JP2022033445A - Polymerizable liquid crystal composition, optical anisotropic film, optical film, polarizer, and image display device - Google Patents

Abstract

To provide a polymerizable liquid crystal composition to be used for forming an optical anisotropic film excellent in all of reverse wavelength dispersion, moisture and heat durability, and amine resistance, and to provide an optical anisotropic film, an optical film, a polarizer, and an image display device.SOLUTION: A polymerizable liquid crystal composition contains a polymerizable liquid crystal compound and a compound represented by the following formula (I-1). An optical anisotropic layer prepared from the polymerizable liquid crystal compound satisfies the following expression (A). The content of the compound represented by the formula (I-1) is more than 50 mass% and 90 mass% or less to the total mass of the polymerizable liquid crystal compound and the compound represented by the formula (I-1). 1.00≤Re(450)/Re(550)≤1.10 (A) (in the expression (A), Re(450) indicates in-plane retardation in 450 nm wavelength of the optical anisotropic layer and Re(550) indicates in-plane retardation in 550 nm wavelength of the optical anisotropic layer). Mes1 and Mes2 indicate each independently a group containing a polymerizable group.SELECTED DRAWING: None

Description

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

The polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is a thin film of a retardation film (optically anisotropic film) because it enables accurate conversion of light wavelength over a wide wavelength range and has a high refractive index. Since it has characteristics such as being able to be transformed, it is being actively researched.
Further, as a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility, a T-type molecular design guideline is generally taken, the wavelength of the major axis of the molecule is shortened, and the wavelength of the minor axis located at the center of the molecule is the long wavelength. Is required to be.
It is known that an ether bond is used for the connection between the short axis skeleton located at the center of the molecule and the long axis of the molecule (see, for example, Patent Document and 2).

Japanese Patent No. 5453798 Japanese Unexamined Patent Publication No. 2018-145192

As a result of examining Patent Documents 1 and 2, the present inventors found that when an ether bond was used to connect the short-axis skeleton located at the center of the molecule and the long-axis of the molecule, the liquid crystal property was not exhibited and the reverse wavelength dispersibility was observed. Clarified the problem of loss.
Further, as a result of examining Patent Document 1, the present inventors have a durability that the birefringence index changes when the formed optically anisotropic film is exposed to high temperature and high humidity (hereinafter, "" It has been clarified that there is a problem of "wet heat durability".
Further, when the present inventors examined Patent Document 1, the durability of the formed optically anisotropic film that the birefringence index was changed by ammonia, which is a basic nucleating substance (hereinafter referred to as “durability”). It is also abbreviated as "amine resistance").

Therefore, the present invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, and a polarizing plate, which are used for forming an optically anisotropic film excellent in all of reverse wavelength dispersibility, wet heat durability, and amine resistance. An object of the present invention is to provide an image display device.

As a result of diligent studies to achieve the above problems, the present inventors use a polymerizable liquid crystal composition containing a predetermined polymerizable liquid crystal compound and a specific amount of a compound represented by the formula (I-1) described later. The present invention was completed by finding that the formed optically anisotropic film has good reverse wavelength dispersibility, wet heat durability, and amine resistance.
That is, it was found that the above problem can be achieved by the following configuration.

[1] A polymerizable liquid crystal compound and a compound represented by the formula (I-1) described later are contained.
The optically anisotropic layer prepared by using the polymerizable liquid crystal compound satisfies the following formula (A), and is satisfied with the following formula (A).
The content of the compound represented by the formula (I-1) described later is more than 50% by mass and 90% by mass or less with respect to the total mass of the polymerizable liquid crystal compound and the compound represented by the formula (I-1) described later. Is a polymerizable liquid crystal composition.
1.00 ≤ Re (450) / Re (550) ≤ 1.10 ... (A)
Here, in the above formula (A), Re (450) represents an in-plane lettering of the optically anisotropic layer at a wavelength of 450 nm, and Re (550) represents an in-plane letter of the optically anisotropic layer at a wavelength of 550 nm. Represents the optics.

