JP2020143205A - Polymerizable liquid crystal composition, optical anisotropic film, optical film, polarizing plate and image display device - Google Patents

Abstract

To provide a polymerizable liquid crystal composition capable of providing an optical anisotropic film having reverse wavelength dispersibility and excellent uniformity without unevenness or alignment defects, and an optical anisotropic film, an optical film and a polarizing plate using the composition.SOLUTION: The polymerizable liquid crystal composition comprises a polymerizable liquid crystal compound showing reverse wavelength dispersibility and a fluoro aliphatic group-containing polymer A containing a structural unit represented by general formula (A-1) and a structural unit derived from a fluoro aliphatic group-containing monomer, in which the molar ratio of the structural unit derived from the fluoro aliphatic group-containing monomer in the fluoro aliphatic group-containing polymer is 40 to 70 mol% in the whole structural units.SELECTED DRAWING: None

Description

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.

A polymerizable compound exhibiting reverse wavelength dispersibility can accurately convert the polarized state in a wide wavelength range, and can thin a retardation film in order to exhibit a large refractive index anisotropy. Because it has the characteristics of, it is being actively researched.
Further, as a polymerizable compound exhibiting inverse wavelength dispersibility, a T-type molecular design guideline is generally taken, the wavelength of the major axis of the molecule is shortened, and the wavelength of the minor axis located at the center of the molecule is lengthened. Compounds have been proposed. (See, for example, Patent Documents 1 to 3).

On the other hand, a retardation film using a polymerizable liquid crystal compound is generally produced by using a coating process, and has a problem of how to realize a uniform and defect-free large-area thin film. Since continuous production of a uniform and defect-free film using an industrially available coating device requires advanced technology, this problem has been solved by attempts such as adding a leveling agent. (See, for example, Patent Document 4).

Japanese Unexamined Patent Publication No. 2010-031223 International Publication No. 2014/010325 Japanese Unexamined Patent Publication No. 2016-081035 Japanese Unexamined Patent Publication No. 11-148080 Japanese Unexamined Patent Publication No. 2004-198511

The inventors have found that the above-mentioned polymerizable compound exhibiting reverse wavelength dispersibility is more difficult to control the orientation of liquid crystal molecules than the liquid crystal compound exhibiting forward wavelength dispersibility. Further, in recent years, the definition of OLED display elements has been improved, and the qualitative and frequent tolerance range for unevenness and defects has been narrowed year by year.

Therefore, the present invention relates to a polymerizable liquid crystal composition capable of providing an optically anisotropic film having reverse wavelength dispersibility, no unevenness or orientation defects, and excellent uniformity, and an optically anisotropic film using the same. An object of the present invention is to provide an optical film and a polarizing plate.

As a result of diligent studies to achieve the above problems, the present inventors have found that the above problems can be overcome by using a polymerizable compound exhibiting reverse wavelength dispersibility and a specific fluoroaliphatic group-containing polymer, and the present invention has been made. Was completed.
That is, it was found that the above problem can be achieved by the following configuration.

[1] Contains a fluoroaliphatic group containing a polymerizable liquid crystal compound exhibiting inverse wavelength dispersibility, a structural unit represented by the general formula (A-1) described later, and a structural unit derived from a fluoroaliphatic group-containing monomer. Contains polymer A,
A polymerizable liquid crystal composition in the fluoroaliphatic group-containing polymer, wherein the structural units derived from the fluoroaliphatic group-containing monomer account for 40 to 70 mol% of the total structural units.
[2] The polymerizable liquid crystal according to [1], wherein in the fluoroaliphatic group-containing polymer A, X is an unsubstituted or substituted naphthyl group as a structural unit represented by the general formula (A-1) described later. Composition.
[3] The polymerizable liquid crystal composition according to [1] or [2], wherein the fluoroaliphatic group-containing polymer A has a mass average molecular weight of 3000 to 10000.
[4] The polymerizable liquid crystal composition according to any one of [1] to [3], further comprising another fluoroaliphatic group-containing polymer B.
[5] The polymerizable liquid crystal composition according to any one of [1] to [4], wherein the polymerizable liquid crystal composition is a polymerizable liquid crystal compound represented by the following formula (1) described later.
[6] The polymerizable liquid crystal composition according to [5], wherein Ar ¹ in the formula (1) described later represents a group represented by the formula (Ar-1) or (Ar-2) described later.
[7] The polymerizable liquid crystal composition according to any one of [1] to [6], wherein the polymerizable liquid crystal composition contains a polymerization initiator.
[8] An optically anisotropic film formed from the polymerizable liquid crystal composition according to any one of [1] to [7].
[9] The optically anisotropic film according to [8], wherein the liquid crystal molecules are fixed in a homogeneous orientation.
[10] An optical film comprising the optically anisotropic film according to [8] or [9].
[11] A polarizing plate containing the optically anisotropic film and the polarizer according to [8] or [9].
[12] An image display device including the optical film according to [10] or the polarizing plate according to [11].

According to the present invention, it is possible to provide an optically anisotropic film, an optical film, a polarizing plate, and an image display device having reverse wavelength dispersibility and excellent surface adhesion and wettability.

FIG. 1A is a schematic cross-sectional view showing an example of the optically anisotropic film of the present invention. FIG. 1B is a schematic cross-sectional view showing another example of the optically anisotropic film of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the polarizing plate of the present invention. FIG. 3 is a diagram showing the relationship between the absorption axis of the polarizer and the in-plane slow axis of the positive A plate in the polarizing plate of the present invention. FIG. 4 is a schematic cross-sectional view showing an example of an organic electroluminescence display device which is an aspect of the image display device of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In addition, in this specification, the numerical value range represented by using "~" means the range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present specification, the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited unless the bonding position is specified, and for example, the formula (for example, described later) will be described later. 1) When D ^{1 in} 1) is -CO-O-, assuming that the position bonded to the Ar ¹ side is * 1 and the position bonded to the G ¹ side is * 2, D ¹ is * 1 -CO-O- * 2 may be used, or * 1-O-CO- * 2 may be used.
Further, in the present specification, the present invention belongs to an angle (for example, an angle such as “90 °”) and its relationship (for example, “orthogonal”, “parallel” and “intersection at 45 °”). It shall include the range of error allowed in the technical field. For example, it means that the angle is within the range of ± 10 °, and the error from the exact angle is preferably 5 ° or less, and more preferably 3 ° or less.

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound exhibiting inverse wavelength dispersibility, a structural unit represented by the general formula (A-1), and a structural unit derived from a fluoroaliphatic group-containing monomer. It contains polymer A (hereinafter, also simply referred to as "fluoroaliphatic group-containing polymer A").

In the present invention, as described above, by using a polymerizable liquid crystal composition containing a fluoroaliphatic group-containing polymer A, which will be described later, together with a polymerizable liquid crystal compound exhibiting inverse wavelength dispersibility, uniform optical differences without unevenness are used. A square membrane can be obtained.
Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.

[Polymerizable compound showing reverse wavelength dispersibility]
The polymerizable compound contained in the polymerizable liquid crystal composition of the present invention and exhibiting inverse wavelength dispersibility is a compound in which the optical anisotropy per thickness increases according to the measurement wavelength in a monodomain homogeneous orientation state. Means. The monodomain homogeneous orientation state can be obtained by providing a gap between two glass substrates provided with a horizontal alignment film and encapsulating the target polymerizable liquid crystal compound in the gap to express the liquid crystal phase. When the target compound is a vertically oriented polymerizable liquid crystal, the horizontal orientation may be replaced with the vertical orientation and the refractive index anisotropy in the thickness direction may be measured.

