JP7182533B2 - Liquid crystal composition, optically anisotropic layer, optical film, polarizing plate and image display device - Google Patents

Description

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

Optical films such as optical compensatory sheets and retardation films are used in various image display devices in order to eliminate image coloring or widen 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 reverse wavelength dispersion ([Claim 1] ]).

JP 2016-081035 A

The present inventors investigated the optically anisotropic layer described in Patent Document 1 and found that there is room for improvement in light resistance.

Accordingly, 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 intensive studies to achieve the above object, the present inventors have found that 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 are contained, and the non-liquid crystal compound has a maximum absorption wavelength of the liquid crystal compound. The inventors have found that the light resistance of the optically anisotropic layer formed is improved by using a liquid crystal composition having a maximum absorption wavelength larger than that of , thereby completing the present invention.
That is, the inventors have found that the above object 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 an aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7) described later. , the liquid crystal composition according to [1].
[3] The liquid crystal composition according to [2], wherein the liquid crystal compound has reverse wavelength dispersion.
[4] The liquid crystal composition according to [2] or [3], wherein the liquid crystal compound is a compound represented by formula (I) described below.
[5] The liquid crystal composition according to [4], wherein D ¹ and D ² in formula (I) to be 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 formula (II) described below.
[7] The liquid crystal composition according to [6], wherein g3 and g4 in formula (II) described later are 0, and ^D11 and ^D12 are single bonds.
[8] The liquid crystal composition according to [6] or [7], wherein D ⁹ and D ¹⁰ in formula (II) to be described later represent —O—.
[9] The liquid crystal composition according to any one of [ ⁶ ] to [8], wherein at least one of L5 and ^L6 in formula (II) described later represents a polymerizable group.
[10] Any aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7) which the liquid crystal compound has and the above formula (Ar- 1) The liquid crystal composition according to any one of [2] to [9], wherein any aromatic ring selected from the group consisting of groups represented by to (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 smectic liquid crystal state.
[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 based on 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 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 of [14].
[16] A polarizing plate comprising the optical film of [15] and a polarizer.
[17] An image display device comprising the optical film of [15] or the polarizing plate of [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.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
In addition, in the present specification, each component may be a substance corresponding to each component either singly or in combination of two or more. Here, when two or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination unless otherwise specified.
In addition, in this specification, the bonding direction of the divalent group (e.g., —CO—NR—) is not particularly limited unless the bonding position is specified. When D ¹ in I) is -CO-NR-, the position where it binds to the G ¹ side ^is *1, and the position where it binds to the Ar ¹ side is *2. -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.
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. , 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 two or more of at least one of a liquid crystal compound and a non-liquid crystal compound, the relationship between at least one pair of the liquid crystal compound and the non-liquid crystal compound satisfies the above ratio. 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, wherein the maximum absorption wavelength B of the non-liquid crystal compound is greater than the maximum absorption wavelength A of the liquid crystal compound. is used, the light resistance of the optically anisotropic layer to be formed is improved.
Although this is not clear in detail, the present inventors presume 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 that is greater than the maximum absorption wavelength A of the liquid crystal compound. It is considered that the absorption of light (in particular, ultraviolet light) by the liquid crystal compound is suppressed as compared with the case where the non-liquid crystal compound is not used, and as a result, the light resistance is improved.
In addition, the non-liquid crystal compound contained in the liquid crystal composition has a maximum absorption wavelength B that is larger (on the long wavelength side) than the maximum absorption wavelength A of the liquid crystal compound. is lower than the energy required to excite the liquid crystal compound, the energy of the liquid crystal compound excited by light can be transferred to the non-liquid crystal compound, resulting in good light resistance. You might also say that.
Further, when both the maximum absorption wavelengths A and B are less than 400 nm, it is possible to suppress coloring (in particular, 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 non-liquid crystal compound to be measured is dissolved in chloroform to prepare a solution having a concentration of 1 mass %.
Next, the prepared solution is placed in a quartz cell (10 mm long square cell), and the absorbance of the solution in the wavelength range of 200 to 800 nm is measured using an ultraviolet visible infrared spectrophotometer U-3100PC (Shimadzu Corporation). .
Next, the maximum absorption wavelength is determined 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 in accordance with the following formula (2) because the optically anisotropic layer formed has better light resistance. It is preferable to satisfy the relationship.
0 nm<BA<20 nm (2)

Each component of the liquid crystal composition of the present invention will be described in detail below.

[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. can be appropriately selected and used.
Here, a liquid crystal compound means a compound that exhibits a liquid crystal state under specific temperature conditions.

In the present invention, the liquid crystal compound is used for the reason that it facilitates the control of the wavelength dispersion of the liquid crystal compound and facilitates the improvement of the compensation when the optically anisotropic layer formed thereby is used as an optical compensation film. , a compound having an aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-7).

In the above formulas (Ar-1) to (Ar-7), * represents the bonding position, that is, the bonding position with the 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 optionally substituted C 6 to 12 aromatic hydrocarbon group, an optionally substituted C 3 to 12 or an optionally substituted alicyclic hydrocarbon group having 6 to 20 carbon atoms, wherein one or more of —CH ₂ — constituting the alicyclic hydrocarbon group are It may be substituted with -O-, -S- or -NH-.

Here, specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and the like.

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

Examples of substituents 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, an alkenyl group, alkynyl groups, halogen atoms, cyano groups, nitro groups, alkylthiol groups, and N-alkylcarbamate groups, among which alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyloxy groups, or halogen atoms 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 (e.g., methyl group, ethyl group, propyl group, isopropyl group, n -butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (e.g., methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.), and 1 carbon atom. An alkoxy group of ∼4 is more preferred, and a methoxy or ethoxy group is particularly preferred.
Examples of the alkoxycarbonyl group include groups 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 isopropoxy A carbonyl group is preferred, and a methoxycarbonyl group is more preferred.
Examples of the alkylcarbonyloxy group include groups 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. or isopropylcarbonyloxy group is preferred, and methylcarbonyloxy group is more preferred.
The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among them, a fluorine atom or a chlorine atom is preferable.

In the above formulas (Ar-1) to (Ar-7), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a carbon monovalent alicyclic hydrocarbon groups of 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups of 6 to 20 carbon atoms, monovalent aromatic heterocyclic groups of 6 to 20 carbon atoms, halogen atoms, cyano groups , a nitro group, —OR ⁷ , —NR ⁸ R ⁹ , —SR ¹⁰ , —COOR ¹¹ , or —COR ¹² , wherein R ⁷ to R ¹² each independently represent a hydrogen atom or represents an alkyl group, and Z ¹ and Z ² may combine with each other to form an aromatic ring.

Here, the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, specifically a methyl group. , 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, methyl group, ethyl group, A tert-butyl group is particularly preferred.
Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, methylcyclohexyl and ethylcyclohexyl. monocyclic saturated hydrocarbon groups such as groups; 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 ]dodecyl group, polycyclic saturated hydrocarbon group such as adamantyl group; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, 2,6-diethylphenyl group, naphthyl group, biphenyl group and the like, and 6 to 12 carbon atoms. is preferably an aryl group (particularly a phenyl group).
Specific examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms include 4-pyridyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like. mentioned.
The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, specific examples of alkyl groups having 1 to 6 carbon atoms represented by R ⁷ to R ¹⁰ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group. tert-butyl, n-pentyl, and n-hexyl groups.

