - (IV), the side chain structure shown in following Table 5 and Table 6 is mentioned, for example.

In addition, in Table 5 and Table 6 below, "*" shown in the side chain structure of K represents the bonding position with an aromatic ring.

In addition, in the side chain structure represented by K2 in Table 5 and K15 in Table 6, the groups adjacent to the acryloyloxy group and the methacryloyl group, respectively, represent a propylene group (a group in which a methyl group is substituted with an ethylene group), and a methyl group represents a mixture of positional isomers with different positions.

[Table 5]

[Table 6]

As the polymerizable liquid crystal compound represented by the formula (1), specifically, for example, for each compound shown in Tables 1 to 4, a compound in which the side chain structures shown in Tables 5 and 6 are appropriately combined. can be heard

In the following description, for example, as a compound represented by the formula (I-2), a compound having a side chain structure represented by K4 in Table 5 is denoted as "compound (I-2-4)", and another Compounds having structural formulas and groups are described in the same manner.

Specific examples of preferred polymerizable liquid crystal compounds are shown in Tables 7 to 10 below.

[Formula 7]

[Table 7]

[Formula 8]

[Table 8]

[Formula 9]

[Table 9]

[Formula 10]

[Table 10]

The mixed crystal of the present invention is not particularly limited as long as it is a mixed crystal represented by the above formula (1) and formed of two or more polymerizable liquid crystal compounds that satisfy any one of the above-mentioned conditions 1 to 5. Mixed crystals (M-1) to (M-12) formed by a combination of a polymerizable liquid crystal compound are preferably mentioned.

Although the mass ratio of the polymerizable liquid crystal compound constituting such a mixed crystal is not particularly limited, each polymerizable liquid crystal compound is preferably contained in an amount of 5 mass % or more with respect to the total mass of the polymerizable liquid crystal compound. Moreover, when comprised from 2 types of polymeric liquid crystal compounds, it is preferable that their mass ratio is 5/95-95/5, and when comprised from 3 types of polymeric liquid crystal compounds, their mass ratio is 5- It is preferable that it is 90/5-90/5-90.

[Table 11]

[Method for preparing mixed tablets]

The method for producing a mixed tablet of the present invention is a carboxylic acid compound represented by Formula (1-1) to be described later, and two kinds represented by Formula (1-2) to be described later and satisfying any one of Conditions 6 to 10 described later. It has the reaction process of making the above phenol compound react to obtain a mixed product, and the crystallization process of crystallizing the said mixed product and obtaining the mixed crystal of this invention mentioned above.

In the present invention, the method for producing the mixed crystal is not limited to the above method, and a method of preparing two or more polymerizable liquid crystal compounds satisfying the above conditions 1 to 5, dissolving them, mixing them, and recrystallizing them. can also be manufactured.

[reaction step]

The reaction step of the method for producing a mixed crystal of the present invention includes a carboxylic acid compound represented by the following formula (1-1), and a carboxylic acid compound represented by the following formula (1-2) and satisfying any one of the following conditions 6 to 10 It is a process of making 2 or more types of phenol compounds react, and obtaining a mixed product.

L ¹ -SP ¹ -D ³ -G ³ -G ¹ -C(=O)-OH … (1-1)

HO-Ar-OH … (1-2)

In Formula (1-1), D ³ , G ¹ , G ³ and SP ¹ are the same as those described as D ³ , G ¹ , G ³ and SP ¹ in Formula (1).

Moreover, in said Formula (1-1), L< ¹ > represents a polymeric group. However, when Ar in said formula (1-2) is an aromatic ring represented by said formula (Ar-3), at least 1 of L ³ and L ⁴ in L ¹ and said formula (Ar-3) represents a polymerizable group indicates.

In addition, in the said Formula (1-2), Ar is the same as what was demonstrated as Ar in the above-mentioned Formula (1).

<Carboxylic acid compound>

As a carboxyl compound represented by said Formula (1-1), the carboxylic acid compound (1)-(26) shown to following Table 12 and Table 13 is mentioned.

In addition, in the structures of the carboxylic acid compound (2) in Table 12 and the carboxylic acid compound (15) in Table 13, the groups adjacent to the acryloyloxy group and the methacryloyl group, respectively, are propylene groups (methyl groups substituted with ethylene groups). group), and a mixture of positional isomers in which the positions of the methyl groups differ.

[Table 12]

[Table 13]

<Phenolic compound>

The phenolic compound represented by said Formula (1-2) is 2 or more types of phenolic compounds which satisfy|fill any one of the following conditions 6 - condition 10.

(Conditions 6 to 10)

Condition 6: Two or more types of phenolic compounds all have an aromatic ring represented by the formula (Ar-1) as Ar in the formula (1-2), and Z ¹ , Z in the formula (Ar-1) Only any one or more of ² and Y ¹ is a different compound.

Condition 7: Two or more types of phenolic compounds all have an aromatic ring represented by the formula (Ar-2) as Ar in the formula (1-2), and each other, Z ¹ , Z in the formula (Ar-2) Only at least one of ² and X is a different compound.

Condition 8: Two or more types of phenolic compounds all have an aromatic ring represented by the formula (Ar-3) as Ar in the formula (1-2), and Z ¹ , Z in the formula (Ar-3) Only any one or more of ² , SP ³ , SP ⁴ , L ³ and L ⁴ is a different compound.

Condition 9: Two or more types of phenolic compounds all have an aromatic ring represented by the formula (Ar-4) as Ar in the formula (1-2), and Z ¹ , Z in the formula (Ar-4) Only any one or more of ² , Z ³ , Ax and Ay is a different compound.

Condition 10: Two or more types of phenolic compounds all have an aromatic ring represented by the formula (Ar-5) as Ar in the formula (1-2), and Z ¹ , Z in the formula (Ar-5) Only any one or more of ² , Z ³ , Ax and Ay is a different compound.

Here, regarding condition 6, "two or more types of phenolic compounds all have an aromatic ring represented by said Formula (Ar-1) as Ar in said Formula (1-2)" means two types of reacting with a carboxylic acid compound. All of the above phenol compounds have an aromatic ring represented by the formula (Ar-1) as Ar in the formula (1-2), for example, as Ar in the formula (1-2), the formula (Ar- It is intended to exclude two types of phenolic compounds comprising a phenol compound having an aromatic ring represented by 1) and a phenol compound having an aromatic ring represented by the formula (Ar-2) as Ar in the formula (1-2). .

In addition, regarding condition 6, "a compound differing from each other only in at least one of Z ¹ , Z ² and Y ¹ in the above formula (Ar-1)” means that the carboxylic acid compound and two or more types of phenolic compounds reacted with each other are Any one or more of Z ¹ , Z ² , and Y ¹ in the formula (Ar-1) is different, and the other structures in the formula (Ar-1) are not different.

In addition, the above-mentioned analysis is the same also in the analysis in other conditions.

As a phenol compound represented by the said Formula (1-2), the compound which substituted K in each compound of Tables 1-4 mentioned above with a hydroxyl group is mentioned, for example.

<Reaction conditions>

Reaction conditions between the carboxylic acid compound represented by the formula (1-1) and two or more phenolic compounds represented by the formula (1-2) and satisfying any one of the following conditions 6 to 10 are not particularly limited. In addition, conventionally known reaction conditions for esterification can be appropriately employed.

For example, the reaction temperature is preferably performed at -10 to 150°C, more preferably at -5 to 120°C, and still more preferably at -5 to 100°C.

Moreover, as for reaction time, it is preferable that it is performed for 10 minutes - 24 hours, It is more preferable that it is performed for 20 minutes - 10 hours, It is more preferable that it is performed for 30 minutes - 8 hours.

[Crystallization process]

The crystallization step included in the method for producing a mixed crystal of the present invention is a step of crystallizing the mixed product obtained in the above reaction step to obtain the mixed crystal of the present invention described above.

