JP2020042149A - Liquid crystal film, optical laminate, circularly polarizing plate, and organic electroluminescence display device - Google Patents

Abstract

To provide a liquid crystal film having an optical anisotropic layer excellent in alignment property and adhesiveness, and to provide an optical laminate, a circularly polarizing plate and an organic EL display device using the optical anisotropic layer.SOLUTION: The liquid crystal film has at least: an optical anisotropic layer formed by using a liquid crystal composition comprising a polymerizable liquid crystal compound and a fluoroaliphatic group-containing copolymer; and a support body. The fluoroaliphatic group-containing copolymer has a repeating unit derived from a fluoroaliphatic group-containing monomer represented by general formula (1) and a repeating unit having a polymerizable group polymerizable with the polymerizable liquid crystal compound. In formula (1), R2 represents a hydrogen atom, a halogen atom or an alkyl group; L2 represents a divalent connecting group; and n represents an integer of 1 to 6.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal film, an optical laminate, a circularly polarizing plate, and an organic electroluminescence display device.

Optical films such as an optical compensatory sheet and a retardation film are used in various image display devices in order to eliminate coloring of an image or enlarge a viewing angle.
A stretched birefringent film has been used as an optical film, but in recent years, it has been proposed to use a film having an optically anisotropic layer made of a liquid crystal compound (liquid crystal film) instead of the stretched birefringent film. .

  For example, it has been proposed to use an optical film having an optically anisotropic layer containing a predetermined fluoroaliphatic group-containing copolymer in order to display a high-quality image without causing unevenness. (Patent Document 1).

  On the other hand, in recent years, the functions required for optical films have become more sophisticated, and it has been proposed to form various optical laminates by combining an optically anisotropic layer and a layer having an optical function to satisfy the requirements. ing. When combining these layers, it has been proposed to bond them together with an adhesive layer (Patent Document 2).

JP-A-2004-198511 WO13 / 137664

In an optically anisotropic layer formed using a liquid crystal compound, there is a demand for uniformly aligning the liquid crystal compound so as not to cause an alignment defect (hereinafter, satisfying such a requirement is referred to as having excellent alignment properties). Also called).
On the other hand, the present inventors formed an optically anisotropic layer having excellent orientation, and bonded the air interface side of such an anisotropic layer to a layer having an optical function (optical functional layer) and the like. In this case, it was found that the adhesion between the optically anisotropic layer and the optical functional layer may be insufficient.

Therefore, an object of the present invention is to provide a liquid crystal film having an optically anisotropic layer having excellent alignment properties and excellent adhesion.
Another object is to provide an optical laminate, a circularly polarizing plate, and an organic EL display device using the optically anisotropic layer.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have formed an optically anisotropic layer using a liquid crystal composition containing a polymerizable liquid crystal compound and a predetermined fluoroaliphatic group-containing copolymer. Thus, it has been found that the object of the present invention is achieved.
That is, the inventors have found that the above-described object can be achieved by the following configuration.

[1]
A liquid crystal film having at least an optically anisotropic layer and a support formed using a liquid crystal composition including a polymerizable liquid crystal compound and a fluoroaliphatic group-containing copolymer,
The fluoroaliphatic group-containing copolymer is a repeating unit having a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the following general formula (1) and a polymerizable group polymerizable with the polymerizable liquid crystal compound. A liquid crystal film having units.
[2]
The liquid crystal composition according to [1], wherein the content of the fluoroaliphatic group-containing copolymer in the liquid crystal composition is 0.01 to 0.20% by mass based on the total mass of the polymerizable liquid crystal compound. LCD film.
[3]
The liquid crystal film according to [1] or [2], wherein n represents an integer of 4 to 6.
[4]
The liquid crystal film according to any one of [1] to [3], wherein the polymerizable liquid crystal compound has a group selected from the group consisting of groups represented by general formulas (A1) to (A5) described below.
[5]
The liquid crystal film according to [4], wherein the polymerizable liquid crystal compound is a compound represented by the following general formula (W).
[6]
The liquid crystal film according to any one of [1] to [5], wherein the fluoroaliphatic group-containing copolymer further has a repeating unit derived from a terminal cyclic hydrocarbon group-containing monomer.
[7]
The liquid crystal film according to [6], wherein the terminal cyclic hydrocarbon group-containing monomer is a compound represented by the following general formula (2).
[8]
The liquid crystal film according to any one of [1] to [7], wherein the fluoroaliphatic group-containing copolymer has a repeating unit derived from a monomer represented by the following general formula (3).
[9]
The liquid crystal film according to any one of [1] to [8], having a photo-alignment layer between the support and the optically anisotropic layer.
[10]
The liquid crystal film according to any one of [1] to [9], wherein the support is detachably provided.
[11]
An optically anisotropic layer formed by using a liquid crystal composition containing a polymerizable liquid crystal compound and a fluoroaliphatic group-containing copolymer, an adhesive layer, and an optical functional layer, an optical laminate having at least:
The optically anisotropic layer and the optical functional layer are bonded via the adhesive layer,
The fluoroaliphatic group-containing copolymer is a repeating unit having a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the following general formula (1) and a polymerizable group polymerizable with the polymerizable liquid crystal compound. An optical laminate having a unit.
[12]
The optical laminate according to [11], wherein the adhesive layer is a layer obtained by curing a photopolymerizable adhesive.
[13]
The optical laminate according to [11] or [12], wherein the optical functional layer is a liquid crystal layer.
[14]
The optical laminate according to any one of [11] to [13], having a polarizer.
[15]
[10] A circularly polarizing plate having the optical laminate according to any one of [14] to [14].
[16]
An organic electroluminescence display device comprising an organic electroluminescence display element and the circularly polarizing plate according to [15].

According to the present invention, it is possible to provide a liquid crystal film having an optically anisotropic layer having excellent orientation and excellent adhesion.
Further, an optical laminate, a circularly polarizing plate, and an organic EL display device using the optically anisotropic layer can be provided.

FIG. 1 is a schematic sectional view showing an example of the liquid crystal film of the present invention. FIG. 2 is a schematic sectional view showing one example of the liquid crystal film of the present invention. FIG. 3 is a schematic sectional view showing an example of the liquid crystal film of the present invention. FIG. 4 is a schematic sectional view showing an example of the optical laminate of the present invention. FIG. 5 is a schematic sectional view showing an example of the optical laminate of the present invention. FIG. 6 is a schematic sectional view showing an example of the circularly polarizing plate of the present invention. FIG. 7 is a schematic sectional view showing one example of the organic electroluminescence (EL) display device of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the components described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In addition, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present specification, a divalent group, denoted (e.g., -CO-O-) binding direction is not particularly limited, for example, ^{D 1} in the general formula (W) to be described later -CO-O -, the, if the position that is attached the position that is attached to Ar side * 1, ^{G 1} side * 2 to, ^{D 1} may be a * 1-CO-O-* 2 , * 1-O-CO- * 2.

In the present specification, (meth) acrylate represents acrylate and methacrylate. (Meth) acrylic acid represents acrylic acid and methacrylic acid. The (meth) acryloyl group represents a methacryloyl group or an acryloyl group.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined by a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation). GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index) It is defined as a polystyrene equivalent value by a detector (Refractive Index Detector).

  In the description of the group (atomic group) in the present specification, the notation that does not indicate substituted or unsubstituted includes a group having a substituent as well as a group having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the “organic group” in the present specification refers to a group containing at least one carbon atom.

Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituent when "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom, and for example, can be selected from the following substituent group T.
(Substituent T)
As the substituent T, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; a phenoxy group and a p-tolyloxy group Aryloxy group; alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy group such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, and acryloyl An acyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group. Aryl group; hydroxy group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; Monoalkylamino groups; dialkylamino groups; arylamino groups; and combinations thereof.

[Liquid crystal film]
The liquid crystal film of the present invention has at least an optically anisotropic layer formed using a liquid crystal composition and a support.
Further, the liquid crystal composition contains a polymerizable liquid crystal compound and a fluoroaliphatic group-containing copolymer.
The fluoroaliphatic group-containing copolymer includes a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the following general formula (1), and a polymerizable group polymerizable with the polymerizable liquid crystal compound. Having a repeating unit.

The mechanism by which the problem of the present invention can be solved by the liquid crystal film having such a configuration is not necessarily clear, but the present inventors think as follows.
First, when an optically anisotropic layer is formed by applying a liquid crystal composition to a support or the like, an additive used to improve the orientation of the optically anisotropic layer is added to the optically anisotropic layer. It is considered that the phenomenon that the adhesiveness of the optically anisotropic layer becomes insufficient due to the uneven distribution on the air interface side has occurred. The unevenly distributed additive easily forms a fragile layer on the air interface side of the optically anisotropic layer, and as a result, when the surface on the air interface side of the optically anisotropic layer and the optical functional layer are bonded, It is considered that the optically anisotropic layer and the optical functional layer and the like are easily separated in such a manner that the fragile layer is separated.

With respect to such a problem, in the present invention, a predetermined fluoroaliphatic group-containing copolymer is used in a liquid crystal composition used for forming an optically anisotropic layer. Since the fluoroaliphatic group-containing copolymer has a repeating unit derived from a terminal cyclic hydrocarbon group-containing monomer, the orientation of the formed optically anisotropic layer can be improved. Furthermore, the fluoroaliphatic group-containing copolymer has a repeating unit having a polymerizable group, and the fluoroaliphatic group-containing copolymer unevenly distributed on the air interface side of the optically anisotropic layer is polymerizable. It can be copolymerized with a liquid crystal compound, and the surface of the optically anisotropic layer can be strengthened. Therefore, separation between the optically anisotropic layer and the optically functional layer as described above does not easily occur, and the adhesion is improved.
Further, when the fluoroaliphatic group-containing copolymer has a repeating unit derived from a monomer represented by the following general formula (3), the adhesion between the optically anisotropic layer and the optically functional layer becomes poor. The present inventors believe that it becomes stronger and the adhesion is further improved.

  Hereinafter, the liquid crystal film of the present invention will be described in detail.

The liquid crystal film of the present invention can be shown, for example, in a schematic sectional view as shown in FIGS.
FIG. 1 shows a liquid crystal film 1A of the present invention in which an optically anisotropic layer 2 is directly laminated on a support 3.
FIG. 2 shows a film 1 </ b> B formed by laminating an optically anisotropic layer 2 on an alignment layer 4 provided on a support 3.
FIG. 3 shows a liquid crystal film 1 </ b> C in which an intermediate layer 5 is provided between a support 3 and an alignment layer 4.
Hereinafter, each layer constituting the liquid crystal film of the present invention will be described.

(Optical anisotropic layer)
<Liquid crystal composition>
The optically anisotropic layer is formed using a liquid crystal composition (composition for forming an optically anisotropic layer). The liquid crystal composition contains at least a fluoroaliphatic group-containing copolymer and a polymerizable liquid crystal compound.
Hereinafter, the components contained in the liquid crystal composition will be described.

(Polymerizable liquid crystal compound)
The liquid crystal composition contains a polymerizable liquid crystal compound.
The polymerizable liquid crystal compound is a liquid crystal compound having at least one polymerizable group.
In general, liquid crystal compounds can be classified into rod-shaped and disk-shaped types according to their shapes. Furthermore, there are low-molecular and high-molecular types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (polymer physics / phase transition dynamics, Masao Doi, page 2, Iwanami Shoten, 1992).
As the polymerizable liquid crystal compound, any liquid crystal compound can be used as long as it has a polymerizable group. Among them, it is preferable to use a rod-shaped polymerizable liquid crystal compound or a disc-shaped polymerizable liquid crystal compound. More preferably, a compound is used.
Note that the liquid crystal composition may include a liquid crystal compound other than the polymerizable liquid crystal compound.