In addition, as described above, Z ¹ and Z ² may combine with each other to form an aromatic ring. For example, Z ¹ and Z ² in the above formula (Ar-1) combine with 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 formula (Ar-1a) below, * represents a bonding position, and Q ¹ , Q ² and Y ¹ are the same as those described in the above formula (Ar-1).

In the above formulas (Ar-2) and (Ar-3), A ³ and A ⁴ are each independently from -O-, -N(R ¹³ )-, -S-, and -CO- represents a group selected from the group consisting of 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.

In the above formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 which may be bonded to a substituent.
The non-metallic atoms of groups 14 to 16 represented by X include, for example, an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. Specific examples of the substituent include: Examples include alkyl groups, alkoxy groups, alkyl-substituted alkoxy groups, cyclic alkyl groups, aryl groups (e.g., phenyl group, naphthyl group, etc.), cyano groups, amino groups, nitro groups, alkylcarbonyl groups, sulfo groups, hydroxyl groups, and the like. be done.

In the above formula (Ar-3), 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 a combination of two or more thereof, wherein R ¹ to R ⁵ each independently represent a hydrogen atom, represents a fluorine atom or an alkyl group having 1 to 12 carbon atoms.

Here, the divalent linking group represented by one embodiment of D ⁷ and D ⁸ includes, for example, -CO-, -O-, -CO-O-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ¹ R ² -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ¹ R ² -, -CO-O-CR ¹ R ² -, - O—CO—CR ¹ R ² —, —CR ¹ R ² —O—CO—CR ¹ R ² —, —CR ¹ R ² —CO—O—CR ¹ R ² —, —NR ⁵ —CR ¹ R ^{2 —} -, and -CO-NR ⁵ -. R ¹ , R ² and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms.
Among these, any one of -CO-, -O- and -CO-O- is preferred.

In the above formula (Ar-3), SP ³ and SP ⁴ are each independently a single bond, a linear or branched C 1-12 alkylene group, or a C 1-12 linear divalent in which one or more —CH ₂ — constituting a chain or branched alkylene group is substituted with —O—, —S—, —NH—, —N(Q)—, or —CO— represents a linking group, and Q represents a substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Here, the linear or branched alkylene group having 1 to 12 carbon atoms represented by one aspect of SP ³ and SP ⁴ includes, for example, 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. In SP ¹ and SP ² , as described above, one or more of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms is —O—, —S—, or —NH. -, -N(Q)-, or -CO- may be a divalent linking group substituted with -CO-, and the substituent represented by Q is Y ¹ in the above formula (Ar-1) The same substituents as those which may be possessed by may be mentioned.

In the above formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group.
Examples of monovalent organic groups represented by L ³ and L ⁴ include alkyl groups, aryl groups, and heteroaryl groups. Alkyl groups may be linear, branched or cyclic, but are preferably linear. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20, even more preferably 1-10. Also, the aryl group may be monocyclic or polycyclic, but is preferably monocyclic. The number of carbon atoms in the aryl group is preferably 6-25, more preferably 6-10. Also, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1-3. A heteroatom 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. In addition, the alkyl group, aryl group and heteroaryl group may be unsubstituted or may 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 heterocyclic ring and has 2 to 30 carbon atoms. represents an organic group.
In the above formulas (Ar-4) to (Ar-7), Ay is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, 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 heterocyclic rings.
Here, the aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
Ax and Ay include those described in paragraphs [0039] to [0095] of WO2014/010325.
Further, specific examples of the alkyl group having 1 to 20 carbon atoms represented by Q ³ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -butyl group, n-pentyl group, n-hexyl group and the like, and the substituents are the same as the substituents that Y ¹ in the above formula (Ar-1) may have. mentioned.

In the present invention, the liquid crystal compound is preferably a liquid crystal compound having reverse wavelength dispersion for the purpose of improving optical compensation.
Here, in the present specification, the "liquid crystal compound having reverse wavelength dispersion" means an in-plane retardation (Re) value or thickness at a specific wavelength (visible light range) of a retardation film produced using the same. It means that when the directional retardation (Rth) value is measured, the Re value or the Rth value becomes equal or higher as the measurement wavelength increases.

Further, in the present invention, the liquid crystal compound is preferably a compound represented by the following formula (I) for the purpose of further improving the optical compensation property. In formula (I) below, Ar represents any aromatic ring selected from the group consisting of the groups represented by formulas (Ar-1) to (Ar-7) described above. However, when q1 in the following formula (I) is 2, a plurality of Ar 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 formula (I) above, a1, a2, g1 and g2 each independently represent 0 or 1; However, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.
In addition, q1 represents 1 or 2 in the above formula (I).
In the above formula (I), D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are each independently a single bond, or -CO-, -O-, -S-, - C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more thereof, and R ¹ to R ⁵ each 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 ^D2 may be the same or different.
In the above formula (I), G ¹ and G ² are each independently an optionally substituted aromatic ring having 6 to 20 carbon atoms, or an optionally substituted carbon represents a divalent alicyclic hydrocarbon group having a number of 5 to 20, wherein one or more —CH ₂ — constituting the alicyclic hydrocarbon group is substituted with —O—, —S— or —NH—; may
In the above formula (I), A ¹ and A ² are each independently an optionally substituted aromatic ring having 6 to 20 carbon atoms, or an optionally substituted carbon represents a divalent alicyclic hydrocarbon group having a number of 5 to 20, wherein one or more —CH ₂ — constituting the alicyclic hydrocarbon group is substituted with —O—, —S— or —NH—; may
In the above formula (I), SP ¹ and SP ² are each independently a single bond, a linear or branched C 1-12 alkylene group, or a C 1-12 linear or a divalent linkage in which one or more of —CH ₂ — constituting a branched alkylene group are substituted with —O—, —S—, —NH—, —N(Q)—, or —CO— group, and Q represents a substituent.
In formula (I) above, L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar is an aromatic ring represented by the above formula (Ar-3), at least one of L ¹ and L 2 and L ³ and L ⁴ in the above formula (Ar- ³ ) is polymerized represents a sexual group.

In formula (I), all of a1, a2, g1 and g2 are preferably 1 because the liquid crystal composition of the present invention tends to exhibit a smectic liquid crystal state.

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

In the above formula (I), the divalent linking groups represented by one embodiment of D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are D ⁷ and D in the above formula (Ar-3) Those similar to those described in ⁸ can be mentioned.
Of these, any one of -CO-, -O- and -CO-O- is preferred, and -CO-O- is particularly preferred for D ¹ and D ² .

In the above formula (I), the aromatic ring having 6 to 20 carbon atoms represented by one embodiment of G ¹ and G ² includes, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, and phenanthroline ring. aromatic heterocycles such as furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, and benzothiazole ring; among them, benzene ring (eg, 1,4-phenyl group, etc.) is preferred.

