JP7094437B2 - Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device - Google Patents

Description

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

A polymerizable compound exhibiting reverse wavelength dispersibility can accurately convert the polarization state over a wide wavelength range, and can thin a retardation film to exhibit a large refractive index anisotropy. Because it has the characteristics of, it is being actively researched.
Further, as a polymerizable compound exhibiting reverse wavelength dispersibility, a T-type molecular design guideline is generally taken, the wavelength of the long axis of the molecule is shortened, and the wavelength of the short axis located at the center of the molecule is lengthened. The above-mentioned compounds have been proposed (see, for example, Patent Documents 1 to 3).

On the other hand, a retardation film using a polymerizable liquid crystal compound is generally manufactured by using a coating process, and has a problem of how to realize a uniform and defect-free large-area thin film. Continuous production of uniform, defect-free film using an industrially available coating device requires advanced technology, and attempts such as adding a leveling agent have been attempted to solve this problem (). For example, see Patent Documents 4-5).

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

By the way, since it is more difficult to control the orientation of liquid crystal molecules in a polymerizable compound exhibiting reverse wavelength dispersibility than in a liquid crystal compound exhibiting forward wavelength dispersibility, it is required to increase the leveling ability and make the coating film uniform. There is.
However, the present inventor naturally lowers the surface energy of the obtained optically anisotropic film when the leveling ability is increased, so that various functional layers such as a scattering layer and other optical anisotropies are used for higher functionality. It was clarified that problems such as insufficient adhesion and uneven optical characteristics occur when providing a sex film, an adhesive layer, and the like.

Therefore, the present invention provides a polymerizable liquid crystal composition having reverse wavelength dispersibility, excellent uniformity without unevenness and orientation defects, and capable of providing an optically anisotropic film that can be stably laminated with various functional layers, and a polymerizable liquid crystal composition. An object of the present invention is to provide an optically anisotropic film, an optical film, and a polarizing plate using the same.

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

[1] A polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility and
It contains at least two fluoroaliphatic group-containing polymers, including a structural unit represented by the formula (A) described later and a structural unit derived from a fluoroaliphatic group-containing monomer.
At least one of the fluoroaliphatic group-containing polymers is a polymer (A-1) represented by an aromatic condensed ring functional group in which X in the formula (A) described later is substituted or unsubstituted.
Among the fluoroaliphatic group-containing polymers, at least one different from the polymer (A-1) is represented by a monocyclic structure functional group in which X in the formula (A) described later is substituted or unsubstituted, and is weight average. A polymerizable liquid crystal composition which is a polymer (A-2) having a molecular weight larger than that of the polymer (A-1).
[2] The polymerizable liquid crystal composition according to [1], wherein the polymer (A-1) has a structural unit represented by a naphthyl group in which X in the formula (A) described later is substituted or unsubstituted.
[3] The polymerizable liquid crystal composition according to [1], wherein the polymer (A-2) has a structural unit represented by a phenyl group in which X in the formula (A) described later is substituted or unsubstituted.
[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein the mass ratio of the polymer (A-1) to the polymer (A-2) is 8: 2 to 4: 6. thing.
[5] The polymerizable liquid crystal composition according to any one of [1] to [4], wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by the formula (1) described later.
[6] The polymerizable liquid crystal composition according to [5], wherein Ar ¹ in the formula (1) described later represents a group represented by the formula (Ar-1) or (Ar-2) described later.
[7] The polymerizable liquid crystal composition according to any one of [1] to [6], further containing a polymerization initiator.
[8] An optically anisotropic film formed from the polymerizable liquid crystal composition according to any one of [1] to [7].
[9] The optically anisotropic film according to [8], wherein the liquid crystal molecules are fixed in a homogenic orientation.
[10] An optical film comprising the optically anisotropic film according to [8] or [9].
[11] The optical film according to [10], which comprises another optically anisotropic film different from the optically anisotropic film.
[12] A polarizing plate containing the optically anisotropic film and the polarizing element according to [8] or [9].
[13] An image display device including the optical film according to [10] or [11] or the polarizing plate according to [12].

According to the present invention, a polymerizable liquid crystal composition having reverse wavelength dispersibility, excellent uniformity without unevenness and orientation defects, and capable of providing an optically anisotropic film that can be stably laminated with various functional layers, and a polymerizable liquid crystal composition. It is possible to provide an optically anisotropic film, an optical film, and a polarizing plate using the same.

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

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, as each component, a substance corresponding to each component may be used alone or in combination of two or more. Here, when two or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
Further, in the present specification, the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited unless the bonding position is specified, and for example, the formula described later (for example) 1) When D ¹ in 1) is -CO-O-, if the position bonded to the Ar ¹ side is * 1 and the position bonded to the G ¹ side is * 2, D ¹ is * 1. -CO-O- * 2 may be used, or * 1-O-CO- * 2 may be used.
Further, in the present specification, the present invention belongs to an angle (for example, an angle such as "90 °") and its relationship (for example, "orthogonal", "parallel" and "intersection at 45 °"). It shall include the range of error allowed in the technical field. For example, it means that the angle is within the range of ± 10 °, and the error from the exact angle is preferably 5 ° or less, and more preferably 3 ° or less.

ここで、上記式（Ａ）中、Ｍｐはポリマー主鎖の一部又は全部を構成する３価の基を表し、Ｌは単結合又は２価の連結基を表し、Ｘは置換又は無置換の環状構造官能基を表す。[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition of the present invention contains at least a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility, a structural unit represented by the following formula (A), and a structural unit derived from a fluoroaliphatic group-containing monomer. Contains two fluoroaliphatic group-containing polymers.
Further, at least one of the above fluoroaliphatic group-containing polymers is a polymer (A-1) represented by an aromatic condensed ring functional group in which X in the following formula (A) is substituted or unsubstituted.
Further, among the above-mentioned fluoroaliphatic group-containing polymers, at least one different from the polymer (A-1) is represented by a monocyclic structure functional group in which X in the following formula (A) is substituted or unsubstituted, and It is a polymer (A-2) having a weight average molecular weight (hereinafter, also abbreviated as “Mw”) larger than that of the polymer (A-1).

Here, in the above formula (A), Mp represents a trivalent group constituting a part or all of the polymer backbone, L represents a single bond or a divalent linking group, and X is substituted or unsubstituted. Represents a cyclic structure functional group.

In the present invention, as described above, it is formed by using predetermined polymers (A-1) and (A-2) together as a fluoroaliphatic group-containing polymer together with a polymerizable liquid crystal compound exhibiting reverse wavelength dispersity. There is no unevenness or alignment defect of the optically anisotropic film, and various functional layers can be stably laminated. In the present invention, the optically anisotropic film having no unevenness or orientation defect and the optically anisotropic film having excellent uniformity have substantially the same meaning.
This is not clear in detail, but the present inventor speculates as follows.
That is, by using two fluoroaliphatic group-containing polymers having different characteristics as described later, the coating film surface is made uniform and the molecular orientation state inside the coating film is stabilized from coating to orientation formation. We believe that it is possible to achieve both the conversion and the control of the surface state when the functional layer is added.
Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.

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

As described above, most of the polymerizable liquid crystal compounds exhibiting reverse wavelength dispersibility have a T-type molecular design guideline, and the wavelength of the major axis of the molecule is shortened to that of the minor axis located in the center of the molecule. It is a compound with a longer wavelength. However, as long as it does not deviate from the gist of the present invention, it may have another structure such as an H-type or a molecular structure in which two T-shapes are connected.