[2] The polymerizable liquid crystal composition according to [1], wherein the polymerizable liquid crystal compound has a transparent point of 160 to 350 ° C.
[3] The polymerizable liquid crystal composition according to [1] or [2], wherein the polymerizable liquid crystal compound is a compound represented by the formula (II) described later.
[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein the polymerizable liquid crystal compound is a compound having four or more ring structures.
[5] X in the formula (Ar-2) described later represents a non-metal atom of Group 14 to 16 to which a substituent may be bonded.
When a substituent is attached to a non-metal atom, the substituents are 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 and a sulfo group. , And the polymerizable liquid crystal composition according to any one of [1] to [4], which comprises only at least one substituent selected from the group consisting of hydroxyl groups.
[6] The polymerizable liquid crystal composition according to any one of [1] to [5], wherein X ¹ and X ² in the formula (I-1) described later represent a linking group represented by —O—. ..
[7] P in the formula (I-3) described later represents any polymerizable group selected from the group consisting of the groups represented by the formulas (P-1) to (P-20) described later. , [1] to [6].

[8] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [7].
[9] The optically anisotropic film according to [8], which satisfies the following formula (III).
0.50 <Re (450) / Re (550) <1.00 ... (III)
Here, in the 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.
[10] An optical film having the optically anisotropic film according to [8] or [9].
[11] A polarizing plate having the optical film according to [10] and a polarizing element.
[12] An image display device having the optical film according to [10] or the polarizing plate according to [11].

According to the present invention, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, and a polarizing plate used for forming an optically anisotropic film having excellent reverse wavelength dispersibility, wet heat durability, and amine resistance. 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.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, as each component, a substance corresponding to each component may be used alone or in combination of two or more. Here, when two or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
Further, in the present specification, the bonding direction of the divalent group (for example, -CO-NR-) described is not particularly limited unless the bonding position is specified, and for example, the formula described later (for example) When X ¹ in I-1) is -CO-NR-, assuming that the position bonded to the L ¹ side is * 1 and the position bonded to the Ar ¹ side is * 2, X ¹ is It may be * 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 the 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, "low wavelength dispersibility") in which the optically anisotropic layer produced by using the polymerizable liquid crystal compound satisfies the following formula (A). It is also abbreviated as "liquid crystal compound".)
Further, the content of the specific compound contained in the polymerizable liquid crystal composition of the present invention is more than 50% by mass and 90% by mass or less with respect to the total mass of the low wavelength dispersible liquid crystal compound and the specific compound.
1.00 ≤ Re (450) / Re (550) ≤ 1.10 ... (A)

Here, in the above formula (A), Re (450) represents an in-plane lettering of the optically anisotropic layer at a wavelength of 450 nm, and Re (550) represents an in-plane letter of the optically anisotropic layer at a wavelength of 550 nm. Represents the optics.
Further, the values of the in-plane retardation and the retardation in the thickness direction refer to the values measured by using AxoScan OPMF-1 (manufactured by Optoscience) and using light of the measurement wavelength.
Specifically, by inputting the average refractive index ((Nx + Ny + Nz) / 3) and the film thickness (d (μm)) in AxoScan OPMF-1.
Slow phase axial direction (°)
Re (λ) = R0 (λ)
Rth (λ) = ((nx + ny) /2-nz) × d
Is calculated.
Although R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, it means Re (λ).

In the present invention, a polymerizable liquid crystal composition prepared so that the content of the specific compound is more than 50% by mass and 90% by mass or less with respect to the total mass of the low wavelength dispersible liquid crystal compound and the specific compound is used. As a result, the inverse wavelength dispersibility, wet heat durability, and amine resistance of the formed optically anisotropic film are all improved.
This is not clear in detail, but the present inventors speculate as follows.
That is, in the formula (I-1) described later, the linking group (X ¹ and X ² ) bonded to the aromatic ring (Ar ¹ and Ar ² ) is a strong bond containing no ester bond, and thus the specific compound. It is considered that the hydrolysis resistance was improved, and as a result, both the wet heat durability and the amine resistance were improved.
Further, the linking group (L ¹ and L ² ) between the linking group (X ¹ and X ² ) and the polymerizable group-containing group (Mes ¹ and Mes ² ) in the formula (I-1) described later is linear. Due to the high alkylene group, even if the content of the specific compound is more than 50% by mass and 90% by mass or less with respect to the total mass of the low wavelength dispersible liquid crystal compound and the specific compound, the low wavelength dispersible liquid crystal compound can be obtained. Since it can be oriented jointly, it is considered that the inverse wavelength dispersibility due to the structure of the specific compound was exhibited.
Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.

