JP2021054909A - Liquid crystal composition, optical anisotropic layer, optical film, polarizing plate and image display device - Google Patents

Abstract

To provide a liquid crystal composition from which an optical anisotropic layer excellent in light fastness can be formed, an optical anisotropic layer, an optical film, a polarizing plate and an image display device.SOLUTION: The liquid crystal composition comprises a liquid crystal compound and a non-liquid crystal compound, in which the liquid crystal compound shows a maximum absorption wavelength A in the wavelength range of 250 nm or longer and shorter than 400 nm, the non-liquid crystal compound shows a maximum absorption wavelength B in the wavelength range of 250 nm or longer and shorter than 400 nm, and the maximum absorption wavelength A and the maximum absorption wavelength B satisfy the relation of expression (1) A<B.SELECTED DRAWING: None

Description

The present invention relates to liquid crystal compositions, optically anisotropic layers, optical films, polarizing plates and image display devices.

Optical films such as optical compensation sheets and retardation films are used in various image display devices for eliminating image coloring or expanding the viewing angle.
A stretched birefringent film has been used as the optical film, but in recent years, it has been proposed to use an optical film having an optically anisotropic layer made of a liquid crystal compound instead of the stretched birefringent film.

As such an optically anisotropic layer, for example, Patent Document 1 describes an optically anisotropic layer obtained by curing a composition containing a liquid crystal compound exhibiting an inverse wavelength dispersion ([Claim 1]. ]).

Japanese Unexamined Patent Publication No. 2016-081035

When the present inventors examined the optically anisotropic layer described in Patent Document 1, it was clarified that there is room for improvement in light resistance.

Therefore, an object of the present invention is to provide a liquid crystal composition, an optically anisotropic layer, an optical film, a polarizing plate, and an image display device capable of forming an optically anisotropic layer having excellent light resistance.

As a result of diligent studies to achieve the above problems, the present inventors include a liquid crystal compound and a non-liquid crystal compound having a maximum absorption wavelength in the wavelength range of 250 nm or more and less than 400 nm, and the maximum absorption wavelength of the non-liquid crystal compound is a liquid crystal compound. The present invention has been completed by finding that the light resistance of the formed optically anisotropic layer is improved by using a liquid crystal composition having a wavelength larger than the maximum absorption wavelength of.
That is, it was found that the above-mentioned problems can be achieved by the following configuration.

[1] A liquid crystal composition containing a liquid crystal compound and a non-liquid crystal compound.
The liquid crystal compound has a maximum absorption wavelength A in the wavelength range of 250 nm or more and less than 400 nm.
The non-liquid crystal compound has a maximum absorption wavelength B in the wavelength range of 250 nm or more and less than 400 nm.
A liquid crystal composition in which the maximum absorption wavelength A and the maximum absorption wavelength B satisfy the relationship of the following formula (1).
A <B ... (1)

[2] Both the liquid crystal compound and the non-liquid crystal compound are compounds having any aromatic ring selected from the group consisting of groups represented by the formulas (Ar-1) to (Ar-7) described later. , [1].
[3] The liquid crystal composition according to [2], wherein the liquid crystal compound has an inverse wavelength dispersibility.
[4] The liquid crystal composition according to [2] or [3], wherein the liquid crystal compound is a compound represented by the formula (I) described later.
[5] The liquid crystal composition according to [4], wherein ^{D 1} and D ² in the formula (I) described later represent −CO—O−.
[6] The liquid crystal composition according to any one of [2] to [5], wherein the non-liquid crystal compound is a compound represented by the formula (II) described later.
[7] The liquid crystal composition according to [6], wherein g3 and g4 in the formula (II) described later are 0, and D ¹¹ and D ^{12 are single bonds.}
[8] The liquid crystal composition according to [6] or [7], wherein ^{D 9} and D ¹⁰ in the formula (II) described later represent −O−.
[9] The liquid crystal composition according to any one of [6] to [8], wherein at least one ^{of L 5} and L ^{6 in} the formula (II) described later represents a polymerizable group.
[10] Any aromatic ring selected from the group consisting of groups represented by the formulas (Ar-1) to (Ar-7) described later of the liquid crystal compound, and the above formula (Ar-) of the non-liquid crystal compound. 1) The liquid crystal composition according to any one of [2] to [9], wherein any of the aromatic rings selected from the group consisting of the groups represented by (Ar-7) has the same structure.
[11] The liquid crystal composition according to any one of [1] to [10], wherein the liquid crystal compound exhibits a liquid crystal state in a smectic phase.
[12] The liquid crystal composition according to any one of [1] to [11], wherein the content of the non-liquid crystal compound is 1 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal compound.
[13] The liquid crystal composition according to any one of [1] to [12], wherein the maximum absorption wavelength A and the maximum absorption wavelength B satisfy the relationship of the following formula (2).
0 nm <BA <20 nm ... (2)

[14] An optically anisotropic layer obtained by polymerizing the liquid crystal composition according to any one of [1] to [13].
[15] An optical film having the optically anisotropic layer according to [14].
[16] A polarizing plate having the optical film according to [15] and a polarizer.
[17] An image display device having the optical film according to [15] or the polarizing plate according to [16].

According to the present invention, it is possible to provide a liquid crystal composition, an optically anisotropic layer, an optical film, a polarizing plate, and an image display device capable of forming an optically anisotropic layer having excellent light resistance.

FIG. 1 is a schematic cross-sectional view showing an example of the optical film of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
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, -CO-NR-) described is not particularly limited unless the bonding position is specified, and for example, the formula (for example, described later) will be described later. When D ^{1 in} I) is -CO-NR-, if the ^{position bonded to the G 1} side is * 1 and the position bonded to the Ar ¹ side is * 2, D ¹ is * 1. It may be -CO-NR- * 2 or * 1-NR-CO- * 2.

[Liquid crystal composition]
The liquid crystal composition of the present invention is a liquid crystal composition containing a liquid crystal compound and a non-liquid crystal compound.
Further, in the liquid crystal composition of the present invention, the liquid crystal compound has a maximum absorption wavelength A in the wavelength range of 250 nm or more and less than 400 nm, and the non-liquid crystal compound has a maximum absorption wavelength B in the wavelength range of 250 nm or more and less than 400 nm. , A liquid crystal composition in which the maximum absorption wavelength A and the maximum absorption wavelength B satisfy the relationship of the following formula (1).
A <B ... (1)
When the liquid crystal composition of the present invention contains at least one of a liquid crystal compound and a non-liquid crystal compound, the above ratio is satisfied in relation to at least one set of the liquid crystal compound and the non-liquid crystal compound. Good.

In the present invention, a liquid crystal composition containing a liquid crystal compound and a non-liquid crystal compound having a maximum absorption wavelength in the wavelength range of 250 nm or more and less than 400 nm, and the maximum absorption wavelength B of the non-liquid crystal compound is larger than the maximum absorption wavelength A of the liquid crystal compound. By using the above, the light resistance of the formed optically anisotropic layer becomes good.
This is not clear in detail, but the present inventors speculate as follows.
That is, the non-liquid crystal compound contained in the liquid crystal composition has a maximum absorption wavelength in the same wavelength region as the liquid crystal compound, and has a maximum absorption wavelength B larger than the maximum absorption wavelength A of the liquid crystal compound. It is considered that the absorption of light (particularly, ultraviolet light) into the liquid crystal compound was suppressed as compared with the case where there was no non-liquid crystal compound, and as a result, the light resistance was improved.
Further, the non-liquid crystal compound contained in the liquid crystal composition has a maximum absorption wavelength B larger (on the long wavelength side) than the maximum absorption wavelength A of the liquid crystal compound, that is, it is necessary to excite the non-liquid crystal compound. Energy is lower than the energy required to excite the liquid crystal compound, so that the energy of the light-excited liquid crystal compound can be transferred to the non-liquid crystal compound, and as a result, the light resistance is improved. You might also say that.
Further, when the maximum absorption wavelengths A and B are both less than 400 nm, it is possible to suppress the coloring (particularly yellowing) of the formed optically anisotropic layer.

In the present invention, the maximum absorption wavelength refers to the maximum absorption wavelength in the absorption spectrum measured by the following method.
<Measurement method>
A liquid crystal compound or a non-liquid crystal compound to be measured is dissolved in chloroform to prepare a solution having a concentration of 1% by mass.
Next, the prepared solution is placed in a quartz cell (10 mm long square cell), and the absorbance in the wavelength range of 200 to 800 nm of the solution is measured using an ultraviolet visible infrared spectrophotometer U-3100PC (Shimadzu Seisakusho). ..
Next, the maximum absorption wavelength is obtained in the obtained absorption spectrum.

In the present invention, the maximum absorption wavelength A of the liquid crystal compound and the maximum absorption wavelength B of the non-liquid crystal compound are represented by the following formula (2) for the reason that the light resistance of the formed optically anisotropic layer is improved. It is preferable to satisfy the relationship.
0 nm <BA <20 nm ... (2)

Hereinafter, each component of the liquid crystal composition of the present invention will be described in detail.