In the above formula (I), the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one embodiment of G ¹ and G ² is preferably a 5- or 6-membered ring. Also, the alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferred. As the divalent alicyclic hydrocarbon group represented by G ¹ and G ² , for example, the description in paragraph [0078] of JP-A-2012-21068 can be referred to, the contents of which are incorporated herein. .

In the present invention, G ¹ and G ² in formula (I) above are preferably cycloalkane rings.
Specific examples of the cycloalkane ring include cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclododecane ring, cyclodocosane ring and the like.
Among 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), for G ¹ and G ² , as a substituent that the aromatic ring having 6 to 20 carbon atoms or the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms may have, includes the same substituents that Y ¹ in the above formula (Ar-1) may have.

In the above formula (I), the aromatic ring having 6 to 20 or more carbon atoms represented by one embodiment of A ¹ and A ² is the same as described for G ¹ and G ² in the above formula (I). mentioned.
In the above formula (I), the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one embodiment of A ¹ and A ² includes G ¹ and G ² in the above formula (I). Those similar to those described above can be mentioned.
Regarding A ¹ and A ² , the substituents that the aromatic ring having 6 to 20 carbon atoms or the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms may have include those of the above formula (Ar- The substituents that Y ¹ in 1) may have are the same as those described above.

In the above formula (I), the linear or branched alkylene group having 1 to 12 carbon atoms represented by one embodiment of SP ¹ and SP ² is SP ³ and SP ⁴ in the above formula (Ar-3). Those similar to those described above can be mentioned.

In formula (I) above, the monovalent organic groups represented by L ¹ and L ² include the same groups as those described for L ³ and L ⁴ in formula (Ar-3) above.

In formula (I), the polymerizable group represented by at least one of L ¹ and L ² is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization.
As the radically polymerizable group, generally known radically polymerizable groups can be used, and acryloyloxy groups and methacryloyloxy groups can be mentioned as suitable groups. In this case, an acryloyloxy group is known to generally have a high polymerization rate, and an acryloyloxy group is preferred from the viewpoint of improving productivity, but a methacryloyloxy group can also be used as the polymerizable group.
As the cationically polymerizable group, generally known cationically polymerizable groups can be used. Specifically, alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and , a vinyloxy group, and the like. Among them, 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 preferred polymerizable groups include polymerizable groups represented by any of the following formulas (P-1) to (P-20).

In the above formula (I), both L ¹ and L ² in the above formula (I) are preferably polymerizable groups, such as an acryloyloxy group or a methacryloyloxy group, for the reason of good durability. is more preferable.

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

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

In the present invention, the compound represented by the above formula (I) is preferably a compound exhibiting a liquid crystal state of a smectic phase because the contrast of the image display device to be produced is improved.

[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. 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, since the non-liquid crystal compound has a structure similar to that of the liquid crystal compound, the compatibility with the liquid crystal compound described above is improved. It is preferably a compound having any aromatic ring selected from the group consisting of groups represented by 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) because the compatibility with the liquid crystal compound described above is improved.
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 formula (II) above, g3 and g4 each independently represent 0 or 1.
Moreover, q2 represents 1 or 2 in the above formula (II).
In the above formula (II), D ⁹ , D ¹⁰ , D ¹¹ and D ¹² are each independently a single bond, or -CO-, -O-, -S-, -C(=S)- , -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or a divalent linking group consisting of a combination of two or more thereof, wherein R ¹ to R ⁵ each independently , represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. However, when q2 is 2, the plurality of D ¹⁰ may be the same or different.
In the above formula (II), G ³ and G ⁴ are each independently an optionally substituted aromatic ring having 6 to 20 carbon atoms, or an optionally substituted carbon represents a divalent alicyclic hydrocarbon group having a number of 5 to 20, wherein one or more —CH ₂ — constituting the alicyclic hydrocarbon group is substituted with —O—, —S— or —NH—; may
In the above formula (II), SP ⁵ and SP ⁶ are each independently a single bond, a straight or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. or a divalent linkage in which one or more of —CH ₂ — constituting a branched alkylene group are substituted with —O—, —S—, —NH—, —N(Q)—, or —CO— group, and Q represents a substituent.
In formula (II) above, L ⁵ and L ⁶ each independently represent a monovalent organic group.
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, a plurality of Ar may be the same or different.

In the present invention, g3 and g4 in the above formula (II) are 0, and ^D11 and ^D12 are single bonds, for the reason that the optically anisotropic layer formed has better light resistance. is preferred. 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 formula (II) above, q2 is preferably 1.

In the above formula (II), the divalent linking group represented by one embodiment of D ⁹ , D ¹⁰ , D ¹¹ and D ¹² is the one described for D ⁷ and D ⁸ in the above formula (Ar-3). and similar ones.

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

^G3 and ^G4 in formula (II) are the same as those described for ^G1 and ^G2 in formula (I) above.

In the above formula (II), the linear or branched alkylene group having 1 to 12 carbon atoms represented by one embodiment of SP ⁵ and SP ⁶ includes SP ³ and SP ⁴ in the above formula (Ar-3). The same as those described in .

In the present invention, SP ⁵ and SP ⁶ are linear or branched alkylene groups having 1 to 12 carbon atoms, or C 1 to 12 It is preferable that one or more —CH ₂ — constituting a linear or branched alkylene group of is a divalent linking group substituted with —O—.

In formula (II) above, the monovalent organic groups represented by L ⁵ and L ⁶ include the same groups as those described for L ³ and L ⁴ in formula (Ar-3) above.

In the present invention, at least one of L ⁵ and L ⁶ in the above formula (II) preferably represents a polymerizable group for the reason that the optically anisotropic layer to be formed has better light resistance. More preferably, represents a polymerizable group.
Examples of the polymerizable group include those exemplified as the polymerizable group represented by at least one of L ¹ and L ² in the above formula (I). Polymerizable groups represented by any one of 1) to (P-20) are preferred.

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

In the present invention, the surface condition of the formed optically anisotropic layer is improved, and the contrast of the image display device having the optically anisotropic layer is improved. It is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass.

In the present invention, since the contrast of the image display device having the formed optically anisotropic layer is improved, the liquid crystal compounds represented by the above formulas (Ar-1) to (Ar-7) have Any aromatic ring (hereinafter also abbreviated as “Ar core”) selected from the group consisting of groups and the Ar core possessed by the above non-liquid crystal compound preferably have the same structure.
When the liquid crystal composition of the present invention contains two or more kinds of at least one of the liquid crystal compound and the non-liquid crystal compound, at least one pair of the liquid crystal compound and the non-liquid crystal compound has an Ar core of the same structure. It's fine if you do.

[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 liquid crystal compounds described above, for the reason that the formed optically anisotropic layer has a good surface condition. is preferred.

Here, the polymerizable group possessed by the polyfunctional liquid crystal compound includes the same polymerizable group capable of radical polymerization or cationic polymerization described in the liquid crystal compound described above, among which the above-described formula (P-1) A polymerizable group represented by any one of (P-20) is preferred.