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

In the above formula (I-1), Ar ¹ and Ar ² are independently selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-7). Represents.
Further, 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 two or more of these, and R ¹ to R ⁵ independently represent a hydrogen atom, a fluorine atom, or a carbon number. Represents 1 to 4 alkyl groups.
Further, in the above formula (I-1), p represents 0 or 1.
Further, in the above formula (I-1), X ¹ and X ² independently represent -O-, -S-, -CO-, -CO-NR ^6- , or a single bond, respectively, and represent R ⁶ Independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

In the above formula (I-1), p represents 0 or 1 as described above, but it is 0, that is, D ¹ and Ar ² in the above formula (I-1) do not exist. Is preferable.

In the above formula (I-1), examples of the divalent linking group represented by one aspect 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 can be mentioned. R ¹ , R ² and R ⁵ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
Of these, any of -CO-, -O-, and -CO-O- is preferable.

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

In the above formula (I-1), Ar ¹ and Ar ² are independently selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-7), as described above. Represents the aromatic ring. In the following equations (Ar-1) to (Ar-7), * indicates the bond position with X ¹ or D ¹ for Ar ¹ , and the bond position with D ¹ or X ² for Ar ² . However, when p is 0, it indicates the bonding position with X ¹ or X ² .

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 Representing an alkyl group having 1 to 6 carbon atoms, Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent. show.
Specific examples of the alkyl group having 1 to 6 carbon atoms indicated by R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Groups, n-pentyl groups, n-hexyl groups and the like can be mentioned.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y ¹ include an aryl group such as a phenyl group, a 2,6-diethylphenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y ¹ include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group and a pyridyl group.
Examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamide group and an alkenyl. Examples thereof include a group, an alkynyl group, a halogen atom, a cyano group, a nitro group, an alkylthiol group, and an N-alkylcarbamate group, among which an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen. Atomic is 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 (for example, methyl group, ethyl group, propyl group, isopropyl group, n). -Butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group or an ethyl group is particularly preferable.
As the alkoxy group, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and an alkoxy group having 1 carbon atom is preferable. Alkoxy groups of -4 are more preferred, and methoxy or ethoxy groups are particularly preferred.
Examples of the alkoxycarbonyl group include a group in which an oxycarbonyl group (—O—CO— group) is bonded to the alkyl group exemplified above, and among them, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group or an isopropoxy. A carbonyl group is preferred, a methoxycarbonyl group is more preferred.
Examples of the alkylcarbonyloxy group include a group in which a carbonyloxy group (-CO-O- group) is bonded to the alkyl group exemplified above, and among them, a methylcarbonyloxy group, an ethylcarbonyloxy group, and an n-propylcarbonyloxy group. A group or an isopropylcarbonyloxy group is preferable, and a methylcarbonyloxy group is more preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom or a chlorine atom is preferable.

Further, in the above formulas (Ar-1) to (Ar-7), Z ¹ , Z ² and Z ³ are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon. A monovalent alicyclic hydrocarbon group having a number of 3 to 20, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁸ , -NR ⁹ R ¹⁰ , or , -SR ¹¹ and 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 be bonded to each other to form an aromatic ring. good.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group and 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 preferable, and methyl group, ethyl group, tert-butyl group. Groups are particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and an ethylcyclohexyl. Monocyclic saturated hydrocarbon groups such as groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as diene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.2.10 ^2,6 ] decyl group, Tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and have 6 to 12 carbon atoms. Aryl groups (particularly phenyl groups) are preferred.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
On the other hand, as the alkyl group having ¹ to ⁶ carbon atoms indicated by R8 to R11, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group. Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.