The crystallization method in the above crystallization step is not particularly limited, and a conventionally known crystallization method (for example, a purification method by recrystallization, etc.) can be appropriately employed. For example, in a solution in which a mixed product is dissolved On the other hand, a method of lowering the temperature in the system, a method of adding a poor solvent, a method of volatilizing the solvent, a method of combining these, and the like can be employed.

[Polymerizable liquid crystal composition]

The polymerizable liquid crystal composition of the present invention is a composition containing the mixed crystal of the present invention described above.

[Other Polymerizable Compounds]

The polymerizable liquid crystal composition of the present invention may contain other polymerizable compounds having one or more polymerizable groups other than the mixed crystal of the present invention as long as solubility is not impaired.

Here, the polymeric group which another polymeric compound has is not specifically limited, For example, an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned. Especially, what has an acryloyl group and a methacryloyl group is preferable.

As another polymeric compound, it is preferable that it is another polymeric compound which has 1 to 4 polymerizable groups from the reason that wet-heat durability of the optically anisotropic film|membrane formed improves more, It is another polymeric compound which has two polymerizable groups more preferably.

As other polymerizable compounds, the compounds described in paragraphs [0073] to [0074] of Japanese Patent Application Laid-Open No. 2016-053709 are exemplified.

Moreover, as another polymeric compound, the compound represented by Formula (M1), (M2), (M3) described in paragraphs [0030] to [0033] of Unexamined-Japanese-Patent No. 2014-077068 is mentioned, More specifically, , specific examples described in paragraphs [0046] to [0055] of the same publication can be given.

Moreover, as another polymeric compound, the thing of the structure of Formula (1) - (3) described in Unexamined-Japanese-Patent No. 2014-198814 can also be used preferably, More specifically, [0020] - [0035 of the same publication ], [0042] to [0050], and [0056] to [0057].

The content in the case of containing such other polymerizable compounds is preferably less than 60 mass %, and 50 mass % or less with respect to the total mass containing the above-mentioned polymerizable liquid crystal compound (I) and polymerizable compound (II). It is more preferable, and it is still more preferable that it is 2-40 mass %.

[Polymerization Initiator]

It is preferable that the polymeric liquid crystal composition of this invention contains the polymerization initiator.

It is preferable that the polymerization initiator to be used is a photoinitiator which can start a polymerization reaction by ultraviolet irradiation.

Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Patent Publication Nos. 2367661 and 2367670), acyl ether (described in US Patent Publication No. 2448828), α-hydrocarbon-substituted aromatic acyl, for example. A rhoin compound (described in U.S. Patent Publication No. 2722512), a polynuclear quinone compound (described in each specification of U.S. Patent Publication Nos. 3046127 and 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (US Patent) Publication No. 3549367), acridine and phenazine compounds (described in Japanese Patent Application Laid-Open No. 60-105667, US Patent No. 4239850) and oxadiazole compounds (described in U.S. Patent No. 4212970), acylphos and fin oxide compounds (described in Japanese Patent Application Laid-Open No. 63-040799, Japanese Unexamined Patent Publication No. Hei 5-029234, Japanese Unexamined Patent Publication No. 10-095788, and Japanese Unexamined Patent Publication No. Hei 10-029997). .

Further, in the present invention, it is also preferable that the polymerization initiator is an oxime-type polymerization initiator, and specific examples thereof include the initiators described in paragraphs [0049] to [0052] of International Publication No. 2017/170443.

〔menstruum〕

It is preferable that the polymeric liquid crystal composition of this invention contains a solvent from viewpoints, such as workability|operativity for forming an optically anisotropic film|membrane.

Specific examples of the solvent include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (eg, dioxane, tetrahydro furan), aliphatic hydrocarbons (eg, hexane, etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatic hydrocarbons (eg, toluene, xylene, trimethyl) benzene, etc.), halogenated carbons (eg, dichloromethane, dichloroethane, dichlorobenzene, 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.), cellosolve acetates, sulfoxide and amides (eg, dimethyl sulfoxide, etc.) and amides (eg, dimethylformamide, dimethylacetamide, etc.), and these may be used alone, or two or more You may use it together.

[leveling agent]

It is preferable that the polymeric liquid crystal composition of this invention maintains the surface of an optically anisotropic film|membrane smooth and contains a leveling agent from a viewpoint of making orientation control easy.

As such a leveling agent, since the leveling effect with respect to addition amount is high, it is preferable that it is a fluorine-type leveling agent or a silicon-type leveling agent, and it is more preferable that it is a fluorine-type leveling agent from a viewpoint that it is hard to produce exudation (bloom, bleed).

As a leveling agent, specifically, for example, the compound described in the description of paragraphs [0079] to [0102] of Unexamined-Japanese-Patent No. 2007-069471, General formula (I) described in Unexamined-Japanese-Patent No. 2013-047204 is represented. Compounds (especially compounds described in paragraphs [0020] to [0032]), compounds represented by general formula (I) described in Japanese Patent Application Laid-Open No. 2012-211306 (compounds particularly described in paragraphs [0022] to [0029]), Japan Liquid crystal alignment promoter represented by the general formula (I) described in Japanese Patent Application Laid-Open No. 2002-129162 (especially the compounds described in paragraphs [0076] to [0078] and [0082] to [0084]), Japanese Patent Application Laid-Open No. 2005-099248 and compounds represented by the general formulas (I), (II) and (III) described in (especially those described in paragraphs [0092] to [0096]) and the like. Moreover, you may combine the function as an orientation control agent mentioned later.

[Orientation controlling agent]

The polymerizable liquid crystal composition of the present invention can contain an orientation controlling agent as needed.

With the orientation controlling agent, in addition to homogeneous orientation, various orientation states such as homeotropic orientation (vertical orientation), oblique orientation, hybrid orientation, and cholesteric orientation can be formed, and a specific orientation state can be made more uniform and more uniform. It can be realized by precise control.

As an orientation control agent which accelerates|stimulates a homogeneous orientation, a low molecular orientation control agent and a polymeric orientation control agent can be used, for example.

As a low molecular orientation control agent, For example, Paragraphs [0009] - [0083] of Unexamined-Japanese-Patent No. 2002-020363, Paragraphs [0111] - [0120] of Unexamined-Japanese-Patent No. 2006-106662, and Unexamined-Japanese-Patent No. 2012, for example. Reference may be made to the description of paragraphs [0021] to [0029] of the -211306 publication, the contents of which are incorporated herein by reference.

In addition, as a polymer orientation control agent, for example, paragraphs [0021] to [0057] of Japanese Patent Application Laid-Open No. 2004-198511, and paragraphs [0121] to [0167] of Japanese Patent Application Laid-Open No. 2006-106662 can be referred to. , the contents of which are incorporated herein by reference.

Moreover, as an orientation controlling agent which forms or accelerates|stimulates a homeotropic orientation, a boronic acid compound and an onium salt compound are mentioned, for example, Specifically, Unexamined-Japanese-Patent No. 2008-225281 [0023] - [0032] Paragraph, [0052] to [0058] of Japanese Patent Application Laid-Open No. 2012-208397, [0024] to [0055] of Japanese Unexamined Patent Publication No. 2008-026730, [0043] to [0055] of Japanese Unexamined Patent Publication No. 2016-193869 Reference may be made to the compounds described in paragraphs, etc., the contents of which are incorporated herein by reference.

On the other hand, the cholesteric orientation can be realized by adding a chiral agent to the polymerizable composition of the present invention, and the turning direction of the cholesteric orientation can be controlled by the direction of the chirality. In addition, the pitch of the cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.

It is preferable that it is 0.01-10 mass % with respect to the total solid mass in a polymeric liquid crystal composition, and, as for content in the case of containing of an orientation control agent, it is more preferable that it is 0.05-5 mass %. If the content is within this range, it is possible to obtain a uniform and highly transparent optically anisotropic film without precipitation, phase separation, orientation defects, or the like while realizing a desired orientation state.