The polymerizable liquid crystal compound preferably has two or more polymerizable groups in one molecule. When two or more polymerizable liquid crystal compounds are used, it is preferable that at least one polymerizable liquid crystal compound has two or more polymerizable groups in one molecule.
After the liquid crystal compound is fixed by polymerization, it is no longer necessary to exhibit liquid crystallinity, but the layer thus formed may be referred to as a liquid crystal layer for convenience. The liquid crystal layer is preferably a layer in which an aligned liquid crystal compound is fixed while maintaining its alignment state.

  The type of the polymerizable group included in the polymerizable liquid crystal compound is not particularly limited, and a functional group capable of performing an addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable. More specifically, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, an epoxy group, or an oxetane group is preferable, and a (meth) acryloyl group is more preferable in that the polymerization reaction is performed at a high speed.

  Examples of the rod-shaped polymerizable liquid crystal compound include the compound described in claim 1 of Japanese Patent Application Laid-Open No. H11-513019 and the compounds described in paragraphs [0026] to [0098] of JP-A-2005-289980. Is mentioned. Examples of the discotic polymerizable liquid crystal compound include compounds described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038. ] The compound described in the above.

  Examples of the rod-shaped polymerizable liquid crystal compound include a liquid crystal compound capable of expressing a smectic phase, for example, JP-A-2006-51178, JP-A-2008-214269, JP-A-2008-19240, and The compounds described in JP-A-2006-276821 are exemplified.

Further, as the rod-shaped polymerizable liquid crystal compound, a polymerizable liquid crystal compound having a maximum absorption wavelength in a wavelength range of 330 to 380 nm is preferable.
Further, the rod-shaped polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having reverse wavelength dispersion.
Here, in the present specification, the “reverse wavelength dispersive” polymerizable liquid crystal compound refers to an in-plane at a specific wavelength (visible light range) of a retardation film (optically anisotropic layer or the like) produced using the same. When the retardation value (Re) is measured, the Re becomes equal or higher as the measurement wavelength increases.
Specifically, a polymerizable liquid crystal compound that can form an optically anisotropic layer satisfying the following formula is preferable.
Re (450) / Re (550) <1.00
Here, in the above formula, Re (450) represents in-plane retardation of the optically anisotropic layer at a wavelength of 450 nm, and Re (550) represents in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm. . The value of the in-plane retardation can be measured using AxoScan OPMF-1 (manufactured by OptoSciences) using light of a measurement wavelength.

-General formulas (A1) to (A5)
The polymerizable liquid crystal compound is preferably a compound having a group selected from the group consisting of groups represented by formulas (A1) to (A5). By having such a group, reverse wavelength dispersion can be easily introduced into the polymerizable liquid crystal compound.

In the general formulas (A1) to (A5), * 1 and * 2 represent bonding positions.
In the general formula (A1), Q ¹ represents N or CH, Q ² represents —S—, —O—, or —N (J ⁵ ) —, and J ⁵ represents a hydrogen atom or a carbon number. 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;
The alkyl group having 1 to 6 carbon atoms represented by J ^5, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl Group, n-pentyl group, n-hexyl group and the like.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented 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 represented by Y ¹ include a heteroaryl group such as a thienyl group, a thiazolyl group, a furyl group, and a pyridyl group.
Examples of the substituent which Y ¹ may have include, for example, 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, methyl group, ethyl group, propyl group, isopropyl group) , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group and the like), more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group) is more preferable. And an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom or a chlorine atom is preferable.

In the general formulas (A1) to (A5), Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 3 to 5 carbon atoms. 20 monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, ^-NJ 6 ^{J 7,} or represents -SJ ^8, J ^{6 to} J ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form an aromatic ring.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable. Specifically, a methyl group and an ethyl group , An isopropyl group, a tert-pentyl group (1,1-dimethylpropyl group), a tert-butyl group, or a 1,1-dimethyl-3,3-dimethyl-butyl group is more preferable, and a methyl group, an ethyl group, or And a tert-butyl group 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 Monocyclic saturated hydrocarbon groups such as ethylcyclohexyl group; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, And a monocyclic unsaturated hydrocarbon group such as cyclodecadiene; 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, tetracyclyl B [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecyl group and polycyclic saturated hydrocarbon group such as adamantyl group; and the like.
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, and a biphenyl group, and an aryl group having 6 to 12 carbon atoms. (Particularly a phenyl group) is preferred.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom, a chlorine atom, or a bromine atom is preferable.
On the other hand, examples of the alkyl group having 1 to 6 carbon atoms represented by J ^{6 to} J ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Group, n-pentyl group, n-hexyl group and the like.

In the general formulas (A2) and (A3), A ³ and A ⁴ are each independently a group consisting of —O—, —N (J ⁹ ) —, —S—, and —CO—. Represents a selected group, and J ⁹ represents a hydrogen atom or a substituent.
Examples of the substituent represented by J ⁹ include the same substituents as those that Y ¹ in the above formula (A1) may have.

In the general formula (A2), X represents a hydrogen atom or a non-metallic atom of Groups 14 to 16 to which a substituent may be bonded.
Examples of the non-metallic atoms of Groups 14 to 16 represented by X include, for example, an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Examples of the substituent include, 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, and a hydroxyl group. No.

In the formula (A3), D ⁵ and D ⁶ each independently represent a single bond, —CO—O—, —C (（S) O—, —CJ ¹ J ² —, or —CJ ¹ J. ^{2 -CJ 3 J 4 -, -} O-CJ 1 J 2 -, - CJ 1 J 2 -O-CJ 3 J 4 -, - CO-O-CJ 1 J 2 -, - O-CO-CJ 1 J ^{2 -, - CJ 1 J 2} -O-CO-CJ 3 J 4 -, - CJ 1 J 2 -CO-O-CJ 3 J 4 -, - NJ 1 -CJ 2 J 3 -, or, -CO- Represents NJ ^1- . J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

In the formula (A3), SP ³ and SP ⁴ each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight-chain or branched alkylene group having 1 to 12 carbon atoms. _Two or more of —CH ₂ — that constitute a chain or branched alkylene group are substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—. Q represents a valent linking group, and Q represents a substituent. Examples of the substituent include the same as the substituent which Y ¹ in the above formula (A1) may have.

In Formula (A3), E ³ and E ⁴ each independently represent a monovalent organic group.

In the general formulas (A4) to (A5), Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represent.
In the general formulas (A4) to (A5), Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of
Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of WO 2014/010325.
Examples of the alkyl group having 1 to 6 carbon atoms represented by Q ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a -Pentyl group, n-hexyl group, and the like. Examples of the substituent include the same substituents as those that Y ¹ in the above formula (A1) may have.

・ General formula (W)
Above all, the polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having a reverse wavelength dispersion represented by the general formula (W).
^{E 1 -SP 1 -A 1 -D 3} -G 1 -D 1 -Ar-D 2 -G 2 -D 4 -A 2 -SP 2 -E 2 ·· (W)

In the general formula (W), Ar represents any group selected from the group consisting of the groups represented by the general formulas (A1) to (A5) described above. In this case, in the following general formula (A1) ~ (A5), * 1 denotes the bonding position to ^{D 1,} * 2 preferably represent a bonding site to the ^{D 2.}

In the above general formula (W), D ¹ , D ² , D ³ and D ⁴ each independently represent a single bond, —CO—O—, —C (（S) O—, —CJ ¹ J ² —, ^{-CJ 1 J 2 -CJ 3 J 4} -, - O-CJ 1 J 2 -, - CJ 1 J 2 -O-CJ 3 J 4 -, - CO-O-CJ 1 J 2 -, - O-CO ^{-CJ 1 J 2 -, - CJ} 1 J 2 -O-CO-CJ 3 J 4 -, - CJ 1 J 2 -CO-O-CJ 3 J 4 -, - NJ 1 -CJ 2 J 3 -, or , -CO-NJ ^1- . J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
In the general formula (W), G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and —CH constituting the alicyclic hydrocarbon group. ₂ - of one or more -O -, - S- or -NH- with optionally substituted.
In the general formula (W), A ¹ and A ² each independently represent an aromatic ring group having 6 or more carbon atoms or a cycloalkylene ring group having 6 or more carbon atoms.
In the formula (W), SP ¹ and SP ² each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight-chain or branched alkylene group having 1 to 12 carbon atoms. A chain in which one or more of —CH ₂ — constituting a chain or branched alkylene group is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—; Q represents a valent linking group, and Q represents a substituent.
In the general formula (W), E ¹ and E ² each independently represent a monovalent organic group, and at least one of E ¹ and E ² represents a polymerizable group. However, when Ar is a group represented by the above general formula (A3), at least one of E ¹ and E ² and E ³ and E ^{4 in} the above general formula (A3) is a polymerizable group. Represent.

In Formula (W), the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G ¹ and G ² is preferably a 5- or 6-membered ring. The alicyclic hydrocarbon group may be saturated or unsaturated, but is preferably a saturated alicyclic hydrocarbon group. As the divalent alicyclic hydrocarbon group represented by G ¹ and G ² , for example, the description in paragraph [0078] of JP-A-2012-21068 can be referred to, and the contents thereof are incorporated herein. .

In the general formula (W), examples of the aromatic ring group having 6 or more carbon atoms represented by A ¹ and A ² include aromatic groups such as a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthroline ring group. And aromatic heterocyclic groups such as a furan ring group, a pyrrole ring group, a thiophene ring group, a pyridine ring group, a thiazole ring group, and a benzothiazole ring group. Especially, a benzene ring group (for example, 1,4-phenyl group etc.) is preferable.
In the general formula (W), examples of the cycloalkylene ring group having 6 or more carbon atoms represented by A ¹ and A ² include a cyclohexane ring group and a cyclohexene ring group. (For example, cyclohexane-1,4-diyl group and the like) are preferable.

In the general formula (W), the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ¹ and SP ² is preferably a methylene group, an ethylene group, a propylene group, or a butylene group.

In the general formula (W), the polymerizable group represented by at least one of E ¹ and E ² is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization.
As the radical polymerizable group, a generally known radical polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferable. In this case, an acryloyl group is generally known to have a high polymerization rate, and an acryloyl group is preferable from the viewpoint of improving productivity. However, a methacryloyl group can be similarly used as a polymerizable group of a highly birefringent liquid crystal.
As the cationic polymerizable group, a generally known cationic polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro ortho ester group, And a vinyloxy group. Above all, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetane group, or a vinyloxy group is more preferable.
Examples of particularly preferred polymerizable groups include the following.

  Preferred examples of the liquid crystal compound represented by the general formula (W) are shown below, but are not limited to these liquid crystal compounds. The 1,4-cyclohexylene groups in the following formulas are all trans-1,4-cyclohexylene groups.

  In the above formula, “*” represents a bonding position.

  In addition, the group adjacent to the acryloyloxy group in the above formulas II-2-8 and II-2-9 represents a propylene group (a group in which a methyl group is substituted by an ethylene group), and the methyl group is located at different positions. Represents a mixture of bodies.

One type of polymerizable liquid crystal compound may be used alone, or two or more types may be used. From the viewpoint of suppressing crystallization of the polymerizable liquid crystal compound and realizing good solubility and liquid crystallinity, it is preferable to use two or more kinds. Further, a polymerizable liquid crystal compound other than those described above may be used.
As the polymerizable liquid crystal compound, a polymerizable liquid crystal compound described in a liquid crystal handbook (edited by Liquid Crystal Handbook Editing Committee, published by Maruzen Co., Ltd. on October 30, 2000) and a known polymerizable liquid crystal compound can be used. Is also good.