[Liquid crystal compound]
The liquid crystal compound contained in the liquid crystal composition of the present invention is not particularly limited as long as it is a compound having a maximum absorption wavelength in the wavelength range of 250 nm or more and less than 400 nm, and in relation to the non-liquid crystal compound described later, the above formula (1) Those satisfying the above relationship can be appropriately selected and used.
Here, the liquid crystal compound means a compound that exhibits a liquid crystal state under a specific temperature condition.

In the present invention, the liquid crystal compound is used for the reason that it is easy to control the wavelength dispersibility of the liquid crystal compound and the compensatory property is easily improved when the optically anisotropic layer formed thereby is used as the optical compensation film. , A compound having any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-7) is preferable.

In the above formulas (Ar-1) to (Ar-7), * represents a bond position, that is, a bond position with a portion other than the aromatic ring contained in the liquid crystal compound.

Further, in the above formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N (R ⁶ )-, and R ⁶ is hydrogen. Represents an atom or an alkyl group having 1 to 6 carbon atoms, Y ¹ is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, and Y 1 may have a substituent and has 3 to 12 carbon atoms. aromatic heterocyclic group, or represents an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent group, -CH 2 constituting the alicyclic hydrocarbon group _- one or more of It may be substituted with —O—, −S− or −NH−.

Here, ^{as the alkyl group having 1 to 6 carbon atoms indicated by R 6} , specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and the like. Examples thereof include a tert-butyl group, an n-pentyl group, and an n-hexyl group.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y ¹ include an aryl group such as a phenyl group, a 2,6-diethylphenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y ¹ include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group and a pyridyl group.
Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms indicated by Y ¹ include a cyclohexylene group, a cyclopentylene group, a norbornene group, and an adamantylene group.

Examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamide group and an alkenyl group. Examples thereof include an alkynyl group, a halogen atom, a cyano group, a nitro group, an alkylthiol group, and an N-alkylcarbamate group, among which an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is used. preferable.
The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n). -Butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, alkyl groups having 1 to 4 carbon atoms are further preferable, and methyl groups or ethyl groups are particularly preferable.
As the alkoxy group, 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 an alkoxy group having 1 carbon number is preferable. Alkoxy groups of ~ 4 are more preferable, and methoxy groups or ethoxy groups are particularly preferable.
Examples of the alkoxycarbonyl group include a group in which an oxycarbonyl group (-O-CO- group) is bonded to the alkyl group exemplified above, and among them, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group or an isopropoxy. A carbonyl group is preferred, and a methoxycarbonyl group is more preferred.
Examples of the alkylcarbonyloxy group include a group in which a carbonyloxy group (-CO-O- group) is bonded to the alkyl group exemplified above, and among them, a methylcarbonyloxy group, an ethylcarbonyloxy group, and an n-propylcarbonyloxy group. A group or an isopropylcarbonyloxy group is preferable, and a methylcarbonyloxy group is more preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom or a chlorine atom is preferable.

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 carbons. A monovalent alicyclic hydrocarbon group having a number of 3 to 20, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent aromatic heterocyclic group having 6 to 20 carbon atoms, a halogen atom, and a cyano group. , Nitro group, -OR ⁷ , -NR ⁸ R ⁹ , -SR ¹⁰ , -COOR ¹¹ , or -COR ¹² , where R ^{7 to} R ¹² are independently hydrogen atoms or 1 to 6 carbon atoms. Representing an alkyl group, Z ¹ and Z ² may be bonded to each other to form an aromatic ring.

Here, 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. , Ethyl group, isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, ethyl group, A tert-butyl group is particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and an ethylcyclohexyl. Monocyclic saturated hydrocarbon groups such as groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as diene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, Tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and have 6 to 12 carbon atoms. Aryl groups (particularly phenyl groups) are preferred.
Specific examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group. Can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, ^{examples of the alkyl group having 1 to 6 carbon atoms represented by R 7 to} R ¹⁰ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl. Examples include groups, tert-butyl groups, n-pentyl groups, n-hexyl groups and the like.

Further, Z ¹ and Z ² may be bonded to each other to form an aromatic ring as described above. For example, Z ¹ and Z ^{2 in} the above formula (Ar-1) may be bonded to each other to form an aromatic ring. Examples of the structure when formed include a group represented by the following formula (Ar-1a). In the following formulas (Ar-1a), * represents a binding ^position, Q 1, ^{Q 2} and ^{Y 1} include the same ones as described in the above formula (Ar-1).

Further, in the above formula (Ar-2) and ^{(Ar-3), A} 3 and ^{A 4} are each ^{independently, -O -, - N (R} 13) -, - S-, and from -CO- Represents a group selected from the group, where R ¹³ represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ^{13 include the same substituents that Y 1} in the above formula (Ar-1) may have.

Further, in the above formula (Ar-2), X represents a non-metal atom of Groups 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Examples of the non-metal atoms of Groups 14 to 16 indicated by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Specific examples of the substituent include a carbon atom having a substituent. 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 and the like can be mentioned. Be done.

Further, in the above formula (Ar-3), D ⁷ and D ⁸ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR ^{1 respectively. R 2 -, - CR 3 =} CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ are each independently a hydrogen atom, It represents a fluorine atom or an alkyl group having 1 to 12 carbon atoms.

Here ^{, examples of the divalent linking group shown in one aspect of D 7} and D ⁸ include -CO-, -O-, -CO-O-, -C (= S) O-, and -CR ¹ R. ^{2 -, - CR 1 R 2} -CR 1 R 2 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 1 R 2 -, - CO-O-CR 1 R 2 -, - O-CO-CR ¹ R ^2- , -CR ¹ R ^2- O-CO-CR ¹ R ^2- , -CR ¹ R ^2- CO-O-CR ¹ R ^2- , -NR ^{5 -CR 1} R ² -, -CO-NR ^5- , and the like can be mentioned. R ¹ , R ² and R ⁵ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms.
Of these, any of -CO-, -O-, and -CO-O- is preferable.

Further, in the above formula (Ar-3), SP ³ and SP ⁴ are independently single-bonded, linear or branched alkylene groups having 1 to 12 carbon atoms, or directly having 1 to 12 carbon atoms. _{Divalent in which one or more of -CH 2-} constituting the chain or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents the linking group of, and Q represents the substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Here ^{, examples of the linear or branched alkylene group having 1 to 12 carbon atoms shown in one aspect of SP 3} and SP ⁴ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. , Methylhexylene group, heptylene group and the like are preferable. As described above, SP ¹ and SP ² _{have one or more of -CH 2-} constituting a linear or branched alkylene group having 1 to 12 carbon atoms of -O-, -S-, and -NH. It may be a divalent linking group substituted with −, −N (Q) − or −CO−, and the substituent represented by Q is Y ^{1 in the above formula (Ar-1).} Examples include those similar to the substituents that may have.

Further, in the above formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group.
Examples of the monovalent organic group represented by L ³ and L ⁴ include an alkyl group, an aryl group, and a heteroaryl group. The alkyl group may be linear, branched or cyclic, but linear is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but monocyclic is preferable. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms. Further, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Further, the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or have a substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.

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 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, Q ³ represents a hydrogen atom or may have a substituent alkyl group having 1 to 6 carbon atoms.
Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of International Publication No. 2014/010325.
The alkyl group having 1 to 20 carbon atoms represented by ^{Q 3,} specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert -Butyl group, n-pentyl group, n-hexyl group and the like can be mentioned, and examples of the substituent include those similar to the substituent that ^{Y 1 in the above formula (Ar-1) may have.} Can be mentioned.

In the present invention, the liquid crystal compound is preferably a liquid crystal compound having an inverse wavelength dispersibility for the reason that the optical compensability is improved.
Here, the term "liquid crystal compound having inverse wavelength dispersibility" as used herein refers to the in-plane retardation (Re) value or thickness of a retardation film produced using the same at a specific wavelength (visible light range). When the retardation (Rth) value in the direction is measured, the Re value or the Rth value becomes equal or higher as the measurement wavelength becomes larger.

Further, in the present invention, the liquid crystal compound is preferably a compound represented by the following formula (I) for the reason that the optical compensatory property is further improved. In the following formula (I), Ar represents any aromatic ring selected from the group consisting of the groups represented by the above-mentioned formulas (Ar-1) to (Ar-7). However, when q1 in the following formula (I) is 2, the plurality of Ars may be the same or different.
^{L 1 -SP 1 -D 5 - (} A 1) a1 -D 3 - (G 1) g1 -D 1 - ^{[Ar-D 2] _{q1 - (G 2) g2 -D}} 4 - (A 2) a2 - D ^6- SP ^2- L ² ... (I)

In the above formula (I), a1, a2, g1 and g2 independently represent 0 or 1, respectively. However, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.
Further, in the above formula (I), q1 represents 1 or 2.
Further, in the above formula (I), D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are independently single-bonded or -CO-, -O-, -S-,-, respectively. ^{C (= S) -, -} CR 1 R 2 -, - CR 3 = CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. However, when q1 is 2, a plurality of D ² may each be the same or different.
Further, in the above formula (I), G ¹ and G ² each independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent or a carbon which may have a substituent. Represents a divalent alicyclic hydrocarbon group of number 5 to 20, _{and one or more of -CH 2-} constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. You may.
Further, in the above formula (I), A ¹ and A ² independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a carbon which may have a substituent. Represents a divalent alicyclic hydrocarbon group of number 5 to 20, _{and one or more of -CH 2-} constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. You may.
Further, in the above formula (I), 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 (I), 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, Ar is, if an aromatic ring represented by the above formula (Ar-3), at least one of ^{L 3} and ^{L 4} in ^{L 1} and ^{L 2} as well as the above-mentioned formula (Ar-3) Polymerization Represents a sex group.