As described above, most of the polymerizable liquid crystal compounds exhibiting inverse wavelength dispersibility have a T-type molecular design guideline, and the wavelength of the major axis of the molecule is shortened to that of the minor axis located in the center of the molecule. Although it is a compound having a longer wavelength, it may have a shape other than that.
In the present invention, the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is preferably a polymerizable liquid crystal compound represented by the following formula (1) (hereinafter referred to as a polymerizable liquid crystal compound (1)).
L ^1- SP ^1- (E ^3- A ¹ ) _m- E ^1- G ^1- D ^1- Ar ^1- D ^2- G ^2- E ^2- (A ^2- E ⁴ ) _n- SP ^2- L ² ... (1)

In the above formula (1), D ¹ , D ² , E ¹ , E ² , E ³ and E ⁴ are independently single-bonded, -CO-O-, -C (= S) O-, and -CR, respectively. ^{1 R 2 -, - CR 1} R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 - ^{, -O-CO-CR 1 R} 2 -, - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 Represents R ³ − or −CO −NR ¹ −. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
Further, in the above formula (1), G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, and are alicyclic. One or more of −CH ₂₋ constituting the hydrocarbon group may be substituted with −O−, −S− or −NH−.
Further, in the above formula (1), A ¹ and A ² may independently have a substituent, a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or 5 carbon atoms. Represents a divalent alicyclic hydrocarbon group of ~ 8, even if one or more of -CH _2- constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. Good.
Further, in the above formula (1), SP ¹ and SP ² are independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. Alternatively, a divalent linkage in which one or more of -CH _2- constituting the branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents a group and Q represents a substituent.
Further, in the above formula (1), L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar ¹ or Ar ² is an aromatic ring represented by the following formula (Ar-3), at least 1 of L ¹ and L ² and L ³ and L ^{4 in} the following formula (Ar-3) One represents a polymerizable group.
Further, the formula (1), m represents an integer of 0 to 2, m is 2, a plurality of E ³ may each have the same or different and a plurality of A ¹ is , Each may be the same or different.
Further, in the above equation (1), n represents an integer of 0 to 2, and when n is 2, the plurality of E ^4s may be the same or different, and the plurality of A ² may be the same or different. , Each may be the same or different.

In the above formula (1), the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G ¹ and G ² is preferably a 5-membered ring or a 6-membered ring. The alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferable. As the divalent alicyclic hydrocarbon group represented by G ¹ and G ² , for example, the description in paragraph [0078] of JP2012-21068A can be referred to, and this content is incorporated in the present specification. ..
Of these, a cyclohexylene group (cyclohexane ring) is preferable, a 1,4-cyclohexylene group is more preferable, and a trans-1,4-cyclohexylene group is even more preferable.
Further, in the above formula (1), the substituent that the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G ¹ and G ² may have is the formula (Ar-1) described later. ) May have the same substituents as Y ¹ in.

In the above formula (1), the divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms represented by A ¹ and A ² include 1,2-phenylene group, 1,3-phenylene group and 1,4-phenylene. Examples thereof include a group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, etc. Among them, 1,4-phenylene group is preferable, and trans-1,4-phenylene group is more preferable. ..
Further, examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by A ¹ and A ² include the same groups as those described with G ¹ and G ² in the above formula (1). , Cyclohexylene group (cyclohexane ring) is preferable, 1,4-cyclohexylene group is more preferable, and trans-1,4-cyclohexylene group is further preferable.

In the above formula (1), examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ¹ and SP ² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene. A group, a methylhexylene group, a heptylene group and the like are preferably mentioned. As described above, SP ¹ and SP ² have one or more of -CH _2- constituting a linear or branched alkylene group having 1 to 12 carbon atoms of -O-, -S-, and -NH. It may be a divalent linking group substituted with −, −N (Q) − or −CO−, and the substituent represented by Q is Y in the formula (Ar-1) described later. Examples thereof include the same substituents that ¹ may have.

In the above formula (1), examples of the monovalent organic group represented by L ¹ and L ² include an alkyl group, an aryl group, and a heteroaryl group. The alkyl group may be linear, branched or cyclic, but linear is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but monocyclic is preferable. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms. Further, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Further, the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or have a substituent. Examples of the substituent include the same substituents that Y ¹ in the formula (Ar-1) described later may have.

In the above formula (1), the polymerizable group represented by at least one of L ¹ and L ² is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and suitable examples thereof include an acryloyl group and a methacryloyl group. In this case, it is known that the acryloyl group is generally faster in terms of polymerization rate, and the acryloyl group is preferable from the viewpoint of improving productivity, but the methacryloyl group can also be used as the polymerizable group in the same manner.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and , Vinyloxy group and the like. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
Examples of particularly preferable polymerizable groups include the following.

In the above formula (1), it is preferable that both L ¹ and L ² in the above formula (1) are polymerizable groups, and are acryloyl group or methacryloyl group, for the reason that the moist heat durability becomes better. Is more preferable.

On the other hand, in the above formula (1), Ar ¹ represents any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-5). In the following formulas (Ar-1) to (Ar-5), * represents the bonding position with D ¹ or D ² in the above formula (I).

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

Further, in the above formulas (Ar-1) to (Ar-5), Z ¹ , Z ² and Z ³ are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon. A monovalent alicyclic hydrocarbon group of number 3 to 20, a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ , or , -SR ⁹ and R ^{6 to} R ⁹ 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. Good.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group (Me). , Ethyl group, isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group (tBu), 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, Ethyl groups and tert-butyl groups are particularly preferred.
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 and an ethylcyclohexyl. Monocyclic saturated hydrocarbon groups such as groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as diene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, Tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and 6 to 12 carbon atoms. Aryl groups (particularly phenyl groups) are preferred.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{6 to} R ⁹ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl. Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.

Further, in the above formula (Ar-2) and ^{(Ar-3), A} 3 and ^{A 4} are each ^{independently, -O -, - N (R} 10) -, - S-, and from -CO- Represents a group selected from the group, where R ¹⁰ represents a hydrogen atom or substituent.
Examples of the substituent represented by R ¹⁰ include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Further, in the above formula (Ar-2), X represents a non-metal atom of Groups 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Examples of the non-metal atoms of Groups 14 to 16 indicated by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Specific examples of the substituent include a carbon atom having a substituent. Is, for example, an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, etc. Can be mentioned.

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

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

Further, in the above formula (Ar-3), L ³ and L ⁴ independently represent monovalent organic groups, respectively, and at least 1 of L ³ and L ⁴ and L ¹ and L ^{2 in} the above formula (1). One represents a polymerizable group.
Examples of the monovalent organic group include those similar to those described in L ¹ and L ² in the above formula (1).
In addition, examples of the polymerizable group include those similar to those described in L ¹ and L ² in the above formula (1).