In the liquid crystal composition, the content of the polymerizable liquid crystal compound is preferably from 50 to 99.99% by mass, more preferably from 65 to 99.5% by mass, and more preferably from 70 to 99.5% by mass, based on the total mass of the solid content of the liquid crystal composition. 99 mass% is more preferred.
One type of polymerizable liquid crystal compound may be used alone, or two or more types may be used.
When two or more polymerizable liquid crystal compounds are used, the total content thereof is preferably within the above range.
The solid content of the liquid crystal composition is a component capable of forming an optically anisotropic layer, and does not include a solvent. In addition, even if the property of the above-mentioned component is liquid, when it can form an optically anisotropic layer, it is calculated as solid content.

In addition, when a polymerizable liquid crystal compound having reverse wavelength dispersion (preferably, a polymerizable liquid crystal compound represented by the general formula (W)) is used as the polymerizable liquid crystal compound, the content of the polymerizable liquid crystal compound may vary depending on optical properties. In light of imparting reverse wavelength dispersion to the isotropic layer, the content is preferably 50% to 100% by mass, more preferably 65% to 95% by mass, and more preferably 70% to 90% by mass, based on the total mass of the liquid crystal compound in the liquid crystal composition. Is more preferred.
The polymerizable liquid crystal compound having reverse wavelength dispersion (preferably, the polymerizable liquid crystal compound represented by the general formula (W)) may be used alone or in combination of two or more. When two or more polymerizable liquid crystal compounds having reverse wavelength dispersibility are used, the total content thereof is preferably within the above range.
Note that the total mass of the liquid crystal compound is the total mass of the compound exhibiting liquid crystallinity in the liquid crystal composition, and when the liquid crystal composition also contains a non-polymerizable liquid crystal compound, not only the polymerizable liquid crystal compound but also And the mass obtained by adding the mass of the non-polymerizable liquid crystal compound.

(Fluoroaliphatic group-containing copolymer)
The liquid crystal composition contains a fluoroaliphatic group-containing copolymer.
The fluoroaliphatic group-containing copolymer has a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the following general formula (1), and a polymerizable group copolymerizable with the polymerizable liquid crystal compound. It is a copolymer having at least a repeating unit. The copolymer may be a random copolymer or a block copolymer.

· General formula (1) in the repeating unit formula derived from the fluoroaliphatic group-containing monomer represented in (1), R ² represents a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine Atom) or an alkyl group.
The alkyl group may have a substituent. The alkyl group preferably has 1 to 6 carbon atoms.
Among them, R ² is preferably a hydrogen atom or a methyl group.

In the general formula (1), L ² represents a divalent linking group.
L ² represents —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—, A divalent linking group selected from —CO—, —SO ₂ —, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a group formed by linking two or more thereof is preferable.
The divalent linking group formed by linking two or more, -CO-O -, - O -CO-O -, - CO-NH -, - CO-O- (CH 2) ma O- ( However, ma represents an integer of 1 to 20).
Among them, as the divalent linking group, -O-, -CO-O-, -CO-NH-, or a group composed of a combination of one or more of these and an alkylene group (for example, the following general formula (L- 1) to (L-3)) are more preferred.
In the following formulas (L-1) to (L-3), * represents a bonding position to the vinylidene group in formula (1). m represents an integer of 1 to 20, preferably 2 to 16, more preferably 2 to 12, and still more preferably 2 to 6.

  In the general formula (1), n represents an integer of 1 to 6, and preferably 4 to 6.

  Examples of the fluoroaliphatic group-containing monomer represented by the general formula (1) are shown below.

The content of the repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (1) is preferably from 5 to 90 mol%, based on all the repeating units of the fluoroaliphatic group-containing copolymer. -80 mol% is more preferable, and 15-75 mol% is still more preferable.
The repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (1) may be used alone or in combination of two or more. When two or more repeating units derived from the fluoroaliphatic group-containing monomer represented by the general formula (1) are used, the total content is preferably within the above range.

-Repeating unit having a polymerizable group The fluoroaliphatic group-containing copolymer also has a repeating unit having a polymerizable group copolymerizable with the above-described polymerizable liquid crystal compound.
The type of the polymerizable group in the repeating unit is not particularly limited as long as it can be copolymerized with the polymerizable liquid crystal compound. The polymerizable group is preferably a functional group capable of performing an addition polymerization reaction, and is preferably a polymerizable ethylenically unsaturated group or a ring polymerizable group. More specifically, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, an epoxy group, or an oxetane group is preferable. Among them, a (meth) acryloyl group is more preferable in that the polymerization reaction is performed at a high speed.
However, from the viewpoint of reactivity, the polymerizable liquid crystal compound preferably has the same polymerizable group as the polymerizable group.
As the repeating unit having a polymerizable group, a repeating unit represented by the general formula (X) is preferable.

In the general formula (X), R ³¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.
L ³¹ is a single bond or a divalent linking group, and is preferably a single bond, —O—, —CO—O—, —CO—NH—, an alkylene group, or an arylene group.
P ³¹ represents a monovalent group containing a polymerizable group. Examples of the polymerizable group are as described above.
P ³¹ is preferably a monovalent group having an ethylenically unsaturated group, is preferably a monovalent group having a group selected from the group consisting of a (meth) acryloyl group and a styryl group, and is preferably a (meth) acryloyl group. Is more preferred.
As P ³¹ , “-alkylene group- (single bond or ether group) -ethylenically unsaturated group” or “-alkylene group-L ^x -alkylene group- (single bond or ether group) -ethylenically unsaturated group” Is preferred. The number of carbon atoms of the alkylene group is preferably independently 1 to 4. ^Lx is a divalent linking group other than an alkylene group, and is preferably -O-, -CO-O-, -CO-NH-, or -O-CO-NH-.

  The repeating unit represented by the general formula (X) is exemplified below.

The content of the repeating unit having a polymerizable group is preferably from 1 to 90 mol%, more preferably from 3 to 80 mol%, even more preferably from 5 to 70 mol%, based on all repeating units of the fluoroaliphatic group-containing copolymer. .
One type of repeating unit having a polymerizable group may be used alone, or two or more types may be used. When two or more repeating units having a polymerizable group are used, the total content is preferably within the above range.

-Repeating unit derived from terminal cyclic hydrocarbon group-containing monomer The fluoroaliphatic group-containing copolymer preferably further has a repeating unit derived from a terminal cyclic hydrocarbon group-containing monomer.
The terminal cyclic hydrocarbon group-containing monomer is a compound having a monovalent cyclic hydrocarbon group.
The cyclic hydrocarbon group may or may not have a substituent.
The cyclic hydrocarbon group may be an aromatic ring group or a group having no aromaticity such as an alicyclic group (such as a cyclohexane ring group or a cyclohexene ring group). Especially, the cyclic hydrocarbon group is preferably an aromatic ring group. In other words, the terminal cyclic hydrocarbon group-containing monomer is preferably a terminal aromatic hydrocarbon-containing monomer.
The cyclic hydrocarbon group may be a single ring or a condensed ring. The cyclic hydrocarbon group which is a condensed ring is preferably a group in which 2 to 5 rings are condensed.
In the cyclic hydrocarbon group, one or more carbon atoms constituting the ring may be substituted with a hetero atom (an oxygen atom, a nitrogen atom, a sulfur atom, or the like). In this case, it is preferable that the cyclic hydrocarbon group is a condensed ring, and in one or more of the rings constituting the condensed ring, all the atoms constituting the ring are carbon atoms.
The cyclic hydrocarbon group preferably has 5 to 30 carbon atoms.

  Examples of the cyclic hydrocarbon group include a substituted or unsubstituted phenyl group, an indenyl group (a methylindenyl group, a methoxyindenyl group, or an indenyl group substituted with a hetero atom (eg, a benzofuranyl group, a thionaphthenyl group) , Indolnyl group, indazonyl group, benzimidazonyl group, benzotriazonyl group, 1-pyrazolepyrazinyl group, etc.), naphthyl group (methylnaphthyl group, cyanonaphthyl group, fluoronaphthyl group, bromonaphthyl group) And 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-pyridopyridazinyl group, a benzotetrazinyl group, and a pteryl group) ), A fluorenyl group (2,7-dimethylfluorenyl) And a fluorenyl group substituted with a hetero atom (for example, a carbazolyl group, a dibenzofuralyl group, and a dibenzothiophenyl group), an anthryl group (a 5-methylanthryl group, and a hetero atom-substituted group) An anthryl group (e.g., a xanthenyl group, an acridinyl group, and a phenazinyl group)), a pyrenyl group, a perylenyl group, or a phenanthrenyl group are preferable, a substituted or unsubstituted naphthyl group is more preferable, and an unsubstituted naphthyl group is more preferable. preferable.

  The terminal cyclic hydrocarbon group-containing monomer is preferably a monomer represented by the general formula (2).

In the general formula (2), R ¹ represents a hydrogen atom, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), or an alkyl group.
The alkyl group may have a substituent. The alkyl group preferably has 1 to 6 carbon atoms.
Among them, R ¹ is preferably a hydrogen atom or a methyl group.

In the general formula (2), L ¹ represents a divalent linking group having an alkylene group having 2 or more carbon atoms which may have a substituent.
L ¹ is ^{"- L} a -AL-L ^{b -"} group represented by are preferred.
Here, AL represents an optionally substituted alkylene group having 2 or more carbon atoms (preferably having 2 to 6 carbon atoms).
L ^a and L ^b each independently represent a single bond or a divalent linking group.
Incidentally, a group L ^a is bonded to the vinylidene group of the general formula [2], a group L ^b is bonded to Y in the general formula (2).
Specific examples of the divalent linking group of L ^a and L ^b, each independently represent a substituted or unsubstituted alkylene group (having 1 to 20 carbon atoms are preferred. For example, a methylene group, an ethylene group, a propylene group, a butylene group and, isopropylene group), preferably an alkenylene group having from 1 to 20 carbon atoms (C2-20 example, vinylene group, butene ^{group), -. O -, -} NR a1 -, - S -, - PR a2 -, -Si (R ^a3 ) (R ^a4 )-, -CO-, -CO-O-, -CO-NRa5-, -O-CO-O-, -O-CO-NR ^a6- , -NR ^a7 —CO—NR ^a8 —, —SO ₂ —, and a group formed by linking two or more thereof are exemplified.
R ^{a1 to} R ^a8 represent a hydrogen atom or a substituent.

Further, L ¹ is also preferably a group represented by formulas (M-1) to (M-7).
In the following general formulas (M-1) to (M-7), * represents a bonding position to a vinylidene group in the general formula (2). p represents an integer of 2 to 20, preferably 2 to 16, more preferably 2 to 12, and still more preferably 2 to 6.

In the general formula (2), Y represents an aromatic ring group which may have a substituent.
The aromatic ring group may be a single ring or a condensed ring. The aromatic ring group which is a condensed ring is preferably a group in which 2 to 5 rings are condensed.
In the aromatic ring group, one or more atoms constituting the ring may be substituted with a hetero atom (an oxygen atom, a nitrogen atom, a sulfur atom, or the like). In this case, it is preferable that the aromatic ring group is a condensed ring, and in one or more of the rings constituting the condensed ring, all of the atoms constituting the ring are carbon atoms.
The aromatic ring group preferably has 5 to 30 carbon atoms.
Specific examples of the aromatic ring group include the same groups as the preferred groups of the cyclic hydrocarbon group of the terminal cyclic hydrocarbon group-containing monomer.