In the present invention, the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is preferably a polymerizable liquid crystal compound represented by the following formula (1) (hereinafter referred to as "polymerizable liquid crystal compound (1)"). ..
L ¹ -SP ^1- (E ³ -A ¹ ) _m -E ¹ -G ¹ -D ¹ -Ar ¹ -D ² -G ² -E ^2- (A ² -E ⁴ ) _n -SP ² -L ² ... (1)

In the above formula (1), D ¹ , D ² , E ¹ , E ² , E ³ and E ⁴ are independently single-bonded, -CO-O-, -C (= S) O-, and -CR, respectively. ¹ R ^2- , -CR ^{1 R 2-CR 3 R 4-, -O-CR 1 R 2- , -CR 1 R 2-O-CR 3 R 4- , -CO - O -} CR ¹ R ^2- , -O-CO-CR ¹ R ^2- , -CR ¹ R ² -O-CO-CR ³ R ^4- , -CR ¹ R ² -CO-O-CR ³ R ^4- , -NR ¹ -CR ² Represents R ^3- or -CO-NR ^1- . R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
Further, in the above formula (1), G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, and are of the alicyclic type. One or more of -CH _2- constituting the hydrocarbon group may be substituted with -O-, -S- or -NH-.
Further, in the above formula (1), A ¹ and A ² each independently have a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a substituent which may have a substituent. It represents a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and one or more of -CH _2- constituting the alicyclic hydrocarbon group is -O-, -S- or-. It may be substituted with NH-.
Further, in the above formula (1), SP ¹ and SP ² are independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. Alternatively, a divalent linkage in which one or more of -CH _2- constituting the branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents a group and Q represents a substituent.
Further, in the above formula (1), L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar ¹ is an aromatic ring represented by the following formula (Ar- ³ ), at ^{least one} of L1 and L2 and L3 and L4 in the following formula (Ar- ³ ) is polymerizable. Represents a group.
Further, in the above equation (1), m represents an integer of 0 to 2, and when m is ² , the plurality of E3s may be the same or different, and the plurality of ^A1s may be different. , Each may be the same or different.
Further, in the above equation (1), n represents an integer of 0 to 2, and when n is ² , the plurality of ^E4s may be the same or different, and the plurality of A2s may be the same or different. , Each may be the same or different.

In the above formula (1), D ¹ , D ² , E ¹ , E ² , E ³ and E ⁴ are preferably any of -CO-, -O-, and -CO-O-. ..

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

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

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

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

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

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

On the other hand, in the above formula (1), Ar ¹ represents any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-7). In the following formulas (Ar-1) to (Ar-7), * represents the bonding position with D ¹ or D ² in the above formula (I).

Here, in the above equation (Ar-1), Q ¹ represents N or CH, Q ² represents —S—, —O—, or —N (R ⁵ ) −, and R ⁵ is. Represents a hydrogen atom or an alkyl group having ¹ to 6 carbon atoms, where Y1 may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic complex having 3 to 12 carbon atoms. Represents a ring group.
Specific examples of the alkyl group having 1 to 6 carbon atoms indicated by R ⁵ include 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. Examples include a group, an n-pentyl group, an n-hexyl group and the like.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y ¹ include an aryl group such as a phenyl group, a 2,6-diethylphenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y ¹ include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group and a pyridyl group.

Further, in the above formula (Ar-1), examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, a halogen atom and the like.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or an isopropyl group) is preferable. , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group or an ethyl group is used. Is particularly preferable.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and carbon. It is more preferably an alkoxy group having the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.

Further, in the above formulas (Ar-1) to (Ar-7), Z ¹ , Z ² and Z ³ are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon. A monovalent alicyclic hydrocarbon group of number 3 to 20, a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ , or , -SR ⁹ and R ⁶ to R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring. good.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group (Me). , Ethyl group, isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group (tBu), 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, Ethyl groups and tert-butyl groups are particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and an ethylcyclohexyl. Monocyclic saturated hydrocarbon groups such as groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as diene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.2.10 ^2,6 ] decyl group, Tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and 6 to 12 carbon atoms. Aryl groups (particularly phenyl groups) are preferred.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, as the alkyl group having 1 to 6 carbon atoms indicated by R ⁶ to R ⁹ , specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group. Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.

Further, in the above formulas (Ar-2) and (Ar ^{- 3} ), A3 and A4 are independently ^derived from -O-, -N (R10)-, -S-, and -CO-, respectively. Represents a group selected from the group, where ^R10 represents a hydrogen atom or substituent.
Examples of the substituent represented by R ¹⁰ include the same substituents that Y ¹ in the above formula (Ar-1) may have.

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

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

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

Further, in the above formula (Ar-3), L ³ and L ⁴ independently represent monovalent organic groups, respectively, and at least 1 of L ³ and L ⁴ and L ¹ and L ² in the above formula (1). One represents a polymerizable group.
Examples of the monovalent organic group include the same groups as those described in L ¹ and L ² in the above formula (1).
Moreover, as the polymerizable group, the same group as those described in L1 and L2 in the above ^formula ( ¹ ) can be mentioned.

Further, in the above formulas (Ar-4) to (Ar-7), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
Further, in the above formulas (Ar-4) to (Ar-7), Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic. Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, ^Q3 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 [0995] of Patent Document 2 (International Publication No. 2014/010325).
Specific examples of the alkyl group having 1 to 6 carbon atoms indicated by ^Q3 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, n-pentyl group, n-hexyl group and the like can be mentioned, and examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have. Can be mentioned.

In the present invention, from the viewpoint of the film strength after curing, Ar ¹ in the above formula (1) may represent a group represented by any of the above formulas (Ar-1) to (Ar-5). It is more preferable to represent a group represented by the above formula (Ar-1) or (Ar-2).

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

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

[Other polymerizable liquid crystal compounds]
The polymerizable liquid crystal composition of the present invention may further contain other polymerizable liquid crystal compounds in addition to the above-mentioned polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility. As such a polymerizable liquid crystal compound, various known compounds can be used, and among them, a rod-shaped liquid crystal compound or a discotic liquid crystal compound is preferable, and a rod-shaped liquid crystal compound is further selected because of its shape similarity to the above-mentioned polymerizable liquid crystal compound (1). preferable.

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

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

[Polymer containing fluoroaliphatic group]
The polymerizable liquid crystal composition of the present invention contains at least two fluoroaliphatic group-containing polymers including a structural unit represented by the formula (A) described later and a structural unit derived from a fluoroaliphatic group-containing monomer. do.

The structural unit derived from the fluoroaliphatic group-containing monomer has the effect of controlling the surface energy of the coating film by the action of fluorine to maintain a uniform coating film, and is a structural unit represented by the formula (A) described later. Is believed to contribute to the formation of an optically anisotropic film without unevenness or defects by stabilizing the orientation state by interacting with the polymerizable liquid crystal compound molecules existing near the surface of the coating film. ..