These orientation controlling agents can also provide a polymerizable functional group, particularly a polymerizable functional group capable of polymerization with the polymerizable liquid crystal compound (mixed crystal) constituting the polymerizable liquid crystal composition of the present invention.

[Other ingredients]

The polymerizable liquid crystal composition of the present invention may contain components other than the above-mentioned components, for example, liquid crystal compounds other than the above-mentioned polymerizable liquid crystal compound, surfactant, tilt angle controller, alignment aid, and plasticizer. , and a crosslinking agent.

[Optical Anisotropic Film]

The optically anisotropic film of this invention is an optically anisotropic film obtained by superposing|polymerizing the polymeric liquid crystal composition of this invention mentioned above.

As a formation method of an optically anisotropic film, after setting it as a desired orientation state using the polymeric liquid crystal composition of this invention mentioned above, for example, the method of fixing by superposition|polymerization, etc. are mentioned.

Although polymerization conditions are not specifically limited here, In superposition|polymerization by light irradiation, it is preferable to use an ultraviolet-ray. The irradiation amount, 10mJ/cm ² ~ 50J/cm ² It is preferable that it is, 20mJ/cm ² ~ 5J/cm ² It is more preferable, 30mJ/cm ² ~ 3J/cm ² It is more preferable, 50 ~ 1000mJ It is particularly preferred that it is /cm ² . Moreover, in order to accelerate|stimulate a polymerization reaction, you may carry out on heating conditions.

In addition, in this invention, an optically anisotropic film can be formed on the arbitrary support body in the optical film of this invention mentioned later, or on the polarizer in the polarizing plate of this invention mentioned later.

It is preferable that the optically anisotropic film|membrane of this invention satisfy|fills following formula (2).

0.50<Re(450)/Re(550)<1.00 … (2)

Here, in the formula (2), Re(450) represents in-plane retardation at a wavelength of 450 nm of the optically anisotropic film, and Re(550) represents in-plane retardation at a wavelength of 550 nm of the optically anisotropic film. In addition, in this specification, when the measurement wavelength of retardation is not specified, let the measurement wavelength be 550 nm.

In addition, the value of in-plane retardation and the retardation of thickness direction says the value measured using the light of a measurement wavelength using AxoScan OPMF-1 (made by Optoscience Corporation).

Specifically, by inputting the average refractive index ((Nx+Ny+Nz)/3) and the film thickness (d(μm)) in AxoScan OPMF-1,

Slow axis direction (°)

Re(λ)=R0(λ)

Rth(λ)=((nx+ny)/2-nz)×d

is calculated

In addition, R0(λ) is expressed as a numerical value calculated by AxoScan OPMF-1, and means Re(λ).

It is preferable that it is a positive A plate or a positive C plate, and, as for the optically anisotropic film|membrane of this invention, it is more preferable that it is a positive A plate.

Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.

When the refractive index in the direction of the slow axis in the film plane (the direction in which the in-plane refractive index is maximized) is nx, the refractive index in the direction orthogonal to the in-plane slow axis and in-plane is ny, and the refractive index in the thickness direction is nz. is one that satisfies the relationship of formula (A1), and a positive C plate satisfies the relationship of formula (C1). In addition, in the positive A plate, Rth shows a positive value, and in the positive C plate, Rth shows a negative value.

Formula (A1) nx>ny≒nz

Formula (C1) nz>nx≒ny

In addition, the above-mentioned "≒" 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, in a positive A plate, for example, (ny-nz) x d (provided that d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in "ny≒nz", and (nx-nz)xd is included in "nx≒nz" also when it is -10-10 nm, Preferably -5-5 nm. In the case of a positive C plate, for example, (nx-ny)×d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, also included in “nx≒ny” .

When the optically anisotropic film of the present invention is a positive A plate, from the viewpoint of functioning as a λ/4 plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, more preferably 130 to 150 nm It is preferable, and it is especially preferable that it is 130-140 nm.

Here, "λ/4 plate" is a plate having a λ/4 function, specifically, a plate having a function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). .

[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, when these drawings do not require special distinction, abbreviated as "Fig. 1") are schematic cross-sectional views each showing an example of the optical film of the present invention.

In addition, FIG. 1 is a schematic diagram, and the relationship of the thickness of each layer, a positional relationship, etc. do not necessarily correspond with an actual thing, and the support body, orientation film, and hard-coat layer shown in FIG. 1 are all arbitrary structural members.

The optical film 10 shown in FIG. 1 has the support body 16, the orientation film 14, and the optically anisotropic film 12 in this order.

Moreover, as shown in FIG. 1B, the optical film 10 may have the hard-coat layer 18 on the side opposite to the side in which the orientation film 14 of the support body 16 was provided, as shown in FIG. 1C. , you may have the hard coat layer 18 on the side opposite to the side on which the orientation film 14 of the optically anisotropic film 12 was provided.

Hereinafter, various members used for the optical film of this invention are demonstrated in detail.

[Optical Anisotropic Film]

The optically anisotropic film which the optical film of this invention has is the optically anisotropic film of this invention mentioned above.

In the optical film of this invention, although it does not specifically limit about the thickness of the said optically anisotropic film, It is preferable that it is 0.1-10 micrometers, and it is more preferable that it is 0.5-5 micrometers.

[Support]

As mentioned above, the optical film of this invention may have a support body as a base material for forming an optically anisotropic film|membrane.

It is preferable that such a support body is transparent, and, specifically, it is preferable that the light transmittance is 80 % or more.

As such a support body, a glass substrate and a polymer film are mentioned, for example, As a material of a polymer film, Cellulose polymer; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; Thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene/propylene copolymer; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamide; imide-based polymers; sulfone-based polymers; polyether sulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymer; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymer; arylate-based polymers; polyoxymethylene-based polymers; An epoxy-type polymer or the polymer which mixed these polymers is mentioned.

Moreover, the aspect which serves also as such a support body may be sufficient as the polarizer mentioned later.

Although it does not specifically limit about the thickness of the said support body in this invention, It is preferable that it is 5-60 micrometers, and it is more preferable that it is 5-30 micrometers.

[Orientation film]

When the optical film of this invention has the arbitrary support bodies mentioned above, it is preferable to have an orientation film between a support body and an optically anisotropic film|membrane. Moreover, the aspect which the above-mentioned support body also serves as an orientation film may be sufficient.

An alignment film generally has a polymer as a main component. As a polymer material for alignment films, there are descriptions in many documents, and many commercial items can be obtained.

As for the polymer material used in this invention, polyvinyl alcohol or a polyimide, and its derivative(s) are preferable. In particular, modified or unmodified polyvinyl alcohol is preferable.

Regarding the alignment film usable in the present invention, for example, the alignment film described in International Publication No. 01/088574, page 43, line 24 to page 49, line 8; Modified polyvinyl alcohol described in paragraphs [0071] to [0095] of Japanese Patent Publication No. 3907735; The liquid crystal aligning film etc. which are formed with the liquid crystal aligning agent of Unexamined-Japanese-Patent No. 2012-155308 are mentioned.

In this invention, it is also preferable to use a photo-alignment film as an alignment film from the reason that it becomes possible to prevent in-plane deterioration by not contacting the alignment film surface at the time of formation of an alignment film.

Although it does not specifically limit as a photo-alignment film, Polymer materials, such as a polyamide compound and a polyimide compound, described in paragraphs [0024] - [0043] of International Publication No. 2005/096041; A liquid crystal aligning film formed by the liquid crystal aligning agent which has a photo-alignment group of Unexamined-Japanese-Patent No. 2012-155308; The brand name LPP-JP265CP by Rolic Technologies, etc. can be used.

