JP7285226B2 - Polymerizable liquid crystal composition, compound, optically anisotropic film, optical film, polarizing plate, and image display device - Google Patents

Description

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

Polymerizable liquid crystal compounds that exhibit reverse wavelength dispersion have characteristics such as the ability to accurately convert light wavelengths over a wide wavelength range, and the ability to make retardation films thinner due to their high refractive index. It has been extensively researched.
In addition, as a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion, a T-type molecular design guideline is generally taken, shortening the wavelength of the long axis of the molecule and lengthening the wavelength of the short axis located in the center of the molecule. are required to be transformed.
Therefore, it is known that a cycloalkylene skeleton having no absorption wavelength is used for connecting the skeleton of the short axis located in the center of the molecule (hereinafter also referred to as "reverse wavelength dispersion manifesting part") and the long axis of the molecule. (See Patent Documents 1 to 3, for example).

JP 2010-031223 A WO2014/010325 JP 2016-081035 A

The present inventors have studied Patent Documents 1 to 3, and found that the optically anisotropic film to be formed has durability such that the birefringence changes when exposed to high temperature and high humidity (hereinafter referred to as " It was clarified that there is a problem of "wet heat durability".
In addition, the inventors of the present invention have studied Patent Documents 1 to 3, and found that the formed optically anisotropic film has durability ( hereinafter also abbreviated as “amine resistance”).

Accordingly, the present invention provides a polymerizable liquid crystal composition, compound, optically anisotropic film, optical film, An object is to provide a polarizing plate and an image display device.

As a result of intensive studies aimed at achieving the above object, the present inventors have found that, when formed into an optically anisotropic layer, a polymerizable liquid crystal compound having a wavelength dispersion property within a predetermined numerical range and a compound represented by the formula (I-1) described later. By using a polymerizable liquid crystal composition blended with a compound represented by the present invention, the optically anisotropic film formed has excellent reverse wavelength dispersion, wet heat durability, and amine resistance. completed.
That is, the inventors have found that the above object can be achieved by the following configuration.

[1] containing a polymerizable liquid crystal compound and a compound represented by formula (I-1) described later,
A polymerizable liquid crystal composition in which an optically anisotropic layer prepared using a polymerizable liquid crystal compound satisfies the following formula (A).
1.00≦Re(450)/Re(550)≦1.10 (A)
Here, in the above formula (A), 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.
[2] The content of the compound represented by formula (I-1) described later is 3 to 70% by mass with respect to the total mass of the polymerizable liquid crystal compound and the compound represented by formula (I-1) described later. The polymerizable liquid crystal composition according to [1].
[3] The polymerizable liquid crystal composition according to [1] or [2], wherein the polymerizable liquid crystal compound is a compound represented by formula (II) described below.
[4] Total value X of the log P value of the group represented by Mes ¹ -L ¹ -X ¹ and the log P value of the group represented by Mes ² -L ² -X ² in formula (I-1) described later and,
The log P value and L ^{6 -SP 4} -D of the group represented by L 5 -SP ³ -D ¹⁰ -(A ³ ) _a1 -D ⁸ -(G ¹ ) _g1 -D ⁶ in formula (II) described later ¹¹ -(A ⁴ ) _a1 -D ⁹ -(G ² ) _g1 -D ⁷ The total value Y of the log P values of the groups represented by the absolute value of the difference is 3.0 or less, in [3] A polymerizable liquid crystal composition as described.
[5] The polymerization according to any one of [1] to [4], wherein Y ¹ in formula (Ar-1) described later is a group having a van der Waals volume of 1.1×10 ² Å ^{3 or} more. liquid crystal composition.
[6] X in the formula (Ar-2) described later represents a nonmetallic atom of Groups 14 to 16 to which a substituent may be attached;
When a substituent is attached to a nonmetallic atom, the substituent is an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group, a cyano group, an amino group, a nitro group, an alkylcarbonyl group, or a sulfo group. , and at least one substituent selected from the group consisting of hydroxyl groups.
[7] The polymerizable liquid crystal composition according to any one of [1] to [6], wherein the polymerizable liquid crystal compound is a compound having 4 or more ring structures.
[8] The polymerizable liquid crystal composition according to any one of [1] to [7], wherein X ¹ and X ² in formula (I-1) to be described later represent a linking group represented by —O—. .
[9] P in formula (I-2) described later represents any polymerizable group selected from the group consisting of groups represented by formulas (P-1) to (P-20) described later. , the polymerizable liquid crystal composition according to any one of [1] to [8].
[10] A compound represented by formula (I-1a) described later.

[11] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [9].
[12] The optically anisotropic film of [11], which satisfies the following formula (III).
0.50<Re(450)/Re(550)<1.00 (III)
Here, in formula (III), Re(450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re(550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm. represents
[13] An optical film having the optically anisotropic film of [11] or [12].
[14] A polarizing plate comprising the optical film of [13] and a polarizer.
[15] An image display device comprising the optical film of [13] or the polarizing plate of [14].

According to the present invention, a polymerizable liquid crystal composition, a compound, an optically anisotropic film, an optical film, which are used for forming an optically anisotropic film excellent in all of reverse wavelength dispersion, wet heat durability and amine resistance, A polarizing plate and an image display device can be provided.

FIG. 1A is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1B is a schematic cross-sectional view showing an example of the optical film of the present invention. FIG. 1C 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 X ¹ in I-1) is -CO-NR-, if the position bonded to the L ¹ side is *1 and the position bonded to the Ar ¹ side is *2, X ¹ is *1-CO-NR-*2 or *1-NR-CO-*2.

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a compound represented by formula (I-1) described later (hereinafter also abbreviated as "specific compound"). is.
Further, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound (hereinafter referred to as "low wavelength dispersion Also abbreviated as "liquid crystal compound").
1.00≦Re(450)/Re(550)≦1.10 (A)
Here, in the above formula (A), 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.
The values of in-plane retardation and retardation in the thickness direction refer to 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).

In the present invention, as described above, by using a polymerizable liquid crystal composition containing a low wavelength dispersion liquid crystal compound and a specific compound, the optically anisotropic film formed has reverse wavelength dispersion, wet heat durability and Both amine resistances are improved.
Although this is not clear in detail, the present inventors presume as follows.
That is, in formula (I-1) described later, the linking groups (X ¹ and X ² ) that bind to the aromatic rings (Ar ¹ and Ar ² ) are strong bonds that do not contain an ester bond. It is believed that the hydrolysis resistance was improved, and as a result, both the wet heat durability and the amine resistance were improved.
Further, the linking groups (L 1 and L 2 ) between the linking groups (X ¹ and X ² ) and the polymerizable group-containing groups ( ^{Mes 1} and Mes ² ) in formula (I- ¹ ) described later are methylene groups. By having a specific compound, the rotation of the specific compound is suppressed, the linearity of the molecule is improved, and as a result, the compatibility with the highly linear low wavelength dispersion liquid crystal compound is improved. It is considered that the wavelength dispersion is developed.
Each component of the polymerizable liquid crystal composition of the present invention will be described in detail below.