Examples of the polyfunctional liquid crystal compound include compounds represented by the formula (M3) described in paragraph [0033] of JP-A-2014-077068, more specifically, [0053] to Examples include those described in paragraph [0055].
Further, other examples of the polyfunctional liquid crystal compound include compounds 8, 29, 59 to 61, 64, and 65 among the compounds described in paragraphs [0027] to [0033] of JP-A-2016-053149. and 69.

In the present invention, the content of the polyfunctional liquid crystal compound in the case of containing the polyfunctional liquid crystal compound is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the liquid crystal compound. is more preferred.

[Polymerization initiator]
The liquid crystal composition of the invention preferably contains a polymerization initiator.
The polymerization initiator used is preferably a photopolymerization initiator capable of initiating the polymerization reaction by irradiation with ultraviolet rays.
Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), and α-hydrocarbon-substituted aromatic compounds. group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. No. 3549367), acridine and phenazine compounds (Japanese Patent Application Laid-Open No. 60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,212,970), acylphosphine Oxide compounds (described in JP-B-63-40799, JP-B-5-29234, JP-A-10-95788, JP-A-10-29997) and the like.
Further, in the present invention, the polymerization initiator is preferably an oxime-type polymerization initiator. agents.

〔solvent〕
The liquid crystal composition of the invention preferably contains a solvent from the viewpoint of workability in forming the optically anisotropic layer to be formed.
Specific examples of solvents include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), and aliphatic hydrocarbons. (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene) , chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve etc.), cellosolve acetates, sulfoxides (e.g., dimethylsulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, etc.), etc., and these may be used singly 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 alignment control.
Such a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because of its high leveling effect relative to the amount added. is more preferable.
Specific examples of the leveling agent include, for example, the compounds described in paragraphs [0079] to [0102] of JP-A-2007-069471, and the general formula described in JP-A-2013-047204 ( Compounds represented by I) (especially compounds described in paragraphs [0020] to [0032]), compounds represented by general formula (I) described in JP-A-2012-211306 (especially [0022] ~ compound described in paragraph [0029]), liquid crystal alignment accelerator represented by general formula (I) described in JP-A-2002-129162 (especially [0076] ~ [0078] and [0082] ~ Compounds described in paragraph [0084]), compounds represented by general formulas (I), (II) and (III) described in JP-A-2005-099248 (especially paragraphs [0092] to [0096] and the compounds described in ). In addition, it may also have a function as an alignment control agent, which will be described later.

[Orientation control agent]
The liquid crystal composition of the present invention can contain an alignment control agent, if necessary.
The alignment control agent can form various alignment states such as homogenous alignment, homeotropic alignment (vertical alignment), tilted alignment, hybrid alignment, cholesteric alignment, and the like. It can be realized with precise control.

As the alignment control agent that promotes homogeneous alignment, for example, a low-molecular alignment control agent or a high-molecular alignment control agent can be used.
Low-molecular alignment control agents include, for example, paragraphs [0009] to [0083] of JP-A-2002-20363, paragraphs [0111]-[0120] of JP-A-2006-106662, and JP-A-2012 The description in paragraphs [0021] to [0029] of JP-211306 can be referred to, and the contents thereof are incorporated herein.
Further, as the polymer orientation control agent, for example, see paragraphs [0021] to [0057] of JP-A-2004-198511 and paragraphs [0121]-[0167] of JP-A-2006-106662. and the contents of which are incorporated herein.

Further, the alignment control agent that forms or promotes homeotropic alignment includes, for example, boronic acid compounds and onium salt compounds. , [0052] to [0058] of JP 2012-208397, [0024] to [0055] of JP 2008-026730, [0043] to [0055] of JP 2016-193869 The compounds described in paragraphs and the like can be taken into consideration, and the contents thereof are incorporated in the specification of the present application.

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

When the alignment 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 mass in the composition. When the content is within this range, it is possible to obtain a uniform and highly transparent cured product free from precipitation, phase separation, orientation defects, etc., while realizing a 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, alignment aids, plasticizers, and cross-linking agents.

[Optically anisotropic layer]
The optically anisotropic layer of the invention is an optically anisotropic layer obtained by polymerizing the liquid crystal composition of the invention described above.
As a method of forming the optically anisotropic layer, for example, a method of using the above-described liquid crystal composition of the present invention to achieve a desired alignment state and then fixing the composition by polymerization can be used.
Here, polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation. The irradiation dose is preferably 10 mJ/cm ² to 50 J/cm ² , more preferably 20 mJ/cm ² to 5 J/cm ² , even more preferably 30 mJ/cm ² to 3 J/cm ² . , 50 to 1000 mJ/cm ² . Moreover, in order to accelerate the polymerization reaction, it may be carried out under heating conditions.
In the invention, the optically anisotropic layer can be formed on any support in the optical film of the invention described later or on the polarizer in the polarizing plate of the invention described later.

The optically anisotropic layer of the invention is preferably an optically anisotropic layer that satisfies 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 retardation of the optically anisotropic layer at a wavelength of 450 nm, and Re(550) represents the in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm. represents a date. In the above formula (IV), Rth(450) represents retardation in the thickness direction of the optically anisotropic layer at a wavelength of 450 nm, and Rth(550) is the retardation in the thickness direction of the optically anisotropic layer at a wavelength of 550 nm. Represents retardation. In this specification, unless the measurement wavelength of retardation is specified, the measurement wavelength is assumed to be 550 nm.
The values of in-plane retardation and retardation in the thickness direction are values measured using AxoScan OPMF-1 (manufactured by Optoscience) using light of the measurement wavelength.
Specifically, by inputting the average refractive index ((Nx+Ny+Nz)/3) and film thickness (d (μm)) in AxoScan OPMF-1,
Slow axis direction (°)
Re(λ)=R0(λ)
Rth(λ)=((nx+ny)/2−nz)×d
is calculated.
Note that R0(λ), which is displayed as a numerical value calculated by AxoScan OPMF-1, means Re(λ).

Moreover, such an optically anisotropic layer is preferably a positive A plate or a positive C plate, 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.
nx is the refractive index in the film in-plane slow axis direction (the direction in which the in-plane refractive index is maximized), ny is the refractive index in the direction perpendicular to the in-plane slow axis, and the refraction in the thickness direction When the rate is nz, the positive A plate satisfies the relationship of formula (A1), and the positive C plate satisfies the relation of formula (C1). The positive A plate shows a positive Rth value, and the positive C plate shows a negative Rth value.
Formula (A1) nx>ny≈nz
Formula (C1) nz>nx≈ny
Note that 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 a positive A plate, for example, (ny-nz) x 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 the case where (nx−nz)×d is −10 to 10 nm, preferably −5 to 5 nm is also included in “nx≈nz”. In addition, for a positive C plate, for example, (nx−ny)×d (where d is the thickness of the film) is also included in “nx≈ny” when it is 0 to 10 nm, preferably 0 to 5 nm.