Further, in the present invention, the thickness of the alignment film is not particularly limited, but from the viewpoint of alleviating surface irregularities that may exist in the support to form an optically anisotropic film of a uniform film thickness, it is preferably 0.01 to 10 μm, and 0.01 to It is more preferable that it is 1 micrometer, and it is still more preferable that it is 0.01-0.5 micrometer.

[hard coat layer]

It is preferable that the optical film of this invention has a hard-coat layer in order to provide the physical strength of a film. Specifically, you may have a hard-coat layer on the side opposite to the side on which the orientation film of the support body was provided (refer FIG. 1B), and you may have a hard-coat layer on the side opposite to the side on which the orientation film of an optically anisotropic film was provided (FIG. 1c). Reference).

As a hard-coat layer, the thing of Paragraph [0190] - [0196] of Unexamined-Japanese-Patent No. 2009-098658 can be used.

[Other optically anisotropic films]

The optical film of the present invention may have another optically anisotropic film separately from 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 another optically anisotropic film is an optically anisotropic film obtained by using the other polymerizable compound (especially the liquid crystal compound) described above without blending any one of the polymerizable liquid crystal compound (I) and the polymerizable compound (II). If it is, it will not specifically limit.

Here, in general, the liquid crystal compound can be classified into a rod-shaped type and a disk-shaped type from the shape thereof. Also, there are low-molecular and high-molecular types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (Physical and Phase Change Dynamics of Polymers, Masaoser Doi, p. 2, Shoten Iwanami, 1992). Although any liquid crystal compound may be used in this invention, 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 types of rod-shaped liquid crystal compounds, two or more types 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 immobilization of the above-mentioned liquid crystal compound, it is more preferable to use a rod-shaped liquid crystal compound having a polymerizable group or a disk-shaped liquid crystal compound, and it is more preferable that the liquid crystal compound has two or more polymerizable groups in one molecule. When the liquid crystal compound is a mixture of two or more types, it is preferable that at least one type 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 paragraphs [0026] to [0098] of Japanese Patent Application Laid-Open No. 11-513019 or 2005-289980 can be preferably used, and as the discotic liquid crystal compound, , For example, paragraphs [0020] to [0067] of Japanese Patent Application Laid-Open No. 2007-108732 or paragraphs [0013] to [0108] of Japanese Patent Application Laid-Open No. 2010-244038 can be preferably used, but are not limited thereto does not

[Ultraviolet absorber]

It is preferable that the optical film of this invention considers the influence of external light (especially ultraviolet-ray), and contains an ultraviolet-ray (UV) absorber.

The ultraviolet absorber may be contained in the optically anisotropic film of the present invention, or may be contained in members other than the optically anisotropic film constituting the optical film of the present invention. As a member other than an optically anisotropic film|membrane, a support body is mentioned suitably, for example.

As the ultraviolet absorber, any conventionally known ultraviolet absorber capable of exhibiting ultraviolet absorbency can be used. Among such ultraviolet absorbers, it is preferable to use a benzotriazole-type or hydroxyphenyltriazine-type ultraviolet absorber from a viewpoint of obtaining the ultraviolet-absorbing ability (ultraviolet-ray-cutting ability) used in an image display device with high ultraviolet absorption.

Moreover, in order to widen the absorption width of an ultraviolet-ray, 2 or more types of ultraviolet absorbers from which a maximum absorption wavelength differs can be used together.

As the ultraviolet absorber, specifically, for example, the compound described in paragraphs [0258] to [0259] of Japanese Patent Application Laid-Open No. 2012-018395, and the compound described in paragraphs [0055] to [0105] of Japanese Patent Application Laid-Open No. 2007-072163 and the like.

Moreover, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 (all made by BASF) etc. can be used as a commercial item.

[Polarizer]

The polarizing plate of this invention has the optical film of this invention mentioned above, and a polarizer.

Further, the polarizing plate of the present invention can be used as a circularly polarizing plate when the optically anisotropic film of the present invention described above is a λ/4 plate (positive A plate).

Further, in the polarizing plate of the present invention, when the optically anisotropic film of the present invention described above is a λ/4 plate (positive A plate), the angle between the slow axis of the λ/4 plate and the absorption axis of the polarizer to be described later is 30 to 60° It is preferable that it is, It is more preferable that it is 40-50 degrees, It is more preferable that it is 42-48 degrees, It is especially preferable that it is 45 degrees.

Here, the “slow axis” of the λ/4 plate means the direction in which the refractive index is maximized in the plane of the λ/4 plate, and the “absorption axis” of the polarizer means the direction with the highest absorbance.

[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 polarizer and reflection type polarizer can be used.

As the absorption-type polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer are used. The iodine-based polarizer and the dye-based polarizer include an application-type polarizer and a stretch-type polarizer, and both can be applied. A polarizer produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching is preferable.

Moreover, as a method of obtaining a polarizer by extending|stretching and dyeing in the state of the laminated|multilayer film which formed the polyvinyl alcohol layer on the base material, Japanese Patent Publication No. 5048120, Japanese Patent No. 5143918, Japanese Patent Publication Nos. 4691205, Japanese Patent Publication No. 4751481 and Japanese Patent Publication No. 4751486 are mentioned, and the well-known technique regarding these polarizers can also be used preferably.

As the reflective polarizer, a polarizer in which thin films having different birefringence are laminated, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wave plate are combined, and the like are used.

Among them, at least one selected from the group consisting of 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 view of better adhesion. It is preferable that it is a polarizer containing dog).

In this invention, although the thickness of a polarizer is not specifically limited, It is preferable that they are 3 micrometers - 60 micrometers, It is more preferable that they are 5 micrometers - 30 micrometers, It is more preferable that they are 5 micrometers - 15 micrometers.

[Adhesive layer]

As for the polarizing plate of this invention, the adhesive layer may be arrange|positioned between the optically anisotropic film in the optical film of this invention, and a polarizer.

As an adhesive layer used for lamination|stacking of an optically anisotropic film and a polarizer, the ratio (tanδ=G"/G') of storage elastic modulus G' and loss elastic modulus G" measured by a dynamic viscoelasticity measuring apparatus is 0.001-1.5, for example. A substance is shown, and what is called a pressure-sensitive adhesive, a substance which creeps easily, etc. are contained. As an adhesive which can be used for this invention, although polyvinyl alcohol type adhesive is mentioned, for example, It is not limited to this.

[Image display device]

The image display apparatus of this invention is an image display apparatus which has the optical film of this invention or the polarizing plate of this invention.

The display element used for the image display apparatus of this invention is not specifically limited, For example, a liquid crystal cell, an organic electroluminescent (it abbreviates as "EL") display panel, a plasma display panel, etc. are mentioned, for example.

Among these, it is preferable that they are a liquid crystal cell and an organic electroluminescent display panel, and it is more preferable that they are a liquid crystal cell. That is, as an image display device of this invention, it is preferable that it is a liquid crystal display device using a liquid crystal cell as a display element, and it is preferable that it is an organic electroluminescence display using an organic electroluminescent display panel as a display element, and it is more preferable that it is a liquid crystal display device.

[Liquid crystal display device]

The liquid crystal display device which is an example of the image display device of this invention is a liquid crystal display device which has the polarizing plate of this invention mentioned above, and a liquid crystal cell.

Further, 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 it is more preferable to use the polarizing plate of the present invention as the polarizing plate on the front side and the rear side. .

Below, the liquid crystal cell which comprises a liquid crystal display device is demonstrated in detail.

<Liquid crystal cell>

The liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, or TN (Twisted Nematic) mode, but limited to these it is not

In the liquid crystal cell of TN mode, the rod-shaped liquid crystalline molecules are substantially horizontally aligned at the time of no voltage application, and are twisted at 60-120 degrees. The liquid crystal cell of TN mode is most used as a color TFT liquid crystal display device, and there exists description in many documents.