In the above formula (I), a1, a2, g1 and g2 are preferably 1 for the reason that the liquid crystal composition of the present invention tends to show the liquid crystal state of the smectic phase.

In the above formula (I), q1 is preferably 1.

In the above formula (I), ^{as the divalent linking group represented by one aspect of D 1} , D ² , D ³ , D ⁴ , D ⁵ and D ^{6 , D 7} and D in the above formula (Ar-3) are used. ^The same as those described in No. 8 can be mentioned.
Of these, any of -CO-, -O-, and -CO-O- is preferable, and in particular, D ¹ and D ² are more preferably -CO-O-.

In the above formula (I) ^{, examples of the aromatic ring having 6 to 20 carbon atoms represented by one aspect of G 1} and G ² include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring. Aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring; among them, a benzene ring (for example, a 1,4-phenyl group) is preferable.

In the above formula (I), the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of ^{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. ..

^{In the present invention, G 1} and G ² in the above formula (I) are preferably cycloalkane rings.
Specific examples of the cycloalkane ring include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclododecane ring.
Of these, a cyclohexane ring is preferred, a 1,4-cyclohexylene group is more preferred, and a trans-1,4-cyclohexylene group is even more preferred.

Further, in the above formula (I), G ¹ and G ² may be represented by an aromatic ring having 6 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms as a substituent. Is the same as the substituent that ^{Y 1} in the above formula (Ar-1) may have.

In the above formula (I), the aromatic rings having 6 to 20 or more carbon atoms represented by one aspect of ^{A 1} and A ² are the same as those described in ^{G 1} and G ^{2 in the above formula (I).} Can be mentioned.
Further, in the above formula (I), as the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of ^{A 1} and A ^{2 , in G 1} and G ² in the above formula (I). Examples are similar to those described.
Regarding A ¹ and A ² , the substituent which the aromatic ring having 6 to 20 carbon atoms or the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms may have is the above-mentioned formula (Ar-). Examples thereof include the same substituents that ^{Y 1 in} 1) may have.

In the above formula (I), the linear or branched alkylene group having 1 to 12 carbon atoms represented by one aspect of ^{SP 1} and SP ^{2 is described in SP 3} and SP ⁴ in the above formula (Ar-3). Examples are similar to those described.

^{Examples of the monovalent organic group represented by L 1} and L ² in the above formula (I) include those similar to those described in ^{L 3} and L ⁴ in the above formula (Ar-3).

In the above formula (I), the ^{polymerizable group represented by at least one of L 1} and L ² is not particularly limited, but a radical-polymerizable or cationically polymerizable polymerizable group is preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and preferred examples thereof include an acryloyloxy group and a methacryloyloxy group. In this case, it is known that the acryloyloxy group is generally faster in terms of polymerization rate, and the acryloyloxy group is preferable from the viewpoint of improving productivity, but the methacryloyloxy 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 polymerizable groups represented by any of the following formulas (P-1) to (P-20).

In the above formula (I), for the reason that the durability is good, ^{it is preferable that both L 1} and L ² in the above formula (I) are polymerizable groups, and are acryloyloxy group or methacryloyloxy group. Is more preferable.

Examples of the compound represented by the above formula (I) include compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, those described in paragraph numbers [0067] to [0073]. Compounds), compounds represented by the general formula (II) described in JP-A-2016-053709 (particularly, compounds described in paragraph numbers [0036] to [0043]), and JP-A-2016-081035. Among the compounds represented by the general formula (1) described (particularly, the compounds described in paragraphs [0043] to [0055]) and the like, those showing the liquid crystal state of the smectic phase can be mentioned.

Further, as the compound represented by the above formula (I), a compound having a structure in which Ar in the above formula (I) is represented by the following formulas Ar-1 to Ar-22 is preferably mentioned, and specifically. Examples of K (side chain structure) in the following formulas Ar-1 to Ar-22 include compounds having the side chain structures shown in Tables 1 to 3 below.
In Tables 1 to 3 below, "*" shown in the side chain structure of K represents the bonding position with the aromatic ring.
Further, in the side chain structures represented by 2-2 in Table 2 below and 3-2 in Table 3 below, the groups adjacent to the acryloyloxy group and the methacryloyl group are propylene groups (methyl groups are ethylene groups, respectively). It represents a substituted group) and represents a mixture of positional isomers with different methyl group positions.

In the present invention, the compound represented by the above formula (I) is preferably a compound showing a liquid crystal state of the smectic phase for the reason that the contrast of the produced image display device is good.

[Non-liquid crystal compound]
The non-liquid crystal compound contained in the liquid crystal composition of the present invention is not particularly limited as long as it is a compound having a maximum absorption wavelength in the wavelength range of 250 nm or more and less than 400 nm, and in relation to the above-mentioned liquid crystal compound, the above formula (1) Those satisfying the above relationship can be appropriately selected and used.
Here, the non-liquid crystal compound means a compound that does not have a liquid crystal state even when the temperature changes.

In the present invention, the non-liquid crystal compound has a structure similar to that of the liquid crystal compound, so that the compatibility with the above-mentioned liquid crystal compound is improved. It is preferable that the compound has any aromatic ring selected from the group consisting of the groups represented by the above formulas (Ar-1) to (Ar-7).

In the present invention, the non-liquid crystal compound is preferably a compound represented by the following formula (II) for the reason that the compatibility with the liquid crystal compound described above becomes better.
^{L 5 -SP 5 -D 11 - (} G 3) g3 -D 9 - ^{[Ar-D 10] _{q2 - (G 4) g4 -D}} 12 -SP 6 -L 6 ··· (II)

In the above formula (II), g3 and g4 independently represent 0 or 1, respectively.
Further, in the above formula (II), q2 represents 1 or 2.
Further, in the above formula (II), D ⁹ , D ¹⁰ , D ¹¹ and D ¹² are independently single-bonded or −CO−, −O−, −S−, −C (= S) −. ^{, -CR 1 R 2 -, -} CR 3 = CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ are each independently , Hydrogen atom, fluorine atom, or alkyl group having 1 to 12 carbon atoms. However, when q2 is 2, the plurality of D ^10s may be the same or different.
Further, in the above formula (II), G ³ and G ⁴ each independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent or a carbon which may have a substituent. Represents a divalent alicyclic hydrocarbon group of number 5 to 20, _{and one or more of -CH 2-} constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. You may.
Further, in the above formula (II), SP ⁵ and SP ⁶ 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 (II), L ⁵ and L ⁶ each independently represent a monovalent organic group.
Further, in the above formula (II), Ar represents any aromatic ring selected from the group consisting of the groups represented by the above formulas (Ar-1) to (Ar-7). However, when q2 is 2, the plurality of Ars may be the same or different.

In the present invention, g3 and g4 in the above formula (II) are 0, and D ¹¹ and D ¹² are single bonds for the reason that the optical anisotropic layer to be formed has better light resistance. Is preferable. That is, the non-liquid crystal compound is preferably a compound represented by the following formula (IIa).
L ⁵ -SP ⁵ -D ⁹ - ^{[Ar-D 10] _{q2 -SP 6 -L 6 ··· (IIa}} )

In the above formula (II), q2 is preferably 1.

In the above formula (II), the ^{divalent linking groups represented by one aspect of D 9} , D ¹⁰ , D ¹¹ and D ¹² are those described in ^{D 7} and D ⁸ in the above formula (Ar-3). The same can be mentioned.

In the present invention, it is preferable that D ⁹ and D ¹⁰ are each independently a divalent linking group consisting of -CO-, -O-, -S-, or a combination of two or more thereof. It is more preferably one of -CO-, -O-, and -CO-O-, because the optically anisotropic layer to be formed has better light resistance and wet heat durability. It is more preferably −O−.

In the above formula (II), the ^{G 3,} and ^{G 4,} include the same as those described in ^{G 1} and ^{G 2} in the above formula (I).

In the above formula (II), as the linear or branched alkylene group having 1 to 12 carbon atoms shown in one aspect of ^{SP 5} and SP ^{6 , SP 3} and SP ^{4 in the above formula (Ar-3) are used.} The same as those described in the above can be mentioned.