  The repeating unit derived from the terminal cyclic hydrocarbon group-containing monomer is exemplified below.

When the fluoroaliphatic group-containing copolymer has a repeating unit derived from a terminal cyclic hydrocarbon group-containing monomer, the content is 5 to 90 mol, based on all the repeating units of the fluoroaliphatic group-containing copolymer. %, More preferably 10 to 80 mol%, even more preferably 15 to 75 mol%.
The repeating unit derived from the terminal cyclic hydrocarbon group-containing monomer may be used alone or in combination of two or more. When two or more types of repeating units derived from the terminal cyclic hydrocarbon group-containing monomer are used, the total content thereof is preferably within the above range.

-Repeating unit having a crosslinkable group The fluoroaliphatic group-containing copolymer may further have a repeating unit having a crosslinkable group.
When the fluoroaliphatic group-containing copolymer has a repeating unit having a crosslinkable group, the adhesion of the optically anisotropic layer is more excellent.
The crosslinkable group is a compound contained in a material (composition) for forming a layer that directly contacts the air interface side of the optically anisotropic layer or a layer that directly contacts the air interface side of the optically anisotropic layer. It is preferable to select a group that can crosslink with the functional group of
For example, when the adhesive layer is directly disposed on the air interface side of the optically anisotropic layer, and when the adhesive layer is made of an epoxy-based adhesive, a repeating unit having a crosslinkable group is a crosslinkable group, It preferably has a group capable of crosslinking with an epoxy group (a hydroxyl group, an oxetane group, an epoxy group, an amino group, etc.). By doing so, the epoxy group of the epoxy adhesive and the crosslinkable group of the repeating unit having a crosslinkable group can be crosslinked, and the adhesion between the optically anisotropic layer and the adhesive layer is further improved.

Examples of the crosslinkable group include a hydroxyl group, an oxetane group, a carboxy group, an amino group (primary, secondary, and tertiary amino groups), an isocyanate group, an epoxy group, and an alkoxysilyl group.
In addition, examples of the functional group that can be cross-linked with these cross-linkable groups include the following combinations.
(Crosslinkable group: functional group) = (hydroxyl group: isocyanate group), (hydroxyl group: benzyl halide group), (hydroxyl group: carboxylic anhydride group), (hydroxyl group: epoxy group), (hydroxyl group: alkoxysilyl group), (Oxetane group: epoxy group), (carboxy group: primary or secondary amino group), (carboxy group: aziridine group), (carboxy group: isocyanate group), (carboxy group: epoxy group), (carboxy group: halogenated) (Benzyl group), (primary or secondary amino group: isocyanate group), (primary, secondary or tertiary amino group: halogenated benzyl group), (primary amino group: aldehydes), (isocyanate group: primary or secondary) Secondary amino group), (isocyanate group: isocyanate group), (isocyanate group: hydroxyl group), (isocyanate group: epoxy group) , (Epoxy group: primary or secondary amino group), (epoxy group: carboxylic acid anhydride group), (epoxy group: hydroxyl group), (epoxy group: epoxy group), (alkoxysilyl group: alkoxysilyl group)
Note that the crosslinkable group is preferably a group different from the polymerizable group of the repeating unit having a polymerizable group. In other words, the crosslinkable group is preferably a group that does not polymerize with the polymerizable liquid crystal compound. For example, the crosslinkable group is preferably other than an ethylenically unsaturated group.

The crosslinkable group may have a substituent when possible.
For example, the oxetane group as the crosslinkable group is preferably a group represented by the following general formula [O]. In the general formula [O], ^RO represents a hydrogen atom or a substituent (preferably an alkyl group having 1 to 3 carbon atoms). * Represents a bonding position.

One type of the repeating unit having a crosslinkable group may be used alone, or two or more types may be used. When two or more types are used, the repeating units having a crosslinkable group may each have the same crosslinkable group, or may have different crosslinkable groups.
Further, one kind of the repeating unit having a crosslinkable group may have two or more crosslinkable groups, and in this case, the two or more crosslinkable groups may be the same or different.

  The repeating unit having a crosslinkable group is preferably a repeating unit represented by the general formula (Y).

In the general formula (Y), ^RY represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.
^LY is a single bond or a divalent linking group, and is preferably a single bond, -O-, -CO-O-, -CO-NH-, an alkylene group, or an arylene group.
P ^Y represents a monovalent group having a crosslinkable group.
Examples of P ^Y, "- alkylene - crosslinkable group" are preferred. The alkylene group preferably has 1 to 4 carbon atoms.

When the fluoroaliphatic group-containing copolymer has a repeating unit having a crosslinkable group, its content is preferably from 5 to 90 mol%, based on all repeating units of the fluoroaliphatic group-containing copolymer. 80 mol% is more preferable, and 10 to 75 mol% is still more preferable.
When two or more repeating units having a crosslinkable group are used, the total content thereof is preferably within the above range.

The fluoroaliphatic group-containing copolymer may further have a repeating unit derived from a monomer represented by the general formula (3).

In the general formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, among which a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable. Is more preferred, and a hydrogen atom or a methyl group is still more preferred.
U ¹ and ^{U 2} are each independently, -O -, - S -, - COO -, - OCO -, - CONH -, - NHCOO -, - NH- represents, -O- or -NH- is preferably , -O- are more preferred.
R ⁴ and R ⁵ represent each independently a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R ⁴ And R ⁵ may be linked to each other via a linking group consisting of these combinations.
Examples of the substituted or unsubstituted aliphatic hydrocarbon group represented by R ⁴ and R ⁵ include an alkyl group, an alkenyl group and an alkynyl group which may have a substituent.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group. , Hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-methylhexyl, cyclopentyl, cyclohexyl Linear, branched or cyclic alkyl groups such as a group, a 1-adamantyl group and a 2-norbornyl group.
Specific examples of the alkenyl group include linear groups such as a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, a 1-cyclopentenyl group, and a 1-cyclohexenyl group. , A branched or cyclic alkenyl group.
Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a 1-octynyl group.

Examples of the substituted or unsubstituted aryl group represented by R ⁴ and R ⁵ include those in which one to four benzene rings form a condensed ring, and those in which a benzene ring and an unsaturated five-membered ring form a condensed ring. Specific examples include phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenabutenyl, fluorenyl, pyrenyl and the like.

Examples of the substituted or unsubstituted heteroaryl group represented by R ⁴ and R ⁵ include a hydrogen atom on a heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. One obtained by removing one to form a heteroaryl group.
Specific examples of the heteroaromatic ring containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom include, for example, pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole , Oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole benzimidazole, anthranyl, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, Examples include quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine and the like.

Examples of the substituent which R ⁴ and R ⁵ may have include monovalent nonmetallic atomic groups except for hydrogen, and are selected from, for example, the following substituent group Y.
(Substituent group Y)
Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ary Rucarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N -Alkyl acylamino group, N-aryl Silamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido Group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, An N ′, N′-dialkyl-N-arylureido group, an N′-aryl-N-alkylureido group, an N′-aryl-N-arylureido group, an N ′, N′-diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido , Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl- N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N- Arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO3H) and The conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfina Moyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfur A famoyl group, an N-alkyl-N-arylsulfamoyl group, an N-acylsulfamoyl group and its conjugate base group, an N-alkylsulfonylsulfamoyl group (—SO 2 NHSO 2 (alkyl)) and its conjugate base group, N-arylsulfonylsulfamoyl group (-SO2NHSO2 ( ryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (-CONHSO2 (alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (-CONHSO2 (aryl)) and its conjugate base group, alkoxysilyl group (-Si (Oalkyl) 3), aryloxysilyl group (-Si (Oaryl) 3), hydroxysilyl group (-Si (OH) 3) and its conjugate base group, phosphono group (-PO3H2) and its conjugate base group A dialkylphosphono group (-PO3 (alkyl) 2), a diarylphosphono group (-PO3 (aryl) 2), an alkylarylphosphono group (-PO3 (alkyl) (aryl)), a monoalkylphosphono group (- PO3H (alkyl)) and its conjugate base group, monoarylphosphono group -PO3H (aryl)) and its conjugate base group, phosphonooxy group (-OPO3H2) and its conjugate base group, dialkylphosphonooxy group (-OPO3 (alkyl) 2), diarylphosphonooxy group (-OPO3 (aryl) 2 ), An alkylarylphosphonooxy group (—OPO3 (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO3H (alkyl)) and its conjugate base group, a monoarylphosphonooxy group (—OPO3H (aryl)) ) And its conjugated base, cyano, nitro, aryl, alkenyl, and alkynyl groups, and these substituents, if possible, combine with each other or with a substituted hydrocarbon group. To form a ring.

R ⁴ and R ⁵ in the above formula (3) are preferably a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, More preferably, they are linked to each other by an atom or an alkylene linking group.

L ³ is a single bond or —O—, —S—, —COO—, —OCO—, —CONR ⁶ —, —NR ⁶ COO—, —CR ⁶ N—, substituted or unsubstituted divalent An aliphatic group, a substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof; R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Represents
L ³ represents —O—, —COO—, —OCO—, —CONR ⁶ —, —NR ⁶ COO—, a substituted or unsubstituted divalent aliphatic group, or a substituted or unsubstituted divalent aromatic group. And a divalent linking group selected from the group consisting of these combinations.
When L ³ contains a substituted or unsubstituted divalent aromatic group, the number of aromatic rings is preferably from 1 to 3, more preferably from 1 to 2, and even more preferably 1. By setting the content in this range, the orientation of the formed optically anisotropic layer can be improved.

Specific examples of the monomer forming the repeating unit represented by the above formula (3) include monomers represented by the following formulas 3-1 to 3-26.

  In the present invention, the content of the repeating unit represented by the above formula (3) is preferably from 1 to 80% by mass, more preferably from 3 to 70% by mass, based on all repeating units, More preferably, it is 5 to 50% by mass.

The fluoroaliphatic group-containing copolymer may have a repeating unit other than those described above.
The weight average molecular weight (Mw) of the fluoroaliphatic group-containing copolymer is preferably from 1,000 to 500,000, more preferably from 1,500 to 400,000, and still more preferably from 2,000 to 300,000.
The number average molecular weight (Mn) of the fluoroaliphatic group-containing copolymer is preferably from 500 to 250,000, more preferably from 1,000 to 200,000, and still more preferably from 1500 to 150,000.
The dispersity (Mw / Mn) of the fluoroaliphatic group-containing copolymer is preferably from 1.00 to 20.00, more preferably from 1.00 to 18.00, and still more preferably from 1.00 to 16.00.
Within this range, it is excellent in miscibility with the liquid crystal composition, and can achieve both uniformity of orientation of the optically anisotropic layer, which is the main feature of the present invention, and adhesion with other optical functional layers. .

In the liquid crystal composition, the content of the fluoroaliphatic group-containing copolymer is preferably from 0.001 to 5.00% by mass, more preferably from 0.01 to 1.00% by mass, based on the total mass of the liquid crystal compound. Preferably, 0.01 to 0.30 mass% is more preferable.
When two or more fluoroaliphatic group-containing copolymers are used, the total content is preferably within the above range.
In addition, the total solid content is intended to be a component forming the optically anisotropic layer, and does not include a solvent. In addition, any component that forms an optically anisotropic layer is regarded as a solid even if its properties are liquid.

