KR102426523B1 - 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 polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device that is excellent in stability after dissolution and can form a good planar optically anisotropic film. The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the following formula (1) and a polymerizable liquid crystal compound represented by the following formula (2).
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)
L ¹ -SP ¹ -D ³ -A ³ -A ¹ -D ¹ -Ar-D ² -A ² -A ⁴ -D ⁴ -SP ² -L ² … (2)

Description

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

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

Polymeric compounds exhibiting reverse wavelength dispersion properties are actively studied because they have 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 becoming

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 to connect 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

When the present inventors examined the polymeric compound exhibiting reverse wavelength dispersion property described in patent documents 1 - 3, depending on the kind of polymeric compound, stability after dissolution may be inferior, As a result, planar It has been clarified that it may be difficult to produce an optically anisotropic film with good 狀).

Therefore, an object of the present invention is to provide a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device that is excellent in stability after dissolution and can form a good planar optically anisotropic film.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination in order to achieve the said subject, the present inventors used together two types of polymeric liquid crystal compounds from which a part of the ring structure contained in a molecular long axis (side chain) differs as a polymeric compound which shows reverse wavelength dispersibility. The polymerizable liquid crystal composition was excellent in stability after dissolution, and it was discovered that a favorable planar optically anisotropic film could be formed, and this invention was completed.

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

[1] A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by Formula (1) to be described later and a polymerizable liquid crystal compound represented by Formula (2) to be described later.

[2] The polymerizable liquid crystal according to [1], wherein D ¹ and D ² in formulas (1) and (2) to be described later are both —CO-O-*, and * represents a bonding position with Ar. composition.

[3] D ³ and D ⁴ in formulas (1) and (2) to be described later are both —CO-O-*, and * represents a bonding position with SP ¹ or SP ² [1] or [ 2], the polymerizable liquid crystal composition.

[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein L ¹ and L ² in Formulas (1) and (2) described later each represent a polymerizable group.

[5] The polymerizable liquid crystal composition according to any one of [1] to [4], wherein A ¹ and A ³ in Formula (2) described later, either one represents a cyclohexane ring and the other represents a benzene ring. .

[6] The polymerizable liquid crystal composition according to any one of [1] to [5], wherein A ² and A ⁴ in Formula (2) to be described later each represent a cyclohexane ring.

[7] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [6].

[8] An optical film having the optically anisotropic film according to [7].

[9] A polarizing plate comprising the optical film according to [8] and a polarizer.

[10] An image display device having the optical film according to [8] or the polarizing plate according to [9].

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in stability after melt|dissolution, and can provide the polymeric liquid crystal composition which can form a favorable planar optically anisotropic film, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.

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.

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, D ¹ is *1-CO-O -*2 may be sufficient, and *1-O-CO-*2 may be sufficient.

[Polymerizable liquid crystal composition]

The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound represented by the following formula (1) (hereinafter also abbreviated as “polymerizable liquid crystal compound (1)”) and a polymerizable liquid crystal compound represented by the following formula (2) ( Hereinafter, it is a polymeric liquid crystal composition containing "polymerizable liquid crystal compound (2)").

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)

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

In the present invention, as described above, the polymerizable liquid crystal composition using the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in combination with a part of the ring structure contained in the side chain is excellent in stability after dissolution. Thus, a good planar optically anisotropic film can be formed.

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

That is, from the result of the comparative examples 1-3 mentioned later, when a polymeric liquid crystal compound (1) is mix|blended independently, it turns out that stability after melt|dissolution is inferior. It is considered that this is because the polymerizable liquid crystal compound (1) is a compound which, alone, adopts a crystal structure with high crystallinity and low solubility.

Therefore, the polymerizable liquid crystal composition in which the polymerizable liquid crystal compound (2) is blended together with the polymerizable liquid crystal compound (1) has a structure similar to each other, and when packing the polymerizable liquid crystal compound (1), the polymerizable liquid crystal compound (1) is polymerizable. Since the liquid crystal compound (2) mixes and packing is inhibited, stability after melt|dissolution is improved, and as a result, it is thought that the favorable planar optically anisotropic film was able to be formed.

Hereinafter, each component of the polymeric liquid crystal composition of this invention is demonstrated in detail.

[Polymerizable Liquid Crystal Compound (1)]

The polymerizable liquid crystal compound (1) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (1).