[Specific compound]
The specific compound contained in the polymerizable liquid crystal composition of the invention is a compound represented by the following formula (I-1).

In the above formula (I-1), Ar ¹ and Ar ² are each independently any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-3) represents
In the above formula (I-1), D ¹ is 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 number of carbon atoms Represents 1 to 4 alkyl groups.
In addition, p represents 0 or 1 in the above formula (I-1).
In formula (I-1) above, X ¹ and X ² each independently represent -O-, -S-, -CO-, -CO-NR ⁶ -, or a single bond, and R ⁶ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
In formula (I-1) above, both L ¹ and L ² represent a methylene group. However, the hydrogen atom contained in the methylene group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a C1-20 group. It may be substituted with an alkyl group.

In the above formula (I-1), p represents 0 or 1 as described above, but is 0, that is, D ¹ and Ar ² in the above formula (I-1) are not present. is preferred.

In the above formula (I-1), examples of the divalent linking group represented by one embodiment of D ¹ include -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 —, —CO—NR ⁵ —, and the like. R ¹ , R ² and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
Among these, any one of -CO-, -O- and -CO-O- is preferred.

In the above formula (I-1), X ¹ and X ² are preferably —O— or —S— for the reason that the optically anisotropic film to be formed has better wet heat durability, and — O- is more preferred.

In the above formula (I-1), Ar ¹ and Ar ² are each independently selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-3), as described above. represents an aromatic ring. In the following formulas (Ar-1) to (Ar-3), * represents the binding position with X ¹ or D ¹ for Ar ¹ , and the binding position with D ¹ or X ² for Ar ² . However, when p is 0, it represents the binding position with ^X1 or ^X2 .

In the above formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N(R ⁷ )-, and R ⁷ is a hydrogen atom or represents an alkyl group having 1 to 6 carbon atoms, and Y ¹ represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms; show.
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl. groups, n-pentyl groups, and n-hexyl groups.
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 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, and an alkenyl groups, 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 are preferred.
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 an isopropylcarbonyloxy group, more preferably a methylcarbonyloxy group.
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 present invention, Y ¹ in the above formula (Ar-1) has a van der Waals volume of 1.1×10 ² Å ³ or more because the optically anisotropic film to be formed has good light resistance. and more preferably a group having a van der Waals volume of 1.1×10 ² Å ³ or more and 1.8×10 ² Å ³ or less.
Here, the van der Waals volume refers to the volume of the region occupied by the van der Waals sphere based on the van der Waals radii of the atoms constituting the substituent. Correlation (Guidelines for drug design and mechanism of action research), 1979, Nankodo, pp. 134-136 calculated using the values and methods described.
Note that van der Waals volume units (Å3) can be converted to SI units with 1 Å ³ =10 ⁻³ nm ³ .

In the above formulas (Ar-1) to (Ar-3), Z ¹ and Z ² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a 20 monovalent alicyclic hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, halogen atom, cyano group, nitro group, —OR ⁸ , —NR ⁹ R ¹⁰ , or —SR ¹¹ , R ⁸ to R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form an aromatic ring.
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 or an ethyl group. , isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferred, methyl group, ethyl group, tert-butyl groups are 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).
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 ⁸ to R ¹¹ 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 the above formulas (Ar-2) and (Ar-3), A ¹ and A ² are each independently from -O-, -N(R ¹² )-, -S-, and -CO- represents a group selected from the group consisting of; R ¹² represents a hydrogen atom or a substituent;
Examples of the substituent represented by R ¹² 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.
Further, 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. is, for example, an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (e.g., a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, etc. is mentioned.

In the present invention, X in the above formula (Ar-2) represents a non-metallic atom of Groups 14 to 16 to which a substituent may be bound, and the non-metallic atom binds the substituent In this case, the substituents include alkyl groups, alkoxy groups, alkyl-substituted alkoxy groups, cyclic alkyl groups, and aryl groups (e.g., phenyl group , naphthyl group, etc.), cyano group, amino group, nitro group, alkylcarbonyl group, sulfo group, and hydroxyl group. It is considered that this is because the increased symmetry of the specific compound facilitates cross-linking.

In the above formula (Ar-3), D ⁴ and D ⁵ 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 4 carbon atoms.
Here, examples of the divalent linking group include the same groups as those described for D ¹ in formula (I-1) above.

In the above formula (Ar-3), SP ¹ and SP ² are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. 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 includes, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylhexylene group, heptylene group and the like. are preferably mentioned.

In the above formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group.
Examples of monovalent organic groups 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.

On the other hand, in the above formula (I-1), Mes ¹ and Mes ² each independently represent a polymerizable group-containing group represented by the following formula (I-2). In the following formula (I-2), * represents the binding position with L ¹ for Mes ¹ , and the binding position with L ² for Mes ² .

In the above formula (I-2), M is 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6 -diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1,3-dioxane-2,5-diyl group .
However, hydrogen atoms contained in these groups are fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, thioisocyano group, or C 1-20 may be substituted with an alkyl group of

In the above formula (I-2), D ² and D ³ each independently represent -O-, -S-, -OCH ₂ -, -CH ₂ CH ₂ -, -CO-, -COO-, -CO-S-, -OCO-O-, -CO-NH-, -SCH ₂ -, -CF ₂ O-, -CF ₂ S-, -CH=CH-COO-, -CH=CH-OCO- , -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -COO-CH ₂ -, -OCO-CH ₂ -, -CH=CH-, -N=N-, -CH=N- , -CH=NN=CH-, -CF=CF-, -C≡C-, or a single bond.

Further, in the above formula (I-2), SP is 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. represents a divalent linking group in which one or more of —CH ₂ — constituting is —O—, —S—, —NH—, —N(Q)—, or —CO—, and Q is , 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 includes, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylhexylene group, heptylene group and the like. are preferably mentioned.

In formula (I-2) above, P represents a polymerizable group.
As the polymerizable group, a polymerizable group capable of radical polymerization or cationic polymerization is preferred.
As the radically polymerizable group, generally known radically polymerizable groups can be used, and acryloyloxy groups and methacryloyloxy groups are preferred. 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 any polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-20). Among them, an acryloyloxy group or a methacryloyloxy group is more preferable. In the following formulas (P-1) to (P-20), * represents the bonding position with SP.

Further, in the above formula (I-2), n represents an integer of 2 or more, preferably an integer of 2 to 5, more preferably an integer of 2 to 4, and 2 or 3 is more preferred.
The plurality of Ms may be the same or different, the plurality of ^D2s may be the same or different, and the plurality of ^D3s may be the same or different. and the plurality of SPs may be the same or different.