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

[Optical film]
The optical film of the invention is an optical film having the optically anisotropic layer of the 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 diagram, and the relationship of thickness and position of each layer does not necessarily match the actual one, and both the support and the alignment film shown in FIG. 1 are 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.
Also, 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, which will be 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 mode or FFS mode liquid crystal display device, a positive A plate and a positive C plate are used. A stack of plates is preferred.
Alternatively, the optically anisotropic layer may be separated from the support and used as an optical film alone.
Various members used in the optical film of the present invention are described in detail below.

[Optically anisotropic layer]
The optically anisotropic layer of the optical film of the invention is the optically anisotropic layer of the invention described above.
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]
The optical film of the invention may have a support as a substrate for forming the optically anisotropic layer, as described above.
Such a support is preferably transparent, and more specifically, preferably has a light transmittance of 80% or more.

Examples of such supports include glass substrates and polymer films. Materials for polymer films include cellulose-based polymers; Polymer; thermoplastic norbornene-based polymer; polycarbonate-based polymer; polyester-based polymer such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymer such as polystyrene, acrylonitrile-styrene copolymer (AS resin); Polyolefin-based polymers such as polymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; vinylidene chloride-based polymer; vinyl alcohol-based polymer; vinyl butyral-based polymer; arylate-based polymer; polyoxymethylene-based polymer;
A polarizer, which will be 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 invention has any of the above supports, it preferably has an alignment film between the support and the optically anisotropic layer. In addition, the above-described support may also serve as an alignment film.

The alignment film generally contains a polymer as a main component. Polymer materials for alignment films are described in many documents, and many commercial products are available.
The polymer material utilized in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. Modified or unmodified polyvinyl alcohol is particularly preferred.
Alignment films that can be used in the present invention include, for example, alignment films described in WO 01/88574, page 43, line 24 to page 49, line 8; ]; a liquid crystal alignment film formed by a liquid crystal alignment agent described in JP-A-2012-155308; and the like.

In the present invention, it is also preferable to use a photo-alignment film as the alignment film, because it is possible to prevent surface deterioration by not contacting the surface of the alignment film during formation of the alignment film.
Although the photo-alignment film is not particularly limited, polymer materials such as polyamide compounds and polyimide compounds described in paragraphs [0024] to [0043] of WO 2005/096041; described in JP-A-2012-155308 A liquid crystal aligning film formed by a liquid crystal aligning agent having a photo-aligning group; LPP-JP265CP (trade name, manufactured by Rolic Technologies) can be used.

In the present invention, the thickness of the alignment film is not particularly limited. It is preferably from 01 to 10 μm, more preferably from 0.01 to 1 μm, even more preferably from 0.01 to 0.5 μm.

[Ultraviolet absorber]
The optical film of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (especially ultraviolet light).
The ultraviolet absorber may be contained in the optically anisotropic layer of the invention, or may be contained in a member other than the optically anisotropic layer constituting the optical film of the invention. Examples of suitable members other than the optically anisotropic layer include supports.
As the ultraviolet absorber, any conventionally known one capable of exhibiting ultraviolet absorbency can be used. Among such UV absorbers, benzotriazole-based or hydroxyphenyltriazine-based UV absorbers can be used from the viewpoint of obtaining UV absorbability (UV-cutting capability) used in image display devices because of their high UV absorbency. preferable.
Two or more ultraviolet absorbers having different maximum absorption wavelengths can be used in combination in order to widen the absorption width of ultraviolet rays.
Specific examples of the ultraviolet absorber include, for example, compounds described in paragraphs [0258] to [0259] of JP-A-2012-18395, paragraphs [0055] to [0105] of JP-A-2007-72163. and the like compounds described in.
In addition, as commercially available products, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, and Tinuvin1577 (all manufactured by BASF) can be used.

[Polarizer]
The polarizing plate of the present invention comprises the above optical film of the present invention and a polarizer.
Moreover, the polarizing plate of the present invention can be used as a circularly 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 circularly 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 The angle formed with the absorption axis is preferably 30 to 60°, more preferably 40 to 50°, even more preferably 42 to 48°, particularly preferably 45°.
The polarizing plate of the present invention can also be used as an optical compensation film for IPS or FFS liquid crystal display devices.
When the polarizing plate of the present invention is used as an optically compensatory film for an IPS or FFS liquid crystal display device, the above-mentioned optically anisotropic layer of the present invention is added to at least one of a laminate of a positive A plate and a positive C plate. plate, the angle formed by the slow axis of the positive A plate layer and the absorption axis of the polarizer described later is preferably orthogonal or parallel. Specifically, the slow axis of the positive A plate layer and More preferably, the angle formed with the absorption axis of the polarizer to be described later is 0 to 5° or 85 to 95°.
Here, the "slow axis" of the λ / 4 plate or positive A plate layer means the direction in which the refractive index is maximized in the plane of the λ / 4 plate or positive A plate layer, and the "absorption axis of the polarizer ” means the direction of highest absorbance.

[Polarizer]
The polarizer included in 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 absorptive polarizers and reflective polarizers can be used. .
As the absorbing polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a polyene-based polarizer, or the like is used. Iodine-based polarizers and dye-based polarizers include coating-type polarizers and stretching-type polarizers, and both can be applied. child is preferred.
In addition, as a method of obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 4691205, Patent No. 4,751,481 and Japanese Patent No. 4,751,486 can be cited, and known techniques relating to these polarizers can also be preferably used.
As a reflective polarizer, a polarizer in which thin films having different birefringences are laminated, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate are combined, and the like are used.
Among these, at least one selected from the group consisting of polyvinyl alcohol-based resins (polymers containing —CH ₂ —CHOH— as repeating units, particularly polyvinyl alcohol and ethylene-vinyl alcohol copolymers, in terms of better adhesion) 1).

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, even more preferably 3 μm to 10 μm.

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

[Adhesive layer]
In the polarizing plate of the invention, an adhesive layer may be arranged between the optically anisotropic layer in the optical film of the 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 by heating is preferred.
Examples of curable adhesive compositions include curable adhesive compositions containing cationic polymerizable compounds and curable adhesive compositions containing radically polymerizable compounds.
The thickness of the adhesive layer is preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm, even more preferably 0.05 to 5 μm. If the thickness of the adhesive layer is within this range, the protective layer or optically anisotropic layer laminated and the polarizer will not be lifted or peeled off, and practically satisfactory adhesive strength 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 liquid crystal cells, organic electroluminescence (hereinafter abbreviated as "EL") display panels, and plasma display panels.
Among these, liquid crystal cells and organic EL display panels are preferred, and liquid crystal cells are more preferred. 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, or an organic EL display device using an organic EL display panel as a display element, and is preferably a liquid crystal display device. more preferred.

[Liquid crystal display device]
A 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-described polarizing plate of the present invention and a liquid crystal cell.
In the present invention, of the polarizing plates provided on both sides of the liquid crystal cell, the polarizing plate of the present invention is preferably used as the front-side polarizing plate, and the polarizing plate of the present invention is used as the front-side and rear-side polarizing plates. is more preferred.
The liquid crystal cell constituting the liquid crystal display device will be described in detail below.