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), G ¹ , G ² , G ³ , and G ⁴ each independently represent the cyclohexane ring which may have a substituent.

Further, 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, fluorine An atom or a C1-C4 alkyl group is represented.

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.

In the formula (1), the cyclohexane ring represented by G ¹ , G ² , G ³ and G ⁴ is preferably a trans-1,4-cyclohexylene group.

^In addition, as a substituent which the cyclohexane ring represented by G1, G2, ^G3 , and G4 ⁱⁿ said Formula ( ¹ ) may have, it is the same as the substituent which Y1 in Formula (Ar- ¹ ) mentioned later may have. thing can be heard

In the formula (1), as the divalent linking group represented by D ¹ , D ² , D ³ and D ⁴ , for example, -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 -, etc. are mentioned. 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 Ar.

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-* It is more preferable that In addition, * represents a bonding position with SP ¹ or SP ² .

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 hetero atoms constituting the heteroaryl group is preferably 1-3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. 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), as L< ¹ > and L< ² >, since the film|membrane intensity|strength after bridge|crosslinking improves, it is preferable that they are all polymeric groups, and it is more preferable that they are an acryloyl group or a methacryloyl group.

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, methoxy ethoxy group, etc.) is more preferable. , 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.

Specific examples of the polymerizable liquid crystal compound represented by the formula (1) include the following formulas (I-1) to (I-8), (II-n), (III-n) and (IV-1). ) to (IV-5) a core (*-Ar-*) represented by any one of and a side chain represented by any one of the following formulas (M-101) to (M-105) (L ¹ -SP ¹ -D ³ -G ³ -G ¹ -D ¹ -*, or *-D ² -G ² -G ⁴ -D ⁴ -SP ² -L ² ) may be used in combination, and among them, compounds shown in Table 1 below (1 -1) to (1-12) are preferably mentioned. In the structure of the core and the side chain, * indicates the bonding position between the core and the side chain.

In addition, in the following description, a following formula (II-n) says the structure represented by Formula (II-2) in the case where n in a formula is 2. The same applies to the following formula (III-n).

[Formula 3]

[Formula 4]

[Table 1]

[Polymerizable Liquid Crystal Compound (2)]

The polymerizable liquid crystal compound (2) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (2).

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

In the formula (2), D ¹ , D ² , D ³ and D ⁴ , SP ¹ and SP ² , L ¹ and L ² , and Ar are the same as those described in the formula (1), and suitable The aspect is also the same.

Moreover, in said Formula ( ² ), ^A1 , A2, ^A3 , and A4 respectively independently represent the cyclohexane ring which may have a substituent, or the ⁶ -membered unsaturated ring which may have a substituent. However, at least one of A ¹ and A ³ represents the 6-membered unsaturated ring which may have a substituent.

In Formula (2), the cyclohexane ring represented by A ¹ , A ² , A ³ and A ⁴ is the same as described as G ¹ , G ² , G ³ and G ⁴ in Formula (1).

Moreover, in said Formula ( ² ), ^a benzene ring, a cyclohexane ring, and a cyclohexadiene ring are mentioned as a ^{6 -} membered unsaturated ring which A1, A2, A3, and A4 represent.

Moreover, as a substituent which the cyclohexane ring and the 6-membered unsaturated ring may have, the thing similar to the substituent which Y< ¹ > in Formula (Ar-1) mentioned above may have is mentioned.

In the formula (2), among A ¹ , A ² , A ³ , and A ⁴ , at least one of A ¹ and A ³ represents a 6-membered unsaturated ring which may have a substituent, but from a viewpoint of improving reverse wavelength dispersibility In, it is preferable that either one of A ¹ and A ³ represents a cyclohexane ring and the other represents a benzene ring, and any one of A ¹ and A ³ represents a trans-1,4-cyclohexylene group, and the other It is more preferable to represent this 1, 4- phenylene group.

Moreover, from a viewpoint of improving reverse wavelength dispersion property, it is preferable that both A2 and A4 ⁱⁿ said Formula ( ² ) represent a cyclohexane ring, and it is more preferable that they represent a trans-1,4-cyclohexylene group. do.