Specific examples of the specific compound include compounds represented by the following formulas (1) to (14). Specifically, K ( Side chain structures) include compounds having side chain structures shown in Tables 1 and 2 below.
In Tables 1 and 2 below, "*" shown in the side chain structure of K represents the bonding position with the aromatic ring.
In the side chain structures represented by 1-2 and the like in Table 1 below, the groups adjacent to the acryloyloxy group and the methacryloyl group respectively represent a propylene group (a group in which a methyl group is substituted with an ethylene group), and methyl Represents a mixture of positional isomers that differ in the position of the groups.

In the present invention, for the reason that the optically anisotropic film to be formed is more likely to exhibit reverse wavelength dispersion, the content of the specific compound is set to It is preferably 3 to 70% by mass, more preferably 5 to 45% by mass, even more preferably 8 to 40% by mass, and particularly preferably 10 to 30% by mass.

[Polymerizable liquid crystal compound]
As described above, the polymerizable liquid crystal compound (low wavelength dispersion liquid crystal compound) contained in the polymerizable liquid crystal composition of the present invention is polymerizable so that the optically anisotropic layer prepared using the compound satisfies the following formula (A). It is a liquid crystal compound, preferably a polymerizable liquid crystal compound that satisfies the following formula (B), and more preferably a polymerizable liquid crystal compound that satisfies the following formula (C).
1.00≦Re(450)/Re(550)≦1.10 (A)
1.00≦Re(450)/Re(550)≦1.08 (B)
1.00≦Re(450)/Re(550)≦1.05 (C)
Here, in the above formulas (A) to (C), Re(450) represents the in-plane retardation of the optically anisotropic layer at a wavelength of 450 nm, and Re(550) represents the optically anisotropic layer at a wavelength of 550 nm. represents the in-plane retardation at .
As the optically anisotropic layer to be measured for the in-plane retardation, ie, the optically anisotropic layer produced using the polymerizable liquid crystal compound, the optically anisotropic layer produced by the following procedure is used.
That is, a polymerizable liquid crystal composition having the following composition is applied by spin coating to a rubbed glass substrate with a polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.).
Next, the coating film is heated and oriented at a temperature exhibiting liquid crystallinity to form a liquid crystal layer.
Next, the film is cooled to a temperature 40° C. lower than the temperature at which liquid crystallinity is exhibited, and orientation is fixed by irradiation with ultraviolet rays of 1000 mJ/cm ² to produce an optically anisotropic film.

―――――――――――――――――――――――――――――――――
Polymerizable liquid crystal composition――――――――――――――――――――――――――――――――――
・Polymerizable liquid crystal compound 15.00 parts by mass ・Photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass ・The following fluorine-containing compound A 0.12 parts by mass ・Chloroform 35.00 parts by mass ―――――――――――――――――――――――――――――

Fluorine-containing compound A

In the present invention, the low wavelength dispersion liquid crystal compound is preferably a compound represented by the following formula (II) for the reason of excellent liquid crystallinity.
L ⁵ -SP ³ -D ¹⁰ -(A ³ ) _a1 -D ⁸ -(G ¹ ) _g1 -D ⁶ -[Ar ³ -D ⁷ ] _q -(G ² ) _g2 -D ⁹ -(A ⁴ ) _a2 -D ¹¹ -SP ⁴ -L ⁶ (II)

In formula (II) 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.
Moreover, q represents 1 or 2 in said formula (II).
In the above formula (II), D ⁶ , D ⁷ , D ⁸ , D ⁹ , D ¹⁰ and D ¹¹ 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 4 carbon atoms. However, when q is 2, a plurality of D ⁷ may be the same or different.
In the above formula (II), G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, and alicyclic One or more —CH ₂ — constituting a hydrocarbon group may be substituted with —O—, —S— or —NH—.
In the above formula (II), A ³ and A ⁴ are each independently an optionally substituted aromatic ring having 6 or more carbon atoms, or an optionally substituted carbon number represents a cycloalkane ring of 6 or more.
In the above formula (II), 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 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, and at least one of L ¹ and L ² represents a polymerizable group.

In formula (II) above, all of a1, a2, g1 and g2 are preferably 1.
Moreover, q is preferably 1 in the above formula (II).

In the above formula (II), the divalent linking group represented by one embodiment of D ⁶ , D ⁷ , D ⁸ , D ⁹ , D ¹⁰ and D ¹¹ includes D ¹ in the above formula (I-1) Examples are the same as those described above.

In formula (II) above, the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G ¹ and G ² is preferably a 5- or 6-membered ring. 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 above formula (II), the substituents that the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms may have for G ¹ and G ² include the above-mentioned formula (Ar-1 ) and the same substituents that Y ¹ may have.

In the above formula (II), examples of aromatic rings having 6 or more carbon atoms represented by ^A3 and ^A4 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, and phenanthroline ring; furan ring; Aromatic heterocycles such as pyrrole ring, thiophene ring, pyridine ring, thiazole ring, and benzothiazole ring; Among them, a benzene ring (eg, 1,4-phenyl group, etc.) is preferred.
In the above formula (II), examples of the cycloalkane ring having 6 or more carbon atoms represented by A ³ and A ⁴ include cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclododecane ring, cyclodocosane ring and the like. Among them, a cyclohexane ring (eg, 1,4-cyclohexylene group) is preferred, and a trans-1,4-cyclohexylene group is more preferred.
Regarding A ³ and A ⁴ , the substituent that the aromatic ring having 6 or more carbon atoms or the cycloalkane ring having 6 or more carbon atoms may have is Y ¹ in the above formula (Ar-1). The same substituents as those which may be possessed may be mentioned.

In the above formula (II), the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ³ and SP ⁴ is as described for SP ¹ and SP ² in the above formula (Ar-3). The same thing as a thing is mentioned. In SP ³ and SP ⁴ , 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 in the above formula (Ar-1) The substituents which ¹ may have may be mentioned.

In the above formula (II), examples of monovalent organic groups represented by ^L5 and ^L6 include an alkyl group, an aryl group, and a heteroaryl group. 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 those similar to the substituent that Y ¹ in the above formula (Ar-1) may have.

In formula (II), the polymerizable group represented by at least one of L ⁵ and L ⁶ includes the same groups as those described for P in formula (I-3) above.

In the above formula (II), both L ⁵ and L ⁶ in the above formula (II) are preferably polymerizable groups, such as an acryloyloxy group or a methacryloyloxy group, for the reason that durability is improved. is more preferable.

On the other hand, in the above formula (II), Ar ³ represents an aromatic ring which may have a substituent. However, when q is 2, a plurality of Ar ³ may be the same or different.
Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthroline rings; aromatic rings such as furan, pyrrole, thiophene, pyridine, thiazole and benzothiazole rings; heterocycle; Among them, a benzene ring (eg, 1,4-phenyl group, etc.) is preferred.
Examples of the substituent that the aromatic ring may have include the same substituents that Y ¹ in the above formula (Ar-1) may have.