Further, in the above formulas (Ar-2) and (Ar-3), A ¹ and A ² are independently derived from -O-, -N (R ¹² )-, -S-, and -CO-, respectively. Represents a group selected from the group, where R ¹² represents a hydrogen atom or substituent.
Examples of the substituent represented by R ¹² include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Further, in the above formula (Ar-2), X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Further, as the non-metal atom of Group 14 to 16 indicated by X, for example, an oxygen atom, a sulfur atom, a hydrogen atom or a nitrogen atom to which a substituent is bonded [= ^N -RN1 and ^RN1 are hydrogen atoms or substituents. Represents. ], A carbon atom to which a hydrogen atom or a substituent is bonded [= C- ( ^RC1 ) ₂ , ^RC1 represents a hydrogen atom or a substituent. ] Can be mentioned.
Specific examples of the substituent include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl group. Examples thereof include a carbonyl group, a sulfo group and a hydroxyl group.

In the present invention, X in the above formula (Ar-2) represents a non-metal atom of Group 14 to 16 to which a substituent may be bonded, and the non-metal atom is bonded to the substituent. If so, the substituents include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, and an aryl group (for example, a phenyl group) for the reason that the wet heat durability of the formed optically anisotropic film becomes better. , Naftyl group, etc.), cyano group, amino group, nitro group, alkylcarbonyl group, sulfo group, and at least one substituent selected from the group consisting of hydroxyl groups. It is considered that this is because the symmetry of the specific compound is increased, which makes it easier to crosslink.

Further, in the above formula (Ar-3), D ⁴ and D ⁵ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR ¹ respectively. R ^2- , -CR ³ = CR ^4- , -NR ^5- , or a divalent linking group consisting of a combination of two or more of these, and R ¹ to R ⁵ are independent hydrogen atoms, respectively. It represents a hydrogen 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 in D ¹ in the above formula (I-1).

Further, in the above formula (Ar-3), SP ¹ and SP ² are independently single-bonded, a linear or branched alkylene group having 1 to 12 carbon atoms, or a direct group having 1 to 12 carbon atoms. One or more of -CH _2- constituting a chain or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents a linking group of, and Q represents a substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.
Here, examples of the linear or branched alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group and a heptylene group. Is preferably mentioned.

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

Further, in the above formulas (Ar-4) to (Ar-7), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
Further, in the above formulas (Ar-4) to (Ar-7), Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic. Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, ^Q3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of International Publication No. 2014/010325.
Specific examples of the alkyl group having 1 to 6 carbon atoms indicated by ^Q3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert. -Butyl group, n-pentyl group, n-hexyl group and the like can be mentioned, and examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have. Can be mentioned.

On the other hand, in the above formula (I-1), L ¹ and L ² each independently represent an alkylene group represented by the following formula (I-2). In the following formula (I-2), * represents the bonding position with Mes ¹ or X ¹ for L ¹ , and represents the bonding position with Mes ² or X ² for L ² .

In the above equation (I-2), m represents an integer of 1 or more, preferably an integer of 2 to 20, more preferably an integer of 2 to 15, and an integer of 2 to 10. Is particularly preferable.

Further, the hydrogen atom contained in the alkylene group represented by the above formula (I-2) 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, and the like. It may be substituted with a thioisocyano group or an alkyl group having 1 to 20 carbon atoms.
Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, a t-butyl group, an amyl group, and a 2-ethylhexyl group. Examples thereof include a nonyl group, a decanyl group, a lauryl group, a cetyl group, a stearyl group, a cyclohexyl group and the like.

Further, one of -CH _2- , which constitutes the alkylene group represented by the above formula (I-2) and is not directly bonded to X ¹ or X ² in the above formula (I-1). Or two or more non-adjacent -CH _2- are -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- It may be substituted with CO-O-, -CO-NH-, -NH-CO-, or -C≡C-.

On the other hand, in the above formula (I-1), Mes ¹ and Mes ² independently represent the polymerizable group-containing group represented by the following formula (I-3). In the following formula (I-3), * represents the bonding position with L ¹ for Mes ¹ and the bonding position with L ² for Mes ² .

On the other hand, in the above formula (I-1), Mes ¹ and Mes ² independently represent the polymerizable group-containing group represented by the following formula (I-3). In the following formula (I-3), * represents the bonding position with L ¹ for Mes ¹ and the bonding position with L ² for Mes ² .