As a polymeric liquid crystal compound represented by said Formula (2), specifically, for example, Formula (I-1) - (I-8), (II-n), (III-n) and (IV-) mentioned above, 1) to the core (*-Ar-*) represented by any one of (IV-5), the above formulas (M-101) to (M-105) and the following formulas (M-1-1) to (M- 1-6), (M-2-1), (M-3-1), (M-4-1), (M-4-2), and a side chain represented by any one of (M-5-1) ( L ¹ -SP ¹ -D ³ -A ³ -A ¹ -D ¹ -*, or *-D ² -A ² -A ⁴ -D ⁴ -SP ² -L ² ) may be combined. Among them, compounds (2-1-1) to (2-12-2) shown in Table 2 below are preferably exemplified. In the structure of the core and the side chain, * indicates the bonding position between the core and the side chain.

In addition, the following formulas (M-1-5), (M-1-6), (M-2-1), (M-3-1), (M-4-1) and (M-4-2) ) each represents a side chain in which two structures shown below were mixed.

[Formula 5]

[Formula 6]

[Table 2]

In the present invention, the content of the polymerizable liquid crystal compound (2) is not particularly limited, but it is preferably 0.05 to 15 mass% based on the total mass of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). , from the reason that durability becomes favorable, it is more preferable that it is 0.1-10 mass %.

[Other Polymerizable Compounds]

The polymerizable liquid crystal composition of the present invention may contain other polymerizable compounds having one or more polymerizable groups in addition to the polymerizable liquid crystal compounds (1) and (2) described above, 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].

It is preferable that content in the case of containing such another polymeric compound is less than 60 mass % with respect to the total mass containing the above-mentioned polymeric liquid crystal compound (1) and polymeric liquid crystal compound (2), and 50 mass % It is more preferable that it is below, 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 (U.S. 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), acylphosphine oxide compounds (described in Japanese Unexamined Patent Publication No. 63-040799, Japanese Unexamined Patent Publication No. 5-029234, Japanese Unexamined Patent Application,

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 the 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 control 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 the 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 in paragraphs [0021] to [0029] of the -211306 publication, the contents of which are incorporated herein by reference.

In addition, as a polymer orientation controlling 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. and, 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 and the like, 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 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 control agents can also provide a polymerizable functional group, especially a polymerizable functional group which can superpose|polymerize with the polymeric liquid crystal compound which comprises the polymeric liquid crystal composition of this 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 (3).

0.50<Re(450)/Re(550)<1.00 … (3)

Here, in the formula (3), 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; polyethersulfone-based polymers; polyether ether ketone-based polymers; polyphenylene sulfide-based polymer; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymer; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; 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.

In addition, 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 having 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 obtained by using the other polymerizable compound (especially the liquid crystal compound) described above without blending either or both of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). It will not specifically limit if it is an optically anisotropic film.

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 can 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 apparatus 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 resins (-CH ₂ -CHOH- as a repeating unit, in particular 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 (hereafter abbreviated as "EL") display panel, a plasma display panel, etc. are mentioned.

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.

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-1)>

The synthesis of the compound (I-1) represented by the following formula (I-1) was performed with reference to the method described in Justus Liebigs Annalen der Chemie, 726, 103-109 (1969).

[Formula 7]

<Synthesis of compound (I-4)>

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

[Formula 8]

<Synthesis of compound (S-1-c)>

[Formula 9]

As shown in the above scheme, 125 g (0.462 mol) of dimethyl 4,4-biphenyldicarboxylic acid (S-1-a) was added to 1000 mL of acetic acid, and after adding 12.5 g of a palladium carbon catalyst (wet product) , 130 ℃, was subjected to catalytic hydrogenation in an autoclave at 2 MPa.

After completion of the reaction, after cooling to room temperature (23°C), the catalyst was removed by filtration.

Then, after distilling off acetic acid under reduced pressure, ethyl acetate and sodium hydrogencarbonate aqueous solution were added. Then, it stirred and liquid-separated, the water layer was removed, and the organic layer was wash|cleaned with 10% brine. Sodium sulfate was added to this solution, dried, and the solvent was concentrated to obtain dimethyl (S-1-b) (130 g) of 4,4'-dicyclohexanedicarboxylic acid.