<Polymer (A-1)>
At least one of the fluoroaliphatic group-containing polymers contained in the polymerizable liquid crystal composition of the present invention is a structural unit in which X in the formula (A) described later is a substituted or unsubstituted aromatic fused ring functional group, and , A polymer (A-1) containing a structural unit derived from a fluoroaliphatic group-containing monomer. Hereinafter, the polymer (A-1) is also referred to as a fluoroaliphatic group-containing polymer (A-1).

The polymer (A-1) contains a structural unit in which X in the formula (A) described later is a substituted or unsubstituted aromatic condensed ring functional group, so that the polymerizable liquid crystal present in the vicinity of the surface of the above-mentioned coating film is present. The inventor believes that it has a large effect of stabilizing the orientation of compound molecules and contributes to the formation of an optically anisotropic film without unevenness or defects.

ここで、上記式（Ａ）中、Ｍｐはポリマー主鎖の一部又は全部を構成する３価の基を表し、Ｌは単結合又は２価の連結基を表し、Ｘは置換又は無置換の環状構造官能基を表す。(1) Structural unit represented by the formula (A) The polymer (A-1) has a structural unit represented by the following formula (A).
The details of the group represented by the following formula (A) will be described below.

Here, in the above formula (A), Mp represents a trivalent group constituting a part or all of the polymer backbone, L represents a single bond or a divalent linking group, and X is substituted or unsubstituted. Represents a cyclic structure functional group.

In the above formula (A), Mp is a trivalent group and constitutes a part or all of the main chain of the polymer.
Examples of Mp include substituted or unsubstituted long chain or branched alkylene groups having 2 to 20 carbon atoms (excluding the number of carbon atoms of the substituent, hereinafter the same applies to those in Mp) (for example, ethylene). Group, propylene group, methylethylene group, butylene group, hexylene group, etc.), substituted or unsubstituted cyclic alkylene group having 3 to 10 carbon atoms (for example, cyclopropylene group, cyclobutylene group, cyclohexylene group, etc.), substituted Alternatively, an unsubstituted vinylene group, a substituted or unsubstituted cyclic vinylene group, a substituted or unsubstituted phenylene group, a group containing an oxygen atom (for example, a group containing an ether group, an acetal group, an ester group, a carbonate group, etc.), nitrogen. Atomic group (eg, amino group, imino group, amide group, urethane group, ureido group, imide group, imidazole group, oxazole group, pyrrole group, anilide group, maleinimide group, etc.), sulfur atom A group (for example, a group containing a sulfide group, a sulfone group, a thiophene group, etc.), a group containing a phosphorus atom (for example, a group containing a phosphin group, a phosphate ester group, etc.), a group containing a silicon atom (for example, a siloxane group, etc.) A group containing () and a group formed by linking two or more of these groups, wherein one of the hydrogen atoms contained in these groups is substituted with a -LX group is preferable. Listed in.
Of these, a substituted or unsubstituted ethylene group, a substituted or unsubstituted methylethylene group, a substituted or unsubstituted cyclohexylene group, a substituted or unsubstituted vinylene group, and hydrogen atoms contained in these groups. A group in which one is substituted with an —LX group is preferable, and it is a substituted or unsubstituted ethylene group, a substituted or unsubstituted methylethylene group, a substituted or unsubstituted vinylene group, and is included in these groups. A group in which one of the hydrogen atoms is substituted with an —LX group is more preferable, a substituted or unsubstituted ethylene group, a substituted or unsubstituted methylethylene group, and one of the hydrogen atoms contained in these groups. Groups in which one is substituted with an —LX group are more preferred, and Mp-1 and Mp-2, which will be described later, are particularly preferred.

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

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

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

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

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

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

In particular, L is a single bond or -O-, -NR ^a11- (where R ^a11 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms), -S-, -C (= O). )-, -S (= O) _2- , and in the case of a divalent linking group selected from the group consisting of groups formed by linking two or more of these, X is substituted or unsubstituted. It is preferable to represent a naphthyl group of.

Hereinafter, specific examples of preferable structural units as the above formula (A) in the polymer (A-1) are shown, but the present invention is not limited thereto.

ここで、上記式（Ｂ）中、Ｍｐ’はポリマーの主鎖の一部を構成する３価の基を表し、Ｌ’は単結合又は２価の連結基を表し、Ｒｆは少なくとも一つのフッ素原子を含有する置換基を表す。(2) Structural Unit Derived from a Fluoroaliphatic Group-Containing Monomer The polymer (A-1) has a structural unit derived from a fluoroaliphatic group-containing monomer together with the structural unit represented by the above formula (A). .. The structural unit is preferably a structural unit represented by the following formula (B). The details of the group represented by the following formula (B) will be described below.

Here, in the above formula (B), Mp'represents a trivalent group constituting a part of the main chain of the polymer, L'represents a single bond or a divalent linking group, and Rf represents at least one fluorine. Represents a substituent containing an atom.

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

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

As Rf, for example, an aliphatic hydrocarbon group having 1 to 30 carbon atoms substituted with at least one fluorine atom (for example, trifluoroethyl group, perfluorohexylethyl group, perfluorohexylpropyl group, perfluorobutylethyl). Group, perfluorooctylethyl group, etc.) are preferably mentioned.

Further, Rf preferably has a CF ₃ group or a CF ₂ H group at the terminal, more preferably has a CF ₃ group, and has an alkyl group having a CF ₃ group at the terminal or a CF ₂ H group at the terminal. It is more preferably an alkyl group.
An alkyl group having ₃ CF groups at the terminal is an alkyl group in which a part or all of hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. Alkyl groups in which 50% or more of hydrogen atoms in the alkyl group having CF ₃ at the terminal are substituted with fluorine atoms are preferable, alkyl groups in which 60% or more are substituted are more preferable, and 70% or more are substituted. Alkyl groups are particularly preferred. The remaining hydrogen atoms may be further substituted with the substituents exemplified as the substituent group D described later.
An alkyl group having a CF ₂ H group at the terminal is an alkyl group in which a part or all of hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. It is preferable that 50% or more of the hydrogen atom in the alkyl group having a CF _2H group at the terminal is substituted with a fluorine atom, more preferably 60% or more is substituted, and 70% or more is substituted. It is especially preferable to have. The remaining hydrogen atoms may be further substituted with the substituents exemplified as the substituent group D described later.

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

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

-Acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group).
An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, a methoxycarbonylamino group or the like. Can be mentioned)
A sulfonylamino group (preferably a sulfonylamino group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, a methanesulfonylamino group or an ethanesulfonylamino. Group etc.)
-Sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, and for example, sulfamoyl group, methyl sulfamoyl group, dimethyl. Sulfamoyl group etc.)

-Alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group).
-Sulfonyl group (preferably a sulfonyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group).
A sulfinyl group (preferably a sulfinyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and an ethanesulfinyl group. Be)
A ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group, a methyl ureido group, etc. Can be mentioned)
-A phosphoric acid amide group (preferably a phosphoric acid amide group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and for example, a diethyl phosphate amide group. Be)
-In addition, hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group. , Cyril group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group) and the like. Can be mentioned.

These substituents may be further substituted with these substituents.
Moreover, when it has two or more substituents, it may be the same or different. Further, if possible, they may be combined with each other to form a ring.