Further, in the above formulas (Ar-4) to (Ar-5), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
Further, in the above formulas (Ar-4) to (Ar-5), Ay is an alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom and a substituent, or an aromatic hydrocarbon ring and aromatic. It represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms.
Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of Patent Document 2 (International Publication No. 2014/010325).
The alkyl group having 1 to 6 carbon atoms represented by ^{Q 3,} specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert Examples thereof include a −butyl group, an n-pentyl group, and an n-hexyl group, and examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have. Can be mentioned.

In the present invention, the polymerizable liquid crystal compound (1) represented by the above formula (1) has an m of 1 in the above formula (1) for the reason that the wet heat durability of the optically anisotropic film becomes better. A ¹ and G ¹ are both cyclohexylene groups which may have a substituent, E ¹ is a single bond, and n in the above formula (1) is 1. It is preferable that both ² and G ² are cyclohexylene groups which may have a substituent and E ² is a single bond, which is a polymerizable liquid crystal compound.

In the present invention, the pKa of the diphenol compound represented by HO-Ar ^1- OH, which is derived from the structure of Ar ^{1 in} the above formula (1), is 11 or less for the reason that the light resistance becomes better. Is preferable.
Here, pKa is the value of the acid dissociation constant in the mixed solvent, which is a volume ratio of tetrahydrofuran (THF) / water = 6/4 at 25 ° C.
As a method for measuring the acid dissociation constant in the present invention, the alkali suitable method described on pages 215 to 217 of the second edition of the Experimental Chemistry Course published by Maruzen Co., Ltd. can be used.

[Polymerizable liquid crystal compound (2)]
The polymerizable liquid crystal composition of the present invention may further contain another polymerizable liquid crystal compound (hereinafter referred to as the polymerizable liquid crystal compound (2)). As such a polymerizable liquid crystal compound, various known compounds can be used. Among them, a rod-shaped liquid crystal compound or a discotic liquid crystal compound is preferable, and a rod-shaped liquid crystal compound is more preferable because of its shape similarity to the polymerizable liquid crystal compound (1).

Examples of the rod-shaped liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, and the like. Phenyldioxans, trans and alkenylcyclohexylbenzonitriles are preferably used. For example, it is described in the polymerizable nematic rod-shaped liquid crystal compound of JP-A-2006-209073.

The polymerizable liquid crystal compound (2) may be monofunctional or may be bifunctional or higher. Moreover, you may use a plurality of kinds.

[Fluoroaliphatic group-containing polymer A]
The polymer A (fluoroaliphatic group-containing polymer A) containing the structural unit represented by the general formula (A) and the structural unit derived from the fluoroaliphatic group-containing monomer, which is contained in the polymerizable liquid crystal composition of the present invention, will be described. To do.

The fluoroaliphatic group-containing polymer A contains a structural unit represented by the general formula (A) and a structural unit derived from a fluoroaliphatic group-containing monomer. The structural unit derived from the fluoroaliphatic group-containing monomer has the effect of controlling the surface energy of the coating film by the action of fluorine to maintain a uniform coating film, and the structural unit represented by the general formula (A) is It is considered that the orientation state is stabilized by some interaction with the polymerizable liquid crystal compound molecules existing near the surface of the coating film, which contributes to the formation of an optically anisotropic film without unevenness or defects.
Hereinafter, each structural unit constituting the polymer will be described.

(1) A structural unit represented by the general formula (A-1)

・ General formula (A-1)
In the general formula (A-1), Mp represents a trivalent group constituting a part or all of the polymer main chain, L represents a single bond or a divalent linking group, and X represents a substituted or unsubstituted aromatic. Represents a group fused ring functional group.

In the general formula (A-1), Mp is a trivalent group and constitutes a part or all of the main chain of the polymer. The Mp is preferably a substituted or unsubstituted long chain or branched alkylene group having 2 to 20 carbon atoms (excluding the number of carbon atoms of the substituent, hereinafter the same for those in Mp) (for example, an ethylene group). , Propylene group, methylethylene group, butylene group, hexylene group, etc.), substituted or unsubstituted cyclic alkylene group having 3 to 10 carbon atoms (for example, cyclopropylene group, cyclobutylene group, cyclohexylene group, etc.), substituted or Unsubstituted vinylene group, substituted or unsubstituted cyclic vinylene group, substituted or unsubstituted phenylene group, group containing oxygen atom (for example, group containing ether group, acetal group, ester group, carbonate group, etc.), nitrogen atom Group containing (for example, amino group, imino group, amide group, urethane group, ureido group, imide group, imidazole group, oxazole group, pyrrol group, anilide group, maleinimide group, etc.), group containing sulfur atom (For example, a group containing a sulfide group, a sulfone group, a thiophene group, etc.), a group containing a phosphorus atom (for example, a group containing a phosphine group, a phosphate ester group, etc.), a group containing a silicon atom (for example, a siloxane group, etc.) A group containing) and a group formed by connecting two or more of these groups, wherein one of the hydrogen atoms contained in the group is substituted with a -LX group, more preferably. Preferably, it is a substituted or unsubstituted ethylene group, a substituted or unsubstituted methylethylene group, a substituted or unsubstituted cyclohexylene group, a substituted or unsubstituted vinylene group, and one of the hydrogen atoms contained in the group is A group substituted with an −LX group, more preferably a substituted or unsubstituted ethylene group, a substituted or unsubstituted methylethylene group, a substituted or unsubstituted vinylene group, which is contained in the group. One of the hydrogen atoms is a group substituted with a —LX group, particularly preferably a substituted or unsubstituted ethylene group, a substituted or unsubstituted methylethylene group, and hydrogen contained in the group. One of the atoms is a group substituted with a -LX group, and specifically, Mp-1 and Mp-2, which will be described later, are preferable.

Specific examples of Mp are shown below, but Mp is not limited thereto. Further, the part represented by * in Mp represents the part connected to L.

The divalent linking group represented by L in the general formula (A-1) is preferably a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms (for example, a methylene group, an ethylene group or a propylene group). , Butylene group, isopropylene group, etc.), alkenylene group having 2 to 20 carbon atoms (for example, vinylene group, butene group, etc.), -O-, -NR ^a1- , -S-, ^{-PR a2-} , -Si (R ^a3 ) (R ^a4 )-, -C (= O)-, -C (= O) O-, -C (= O) NR ^a5- , -OC (= O) O-, -OC (= O) NR ^a6 −, −NR ^a7 C (= O) NR ^a8 −, − ( ^−O ) ₂ CH −, and a divalent linking group selected from groups formed by linking two or more of these. is there.
Here, R ^{a1 to} R ^a8 represent substitutable substituents, and for example, a hydrogen atom, a halogen atom, an alkyl group (a monocycloalkyl group containing one or more ring structures, a cycloalkyl group such as a bicycloalkyl group) may be used. Includes), alkenyl group (including cycloalkenyl group, bicycloalkenyl group), alkynyl group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, amino group (anilino) (Excluding groups), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, mercapto group, alkylthio group, sulfamoyl group, sulfo group, alkylsulfinyl group, alkylsulfonyl group, acyl group, alkoxycarbonyl group, imide group, phosphino group , Phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group as examples, and hydrogen atom and alkyl group are preferable.