<Liquid crystal cell>
Liquid crystal cells used in liquid crystal display devices are VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, FFS (Fringe-Field-Switching) mode, or TN (Twisted Bend) mode. Nematic), but not limited to these.
In the TN mode liquid crystal cell, the rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted at an angle of 60 to 120°. TN mode liquid crystal cells are most commonly used as color TFT liquid crystal display devices, and are described in many documents.
In the VA mode liquid crystal cell, the rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied. VA mode liquid crystal cells include (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied and substantially horizontally aligned when voltage is applied (Japanese Unexamined Patent Application Publication No. 2-2002). 176625), and (2) a liquid crystal cell in which the VA mode is multi-domained (MVA mode) for widening the viewing angle (SID97, Digest of tech. Papers (preliminary collection) 28 (1997) 845). ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is performed when voltage is applied (Proceedings of the Japan Liquid Crystal Forum 58-59 (1998)) and (4) Survival mode liquid crystal cells (presented at LCD International 98). Moreover, any of PVA (Patterned Vertical Alignment) type, optical alignment type, and PSA (Polymer-Sustained Alignment) type may be used. Details of these modes are described in detail in JP-A-2006-215326 and JP-A-2008-538819.
In the IPS mode liquid crystal cell, the rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond planarly by applying an electric field parallel to the substrate surface. In the IPS mode, a black display is obtained when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are perpendicular to each other. A method of using an optical compensatory sheet to reduce leakage light during black display in an oblique direction and improve the viewing angle is disclosed in Japanese Patent Application Laid-Open Nos. H10-54982, H11-202323, and H9-292522. JP-A-11-133408, JP-A-11-305217 and JP-A-10-307291.

[Organic EL display device]
An organic EL display device, which is an example of the image display device of the present invention, includes, from the viewing side, a polarizer, a λ/4 plate (positive A plate) comprising the optically anisotropic layer of the present invention, and an organic EL display device. A preferred embodiment includes a display panel in this order.
Also, the organic EL display panel is a display panel configured using an organic EL element in which an organic light-emitting layer (organic electroluminescence layer) is 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 further detail based on examples below. The materials, amounts used, proportions, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below.

[Example 1]
[Preparation of protective film 1]
<Preparation of Core Layer Cellulose Acylate Dope 1>
A core layer cellulose acylate dope 1 was prepared by putting the following composition into a mixing tank and stirring to dissolve each component.
――――――――――――――――――――――――――――――――
Core layer cellulose acylate dope 1
――――――――――――――――――――――――――――――――
・Cellulose acetate having a degree of acetyl substitution of 2.88 100 parts by mass ・Ester oligomer (Compound 1-1 below) 10 parts by mass ・Durability improving agent (Compound 1-2 below) 4 parts by mass ・Ultraviolet absorber (Compound 1- below 3) 3 parts by weight methylene chloride (first solvent) 438 parts by weight methanol (second solvent) 65 parts by weight―――――――――――――――――――――――― ――――――――

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 was added 10 parts by mass of the following matting agent dispersion 1 to prepare an outer layer cellulose acylate dope 1 .
――――――――――――――――――――――――――――――――
Matting agent 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 1 part by mass――――――――――――――――――――――――――――――――

<Production 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 a casting port. In a state where the solvent content of the film on the drum is about 20% by mass, the film is stripped from the drum, and both ends in the width direction of the obtained film are fixed with tenter clips, and the residual solvent in the film is 3 to 15 mass. %, the film was stretched 1.2 times in the transverse direction and dried. Thereafter, the obtained film was conveyed between rolls of a 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 a hard coat layer, a hard coat curable composition (hard coat 1) shown in Table 4 below was prepared.

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

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

[Preparation of polarizing plate 1 with single-sided protective film]
(1) Saponification of film After immersing the prepared protective film 1 with a hard coat layer in a 4.5 mol/L sodium hydroxide aqueous solution (saponification solution) adjusted to 37°C for 1 minute, the film was washed with water, After that, it was immersed in a 0.05 mol/L sulfuric acid aqueous solution for 30 seconds, and then passed through a water washing bath. Then, the obtained film is repeatedly drained with an air knife three times, and after removing the water, it is dried by staying in a drying zone at 70 ° C. for 15 seconds to prepare a saponified protective film 1 with a hard coat layer. did.
(2) Fabrication of Polarizer According to the 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, stretching in the longitudinal direction. The polarizer manufactured in this manner was designated as polarizer 1.
(3) Bonding The thus obtained polarizer 1 and the saponified protective film 1 with a hard coat layer were bonded together using a 3% aqueous solution of PVA (PVA-117H, manufactured by Kuraray Co., Ltd.) as an adhesive. A polarizing plate 1 with a protective film on one side (hereinafter also simply referred to as "polarizing plate 1") was produced by roll-to-roll lamination so that the polarizing axis and the longitudinal direction of the film were perpendicular to each other. At this time, the cellulose acylate film side of the protective film was attached to the polarizer side.

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

[Production of protective film 2]
<Preparation of Core Layer Cellulose Acylate Dope 2>
A core layer cellulose acylate dope 2 was prepared by putting the following composition into a mixing tank and stirring to dissolve each component.
――――――――――――――――――――――――――――――――
Core layer cellulose acylate dope 2
――――――――――――――――――――――――――――――――
・100 parts by mass of cellulose acetate having a degree of acetyl substitution of 2.88 ・12 parts by mass of the following polyester ・4 parts by mass of the durability improving agent (above compound 1-2) ・430 parts by mass of methylene chloride (first solvent) ・Methanol (second 2 solvent) 64 parts by mass――――――――――――――――――――――――――――――――

Polyester (number average molecular weight 800)

<Production of Outer Layer Cellulose Acylate Dope 2>
To 90 parts by mass of the core layer cellulose acylate dope 2 was added 10 parts by mass of the following matting agent solution to prepare an outer layer cellulose acylate dope 2 .
――――――――――――――――――――――――――――――――
Matting agent 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――――――――――――――――――――――――――――――――

<Production of protective film 2>
The core layer cellulose acylate dope 2 and the outer layer cellulose acylate dope 2 were filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm. Three layers of the acylate dope 2 were simultaneously cast on a drum at 20° C. through a casting port (band casting machine).
Next, in a state where the solvent content of the film on the drum is about 20% by mass, the film is peeled off from the drum, both ends of the film in the width direction are fixed with tenter clips, and the film is stretched in the horizontal direction at a draw ratio of 1.1 times. It dried while drying.
Thereafter, the obtained film was further dried by transporting it between rolls of a heat treatment apparatus, and a cellulose acylate film 2 having a thickness of 40 μm was produced as a protective film 2 . As a result of measuring the retardation of protective film 2, Re=1 nm and Rth=-5 nm.

[Preparation of first optically anisotropic layer 1]
<Preparation of composition 1 for photo-alignment film>
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 butyl acetate/methyl ethyl ketone (80 parts by mass/20 parts by mass) to prepare a composition for a photo-alignment film. prepared the product.