No further purification was performed, followed by 4,4'-dicyclohexanedicarboxylic acid dimethyl (130 g), potassium hydroxide pellets (manufactured by Aldrich, purity 90%) 86.3 g, cumene 1300 mL, and polyethylene glycol 2000 ( Tokyo Kasei Kogyo Co., Ltd.) 10 mL was mixed, the Dean-Stark tube was attached, and it heat-stirred at 120 degreeC. After distilling off methanol, heating and refluxing was continued for 20 hours, making the outside temperature 180 degreeC, and distilling off a solvent. Reaction progress was confirmed by NMR (Nuclear Magnetic Resonance), and after completion|finish of reaction, it cooled, 1300 mL of ethanol was added to the reaction liquid, and the potassium salt which precipitated was collected by filtration.

Next, this potassium salt was melt|dissolved in 1300 ml of water, and concentrated hydrochloric acid was added under ice-cooling until pH of the system became 3, the precipitated carboxylic acid was collected by filtration, and the crude body was collect|recovered.

The recovered crude product was suspended in 500 mL of acetone, stirred at 50° C. for 30 minutes, cooled to room temperature, and filtered to obtain 93.9 g of crystals of dicyclohexanedicarboxylic acid (S-1-c) (yield 80%). ) was obtained.

[Formula 10]

As shown in the above scheme, 10.0 g (39.3 mmol) of compound (S-1-c), 50 mL of N,N-dimethylacetamide (DMAc), 8.0 ml (78.6 mmol) of triethylamine, and 2,6- 433 mg of di-t-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. After adding 40 mL of hexane to the residue and precipitating a crystal|crystallization, after cooling to 5 degreeC and stirring under ice water for 30 minutes, the crude body was collected by filtration. The obtained crude product was suspended in 40 mL of hexane and stirred for 30 minutes, then filtered and blow-dried to obtain 5.39 g of compound (S-1-d) (yield 36%).

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

[Formula 11]

As shown in the above scheme, compound (S-1-d) 12.90 g (33.9 mmol), toluene 40 mL, N,N-dimethylformamide (DMF) 2.82 g, and 2,6-di-t-butyl- 15 mg of 4-methylphenol was mixed at room temperature, and the internal temperature was cooled to 5 degreeC. Thionyl chloride (SOCl ₂ ) 3.94 g (33.1 mmol) was added dropwise to the mixture so that the internal temperature did not rise above 10°C. After stirring at 20°C for 30 minutes, the separated lower layer was removed. The internal temperature was cooled to 5°C, and a tetrahydrofuran (THF) solution (100 ml) of 3.83 g (15.4 mmol) of compound (I-1) was added. After dripping 8.57 g (66.3 mmol) of N,N- diisopropylethylamine (DIPEA) so that internal temperature might not rise to 10 degreeC or more, it stirred at room temperature for 2 hours. After stirring, 100 mL of isopropyl alcohol and 50 mL of water were added dropwise sequentially to stop the reaction, and the precipitated crystals were separated by filtration. After dissolving the obtained crude body in 90 mL of THF, 200 mL of isopropyl alcohol was added and 13.5 g (13.9 mmol) of polymeric liquid crystal compounds (1-1) were obtained by recrystallizing (yield 90%).

[Synthesis of polymerizable liquid crystal compound (1-3)]

[Formula 12]

As shown in the above scheme, compound (S-1-d) 2.53 g (6.65 mmol), toluene 8 mL, N,N-dimethylformamide (DMF) 0.5 mL, 2,6-di-t-butyl-4 -Methylphenol 33mg 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 20°C for 30 minutes, the separated lower layer was removed. The inner temperature was cooled to 5°C, and 0.92 g (3.02 mmol) of compound (I-4) in tetrahydrofuran (THF) solution (10 ml) was added. After dripping 2.90 ml (16.6 mmol) of N,N- diisopropylethylamine (DIPEA) so that internal temperature might not rise to 10 degreeC or more, it stirred at 30 degreeC for 2 hours. After stirring, 15 ml of 1N hydrochloric acid and 15 ml of ethyl acetate were added, the reaction was stopped, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure and concentrated. 30 mL of isopropyl alcohol was dripped at the internal temperature of 40 degreeC to the obtained concentrate, after that, the crystal|crystallization was precipitated by cooling to the internal temperature of 5 degreeC, and it separated by filtration. After the obtained crude product was dissolved in 10 mL of ethyl acetate, 35 mL of isopropyl alcohol was added thereto and recrystallized to obtain 2.65 g (2.58 mmol) of the polymerizable liquid crystal compound (I-3) (yield 85%).