In the above formula (I-3), M is a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6. -Represents a diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group. ..
However, the hydrogen atom contained in these groups 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 1 to 20 carbon atoms. It may be substituted with an alkyl group of.

Further, in the above formula (I-3), D ² and D ³ are independently -O-, -S-, -OCH _2- , -CH ₂ CH _2- , -CO-, -COO-, respectively. -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-3), 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 the above is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where 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, examples of the linear or branched alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group and a heptylene group. Is preferably mentioned.

Further, in the above formula (I-3), P represents a polymerizable group.
As the polymerizable group, a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and suitable examples thereof include an acryloyloxy group and a methacryloyloxy group. In this case, it is known that the acryloyloxy group is generally faster in terms of the polymerization rate, and the acryloyloxy group is preferable from the viewpoint of improving productivity, but the methacryloyloxy group can also be used as the polymerizable group in the same manner.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and , Vinyloxy group and the like. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
Examples of particularly preferable polymerizable groups include any polymerizable group selected from the group consisting of the groups represented by the following formulas (P-1) to (P-20). Of these, acryloyloxy group or methacryloyloxy group is more preferable. In the following equations (P-1) to (P-20), * represents the bonding position with the SP.

Further, in the above formula (I-3), 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 preferable.
The plurality of Ms may be the same or different, the plurality of D ^2s may be the same or different, and the plurality of D ^3s may be the same or different. 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), and specifically, K (specifically, K (1) to (14) in the following formulas (1) to (14). Examples of the side chain structure) include compounds having the side chain structure shown in Table 1 below.
In Table 1 below, "*" shown in the side chain structure of K represents the bonding position with the aromatic ring.
Further, in the side chain structure represented by 1-7 and 1-12 in Table 1 below, the group adjacent to the acryloyloxy group and the methacryloyl group, respectively, is a propylene group (a group in which a methyl group is replaced with an ethylene group). Represents a mixture of positional isomers with different positions of methyl groups.

In the present invention, the content of the specific compound is more than 50% by mass and 90% by mass or less with respect to the total mass of the polymerizable liquid crystal compound (low wavelength dispersible liquid crystal compound) described later and the specific compound, and the formed optics. It is preferably more than 50% by mass and 80% by mass or less, more preferably more than 50% by mass and 70% by mass or less, and more preferably 50% by mass, because the inverse wavelength dispersibility is more easily exhibited in the anisotropic film. It is more preferably more than 60% by mass.

[Polymerizable liquid crystal compound]
As described above, the polymerizable liquid crystal compound (low wavelength dispersible liquid crystal compound) contained in the polymerizable liquid crystal composition of the present invention has a polymerizable layer in which the optically anisotropic layer produced using the compound satisfies the following formula (A). It is a liquid crystal compound, preferably a polymerizable liquid crystal compound satisfying the following formula (B), and more preferably a polymerizable liquid crystal compound satisfying 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 wavelength of the optically anisotropic layer at 550 nm. Represents the in-plane lettering in.
Further, as the optically anisotropic layer to be measured for the in-plane retardation, that is, the optically anisotropic layer prepared by using the polymerizable liquid crystal compound, the optically anisotropic layer prepared by the following procedure is used.
That is, the polymerizable liquid crystal composition having the following composition is applied to a glass substrate with a rubbing-treated polyimide alignment film (SE-150 manufactured by Nissan Chemical Industry Co., Ltd.) by spin coating.
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 from a temperature exhibiting liquid crystallinity to a temperature 40 ° C. lower, and the 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 transparent point of the low wavelength dispersible liquid crystal compound is the reason why the inverse wavelength dispersibility of the formed optically anisotropic film is better, the wet heat durability and the amine resistance are also better. The temperature is preferably 160 to 350 ° C, more preferably 170 to 320 ° C, further preferably 180 to 310 ° C, and particularly preferably 190 to 300 ° C.
Here, the "transparency point" means "the temperature at which the liquid crystal phase changes to an isotropic liquid (Iso)", and specifically, the difference transition temperature between the nematic phase and the isotropic phase, or It refers to the phase transition temperature between the smectic phase and the isotropic phase.
Further, when the transparent point is 160 to 350 ° C., the temperature at which the phase transition to Iso is sufficiently high, and as a result, the degree of orientation order (order parameter) is also high, so that the reverse wavelength dispersibility and the like are improved. Conceivable.