(Polymerization initiator)
The liquid crystal composition may include a polymerization initiator.
The polymerization initiator used is selected according to the type of polymerization reaction, and includes, for example, a thermal polymerization initiator and a photopolymerization initiator.
Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, oxime esters, and onium salts. If necessary, it can be combined with a sensitizer and / or a chain transfer agent.
In the liquid crystal composition, the content of the polymerization initiator is preferably from 0.01 to 20% by mass, and more preferably from 0.5 to 20% by mass, based on the total content of the polymerizable liquid crystal compound and the non-liquid crystalline polymerizable monomer described below. 5 mass% is more preferable.
The polymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used, the total content is preferably within the above range.

(Non-liquid crystalline polymerizable monomer)
The liquid crystal composition may contain a non-liquid crystal polymerizable monomer from the viewpoint of uniformity of the coating film and strength of the film.
Examples of the non-liquid crystalline polymerizable monomer include radical polymerizable and cationic polymerizable compounds. For example, a polyfunctional radical polymerizable monomer can be used, and a compound which is copolymerizable with the above-described liquid crystal compound having a polymerizable group is preferable. For example, esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acrylate Methylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3- Cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid) 2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Particularly, polyhydric alcohol and (meth) acrylic acid Esters are preferred.
In the liquid crystal composition, the content of the non-liquid crystal polymerizable monomer is preferably from 1 to 50% by mass, more preferably from 2 to 30% by mass, based on the total mass of the polymerizable liquid crystal compound.
The non-liquid crystalline polymerizable monomer may be used alone or in combination of two or more.
When two or more non-liquid crystalline polymerizable monomers are used, the total content thereof is preferably within the above range.

(Organic solvent)
The liquid crystal composition may include an organic solvent. As the organic solvent, those capable of completely dissolving the polymerizable liquid crystal compound described above are preferable, and a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable.
Examples of the organic solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate; ester solvents such as γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; pentane, hexane, and heptane Aliphatic hydrocarbon solvents, such as toluene; xylene, etc .; aromatic hydrocarbon solvents, acetonitrile, etc. Lil solvent; tetraethylene glycol dimethyl ether, tetrahydrofuran, and ether solvents such as dimethoxyethane; chlorine-containing solvent of chloroform and chlorobenzene; and the like.

The content of the organic solvent in the liquid crystal composition is determined by the solubility of the solid, the viscosity of the liquid, the pot life of the coating liquid, the suitability of the coating machine and the coating method, the uniformity and thickness of the coated film, and the control of the alignment. It can be adjusted appropriately from a viewpoint or the like.
The content of the organic solvent in the liquid crystal composition is, for example, preferably such that the solid content concentration of the liquid crystal composition is 13 to 50% by mass, and more preferably 15 to 40% by mass.
The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used, the total content thereof is preferably within the above range.

(Other components)
The liquid crystal composition may contain other components other than those described above.
As other components, for example, from the viewpoint of adjusting the orientation of the optically anisotropic layer, a surfactant, a chiral agent, or the like may be used.
In addition, from the viewpoints of adjusting the viscosity of the liquid crystal composition, phase transition temperature, alignment uniformity, adjusting the film physical properties of the optically anisotropic layer, and adjusting the optical characteristics, a sub liquid crystal compound (non-polymerizable liquid crystal compound) is used. May be used. The sub liquid crystal compound may be a low molecular liquid crystal compound. Further, the sub liquid crystal compound may be a main chain type liquid crystal polymer or a side chain type liquid crystal polymer.
From the viewpoints of imparting a pot life to the liquid crystal composition and improving the durability of the optically anisotropic layer, a polymerization inhibitor, an antioxidant, an ultraviolet absorber and the like may be used.
From the viewpoint of further function addition, adjustment of liquid physical properties, and adjustment of film physical properties, plasticizers, retardation adjusters, dichroic dyes, fluorescent dyes, photochromic dyes, thermochromic dyes, photoisomerizable materials, photodimerization Materials, nanoparticles, thixotropic agents and the like may be added.

<Formation method>
The method for forming the optically anisotropic layer using the liquid crystal composition is not particularly limited. For example, a liquid crystal composition is applied directly on a support to form a coating film, and the obtained coating film is heated. The optically anisotropic layer can be formed by performing orientation forming treatment such as cooling and / or curing treatment (irradiation of ultraviolet rays (light irradiation treatment) or heat treatment). Further, a liquid crystal composition may be coated on an alignment film described later, and the same processing as described above may be performed to form an optically anisotropic layer.
The liquid crystal composition can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method).

  In the present invention, the thickness of the optically anisotropic layer is not particularly limited, but is preferably from 0.1 to 10 μm, more preferably from 0.5 to 5 μm.

<Orientation and optical properties of optically anisotropic layer>
The optically anisotropic layer can be aligned in various alignment states such as horizontal alignment, vertical alignment, inclined alignment, hybrid alignment, random homogeneous alignment, and cholesteric alignment. Various optical characteristics can be imparted by appropriately selecting the state.

  For example, as a preferred embodiment, the optically anisotropic layer may be a positive A plate. A positive A plate can be obtained by horizontally aligning a rod-shaped polymerizable liquid crystal compound. Further, when the in-plane retardation Re (550) is 100 to 160 nm (preferably 120 to 150 nm), it can be suitably used as a positive uniaxial λ / 4 plate. When Re (550) is in the range of 250 to 300 nm, it can be used as a positive uniaxial λ / 2 plate. Here, Re (550) represents in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm. The value of the in-plane retardation can be measured using AxoScan OPMF-1 (manufactured by OptoScience).

  As a preferred embodiment, the optically anisotropic layer may be a positive C plate. A positive C plate can be obtained by vertically aligning a rod-shaped polymerizable liquid crystal compound. The thickness direction retardation Rth (550) is, for example, 20 to 200 nm, and preferably 50 to 120 nm from the viewpoint of imparting various optical compensation functions and / or viewing angle improving functions.

  Alternatively, the optically anisotropic layer may be a negative A plate or a negative C plate. In addition, the cholesteric alignment of the liquid crystal layer can impart optical rotation, wavelength selective reflection, and the like.

In this specification, the A plate is defined as follows.
There are two types of A plates, a positive A plate (positive A plate) and a negative A plate (negative A plate), and the slow axis direction in the film plane (the direction in which the refractive index in the plane is the maximum). ) Is nx, the refractive index in the direction orthogonal to the in-plane slow axis in the plane is ny, and the refractive index in the thickness direction is nz, the positive A plate satisfies the relationship of formula (A1). And the negative A plate satisfies the relationship of the formula (A2). The positive A plate has a positive Rth value, and the negative A plate has a negative Rth value.
Formula (A1) nx> ny ≒ nz
Formula (A2) ny <nx ≒ nz
Note that the above “≒” includes not only a case where both are completely the same but also a case where both are substantially the same. “Substantially the same” means, for example, “ny ≒ nz” when (ny−nz) × d (where d is the thickness of the film) is −10 to 10 nm, preferably −5 to 5 nm. In the case where (nx−nz) × d is −10 to 10 nm, preferably −5 to 5 nm, “nx ≒ nz” is also included.
There are two types of C plates, a positive C plate (positive C plate) and a negative C plate (negative C plate). The positive C plate satisfies the relationship of the formula (C1). This satisfies the relationship of Expression (C2). The positive C plate has a negative value of Rth, and the negative C plate has a positive value of Rth.
Formula (C1) nz> nx ≒ ny
Formula (C2) nz <nx ≒ ny
Note that the above “≒” includes not only a case where both are completely the same but also a case where both are substantially the same. The term “substantially the same” means that, for example, (nx−ny) × d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm. It is.

Further, the wavelength dispersion of optical anisotropy can be appropriately adjusted by adjusting the polymerizable liquid crystal compound and other components used in the liquid crystal composition.
The optically anisotropic layer preferably exhibits reverse wavelength dispersion. As a specific example, the optically anisotropic layer preferably satisfies the following formula (II) as a uniaxial retardation layer.
Δn (450) / Δn (550) <1.00 (II)
Here, in the formula (II), Δn (450) represents the difference between the refractive index maximum direction at a wavelength of 450 nm of the optically anisotropic layer and the refractive index difference in the direction perpendicular thereto, and Δn (550) represents the optically anisotropic layer. Represents the difference in the refractive index between the maximum refractive index direction and the direction perpendicular thereto at a wavelength of 550 nm.

(Support)
The liquid crystal film of the present invention has a support as described above. The support is not particularly limited, and various known materials can be used. Among them, a long polymer film is preferable from the viewpoint of enabling continuous production.
Examples of the polymer film include polyolefin and cyclic olefin resins such as polypropylene and norbornene polymers; polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polymethacrylates such as polymethyl methacrylate Polyacrylic acid esters; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; and polymer films formed from these copolymers and the like. These polymer films can be appropriately selected from the viewpoints of tensile modulus, flexural modulus, parallel light transmittance, haze, optical anisotropy, optical isotropy, easy peeling property, easy adhesive property and the like.

In the present invention, from the viewpoint of obtaining an optically anisotropic layer having a uniform orientation, in the case where the liquid crystal composition is directly applied to the support to form the optically anisotropic layer, the coated surface of the support is smooth. It is preferable that the surface roughness Ra is 3 to 50 nm.
When an alignment layer described below is provided on a support and the liquid crystal composition is applied to the alignment layer to form an optically anisotropic layer, the surface of the alignment layer only needs to be smooth, and the surface roughness Ra Is preferably 3 to 50 nm. It is also possible to provide an intermediate layer or the like to be described later and adjust the surface roughness thereof.

  In addition, when using a long polymer film, the coated surface of the liquid crystal composition on the support is preferably used in order to prevent the transfer of the shape between the film surfaces and the blocking phenomenon in the state of a roll of the manufactured liquid crystal film. An anti-blocking treatment or a mat treatment or the like can be performed on the surface on the opposite side to the above. Further, a knurling may be provided at the end of the film.

  It is also preferable that the support is provided so as to be peelable. That is, in the liquid crystal film, the support is preferably arranged so as to be peelable from an adjacent layer. At this time, when the optically anisotropic layer is directly disposed on the support, it is preferable that the optically anisotropic layer can be peeled off at the interface between the support and the optically anisotropic layer. When an orientation layer and / or another layer (intermediate layer) described below is disposed between the support and the optically anisotropic layer, an arbitrary layer between the support and the optically anisotropic layer is provided. Preferably, it can be peeled off at the interface or within the layer.

(Orientation layer)
The liquid crystal film of the present invention may have an alignment layer, if necessary. From the viewpoint that it is easy to obtain an optically anisotropic layer having better orientation, it is preferable to provide an alignment layer on a support and further provide the above-described optically anisotropic layer on the alignment layer. That is, the liquid crystal film of the present invention preferably has a photo-alignment layer between the support and the optically anisotropic layer.

As the alignment layer, various known alignment layers can be used. For example, a rubbing film made of an organic compound such as a polymer (rubbing alignment film), an obliquely deposited inorganic compound film, a film having microgrooves, and A film obtained by accumulating an LB film (Langmuir-Blodgett film) formed by an Langmuir-Blodgett method using an organic compound (for example, ω-tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearylate) is used. No.
From the viewpoint of preventing alignment defects caused by foreign matter, a photo-alignment layer made of a photo-alignment film is also preferable as the alignment layer.

  As the rubbing alignment film, for example, a coating film of polyimide, polyvinyl alcohol, a polymer having a polymerizable group described in JP-A-9-152509, and JP-A-2005-97377, JP-A-2005-99228 And an alignment film described in JP-A-2005-128503.