In the present invention, the low-wavelength dispersion liquid crystal compound preferably has 4 or more ring structures, more preferably 5, because liquid crystallinity is easily exhibited.

Specific examples of the low wavelength dispersion liquid crystal compound preferably include compounds represented by the following formulas (15) to (17), specifically, the following formulas (15) to (17) Examples of K (side chain structure) in the above include compounds having side chain structures shown in Tables 1 and 2 above.

In the present invention, the content of the low-wavelength-dispersion liquid crystal compound is higher than that of the specific compound and the low-wavelength-dispersion liquid crystal compound, because the optically anisotropic film to be formed is more likely to exhibit reverse wavelength dispersion. It is preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total mass. The upper limit is preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less.

In the present invention, the ^logP value ^and the ^{Mes 2} -L ² -X The total value X of the log P values of the groups represented by ² and L ⁵ -SP ³ -D ¹⁰ -(A ³ ) _a1 -D ⁸ -(G ¹ ) in the above formula (II) sum of the logP values of the group represented by _g1 - ^D6 and the logP values of the group represented by ^L6 - ^SP4 - ^D11- ( ^A4 ) _a1 - ^D9- ( ^G2 ) _g1 - ^D7 It is preferable to use a combination of the specific compound and the low wavelength dispersion liquid crystal compound so that the absolute value of the difference between Y and Y is 3.0 or less.
Here, the logP value is an index that expresses the hydrophilicity and hydrophobicity of a chemical structure, and is sometimes called a hydrophilicity/hydrophobicity parameter. LogP values can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver.4.1.07). Also, OECD Guidelines for the Testing of Chemicals, Sections 1, Test No. It can also be obtained experimentally by the method of 117 or the like. In the present invention, unless otherwise specified, the value calculated by inputting the structural formula of the compound into HSPiP (Ver.4.1.07) is employed as the logP value.

[Other polymerizable compounds]
The polymerizable liquid crystal composition of the present invention may contain other polymerizable compounds having one or more polymerizable groups in addition to the low wavelength dispersion liquid crystal compound described above.
Here, the polymerizable group possessed by the other polymerizable compound is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group and an allyl group. Among them, it is preferable to have an acryloyl group or a methacryloyl group.

Other polymerizable compounds include compounds described in paragraphs [0073] to [0074] of JP-A-2016-053709.
Further, other polymerizable compounds include compounds represented by formulas (M1), (M2), and (M3) described in paragraphs [0030] to [0033] of JP-A-2014-077068. More specifically, specific examples described in paragraphs [0046] to [0055] of the publication can be mentioned.
Further, as other polymerizable compounds, those having structures of formulas (1) to (3) described in JP-A-2014-198814 can also be preferably used, and more specifically, [0020 ] to [0035], [0042] to [0050], and [0056] to [0057].

The content when such other polymerizable compound is contained is preferably less than 50% by mass, more preferably 40% by mass or less, relative to the mass of the low wavelength dispersion liquid crystal compound described above. It is preferably 2 to 30% by mass, and more preferably 2 to 30% by mass.

[Polymerization initiator]
The polymerizable 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 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 polymerizable liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability for forming an optically anisotropic film.
Specific examples of the solvent include ketone solvents (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ether solvents (eg, dioxane, tetrahydrofuran, etc.), cyclic amide solvents, Solvents (e.g., N-methylpyrrolidone, N-ethylpyrrolidone, N,N'-dimethylimidazolidinone, etc.), aliphatic hydrocarbon solvents (e.g., hexane, etc.), alicyclic hydrocarbon solvents (e.g., cyclohexane etc.), aromatic hydrocarbon solvents (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbon solvents (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), ester solvents (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohol solvents (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolve solvents (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetate solvents, sulfoxide solvents ( For example, dimethyl sulfoxide, etc.), linear amide solvents (eg, dimethylformamide, dimethylacetamide, etc.), etc., may be used alone, or two or more thereof may be used in combination.

In the present invention, among the solvents described above, at least one solvent selected from the group consisting of ketone solvents, ether solvents and cyclic amide solvents is used because the effect of the present invention for suppressing an increase in filtration pressure is manifested. It is preferably a seed solvent.

[Leveling agent]
The polymerizable liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the optically anisotropic film smooth and facilitating alignment control.
Such a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because it has a high leveling effect with respect 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] ~ [0084] paragraph), compounds represented by general formulas (I), (II) and (III) described in JP-A-2005-099248 (especially [0092] to [0096] paragraphs compounds described in ) and the like. In addition, it may also have a function as an alignment control agent, which will be described later.

[Orientation control agent]
The polymerizable liquid crystal composition of the invention may contain an alignment control agent, if necessary.
The alignment control agent can form various alignment states such as homogenous alignment, homeotropic alignment (perpendicular alignment), tilt 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 alignment 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] paragraphs of JP-A-2012-208397, [0024]-[0055] paragraphs of JP-A-2008-026730, [0043]-[0055] of JP-A-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 polymerizable liquid crystal composition of the present invention, and the direction of chirality can control the turning direction of 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 thereof is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid mass in the polymerizable liquid crystal composition. more preferred. When the content is within this range, a uniform and highly transparent optically anisotropic film can be obtained without precipitation, phase separation, orientation defects, etc., while realizing a desired orientation state.
These alignment control agents can further impart a polymerizable functional group, particularly a polymerizable functional group capable of polymerizing with the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention.

[Other ingredients]
The polymerizable liquid crystal composition of the present invention may contain components other than the components described above. agents, cross-linking agents, and the like.

[Compound]
The compound of the present invention is a compound represented by the following formula (I-1a).

Here, the compound represented by the above formula (I-1a) is Ar ¹ and Ar ² in the above formula (I-1) among the specific compounds contained in the polymerizable liquid crystal composition of the present invention. is limited to the aromatic ring represented by the above formula (Ar-1) or (Ar-2), and the van der Waals volume of Y ¹ in the above formula (Ar-1) is 1.1 × 10 ² Å ³ or more, and when X in the above formula (Ar-1) represents a nonmetallic atom of Groups 14 to 16 to which a substituent is bonded, the substituent is an alkyl group or an alkoxy group , an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group, a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, and a hydroxyl group. is.

[Optically anisotropic film]
The optically anisotropic film of the present invention is an optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition of the present invention described above.
As a method for forming an optically anisotropic film, for example, a method of using the above-described polymerizable liquid crystal composition of the present invention to achieve a desired alignment state and then fixing the composition by polymerization can be used. In particular, in the present invention, it is preferable to form an optically anisotropic film after the step of storing the polymerizable liquid crystal composition of the present invention after preparing it.
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 film can be formed on an arbitrary 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 film of the present invention preferably satisfies the following formula (III).
0.50<Re(450)/Re(550)<1.00 (III)
Here, in the above formula (III), Re(450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re(550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm. represents a date. In this specification, unless the measurement wavelength of retardation is specified, the measurement wavelength is 550 nm.