In the present invention, the low wavelength dispersible liquid crystal compound is preferably a compound represented by the following formula (II) because of its 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 the above formula (II), a1, a2, g1 and g2 independently represent 0 or 1, respectively. However, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.
Further, in the above formula (II), q represents 1 or 2.
Further, in the above formula (II), D ⁶ , D ⁷ , D ⁸ , D ⁹ , D ¹⁰ and D ¹¹ are independently single-bonded or -CO-, -O-, -S-,-, respectively. C (= S)-, -CR ¹ R ^2- , -CR ³ = CR ^4- , -NR ^5- , or a divalent linking group consisting of two or more of these, representing R ¹ to R. ⁵ independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. However, when q is 2, the plurality of D ^7s may be the same or different.
Further, 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 are of the alicyclic type. One or more of -CH _2- constituting the hydrocarbon group may be substituted with -O-, -S- or -NH-.
Further, in the above formula (II), A ³ and A ⁴ each independently have an aromatic ring having 6 or more carbon atoms which may have a substituent or a carbon number which may have a substituent. Represents 6 or more cycloalkane rings.
Further, in the above formula (II), SP ³ and SP ⁴ are independently single-bonded, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. Alternatively, a divalent linkage in which one or more of -CH _2- constituting the branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-. Represents a group and Q represents a substituent.
Further, in the above formula (II), L ⁵ and L ⁶ each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group.

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

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

In the above formula (II), the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G ¹ and G ² is preferably a 5-membered ring or a 6-membered ring. The alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferable. As the divalent alicyclic hydrocarbon group represented by G ¹ and G ² , for example, the description in paragraph [0078] of JP2012-21068A can be referred to, and the content thereof is incorporated in the present specification. ..

Further, in the above formula (II), as the substituent which the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms may have for G ¹ and G ² , the above-mentioned formula (Ar-1) is used. ), The same as the substituent that Y ¹ may have.

In the above formula (II), examples of the aromatic ring having 6 or more carbon atoms represented by A ³ and A ⁴ include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; a furan ring. Aromatic heterocycles such as a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring; Of these, a benzene ring (for example, a 1,4-phenyl group) is preferable.
Further, in the above formula (II), examples of the cycloalkane ring having ⁶ or more carbon atoms represented by A3 and A4 include a cyclohexane ring, a ^cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclododecane ring. Of these, a cyclohexane ring (for example, a 1,4-cyclohexylene group) is preferable, and a trans-1,4-cyclohexylene group is more preferable.
Regarding A ³ and A ⁴ , Y ¹ in the above-mentioned formula (Ar-1) is a substituent that may be contained in an aromatic ring having 6 or more carbon atoms or a cycloalkane ring having 6 or more carbon atoms. Examples include the same substituents that may have.

In the above formula (II), the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ³ and SP ⁴ has been described in SP ¹ and SP ² in the above formula (Ar-3). Something similar to the one. As described above, in SP ³ and SP ⁴ , one or more of -CH _2- constituting a linear or branched alkylene group having 1 to 12 carbon atoms are -O-, -S-, and -NH. It may be a divalent linking group substituted with −, −N (Q) − or −CO—, and the substituent represented by Q is Y in the above-mentioned formula (Ar-1). Examples thereof include the same substituents that ¹ may have.

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

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

In the above formula (II), it is preferable that both L ⁵ and L ⁶ in the above formula (II) are polymerizable groups, and are acryloyloxy group or methacryloyloxy group, for the reason that the durability is good. 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, the plurality of Ar ^3s may be the same or different.
Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; aromatic rings such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring. Heterocycle; Of these, a benzene ring (for example, a 1,4-phenyl group) is preferable.
Examples of the substituent that the aromatic ring may have include the same substituents that Y ¹ in the above-mentioned formula (Ar-1) may have.

In the present invention, the polymerizable liquid crystal compound preferably has four or more ring structures, and more preferably five, because the liquid crystal property is easily exhibited.