The composition for forming a photo-alignment film used for forming the photo-alignment film that can be used in the present invention is described in many documents and the like. For example, WO08 / 056597, JP-A-2008-76839, and a material using an azo compound described in JP-A-2009-109831; JP-A-2012-155308, JP-A-2014-26261 JP-A-2014-123091, and JP-A-2015-26050; photo-alignable polyorganosiloxane composite materials; cinnamic acid group-containing cellulose ester materials described in JP-A-2012-234146; 145660 and a material utilizing the photo-Fries rearrangement reaction or a similar reaction thereof described in JP-A-2013-238717; Gazette, JP-T-2006-535158 WO10 / 150748, WO11 / 126022, WO13 / 054784, WO14 / 104320, and WO16 / 002722, which are capable of photodimerization (for example, cinnamate compounds, chalcone compounds, and And / or a material in which a coumarin compound is pendant to various polymers) can be used for the composition for forming a photo-alignment film.
Above all, from the viewpoints of irradiation energy and alignment regulating power required for photo alignment, a photo alignment film using a photoisomerization reaction of an azo group or a photo alignment film using a photo reaction of a cinnamate compound is preferable.

  If necessary, the composition for forming an alignment film (preferably, the composition for forming a photo-alignment film) used for forming the alignment film may include a crosslinking agent, a binder, a plasticizer, a sensitizer, a crosslinking catalyst, and an adhesive force. Conditioning agents, leveling agents and the like can be added.

  The thickness of the alignment layer is not particularly limited and can be appropriately selected depending on the purpose. For example, 10 to 1000 nm is preferable, and 10 to 300 nm is more preferable. The surface roughness of the alignment layer is as described above.

[Other layers (intermediate layers)]
The liquid crystal film of the present invention may further include other layers as necessary. For example, a smoothing layer, an easy-adhesion layer, an easy-peeling layer, a light-shielding layer, a coloring layer, a fluorescent layer, an oxygen barrier layer, and a water vapor barrier layer are exemplified. A layer having one or more functions of such a layer is generically called an intermediate layer. The intermediate layer may be a layer having a function other than the functions described above.
The intermediate layer can be provided, for example, between the support and the optically anisotropic layer and / or between the support and the above-mentioned alignment layer to exhibit various functions.

〔Production method〕
The liquid crystal film of the present invention can be produced, for example, by sequentially laminating and applying a composition (liquid crystal composition or the like) for forming each layer on a support.
One preferred embodiment includes an embodiment having the following steps (1) to (4) in order.
(1) Step of applying a composition for forming an alignment film on a support to obtain a coating film (coating step)
(2) a step of subjecting the coating film to a rubbing treatment or a photo-alignment treatment to impart an alignment regulating force, thereby forming the coating film as an alignment layer (alignment regulating force applying step)
(3) Step of applying the liquid crystal composition on the alignment layer (4) Step of fixing the alignment state after aligning the polymerizable liquid crystal compound The step (3) and subsequent steps are performed as a method of forming an optically anisotropic layer. It is as stated.

<Coating process>
The application method in the application step is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include spin coating, die coating, gravure coating, flexographic printing, and inkjet printing. It is preferable that the application of the composition for forming an alignment film is accompanied by a solvent removing step (drying step), and a post-baking step can be further involved.

<Orientation regulating force applying step>
The alignment regulating force applying step is a step of performing a rubbing treatment, a light irradiation treatment, or the like on the coating film formed using the alignment film forming composition. The rubbing treatment can be performed by a conventionally known method.
In the light irradiation treatment on the coating film formed using the composition for forming a photo-alignment film, it is preferable to irradiate polarized light. The polarized light is not particularly limited, and includes, for example, linearly polarized light, circularly polarized light, and elliptically polarized light. Among them, linearly polarized light is preferable. It is preferable to irradiate polarized light from a vertical direction from the viewpoint of forming a horizontally aligned liquid crystal layer, and it is preferable to irradiate polarized light from an oblique direction from the viewpoint of providing tilt alignment or tilt.

The wavelength of polarized light or non-polarized light is not particularly limited as long as the coating formed from the composition for forming a photo-alignment film can be provided with the ability to control the alignment of the polymerizable liquid crystal compound and the like. Examples of the type of light used include ultraviolet light, near ultraviolet light, and visible light. Among them, near ultraviolet rays of 250 to 450 nm are preferable.
Examples of the light source for irradiating polarized or non-polarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a laser, and an LED (light emitting diode). If necessary, the wavelength range to be irradiated can be limited by using an interference filter or a color filter for ultraviolet light or visible light obtained from the light source. In addition, linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for light from these light sources.

The integrated amount of polarized light or non-polarized light is not particularly limited as long as the coating film of the composition for forming a photo-alignment film can be provided with the ability to control the alignment of a polymerizable liquid crystal compound or the like. cm ² is preferable, and 3 to 100 mJ / cm ² is more preferable.
The illuminance of polarized light or non-polarized light is not particularly limited as long as the alignment control ability for the liquid crystal compound can be imparted to the coating film of the composition for forming a photoalignment film, but is preferably 0.1 to 300 mW / cm ^2. Preferably, it is 1 to 100 mW / cm ² .

[Optical laminate]
The optical laminate of the present invention is an optical laminate having the above-described liquid crystal composition, an optically anisotropic layer, an adhesive, and an optical functional layer, wherein the optically anisotropic layer and the optical functional layer Are joined via an adhesive layer.
For example, the optical laminate of the present invention is schematically shown in FIG. In the optical laminate 10A of FIG. 4, a support 3, an orientation layer 4, an optically anisotropic layer 2, an adhesive layer 11, and an optical functional layer 20 are laminated in this order. Among these, the support 3, the alignment layer 4, and the optically anisotropic layer 2 were the liquid crystal films described above, and the surface of the optically anisotropic layer 2 included in the liquid crystal film on the air interface side was the optical functional layer. 20 (the adherend) via an adhesive layer 11.
In the optical laminate of the present invention, the optical functional layer may be further bonded to a different layer (for example, another optical functional layer or the like).
Further, in the optical laminate of the present invention, the surface of the optically anisotropic layer that is not on the air interface side may be further joined to a different layer (for example, a support or another optical functional layer).

In a state where the optically anisotropic layer is bonded to the optical functional layer, the support constituting the liquid crystal film of the present invention may be peeled off and removed if necessary.
In peeling and removing the support, when the optically anisotropic layer is directly provided on the support, the support can be peeled off at the interface between the support and the optically anisotropic layer. When an orientation layer and / or another layer (intermediate layer) is provided between the support and the optically anisotropic layer, any interface or layer between the support and the optically anisotropic layer may be provided. May be used for peeling.
The optical laminate from which such a support has been removed is schematically shown in FIG. 5, for example. In the optical laminate 10B of FIG. 5, the optically anisotropic layer 2, the adhesive layer 11, and the optical functional layer 20 are laminated in this order. In this optical laminate, the optically anisotropic layer 2 and the optical functional layer 20 are joined via the adhesive layer 11.
The optical laminate of FIG. 5 may be obtained by peeling the support 3 and the alignment layer 4 from the optical laminate of FIG.

(Optical functional layer)
As the optical function layer, layers having various functions such as a polarizer, an optically isotropic layer, a retardation layer, an optical rotation layer, a reflection layer, a scattering layer, a coloring layer, and a fluorescent layer can be used.
One optical function layer may have a plurality of functions among the above-described layers. Further, one optical function layer may be composed of a plurality of layers. At least one of the plurality of layers constituting the optical function layer may be a layer having no optical function.
For example, the optical functional layer is preferably a polarizer or a retardation layer.
Further, the optical function layer is preferably a liquid crystal layer. Note that the liquid crystal layer used as the optical function layer may be formed using the above-described liquid crystal composition or may be formed using another composition. Such a liquid crystal layer can be used, for example, as a retardation layer.

<Polarizer>
The polarizer is not particularly limited as long as it has a function of converting light into specific polarized light, and examples thereof include conventionally known absorption-type polarizers and reflection-type polarizers.
Examples of the absorption linear polarizer include an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer. As the iodine-based polarizer and the dye-based polarizer, both a coating polarizer and a stretch polarizer can be used. A polarizer produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching the film is preferred from the viewpoint of excellent versatility.
As the reflective polarizer, for example, a polarizer obtained by laminating thin films having different birefringence, a reflective linear polarizer such as a wire grid polarizer, and a reflective circular polarizer including a cholesteric liquid crystal having a selective reflection region. Is mentioned.

Although the thickness of the polarizer is not particularly limited, it is preferably 1 to 60 μm, more preferably 1 to 30 μm, and still more preferably 2 to 20 μm.
In addition, besides disposing a polarizer as an optical functional layer to be bonded via an adhesive layer to the surface of the optically anisotropic layer that was on the air interface side, the surface of the optically anisotropic layer that was on the air interface side It is also preferable that a polarizer is disposed on the opposite surface directly or via another layer (such as an adhesive layer).

<Retardation layer>
The retardation layer used as the optical function layer is not particularly limited, and various known layers can be used. For example, a polymer film and a stretched and oriented film thereof, a layer formed using a composition containing a liquid crystal compound (liquid crystal layer), a layer obtained by aligning an inorganic substance, and the like can be used without limitation.
The liquid crystal film disclosed in the present invention or the optically anisotropic layer thereof may be used as a retardation layer (optical function layer). That is, the liquid crystal film of the present invention or a plurality of optically anisotropic layers thereof may be combined to form an optical laminate.

(Adhesive layer)
In the optical laminate of the present invention, an adhesive layer is used to join the optically anisotropic layer of the liquid crystal film of the present invention, which was on the air interface side, to the optical functional layer. As the adhesive for forming the adhesive layer, various known materials can be used, for example, a pressure-sensitive adhesive, a hot-melt adhesive, a thermosetting adhesive, a light-curing adhesive, and a humidity-curing adhesive. And a dry-solidified adhesive.

Above all, the adhesive layer is preferably a layer obtained by curing a photo-curable adhesive because the adhesive layer can be made thinner, can be quickly cured, and has excellent physical properties after curing. Examples of the photo-curable adhesive include an ultraviolet-curable adhesive (UV adhesive).
Examples of the photocurable adhesive include a radical polymerization type (for example, an acrylic adhesive) and a cationic polymerization type (for example, an epoxy adhesive). Further, the adhesive is preferably a non-solvent adhesive in that the influence on the optical function layer can be suppressed to a small value.

  As a method of forming the adhesive layer, for example, an adhesive may be applied to the air interface side of the optically anisotropic layer, and then the applied adhesive may be brought into contact with the optical functional layer to join them. Further, after the adhesive is applied on the optical functional layer, the applied adhesive and the optically anisotropic layer may be brought into contact with each other and joined.

  Prior to contact with the adhesive, an easy adhesion treatment can be applied to the air interface side of the optically anisotropic layer. Examples of the easy adhesion treatment include an active energy ray irradiation treatment, a plasma treatment, a corona treatment, and a vapor deposition treatment. Plasma treatment or corona treatment is preferred because only the surface is treated and the influence on the optical properties of the optically anisotropic layer can be minimized.

(Function of optical laminate)
The optical laminate of the present invention can be applied to various uses depending on the optical functional layer used.