An example of an alkyl group having a CF ₃ group at the terminal or an alkyl group having a CF _2H group at the terminal is shown below.
R1: n-C ₈ F _17-
R2: n-C ₆ F _13-
R3: n-C ₄ F _9-
R4: n-C ₈ F _17- (CH ₂ ) _2-
R5: n-C ₆ F _13- (CH ₂ ) _3-
R6: n-C ₄ F _9- (CH ₂ ) _2-
R7: H- (CF ₂ ) _8-
R8: H- (CF ₂ ) _6-
R9: H- (CF ₂ ) _4-
R10: H- (CF ₂ ) _8- (CH ₂ ) _2-
R11: H- (CF ₂ ) _6- (CH ₂ ) _3-
R12: H- (CF ₂ ) _4- (CH ₂ ) _2-
R13: n-C ₇ F _15- (CH ₂ ) _2-
R14: n-C ₆ F _13- (CH ₂ ) _3-
R15: n-C ₄ F _9- (CH ₂ ) _2-

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

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

In the polymer (A-1) used in the present invention, the content of the group represented by the above formula (A) is preferably 25 to 80 mol%, more preferably 30 to 60 mol% as the molar ratio to all the constituent units. preferable.
The content of the repeating unit (preferably the group represented by the above formula (B)) derived from the fluoroaliphatic group-containing monomer in the polymer (A-1) used in the present invention is mol to all the constituent units. The ratio is 20 to 75 mol%, more preferably 30 to 70 mol%.
The content of the constituent units other than the above two types is preferably 60% by mass or less, more preferably 50% by mass or less.

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

Further, the molecular weight range of the polymer (A-1) used in the present invention is a weight average molecular weight (Mw), preferably 30 to 1,000,000, and more preferably 5,000 to 50,000. Within this range, the solubility in the composition and the leveling ability are high, and the adhesion after the surface treatment and the effect of improving the wettability are high. Further, the molecular weight distribution of the polymer used in the present invention (Mw / Mn and Mw are weight average molecular weights) is preferably 1 to 4, more preferably 1.5 to 4.
Here, the weight average molecular weight in the present invention is a value measured by a gel permeation chromatograph (GPC) method under the conditions shown below.
-Solvent (eluent): THF (tetrahydrofuran)
-Device name: TOSOH HLC-8320GPC
-Column: Use by connecting three TOSOH TSKgel Super HZM-H (4.6 mm x 15 cm)-Column temperature: 40 ° C.
-Sample concentration: 0.1% by mass
-Flow velocity: 1.0 ml / min
-Calibration curve: TSK standard polystyrene made by TOSOH A calibration curve with 7 samples from Mw = 2800000 to 1050 (Mw / Mn = 1.03 to 1.06) is used.

<Polymer (A-2)>
At least one of the fluoroaliphatic group-containing polymers contained in the polymerizable liquid crystal composition of the present invention is a structural unit in which X in the above formula (A) is a substituted or unsubstituted monocyclic functional group, and fluoro. It is a polymer containing a structural unit derived from an aliphatic group-containing monomer and having a weight average molecular weight larger than that of the above polymer (A-1). Hereinafter, the polymer (A-2) is also referred to as a fluoroaliphatic group-containing polymer (A-2).

The polymer (A-2) is chemically similar to the polymer (A-1) in terms of chemical structure, but has a larger weight average molecular weight than the polymer (A-1). Even if it is unevenly distributed, it is considered that the polymer (A-1) is stably and strongly unevenly distributed toward the air interface side without weakening the orientation stabilizing action. Further, although the mechanism is unknown, the polymer (A-2) has a structural unit in which X in the above formula (A) is a substituted or unsubstituted monocyclic structure functional group, so that the polymer (A-2) constitutes a laminate. The present inventor has found that the effect of increasing the surface energy is large by the various surface modification treatments performed in. As a result, the present inventor believes that the outermost surface state of the optically anisotropic layer can be easily controlled while maintaining good uniformity and orientation of the coating film.

In the polymer (A-2), among the elements constituting the structural unit represented by the above formula (A), those having the same Mp and L as the Mp and L in the polymer (A-1) can be selected. The Mp and L of the compound to be combined as the polymer (A-1) and the Mp and L of the compound to be combined as the polymer (A-2) may be the same or may be different. Further, the structural unit derived from the fluoroaliphatic group-containing monomer is also the same as that described in the polymer (A-1).

In the polymer (A-2), the number of rings of the substituted or unsubstituted monocyclic functional group represented by X in the above formula (A) is not particularly limited, but is substituted or substituted with 3 to 20 carbon atoms. An unsubstituted cyclic aliphatic group (for example, an unsubstituted cyclopropyl group, an unsubstituted cyclobutyl group, an unsubstituted cyclopentyl group, a cyclohexyl group, a pentylcyclohexyl group, a propylcyclohexyl group, etc.), a substituent having 6 to 30 carbon atoms or Unsubstituted phenyl group (eg, unsubstituted phenyl group, cyanophenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, octyloxyphenyl group, halogen atom substituted phenyl group, trifluoromethylphenyl group, trifluoromethoxy) A phenyl group, a perfluorohexylethyloxyphenyl group, a hydroxybutylphenyl group, a carboxyphenyl group, a sulfophenyl group, etc.), or a substituted or unsubstituted heterocyclic group (for example, a furan group, a thiophene group, a pyridyl group, a dimethylamino group). (Pyridyl group, N-methylimidazolyl group, etc.) can be mentioned.

In the polymer (A-2), the X in the above formula (A) is preferably a substituted or unsubstituted cyclohexyl group or a substituted or unsubstituted phenyl group, and is substituted with 6 to 15 carbon atoms. Alternatively, it is more preferably an unsubstituted cyclohexyl group or a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, and further preferably a substituted or unsubstituted phenyl group having 6 to 15 carbon atoms. , It is particularly preferable that it is a substituted phenyl group having 6 to 10 carbon atoms.

In particular, L is a single bond or -O-, -NR ^a11- (where R ^a11 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms), -S-, -C (= O). )-, -S (= O) _2- , and in the case of a divalent linking group selected from the group consisting of groups formed by linking two or more of these, X is substituted or unsubstituted. It is preferable to represent the phenyl group of.

Hereinafter, specific examples of preferable structural units as the above formula (A) in the polymer (A-2) will be shown, but the present invention is not limited thereto.

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

In the polymer (A-2) used in the present invention, the content of the group represented by the above formula (A) is preferably 25 to 80 mol%, more preferably 30 to 60 mol% as the molar ratio to all the constituent units. preferable.
The content of the repeating unit (preferably the group represented by the above formula (B)) derived from the fluoroaliphatic group-containing monomer in the polymer (A-2) used in the present invention is mol to all the constituent units. The ratio is 20 to 75 mol%, more preferably 30 to 70 mol%.
The content of the constituent units other than the above two types is preferably 60% by mass or less, more preferably 50% by mass or less.

Further, the molecular weight range of the polymer (A-2) used in the present invention is a weight average molecular weight (Mw), preferably 30 to 1,000,000, and more preferably 5,000 to 50,000. Within this range, the solubility in the composition and the leveling ability are high, and the adhesion after the surface treatment and the effect of improving the wettability are high. Further, the molecular weight distribution of the polymer used in the present invention (Mw / Mn and Mw are weight average molecular weights) is preferably 1 to 4, more preferably 1.5 to 4.

The weight average molecular weight of the polymer (A-2) is larger than the weight average molecular weight of the polymer (A-1), but is preferably 10,000 or more.