More preferably, L in the general formula (A-1) is −O−, −NR ^a11− (where R ^a11 represents a hydrogen atom and an aliphatic hydrocarbon group having 1 to 10 carbon atoms), −S. -, -C (= O)-, -S (= O) _2- , and substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, and groups formed by connecting two or more of these. A divalent linking group selected from, in particular -C (= O) O-, -OC (= O)-, -O-, -OC (= O) O-, -C (= O). Select from NH-, -NHC (= O)-, -C (= O) O (CH ₂ ) _m O-,-(CH ₂ ) m-, and groups formed by connecting two or more of these. The divalent linking group to be used is preferred.
Here, m represents an integer of 1 to 20. m is preferably 1 to 16, more preferably 2 to 12, and even more preferably 2 to 6 in order to appropriately adjust the degree of freedom of X. By appropriately adjusting the degree of freedom of X, the interaction with the liquid crystal to be oriented can be increased, the orientation of X can be controlled more, and the average tilt angle can be controlled more effectively.
Further, a linking group as shown below, which is formed by linking two or more of the linking groups, is also preferable. The part represented by * in L represents a part connected to Mp. In the following formula, m represents an integer of 1 to 20, and is synonymous with the above "m", and a preferable range is also synonymous.

Further, when Mp in the general formula (A-1) represents the Mp-1 or Mp-2, L is −O− and −NR ^a11− (R ^a11 is a hydrogen atom and the number of carbon atoms is 1. (10) Aliphatic hydrocarbon groups), -S-, -C (= O)-, -S (= O) _2- , and substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, and It is preferably a divalent linking group selected from a group formed by linking two or more of these, and −O−, −C (= O) O−, and −C (= O) NH. -, And a group selected from a divalent linking group consisting of a combination of one or more of these and an alkylene group is more preferable. For example, the above L-1, L-2, L-3, L-6 and the like.

The number of rings of the substituted or unsubstituted aromatic condensed ring functional group represented by X in the general formula (A-1) is not particularly limited, but a group in which 2 to 5 rings are condensed is a group. preferable. Not only a hydrocarbon-based aromatic fused ring in which the atom constituting the ring is only a carbon atom, but also an aromatic fused ring in which a heterocycle having a hetero atom as a ring-constituting atom is condensed may be used. X is a substituted or unsubstituted indenyl group having 5 to 30 carbon atoms (methylindenyl group, medoxyindenyl group, or heteroatosubstituted indenyl group, for example, benzofuranyl group, thionaphthenyl group, indolnyl group. , Indazolnyl group, benzimidazolnyl group, benzotriazolnyl group, 1-pyrazolpyrazinyl group, etc.), substituted or unsubstituted naphthyl group having 6 to 30 carbon atoms (methylnaphthyl group, cyanaunaphthyl group, fluoronaphthyl, etc.) A group, a bromonaphthyl group, or a naphthyl group substituted with a hetero atom, for example, a quinolyl group, an isoquinolyl group, a quinazolyl group, a quinoxalyl group, a 6,7-pyridopyridadinyl group, a benzotetrazynyl group, a pteryl group. Etc.), a substituted or unsubstituted fluorenyl group having 12 to 30 carbon atoms (2,7-dimethylfluorenyl group, or a fluorenyl group substituted with a hetero atom, for example, a carbazolyl group, a dibenzofuraryl group, a dibenzothio Phenyl group, etc.), anthryl group (5-methylanthryl group, or anthryl group substituted with a hetero atom, for example, xanthenyl group, acridinyl group, phenazinyl group, etc.), pyrenyl group, perylenyl group, phenanthrenyl group, etc. Is preferable.

In the general formula (A-1), X is more preferably a substituted or unsubstituted indenyl group having 5 to 30 carbon atoms, or a substituted or unsubstituted naphthyl group having 6 to 30 carbon atoms, and further. A substituted or unsubstituted naphthyl group having 10 to 30 carbon atoms is preferable, and a naphthyl group having 10 to 20 carbon atoms substituted or unsubstituted is particularly preferable.

In particular, L is a single bond or -O-, -NR ^a11- (where R ^a11 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms), -S-, -C (= O)- , And −S (= O) ₂ −, and in the case of a divalent linking group selected from a group formed by linking two or more of these, X is a substituted or unsubstituted naphthyl group. It is preferable to represent.

Specific examples of preferable structural units as the general formula (A-1) are shown below, but the present invention is not limited thereto.

(2) Constituent Unit Derived from a Fluoroaliphatic Group-Containing Monomer The polymer (A) used in the present invention is derived from a fluoroaliphatic group-containing monomer together with the structural unit represented by the general formula (A-1). Has a structural unit. The structural unit is preferably a structural unit represented by the following general formula (A-2). The details of the group represented by the general formula (A-2) will be described below.

・ General formula (A-2)

In the general formula (A-2), Mp'represents a trivalent group constituting a part of the main chain of the polymer, L'represents a single bond or a divalent linking group, and Rf represents at least one fluorine atom. Represents a substituent containing.

Mp'is synonymous with Mp in the general formula (A-1), and the preferred range is also synonymous.
L'preferably -O-, -NR ^a11- (where R ^a11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms). , -S-, -C (= O)-, -S (= O) _2- , and substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, and formed by connecting two or more of these. It is a divalent linking group selected from the groups to be used.
As a divalent linking group formed by linking two or more, -C (= O) O-, -OC (= O)-, -OC (= O) O-, -C (= O) NH -, -NHC (= O)-, -C (= O) O (CH ₂ ) _ma O- (where ma represents an integer of 1 to 20) and the like.

Further, when Mp'in the general formula (A-2) represents the Mp-1 or Mp-2, L'is -O- and -NR ^a11- (R ^a11 is a hydrogen atom and a carbon atom. Represents an aliphatic hydrocarbon group of numbers 1 to 10.), -S-, -C (= O)-, -S (= O) _2- , and substituted or unsubstituted having 1 to 20 carbon atoms. It is preferably a divalent linking group selected from an alkylene group and a group formed by linking two or more of these groups, preferably -O-, -C (= O) O-, and -C. (= O) NH- and a divalent linking group selected from a group consisting of a combination of one or more of these and an alkylene group (for example, the above L-1, L-2, L-3, etc.). Is more preferable.

Rf is an aliphatic hydrocarbon group having 1 to 30 carbon atoms substituted with at least one fluorine atom (for example, trifluoroethyl group, perfluorohexyl ethyl group, perfluorohexyl propyl group, perfluorobutyl ethyl group, per). Fluorooctylethyl group, etc.) and the like are preferable examples. Further, Rf is selected from the group consisting terminated, preferably has a CF ₃ group or CF ₂ H group, and more preferably has a CF ₃ group.

More preferred as Rf, an alkyl group or terminal having a CF ₃ group at the terminal is an alkyl group having a CF ₂ H group. An alkyl group having ₃ CF groups at the terminal is an alkyl group in which a part or all of hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. Alkyl groups in which 50% or more of hydrogen atoms in the alkyl group having ₃ CF groups at the terminal are substituted with fluorine atoms are preferable, alkyl groups in which 60% or more are substituted are more preferable, and 70% or more are substituted. Alkyl groups are particularly preferred. The remaining hydrogen atoms may be further substituted with substituents exemplified as Substituent Group D described later.
An alkyl group having a CF ₂ H group at the terminal is an alkyl group in which a part or all of hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. Preferably at least 50% of the hydrogen atoms in the alkyl group having a CF ₂ H group are substituted with fluorine atoms, and more preferable to be substituted is 60% or more, are substituted more than 70% It is especially preferable to have. The remaining hydrogen atoms may be further substituted with substituents exemplified as Substituent Group D described later.