The optically anisotropic film of the invention is preferably a positive A plate or a positive C plate, more preferably a positive A plate.

Here, a positive A plate (positive A plate) and a 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 film of the present invention is a positive A plate, Re(550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, from the viewpoint of functioning as a λ/4 plate. It is more preferably 130 to 150 nm, particularly preferably 130 to 140 nm.
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 film of the invention.
FIGS. 1A, 1B, and 1C (hereinafter abbreviated as “FIG. 1” when there is no particular need to distinguish between these drawings) are schematic cross-sectional views each showing an example of the optical film of the present invention.
Note that FIG. 1 is a schematic diagram, and the thickness relationship and positional relationship of each layer do not necessarily match the actual ones. It is a member.
The optical film 10 shown in FIG. 1 has a support 16, an alignment film 14, and an optically anisotropic film 12 in this order.
Further, the optical film 10 may have a hard coat layer 18 on the side opposite to the side of the support 16 on which the alignment film 14 is provided, as shown in FIG. 1B, and as shown in FIG. A hard coat layer 18 may be provided on the side of the optically anisotropic film 12 opposite to the side on which the alignment film 14 is provided.
Various members used in the optical film of the present invention are described in detail below.

[Optical anisotropic film]
The optically anisotropic film of the optical film of the present invention is the optically anisotropic film of the present invention described above.
In the optical film of the present invention, the thickness of the optically anisotropic film 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 an optically anisotropic film, 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, and materials for the 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 30 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 film. In addition, the above-described support may also serve as an alignment film.

The alignment film is generally composed mainly of polymer. 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.
The alignment film that can be used in the present invention includes, for example, the alignment film 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.
The photo-alignment film is not particularly limited, but 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.

[Hard coat layer]
The optical film of the invention preferably has a hard coat layer in order to impart physical strength to the film. Specifically, a hard coat layer may be provided on the opposite side of the support to the side on which the alignment film is provided (see FIG. 1B). may have a hardcoat layer on the opposite side (see FIG. 1C).
As the hard coat layer, those described in paragraphs [0190] to [0196] of JP-A-2009-98658 can be used.

[Other optically anisotropic films]
The optical film of the invention may have another optically anisotropic film apart from the optically anisotropic film of the invention.
That is, the optical film of the invention may have a laminated structure of the optically anisotropic film of the invention and another optically anisotropic film.
Such other optically anisotropic film is an optically anisotropic film obtained by using the above-described reverse wavelength dispersion liquid crystal compound or other polymerizable compound (especially liquid crystal compound) without blending the above-described specific compound. It is not particularly limited as long as it is a film.
Here, liquid crystal compounds can generally be classified into a rod-like type and a disk-like type according to their shape. Furthermore, there are low-molecular-weight and high-molecular-weight types, respectively. Polymers generally refer to those having a degree of polymerization of 100 or more (Polymer Physics: Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). Although any liquid crystal compound can be used in the present invention, it is preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound (disk-like liquid crystal compound). Two or more kinds of rod-like liquid crystal compounds, two or more kinds of discotic liquid crystal compounds, or mixtures of rod-like liquid crystal compounds and discotic liquid crystal compounds may be used. For immobilization of the liquid crystal compound described above, it is more preferable to form using a rod-like liquid crystal compound or discotic liquid crystal compound having a polymerizable group, and the liquid crystal compound may have two or more polymerizable groups in one molecule. More preferred. In the case of a mixture of two or more liquid crystal compounds, at least one liquid crystal compound preferably has two or more polymerizable groups in one molecule.
As the rod-like liquid crystal compound, for example, those described in claim 1 of JP-A-11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and discotic As the liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 can be preferably used. but not limited to these.

[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 film of the invention, or may be contained in a member other than the optically anisotropic film constituting the optical film of the invention. Examples of suitable members other than the optically anisotropic film 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 (ultraviolet cut ability) used in image display devices because of their high UV absorbency. preferable.
Moreover, 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 film of the present invention is a λ/4 plate (positive A plate).
Further, in the polarizing plate of the present invention, when the above-mentioned optically anisotropic film of the present invention is a λ/4 plate (positive A plate), the slow axis of the λ/4 plate and the absorption axis of the polarizer, which will be described later, The angle formed by the two is preferably 30 to 60°, more preferably 40 to 50°, even more preferably 42 to 48°, and particularly preferably 45°.
Here, the "slow axis" of the λ / 4 plate means the direction in which the refractive index is maximized in the plane of the λ / 4 plate, and the "absorption axis" of the polarizer means the direction of the highest absorbance do.

[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, and the like are 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, there are disclosed in Japanese Patent Nos. 5048120, 5143918, 4691205, and 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 the 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 them, polyvinyl alcohol-based resins (polymers containing —CH ₂ —CHOH— as repeating units, particularly polyvinyl alcohol and ethylene-vinyl alcohol copolymers) are selected from the group consisting of at least one ) is preferably a polarizer.

In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 30 μm, even more preferably 5 μm to 15 μm.

[Adhesive layer]
In the polarizing plate of the invention, a pressure-sensitive adhesive layer may be arranged between the optically anisotropic film in the optical film of the invention and the polarizer.
As the pressure-sensitive adhesive layer used for laminating the optically anisotropic film and the polarizer, for example, the ratio of the storage elastic modulus G′ to the loss elastic modulus G″ measured by a dynamic viscoelasticity measuring device (tan δ= G″/G′) refers to substances with a ratio of 0.001 to 1.5, including 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.

[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 preferable, and liquid crystal cells are more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, 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 polarizing plate of the present invention described above 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) mode is preferred, but not limited to these.
In the TN mode liquid crystal cell, the rod-like liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are twisted at 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, 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). In addition, 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 Japanese Unexamined Patent Application Publication No. 2006-215326 and Japanese National Publication of International Patent Application No. 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. 10-54982, 11-202323 and 9-292522. 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) made of the optically anisotropic film 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 more detail below based on examples. 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.

[Synthesis of specific compound (I-1-1)]

As shown in the scheme above, 100 g of trans-4-hydroxycyclohexanecarboxylic acid and 79.6 g of triethylamine were mixed with 300 mL of DMAc (dimethylacetamide) and 200 mL of toluene. Then, the inside temperature was heated to 85° C., and 74.0 g of benzyl bromide was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred at an internal temperature of 85°C for 1 hour, cooled to 45°C, and 200 ml of toluene was added. After the obtained solution was concentrated by an evaporator, 100 ml of ethyl acetate and 200 ml of hexane were added, and the precipitated solid was collected by filtration to obtain compound (I-1-1a).

Then, 40.0 g of compound (I-1-1a) was mixed with 400 mL of THF (tetrahydrofuran). Then, the internal temperature was cooled to 10° C., and 140 ml of borane-tetrahydrofuran complex (8.5% tetrahydrofuran solution) was slowly added dropwise. After the dropwise addition, the mixture was stirred at an internal temperature of 10° C. for 1 hour, and then separated with 250 ml of dilute hydrochloric acid, twice with saturated saline, and once with an aqueous sodium hydrogen carbonate solution. After concentrating the resulting solution with an evaporator, 100 mL of hexane was added, and the precipitated solid was collected by filtration to obtain compound (I-1-1b).