Further, the above-mentioned polymers A-1 and polymer A-2 are block copolymers in which the constituent units are regularly introduced even if they are random copolymers in which the constituent units are irregularly introduced. In the case of a block copolymer, each constituent unit may be synthesized in any order of introduction, and the same constituent component may be used twice or more.
Further, the group represented by the above formula (A), the group represented by the above formula (B), and the like may be of only one type, or may be of two or more types. When two or more structural units of the above formula (A) are contained, it is preferable that X is the same fused ring skeleton (combination of substituted and unsubstituted). In the case of two or more types, the above content is the total content.

The addition amount range of the polymer (A-1) and the polymer (A-2) used in the present invention is preferably 0.01 to 5% by mass with respect to the total solid content of the polymerizable liquid crystal composition in the total amount thereof. It is more preferably 0.1 to 1.0% by mass, and further preferably 0.05 to 0.5% by mass. In this range, leveling and orientation control are good, and it is possible to suppress the embossment (bloom or bleeding) of these polymers on the surface of the optically anisotropic layer during film formation or with time.

The polymer (A-1) is preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.1% by mass, based on the total solid content of the polymerizable liquid crystal composition. Yes, more preferably 0.05 to 0.09% by mass.
The polymer (A-2) is preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.1% by mass, based on the total solid content of the polymerizable liquid crystal composition. Yes, more preferably 0.03 to 0.08% by mass.
The ratio of the polymer (A-1) and the polymer (A-2) is not particularly limited, but the mass ratio in the range of 8: 2 to 4: 6 is effective in controlling the orientation state and reducing unevenness, and is laminated. It is preferable in that all the control of the surface state in constructing the body is satisfied at a high level.

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

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

[Polymer initiator]
The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-hydrocarbon-substituted fragrances. Group acyloin compounds (described in US Pat. No. 2,725,512), polynuclear quinone compounds (described in US Pat. Nos. 3,46127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketones (US Pat. 3549365 (described in US Pat. No. 3,549,67), an acridin and a phenazine compound (Japanese Patent Laid-Open No. 60-105667, described in US Pat. No. 4,239,850), an oxadiazole compound (described in US Pat. No. 4,212,970), acylphosphine. Examples thereof include oxide compounds (described in Japanese Patent Application Laid-Open No. 63-40799, Japanese Patent Application Laid-Open No. 5-29234, Japanese Patent Application Laid-Open No. 10-95788, Japanese Patent Application Laid-Open No. 10-29997) and the like.

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

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

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

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

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

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

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

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

1A and 1B are schematic cross-sectional views showing an example of the optically anisotropic film of the present invention.
The optically anisotropic film 10 shown in FIG. 1A has only the positive A plate 12, and the optically anisotropic film 10 shown in FIG. 1B has a positive A plate 12 and a positive C plate 14 laminated in this order. This is an aspect.

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

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

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

In the present invention, the values of the in-plane retardation and the retardation in the thickness direction refer to the values measured by using AxoScan OPMF-1 (manufactured by Optoscience) and using light of a measurement wavelength.
Specifically, by inputting the average refractive index ((Nx + Ny + Nz) / 3) and the film thickness (d (μm)) in AxoScan OPMF-1.
Slow phase axial direction (°)
Re (λ) = R0 (λ)
Rth (λ) = ((nx + ny) /2-nz) × d
Is calculated.
Although R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, it means Re (λ).

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

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

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

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

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

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

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

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

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

The alignment film is generally composed of a polymer as a main component. The polymer material for an alignment film has been described in a large number of documents, and a large number of commercially available products are available.
The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and its derivatives. Particularly modified or unmodified polyvinyl alcohol is preferable.
For the alignment film that can be used in the present invention, for example, the alignment film described in International Publication No. 01/88574, page 43, lines 24 to 49, line 8; paragraphs [0071] to [00905] of Japanese Patent No. 3907735. ] The modified polyvinyl alcohol described in [2]; a liquid crystal alignment film formed by the liquid crystal alignment agent described in JP-A-2012-155308; and the like.

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

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

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

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

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

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

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

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

[Polarizer]
The polarizing plate of the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into a specific linear polarization, and conventionally known absorption-type and reflection-type splitters can be used. ..
As the absorption type polarizing element, an iodine-based polarizing element, a dye-based polarizing element using a dichroic dye, a polyene-based polarizing element, and the like are used. Iodine-based splitters and dye-based splitters include coated and stretched splitters, both of which can be applied, but polarized light produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching it. Children are preferred.
Further, as a method for obtaining a polarizing element by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 4691205, and Patent No. 5048120, Patent No. Japanese Patent No. 4751481 and Japanese Patent No. 4751486 can be mentioned, and known techniques relating to these substituents can also be preferably used.
As the reflective classifier, a splitter in which thin films having different birefringences are laminated, a wire grid type splitter, a carboxylator in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined, and the like are used.
Among them, a polyvinyl alcohol-based resin (a polymer containing _-CH2 -CHOH- as a repeating unit. In particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers) is excellent in adhesion. It is preferable that the polymer contains one).

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

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

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

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

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

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

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

Hereinafter, the features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the specific examples shown below.

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

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

―――――――――――――――――――――――――――――――――
(Polymerizable Liquid Crystal Composition A-1)
―――――――――――――――――――――――――――――――――
-The following polymerizable liquid crystal compound L-1 42.00 parts by mass-The following polymerizable liquid crystal compound L-2 42.00 parts by mass-The following polymerizable liquid crystal compound L-3 16.00 parts by mass-The following polymerization initiator PI-1 0.50 parts by mass, polymer T-1 below 0.09 parts by mass, polymer T-2 below 0.06 parts by mass, cyclopentanone 235.00 parts by mass ―――――――――――――― ―――――――――――――――――――
In the structural formulas of the following polymerizable liquid crystal compound L-1 and the polymerizable liquid crystal compound L-2, the group adjacent to the acryloyloxy group represents a propylene group (a group in which a methyl group is replaced with an ethylene group) and is polymerizable. The liquid crystal compounds L-1 and L-2 represent a mixture of positional isomers having different positions of methyl groups.

Polymerizable liquid crystal compound L-1

Polymerizable liquid crystal compound L-2

Polymerizable liquid crystal compound L-3

Polymerization Initiator PI-1

Polymer T-1 (fluoroaliphatic group-containing polymer (A-1), Mw = 27200)

Polymer T-2 (fluoroaliphatic group-containing polymer (A-2), Mw = 31600)

[Manufacturing of optical film A (reference example)]
Instead of the polymerizable liquid crystal composition A-1, the optically anisotropic layer coating liquid (D) described in paragraph [0125] of International Publication No. 2013/137464 was used, and drying conditions and UV irradiation conditions were used. The optical film A including the optically anisotropic film A was prepared in the same manner as in Example 1-1, except that the conditions described in the paragraph of the publication [0124] were changed.