In the liquid crystal cell of the VA mode, rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied. In the liquid crystal cell of VA mode, (1) the liquid crystal cell of VA mode in the narrow sense in which rod-shaped liquid crystalline molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when voltage is applied (Japanese Patent Application Laid-Open No. In addition to (2) described in No. 2-176625), (2) a liquid crystal cell (SID97, Digest of tech. 1997) 845), (3) liquid crystal cell in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically aligned when no voltage is applied, and torsional multi-domain alignment is applied when voltage is applied (Preview of the Japan Liquid Crystal Conference 58-59 (1998)) and (4) liquid crystal cells in SURVIVAL mode (presented in LCD International 98). Moreover, any of PVA(Patterned Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA(Polymer-Sustained Alignment) may be sufficient. About the details of these modes, there exists a detailed description in Unexamined-Japanese-Patent No. 2006-215326 and Unexamined-Japanese-Patent No. 2008-538819.

In the liquid crystal cell of the IPS mode, rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and when an electric field parallel to the substrate surface is applied, the liquid crystal molecules respond in a planar manner. In the IPS mode, black display is performed in a state in which no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other. A method for improving a viewing angle by reducing leakage light during black display in an oblique direction by using an optical compensatory sheet is disclosed in Japanese Patent Laid-Open Nos. 10-054982 and Hei 11-202323 It is disclosed in Patent Publication No. 9-292522, Japanese Unexamined Patent Publication No. Hei 11-133408, Japanese Unexamined Patent Publication No. 11-305217, and Japanese Unexamined Patent Publication No. Hei 10-307291.

[Organic EL display device]

As an organic EL display device that is an example of the image display device of the present invention, for example, from the viewer side, a λ/4 plate (positive A plate) made of a polarizer, an optically anisotropic film of the present invention, and an organic EL display panel are formed. The aspect having in order is mentioned suitably.

Moreover, an organic electroluminescent display panel is a display panel comprised using the organic electroluminescent element formed by pinching|interposing an organic light emitting layer (organic electroluminescence layer) between electrodes (between a cathode and an anode). The structure in particular of an organic electroluminescent display panel is not restrict|limited, A well-known structure is employ|adopted.

Example

The present invention will be described in more detail below based on examples. Materials, usage amounts, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.

[Synthesis of Compound (I-1a)]

The synthesis of compound (I-1a) represented by the following formula (I-1a) refers to the method described in Justus Liebigs Annalen der Chemie, 726, 103-109 (1969), malononitrile, carbon disulfide and benzoquinone synthesized with

[Formula 11]

[Synthesis of Compound (I-2a)]

The compound (I-2a) represented by the following formula (I-2a) was synthesized in the same manner as in the compound (I-1a) except that benzoquinone was changed to 2-methylbenzoquinone.

[Formula 12]

[Synthesis of compound (I-3a)]

The compound (I-3a) represented by the following formula (I-3a) was synthesized by the method described in the paragraph (Example 16) of Japanese Patent Application Laid-Open No. 2016-081035 (Example 16).

[Formula 13]

[Synthesis of compound (I-4a)]

The compound (I-4a) represented by the following formula (I-4a) was synthesized in the same manner as in the compound (I-1a) except that benzoquinone was changed to 2-t-butylbenzoquinone.

[Formula 14]

[Synthesis of compound (I-6a)]

The compound (I-6a) represented by the following formula (I-6a) was synthesized by the method described in paragraphs [0180] to [0182] (Example 18) of Japanese Patent Application Laid-Open No. 2016-081035.

[Formula 15]

[Synthesis of compound (I-7a)]

The compound (I-7a) represented by the following formula (I-7a) was synthesized by the method described in paragraphs [0193] to [0194] (Example 22) of Japanese Patent Application Laid-Open No. 2016-081035.

[Formula 16]

[Synthesis of carboxylic acid compound (4)]

<Synthesis of dicarboxylic acid compound (4a)>

63 g (0.24 mol) of dimethyl 4,4-biphenyldicarboxylic acid was added to 500 mL of acetic acid, and 6.3 g of a palladium carbon catalyst (wet) was added, followed by catalytic hydrogenation at 130°C and 2 MPa in an autoclave.

After completion of the reaction, the catalyst was removed by filtration after cooling to room temperature. Acetic acid was distilled off under reduced pressure, and then ethyl acetate and aqueous sodium hydrogen carbonate solution were added, stirred, and liquid-separated to remove the aqueous layer, and the organic layer was washed with 10% brine. Sodium sulfate was added to this solution, dried, and the solvent was concentrated to obtain dimethyl 4,4'-dicyclohexanedicarboxylic acid (65 g).

No further purification was performed, and then, 4,4'-dicyclohexanedicarboxylic acid dimethyl (65 g), potassium hydroxide pellets (purity 90%) 43.2 g, cumene 650 mL, and polyethylene glycol (PEG2000) 5 mL were mixed. Then, a Dean Stark tube was attached and the mixture was heated and stirred at 100°C. After distilling off methanol, heating and refluxing was continued for 10 hours, making the outside temperature 160 degreeC, and distilling off a solvent. After completion of the reaction, cooling and adding 650 mL of ethanol to the reaction solution, the precipitated potassium salt was collected by filtration.

Next, this potassium salt was melt|dissolved in 650 ml of water, and concentrated hydrochloric acid was added under ice-cooling until the pH of the system became 3, the precipitated carboxylic acid was collected by filtration, and the crude body was collect|recovered.

The recovered crude body was suspended in 250 mL of acetone and stirred for 30 minutes, and then crystals were collected by filtration. In this way, 44.6 g (yield 76%) of a crystal of dicyclohexanedicarboxylic acid (4a) was obtained. HPLC purity (210 nm) was 92.2%.

<Synthesis of carboxylic acid compound (4)>

[Formula 17]

As shown in the above scheme, 10.0 g (39.3 mmol) of compound (4a), 50 mL of N,N-dimethylacetamide (DMAc), 8.0 ml (78.6 mmol) of triethylamine, and 2,6-di-t- 433 mg of butyl-4-methylphenol was mixed at room temperature (23°C).

9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate was added to the mixture, and it stirred at 100 degreeC for 5 hours. After cooling to room temperature, 30 ml of 1N hydrochloric acid and 50 ml of toluene were added, followed by stirring at 40° C., followed by liquid separation. The organic layer was washed sequentially with a 5% aqueous sodium hydrogen carbonate solution, a 1% aqueous sodium hydrogen carbonate solution, and a 1% aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. The residue was recrystallized from ethanol/toluene/n-hexane to obtain 4.78 g (12.6 mmol) of carboxylic acid compound (4) (yield 32%).

Moreover, all the aqueous layers at the time of liquid separation were collected, hydrochloric acid was dripped until the liquid became acidic, unreacted compound (4a) was precipitated, and it filtrated. This crude product was added to 10 mL of acetone and filtered after stirring for 30 minutes to recover 1.6 g of compound (4a) (recovery yield: 16%).

1H ^- NMR (Nuclear Magnetic Resonance) of the obtained carboxylic acid compound (4) is shown below.

¹ H-NMR (solvent: CDCl ₃ )δ (ppm): 1.0-1.1 (m, 6H), 1.3-1.5 (m, 4H), 1.7-1.8 (m, 8H), 2.0-2.1 (m, 4H) , 2.2 (tt, 1H), 2.2 (tt, 1H), 4.1 (t, 2H), 4.2 (t, 2H), 5.8 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H)

[Synthesis of polymerizable liquid crystal compound (I-1-4)]

[Formula 18]

As shown in the above scheme, 2.53 g (6.65 mmol) of carboxylic acid compound (4), 12.6 mL of ethyl acetate (EA), 3.80 mL of N,N-dimethylacetamide (DMAc), and 2,6-di-t- 33 mg of butyl-4-methylphenol was mixed at room temperature, and internal temperature was cooled to 5 degreeC. To the mixture, 0.58 ml (7.98 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, a solution (12.6 ml) of 0.75 g (3.02 mmol) of compound (I-1a) in tetrahydrofuran (THF) (12.6 ml) was added. After dripping 2.90 ml (16.6 mmol) of N,N- diisopropylethylamine (DIPEA), it stirred at room temperature for 2 hours. After stirring, 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. By recrystallizing using tetrahydrofuran (THF) and isopropanol, 2.79 g (2.87 mmol) of a polymerizable liquid crystal compound (I-1-4) was obtained (yield 95%).