^{In the present invention, SP 5} and SP ⁶ are linear or branched alkylene groups having 1 to 12 carbon atoms or 1 to 12 carbon atoms for the reason that the compatibility with the liquid crystal compound described above is good. _{It is preferable that one or more of −CH 2−} constituting the linear or branched alkylene group of the above is a divalent linking group substituted with −O−.

^{Examples of the monovalent organic group represented by L 5} and L ⁶ in the above formula (II) include those similar to those described in ^{L 3} and L ⁴ in the above formula (Ar-3).

^{In the present invention, at least one of L 5} and L ^{6 in} the above formula (II) preferably represents a polymerizable group because the optically anisotropic layer to be formed has better light resistance. It is more preferable that the optics represent a polymerizable group.
Here, examples of the polymerizable group include those similar to those exemplified as the polymerizable group represented by at least one ^{of L 1} and L ^{2 in} the above formula (I), and among them, the above formula (P-). The polymerizable group represented by any one of 1) to (P-20) is preferably mentioned.

As the compound represented by the above formula (II), a compound having a structure in which Ar in the above formula (II) is represented by the following formulas Ar-1 to Ar-22 is preferably mentioned. Examples of K (side chain structure) in the following formulas Ar-1 to Ar-22 include compounds having a side chain structure represented by the following K-1 to K-58.
The "*" shown in the side chain structure represented by K-1 to K-58 below represents the bonding position with the aromatic ring. Further, in the side chain structure represented by the following K-3, K-4, K-31, K-32, K-53 and K-54, the group adjacent to the acryloyloxy group and the methacryloyl group is a propylene group, respectively. Represents (a group in which a methyl group is replaced with an ethylene group), and represents a mixture of positional isomers having different positions of the methyl group.

In the present invention, the content of the non-liquid crystal compound is determined by the liquid crystal compound because the planar shape of the formed optically anisotropic layer becomes good and the contrast of the image display device having the optically anisotropic layer becomes better. It is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass.

In the present invention, it is represented by the above formulas (Ar-1) to (Ar-7) contained in the above-mentioned liquid crystal compound for the reason that the contrast of the image display device having the formed optically anisotropic layer becomes better. It is preferable that any aromatic ring (hereinafter, also abbreviated as “Ar core”) selected from the group consisting of groups and the Ar core contained in the above-mentioned non-liquid crystal compound have the same structure.
When the liquid crystal composition of the present invention contains at least one of a liquid crystal compound and a non-liquid crystal compound, it has an Ar core having the same structure due to the relationship between at least one set of the liquid crystal compound and the non-liquid crystal compound. You just have to do it.

[Polyfunctional liquid crystal compound]
The liquid crystal composition of the present invention contains a polyfunctional liquid crystal compound having three or more polymerizable groups in addition to the above-mentioned liquid crystal compound for the reason that the surface shape of the optically anisotropic layer to be formed is good. Is preferable.

Here, examples of the polymerizable group contained in the polyfunctional liquid crystal compound include those similar to the radically polymerizable or cationically polymerizable polymerizable group described in the above-mentioned liquid crystal compound, and among them, the above-mentioned formula (P-1). A polymerizable group represented by any of (P-20) is preferable.

Examples of the polyfunctional liquid crystal compound include compounds represented by the formula (M3) described in paragraph [0033] of JP-A-2014-0770668, and more specifically, [0053] to [0053] to JP-A-2014. Specific examples described in paragraph [0055] can be mentioned.
Further, as another example of the above-mentioned polyfunctional liquid crystal compound, among the compounds described in paragraphs [0027] to [0033] of JP-A-2016-053149, compounds 8, 29, 59 to 61, 64, 65 And 69.

In the present invention, when the polyfunctional liquid crystal compound is contained, the content of the polyfunctional liquid crystal compound is preferably 1 to 100 parts by mass and 5 to 50 parts by mass with respect to 100 parts by mass of the liquid crystal compound. Is more preferable.

[Polymerization initiator]
The 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. No. 2,376,661 and US Pat. No. 2,376,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrances. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents). 3549367 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 421,970), acylphosphine. Examples thereof include oxide compounds (described in 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.
Further, in the present invention, the polymerization initiator is preferably an oxime type polymerization initiator, and specific examples thereof are described in paragraphs [0049] to [0052] of International Publication No. 2017/170443. Agents are mentioned.

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

[Leveling agent]
The liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the optically anisotropic layer to be formed smooth and facilitating orientation control.
Such a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because it has a high leveling effect on the amount of addition, and a fluorine-based leveling agent from the viewpoint of less likely to cause crying (bloom, bleed). Is more preferable.
Specific examples of the leveling agent include the compounds described in paragraphs [0079] to [0102] of JP-A-2007-069471, and the general formulas described in JP-A-2013-047204. The compound represented by I) (particularly the compound described in paragraphs [0020] to [0032]) and the compound represented by the general formula (I) described in JP2012-211306 (particularly [0022]). -The compound described in paragraph [0029], the liquid crystal orientation promoter represented by the general formula (I) described in JP-A-2002-129162 (particularly [0076] to [0078] and [0082]- Compounds described in paragraph [0084], compounds represented by general formulas (I), (II) and (III) described in JP-A-2005-09248 (particularly paragraphs [0092] to [0996]). The compounds described in (1) and the like. In addition, it may also have a function as an orientation control agent described later.

[Orientation control agent]
The liquid crystal composition of the present invention may contain an orientation control agent, if necessary.
The orientation control agent can form various orientation states such as homeotropic orientation (vertical orientation), tilt orientation, hybrid orientation, and cholesteric orientation in addition to homogenius orientation, and can make a specific orientation state more uniform and more uniform. It can be realized by precise control.

As the orientation control agent that promotes homogenous orientation, for example, a low-molecular-weight orientation control agent or a high-molecular-weight orientation control agent can be used.
Examples of the low-molecular-weight orientation control agent include paragraphs [0009] to [0083] of JP-A-2002-20363, paragraphs [0111] to [0120] of JP-A-2006-106662, and JP-A-2012. The description in paragraphs [0021] to [0029] of JP-A-21306 can be taken into consideration, and this content is incorporated in the present specification.
Further, as the polymer orientation control agent, for example, paragraphs [0021] to [0057] of JP-A-2004-198511 and paragraphs [0121] to [0167] of JP-A-2006-106662 are referred to. And this content is incorporated herein by reference.

Examples of the orientation control agent for forming or promoting homeotropic orientation include boronic acid compounds and onium salt compounds. Specifically, paragraphs [0023] to [0032] of JP-A-2008-225281. , Paragraphs [0052] to [0058] of JP2012-208397A, paragraphs [0024] to [0055] of JP2008-026730, and [0043] to [0055] of JP2016-193869. The compounds described in paragraphs and the like can be taken into account, the contents of which are incorporated herein by reference.

On the other hand, the cholesteric orientation can be realized by adding a chiral agent to the liquid crystal composition of the present invention, and the turning direction of the cholesteric orientation can be controlled by the direction of the chiral property.
The pitch of the cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.

When the orientation control agent is contained, the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content mass in the composition. When the content is in this range, a uniform and highly transparent cured product can be obtained without precipitation, phase separation, orientation defects, etc., while achieving the desired orientation state.

[Other ingredients]
The liquid crystal composition of the present invention may contain components other than those described above, and examples thereof include surfactants, tilt angle control agents, orientation aids, plasticizers, and cross-linking agents.

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

The optically anisotropic layer of the present invention is preferably an optically anisotropic layer satisfying the following formula (III) or the following formula (IV).
0.50 <Re (450) / Re (550) <1.00 ... (III)
0.50 <Rth (450) / Rth (550) <1.00 ... (IV)
Here, in the above formula (III), Re (450) represents the in-plane lettering of the optically anisotropic layer at a wavelength of 450 nm, and Re (550) represents the in-plane letter of the optically anisotropic layer at a wavelength of 550 nm. Represents the optics. Further, in the above formula (IV), Rth (450) represents the retardation of the optically anisotropic layer in the thickness direction at a wavelength of 450 nm, and Rth (550) represents the retardation of the optically anisotropic layer in the thickness direction 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.
The values of in-plane retardation and retardation in the thickness direction refer to values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Optoscience).
Specifically, by inputting the average refractive index ((Nx + Ny + Nz) / 3) and the film thickness (d (μm)) in AxoScan OPMF-1.
Slow 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).

Further, such an optically anisotropic layer is preferably a positive A plate or a positive C plate, and more preferably a positive C plate.

Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
The refractive index in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized) is nx, the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny, and the refraction in the thickness direction. When the rate is nz, the positive A plate satisfies the relation of the formula (A1), and the positive C plate satisfies the relation of the formula (C1). The positive A plate shows a positive value for Rth, and the positive C plate shows a negative value for Rth.
Equation (A1) nx> ny≈nz
Equation (C1) nz> nx≈ny
The above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same.
“Substantially the same” means that, for example, in the positive A plate, (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". Further, in the positive C plate, for example, when (nx−ny) × d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, it is also included in “nx≈ny”.