Specific examples of the low wavelength dispersible liquid crystal compound include compounds represented by the following formulas (15) to (30), and specifically, the following formulas (15) to (30). Examples of K (side chain structure) in the compound include compounds having side chain structures shown in Tables 2 and 3 below, respectively.
Further, in the side chain structure represented by 2-1 in Table 2 and 3-2 in Table 3 below, the group adjacent to the acryloyloxy group and the methacryloyl group is a propylene group (methyl group becomes an ethylene group, respectively). Represents a substituted group) and represents a mixture of positional isomers with different methyl group positions.

In the present invention, the liquid crystal property of the polymerizable liquid crystal composition is more easily expressed, and the inverse wavelength dispersibility of the formed optically anisotropic film is an ideal value (Re (450) / Re (550)). The content of the low wavelength dispersible liquid crystal compound is preferably 20% by mass or more, preferably 30% by mass, based on the total mass of the above-mentioned specific compound and the low wavelength dispersible liquid crystal compound. % Or more, more preferably 40% by mass or more. The upper limit is less than 50% by mass.

[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 above-mentioned low wavelength dispersible liquid crystal compound.
Here, the polymerizable group of 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 and a methacryloyl group.

Examples of other polymerizable compounds include the compounds described in paragraphs [0073] to [0074] of JP-A-2016-053709.
Examples of other polymerizable compounds include compounds represented by the 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 same publication can be mentioned.
Further, as the other polymerizable compound, those having the structures of the formulas (1) to (3) described in JP-A-2014-198814 can be preferably used, and more specifically, those having the structure of the same publication can be used. ]-[0035], [0042]-[0050], [0056]-[0057] Specific examples described in paragraphs may be mentioned.

When such another polymerizable compound is contained, the content is preferably less than 50% by mass and more preferably 40% by mass or less with respect to the mass of the above-mentioned low wavelength dispersible liquid crystal compound. It is preferably 2 to 30% by mass, and more preferably 2 to 30% by mass.

[Initiator of polymerization]
The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrances. Group acidloin compounds (described in US Pat. No. 2,725,512), polynuclear quinone compounds (described in US Pat. Nos. 3,416127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patent). 3549365 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 421,970), acylphosphine. Examples thereof include oxide compounds (described in Japanese Patent Publication No. 63-40799, Japanese Patent Application Laid-Open No. 5-29234, Japanese Patent Application Laid-Open No. 10-95788, Japanese Patent Application Laid-Open No. 10-29997) and the like.
Further, in the present invention, it is also preferable that the polymerization initiator is an oxime-type polymerization initiator, and specific examples thereof are described in paragraphs [0049] to [0052] of International Publication No. 2017/170443. Agents are mentioned.

〔solvent〕
The 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 a ketone solvent (for example, acetone, 2-butanone, methylisobutylketone, cyclohexanone, cyclopentanone, etc.), an ether solvent (for example, dioxane, tetrahydrofuran, etc.), and a cyclic amide solvent. Solvents (eg, N-methylpyrrolidone, N-ethylpyrrolidone, N, N'-dimethylimidazolidinone, etc.), aliphatic hydrocarbon solvents (eg, hexane, etc.), alicyclic hydrocarbon solvents (eg, cyclohexane). Aromatic hydrocarbon solvents (eg toluene, xylene, trimethylbenzene, etc.), halogenated carbon solvents (eg dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), ester solvents (eg, methyl acetate, etc.) Ethyl acetate, butyl acetate, etc.), water, alcohol solvent (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolve solvent (eg, methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetate solvent, sulfoxide solvent (eg, methyl cellosolve, ethyl cellosolve, etc.) For example, dimethylsulfoxide and the like), chain amide-based solvents (for example, dimethylformamide, dimethylacetamide, etc.) and the like can be mentioned, and these may be used alone or in combination of two or more.