¹ H-NMR of the obtained polymerizable liquid crystal compound (I-1-4) is shown below.

¹ H-NMR (solvent: CDCl ₃ )δ (ppm): 1.0-1.2 (m, 12H), 1.3-1.5 (m, 4H), 1.5-1.6 (m, 4H), 1.7-1.8 (m, 8H) , 1.8-2.0(m, 8H), 2.0-2.1(m, 4H), 2.1-2.2(m, 4H), 2.2(tt, 2H), 2.5(tt, 2H), 4.1(t, 4H), 4.2 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.3 (s, 2H)

[Synthesis of polymerizable liquid crystal compound (I-2-4), etc.]

In place of compound (I-1a), compound (I-2a), compound (I-3a), compound (I-4a), compound (I-6a) and compound (I-7a) were respectively changed to, Polymerizable liquid crystal compound (I-2-4), polymerizable liquid crystal compound (I-3-4), polymerizable liquid crystal compound represented by the following formulas in the same manner as in the synthesis method of polymerizable liquid crystal compound (I-1-4) (I-4-4), a polymerizable liquid crystal compound (I-6-4), and a polymerizable liquid crystal compound (I-7-4) were synthesized.

[Formula 19]

[Example 1]

[Synthesis of mixed crystal (M-1-1)]

0.5 g of a polymerizable liquid crystal compound (I-2-4) and 1.5 g of a polymerizable liquid crystal compound (I-4-4) were dissolved in 5 mL of chloroform.

Next, 20 mL of methanol is slowly added dropwise to this solution, and the precipitated solid is isolated by filtration and blow-dried at 40° C. to obtain a polymerizable liquid crystal compound (I-2-4) and a polymerizable liquid crystal compound (I-4). 1.8 g of a mixed crystal (M-1-1) of -4) was obtained (recovery rate: 90%).

The obtained mixed crystal (M-1-1) had a phase transition temperature of "C 136 N 230 I". In addition, this notation is a notation indicating that the phase transition temperature from the crystalline state to the nematic phase is 136°C, and the phase transition temperature from the nematic phase to the isotropic liquid is 230°C.

Moreover, the peak temperature by DSC of the obtained mixed crystal (M-1-1) was 136 degreeC.

Here, since the peak temperature by DSC of the polymerizable liquid crystal compound (I-2-4) alone is 228°C, and the peak temperature by DSC of the polymerizable liquid crystal compound (I-4-4) alone is 137°C, the obtained It was found that the mixed crystal (M-1-1) was a different crystal from the polymerizable liquid crystal compound (I-2-4) and the polymerizable liquid crystal compound (I-4-4).

Further, X-ray diffraction measurements of the obtained mixed crystal (M-1-1), the polymerizable liquid crystal compound (I-2-4) and the polymerizable liquid crystal compound (I-4-4) were performed, respectively, in FIGS. 2A to 2C . The spectrum shown in was obtained. From this spectrum, it can be seen that the obtained mixed crystal (M-1-1) exhibits a diffraction pattern different from that of the polymerizable liquid crystal compound (I-2-4) and the polymerizable liquid crystal compound (I-4-4), It was found that the crystal structure was changed.

[Examples 2-4]

In the same manner as for mixed crystal (M-1-1), except that the mass ratio of the polymerizable liquid crystal compound (I-2-4) to the polymerizable liquid crystal compound (I-4-4) was changed to the value shown in Table 14 below. , mixed crystals (M-1-2) to mixed crystals (M-1-4) were synthesized.

In addition, the DSC peak temperature of the obtained mixed crystal (M-1-2) is 137°C, the DSC peak temperature of the mixed crystal (M-1-3) is 136°C, and that of the mixed crystal (M-1-4) The peak temperature by DSC was 127°C.

[Example 5]

[Synthesis of mixed crystal (M-2-1)]

Dissolve 0.5 g of a polymerizable liquid crystal compound (I-1-4), 0.5 g of a polymerizable liquid crystal compound (I-2-4), and 1.0 g of a polymerizable liquid crystal compound (I-4-4) in 5 mL of chloroform did it

Next, 20 mL of methanol is slowly added dropwise to this solution, and the precipitated solid is isolated by filtration and blow-dried at 40°C, whereby the polymerizable liquid crystal compound (I-1-4) and the polymerizable liquid crystal compound (I-2) -4) and 1.8 g of a mixed crystal (M-2-1) of a polymerizable liquid crystal compound (I-4-4) were obtained (recovery rate: 90%).

The obtained mixed crystal (M-2-1) had a phase transition temperature of "C 128 SA 136-160 N 242 I". In addition, this notation indicates that the phase transition temperature from the crystalline state to the smecking A phase is 128 °C, the phase transition temperature from the smecking A phase to the nematic phase is 136 to 160 °C, and the phase transition temperature from the nematic phase to the isotropic liquid is It is a notation indicating that it is 242°C.

Moreover, the peak temperature by DSC of the obtained mixed crystal (M-2-1) was 126 degreeC.

In addition, the peak temperature by DSC of the polymerizable liquid crystal compound (I-1-4) alone is 139°C, and the peak temperature by DSC of the polymerizable liquid crystal compound (I-2-4) alone is 228°C, Since the peak temperature by DSC of the liquid crystal compound (I-4-4) alone is 137°C, the obtained mixed crystal (M-2-1) is a polymerizable liquid crystal compound (I-1-4), a polymerizable liquid crystal compound (I) -2-4) and the polymerizable liquid crystal compound (I-4-4) were found to have different crystals.

[Examples 6-7]

Except for changing the mass ratio of the polymerizable liquid crystal compound (I-1-4), the polymerizable liquid crystal compound (I-2-4), and the polymerizable liquid crystal compound (I-4-4) to the values shown in Table 14 below, Mixed crystal (M-2-2) and mixed crystal (M-2-3) were synthesized in the same manner as for mixed crystal (M-2-1).

Moreover, the peak temperature by DSC of the obtained mixed crystal (M-2-2) was 123 degreeC, and the peak temperature by DSC of the obtained mixed crystal (M-2-3) was 124 degreeC.

[Examples 8-15]

Each mixed crystal shown in Table 14 was synthesized in the same manner as in Example 1 except that the type of the polymerizable liquid crystal compound and the mass ratio were changed to the values shown in Table 14 below.

[Comparative Example 1]

A liquid crystal mixture in which 1.0 g of the polymerizable liquid crystal compound (I-2-4) and 1.0 g of the polymerizable liquid crystal compound (I-4-4) were mixed was prepared.

[Comparative Example 2]

A liquid crystal mixture obtained by mixing 0.5 g of a polymerizable liquid crystal compound (I-1-4), 0.5 g of a polymerizable liquid crystal compound (I-2-4), and 1.0 g of a polymerizable liquid crystal compound (I-4-4) is prepared. did.

[Comparative Example 3]

A liquid crystal mixture obtained by mixing 0.8 g of a polymerizable liquid crystal compound (I-1-4), 0.6 g of a polymerizable liquid crystal compound (I-2-4), and 0.6 g of a polymerizable liquid crystal compound (I-4-4) is prepared. did.