[Synthesis of polymerizable liquid crystal compound (1-9)]

According to the method described in paragraphs [0161] to [0163] of Japanese Patent Application Laid-Open No. 2010-084032, a polymerizable liquid crystal compound (1-9) represented by the following formula was synthesized.

[Formula 13]

<Synthesis of compound (S-2-c)>

[Formula 14]

As shown in the above scheme, a suspension of 60.0 g of aluminum chloride and 30.0 g of acetyl chloride and 120 mL of carbon disulfide was cooled to -50°C, and 30.0 g of cyclohexane was added dropwise. After stirring at -20 degreeC or less for 15 minutes, the solution part was removed, benzene 300mL was added, and it stirred at 45 degreeC for 3 hours. The reaction solution was cooled on ice, the reaction was stopped with 100 mL of 1N hydrochloric acid, and the organic layer was washed with 1N hydrochloric acid and 10% aqueous NaOH solution. The reaction solution was dried over magnesium sulfate, and then purified by silica gel column chromatography to obtain 32.0 g of compound (S-2-a).

17.3 g of aluminum chloride and 100 mL of dichloroethane were cooled to 5-10 degreeC, and 12.9 g of compound (S-2-a) was added. 5.1 g of acetyl chlorides were dripped at 5-10 degreeC, and it stirred at 5-10 degreeC for 1 hour. 100 mL of water was added, reaction was stopped, and the organic layer was dried over magnesium sulfate. Purification was performed by silica gel column chromatography to obtain 9.3 g (yield: 60%) of compound (S-2-b).

After adding 0.28 g of tetrabutylammonium chloride and 2.8 g of sodium sulfate to a solution of 75.0 g of sodium hypochlorite and 13.9 g of sodium hydroxide, 8.6 g of compound (S-2-b) was added, followed by stirring at 60° C. for 3 hours. did. After cooling to room temperature, the pH was adjusted to 2 with 30% sulfuric acid, the precipitated carboxylic acid was collected by filtration, and the crude product was recovered. The recovered crude product was suspended in 50 mL of acetone, stirred at 50°C for 30 minutes, cooled to room temperature, and filtered to obtain 7.8 g (yield: 90%) of compound (S-2-c).

<Synthesis of compound (S-2-d)>

[Formula 15]

Then, as shown in the above scheme, 5.0 g (20 mmol) of compound (S-2-c), 50 mL of N,N-dimethylacetamide (DMAc), 5.6 ml (40 mmol) of triethylamine, and 2,6- 43 mg of di-t-butyl-4-methylphenol was mixed at room temperature. 4.9 g (22 mmol) of 4-methylsulfonyloxybutyl acrylate was added to the mixture, and it stirred at 100 degreeC for 5 hours. After cooling to room temperature, 12.5 ml of 1N hydrochloric acid and 25 ml of toluene were added, and the mixture was stirred at 40° C., followed by 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. Purification by silica gel column chromatography gave 2.6 g of compound (S-2-d) (yield 35%).

[Synthesis of polymerizable liquid crystal compound (2-1-7)]

[Formula 16]

Compound (S-2-d) 1.0 g (2.7 mmol), ethyl acetate (EA) 10 mL, N,N-dimethylacetamide (DMAc) 3 mL, 2,6-di-t-butyl-4-methylphenol 5 mg were mixed at room temperature, and the internal temperature was cooled to 5°C. To the mixture, 0.24 mL (3.2 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise so that the internal temperature did not rise above 10°C. After stirring at 5°C for 1 hour, 0.30 g (1.2 mmol) of compound (I-1) in tetrahydrofuran (THF) (5 ml) was added. After 0.94 ml (5.4 mmol) of N,N- diisopropylethylamine (DIPEA) was dripped, it stirred at room temperature for 6 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. The obtained crude product was purified by silica gel column chromatography to obtain 1.0 g (1.1 mmol) of a polymerizable liquid crystal compound (2-1-7) (yield 88%).

<Synthesis of compound (S-1-e)>

[Formula 17]

Compound (S-1-d) 30.0 g (79 mmol), Compound (I-1) 39.2 g (158 mmol), tetrahydrofuran 525 mL, chloroform 175 mL, 2,6-di-t-butyl-4-methylphenol 0.44 g was mixed at room temperature, and 22.7 g (119 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimido hydrochloride was added. 1.44 g of dimethylaminopyridine was added, and it stirred at room temperature for 3 hours. 220 ml of 1N hydrochloric acid and 220 ml of ethyl acetate were added, the reaction was stopped, and liquid separation was performed. The organic layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and brine, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography to obtain 25.0 g (41 mmol) of compound (S-1-e) (yield 52%).