Substituent group D
Alkyl group (preferably the number of carbon atoms (referred to as the number of carbon atoms contained in the substituent, hereinafter the same for the substituent group D) 1 to 20, more preferably the number of carbon atoms 1 to 12, particularly preferably 1 carbon atom. Alkyl groups of ~ 8, for example, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. An alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a vinyl group and a 2-butenyl group. , 3-Pentenyl group and the like), alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example. A propargyl group, a 3-pentynyl group, etc.), a substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms). It is an amino group, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, etc.),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group. An acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as an acetyl group, a formyl group, a pivaloyl group, etc. An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, a methoxycarbonyl group, An acyloxy group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as an acyloxy group, such as an ethoxycarbonyl group or the like. Etc.)

Acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group), alkoxycarbonylamino. A group (preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group). A sulfonylamino group (preferably a sulfonylamino group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methanesulfonylamino group and an ethanesulfonylamino group. , Etc.), a sulfamoyl group (preferably a sulfamoyl group having 0 to 20, more preferably 0 to 16 carbon atoms, particularly preferably a sulfamoyl group having 0 to 12 carbon atoms, for example, a sulfamoyl group, a methylsul. Famoyl group, dimethylsulfamoyl group, etc.).

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group). A sulfonyl group (preferably a sulfonyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group). A sulfinyl group (preferably a sulfinyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and an ethanesulfinyl group. ), Ureid group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group, a methyl ureido group. , Etc.), a phosphate amide group (preferably a phosphate amide group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, diethyl. Phosphate amide group), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, A hydrazino group, an imino group, a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, for example, a trimethylsilyl group and the like. Includes). These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, it may be the same or different. Further, if possible, they may be combined with each other to form a ring.

It is shown in the alkyl group or terminal having a CF ₃ group at the end of the examples of the alkyl group having a CF ₂ H group below.
R1: n-C ₈ F _17-
R2: n-C ₆ F _{13-
R3: n-C 4 F 9} -
R4: n−C ₈ F ₁₇ − (CH ₂ ) ₂ −
R5: n−C ₆ F ₁₃ − (CH ₂ ) ₃ −
R6: n−C ₄ F ₉ − (CH ₂ ) ₂ −
_{R7: H- (CF 2) 8} -
R8: H- (CF ₂ ) _{6-
R9: H- (CF 2) 4} -
_{R10: H- (CF 2) 8} - (CH 2) 2 -
R11: H- (CF ₂ ) _6- (CH ₂ ) _{3-
R12: H- (CF 2) 4} - (CH 2) 2 -
R13: n−C ₇ F ₁₅ − (CH ₂ ) ₂ −
R14: n−C ₆ F ₁₃ − (CH ₂ ) ₃ −
R15: n−C ₄ F ₉ − (CH ₂ ) ₂ −

Specific examples of the structural unit derived from the fluoroaliphatic group-containing monomer used in the present invention will be shown below, but the present invention is not limited thereto.

Further, the polymer used in the present invention includes a structural unit containing a structure represented by the general formula (A-1), a structural unit derived from a fluoroaliphatic group-containing monomer (A-2), and the like. It may contain a structural unit derived from a monomer copolymerizable with the monomer forming these structural units.

The content of the repeating unit (preferably the group represented by the general formula (A-2)) derived from the fluoroaliphatic group-containing monomer in the polymer used in the present invention is 40 to 40 to the molar ratio to all the constituent units. It is 75 mol%. It is more preferably 45 to 70 mol%, and particularly preferably 50 to 65 mol%.
The content of the group represented by the general formula (A-1) in the polymer used in the present invention is preferably 1 to 60 mol%, more preferably 3 to 25 mol%, as the molar ratio to all the constituent units.
The content of the structural units other than the above two types is preferably 60% by mass or less, more preferably 50% by mass or less.

Further, these copolymers may be a random copolymer in which each structural unit is irregularly introduced, or a block copolymer in which each structural unit is regularly introduced, and may be a block copolymer. Each constituent unit in a certain case may be synthesized in any order of introduction, and the same constituent component may be used twice or more.
Further, the group represented by the general formula (A), the group represented by the general formula (B), and the like may be of only one type or of two or more types. When two or more structural units of the general formula (A) are contained, it is preferable that X is the same fused ring skeleton (combination of substitution and non-substitution). In the case of two or more types, the above content is the total content.

Further, the molecular weight range of the polymer used in the present invention is a number average molecular weight (Mn), preferably 3000 to 10000, and more preferably 5000 to 9000. Within this range, the solubility in the composition and the leveling ability are high, and the effect of improving the adhesion and the wettability of the optically anisotropic film after the surface treatment is high. The molecular weight distribution of the polymer used in the present invention (Mw / Mn and Mw are weight average molecular weights) is preferably 1 to 4, more preferably 1.5 to 4.

The addition amount range of the polymer used in the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass, and further preferably 0.1 to 5.0% by mass with respect to the liquid crystal compound. It is 0.5 to 2.5% by mass.
Further, when two or more kinds of polymers used in the present invention are added as needed, the addition amount is the total addition amount.

The synthesis of the polymer used in the present invention can be carried out by applying a known method. The polymer used in the present invention can be synthesized by any one of addition, condensation and substitution reactions, or a combination thereof. Although there is no particular limitation, when the polymer used in the present invention contains an ethylenically repeating unit, it is convenient and preferable to synthesize it by utilizing a radical polymerization reaction of an ethylenically unsaturated compound corresponding to the repeating unit.

As the fluoroaliphatic group-containing polymer used in the present invention, a fluoroaliphatic group-containing polymer B different from the fluoroaliphatic group-containing polymer A may be added in addition to the above-mentioned fluoroaliphatic group-containing polymer A. Specific examples of these fluoroaliphatic group-containing polymers include compounds described in JP-A-2010-111110, JP-A-2008-231396, and the like.

[Polyfunctional polymerizable monomer]
The polymerizable liquid crystal composition of the present invention has the above-mentioned formulas (1) and (2) from the viewpoint of firmly aggregating the optically anisotropic film, suppressing the aggregation and breaking of the film, and realizing a laminated body having excellent adhesion. It is preferable that the compound does not correspond to any of the above and contains a polymerizable compound (polyfunctional polymerizable monomer) having two or more polymerizable groups.
The polyfunctional polymerizable monomer is preferably a polyfunctional radical polymerizable monomer. Specific examples of the polyfunctional radically polymerizable monomer include the polymerizable monomers described in paragraphs [0018] to [0020] in JP-A-2002-296423.
When the polyfunctional polymerizable monomer is contained, the content is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, based on the total mass of the liquid crystal compound.

[Polymerization initiator]
The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrances. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,416127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US Pat. 35493667 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 421,970), acylphosphine. Examples thereof include oxide compounds (described in JP-A-63-40799, JP-A-5-29234, JP-A-10-95788, JP-A-10-29997).

In the present invention, the polymerization initiator is preferably an oxime-type polymerization initiator, specifically, a polymerization initiator represented by the following formula (I), for the reason that the wet heat durability becomes better. It is more preferable to have it.