When the optically anisotropic layer is a positive A plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, and 130 to 150 nm from the viewpoint of functioning as a λ / 4 plate. It is more preferably 130 to 140 nm, and particularly preferably 130 to 140 nm.
Here, the "λ / 4 plate" is a plate having a λ / 4 function, and specifically, a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light). It is a plate having.

[Optical film]
The optical film of the present invention is an optical film having the optically anisotropic layer of the present invention.
FIG. 1 is a schematic cross-sectional view showing an example of the optical film of the present invention.
Note that FIG. 1 is a schematic view, and the thickness relationship and positional relationship of each layer do not always match the actual ones, and the support and the alignment film shown in FIG. 1 are all arbitrary constituent members.
The optical film 10 shown in FIG. 1 has a support 16, an alignment film 14, and an optically anisotropic layer 12 as a cured product in this order.
Further, the optically anisotropic layer 12 may be a laminate of two or more different optically anisotropic layers. For example, when the polarizing plate of the present invention described later is used as a circular polarizing plate, or when the optical film of the present invention is used as an optical compensation film for an IPS type or FFS type liquid crystal display device, a positive A plate and a positive C are used. It is preferably a laminate of plates.
Further, the optically anisotropic layer may be peeled off from the support and the optically anisotropic layer alone may be used as an optical film.
Hereinafter, various members used in the optical film of the present invention will be described in detail.

[Optically anisotropic layer]
The optically anisotropic layer of the optical film of the present invention is the above-mentioned optically anisotropic layer of the present invention.
In the optical film of the present invention, the thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

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

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

In the present invention, the thickness of the support is not particularly limited, but is preferably 5 to 60 μm, more preferably 5 to 40 μm.

[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 layer. The support described above may also serve as an alignment film.

The alignment film generally contains 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, or a derivative thereof. Particularly modified or unmodified polyvinyl alcohol is preferable.
Regarding the alignment film that can be used in the present invention, for example, the alignment film described in International Publication No. 01/88574, p. 43, p. 24 to p. 49, p. 8; ], And the like; a liquid crystal alignment film formed by the liquid crystal alignment agent described in Japanese Patent Application Laid-Open No. 2012-155308; and the like.

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

Further, in the present invention, the thickness of the alignment film is not particularly limited, but from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic layer 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.

[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 rays).
The ultraviolet absorber may be contained in the optically anisotropic layer of the present invention, or may be contained in a member other than the optically anisotropic layer constituting the optical film of the present invention. As the member other than the optically anisotropic layer, for example, a support is preferably mentioned.
As the ultraviolet absorber, any conventionally known one capable of exhibiting ultraviolet absorption can be used. Among such ultraviolet absorbers, a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber may be used from the viewpoint of obtaining the ultraviolet absorbing ability (ultraviolet blocking ability) used in an image display device because of its high ultraviolet absorbing ability. preferable.
Further, in order to widen the absorption range of ultraviolet rays, two or more kinds of ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.
Specific examples of the ultraviolet absorber include the compounds described in paragraphs [0258] to [0259] of JP2012-18395, paragraphs [0055] to [0105] of JP2007-72163. Examples thereof include the compounds described in.
Further, as commercially available products, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 (all manufactured by BASF) and the like can be used.

[Polarizer]
The polarizing plate of the present invention has the above-mentioned optical film of the present invention and a polarizer.
Further, the polarizing plate of the present invention can be used as a circular polarizing plate when the optically anisotropic layer of the present invention described above is a λ / 4 plate (positive A plate).
When the polarizing plate of the present invention is used as a circular polarizing plate, the optically anisotropic layer of the present invention described above is a λ / 4 plate (positive A plate), and the slow axis of the λ / 4 plate and the polarizer described later are used. The angle formed by the absorption shaft is preferably 30 to 60 °, more preferably 40 to 50 °, further preferably 42 to 48 °, and particularly preferably 45 °.
Further, the polarizing plate of the present invention can also be used as an optical compensation film for an IPS type or FFS type liquid crystal display device.
When the polarizing plate of the present invention is used as an optical compensation film for an IPS type or FFS type liquid crystal display device, the above-mentioned optically anisotropic layer of the present invention is used at least one of a laminate of a positive A plate and a positive C plate. It is preferable that the angle formed by the slow axis of the positive A plate layer and the absorption axis of the polarizer described later is orthogonal or parallel, and specifically, the slow axis of the positive A plate layer and the slow axis of the positive A plate layer. It is more preferable that the angle formed by the polarizing element described later with the absorption axis is 0 to 5 ° or 85 to 95 °.
Here, the "slow phase axis" of the λ / 4 plate or the positive A plate layer means the direction in which the refractive index is maximized in the plane of the λ / 4 plate or the positive A plate layer, and the "absorption axis" of the polarizer. "" Means the direction of the highest absorbance.

[Polarizer]
The polarizer of the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorption type polarizers and reflection type polarizers can be used. ..
As the absorption type polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a polyene-based polarizer, and the like are used. Iodine-based polarized light and dye-based polarized light include coated and stretched polarized light, and both can be applied. However, 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 polarizer by stretching and dyeing a laminated film having a polyvinyl alcohol layer formed on a substrate, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 46910205, and Japanese Patent No. Japanese Patent No. 4751481 and Japanese Patent No. 4751486 can be mentioned, and known techniques relating to these polarizers can also be preferably used.
As the reflective polarizer, a polarizer in which thin films having different birefringences are laminated, a wire grid type polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined, and the like are used.
Of these, in terms of adhesion more excellent, polyvinyl alcohol-based resin (polymer containing as a repeating unit -CH ₂ -CHOH-, in particular, polyvinyl alcohol and ethylene - at least selected from the group consisting of vinyl alcohol copolymer It is preferable that the polymer contains one).

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 3 μm to 30 μm, and even more preferably 3 μm to 10 μm.

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

[Adhesive layer]
In the polarizing plate of the present invention, an adhesive layer may be arranged between the optically anisotropic layer in the optical film of the present invention and the polarizer.
As the adhesive layer used for laminating the cured product and the polarizer, a curable adhesive composition that is cured by irradiation with active energy rays or heating is preferable.
Examples of the curable adhesive composition include a curable adhesive composition containing a cationically polymerizable compound and a curable adhesive composition containing a radically polymerizable compound.
The thickness of the adhesive layer is preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm, and even more preferably 0.05 to 5 μm. When the thickness of the adhesive layer is within this range, floating or peeling does not occur between the laminated protective layer or the optically anisotropic layer and the polarizer, and a practically acceptable adhesive force can be obtained.

[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 a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, an FFS (Fringe-Field-Switching) mode, or a TN (Twisted) mode. Nematic) is preferable, but the present invention 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 in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. 2-). In addition to (described in Japanese Patent Application Laid-Open No. 176625), (2) a liquid crystal cell (SID97, Digital of technique. Papers (Proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for expanding the viewing angle). ), (3) Liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied. (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98) are included. Further, it may be any of PVA (Patternized Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment). Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819.
In the liquid crystal cell in the IPS mode, the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane by applying an electric field parallel to the substrate surface. In the IPS mode, the display is black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other. Methods for reducing leakage light 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]
Examples of the organic EL display device which is an example of the image display device of the present invention include, from the visual side, a λ / 4 plate (positive A plate) composed of a polarizer, an optically anisotropic layer of the present invention, and an organic EL. A mode in which the display panel and the display panel are provided in this order is preferably mentioned.
Further, the organic EL display panel is a display panel configured by using an organic EL element having an organic light emitting layer (organic electroluminescence layer) sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

The present invention will be described in more detail below based on examples. The materials, amounts used, 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 examples shown below.

[Example 1]
[Preparation of protective film 1]
<Preparation of core layer cellulose acylate dope 1>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a core layer cellulose acylate dope 1.
――――――――――――――――――――――――――――――――
Core layer Cellulose acylate dope 1
――――――――――――――――――――――――――――――――
・ 100 parts by mass of cellulose acetate with an acetyl substitution degree of 2.88 ・ 10 parts by mass of ester oligomer (compound 1-1 below) ・ Durability improver (compound 1-2 below) 4 parts by mass ・ Ultraviolet absorber (compound 1-below) 3) 3 parts by mass, methylene chloride (first solvent) 438 parts by mass, methanol (second solvent) 65 parts by mass ―――――――――――――――――――――――― ――――――――

Compound 1-1

Compound 1-2

Compound 1-3

<Preparation of outer layer cellulose acylate dope 1>
To 90 parts by mass of the core layer cellulose acylate dope 1, 10 parts by mass of the following matting agent dispersion 1 was added to prepare an outer layer cellulose acylate dope 1.
――――――――――――――――――――――――――――――――
Matte solution ――――――――――――――――――――――――――――――――
-Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass-Methylene chloride (first solvent) 76 parts by mass-Methanol (second solvent) 11 parts by mass-Core layer cellulose acylate dope 11 1 part by mass ――――――――――――――――――――――――――――――――

<Preparation of protective film 1>
Three layers of the core layer cellulose acylate dope 1 and the outer layer cellulose acylate dope 1 on both sides thereof were simultaneously cast on a drum at 20 ° C. from the casting port. With the solvent content of the film on the drum being approximately 20% by mass, the film was peeled off from the drum, and both ends of the obtained film in the width direction were fixed with tenter clips, and the residual solvent in the film was 3 to 15% by mass. In the% state, the film was stretched 1.2 times in the transverse direction and dried. Then, the obtained film was conveyed between the rolls of the heat treatment apparatus to prepare a cellulose acylate film 1 having a thickness of 25 μm, which was used as a protective film 1.