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

Thermal acid generator D1

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

―――――――――――――――――――――――――――――――――
Optically anisotropic layer-forming composition 1
―――――――――――――――――――――――――――――――――
42.00 parts by mass of liquid crystal compound R1 below 42.00 parts by mass of liquid crystal compound R2 below 4.00 parts by mass of polyfunctional compound T1 below 12.00 parts by mass of polymerizable compound A1 below 0.00 part by mass of polymerization initiator S1 below 50 parts by mass 0.15 parts by mass of the following leveling agent P1 Hisolv MTEM (manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts by mass NK Ester A-200 (manufactured by Shin-Nakamura Chemical 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-dispersing liquid crystal compound A1 below represents a propylene group (a group in which a methyl group is substituted with an ethylene group), and the reverse-dispersing liquid crystal compound A1 below has positional isomerism in which the position of the methyl group is different. 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 are a:b:c=66:26:8 and show the content (mol %) of each repeating unit with respect to all repeating units in the resin. ]

<Production of first optically anisotropic layer 1>
The previously prepared composition 1 for photo-alignment film was applied to one surface of the produced protective film 2 using a bar coater. After coating, the film was dried on a hot plate at 120° C. for 5 minutes to remove the solvent and form a photoisomerizable composition layer having a thickness of 0.2 μm. A photo-alignment film 1 was formed by irradiating the obtained photoisomerizable composition layer with polarized ultraviolet rays (10 mJ/cm ² , using an ultra-high pressure mercury lamp).
Next, the previously prepared optically anisotropic layer-forming composition 1 was applied onto the photo-alignment 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. After that, the obtained film was kept at 60° C., and the orientation was fixed by ultraviolet irradiation (500 mJ/cm ² , using an ultra-high pressure mercury lamp) in a nitrogen atmosphere (oxygen concentration: 100 ppm). A tropic layer 1 was produced. 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, indicating reverse wavelength dispersion.

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

―――――――――――――――――――――――――――――――――
Optically anisotropic layer-forming composition 2
―――――――――――――――――――――――――――――――――
10.0 parts by mass of the liquid crystal compound R1 47.0 parts by mass of the liquid crystal compound R2 35.0 parts by mass of the liquid crystal compound R3 below 8.0 parts by mass of the polyfunctional compound T1 4.5 parts by mass of the polymerizable compound B1 below Part by mass 5.0 parts by mass of the following non-liquid crystal compound C1 Monomer K1 (A-600, manufactured by Shin Nakamura Chemical Co., Ltd.) 10.0 parts by mass 1.5 parts by mass of the polymerization initiator S1 The following surfactant Agent P2 0.4 parts by mass Surfactant P3 below 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 (% by 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 (% by mass) of each repeating unit with respect to all repeating units. ]

<Production of second optically anisotropic layer 1>
The coating side surface of the first optically anisotropic layer 1 was subjected to corona treatment at a discharge amount of 150 W·min/m ² , and the optically anisotropic layer-forming composition 2 was applied to the corona-treated surface with a wire bar. applied.
Then, it was heated with hot air at 70° C. for 90 seconds in order to dry the solvent of the composition and to ripen the orientation of the liquid crystal compound. Under a nitrogen purge, ultraviolet irradiation (300 mJ/cm ² ) is performed at 40° C. with an oxygen concentration of 0.1% to fix the orientation of the liquid crystal compound, and a second optically anisotropic layer is formed on the first optically anisotropic layer 1 . Layer 1 was made. The thickness direction retardation Rth2(550) 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 prepared first optically anisotropic layer 1 and the second optically anisotropic layer 1 on the side of the second optically anisotropic layer 1 was the polarizer surface of the prepared polarizing plate 1 with a protective film on one side. and bonded together using an adhesive so that the absorption axis of the polarizer and the slow axis of the optically anisotropic layer are parallel to each other. The protective film 2 of the first optically anisotropic layer 1 was peeled off, and the first polarizing plate of Example 1 was produced. As the adhesive, a 3% aqueous solution of PVA (PVA-117H manufactured by Kuraray Co., Ltd.) was used. At this time, the adhesion between the polarizer and the optical compensation layer was practically sufficient.

[Preparation of protective film 3]
<Preparation of PMMA (polymethyl methacrylate) dope>
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 ・Sumilizer 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 onto a stainless steel band (casting support) from a casting die (band casting machine).
Next, the film was peeled off in a state where the solvent content in the casting film was approximately 20% by mass, and both ends of the film in the width direction were fixed with tenter clips. .
After that, the obtained film was further dried by conveying it between rolls of a heat treatment apparatus, and a PMMA film having a thickness of 20 μm was produced as a protective film 3 .

[Preparation of second polarizing plate]
<Preparation of adhesive liquid>
Adhesive liquid A was prepared by mixing the following compounds at the stated ratio.
Aronix M-220 (manufactured by Toagosei Co., Ltd.): 20 parts by mass 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.): 40 parts by mass 2-ethylhexyl acrylate (manufactured by Mitsubishi Chemical Corporation): 40 parts by mass Irgacure 907 ( BASF): 1.5 parts by mass KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.): 0.5 parts by mass

The surface of the protective film 3 to which the polarizer was attached was subjected to corona treatment at 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. After that, the adhesive-coated surface was attached to the polarizer surface of the polarizing plate 2 with a single-sided protective film, and ultraviolet rays of 300 mJ/cm ² were irradiated from the substrate side of the protective film 3 at 40° C. in an air atmosphere. After that, it was dried at 60° C. for 3 minutes to prepare a second polarizing plate of Example 1.

[Fabrication of liquid crystal display device]
The front and back polarizing plates of a commercially available liquid crystal display device (iPad (registered trademark), manufactured by Apple Inc.) (liquid crystal display device including an FFS mode liquid crystal cell) were peeled off, and the first optically anisotropic layer 1 and the The first polarizing plate including the second optically anisotropic layer 1 is on the viewing 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 A liquid crystal display device of Example 1 was produced by bonding with a 20 μm acrylic pressure-sensitive adhesive so that the alignment direction of the liquid crystal in the cell was perpendicular to the absorption axis of the polarizer in the first polarizing plate.
In addition, the liquid crystal cell in the liquid crystal display 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. 2 nm. The Δn·d of the liquid crystal compound in the liquid crystal cell was 340, and the tilt angle between the liquid crystal compound and the substrate surface was 0.1°.