In the above formula (I), X ² represents a hydrogen atom or a halogen atom.
Further, in the above formula (I), Ar ³ represents a divalent aromatic group, and D ⁵ represents a divalent organic group having 1 to 12 carbon atoms.
Further, in the above formula (I), R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and Y ² represents a monovalent organic group.

In the above formula (I), examples of the halogen atom represented by X ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a chlorine atom is preferable.
Further, in the above formula (I), examples of the divalent aromatic group represented by Ar ³ include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; a furan ring and a pyrrole ring. , Aromatic heterocycles such as thiophene ring, pyridine ring, thiazole ring, benzothiazole ring; and the like.
Further, in the above formula (I), examples of the divalent organic group having 1 to 12 carbon atoms represented by D ⁵ include a linear or branched alkylene group having 1 to 12 carbon atoms, which are specific. A methylene group, an ethylene group, a propylene group and the like are preferably mentioned.
Further, in the above formula (I), as the alkyl group having 1 to 12 carbon atoms represented by R ¹¹ , specifically, for example, a methyl group, an ethyl group, a propyl group and the like are preferably mentioned.
Further, in the above formula (I), examples of the monovalent organic group represented by Y ² include a functional group containing a benzophenone skeleton ((C ₆ H ₅ ) ₂ CO). Specifically, a functional group containing a benzophenone skeleton in which the terminal benzene ring is unsubstituted or monosubstituted, such as the groups represented by the following formulas (Ia) and the following formula (Ib), is preferable. In the following formula (Ia) and the following formula (Ib), * represents a bond position, that is, a bond position of the carbonyl group in the above formula (I) with a carbon atom.

Examples of the oxime-type polymerization initiator represented by the above formula (I) include a compound represented by the following formula (S-1) and a compound represented by the following formula (S-2). ..

In the present invention, the content of the polymerization initiator is not particularly limited, but the solid content of the polymerizable liquid crystal composition is preferably 0.01 to 20% by mass, preferably 0.5 to 5% by mass. Is more preferable.

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

[Other ingredients]
The polymerizable liquid crystal composition of the present invention may contain a component other than the above-mentioned components, for example, a liquid crystal compound other than the above-mentioned polymerizable liquid crystal compound, a surfactant, a tilt angle control agent, an orientation auxiliary, and a plasticizer. Examples thereof include agents and chiral agents for cholesteric orientation.

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

The thickness of the optically anisotropic film of the present invention can be arbitrarily set from the required phase difference, but is typically 0.1 to 10 μm, preferably 0.1 to 5 μm. Is more preferable, and more preferably 0.1 μm or more and less than 3 μm.

When the optically anisotropic film of the present invention is obtained by fixing the orientation of the polymerizable liquid crystal compound (1) or the like by homogenic orientation, the polymerizable liquid crystal compound (1) has anti-wavelength dispersibility. , The following formula (3) is satisfied, and when the following formula (3) is satisfied, it is preferable that the following formula (4) is further satisfied.
Re (450) / Re (550) <1 ... (3)
0.50 <Re (450) / Re (550) <1.00 ... (4)

In the above formulas (3) and (4), Re (450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm. Represents a letteration. In this specification, when the measurement wavelength of the retardation is not specified, the measurement wavelength is 550 nm.

In the present invention, the values of in-plane retardation and retardation in the thickness direction refer to values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Optoscience).
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.
Although R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, it means Re (λ).

The optically anisotropic layer of the present invention can take an arbitrary orientation state, and can take, for example, homeotropic orientation, twist nematic orientation, cholesteric orientation, hybrid orientation, spray orientation, etc. in addition to the homogenius orientation described above. Since the polymerizable liquid crystal composition of the present invention is highly effective in giving uniform and uniform optical anisotropy especially in the case of homogenius orientation, twist nematic orientation and cholesteric orientation, it is possible to take homogenius orientation, twist nematic orientation and cholesteric orientation. It is preferable, and it is particularly preferable that the orientation is homogeneous.

When the orientation of the polymerizable liquid crystal compound (1) or the like is fixed by a homogeneous orientation, the optically anisotropic layer can exhibit the characteristics of a positive A plate. Here, the positive A plate (positive A plate) is defined as follows.
The refractive index in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized) is nx, the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny, and the refraction in the thickness direction. When the rate is nz, the positive A plate satisfies the relation of the formula (A1).
Equation (A1) nx> ny≈nz
The above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same.
“Substantially the same” means that in a positive A plate, for example, (ny-nz) × d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in "ny≈nz", and when (nx-nz) xd is -10 to 10 nm, preferably -5 to 5 nm, it is also included in "nx≈nz".

[Optical film]
The optical film of the present invention is an optical film having the optically anisotropic film of the present invention.
Hereinafter, various members used in the optical film of the present invention will be described in detail.

[Optically anisotropic film]
The optically anisotropic film of the optical film of the present invention is as described above.

In the formation, in particular, when the polymerizable liquid crystal composition of the present invention is fixed in a homogeneous orientation directly on a long support or via an alignment film, an optically anisotropic film is formed. The slow axis of the sex membrane can be controlled. The angle formed by the slow axis of the optically anisotropic film with the longitudinal direction of the elongated support can be appropriately set depending on the application of the optically anisotropic film. For example, it can be 0 ° or 90 ° (parallel or orthogonal) with respect to the longitudinal direction and can have an angle of 10-80 °. For example, when the polarizing plate to be described later is used for forming a circular polarizing plate in combination with a linear polarizing element having a long shape and an absorption axis in the longitudinal direction thereof, the slow axis of the optically anisotropic film and the optical film By setting the angle formed by the longitudinal direction in the range of 40 to 50 °, it is possible to manufacture a circularly polarizing plate by a roll-to-roll process having excellent productivity, which is preferable.

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

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

In the present invention, the thickness of the support is not particularly limited, but is preferably 5 to 60 μm, and more preferably 5 to 30 μm.
Further, the supports may both form an optical film, or may be separated from the optically anisotropic film as a temporary support and use only the optically anisotropic film.

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

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

In the present invention, it is also preferable to use a photoalignment film as the alignment film because it is possible to prevent surface deterioration by not contacting the surface of the alignment film when forming the alignment film.
The photoalignment film is not particularly limited, but is a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; described in JP2012-155308A. A liquid crystal alignment film formed by a liquid crystal alignment agent having a photo-oriented group; a trade name LPP-JP265CP manufactured by Polyimide, Inc. can be used.

Further, in the present invention, the thickness of the alignment film is not particularly limited, but from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic film having a uniform film thickness, 0. It is preferably 01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[Hard coat layer]
The optical film of the present invention can be provided with a hard coat layer in order to impart the physical strength of the film. Specifically, the hard coat layer may be provided on the side opposite to the side where the alignment film of the support is provided, and the hard coat layer may be provided on the side opposite to the side where the alignment film of the optically anisotropic film is provided. It may have a coat layer.
As the hard coat layer, those described in paragraphs [0190] to [0196] of JP-A-2009-98658 can be used.

[Other optically anisotropic membranes]
The optical film of the present invention may have another optically anisotropic film in addition to the optically anisotropic film of the present invention. That is, the optical film of the present invention may have a laminated structure of the optically anisotropic film of the present invention and another optically anisotropic film.
Other such optically anisotropic films include a polymer film, a film in which the orientation state of an arbitrary liquid crystal compound is fixed (also simply referred to as “liquid crystal film”), and an optically anisotropic inorganic substance oriented on a resin. An example is a film that has been fixed in place, and can be combined with any film. The laminated structure may be via an adhesive layer, or may be directly laminated by direct coating or self-adhesiveness. Further, a plurality of optically anisotropic films of the present invention having different optical characteristics may be stacked.