[Preparation of protective film 1 with hard coat layer]
As a coating liquid for forming the hard coat layer, the curable composition for hard coat (hard coat 1) shown in Table 4 below was prepared.

In Table 4 above, the structure of UV initiator 1 is shown below.

The curable composition 1 for hard coating is applied onto the surface of the protective film 1 prepared above, then dried at 100 ° C. for 60 seconds, and UV is 1.5 kW under the condition of nitrogen 0.1% or less. , 300 mJ was irradiated and cured to prepare a protective film 1 with a hard coat layer having a hard coat layer having a film thickness of 5 μm. The film thickness of the hard coat layer was adjusted by using a slot die and adjusting the coating amount by the die coating method.

[Preparation of Polarizing Plate 1 with Single-sided Protective Film]
(1) Saponification of film The prepared protective film 1 with a hard coat layer was immersed in a 4.5 mol / L sodium hydroxide aqueous solution (saponification solution) whose temperature was adjusted to 37 ° C. for 1 minute, and then the film was washed with water. Then, it was immersed in a 0.05 mol / L aqueous sulfuric acid solution for 30 seconds, and then further passed through a water washing bath. Then, the obtained film was drained three times with an air knife, and after the water was dropped, the film was allowed to stay in a drying zone at 70 ° C. for 15 seconds to be dried to prepare a protective film 1 with a saponified hard coat layer. did.
(2) Preparation of Polarizer According to an example of JP-A-2016-148724, a polarizer having a film thickness of 15 μm was prepared by giving a peripheral speed difference between two pairs of nip rolls and stretching in the longitudinal direction. The polarizer produced in this way was designated as the polarizer 1.
(3) Laminating The polarizing element 1 thus obtained and the saponified protective film 1 with a hard coat layer were used as an adhesive using a 3% aqueous solution of PVA (manufactured by Kuraray Co., Ltd., PVA-117H) as an adhesive. A polarizing plate 1 with a single-sided protective film (hereinafter, also simply referred to as “polarizing plate 1”) was produced by laminating them in a roll-to-roll manner so that the polarization axis and the longitudinal direction of the film were orthogonal to each other. At this time, the protective film was bonded so that the cellulose acylate film side was on the polarizer side.

[Preparation of polarizing plate 2 with single-sided protective film]
In the production of the polarizing plate 1, the polarizing plate 2 with a single-sided protective film (hereinafter, also simply referred to as “polarizing plate 2”) was produced in the same manner except that the hard coat layer was not provided on the surface of the protective film 1. In the following examples and comparative examples, unless otherwise specified, each liquid crystal display device was manufactured by using the polarizing plate 1 on the visual recognition side and the polarizing plate 2 on the backlight side.

[Preparation of protective film 2]
<Preparation of core layer cellulose acylate dope 2>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a core layer cellulose acylate dope 2.
――――――――――――――――――――――――――――――――
Core layer Cellulose acylate dope 2
――――――――――――――――――――――――――――――――
・ 100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.88 ・ 12 parts by mass of the following polyester ・ 4 parts by mass of the durability improver (the compound 1-2) ・ Methylene chloride (first solvent) 430 parts by mass ・ Methanol (No. 1) 2 Solvent) 64 parts by mass ――――――――――――――――――――――――――――――――

Polyester (number average molecular weight 800)

<Preparation of outer layer cellulose acylate dope 2>
The following matting solution was added to 90 parts by mass of the core layer cellulose acylate dope 2 by 10 parts by mass to prepare an outer layer cellulose acylate dope 2.
――――――――――――――――――――――――――――――――
Matte solution ――――――――――――――――――――――――――――――――
-Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass-Methylene chloride (first solvent) 76 parts by mass-Methanol (second solvent) 11 parts by mass-Core layer cellulose acylate dope 1 part by mass ――――――――――――――――――――――――――――――――

<Preparation of protective film 2>
After filtering the core layer cellulose acylate dope 2 and the outer layer cellulose acylate dope 2 with a filter paper having an average pore diameter of 34 μm and a sintered metal filter having an average pore diameter of 10 μm, the core layer cellulose acylate dope 2 and outer layer cellulose on both sides thereof are filtered. Three layers of acylate dope 2 were simultaneously cast on a drum at 20 ° C. from the casting port (band casting machine).
Next, with the solvent content of the film on the drum being approximately 20% by mass, the film was peeled off from the drum, both ends in the width direction of the film were fixed with tenter clips, and the film was stretched laterally at a stretching ratio of 1.1 times. It was dry while doing.
Then, the obtained film was further dried by transporting it between the rolls of the heat treatment apparatus to prepare a cellulose acylate film 2 having a film thickness of 40 μm, which was used as a protective film 2. As a result of measuring the phase difference of the protective film 2, Re = 1 nm and Rth = -5 nm.

[Preparation of First Optical Anisotropy Layer 1]
<Preparation of Composition 1 for Photo-Orientation Film>
To butyl acetate / methyl ethyl ketone (80 parts by mass / 20 parts by mass), 8.4 parts by mass of the following copolymer C1 and 0.3 parts by mass of the following thermal acid generator D1 were added to form a photoaligning film. The thing was prepared.

Copolymer C1 (Weight average molecular weight: 40,000, the numerical value in the following formula indicates the content (mass%) of each repeating unit)

Thermoacid generator D1

<Preparation of composition 1 for forming an optically anisotropic layer>
A composition 1 for forming an optically anisotropic layer having the following composition was prepared.

―――――――――――――――――――――――――――――――――
Composition for forming an optically anisotropic layer 1
―――――――――――――――――――――――――――――――――
-The following liquid crystal compound R1 42.00 parts by mass-The following liquid crystal compound R2 42.00 parts by mass-The following polyfunctional compound T1 4.00 parts by mass-The following polymerizable compound A1 12.00 parts by mass-The following polymerization initiator S1 0. 50 parts by mass ・ The following leveling agent P1 0.15 parts by mass ・ High solve MTEM (manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts by mass ・ NK ester A-200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 1.00 parts by mass ・ Methyl ethyl ketone 424 .8 parts by mass ――――――――――――――――――――――――――――――――――
The group adjacent to the acryloyloxy group of the reverse dispersion liquid crystal compound A1 below represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and the reverse dispersion liquid crystal compound A1 below has a positional isomer with a different methyl group position. Represents a mixture of bodies.

Liquid crystal compound R1

Liquid crystal compound R2

Polyfunctional compound T1

Polymerizable compound A1

Polymerization initiator S1

Leveling agent P1 [In the following formula: a to c is a: b: c = 66: 26: 8, and indicates the content (mol%) of each repeating unit with respect to all the repeating units in the resin. ]

<Preparation of the first optically anisotropic layer 1>
The composition 1 for a photoalignment film prepared above was applied to one side of the prepared protective film 2 with a bar coater. After coating, the solvent was removed by drying on a hot plate at 120 ° C. for 5 minutes to form a photoisomerization composition layer having a thickness of 0.2 μm. The obtained photoisomerization composition layer was irradiated with polarized ultraviolet rays (10 mJ / cm ² , using an ultrahigh pressure mercury lamp) to form a photoalignment film 1.
Next, the composition 1 for forming an optically anisotropic layer prepared above was applied onto the photoalignment film 1 with a bar coater to form a composition layer. The formed composition layer was once heated to 110 ° C. on a hot plate and then cooled to 60 ° C. to stabilize the orientation. Then, the obtained film was kept at 60 ° C., ^{and the orientation was fixed by ultraviolet irradiation (500 mJ / cm 2} , using an ultrahigh pressure mercury lamp) under a nitrogen atmosphere (oxygen concentration 100 ppm), and the first optical anisotropy having a thickness of 2 μm was obtained. The anisotropic layer 1 was prepared. The in-plane retardation Re1 (550) of the obtained first optically anisotropic layer 1 was 130 nm, and Re1 (450) / Re1 (550) was 0.85, showing anti-wavelength dispersibility.

[Preparation of the second optically anisotropic layer 1]
<Preparation of composition 2 for forming an optically anisotropic layer>
A composition 2 for forming an optically anisotropic layer having the following composition was prepared.