[solubility]

The mixed crystal synthesized in Examples, the liquid crystal mixture prepared in Comparative Examples, and the polymerizable liquid crystal compound (I-1-4) and the polymerizable liquid crystal compound (I-2-4) synthesized earlier as Reference Examples 1-3 and polymerizable The solubility of liquid crystal compound (I-4-4) was measured by the method shown below. The results are shown in Table 14 below.

First, 50 mg of an object to be measured was weighed in a 1.5 mL sample bottle, and a solvent was added until the solid content became 40 wt% (75 mg). Then, after shaking well by hand at 50 degreeC, and leaving it to stand at room temperature (23 degreeC) for 10 minutes, the solvent was visually observed, and if there was no suspension, it was complete|finished and solubility was judged as 40 mass %.

On the other hand, if there was a dissolved residue, a solvent was added so that the solid content was 35 wt% (+18 mg). Then, after shaking well by hand at 50 degreeC, and leaving it to stand for 10 minutes at room temperature (23 degreeC), the solvent was visually observed, and if it was a state without suspension, it was complete|finished, and solubility was judged as 35 mass %.

Moreover, the solvent was added so that it might become 30 mass % if there was more dissolution residue. The same operation was performed in units of 5 mass %, repeated until it became 5 mass %, and when there was a dissolution residue, it was judged to be less than 5 mass % solubility (<5 mass %), and it was complete|finished. As a solvent for solubility measurement, CPN (cyclopentanone) was used.

A: The solubility with respect to CPN is 30 mass % or more

B: The solubility with respect to CPN is 25 mass % or more and less than 30 mass %

C: The solubility with respect to CPN is 20 mass % or more and less than 25 mass %

D: Solubility to CPN is 10% by mass or more and less than 20% by mass

E: Solubility in CPN is 10% by mass or less

[Table 14]

From the results shown in Table 14, it can be seen that the solubility of the polymerizable liquid crystal composition is improved by using two or more kinds of polymerizable liquid crystal compounds satisfying predetermined conditions and using a mixed crystal formed from these polymerizable liquid crystal compounds. There were (Examples 1-15).

[Example 16]

[Synthesis of mixed crystal (M-I-5)]

[Formula 20]

As shown in the above scheme, 3.35 g (8.80 mmol) of carboxylic acid compound (4), 10 mL of toluene, 0.77 mL of N,N-dimethylformamide (DMF), and 2,6-di-t-butyl-4-methyl 35 mg of phenol was mixed at room temperature, and internal temperature was cooled to 5 degreeC. To the mixture, 0.70 ml (9.60 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, after removing the separated lower layer, 0.40 g (1.60 mmol) of compound (I-1a), 0.73 g (2.40 mmol) of compound (I-4a) in tetrahydrofuran (THF) solution ( 27 ml) was added. After dripping 3.14 ml (18.0 mmol) of N,N- diisopropylethylamine (DIPEA), it stirred at room temperature for 2 hours. After stirring, 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. After washing the organic layer with 10% brine, the solvent was distilled off under reduced pressure. To the concentrate, 30 mL of isopropyl alcohol (IPA) was slowly added dropwise, and the precipitated crude body was collected by filtration. The crude body was suspended in IPA 30mL at 5 degreeC, and it stirred for 30 minutes. Thereafter, the mixture was collected by filtration at 5°C to obtain 3.43 g of mixed crystal (M-1-5) (yield: 85%).

The obtained mixed crystal (M-1-5) was evaluated for solubility by the method described above, and the evaluation result was "A".

[Examples 17 to 21, Reference Examples 4 to 5 and Comparative Example 4]

[Synthesis of Comparative Compound 1]

Comparative compound 1 represented by the following formula was synthesized by the method described in paragraphs [0159] to [0164] of JP-A 2009-242718 (Reference Example 1).

[Formula 21]

[Production of optical film]

A polymerizable composition (coating liquid for an optically anisotropic film) having the following composition was prepared, and applied to a glass substrate containing a rubbing-treated polyimide alignment film (SE-150 manufactured by Nissan Chemical Industry Co., Ltd.) by spin coating. The coating film was orientation-processed at 200 degreeC, and the liquid crystal layer was formed. Then, it cooled to 135 degreeC, orientation fixation was performed by ultraviolet irradiation of 1000 mJ/cm< ² >, the optically anisotropic film|membrane was formed, and the optical film for wavelength dispersion measurement was obtained.

------------------------------------------------------------ -----------

Coating solution for optically anisotropic film

------------------------------------------------------------ -----------

- Mixed crystal etc. (compounds shown in Table 15 below) 15.00 parts by mass

- 0.075 mass parts of following polymerization initiator S-1 (oxime type)

- 0.023 parts by mass of the following fluorine-containing compound A

· 36.3 parts by mass of cyclopentanone

------------------------------------------------------------ -----------

[Formula 22]

<Retardation>

With respect to the produced optical film, using Axo Scan (OPMF-1, Opto Science Co., Ltd.), a retardation value (Re (450)) of a wavelength of 450 nm and a retardation value of a wavelength of 550 nm (Re (550)) were measured, , Re(450)/Re(550) was calculated. Moreover, the following reference|standard evaluated the obtained calculation result. The results are shown in Table 15 below.

A: Re(450)/Re(550) is less than 0.67

B: Re(450)/Re(550) is 0.67 or more and less than 0.87

C: Re(450)/Re(550) is 0.87 or more

<Face>

About the produced optical film, the planar shape was confirmed with a polarizing microscope and the naked eye, and the following references|standards evaluated it. The results are shown in Table 15 below.

A: No bright spots or striped defects are seen.

B: Some defects in bright spots or streaks are seen

C: There are many defects in bright spots or streaks

D: not oriented

<Moist heat durability>

Test conditions of moist heat durability performed the test left to stand for 500 hours in the environment of 85% of 85 degreeC relative humidity. Re (550) of the optical film after the test was measured, and the following references|standards evaluated moist-heat durability. The results are shown in Table 15 below.

A: The amount of change of Re(550) after the test with respect to the initial phase difference value is less than 10% of the initial value

B: The amount of change of Re(550) after the test with respect to the initial phase difference value is 10% or more and less than 30% of the initial value

C: The amount of change in Re(550) after the test with respect to the initial phase difference value is 30% or more of the initial value

[Table 15]

From the results shown in Table 15 above, the optically anisotropic film formed using the mixed crystal is superior in reverse wavelength dispersion, in-plane and wet heat durability to equal or greater than that of the optically anisotropic film formed by using the polymerizable liquid crystal compound alone. could know that

10 optical film
12 Optically anisotropic film
14 alignment layer
16 support
18 hard coat layer

Claims (11)

A mixed crystal formed of two or more polymerizable liquid crystal compounds represented by the following formula (1) and satisfying any one of the following conditions 1 to 5.
L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ¹ -Ar-D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² … (One)
In the formula (1), D ¹ , D ² , D ³ and D ⁴ are each independently a single bond or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more thereof, R ¹ to R ⁵ are each independently a hydrogen atom, a fluorine atom, Or a C1-C4 alkyl group is represented.
G ¹ , G ² , G ³ , and G ⁴ each independently represent a cycloalkane ring having 6 or more carbon atoms which may have a substituent.
SP ¹ and SP ² are each independently one of -CH ₂ - constituting a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms The above represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and 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 Ar is an aromatic ring represented by a following formula (Ar-3), at least 1 of L< ³ > and L< ⁴ > in L< ¹ > and L< ² > and following formula (Ar-3) represents a polymeric group.
Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).