  For example, a polarizing plate for a liquid crystal display device having an optical compensation function can be configured by including at least a polymer film, an absorption linear polarizer, an adhesive layer, and an optically anisotropic layer in this order. At this time, the optically anisotropic layer may be provided with an appropriate optical anisotropy in accordance with the type of the liquid crystal display device to be applied. The polymer film may have an antiglare layer, an antireflection layer, a brightness enhancement layer, or the like. Other retardation layers may be combined in order to adjust light leakage and color in the oblique direction.

For example, by using the optical laminate of the present invention, a circularly polarizing plate having the optical laminate of the present invention can be produced. The circularly polarizing plate may partially include the optical laminate of the present invention, or may be the optical laminate of the present invention itself.
Such a circularly polarizing plate is schematically shown in FIG. 6, for example. 6 includes a polymer film (not shown), a polarizer 40 which is a linear polarizer (preferably an absorption type linear polarizer), a support 3, an alignment layer 4, and an optically anisotropic layer. 2, the adhesive layer 11 and the optical function layer 20 are provided in this order.
As long as the circularly polarizing plate of FIG. 6 has the polarizer 40 as a linear polarizer, the optically anisotropic layer 2, the adhesive layer 11, and the optical functional layer 20 in at least this order, the other layers It may be omitted.
In the circularly polarizing plate of FIG. 6, the optically anisotropic layer preferably functions as a λ / 4 plate.
In the circularly polarizing plate shown in FIG. 6, light leakage in the oblique direction can be suppressed by using the optical functional layer 20 as a positive C plate.
Further, an optical laminate having at least the optically anisotropic layer 2, the adhesive layer 11, and the polarizer 40 as a linear polarizer in this order may be used as a circularly polarizing plate. In this case, it is also preferable to dispose a positive C plate on the surface of the optically anisotropic layer 2 opposite to the surface on which the adhesive layer 11 exists.
The display quality of the circularly polarizing plate can be improved by incorporating it into an organic EL display device as described later.

  Also, a wideband λ / 4 plate can be configured by combining the λ / 4 plate and the λ / 2 plate. At this time, it is preferable that at least one of the λ / 4 plate and the λ / 2 plate is the liquid crystal film of the present invention or the optically anisotropic layer thereof. All of the positive C plate, λ / 4 plate, and λ / 2 plate described above can be used as the liquid crystal film of the present invention or the optically anisotropic layer thereof, and an optical laminate having excellent adhesion between layers can be obtained. It is preferred in that respect.

  Other applications of the optical laminate of the present invention include: a brightness enhancement plate, a reflective polarizing plate, a wavelength selective reflection element, a reflection reduction layer, a pattern retarder, a collimator element, an authenticity determination seal, a hologram element, a design member, And decorative materials.

[Image display device]
The optical laminate of the present invention can be applied to an image display device.
The display element used for the image display device is not particularly limited, and examples thereof include a liquid crystal cell, an organic EL display element, and a plasma display panel. The optical laminate of the present invention can be used for optical compensation to improve display image quality, and is also used to suppress a decrease in display image quality due to external light being reflected by a display element. You can also.

(Liquid crystal display)
A liquid crystal display device, which is an example of an image display device, is a liquid crystal display device including the above-described optical laminate of the present invention and a liquid crystal cell. The liquid crystal cell includes a VA (Virtual Alignment) mode, an OCB (Optical Compensated Bend) mode, an IPS (In-Place-Switching) mode, or a TN (Twisted Nematic). Other methods may be used. By applying the optical laminate of the present invention to the optical compensation configuration and the brightness enhancement configuration adapted to the liquid crystal cell and combining them, excellent wide viewing angle characteristics, prevention of light leakage of black display, and high brightness display can be realized.

[Organic EL display]
It is also preferable that the organic EL display device has the above-mentioned circularly polarizing plate. In this case, the circularly polarizing plate preferably functions as an anti-reflection plate.
Such an organic EL display device is schematically illustrated in FIG. 7, for example. The organic EL display device 100 shown in FIG. 7 includes an organic EL display element 50, an optical function layer 20, an adhesive layer 11, an optically anisotropic layer 2, an alignment layer 4, a support 3, and a linear polarizer (preferably an absorption layer). A linear polarizer).
The optical functional layer 20, the adhesive layer 11, the optically anisotropic layer 2, the alignment layer 4, the support 3, and the polarizer 40 in the organic EL display device 100 shown in FIG. 7 correspond to the circularly polarizing plate shown in FIG.
When the organic EL display device has the above-described configuration, when the organic EL display device 100 is observed from the polarizer 40 side, external light is reflected on an electrode of the organic EL display element or the like to reduce display contrast. It is possible to suppress the phenomenon of deterioration and to enable high-quality display.
Known configurations can be widely used as the organic EL display element. Further, the organic EL display device may further include a touch panel.

  Hereinafter, the present invention will be described in more detail with reference to examples. Materials, used amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[Examples 1 to 6 and Comparative Examples 1 and 2]
(Preparation of photo-alignment film forming composition)
A material for forming a photo-alignment film described in Example 1 of WO 2016/002722 was prepared and used for producing the liquid crystal film of the present invention.

(Preparation of liquid crystal composition)
A liquid crystal composition 1 having the following composition was prepared. In addition, among the leveling agents used in the following liquid crystal composition, FA-1 and FA-2 are a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the general formula (1) and the polymerizable liquid crystal compound described above. And a fluoroaliphatic group-containing copolymer having a repeating unit having a polymerizable group capable of polymerizing with

――――――――――――――――――――――――――――――――
Liquid crystal composition 1
――――――――――――――――――――――――――――――――
-43.00 parts by mass of the following polymerizable liquid crystal compound L-3-43.00 parts by mass of the following polymerizable liquid crystal compound L-4-14.00 parts by mass of the following polymerizable liquid crystal compound A-1-the following polymerization initiator S-1 (Oxime esters) 0.50 parts by mass. 0.23 parts by mass of the following leveling agent FA-1. 2.00 parts by mass of Hisolve MTEM (manufactured by Toho Chemical Industry Co., Ltd.). 1.00 parts by mass pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
6.00 parts by mass, methyl ethyl ketone (solvent) 160.00 parts by mass, cyclopentanone (solvent) 51.00 parts by mass -------------------------------------------------------------------------- ―――――――――
In addition, the group adjacent to the acryloyloxy group of the following polymerizable liquid crystal compounds L-3 and L-4 represents a propylene group (a group in which a methyl group is substituted by an ethylene group), and the following polymerizable liquid crystal compounds L-3 and L-4: -4 represents a mixture of positional isomers having different methyl groups.

Polymerizable liquid crystal compound L-3

Polymerizable liquid crystal compound L-4

Polymerizable liquid crystal compound A-1

Polymerization initiator S-1

Leveling agent FA-1
In the resin represented by the following structural formula, a to c are a: b: c = 60: 30: 10, and indicate the content (mol%) of each repeating unit with respect to all repeating units in the resin.
The weight average molecular weight is 25,800 and the degree of dispersion is 2.90.

Liquid crystal compositions 2 to 8
Liquid crystal compositions 2 to 8 were prepared in the same manner as in composition 1, except that the leveling agent FA-1 was changed to the polymer shown in Table 1.

[Preparation of Cellulose Acylate Film 1]
(Preparation of core layer cellulose acylate dope)
The following composition was put into a mixing tank and stirred to dissolve each component, thereby preparing a cellulose acetate solution used as a cellulose acylate dope in the core layer.
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Core layer cellulose acylate dope ――――――――――――――――――――――――――――――
-100 parts by mass of cellulose acetate having a degree of acetyl substitution of 2.88-12 parts by mass of a polyester compound B described in Examples of JP-A-2005-227955-2 parts by mass of the following compound G-methylene chloride (first solvent) 430 parts by weight, methanol (second solvent) 64 parts by weight ――――――――――――――――――――――――――――――――

Compound G

(Preparation of outer layer cellulose acylate dope)
10 parts by mass of the following matting agent solution was added to 90 parts by mass of the above-mentioned core layer cellulose acylate dope to prepare a cellulose acetate solution used as the outer layer cellulose acylate dope.
――――――――――――――――――――――――――――――――
Matting agent solution ――――――――――――――――――――――――――――――
-2 parts by mass of silica particles having an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.)-76 parts by mass of methylene chloride (first solvent)-11 parts by mass of methanol (second solvent)-The above-mentioned core layer cellulose acylate Rate dope 1 part by mass ――――――――――――――――――――――――――――――――

(Production of Cellulose Acylate Film 1)
After the core layer cellulose acylate dope and the outer layer cellulose acylate dope are filtered through a filter paper having an average pore diameter of 34 μm and a sintered metal filter having an average pore diameter of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate dope are provided on both sides thereof. And three layers were simultaneously cast from a casting port onto a drum at 20 ° C. (band casting machine). The film was peeled off at a solvent content of about 20% by mass, and both ends in the width direction of the film were fixed with tenter clips, and dried while being stretched in the transverse direction at a stretching ratio of 1.1 times. Thereafter, the obtained film was further dried by being conveyed between rolls of a heat treatment apparatus to produce an optical film having a thickness of 40 μm, which was used as a cellulose acylate film 1. The core layer of the cellulose acylate film 1 had a thickness of 36 μm, and the outer layers disposed on both sides of the core layer had a thickness of 2 μm. The in-plane retardation of the obtained cellulose acylate film 1 at a wavelength of 550 nm was 0 nm.
The obtained cellulose acylate film 1 was used as a support.

[Production of liquid crystal film]
The composition for forming a photo-alignment film prepared above was applied to one surface of the produced cellulose acylate film 1 with a bar coater.
After applying the composition for forming a photo-alignment film, the obtained film was dried on a hot plate at 120 ° C. for 1 minute to remove the solvent, thereby forming a composition layer for forming a photo-alignment film having a thickness of 0.3 μm. .
The photo-alignment layer was formed by irradiating the obtained photo-alignment film forming composition layer with polarized ultraviolet rays (10 mJ / cm ² , using an ultra-high pressure mercury lamp).
Next, the liquid crystal compositions 1 to 7 prepared above were respectively applied on the photo-alignment layer with a bar coater to form a liquid crystal composition layer.
After the formed liquid crystal composition layer was once heated to 110 ° C. on a hot plate, it was cooled to 60 ° C. to stabilize the alignment.
Thereafter, the orientation was fixed by UV irradiation (500 mJ / cm ² , using an ultrahigh pressure mercury lamp) under a nitrogen atmosphere (oxygen concentration: 100 ppm) under a nitrogen atmosphere (oxygen concentration: 100 ppm) to form an optically anisotropic layer having a thickness of 2.3 μm. A liquid crystal film was produced. The in-plane retardation at a wavelength of 550 nm of the obtained liquid crystal film was 140 nm.

<Evaluation of orientation>
The prepared liquid crystal film was observed using a polarizing microscope while being shifted from the extinction position twice. The state in which there was no partial light-dark difference when observed was evaluated that the liquid crystal director was uniformly aligned (excellent alignment).
The observation results were classified according to the following criteria. The results are shown in Table 1 below.
AA: The liquid crystal director is finely aligned and aligned, and the display performance is very excellent. A: The liquid crystal director is uniformly aligned and aligned, and the display performance is excellent. B: The disturbance of the liquid crystal director is partial, and the surface state is stable. C: The liquid crystal director is greatly disturbed, the surface state is not stable, and the display performance is very poor.