[Manufacturing of circular polarizing plate 1]
The surface of the support TD80UL (manufactured by FUJIFILM Corporation) was subjected to alkali saponification treatment. Specifically, the support is immersed in a 1.5-specified sodium hydroxide aqueous solution at 55 ° C. for 2 minutes, the removed support is washed in a water-washing bath at room temperature, and 0.1-specified sulfuric acid is washed at 30 ° C. Was neutralized using. Then, the obtained support was washed again in a water washing bath at room temperature, and further dried with warm air at 100 ° C.
Next, a roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution, and the stretched film was dried to obtain a polarizing element having a thickness of 20 μm.
The obtained polarizing element and the support (TD80UL) subjected to the alkali saponification treatment were bonded together to obtain a polarizing plate having the polarizing element exposed on one side.
Next, the longitudinal direction of the polarizing plate and the longitudinal direction of the optical film 1 are made parallel to each other, and the exposed surface of the polarizing element in the polarizing plate and the surface of the triacetyl cellulose film in the optical film 1 are attached to a pressure sensitive adhesive (SK). -2057, manufactured by Soken Kagaku Co., Ltd.) was used for continuous bonding.
Next, the surface of the optical anisotropic film side of the optical film 1 and the surface of the film containing the positive C plate (positive C plate film 1) prepared according to the description in paragraphs [0124] to [0126] of JP-A-2015-200861. And are bonded together using a pressure-sensitive adhesive (SK-2057, manufactured by Soken Kagaku Co., Ltd.), and then the temporary support for formation in the positive C plate is peeled off to optical anisotropy only the positive C plate. Transferred onto the film A-1 to prepare a circular polarizing plate 1. In the obtained circularly polarizing plate, no uneven bonding due to poor adhesion between layers was observed.
Further, a circularly polarized plate was similarly produced by using the optical film A instead of the optical film 1.
The following evaluations were made on these circularly polarizing plates. The results are shown in Table 1 below.

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

<Surface energy>
After corona treatment was applied to the surface of the obtained optically anisotropic film, a 5 cm square sample was cut out, and the surface was washed with a solvent to remove foreign substances and the like. K. Owens: J.M. Apple. Polym. Sci. , 13, 1741 (1969), and the contact angle was measured using pure water and methylene iodide on each surface of the sample to be measured.

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

<Tape peeling>
A grid tape peeling test was performed in accordance with JIS D0202-1988.
A cellophane tape (trade name: CT24, manufactured by Nichiban Co., Ltd.) was adhered to the optically anisotropic film side of the obtained circular polarizing plate using a rubbing rod, and then peeled off. Judgment was expressed by the number of squares to be peeled out of 100 squares, and was evaluated according to the following criteria.
A: No peeling B: With peeling of 1 to 5 squares C: Peeling of 6 squares or more is seen

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

[Example 1-2]
[Preparation of positive C plate film 2]
The following composition C-2 was continuously applied onto a TG40 (manufactured by FUJIFILM Corporation) support as a temporary support for formation. The coating film formed on the temporary support for formation is heated to 60 ° C. under a heating atmosphere and irradiated with ultraviolet rays (300 mJ / cm ² ) at 70 ° C. at an oxygen concentration of 100 ppm under a nitrogen purge to fix the orientation of the liquid crystal compound. By doing so, a positive C plate film 2 including a retardation film (positive C plate) was produced. The thickness of the retardation film was 0.4 μm.

―――――――――――――――――――――――――――――――――
(Composition C-2)
―――――――――――――――――――――――――――――――――
-The following rod-shaped liquid crystal compound (M-1) 83 parts by mass-The following rod-shaped liquid crystal compound (M-2) 15 parts by mass-The following rod-shaped liquid crystal compound (M-3) 2 parts by mass-The following urethane monomer (EBECRYL1290,
(Manufactured by Dycel Ornex) 3.3 parts by mass ・ The following polymerization initiator (IrgacureOXE01,
(Manufactured by BASF) 4 parts by mass, the following fluorine-based polymer (M-4) 3 parts by mass, the following fluorine-based polymer (M-5) 0.3 parts by mass, the following onium compound S01 1.5 parts by mass, toluene 552 parts by mass・ Methyl ethyl ketone (MEK) 138 parts by mass ――――――――――――――――――――――――――――――――――

Rod-shaped liquid crystal compound (M-1)

Rod-shaped liquid crystal compound (M-2)

Rod-shaped liquid crystal compound (M-3)

Urethane monomer

Polymerization initiator

Fluorine polymer (M-4)

Fluorine polymer (M-5)

Onium salt compound S01

[Manufacturing of optical film 2]
The optically anisotropic film-side surface of the optical film 1 produced in Example 1-1 and the retardation film-side surface of the positive C plate film 2 produced above are bonded to a pressure-sensitive adhesive (SK-2057, Soken Kagaku). By using (manufactured by Co., Ltd.) to bond and then peeling off the temporary support for formation in the positive C plate film 2, the positive C plate is placed on the optically anisotropic film of the optical film 1 via a pressure-sensitive adhesive. An optical film 2 in which only the retardation film of the film 2 was laminated was produced.

<Chemical durability evaluation>
The optical film 2 was cut into 40 mm squares, and the support side was bonded to a glass plate using a pressure-sensitive adhesive (SK-2057, manufactured by Soken Chemical Co., Ltd.) to prepare a laminated body. Next, a screw cap bottle containing a 2 mol% ammonia solution was prepared, the bottle mouth (diameter 2 cm) was closed on the optical film 2 side, and the optical film 2 was exposed to the ammonia gas in the bottle.
After a lapse of a certain exposure time, the optical film 2 is removed, the front retardation Re (550) of the optical film 2 is measured using an Axo Scan (0PMF-1, manufactured by Axometrics), and after the measurement, the same exposure is performed again. I repeated that. The change in the front retardation Re (550) of the optical film 2 with respect to the exposure for a total of 120 minutes was within 20% with respect to the exposure before ammonia exposure.

[Preparation of circular polarizing plate 2]
A circular polarizing plate 2 was produced in the same manner as the circular polarizing plate 1 except that the positive C plate film 2 was used instead of the positive C plate film 1. The surface evaluation with the circular polarizing plate described above was good in both unevenness and bright spots. The tape peeling was also evaluated as A.
In the above-mentioned mounting on the organic EL display device, the blackness of the OLED panel was evaluated in the same manner except that the circularly polarizing plate 2 was used instead of the circularly polarizing plate 1, and the color of the reflected light on the panel was neutral. It was a firm black (evaluation: A).

From the results shown in Table 1 above, the optically anisotropic film formed from the polymerizable liquid crystal composition of the present invention is uneven as compared with the optically anisotropic film formed from the conventional forward-dispersible polymerizable liquid crystal composition. It was also found that it is possible to provide an OLED display device having excellent display performance at the time of black display by realizing reverse wavelength anisotropy while suppressing defects equally. In addition, the obtained optical film had no poor adhesion or unevenness.

[Example 2-1]
[Manufacturing of optical film 2-1]
The optically anisotropic film 1 was formed on the alignment film P-1 by the same method as in Example 1-1.
Next, the surface of the optically anisotropic film 1 was subjected to corona treatment with a discharge amount of 100 W · min / m ² .

[Formation of alignment film]
The following composition B is applied to the surface of the optically anisotropic film 1 treated with corona with a wire bar coater # 2.4, dried at 60 ° C. for 30 seconds, and then 120 W / cm using a high-pressure mercury lamp. In ² , UV irradiation was performed at 30 ° C. for 30 seconds to form an alignment film.