[Synthesis of polymerizable liquid crystal compound (2-1-5)]

[Formula 18]

Compound (S-1-e) 1.63 g (2.7 mmol), Compound (S-2-d) 1.0 g (2.7 mmol), tetrahydrofuran 20 mL, chloroform 6 mL, 2,6-di-t-butyl-4 15 mg of -methylphenol was mixed at room temperature, and 0.61 g (3.2 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimido hydrochloride was added. Dimethylaminopyridine 0.05 g was added, and it stirred at room temperature for 3 hours. 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added, the reaction was stopped, and liquid separation was performed. The organic layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and brine, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography to obtain 2.2 g (2.3 mmol) of a polymerizable liquid crystal compound (2-1-5) (yield 85%).

[Synthesis of polymerizable liquid crystal compound (2-3-1)]

In the same manner as in the polymerizable liquid crystal compound (2-1-5), except that the compound (I-1) used for the synthesis of the compound (S-1-e) was replaced with the compound (I-4), by the following formula The resulting polymerizable liquid crystal compound (2-3-1) was synthesized.

[Formula 19]

[Synthesis of polymerizable liquid crystal compound (2-9-2)]

In the same manner as in the polymerizable liquid crystal compound (2-1-7), except that the compound I described in paragraph [0161] of JP 2010-084032 A was used instead of the compound (I-1), represented by the following formula A polymerizable liquid crystal compound (2-9-2) was synthesized.

[Formula 20]

[solubility]

The measurement of the solubility of the synthesize|combined polymeric liquid crystal compound was performed by the method shown below. The results are shown in Tables 3 and 4 below. In addition, in the following 3 and Table 4, the solubility evaluation of Examples 1-8 was evaluated with the mixture which mixed the polymeric liquid crystal compound described in following Table 3 and Table 4 in the ratio described in following Table 3 and Table 4. .

First, 1.0g of a polymeric liquid crystal compound was measured as a total amount to a 10 mL sample bottle, and 1.5g of solvents were added until solid content became 40 mass %. Then, after shaking well by hand at 50 degreeC, and leaving it to stand for 10 minutes at room temperature (23 degreeC), it was complete|finished when visually observed and cleared, and it determined with the solubility of 40 mass %.

On the other hand, if there was a dissolution residue, the solvent was added so that solid content might become 35 mass % (+0.36 g). Then, after shaking well by hand at 50 degreeC, and leaving it to stand at room temperature (23 degreeC) for 10 minutes, when visually observed and clearing, it was complete|finished, and it determined with 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 melt|dissolution residue, it was judged to be less than 5 mass % (<5 mass %) of solubility, and it was complete|finished. As a solvent for solubility measurement, CPN (cyclopentanone) was used.

A: 20% or more solubility in CPN

B: Solubility to CPN is 10% or more and less than 20%

C: Solubility to CPN is 5% or more and less than 10%

D: Solubility to CPN is 5% or less

[Dissolution stability]

The measurement of the solubility stability of the polymeric liquid crystal compound synthesize|combined by the Example and the comparative example was performed by the method shown below. The results are shown in Tables 3 and 4 below. In addition, in the following 3 and Table 4, the evaluation of the dissolution stability of Examples 1-8 is evaluated as a mixture in which the polymerizable liquid crystal compounds described in Tables 3 and 4 are mixed in the ratios described in Tables 3 and 4 below. did.

Specifically, 1.0 g of a polymerizable liquid crystal compound is weighed as a total amount in a 10 mL sample bottle, and a solvent is added until it reaches a predetermined solid content (15 mass % in Table 3, 30 mass % in Table 4), then 50 The mixture was shaken well by hand at ℃, left to stand at room temperature (23℃) for 10 minutes, and then visually observed.

Thereafter, the sample bottle containing the solution was aged at 23° C. for 28 days. The liquid was prepared and the presence or absence of precipitation was visually confirmed after 14 days and 28 days.

As a solvent for dissolution stability measurement, CPN (cyclopentanone) was used.

A: No precipitation was observed, and the liquid was cleared.