Then, 38.5 g of compound (I-1-1b) and 14.1 g of methanesulfonyl chloride were mixed with 385 mL of ethyl acetate. Then, the internal temperature was cooled to 10° C., and 14.1 g of triethylamine was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at an internal temperature of 10° C. for 1 hour, and then separated once with 250 ml of dilute hydrochloric acid, once with saturated brine, and once with an aqueous sodium hydrogen carbonate solution. The resulting solution was concentrated by an evaporator and purified by column chromatography to obtain compound (I-1-1c).

Then, 17.3 g of compound (I-1-1c), 5.00 g of compound (I-1-1d), and 8.35 g of potassium carbonate were mixed with 150 ml of DMAc. Then, the mixture was heated to an internal temperature of 85°C and stirred for 6 hours. After that, the temperature was returned to room temperature (23° C.), water was added, and the precipitated solid was taken out by filtration. The collected solid was mixed with methanol and stirred at room temperature for 1 hour, after which the solid was collected by filtration to obtain compound (I-1-1e).

Then, 2.00 g of compound (I-1-1e) was mixed with 350 ml of THF and 65 ml of ethanol. Then, the internal temperature was heated to 50° C., 9.20 ml of 40% aqueous sodium hydroxide solution was added, and the mixture was stirred for 2 hours. Thereafter, the temperature was returned to room temperature (23° C.), 10.0 ml of dilute hydrochloric acid was added, the mixture was concentrated by an evaporator, and the precipitated solid was collected by filtration. The collected solid was mixed with methanol and stirred at room temperature for 1 hour, after which the solid was collected by filtration to obtain compound (I-1-1f).

Then, 1.00 g of compound (I-1-1f) and 0.100 g of dibutylhydroxytoluene were mixed with 10.0 mL of THF and 10.0 ml of DMAc. Then 0.263 ml of thionyl chloride was added and stirred for 30 minutes. After that, 0.70 g of compound (I-1-1 g) and 0.832 mL of diisopropylethylamine were added and stirred for 30 minutes. Next, methanol was added, the precipitated solid was filtered out, and the resulting solid was purified by column chromatography to obtain 0.234 g of compound (I-1-1) (yield 17%).
¹ H-NMR (Nuclear Magnetic Resonance) data of the obtained compound (I-1-1) are shown below.
¹ H NMR (CDCl ₃ ) δ (ppm) = 1.09 (m, 16H), 1.44 (m, 4H), 1.70-2.05 (m, 26H), 2.21 (m, 2H) , 3.85 (m, 4H), 4.12 (m, 4H), 4.22 (m, 4H), 5.85 (m, 2H), 6.15 (m, 2H), 6.45 ( m, 2H), 6.74 (s, 2H)

[Synthesis of specific compound (I-1-4)]
Instead of the compound (I-1-1d), except for using the compound 11-d described in paragraphs [0282] to [0290] of JP-A-2013-71956, the above specific compound (I-1-1) A specific compound (I-1-4) was synthesized in the same manner as the synthesis method of.

[Synthesis of other specific compounds]
In place of compound (I-1-1c) and/or compound (I-1-1d), a compound having a mesylate group synthesized using a conventional method and/or phenol, depending on the structure of the specific compound to be synthesized Other specific compounds were synthesized in the same manner as the synthesis method of the specific compound (I-1-1) except that the compound was used.

[Example 1]
[Preparation of optical film]
A polymerizable liquid crystal composition having the following composition was prepared and applied to a rubbed glass substrate with a polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.) by spin coating.
The coating film was subjected to orientation treatment at the temperature shown in Table 3 below to form a liquid crystal layer.
Thereafter, the film was cooled to the exposure temperature shown in Table 3 below, and orientation was fixed by irradiation with ultraviolet rays of 1000 mJ/cm ² to form an optically anisotropic film, thereby producing an optical film.

―――――――――――――――――――――――――――――――――
Coating solution for optically anisotropic layer――――――――――――――――――――――――――――――――――
· The following polymerizable liquid crystal compound (II-1) 12.00 parts by mass · The following specific compound (I-1-1) 3.00 parts by mass · Photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass・ 0.12 parts by mass of the following fluorine-containing compound A ・ 35.00 parts by mass of chloroform ―――――――――――――――――――――――――――――――― ―

Polymerizable liquid crystal compound (II-1)

Specific compound (I-1-1)

Fluorine-containing compound A

[Examples 2 to 10]
An optical film was produced in the same manner as in Example 1, except that the polymerizable liquid crystal compound or specific compound was changed to the compound shown in Table 3 below.

[Comparative Examples 1 and 2]
An optical film was produced in the same manner as in Example 1, except that the polymerizable liquid crystal compound or specific compound was changed to the compound shown in Table 3 below.

<log P value>
For the polymerizable liquid crystal compounds and specific compounds used in Examples ^and Comparative Examples, ^the log P ^value and Mes ² the total value X of the logP values of the groups represented by -L ² -X ² and L ⁵ -SP ³ -D ¹⁰ -(A ³ ) _a1 -D ⁸ -(G ¹ ) _g1 in the above formula (II) sum Y of the log P values of the group represented by -D ⁶ and the log P values of the group represented by L ⁶ -SP ⁴ -D ¹¹ -(A ⁴ ) _a1 -D ⁹ -(G ² ) _g1 -D ⁷ and the absolute value of the difference (ΔlogP) was calculated. The results are shown in Table 3 below.

<Van der Waals volume>
Among the specific compounds used in Examples and Comparative Examples, specific compound (I-1-4), specific compound (I-1-5) and specific compound (I-1-7) were prepared by the method described above. , the van der Waals volume of the structure corresponding to Y ¹ in the above formula (Ar-1) was calculated. The results are shown in Table 3 below.

<Retardation>
The retardation value (Re(450)) at a wavelength of 450 nm and the retardation value (Re(550)) at a wavelength of 550 nm were measured using Axo Scan (OPMF-1, manufactured by Optoscience) for the produced optical film. was measured and Re(450)/Re(550) was calculated. These results are shown in Table 3 below.
Further, the optically anisotropic layer prepared by the method described above using the polymerizable liquid crystal compounds used in Examples and Comparative Examples also had a retardation value (Re(450)) at a wavelength of 450 nm and a retardation value at a wavelength of 550 nm. A value (Re(550)) was measured, and Re(450)/Re(550) was calculated. These results are shown in Table 3 below.