―――――――――――――――――――――――――――――――――
(Composition B)
―――――――――――――――――――――――――――――――――
-The following polymerizable compound P-1 33.00 parts by mass-The following polymerizable compound P-2 67.00 parts by mass-The following polymerization initiator PI-1 4.00 parts by mass-Methyl acetate 173.33 parts by mass-Cyclohexanone 173 .33 Mass part ――――――――――――――――――――――――――――――――――

Polymerizable compound P-1

Polymerizable compound P-2 (mass ratio of the following compounds = 50:50)

Polymerization Initiator PI-1

[Formation of positive C plate]
The following composition C was applied on the optical film 1 on which the alignment film was formed with a wire bar coater # 2.4, and heated in a constant temperature bath at 100 ° C. for 2 minutes to orient the rod-shaped liquid crystal compound (homeo). Tropic orientation). Next, after cooling to 40 ° C., using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under nitrogen purge, an illuminance of 190 mW / cm ² and an irradiation amount of 300 mJ. The coating layer was cured by irradiating with ultraviolet rays of / cm ² , and an optical film 2-1 was produced.

―――――――――――――――――――――――――――――――――
(Composition C)
―――――――――――――――――――――――――――――――――
-The following rod-shaped liquid crystal compound (M-4) 80.00 parts by mass-The following rod-shaped liquid crystal compound (M-5) 20.00 parts by mass-The following polymerization initiator PI-2 3.00 parts by mass-The following polymerization initiator PI- 3 1.00 parts by mass ・ The following leveling agent Y-1 0.40 parts by mass ・ The following leveling agent Y-2 0.05 parts by mass ・ The following polymerizable compound P-3 5.00 parts by mass ・ The following vertical alignment agent S- 1 1.00 parts by mass ・ The following vertical alignment agent S-2 0.50 parts by mass ・ Methyl ethyl ketone 318.06 parts by mass ・ Cyclohexanone 51.78 parts by mass ――――――――――――――――― ――――――――――――――――

Rod-shaped liquid crystal compound (M-4)

Rod-shaped liquid crystal compound (M-5)

Polymerization Initiator PI-2

Polymerization Initiator PI-3

Leveling agent Y-1

Leveling agent Y-2

Polymerizable compound P-3

Vertical alignment agent S-1

Vertical alignment agent S-2

[Manufacturing of circular polarizing plate]
The surface of the support TD80UL (manufactured by FUJIFILM Corporation) was subjected to alkali saponification treatment. Specifically, the support is immersed in a 1.5-specified sodium hydroxide aqueous solution at 55 ° C. for 2 minutes, the removed support is washed in a water-washing bath at room temperature, and 0.1-specified sulfuric acid is washed at 30 ° C. Was neutralized using. Then, the obtained support was washed again in a water washing bath at room temperature, and further dried with warm air at 100 ° C.
Next, a roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution, and the stretched film was dried to obtain a polarizing element having a thickness of 20 μm.
The obtained polarizing element and the support (TD80UL) subjected to the alkali saponification treatment were bonded together to obtain a polarizing plate having the polarizing element exposed on one side.
Next, the longitudinal direction of the polarizing plate is made parallel to the optical film 2-1 and the exposed surface of the polarizing element in the polarizing plate and the surface of the triacetyl cellulose film in the optical film 2-1 are attached to each other with a pressure sensitive adhesive. (SK-2057, manufactured by Soken Kagaku Co., Ltd.) was continuously bonded to prepare a circular polarizing plate.

[Examples 2-2 to 2-9 and Comparative Examples 2-1 to 2-4]
The same method as in Example 2-1 (and Example 1-1) was used except that the polymerizable liquid crystal composition A-1 forming the optically anisotropic film 1 was changed to the composition shown in Table 2 below. An optically anisotropic film was formed.
Next, an optical film on which a positive C plate was formed was produced in the same manner as in Example 2-1.
Next, a circularly polarizing plate was produced in the same manner as in Example 2-1.

The structures of the polymerizable liquid crystal compound and the fluoroaliphatic group-containing polymer in Table 2 are shown below.

Polymerizable liquid crystal compound L-1

Polymerizable liquid crystal compound L-2

Polymerizable liquid crystal compound L-3

Polymerizable liquid crystal compound L-5

Polymerizable liquid crystal compound L-6

Polymerizable liquid crystal compound L-7

Polymerizable liquid crystal compound L-8

Polymerizable liquid crystal compound M-1

Polymerizable liquid crystal compound M-2

Polymerizable liquid crystal compound M-3

Polymer T-1 (fluoroaliphatic group-containing polymer (A-1), Mw = 27200)

Polymer T-2 (fluoroaliphatic group-containing polymer (A-2), Mw = 31600)

Polymer T-3 (fluoroaliphatic group-containing polymer (A-1), Mw = 25300)

Polymer T-4 (fluoroaliphatic group-containing polymer (A-2), Mw = 27800)

Polymer T-5 (fluoroaliphatic group-containing polymer (A-2), Mw = 30200)

Polymer T-6 (fluoroaliphatic group-containing polymer (A-2), Mw = 13300)

[evaluation]
The following evaluations were performed on the optically anisotropic films formed in Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-4, and the produced optical films and circular polarizing plates. The results are shown in Table 3 below.

[Surface of optically anisotropic film]
The above-mentioned optically anisotropic film before corona treatment is placed between a set of polarizing plates, and each film is adjusted so as to have a quenching position and placed on a surface light source. The presence or absence of light leakage and bright spots due to orientation defects was evaluated.
<Alignment unevenness>
A: There is no uneven orientation and the quenching is uniform (good).
B: Very slight light leakage with unclear boundaries is seen (practical level)
C: The boundary is not clear, but there is a clear alignment unevenness that is visible as a clear light leak. D: There is a clear boundary alignment unevenness, and a clear light leak is visible. <Bright spot>
A: There are no bright spots and the quenching is uniform (good).
C: Bright spots are seen and light leakage is visible.

[Surface of optical film]
Each optical film on which the positive C plate layer is laminated is placed between a set of polarizing plates, and each film is adjusted so as to have a quenching position and placed on a surface light source. We evaluated the presence or absence of light leakage due to light leakage and bright spots due to orientation defects.
<Alignment unevenness>
A: There is no uneven orientation and the quenching is uniform (good).
B: Orientation unevenness with unclear boundaries is seen (practical level)
C: There is a clear alignment unevenness at the boundary, and clear light leakage is visible. <Bright spot>
A: There are no bright spots and the quenching is uniform (good).
B: 1 to 5 bright spots can be seen per 10 cm square C: 6 or more bright spots can be seen per 10 cm square

[Peeling test of optical film]
A cross-cut test (a grid tape peeling test) based on JIS D0202-1988 was carried out on the optical film on which the positive C plate layer was laminated. Nitto cellophane tape (registered trademark) was used as the tape. The sample pieces after the peeling test were observed and evaluated as follows.
A: No peeling B: With peeling of 1 to 5 squares C: Peeling of 6 squares or more is seen

[OLED panel blackish]
The organic EL is as described above except that the circular polarizing plates produced in Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-4 are used instead of the circular polarizing plate 1 of Example 1-1. An organic EL display device was manufactured by laminating on a display panel.
The produced organic EL display device was displayed in black under a bright room, and the color of the panel reflected light was visually evaluated. However, in the evaluation of blackness, light leakage due to the bright spots of the optical film was clearly excluded.
A: When it is a neutral and firm black
B: If there is a slight black floating or if it is a slightly tinted black C: If it is clearly floating black or if it appears to be clearly tinted