[UV absorber]
The optical film of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (particularly ultraviolet light).
The ultraviolet absorber may be contained in the optically anisotropic film of the present invention, or may be contained in a member other than the optically anisotropic film constituting the optical film of the present invention. As the member other than the optically anisotropic film, for example, a support is preferably mentioned.
As the ultraviolet absorber, any conventionally known one capable of exhibiting ultraviolet absorption can be used. Among such ultraviolet absorbers, a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber may be used from the viewpoint of obtaining the ultraviolet absorbing ability (ultraviolet blocking ability) used in an image display device because of its high ultraviolet absorbing ability. preferable.
Further, in order to widen the absorption range of ultraviolet rays, two or more kinds of ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.
Specific examples of the ultraviolet absorber include the compounds described in paragraphs [0258] to [0259] of JP2012-18395A, paragraphs [0055] to [0105] of JP2007-72163A. Examples thereof include the compounds described in.
Further, as commercially available products, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 1577 (all manufactured by BASF) and the like can be used.

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

FIG. 2 is a schematic cross-sectional view showing an example (circular polarizing plate) of the polarizing plate of the present invention.
The circular polarizing plate 16 shown in FIG. 2 includes a polarizer 18, a positive A plate 12, and a positive C plate 14 in this order. In FIG. 2, the circular polarizing plate 16 is arranged in the order of the polarizer 18, the positive A plate 12, and the positive C plate 14, but the present invention is not limited to this embodiment, and for example, the polarizer and the positive C are arranged. The plates may be arranged in the order of the positive A plate and the positive A plate.

FIG. 3 is a diagram showing the relationship between the absorption axis of the polarizer and the in-plane slow axis of the positive A plate in the polarizing plate of the present invention.
In FIG. 3, the arrow in the polarizer 18 indicates the direction of the absorption axis, and the arrow in the positive A plate 12 indicates the direction of the in-plane slow-phase axis in the layer.

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

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 1 μm to 60 μm, more preferably 2 μm to 30 μm, and even more preferably 5 μm to 15 μm.

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

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

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

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

[Organic EL display device]
Examples of the organic EL display device which is an example of the image display device of the present invention include, from the visual side, a polarizer, a λ / 4 plate (positive A plate) made of the optically anisotropic film of the present invention, and an organic EL. A mode having a display panel in this order is preferably mentioned.

The organic EL display device will be described with reference to the drawings. FIG. 4 shows a schematic cross-sectional view showing an example of an organic EL display device which is an aspect of the image display device of the present invention.
The organic EL display device 20 shown in FIG. 4 has a linear polarizer 18, a positive A plate 12, a positive C plate 14, and an organic EL display panel 22 in this order. As shown in FIG. 4, the linear polarizing element 18 in the circularly polarizing plate 16 is arranged on the viewing side.
Further, the organic EL display panel 22 is a display panel configured by using an organic EL element having an organic light emitting layer (organic electroluminescence layer) sandwiched between electrodes (between the cathode and the anode).
The configuration of the organic EL display panel 22 is not particularly limited, and a known configuration is adopted.

Hereinafter, the features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, amounts used, proportions, treatment contents, 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 limiting by the specific examples shown below.

[Example 1]

[Manufacturing Example 1]
<Preparation of alignment film P-1>
A coating liquid 1 for a photoalignment film was prepared on a commercially available triacetyl cellulose film (manufactured by Fujifilm, trade name: Z-TAC) with reference to JP2012-155308A and Example 3 description. , Applied with a wire bar. The alignment film P-1 having a thickness of 300 nm was prepared by drying with warm air at 60 ° C. for 60 seconds.

(Example 1)
<Formation of optically anisotropic film A-1>
The following composition A-1 was continuously applied on a support provided with the above-mentioned alignment film P-1. The coating film formed on the alignment film P-1 is heated to 180 ° C. under a heating atmosphere, then cooled to 120 ° C., and is coated with 100 mJ / cm ² ultraviolet rays at a wavelength of 365 nm using a high-pressure mercury lamp under a nitrogen atmosphere. By irradiating the film, the orientation of the liquid crystal compound was fixed, and an optical film 1 containing the optically anisotropic film A-1 was produced.

―――――――――――――――――――――――――――――――――
(Composition A-1)
―――――――――――――――――――――――――――――――――
-The following polymerizable liquid crystal compound L-1 42.00 parts by mass-The following polymerizable liquid crystal compound L-2 42.00 parts by mass-The following polymerizable liquid crystal compound L-3 16.00 parts by mass-The following polymerization initiator PI-1 0.50 parts by mass, the following leveling agent T-1 0.09 parts by mass, cyclopentanone 235.00 parts by mass ―――――――――――――――――――――――― ―――――――――

Polymerizable liquid crystal compound L-1

Polymerizable liquid crystal compound L-2

Polymerizable liquid crystal compound L-3

Polymerization Initiator PI-1

Leveling agent T-1 (fluoroaliphatic group-containing polymer A)

(Reference example 1)
Instead of the polymerizable liquid crystal composition A-1, the optically anisotropic layer coating liquid (D) described in paragraph [0125] of International Publication WO2013 / 137464 was used, and the drying conditions and UV irradiation conditions were set. An optical film A containing the optically anisotropic film A was prepared in the same manner as in Example 1 except that the conditions described in the paragraph of the publication [0124] were changed.

[Preparation of circularly polarizing plate 1]
The surface of the support TD80UL (manufactured by FUJIFILM Corporation) was subjected to alkali saponification treatment. Specifically, the support is immersed in a 1.5-standard sodium hydroxide aqueous solution at 55 ° C. for 2 minutes, the removed support is washed in a water-washing bath at room temperature, and 0.1-standard sulfuric acid is washed at 30 ° C. Neutralized with. Then, the obtained support was washed again in a water washing bath at room temperature, and further dried with warm air at 100 ° C.
Next, a roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution, and the stretched film was dried to obtain a polarizer having a thickness of 20 μm.
The obtained polarizing element and the support (TD80UL) subjected to the alkali saponification treatment were bonded to each other to obtain a polarizing plate in which the polarizer was exposed on one side.
Next, the longitudinal direction of the polarizing plate and the longitudinal direction of the optical film 1 are made parallel to each other, and an optically anisotropic layer 1 of the exposed surface of the polarizer in the polarizing plate and the triacetyl cellulose film in the optical film 1 is formed. The surface on the opposite side was continuously bonded to the opposite surface using a pressure-sensitive adhesive (SK-2057, manufactured by Soken Kagaku Co., Ltd.).
Next, the surface of the optical film 1 on the optically anisotropic film side and the surface of the positive C plate C-1 in the film C-1 produced above are bonded to a pressure-sensitive adhesive (SK-2057, manufactured by Soken Kagaku Co., Ltd.). ), And then the temporary support for formation in the film C-1 is peeled off to transfer only the positive C plate C-1 onto the optically anisotropic film A-1. Was produced.
Further, a circularly polarized plate was similarly prepared by using the optical film A instead of the optical film 1.
The following evaluations were performed on these circularly polarizing plates. The results are shown in Table 1.