<Damp heat durability>
As the wet heat durability test condition, a test was conducted in which the sample was left for 500 hours in an environment of 85° C. and a relative humidity of 85%.
Re (550) of the optical film before the test and Re (550) of the optical film after the test were measured, and wet heat durability was evaluated according to the following criteria. The results are shown in Table 3 below.
A: The amount of change in Re (550) after the test relative to Re (550) before the test is less than 10% of Re (550) before the test B: Re (550) after the test relative to Re (550) before the test The amount of change is 10% or more and less than 30% of Re (550) before test C: The amount of change in Re (550) after test relative to Re (550) before test is 30% or more of Re (550) before test

<Amine resistance>
Amine resistance was tested under the condition that a 2 mol % solution of NH ₃ /MeOH was put into a vial, an optical film was placed at the outlet of the vial, and the test was left for 10 hours.
The Re (550) of the optical film before the test and the Re (550) of the optical film after the test were measured, and the amine resistance was evaluated according to the following criteria. The results are shown in Table 3 below.
A: The amount of change in Re (550) after test relative to Re (550) before test is less than 10% of Re (550) before test B: Re (550) after test relative to Re (550) before test The amount of change is 10% or more and less than 30% of Re (550) before test C: The amount of change in Re (550) after test relative to Re (550) before test is 30% or more of Re (550) before test

<Light resistance>
For the prepared optical film, the glass substrate was set in a xenon irradiation machine (SX75 manufactured by Suga Test Instruments Co., Ltd.) so that the coating film of the polymerizable liquid crystal composition became the irradiation surface, and a #275 filter was used for 200 hours. An irradiation test was performed.
The Re (550) of the optical film before the test and the Re (550) of the optical film after the test were measured, and the light resistance was evaluated according to the following criteria. The results are shown in Table 3 below.
A: The amount of change in Re (550) after the test relative to Re (550) before the test is less than 5% of Re (550) before the test B: Re (550) after the test relative to Re (550) before the test The amount of change is 5% or more and less than 15% of Re (550) before test C: The amount of change in Re (550) after test relative to Re (550) before test is 15% or more of Re (550) before test

The structures of the polymerizable liquid crystal compounds and the like in Table 3 are as shown below.

Polymerizable liquid crystal compound (II-1)

Polymerizable liquid crystal compound (II-2)

Polymerizable liquid crystal compound (II-3)

Polymerizable liquid crystal compound (II-4)

Polymerizable liquid crystal compound (II-5) [comparative compound]

Specific compound (I-1-1)

Specific compound (I-1-2)

Specific compound (I-1-3)

Specific compound (I-1-4)

Specific compound (I-1-5)

Specific compound (I-1-6)

Specific compound (I-1-7)

Specific compound (I-1-8) [comparative compound]

From the results shown in Table 3, it was found that when the specific compound was not blended, the optically anisotropic film formed was inferior in reverse wavelength dispersion, wet heat durability, and amine resistance, and was also inferior in light resistance ( Comparative example 1).
It was also found that the optically anisotropic film formed did not exhibit reverse wavelength dispersion when the low wavelength dispersion liquid crystal compound was not blended (Comparative Example 2).
On the other hand, it was found that an optically anisotropic film excellent in all of reverse wavelength dispersion, wet heat durability and amine resistance can be formed when a low wavelength dispersion liquid crystal compound and a specific compound are blended (Example 1-10).
In particular, from the comparison between Example 2 and Example 9, the log P value of the group represented by Mes ¹ -L ¹ -X ¹ in the above formula (I-1) and Mes ² -L ² -X ² and the group represented by L ⁵ -SP ³ -D ¹⁰ -(A ³ ) _a1 -D ⁸ -(G ¹ ) _g1 -D ⁶ in the above formula (II) and the total value Y of the log P values of the group represented by L ⁶ -SP ⁴ -D ¹¹ -(A ⁴ ) _a1 -D ⁹ -(G ² ) _g1 -D ⁷ and the absolute value of the difference between When the specific compound and the low wavelength dispersion liquid crystal compound are used in combination so that the value becomes 3.0 or less, the reverse wavelength dispersion of the formed optically anisotropic film is improved, and the light resistance is also improved. rice field.
In addition, from the comparison of Examples 7, 8 and 10, it can be seen that when Y ¹ in the above formula (Ar-1) is a group having a van der Waals volume of 1.1×10 ² Å ^{3 or} more, the optical It was found that the reverse wavelength dispersion of the anisotropic film was improved, and the light resistance was also improved.

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

Claims (14)

containing a polymerizable liquid crystal compound and a compound represented by the following formula (I-1),
A polymerizable liquid crystal composition in which an optically anisotropic layer prepared using the polymerizable liquid crystal compound satisfies the following formula (A).
1.00≦Re(450)/Re(550)≦1.10 (A)
Here, in the formula (A), 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 internal retardation.

Here, in the formula (I-1),
Ar ¹ and Ar ² each independently represent any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar- 2 ) and (Ar-3).
D ¹ is a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or , represents 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 4 carbon atoms.
p represents 0 or 1;
X ¹ and X ² each independently represent -O-, -S-, -CO-, -CO-NR ⁶ -, or a single bond, and R ⁶ each independently represents a hydrogen atom or a fluorine atom , or represents an alkyl group having 1 to 4 carbon atoms.
Both L ¹ and L ² represent a methylene group. However, the hydrogen atom contained in the methylene group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a C1-20 group. may be substituted with an alkyl group of
Mes ¹ and Mes ² each independently represent a polymerizable group-containing group represented by the following formula (I-2).

Here, in the above formulas (Ar- 2 ) and (Ar-3),
* represents the binding position with ^X1 or ^D1 for ^Ar1 , and the binding position with ^D1 or ^X2 for ^Ar2 .
Z ¹ and Z ² are each independently 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, or 6 to 20 carbon atoms. a monovalent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, —OR ⁸ , —NR ⁹ R ¹⁰ , or —SR ¹¹ , wherein R ⁸ to R ¹¹ each independently represent a hydrogen atom Alternatively, it represents an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form an aromatic ring.
A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -N(R ¹² )-, -S- and -CO-, and R ¹² 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 ⁴ and D ⁵ 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 represents an alkyl group.
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
^L3 and ^L4 each independently represent a monovalent organic group.