From the results shown in Tables 2 and 3 above, when a composition containing no polymer (A-2) is used as the fluoroaliphatic group-containing polymer, the formed optically anisotropic film has orientation defects. In addition, it was found that an orientation defect was also observed in the optical film on which the positive C plate was laminated (Comparative Example 2-1).
Further, when a composition containing no polymer (A-1) is used as the fluoroaliphatic group-containing polymer, the optically anisotropic film formed has uneven orientation, and a positive C plate is formed. It was found that the laminated optical films also showed uneven orientation (Comparative Example 2-2).
Further, when a polymer having a weight average molecular weight smaller than that of the polymer (A-2) is used as the polymer (A-2) as the fluoroaliphatic group-containing polymer, the formed optically anisotropic film has a positive C. It was found that an orientation defect was observed in the optical film in which the plates were laminated (Comparative Example 2-3).
Further, it was found that the formed optically anisotropic film did not have the reverse wavelength dispersibility when the polymerizable liquid crystal compound showing the reverse wavelength dispersibility was used (Comparative Example 2-4).
On the other hand, when a polymerizable liquid crystal composition exhibiting reverse wavelength dispersibility and a polymerizable liquid crystal composition in which the polymers (A-1) and (A-2) are used in combination as the fluoroaliphatic group-containing polymer is used. It was found that there was no unevenness or alignment defect in the formed optically anisotropic film, and there was no unevenness or alignment defect in the optical film on which the positive C plate was laminated (Examples 2-1 to 2-9). ..

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

Claims (13)

Polymerizable liquid crystal compounds showing reverse wavelength dispersity,
It contains at least two fluoroaliphatic group-containing polymers, including a structural unit represented by the following formula (A) and a structural unit derived from a fluoroaliphatic group-containing monomer.
At least one of the fluoroaliphatic group-containing polymers is a polymer (A-1) represented by an aromatic fused ring functional group in which X in the following formula (A) is substituted or unsubstituted.
Among the fluoroaliphatic group-containing polymers, at least one different from the polymer (A-1) is represented by a monocyclic structure functional group in which X in the following formula (A) is substituted or unsubstituted, and by weight. A polymerizable liquid crystal composition which is a polymer (A-2) having an average molecular weight larger than that of the polymer (A-1).

Here, in the formula (A), Mp represents a trivalent group constituting a part or all of the polymer backbone, L represents a single bond or a divalent linking group, and X is substituted or unsubstituted. Represents a cyclic structure functional group. The polymerizable liquid crystal composition according to claim 1, wherein the polymer (A-1) has a structural unit represented by a naphthyl group in which X in the formula (A) is substituted or unsubstituted. The polymerizable liquid crystal composition according to claim 1, wherein the polymer (A-2) has a structural unit represented by a phenyl group in which X in the formula (A) is substituted or unsubstituted. The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein the polymer (A-1) and the polymer (A-2) have a mass ratio of 8: 2 to 4: 6. .. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by the following formula (1).
L ¹ -SP ^1- (E ³ -A ¹ ) _m -E ¹ -G ¹ -D ¹ -Ar ¹ -D ² -G ² -E ^2- (A ² -E ⁴ ) _n -SP ² -L ² ... (1)
Here, in the above formula (1),
D ¹ , D ² , E ¹ , E ² , E ³ and E ⁴ are independently single-bonded, -CO-O-, -C (= S) O-, -CR ¹ R ^2- , -CR, respectively. ¹ R ² -CR ^{3 R 4-, -O-CR 1 R 2-, -CR 1 R 2-O-CR 3 R 4-, -CO-O-CR 1 R 2- , -O - CO -} CR ¹ R ^2- , -CR ¹ R ² -O-CO-CR ³ R ^4- , -CR ¹ R ² -CO-O-CR ³ R ^4- , -NR ¹ -CR ² R ^3- , or- Represents CO-NR ^1- . R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, and constitutes the alicyclic hydrocarbon group-CH. One or more of _2- may be substituted with -O-, -S- or -NH-.
A ¹ and A ² each independently have a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or 5 to 5 carbon atoms which may have a substituent. Represents a divalent alicyclic hydrocarbon group of 8, even if one or more of -CH _2- constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. good.
SP ¹ and SP ² independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -CH _2- represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where Q is a substituent. Represents.
L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar ¹ is an aromatic ring represented by the following formula (Ar- ³ ), at ^{least one} of L1 and L2 and L3 and L4 in the following formula (Ar- ³ ) is polymerizable. Represents a group.
m represents an integer of 0 to 2, and when m is ² , the plurality of E3s may be the same or different, and the plurality of ^A1s may be the same or different. You may.
n represents an integer of 0 to 2, and when n is ² , the plurality of ^E4s may be the same or different, and the plurality of A2s may be the same or different. You may.
Ar ¹ represents any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-7).

Here, in the above equations (Ar-1) to (Ar-7),
* Represents the bonding position with D ¹ or D ² .
Q ¹ represents N or CH.
^Q2 represents -S-, -O-, or -N ⁽ R5)-, and R5 represents a hydrogen atom or an alkyl group having 1 to ⁶ carbon atoms.
Y1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have ^a substituent, or an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent.
Z ¹ , Z ² , Z ³ and Z ⁴ independently have a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. , A monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ or -SR ⁹ , where R ⁶ to R ⁹ are Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.
A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹⁰ )-, -S-, and -CO-, where R ¹⁰ is a hydrogen atom or Represents a substituent.
X represents a group 14-16 non-metal atom to which a hydrogen atom or a substituent may be bonded.
D ³ and D ⁴ are independently single-bonded, -CO-O-, -C (= S) O-, -CR ^{1 R 2-, -CR 1 R 2 - CR 3} R ^4- , -O, respectively. -CR ¹ R ^2- , -CR ¹ R ^2- , -O-CR ³ R ^4- , -CO-O-CR ¹ R ^2- , -O-CO-CR ¹ R ^2- , -CR ¹ R ² -O -CO-CR ³ R ^4- , -CR ¹ R ² -CO-O-CR ³ R ^4- , -NR ¹ -CR ² R ^3- , or -CO-NR ^1- . R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
SP ³ and SP ⁴ independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -CH _2- represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where Q is a substituent. Represents.
L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ and L ² in the above formula (1) represents a polymerizable 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 heterocycle.
Ay has a hydrogen atom, an alkyl group having 1 to 12 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 heterocycle. , Represents an organic group having 2 to 30 carbon atoms.
The aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
^Q3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. The polymerizable liquid crystal composition according to claim 5, wherein Ar ¹ in the formula (1) represents a group represented by the formula (Ar-1) or (Ar-2). The polymerizable liquid crystal composition according to any one of claims 1 to 6, further comprising a polymerization initiator. An optically anisotropic film formed from the polymerizable liquid crystal composition according to any one of claims 1 to 7. The optically anisotropic film according to claim 8, wherein the liquid crystal molecules are fixed in a homogenic orientation. An optical film comprising the optically anisotropic film according to claim 8 or 9. The optical film according to claim 10, further comprising another optically anisotropic film different from the optically anisotropic film. A polarizing plate comprising the optically anisotropic film and a polarizing element according to claim 8 or 9. An image display device comprising the optical film according to claim 10 or 11 or the polarizing plate according to claim 12.

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