―――――――――――――――――――――――――――――――――
Composition for forming an optically anisotropic layer 2
―――――――――――――――――――――――――――――――――
-The liquid crystal compound R1 10.0 parts by mass-The liquid crystal compound R2 47.0 parts by mass-The liquid crystal compound R3 35.0 parts by mass-The polyfunctional compound T1 8.0 parts by mass-The polymerizable compound B1 4.5 By mass: 5.0 parts by mass of the following non-liquid crystal compound C1 ・ Monomer K1 (A-600, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 10.0 parts by mass ・ 1.5 parts by mass of the polymerization initiator S1 ・ The following surface activity Agent P2 0.4 parts by mass, the following surfactant P3 0.5 parts by mass, acetone 175.0 parts by mass, propylene glycol monomethyl ether acetate 75.0 parts by mass ―――――――――――――― ―――――――――――――――――――

Liquid crystal compound R3

Polymerizable compound B1

Non-liquid crystal compound C1

Surfactant P2 [Weight average molecular weight: 15000, the numerical value in the following formula indicates the content (mass%) of each repeating unit with respect to all repeating units. ]

Surfactant P3 [Weight average molecular weight: 11200, the numerical value in the following formula indicates the content (mass%) of each repeating unit with respect to all repeating units. ]

<Preparation of the second optically anisotropic layer 1>
The surface of the first optically anisotropic layer 1 on the coating side is ^{subjected to corona treatment with a discharge amount of 150 W · min / m 2} , and the composition 2 for forming the optically anisotropic layer is applied to the surface treated with the corona with a wire bar. It was applied.
Then, for drying of the solvent of the composition and orientation aging of the liquid crystal compound, it was heated with warm air at 70 ° C. for 90 seconds. Under a nitrogen purge, ultraviolet irradiation (300 mJ / cm ² ) was performed at an oxygen concentration of 0.1% at 40 ° C. to fix the orientation of the liquid crystal compound, and the second optical anisotropy was placed on the first optically anisotropic layer 1. Layer 1 was made. The retardation Rth2 (550) in the thickness direction of the obtained second optically anisotropic layer 1 was −100 nm, and Rth2 (450) / Rth2 (550) was 0.95.

[Preparation of first polarizing plate]
The surface of the laminated body of the produced first optically anisotropic layer 1 and the second optically anisotropic layer 1 on the side of the second optically anisotropic layer 1 is the polarizer surface of the prepared polarizing plate 1 with a single-sided protective film. Then, they were bonded together using an adhesive so that the absorption axis of the polarizer and the slow axis of the optically anisotropic layer were in parallel directions. The protective film 2 of the first optically anisotropic layer 1 was peeled off to prepare the first polarizing plate of Example 1. As the adhesive, a 3% aqueous solution of PVA (manufactured by Kuraray Co., Ltd., PVA-117H) was used. At this time, the polarizer and the optical compensation layer had sufficient adhesiveness for practical use.

[Preparation of protective film 3]
<Preparation of PMMA (polymethyl methacrylate) doping>
The following dope composition was put into a mixing tank and stirred to dissolve each component to prepare a PMMA dope.
―――――――――――――――――――――――――――――――
PMMA dope ――――――――――――――――――――――――――――――――
・ PMMA resin 100 parts by mass ・ Sumilyzer GS (manufactured by Sumitomo Chemical Co., Ltd.) 0.1 parts by mass ・ dichloromethane 426 parts by mass ・ Methanol 64 parts by mass ―――――――――――――――――――― ―――――――――――

<Preparation of protective film 3>
The prepared PMMA dope was uniformly cast from a casting die on a stainless steel band (casting support) (band casting machine).
Next, the film was peeled off with the solvent content in the cast film being approximately 20% by mass, both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched in the lateral direction at a stretching ratio of 1.1 times. ..
Then, the obtained film was further dried by transporting it between the rolls of the heat treatment apparatus to prepare a PMMA film having a film thickness of 20 μm, which was used as a protective film 3.

[Preparation of second polarizing plate]
<Preparation of adhesive liquid>
The following compounds were mixed in the ratio described to prepare an adhesive liquid A.
Aronix M-220 (manufactured by Toa Synthetic Co., Ltd.): 20 parts by mass 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Chemical Co., Ltd.): 40 parts by mass -2-ethylhexyl acrylate (manufactured by Mitsubishi Chemical Corporation): 40 parts by mass Irgacure907 (manufactured by Mitsubishi Chemical Corporation) BASF): 1.5 parts by mass KAYACURE DETX-S (manufactured by Nippon Kasei Chemical Co., Ltd.): 0.5 parts by mass

The polarizing element bonding surface of the protective film 3 ^{was corona-treated with a discharge amount of 150 W · min / m 2} , and then the adhesive liquid A was applied so as to have a film thickness of 0.5 μm. Then, the adhesive-coated surface was bonded to the polarizing element surface of the polarizing plate 2 with a single-sided protective film, and ultraviolet rays were irradiated at ^{300 mJ / cm 2 from the base material side of the protective film 3 at 40 ° C. in an atmospheric atmosphere.} Then, it dried at 60 degreeC for 3 minutes to prepare the second polarizing plate of Example 1.

[Manufacturing of liquid crystal display device]
The first optically anisotropic layer 1 and the above-mentioned prepared first optically anisotropic layer 1 and the above-mentioned prepared first optically anisotropic layer 1 and The first polarizing plate including the second optically anisotropic layer 1 is on the visual recognition side, the second polarizing plate is on the backlight side, and the absorption axes of the polarizers in the respective polarizing plates are orthogonal to each other, and the liquid crystal is displayed. The liquid crystal display device of Example 1 was produced by laminating with a 20 μm acrylic pressure-sensitive adhesive so that the orientation direction of the liquid crystal in the cell was orthogonal to the absorption axis of the polarizer in the first polarizing plate.
The liquid crystal cell in the liquid crystal display device includes a color filter layer on the substrate on the first polarizing plate side and a TFT layer on the substrate on the second polarizing plate side, and each Rth (550) is 10 nm and It was 2 nm. Further, Δn · d of the liquid crystal compound in the liquid crystal cell was 340, and the tilt angle of the liquid crystal compound with respect to the substrate surface was 0.1 °.

[Examples 2 to 3 and Comparative Examples 1 to 4]
In the composition 2 for forming an optically anisotropic layer used for forming the second optically anisotropic layer, the same method as in Example 1 was used except that the liquid crystal compound and the non-liquid crystal compound were changed to the compounds shown in Table 5 below. , A liquid crystal display device was manufactured.

[Evaluation]
<Front contrast (front CR)>
First, a liquid crystal display device for evaluation criteria was provided by the same method as in Example 1 except that the first polarizing plate and the second polarizing plate were changed to polarizing plate 0 in which the positive A plate and the positive C plate were not bonded. Made.
Regarding the liquid crystal display device manufactured for the examples, comparative examples, and evaluation criteria, the brightness (Yw) from the direction perpendicular to the panel in the white display and the brightness (Yb) from the direction perpendicular to the panel in the black display are commercially available. The contrast ratio (Yw / Yb) in the direction perpendicular to the panel was calculated by measuring using the liquid crystal viewing angle and chromaticity characteristic measuring device Ezcontlast (manufactured by ELDIM) of .. The results are shown in Table 5 below.
A: Front contrast is 90% or more of the evaluation standard liquid crystal display device B: Front contrast is 80% or more and less than 90% of the evaluation standard liquid crystal display device C: Front contrast is the evaluation standard liquid crystal display 70% or more and less than 80% with respect to the device D: Front contrast is less than 70% with respect to the liquid crystal display device for evaluation criteria

<Light resistance>
The prepared laminate of the first optically anisotropic layer and the second optically anisotropic layer was exposed to light for 100 hours using the super xenon weather meter SX75.
At this time, a protective film 1 was sandwiched between the laminated body and the super xenon weather meter SX75, and the light was arranged so as to enter from the second optically anisotropic layer.
By comparing the exposed sample with a similar unexposed sample, the change in color of the film and the change in retardation (Rth) in the thickness direction of the second optically anisotropic layer were evaluated. The results are shown in Table 5 below.
(Color change)
A: For samples not exposed to the xenon weather meter, Δb * ≤ 2.0
B: 2.0 <Δb * ≦ 4.0 for samples not exposed to the xenon weather meter
C: 4.0 <Δb * for samples not exposed to the xenon weather meter
(Phase difference change)
A: ΔRth ≤ 5 nm for samples not exposed to the xenon weather meter
B: 5 nm <ΔRth ≦ 10 nm for samples not exposed to xenon weather meter
C: 10 nm <ΔRth for samples not exposed to xenon weather meter

In Table 5 above, the structures of the liquid crystal compound and the non-liquid crystal compound are shown below.