Here, in the formula (I-2),
* represents the binding position with ^L1 for ^Mes1 , and the binding position with ^L2 for ^Mes2 .
M is a 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4 -diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1,3-dioxane-2,5-diyl group. However, hydrogen atoms contained in these groups are fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, thioisocyano group, or C 1-20 may be substituted with an alkyl group of
D ² and D ³ are each independently -O-, -S-, -OCH ₂ -, -CH ₂ CH ₂ -, -CO-, -COO-, -CO-S-, -OCO-O- , -CO-NH-, -SCH ₂ -, -CF ₂ O-, -CF ₂ S-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH ₂ CH ₂ -, - OCO-CH ₂ CH ₂ -, -COO-CH ₂ -, -OCO-CH ₂ -, -CH=CH-, -N=N-, -CH=N-, -CH=N-N=CH-, -CF=CF-, -C≡C-, or represents a single bond.
SP is a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms. represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)- or -CO-, and Q represents a substituent.
P represents a polymerizable group.
n represents an integer of 2 or more, the plurality of M may be the same or different, the plurality of ^D2 may be the same or different, and the plurality of ^D3 may be , may be the same or different, and a plurality of SPs may be the same or different. The content of the compound represented by the formula (I-1) is 3 to 70% by mass with respect to the total mass of the polymerizable liquid crystal compound and the compound represented by the formula (I-1). Item 1. The polymerizable liquid crystal composition according to item 1. 3. The polymerizable liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal compound is a compound represented by the following formula (II).
L ⁵ -SP ³ -D ¹⁰ -(A ³ ) _a1 -D ⁸ -(G ¹ ) _g1 -D ⁶ -[Ar ³ -D ⁷ ] _q -(G ² ) _g2 -D ⁹ -(A ⁴ ) _a2 -D ¹¹ -SP ⁴ -L ⁶ (II)
Here, in the formula (II),
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.
q represents 1 or 2;
D ⁶ , D ⁷ , D ⁸ , D ⁹ , D ¹⁰ and D ¹¹ 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 4 carbon atoms. However, when q is 2, a plurality of D ⁷ may be the same or different.
G ¹ and G ² each independently represents a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, and -CH ₂ constituting the alicyclic hydrocarbon group. One or more of - may be substituted with -O-, -S- or -NH-.
A ³ and A ⁴ each independently represent an optionally substituted aromatic ring having 6 or more carbon atoms or an optionally substituted cycloalkane ring having 6 or more carbon atoms.
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
^L5 and ^L6 each independently represent a monovalent organic group, and at least one of ^L5 and ^L6 represents a polymerizable group.
Ar ³ represents an aromatic ring optionally having a substituent. However, when q is 2, a plurality of Ar ³ may be the same or different. the total value X of the log P values of the group represented by Mes ¹ -L ¹ -X ¹ and the log P value of the group represented by Mes ² -L ² -X ² in the formula (I-1);
The log P value and L ⁶ -SP ⁴ -D ¹¹ of the group represented by L ⁵ -SP ³ -D ¹⁰ -(A ³ ) _a1 -D ⁸ -(G ¹ ) _g1 -D ⁶ in the formula (II) -(A ⁴ ) _a1 -D ⁹ -(G ² ) _g1 -D ⁷ The absolute value of the difference between the sum Y of the log P values of the groups represented by -(G 2 ) g1 -D 7 is 3.0 or less. polymerizable liquid crystal composition. Ar ¹ and Ar ² in the formula (I-1) represent an aromatic ring represented by the formula (Ar-2);
X in the formula (Ar-2) represents a nonmetallic atom of groups 14 to 16 to which a substituent may be attached,
When the substituent is bonded to the nonmetallic atom, the substituent is an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group, a cyano group, an amino group, a nitro group, or an alkylcarbonyl group. 5. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein only at least one substituent selected from the group consisting of , a sulfo group, and a hydroxyl group. 6. The polymerizable liquid crystal composition according to any one of claims 1 to 5 , wherein the polymerizable liquid crystal compound is a compound having 4 or more ring structures. 7. The polymerizable liquid crystal composition according to any one of claims 1 to 6 , wherein X ¹ and X ² in formula (I-1) represent a linking group represented by -O-. P in the formula (I-2) represents any polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-20), claims 1 to 8. The polymerizable liquid crystal composition according to any one of 7 .

Here, in the above formulas (P-1) to (P-20), * represents the bonding position with SP. A compound represented by the following formula (I-1a).

Here, in the formula (I-1a),
Ar ¹ and Ar ² each independently represent an aromatic ring represented by the following formula ( Ar-2).
D ¹ is a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ¹ R ² -, -CR ³ =CR ⁴ -, -NR ⁵ -, or , represents a divalent linking group consisting of a combination of two or more thereof, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
p represents 0 or 1;
X ¹ and X ² each independently represent -O-, -S-, -CO-, -CO-NR ⁶ -, or a single bond, and R ⁶ each independently represents a hydrogen atom or a fluorine atom , or represents an alkyl group having 1 to 4 carbon atoms.
Both L ¹ and L ² represent a methylene group. However, the hydrogen atom contained in the methylene group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a C1-20 group. may be substituted with an alkyl group of
Mes ¹ and Mes ² each independently represent a polymerizable group-containing group represented by the following formula (I-2).

Here, in the above formula (Ar-2) ,
* represents the binding position with ^X1 or ^D1 for ^Ar1 , and the binding position with ^D1 or ^X2 for ^Ar2 .
Z ¹ and Z ² are each independently 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, or 6 to 20 carbon atoms. a monovalent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, —OR ⁸ , —NR ⁹ R ¹⁰ , or —SR ¹¹ , wherein R ⁸ to R ¹¹ each independently represent a hydrogen atom Alternatively, it represents an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form an aromatic ring.
A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -N(R ¹² )-, -S- and -CO-, and R ¹² 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. However, when the substituent is bonded to the nonmetallic atom, the substituent is an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group, a cyano group, an amino group, a nitro group, an alkyl Only at least one substituent selected from the group consisting of a carbonyl group, a sulfo group and a hydroxyl group.

Here, in the formula (I-2),
* represents the binding position with ^L1 for ^Mes1 , and the binding position with ^L2 for ^Mes2 .
M is a 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4 -diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1,3-dioxane-2,5-diyl group. However, hydrogen atoms contained in these groups are fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, thioisocyano group, or C 1-20 may be substituted with an alkyl group of
D ² and D ³ each independently represent -O-, -S-, -OCH ₂ -, -CH ₂ CH ₂ -, -CO-, -COO-, -CO-S-, -OCO-O- , -CO-NH-, -SCH ₂ -, -CF ₂ O-, -CF ₂ S-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH ₂ CH ₂ -, - OCO-CH ₂ CH ₂ -, -COO-CH ₂ -, -OCO-CH ₂ -, -CH=CH-, -N=N-, -CH=N-, -CH=N-N=CH-, -CF=CF-, -C≡C-, or represents a single bond.
SP is a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms. represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)- or -CO-, and Q represents a substituent.
P represents a polymerizable group.
n represents an integer of 2 or more, the plurality of M may be the same or different, the plurality of ^D2 may be the same or different, and the plurality of ^D3 may be , may be the same or different, and a plurality of SPs may be the same or different. An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 8 . 11. The optically anisotropic film according to claim 10 , which satisfies the following formula (III).
0.50<Re(450)/Re(550)<1.00 (III)
Here, in formula (III), Re(450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re(550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm. Represents retardation. An optical film comprising the optically anisotropic film according to claim 10 or 11 . A polarizing plate comprising the optical film according to claim 12 and a polarizer. An image display device comprising the optical film according to claim 12 or the polarizing plate according to claim 13 .

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