Here, in the formulas (Ar-1) to (Ar-5), * represents a bonding position with D ¹ or D ² .
Moreover, Q ¹ represents N or CH.
Moreover, ^Q2 represents -S-, -O-, or -N(R6)-, and ^R6 represents a hydrogen atom or a C1 ^- C6 alkyl group.
Moreover, Y< ¹ > represents a C6-C12 aromatic hydrocarbon group or a C3-C12 aromatic heterocyclic group which may have a substituent.
In addition, Z ¹ , Z ² and Z ³ are each independently 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 1 having 6 to 20 carbon atoms. represents a valent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, -OR ⁷ , -NR ⁸ R ⁹ , or -SR ¹⁰ , R ⁷ to R ¹⁰ are each independently a hydrogen atom or carbon number An alkyl group of 1 to 6 is represented, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.
In addition, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N(R ¹¹ )-, -S-, and -CO-, and R ¹¹ is a hydrogen atom or a substituent indicates
In addition, X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded.
In addition, D ⁵ and D ⁶ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group composed of a combination of two or more thereof, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
In addition, SP ³ and SP ⁴ are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or -CH ₂ - constituting a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -O-, -S-, -NH-, -N(Q)-, or -CO- represents the substituted divalent coupling group, Q represents a substituent.
Moreover, L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ and L ² in the formula (1) represents a polymerizable group.
Moreover, Ax represents a C2-C30 organic group which has at least 1 aromatic ring chosen from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Moreover, Ay is a C2-C30 organic group which has a hydrogen atom, a C1-C12 alkyl group which may have a substituent, or at least 1 aromatic ring selected from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. indicates.
Moreover, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may couple|bond together, and may form the ring.
Moreover, Q< ³ > represents a C1-C6 alkyl group which may have a hydrogen atom or a substituent.
Condition 1: The two or more types of polymerizable liquid crystal compounds each have an aromatic ring represented by the formula (Ar-1) as Ar in the formula (1), and each other, Z ¹ in the formula (Ar-1), Only any one or more of Z ² and Y ¹ is a different compound.
Condition 2: The two or more polymerizable liquid crystal compounds all have an aromatic ring represented by the formula (Ar-2) as Ar in the formula (1), and Z ¹ in the formula (Ar-2) Only at least one of Z ² and X is a different compound.
Condition 3: The said two or more types of polymeric liquid crystal compounds all have the aromatic ring represented by the said Formula (Ar-3) as Ar in the said Formula (1), and mutually, Z< ¹ > in the said Formula (Ar-3), Only one or more of Z ² , SP ³ , SP ⁴ , L ³ and L ⁴ is a different compound.
Condition 4: The two or more types of polymerizable liquid crystal compounds all have an aromatic ring represented by the formula (Ar-4) as Ar in the formula (1), and each other, Z ¹ in the formula (Ar-4), Only one or more of Z ² , Z ³ , Ax and Ay is a different compound.
Condition 5: The two or more polymerizable liquid crystal compounds each have an aromatic ring represented by the formula (Ar-5) as Ar in the formula (1), and each other, Z ¹ in the formula (Ar-5), Only one or more of Z ² , Z ³ , Ax and Ay is a different compound. The method according to claim 1,
A mixed crystal wherein both D ¹ and D ² in the formula (1) are *-CO-O-, and * represents a bonding position with G ¹ or G ² . The method according to claim 1 or 2,
A mixed crystal in which all of G ¹ , G ² , G ³ and G ⁴ in the formula (1) represent a cyclohexane ring. The method according to claim 1 or 2,
A mixed crystal wherein both D ³ and D ⁴ in the formula (1) are *-CO-O-, and * represents a bonding position with G ³ or G ⁴ . The method according to claim 1 or 2,
A mixed crystal in which both L ¹ and L ² in the formula (1) represent a polymerizable group. A reaction to obtain a mixed product by reacting a carboxylic acid compound represented by the following formula (1-1) with two or more phenolic compounds represented by the following formula (1-2) and satisfying any one of the following conditions 6 to 10 A method for producing a mixed crystal, comprising: a step; and a crystallization step of crystallizing the mixed product to obtain the mixed crystal according to claim 1 or 2.
L ¹ -SP ¹ -D ³ -G ³ -G ¹ -C(=O)-OH … (1-1)
HO-Ar-OH … (1-2)
In the formula (1-1), D ³ is a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group composed of a combination of two or more thereof, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ³ each independently represent a cycloalkane ring having 6 or more carbon atoms which may have a substituent.
SP ¹ is at least one of -CH ₂ - constituting a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms -O-, - A divalent linking group substituted with S-, -NH-, -N(Q)-, or -CO- is represented, and Q represents a substituent.
L ¹ represents a polymerizable group. However, when Ar in said formula (1-2) is an aromatic ring represented by a following formula (Ar-3), at least 1 of L< ³ > and L< ⁴ > in L< ¹ > and following formula (Ar-3) is a polymeric group indicates.
In the formula (1-2), Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).

Here, in the formulas (Ar-1) to (Ar-5), * represents a bonding position with a hydroxyl group.
Moreover, Q ¹ represents N or CH.
Moreover, ^Q2 represents -S-, -O-, or -N(R6)-, and ^R6 represents a hydrogen atom or a C1 ^- C6 alkyl group.
Moreover, Y< ¹ > represents a C6-C12 aromatic hydrocarbon group or a C3-C12 aromatic heterocyclic group which may have a substituent.
In addition, Z ¹ , Z ² and Z ³ are each independently 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 1 having 6 to 20 carbon atoms. represents a valent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, -OR ⁷ , -NR ⁸ R ⁹ , or -SR ¹⁰ , R ⁷ to R ¹⁰ are each independently a hydrogen atom or carbon number An alkyl group of 1 to 6 is represented, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.
In addition, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N(R ¹¹ )-, -S-, and -CO-, and R ¹¹ is a hydrogen atom or a substituent indicates
In addition, X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded.
In addition, D ⁵ and D ⁶ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group composed of a combination of two or more thereof, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
In addition, SP ³ and SP ⁴ are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or -CH ₂ - constituting a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -O-, -S-, -NH-, -N(Q)-, or -CO- represents the substituted divalent coupling group, Q represents a substituent.
In addition, L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ in the formula (1-1) represents a polymerizable group.
Moreover, Ax represents a C2-C30 organic group which has at least 1 aromatic ring chosen from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Moreover, Ay is a C2-C30 organic group which has a hydrogen atom, a C1-C12 alkyl group which may have a substituent, or at least 1 aromatic ring selected from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. indicates.
Moreover, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may couple|bond together, and may form the ring.
Moreover, Q< ³ > represents a C1-C6 alkyl group which may have a hydrogen atom or a substituent.
Condition 6: All of the two or more types of phenolic compounds have an aromatic ring represented by the formula (Ar-1) as Ar in the formula (1-2), and Z ¹ in the formula (Ar-1), Only any one or more of Z ² and Y ¹ is a different compound.
Condition 7: Both of the two or more phenolic compounds have an aromatic ring represented by the formula (Ar-2) as Ar in the formula (1-2), and each other, Z ¹ in the formula (Ar-2), Only at least one of Z ² and X is a different compound.
Condition 8: The two or more types of phenolic compounds all have an aromatic ring represented by the above formula (Ar-3) as Ar in the above formula (1-2), and Z ¹ in the above formula (Ar-3), Only one or more of Z ² , SP ³ , SP ⁴ , L ³ and L ⁴ is a different compound.
Condition 9: The two or more types of phenolic compounds all have an aromatic ring represented by the above formula (Ar-4) as Ar in the above formula (1-2), and Z ¹ , in the above formula (Ar-4), Only one or more of Z ² , Z ³ , Ax and Ay is a different compound.
Condition 10: The two or more types of phenolic compounds all have an aromatic ring represented by the above formula (Ar-5) as Ar in the above formula (1-2), and Z ¹ in the above formula (Ar-5), Only one or more of Z ² , Z ³ , Ax and Ay is a different compound. A polymerizable liquid crystal composition comprising the mixed crystal according to claim 1. An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to claim 7. The optical film which has the optically anisotropic film|membrane of Claim 8. The polarizing plate which has the optical film of Claim 9, and a polarizer. The image display device which has the optical film of Claim 9, or the polarizing plate of Claim 10.

Images