[Production of anti-reflection plate for organic EL (circular polarizing plate)]
(Preparation of positive C plate film 1)
As a temporary support, a commercially available triacetyl cellulose film “Z-TAC” (manufactured by FUJIFILM Corporation) was used (this is referred to as a cellulose acylate film 2). After passing the cellulose acylate film 2 through a dielectric heating roll at a temperature of 60 ° C. and raising the film surface temperature to 40 ° C., an alkali solution having the following composition is applied to one surface of the film using a bar coater. The resulting film was applied at a rate of 14 ml / m ² , heated to 110 ° C., and transported under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. for 10 seconds. Subsequently, 3 ml / m ^{2 of} pure water was applied to the obtained film using the same bar coater. Next, after repeating washing with a fountain coater and draining with an air knife three times, the obtained film was conveyed to a drying zone at 70 ° C. for 10 seconds and dried to prepare a cellulose acylate film 2 having been subjected to an alkali saponification treatment.

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Alkaline solution ――――――――――――――――――――――――――――――――
・ 4.7 parts by mass of potassium hydroxide ・ 15.8 parts by mass of water ・ 63.7 parts by mass of isopropanol ・ Surfactant SF-1
(C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂₀ H) 1.0 part by mass / propylene glycol 14.8 parts by mass ―――――――――――

The coating liquid for forming an alignment film having the following composition was continuously applied to the alkali-saponified cellulose acylate film 2 using a # 8 wire bar. The applied coating liquid for forming an alignment film was dried with hot air at 60 ° C. for 60 seconds and further with hot air at 100 ° C. for 120 seconds to form an alignment film.
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Composition of the coating liquid for forming the alignment film ――――――――――――――――――――――――――――――――
・ Polyvinyl alcohol (Kuraray, PVA103) 2.4 parts by mass ・ Isopropyl alcohol 1.6 parts by mass ・ Methanol 36 parts by mass ・ Water 60 parts by mass ――――――――――――――――――― ――――――――――――――

The following coating liquid N for an optically anisotropic film was applied onto the cellulose acylate film 2 having an alignment film prepared as described above. The applied coating solution N for an optically anisotropic film was aged at 60 ° C. for 60 seconds, and then 1000 mJ / cm ² in air using a 70 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). Irradiated with ultraviolet light of cm ² . Thus, the state in which the rod-shaped polymerizable liquid crystal compound was vertically aligned was fixed, and the positive C plate film 1 was manufactured. In the positive C plate film 1, the retardation in the thickness direction at a wavelength of 550 nm was −60 nm.
――――――――――――――――――――――――――――――――
Composition of coating liquid N for optically anisotropic film ――――――――――――――――――――――――――――――
-80 parts by mass of the following polymerizable liquid crystal compound L-1-20 parts by mass of the following polymerizable liquid crystal compound L-2-1 part by mass of a vertical aligning agent (S01 below)-0.5 part by mass of a vertical aligning agent (S02 below)-ethylene Oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 8 parts by mass Irgacure 907 (manufactured by BASF) 3 parts by mass Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass The following compound B03 0.4 parts by mass, 170 parts by mass of methyl ethyl ketone, 30 parts by mass of cyclohexanone ――――――――――――――――――――――――――――――――

(Production of circularly polarizing plate)
The surface of the optically anisotropic layer of the produced liquid crystal film was subjected to corona treatment, and further coated with an epoxy-based ultraviolet (UV) adhesive. The positive C plate film 1 produced above was transferred thereto, and the UV adhesive was UV-cured. Then, the cellulose acylate film 2 was removed. Further, a PVA (polyvinyl alcohol) polarizing plate with a protective film was bonded to the cellulose acylate film 1 side of the optical laminate via a pressure-sensitive adhesive to obtain a circularly polarizing plate.

<Interfacial peeling force between UV adhesive and optical laminate>
A part where the UV adhesive is not applied (non-coated part) is formed between the produced optically laminated body of the circularly polarizing plate and the positive C plate film 1, and this non-coated part is used as a gripping part and is defined as JIS 6854. According to -2, a 180 ° peeling force was measured (unit: N / 25 mm). The measurement results were classified according to the following criteria. The results are shown in Table 2 below.
AA: very excellent in adhesiveness as soon as the film breaks immediately after the start of measurement A: exhibits a peeling force higher than 1.6 N / 25 mm and is excellent in adhesiveness B: peels 1.0 to 1.6 N / 25 mm C: exhibits a peeling force of less than 1.0 N / 25 mm, and is extremely poor in adhesiveness.

  From the results of the examples, it was confirmed that the optically anisotropic layer included in the liquid crystal film of the present invention had excellent orientation and adhesion.

Reference Signs List 1A, 1B, 1C Liquid crystal film 2 Optically anisotropic layer 3 Support 4 Alignment layer 5 Intermediate layer 10A, 10B, 10C Optical laminate 11 Adhesive layer 20 Optical functional layer 40 Polarizer 50 Organic EL display device 100 Organic EL display device

Claims (16)

A liquid crystal film having at least an optically anisotropic layer and a support formed using a liquid crystal composition including a polymerizable liquid crystal compound and a fluoroaliphatic group-containing copolymer,
The fluoroaliphatic group-containing copolymer comprises a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the general formula (1) and a repeating unit having a polymerizable group polymerizable with the polymerizable liquid crystal compound. Having a liquid crystal film.
In the general formula (1), R ² represents a hydrogen atom, a halogen atom, or an alkyl group.
L ² represents a divalent linking group.
n represents an integer of 1 to 6.   2. The liquid crystal composition according to claim 1, wherein the content of the fluoroaliphatic group-containing copolymer in the liquid crystal composition is 0.01 to 0.30% by mass based on the total mass of the polymerizable liquid crystal compound. 3. LCD film.   The liquid crystal film according to claim 1, wherein n represents an integer of 4 to 6. The liquid crystal film according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound has a group selected from the group consisting of groups represented by formulas (A1) to (A5).
In the general formulas (A1) to (A5), * 1 and * 2 represent bonding positions.
Q ¹ represents N or CH.
Q ² represents —S—, —O—, or —N (J ⁵ ) —, and J ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
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.
Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, Represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, —NJ ⁶ J ⁷ , or —SJ ⁸ , wherein J ^{6 to} J ⁸ are each independently hydrogen Represents an atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form an aromatic ring.
A ³ and A ⁴ each independently represent a group selected from the group consisting of —O—, —N (J ⁹ ) —, —S—, and —CO—, and J ⁹ is hydrogen Represents an atom or a substituent.
X represents a hydrogen atom or a non-metallic atom of Groups 14 to 16 to which a substituent may be bonded.
Further, ^{D 5} and ^{D 6} are each independently a single ^{bond, -CO-O -, - C} (= S) O -, - CJ 1 J 2 -, - CJ 1 J 2 -CJ 3 J 4 -, ^{-O-CJ 1 J 2 -,} - CJ 1 J 2 -O-CJ 3 J 4 -, - CO-O-CJ 1 J 2 -, - O-CO-CJ 1 J 2 -, - CJ 1 J 2 —O—CO—CJ ³ J ⁴ —, —CJ ¹ J ² —CO—O—CJ ³ J ⁴ —, —NJ ¹ —CJ ² J ³ —, or —CO—NJ ¹ —. J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
SP ³ and SP ⁴ each independently represent 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 —CH ₂ — constituting the group represents a divalent linking group substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—; Represents a substituent.
E ³ and E ⁴ each independently represent a monovalent organic group.
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 heterocyclic ring.
Ay is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represents an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. The liquid crystal film according to claim 4, wherein the polymerizable liquid crystal compound is a compound represented by the general formula (W).
^{E 1 -SP 1 -A 1 -D 3} -G 1 -D 1 -Ar-D 2 -G 2 -D 4 -A 2 -SP 2 -E 2 ·· (W)
In general formula (W), Ar represents any group selected from the group consisting of groups represented by general formulas (A1) to (A5).
D ^{1, D} 2, ^{D 3} and ^{D 4} each independently represent a single bond, -CO-O -, - C (= S) O -, - CJ 1 J 2 -, - CJ 1 J 2 -CJ 3 ^{J 4 -, - O-CJ} 1 J 2 -, - CJ 1 J 2 -O-CJ 3 J 4 -, - CO-O-CJ 1 J 2 -, - O-CO-CJ 1 J 2 -, - ^{CJ 1 J 2 -O-CO-} CJ 3 J 4 -, - CJ 1 J 2 -CO-O-CJ 3 J 4 -, - NJ 1 -CJ 2 J 3 -, or, -CO-NJ ¹ - a Represent. J ¹ , J ² , J ³ and J ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and at least one of —CH ₂ — constituting the alicyclic hydrocarbon group is —O -, -S- or -NH- may be substituted.
A ¹ and A ² each independently represent an aromatic ring group having 6 or more carbon atoms or a cycloalkylene ring group having 6 or more carbon atoms.
SP ¹ and SP ² each independently represent 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 constituting —CH ₂ — represents a divalent linking group substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—, and Q is Represents a substituent.
E ¹ and E ² each independently represent a monovalent organic group, and at least one of E ¹ and E ² represents a polymerizable group. However, when Ar is a group represented by the general formula (A3), at least one of E ¹ and E ² and E ³ and E ^{4 in} the general formula (A3) represents a polymerizable group.   The liquid crystal film according to any one of claims 1 to 5, wherein the fluoroaliphatic group-containing copolymer further has a repeating unit derived from a terminal cyclic hydrocarbon group-containing monomer. The liquid crystal film according to claim 6, wherein the terminal cyclic hydrocarbon group-containing monomer is a compound represented by the general formula (2).
In the general formula (2), R ¹ represents a hydrogen atom, a halogen atom, or an alkyl group.
L ¹ represents a divalent linking group having an alkylene group having 2 or more carbon atoms which may have a substituent.
Y represents an aromatic ring group which may have a substituent. The liquid crystal film according to any one of claims 1 to 7, wherein the fluoroaliphatic group-containing copolymer has a repeating unit derived from a monomer represented by the general formula (3).
In the general formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. U ¹ and ^{U 2} are each independently, -O -, - S -, - COO -, - OCO -, - CONH -, - NHCOO -, - represents a NH-. R ⁴ and R ⁵ represent each independently a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R ⁴ And R ⁵ may be linked to each other via a linking group consisting of these combinations. L ³ is a single bond or —O—, —S—, —COO—, —OCO—, —CONR ⁶ —, —NR ⁶ COO—, —CR ⁶ N—, substituted or unsubstituted divalent An aliphatic group, a substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof; R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Represents   The liquid crystal film according to claim 1, further comprising a photo-alignment layer between the support and the optically anisotropic layer.   The liquid crystal film according to claim 1, wherein the support is provided so as to be peelable. An optically anisotropic layer formed by using a liquid crystal composition containing a polymerizable liquid crystal compound and a fluoroaliphatic group-containing copolymer, an adhesive layer, and an optical functional layer, an optical laminate having at least:
The optically anisotropic layer and the optical functional layer are bonded via the adhesive layer,
The fluoroaliphatic group-containing copolymer comprises a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the general formula (1) and a repeating unit having a polymerizable group polymerizable with the polymerizable liquid crystal compound. An optical laminate.
In the general formula (1), R ² represents a hydrogen atom, a halogen atom, or an alkyl group.
L ² represents a divalent linking group.
n represents an integer of 1 to 6.   The optical laminate according to claim 11, wherein the adhesive layer is a layer obtained by curing a photopolymerizable adhesive.   The optical laminate according to claim 11, wherein the optical function layer is a liquid crystal layer.   The optical laminate according to any one of claims 11 to 13, further comprising a polarizer.   A circularly polarizing plate comprising the optical laminate according to any one of claims 11 to 14.   An organic electroluminescence display device, comprising: an organic electroluminescence display element; and the circularly polarizing plate according to claim 15.