B: A precipitate is not seen, but there is some turbidity in the liquid.

C: Some precipitates are seen.

D: A large amount of precipitates are seen.

E: The whole liquid is solidified.

[Examples 1 to 8 and Comparative Examples 1 to 3]

[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 liquid for optically anisotropic film

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

-Polymerizable liquid crystal compound (1) (compounds listed in Table 3 or Table 4 below)

-Polymerizable liquid crystal compound (2) (compounds listed in Table 3 or Table 4 below)

・Photoinitiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass

・0.12 parts by mass of the following fluorine-containing compound A

・Cyclopentanone 85.00 parts by mass

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

Here, content of the said polymeric liquid crystalline compound (1) and (2) was 15 mass parts in total, and was mix|blended by the ratio (%) shown in following Table 3 and following Table 4, respectively.

In addition, in Table 4 below, the mixing ratio of the polymerizable liquid crystal compound (1-1) and (1-3) as the polymerizable liquid crystal compound (1) is 1:1, and the polymerizable liquid crystal compound (2) is polymerizable. The mixing ratio of the liquid crystal compound (2-1-5) and (2-3-1) is 1:1.

[Formula 21]

[Face]

About the produced optical film, the planar shape was confirmed with a polarization microscope and visual observation, and the following references|standards evaluated it.

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: Defects on the entire surface, or no orientation

[Table 3]

[Table 4]

From the results shown in Tables 3 and 4 above, it was found that when the polymerizable liquid crystal compound (2) was not blended, that is, the polymerizable liquid crystal compound (1) was poor in dissolution stability as a single unit (Comparative Example) 1-3).

On the other hand, it turned out that the mixture of a polymeric liquid crystal compound (1) and a polymeric liquid crystal compound (2) became favorable in dissolution stability, and the planar shape of the optical film formed using this also became favorable (Examples 1-8). ).

Claims (10)

The polymerizable liquid crystal compound represented by the following formula (1) and the polymerizable liquid crystal compound represented by the following formula (2) are contained, and the content of the polymerizable liquid crystal compound represented by the formula (2) is represented by the formula (1). The polymerizable liquid crystal composition which is 0.05-15 mass % with respect to the total mass of a polymeric liquid crystal compound represented by a compound and Formula (2).
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)
L ¹ -SP ¹ -D ³ -A ³ -A ¹ -D ¹ -Ar-D ² -A ² -A ⁴ -D ⁴ -SP ² -L ² … (2)
In the formula (1), G ¹ , G ² , G ³ , and G ⁴ each independently represent the cyclohexane ring which may have a substituent.
In the formula (2), A ¹ , A ² , A ³ , and A ⁴ each independently represent the cyclohexane ring which may have a substituent, or the 6-membered unsaturated ring which may have a substituent. However, at least one of A ¹ and A ³ represents the 6-membered unsaturated ring which may have a substituent.
In the formulas (1) and (2), 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 an alkyl group having 1 to 4 carbon atoms.
In addition, SP ¹ and SP ² 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 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.
Moreover, Ar represents any aromatic ring chosen from the group which consists of groups represented by following formula (Ar-1) - (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 14-16 to which a substituent may couple|bond.
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 and L ² in the formula (1) or (2) 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 heterocycle. 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. The method according to claim 1,
Both D ¹ and D ² in the formulas (1) and (2) are —CO-O-*, and * represents a bonding position with Ar, the polymerizable liquid crystal composition. The method according to claim 1 or 2,
The polymerizable liquid crystal composition in which D ³ and D ⁴ in the formulas (1) and (2) are both —CO-O-*, and * represents a bonding position with SP ¹ or SP ² . The method according to claim 1 or 2,
The polymerizable liquid crystal composition in which both L ¹ and L ² in the formulas (1) and (2) represent a polymerizable group. The method according to claim 1 or 2,
The polymerizable liquid crystal composition in which any one of A ¹ and A ³ in the formula (2) represents a cyclohexane ring and the other represents a benzene ring. The method according to claim 1 or 2,
The polymerizable liquid crystal composition in which both A ² and A ⁴ in the formula (2) represent a cyclohexane ring. An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to claim 1. The optical film which has the optically anisotropic film|membrane of Claim 7. The polarizing plate which has the optical film of Claim 8, and a polarizer. The image display device which has the optical film of Claim 8, or the polarizing plate of Claim 9.

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