Liquid crystal compound R1

Liquid crystal compound R2

Liquid crystal compound R6

Non-liquid crystal compound C1

Non-liquid crystal compound C2

Non-liquid crystal compound C3

Non-liquid crystal compound Z1

From the results shown in Table 5 above, it was found that the light resistance of the formed optically anisotropic layer was inferior when the non-liquid crystal compound was not blended (Comparative Example 1).
Further, even when a non-liquid crystal compound is blended, if the maximum absorption wavelength B of the non-liquid crystal compound is smaller than the maximum absorption wavelength A of the liquid crystal compound, the light resistance of the formed optically anisotropic layer is still inferior. Was found (Comparative Examples 2 to 4).
On the other hand, it was found that when a liquid crystal composition in which the maximum absorption wavelength B of the non-liquid crystal compound is larger than the maximum absorption wavelength A of the liquid crystal compound is used, the light resistance of the formed optically anisotropic layer is improved ( Examples 1 to 3).
In particular, from the comparison between Example 1 and Example 2, it was found that the contrast of the image display device is good when the Ar core of the liquid crystal compound and the Ar core of the non-liquid crystal compound have the same structure. ..
Further, from the comparison between Example 1 and Example 3, when the non-liquid crystal compound is represented by the above formula (II) ^{, at least one of L 5} and L ^{6 in} the above formula (II) is a polymerizable group. It was found that the light resistance of the formed optically anisotropic layer became better.

10 Optical film 12 Optically anisotropic layer 14 Alignment film 16 Support 18 Hard coat layer

Claims (17)

A liquid crystal composition containing a liquid crystal compound and a non-liquid crystal compound.
The liquid crystal compound has a maximum absorption wavelength A in the wavelength range of 250 nm or more and less than 400 nm.
The non-liquid crystal compound has a maximum absorption wavelength B in the wavelength range of 250 nm or more and less than 400 nm.
A liquid crystal composition in which the maximum absorption wavelength A and the maximum absorption wavelength B satisfy the relationship of the following formula (1).
A <B ... (1) Claimed that the liquid crystal compound and the non-liquid crystal compound are both compounds having any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-7). Item 2. The liquid crystal composition according to Item 1.

Here, in the above formulas (Ar-1) to (Ar-7),
* Represents the bond position.
Q ¹ represents an N or CH.
Q ² is, -S -, - O-, or, -N ^{(R 6)} - represents, ^{R 6} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ has an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, or a substituent. It represents an alicyclic hydrocarbon group having 6 to 20 carbon atoms _{, and one or more of −CH 2} − constituting the alicyclic hydrocarbon group is −O—, −S— or −NH−. It may be replaced.
Z ¹ , Z ² and Z ³ independently have a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a carbon number of carbon atoms. 6 to 20 monovalent aromatic hydrocarbon groups, 6 to 20 carbon number monovalent aromatic heterocyclic groups, halogen atoms, cyano groups, nitro groups, -OR ⁷ , -NR ⁸ R ⁹ , -SR ¹⁰ , -COOR ¹¹ or -COR ¹² , R ^{7 to} R ¹² independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² are bonded to each other and aromatic. A ring may be formed.
A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹³ )-, -S-, and -CO-, where R ¹³ is a hydrogen atom or Represents a substituent.
X represents a non-metal atom of Group 14-16 to which a hydrogen atom or a substituent may be bonded.
D ⁷ and ^{D 8} are each independently a single bond, or, -CO -, - O -, - S -, - C (= S) -, - CR 1 R 2 -, - CR 3 = CR 4 - , -NR ^5- , or a divalent linking group consisting of two or more of these, and R ^{1 to} R ⁵ each independently have a hydrogen atom, a fluorine atom, or 1 to 12 carbon atoms. Represents an alkyl group.
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, respectively. -CH ₂ - of one or more -O -, - S -, - NH -, - N (Q) -, or a divalent linking group which is substituted in -CO-, Q is a substituted group Represents.
L ³ and L ⁴ each independently represent a monovalent organic group.
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic 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.
Q ³ are a hydrogen atom or may have a substituent alkyl group having 1 to 20 carbon atoms. The liquid crystal composition according to claim 2, wherein the liquid crystal compound has an inverse wavelength dispersibility. The liquid crystal composition according to claim 2 or 3, wherein the liquid crystal compound is a compound represented by the following formula (I).
^{L 1 -SP 1 -D 5 - (} A 1) a1 -D 3 - (G 1) g1 -D 1 - ^{[Ar-D 2] _{q1 - (G 2) g2 -D}} 4 - (A 2) a2 - D ^6- SP ^2- L ² ... (I)
Here, in the above formula (I),
a1, a2, g1 and g2 independently represent 0 or 1, respectively. However, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.
q1 represents 1 or 2.
D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR. ^{1 R 2 -, - CR 3} = CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ are each independently a hydrogen atom , Fluorine atom, or an alkyl group having 1 to 12 carbon atoms. However, when q1 is 2, a plurality of D ² may each be the same or different.
G ¹ and G ² are independently aromatic rings having 6 to 20 carbon atoms which may have a substituent, or divalent alicyclic compounds having 5 to 20 carbon atoms which may have a substituent. Representing a cyclic hydrocarbon group _{, one or more of −CH 2−} constituting the alicyclic hydrocarbon group may be substituted with −O−, −S− or −NH−.
A ¹ and A ² are independently aromatic rings having 6 to 20 carbon atoms which may have a substituent, or divalent alicyclic compounds having 5 to 20 carbon atoms which may have a substituent. Representing a cyclic hydrocarbon group _{, one or more of −CH 2−} constituting the alicyclic hydrocarbon group may be substituted with −O−, −S− or −NH−.
SP ¹ and SP ² independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms, respectively. -CH ₂ - of one or more -O -, - S -, - NH -, - N (Q) -, or a divalent linking group which is substituted in -CO-, Q is a substituted group Represents.
L ¹ and L ² each independently represent a monovalent organic group, ^{and at least one of L 1} and L ² represents a polymerizable group. However, Ar is the formula (Ar-3) if an aromatic ring represented by, at least one polymerizable group ^{L 1} and ^{L 2} as well as the equation ^L of (Ar-3) ³ and ^{L 4} Represents.
Ar represents any aromatic ring selected from the group consisting of the groups represented by the formulas (Ar-1) to (Ar-7). However, when q1 is 2, the plurality of Ars may be the same or different. The liquid crystal composition according to claim 4, ^{wherein D 1} and D ² in the formula (I) represent −CO—O−. The liquid crystal composition according to any one of claims 2 to 5, wherein the non-liquid crystal compound is a compound represented by the following formula (II).
^{L 5 -SP 5 -D 11 - (} G 3) g3 -D 9 - ^{[Ar-D 10] _{q2 - (G 4) g4 -D}} 12 -SP 6 -L 6 ··· (II)
Here, in the above formula (II),
g3 and g4 independently represent 0 or 1, respectively.
q2 represents 1 or 2.
D ⁹ , D ¹⁰ , D ¹¹ and D ¹² are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR ^{1 R 2} -,-, respectively. ^{CR 3 = CR 4 -, -} NR 5 -, or a divalent linking group formed from these two or more ^thereof, R 1 to R ⁵ are each independently a hydrogen atom, a fluorine atom, or Represents an alkyl group having 1 to 12 carbon atoms. However, when q2 is 2, the plurality of D ^10s may be the same or different.
G ³ and G ⁴ each independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a divalent alicyclic having 5 to 20 carbon atoms which may have a substituent. Representing a cyclic hydrocarbon group _{, one or more of −CH 2−} constituting the alicyclic hydrocarbon group may be substituted with −O−, −S− or −NH−.
SP ⁵ and SP ⁶ independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms, respectively. -CH ₂ - of one or more -O -, - S -, - NH -, - N (Q) -, or a divalent linking group which is substituted in -CO-, Q is a substituted group Represents.
L ⁵ and L ⁶ each independently represent a monovalent organic group.
Ar represents any aromatic ring selected from the group consisting of the groups represented by the formulas (Ar-1) to (Ar-7). However, when q2 is 2, the plurality of Ars may be the same or different. The liquid crystal composition according to claim 6, wherein g3 and g4 in the formula (II) are 0, and D ¹¹ and D ^{12 are single bonds.} The liquid crystal composition according to claim 6 or 7, ^{wherein D 9} and D ¹⁰ in the formula (II) represent −O−. The liquid crystal composition according to any one of claims 6 to 8, wherein at least one ^{of L 5} and L ^{6 in} the formula (II) represents a polymerizable group. Any aromatic ring selected from the group consisting of the groups represented by the formulas (Ar-1) to (Ar-7) contained in the liquid crystal compound, and the formula (Ar-1) contained in the non-liquid crystal compound. The liquid crystal composition according to any one of claims 2 to 9, wherein any aromatic ring selected from the group consisting of the groups represented by (Ar-7) has the same structure. The liquid crystal composition according to any one of claims 1 to 10, wherein the liquid crystal compound indicates a liquid crystal state of a smectic phase. The liquid crystal composition according to any one of claims 1 to 11, wherein the content of the non-liquid crystal compound is 1 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal compound. The liquid crystal composition according to any one of claims 1 to 12, wherein the maximum absorption wavelength A and the maximum absorption wavelength B satisfy the relationship of the following formula (2).
0 nm <BA <20 nm ... (2) An optically anisotropic layer obtained by polymerizing the liquid crystal composition according to any one of claims 1 to 13. An optical film having the optically anisotropic layer according to claim 14. A polarizing plate having the optical film according to claim 15 and a polarizer. An image display device having the optical film according to claim 15 or the polarizing plate according to claim 16.

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