<Measurement of optical characteristics>
The front retardation Re (450) and Re (550) of the optical film 1 were measured using AxoScan OPMF-1 (manufactured by Optoscience).

<Surface>
A mirror-treated aluminum plate was attached to the optically anisotropic film side of the obtained circularly polarizing plate using an adhesive, and the reflected light was visually observed under illumination of 500 lux, and light leakage due to uneven orientation was observed. In addition, the presence or absence of bright spots due to orientation defects was evaluated.

(Mounting on organic EL display device)
The GALAXY SIV manufactured by SAMSUNG, which is mounted on the organic EL display panel, was disassembled, the circularly polarizing plate was peeled off, and the circularly polarizing plates of the examples were laminated on the organic EL display panel to prepare an organic EL display device.
(OLED panel blackish)
The produced organic EL display device was displayed in black under a bright room, and the color of the panel reflected light was visually evaluated.
A: When it is neutral and tight black
B: If there is a slight black floating or if it is a slightly tinted black C: If it is clearly floating black or if it appears to be clearly tinted

From the results shown in Table 1 above, the optically anisotropic layer formed from the polymerizable liquid crystal composition of the present invention is uneven as compared with the optically anisotropic film formed from the conventional forward-dispersible polymerizable liquid crystal composition. It was found that it is possible to provide an OLED display device having excellent display performance at the time of black display by realizing inverse wavelength dispersibility while suppressing defects equally.

10 Optically anisotropic film 12 Positive A plate 14 Positive C plate 16 Circularly polarizing plate 18 Polarizer 20 Organic EL display device 22 Organic EL display panel

Claims (12)

It contains a polymerizable liquid crystal compound exhibiting inverse wavelength dispersibility, and a fluoroaliphatic group-containing polymer A containing a structural unit represented by the general formula (A-1) and a structural unit derived from a fluoroaliphatic group-containing monomer. ,
A polymerizable liquid crystal composition in the fluoroaliphatic group-containing polymer, wherein the structural units derived from the fluoroaliphatic group-containing monomer account for 40 to 70 mol% of the total structural units.
・ General formula (A-1)
(In the general formula (A-1), Mp represents a trivalent group constituting a part or all of the polymer main chain, L represents a single bond or a divalent linking group, and X is substituted or unsubstituted. Represents an aromatic condensed ring functional group.) The polymerizable liquid crystal composition according to claim 1, wherein the fluoroaliphatic group-containing polymer A is a naphthyl group in which X is substituted or substituted as a structural unit represented by the general formula (A-1). The polymerizable liquid crystal composition according to claim 1 or 2, wherein the fluoroaliphatic group-containing polymer A has a mass average molecular weight of 3000 to 10000. The polymerizable liquid crystal composition according to any one of claims 1 to 3, further comprising another fluoroaliphatic group-containing polymer B. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein the polymerizable liquid crystal composition is a polymerizable liquid crystal compound represented by the following formula (1).
L ^1- SP ^1- (E ^3- A ¹ ) _m- E ^1- G ^1- D ^1- Ar ^1- D ^2- G ^2- E ^2- (A ^2- E ⁴ ) _n- SP ^2- L ² ... (1)
(In the formulas (1) and (2), D ¹ , D ² , E ¹ , E ² , E ³ and E ⁴ are independently single-bonded, -CO-O-, and -C (= S). ^{O -, - CR 1 R 2} -, - CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 3 R 4 -, - CO-O- ^{CR 1 R 2 -, - O} -CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - Represents NR ^1- CR ² R ³ − or −CO −NR ¹ −. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or 1 to 4 carbon atoms. Represents the alkyl group of.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, and constitute the alicyclic hydrocarbon group-CH. ₂ - of one or more -O -, - S- or -NH- with optionally substituted.
Each of A ¹ and A ² may independently have a substituent, a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or a divalent alicyclic group having 5 to 8 carbon atoms. One or more of -CH _2- representing the hydrocarbon group and constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-.
SP ¹ and SP ² independently constitute 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, respectively. -CH ₂ - of one or more -O -, - S -, - NH -, - N (Q) -, or a divalent linking group which is substituted in -CO-, Q is a substituted group Represents.
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 ¹ or Ar ² is an aromatic ring represented by the following formula (Ar-3), at least 1 of L ¹ and L ² and L ³ and L ^{4 in} the following formula (Ar-3) One represents a polymerizable group.
m represents an integer of 0 to 2, and when m is 2, the plurality of E ^3s may be the same or different, and the plurality of A ^1s may be the same or different. You may.
n represents an integer of 0 to 2, when n is 2, a plurality of E ⁴ may each have the same or different and a plurality of A ² are different from each other be the same You may.
Ar ¹ represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5), and Ar ² represents any of the aromatic rings represented by the following formulas (Ar-1) to (Ar-1) to ( Represents any aromatic ring selected from the group consisting of groups represented by Ar-6).
Here, in the formulas (Ar-1) to (Ar-6), * represents the bonding position with D ¹ or D ² .
Further, Q ¹ represents N or CH.
Further, Q ² represents -S-, -O-, or -N (R ⁵ )-, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Further, Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
Further, Z ¹ , Z ² , Z ³ and Z ⁴ independently have a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic hydrocarbon having 3 to 20 carbon atoms. Represents a hydrogen group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ or -SR ⁹ , and R ^{6 to} R ⁹ Represent each independently as 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.
Further, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹⁰ )-, -S-, and -CO-, and R ¹⁰ is hydrogen. Represents an atom or substituent.
Further, X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Moreover, ^{D 3} and ^{D 4} each independently represent a single ^{bond, -CO-O -, - C} (= S) O -, - CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, ^{-O-CR 1 R 2 -,} - CR 1 R 2 -O-CR 3 R 4 -, - CO-O-CR 1 R 2 -, - O-CO-CR 1 R 2 -, - CR 1 R 2 ^{-O-CO-CR 3 R 4} -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 R 3 -, or, -CO-NR ¹ - represents a. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
Further, SP ³ and SP ⁴ independently have 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. One or more of the constituent −CH ₂₋ represents a divalent linking group substituted with −O−, −S−, −NH−, −N (Q) −, or −CO−, where Q represents a divalent linking group. Represents a substituent.
Further, L ³ and L ⁴ independently represent monovalent organic groups, respectively, and at least one of L ³ and L ⁴ and L ¹ and L ^{2 in} the above formula (1) or (2) has a polymerizable group. Represent.
In addition, 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, Ay is an alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom and a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Represents an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms. ) The polymerizable liquid crystal composition according to claim 5, wherein Ar ¹ in the formula (1) represents a group represented by the formula (Ar-1) or (Ar-2). The polymerizable liquid crystal composition according to any one of claims 1 to 6, wherein the polymerizable liquid crystal composition contains a polymerization initiator. An optically anisotropic film formed from the polymerizable liquid crystal composition according to any one of claims 1 to 7. The optically anisotropic film according to claim 8, wherein the liquid crystal molecules are fixed in a homogeneous orientation. An optical film comprising the optically anisotropic film according to claim 8 or 9. A polarizing plate comprising the optically anisotropic film and a polarizer according to claim 8 or 9. An image display device comprising the optical film according to claim 10 or the polarizing plate according to claim 11.