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

〔evaluation〕
<Front contrast (front CR)>
First, a liquid crystal display device for evaluation criteria was prepared in the same manner 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 devices prepared for Examples and Comparative Examples and evaluation criteria, the luminance (Yw) in the direction perpendicular to the panel in white display and the luminance (Yb) in the direction perpendicular to the panel in black display were measured on the market. The liquid crystal viewing angle was measured using a chromaticity characteristic measuring device Ezcontrast (manufactured by ELDIM), the contrast ratio (Yw / Yb) in the vertical direction to the panel was calculated, and the front contrast was evaluated according to the following criteria. . The results are shown in Table 5 below.
A: Front contrast is 90% or more with respect to the liquid crystal display device for evaluation reference B: Front contrast is 80% or more and less than 90% with respect to the liquid crystal display device for evaluation reference C: Liquid crystal display for evaluation reference with front contrast 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 a super xenon weather meter SX75.
At this time, a protective film 1 was sandwiched between the laminate and the super xenon weather meter SX75, and the laminate was arranged so that light was incident 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: Δb*≤2.0 for samples not exposed to the xenon weather meter
B: 2.0 < Δb* ≤ 4.0 for samples not exposed to the xenon weather meter
C: 4.0<Δb* for sample not exposed to 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 the xenon weathermeter
C: 10 nm<ΔRth for sample not exposed to xenon weather meter

The structures of the liquid crystal compounds and the non-liquid crystal compounds in Table 5 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, it was found that the light resistance of the optically anisotropic layer formed 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 optically anisotropic layer formed has good light resistance ( Examples 1-3).
In particular, from a comparison between Example 1 and Example 2, it was found that when the Ar core of the liquid crystal compound and the Ar core of the non-liquid crystal compound had the same structure, the contrast of the image display device was improved. .
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 has been found that the optically anisotropic layer formed has better light resistance.

REFERENCE SIGNS LIST 10 optical film 12 optically anisotropic layer 14 alignment film 16 support 18 hard coat layer

Claims (13)

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 a wavelength range of 250 nm or more and less than 400 nm,
The maximum absorption wavelength A and the maximum absorption wavelength B satisfy the relationship of the following formula (1),
A<B (1)
Both the liquid crystal compound and the non-liquid crystal compound are compounds having an aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-7),
The liquid crystal compound is a compound represented by the following formula (I),
A liquid crystal composition, wherein the non-liquid crystal compound is a compound represented by the following formula (II).

Here, in the above formulas (Ar-1) to (Ar-7),
* represents a binding position.
Q ¹ represents N or CH.
Q ² represents -S-, -O- or -N(R ⁶ )-, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ is an optionally substituted C 6-12 aromatic hydrocarbon group, an optionally substituted C 3-12 aromatic heterocyclic group, or a substituted represents an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, and one or more of —CH ₂ — constituting the alicyclic hydrocarbon group is —O—, —S— or —NH— may be substituted.
Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, monovalent aromatic heterocyclic group of 6 to 20 carbon atoms, halogen atom, cyano group, nitro group, -OR 7 , ^-NR 8 ^R 9 ^, -SR ¹⁰ , —COOR ¹¹ , or —COR ¹² , R ⁷ to R ¹² each 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 to form an 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-, and R ¹³ is a hydrogen atom or represents a substituent.
X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 which may be bonded to a substituent.
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 a combination of two or more thereof, wherein R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or a represents an alkyl group.
SP ³ and SP ⁴ each independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of —CH ₂ — represents a divalent linking group substituted with —O—, —S—, —NH—, —N(Q)—, or —CO—, and Q is a substituent represents
L3 and L4 ^{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 aromatic hydrocarbon rings and aromatic heterocyclic rings.
Ay has at least one aromatic ring selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon ring and an aromatic heterocyclic ring , represents an organic group having 2 to 30 carbon atoms.
The aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms.
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 each independently represent 0 or 1; 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 each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² —, —CR ³ ═CR ⁴ —, —NR ⁵ —, or a divalent linking group consisting of a combination of two or more thereof, wherein R ¹ to R ⁵ each independently represent a hydrogen atom , a fluorine atom or an alkyl group having 1 to 12 carbon atoms. However, when q1 is 2, a plurality of D2 ^may be the same or different.
G ¹ and G ² are each independently an optionally substituted aromatic ring having 6 to 20 carbon atoms or an optionally substituted divalent alicyclic ring having 5 to 20 carbon atoms. represents a cyclic hydrocarbon group, and one or more —CH ₂ — constituting the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—.
A ¹ and A ² are each independently an optionally substituted aromatic ring having 6 to 20 carbon atoms or an optionally substituted divalent alicyclic ring having 5 to 20 carbon atoms. represents a cyclic hydrocarbon group, and one or more —CH ₂ — constituting the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—.
SP ¹ and SP ² each independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of —CH ₂ — represents a divalent linking group substituted with —O—, —S—, —NH—, —N(Q)—, or —CO—, and Q is a substituent represents
L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar is an aromatic ring represented by the formula (Ar-3), at least one of L ¹ and L ² and L ³ and L ⁴ in the formula (Ar-3) is a polymerizable group represents
Ar represents any aromatic ring selected from the group consisting of the groups represented by formulas (Ar-1) to (Ar-7). However, when q1 is 2, a plurality of Ar may be the same or different.
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 formula (II),
g3 and g4 represent 0;
q2 represents 1 or 2;
D ⁹ and D ¹⁰ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ - , —NR ⁵ —, or a divalent linking group consisting of a combination of two or more thereof, wherein R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or a represents an alkyl group. However, when q2 is 2, the plurality of D ¹⁰ may be the same or different.
D ¹¹ and D ¹² represent single bonds.
G ³ and G ⁴ are each independently an optionally substituted aromatic ring having 6 to 20 carbon atoms or an optionally substituted divalent alicyclic ring having 5 to 20 carbon atoms. represents a cyclic hydrocarbon group, and one or more —CH ₂ — constituting the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—.
SP ⁵ and SP ⁶ each independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of —CH ₂ — represents a divalent linking group substituted with —O—, —S—, —NH—, —N(Q)—, or —CO—, and Q is a substituent represents
L5 and L6 ^{each independently} represent a monovalent organic group.
Ar represents any aromatic ring selected from the group consisting of the groups represented by formulas (Ar-1) to (Ar-7). However, when q2 is 2, a plurality of Ar may be the same or different. 2. The liquid crystal composition according to claim 1 , wherein said liquid crystal compound has reverse wavelength dispersion. 3. The liquid crystal composition according to claim 1 , wherein D ¹ and D ² in formula (I) represent -CO-O-. The liquid crystal composition according to any one of claims 1 to 3 , wherein D ⁹ and D ¹⁰ in formula (II) represent -O-. 5. The liquid crystal composition according to any one of claims 1 to 4 , wherein at least one of L ⁵ and L ⁶ in formula (II) represents a polymerizable group. Any aromatic ring selected from the group consisting of groups represented by the formulas (Ar-1) to (Ar-7) possessed by the liquid crystal compound, and the formula (Ar-1) possessed by the non-liquid crystal compound 6. The liquid crystal composition according to any one of claims 1 to 5 , wherein any one of the aromatic rings selected from the group consisting of groups represented by to (Ar-7) has the same structure. 7. The liquid crystal composition according to claim 1 , wherein the liquid crystal compound exhibits a smectic phase liquid crystal state. 8. The liquid crystal composition according to any one of claims 1 to 7 , wherein the content of said non-liquid crystal compound is 1 to 20 parts by mass with respect to 100 parts by mass of said liquid crystal compound. 9. The liquid crystal composition according to any one of claims 1 to 8 , wherein said maximum absorption wavelength A and said 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 9 . An optical film comprising the optically anisotropic layer according to claim 10 . A polarizing plate comprising the optical film according to claim 11 and a polarizer. An image display device comprising the optical film according to claim 11 or the polarizing plate according to claim 12 .

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