In the present invention, among the above-mentioned solvents, at least one selected from the group consisting of a ketone solvent, an ether solvent and a cyclic amide solvent for the reason that the effect of the present invention for suppressing an increase in filtration pressure becomes apparent. 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 orientation control.
As such a leveling agent, a fluorine-based leveling agent or a silicon-based leveling agent is preferable because it has a high leveling effect on the amount of addition, and a fluorine-based leveling agent is less likely to cause crying (bloom, bleed). Is more preferable.
Specific examples of the leveling agent include the compounds described in paragraphs [0079] to [0102] of JP-A-2007-069471, and the general formulas described in JP-A-2013-047204. The compound represented by I) (particularly the compound described in paragraphs [0020] to [0032]) and the compound represented by the general formula (I) described in JP-A-2012-211306 (particularly [0022]. -The compound described in paragraph [0029], the liquid crystal alignment promoter represented by the general formula (I) described in JP-A-2002-129162 (particularly [0076] to [0078] and [0082]- Compounds described in paragraph [0084], compounds represented by the general formulas (I), (II) and (III) described in JP-A-2005-09248 (particularly, paragraphs [0092] to [00906]. The compounds described in 1) and the like. In addition, it may also have a function as an orientation control agent described later.

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

As the orientation control agent that promotes homogenius orientation, for example, a small molecule orientation control agent or a polymer orientation control agent can be used.
Examples of the small molecule orientation control agent include 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 the Publication No. 211306 can be referred to, and this content is incorporated in the present specification.
Further, as the polymer orientation control agent, for example, paragraphs [0021] to [0057] of JP-A-2004-198511 and paragraphs [0121]-[0167] of JP-A-2006-106662 are referred to. And this content is incorporated herein by reference.

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

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

When the orientation control agent is contained, the content is preferably 0.01 to 10% by mass, and preferably 0.05 to 5% by mass, based on the total solid content mass in the polymerizable liquid crystal composition. More preferred. When the content is in this range, it is possible to obtain a uniform and highly transparent optically anisotropic film without precipitation, phase separation, orientation defects, etc., while achieving a desired orientation state.
These orientation control agents can further impart a polymerizable functional group, particularly a polymerizable functional group that can be polymerized 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 a component other than the above-mentioned components, for example, a liquid crystal compound other than the above-mentioned polymerizable liquid crystal compound, a surfactant, a tilt angle control agent, an orientation aid, and a plasticizer. Agents, cross-linking agents and the like can be mentioned.

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

The optically anisotropic membrane 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 an in-plane lettering of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents an in-plane letter of the optically anisotropic film at a wavelength of 550 nm. Represents the optics. If the measurement wavelength of the retardation is not specified in the present specification, the measurement wavelength is 550 nm.

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

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

When the optically anisotropic 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, and particularly preferably 130 to 140 nm.
Here, the "λ / 4 plate" is a plate having a λ / 4 function, and specifically, a function of converting linear polarization of a specific wavelength into circular polarization (or circular polarization into linear polarization). It is a plate having.

[Optical film]
The optical film of the present invention is an optical film having the optically anisotropic film of the present invention.
1A, 1B and 1C (hereinafter, these drawings are abbreviated as "FIG. 1" when no particular distinction is required) are schematic cross-sectional views showing an example of the optical film of the present invention, respectively.
Note that FIG. 1 is a schematic diagram, and the thickness relationship and positional relationship of each layer do not always match the actual ones, and the support, alignment film, and hard coat layer shown in FIG. 1 all have an arbitrary configuration. 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, as shown in FIG. 1B, the optical film 10 may have the hard coat layer 18 on the side opposite to the side where the alignment film 14 of the support 16 is provided, and as shown in FIG. 1C, the optical film 10 may have a hard coat layer 18. The 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.
Hereinafter, various members used in the optical film of the present invention will be described in detail.

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

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

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

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

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

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

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

[Hard coat layer]
The optical film of the present invention preferably has a hardcoat layer in order to impart physical strength to the film. Specifically, the hardcourt layer may be provided on the side opposite to the side where the alignment film of the support is provided (see FIG. 1B), and the side where the alignment film of the optically anisotropic film is provided. May have a hardcourt 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 present invention may have another optically anisotropic film in addition to the optically anisotropic film of the present invention.
That is, the optical film of the present invention may have a laminated structure of the optically anisotropic film of the present invention and another optically anisotropic film.
Such other optically anisotropic films are optically anisotropic obtained by using the above-mentioned inverse wavelength dispersible liquid crystal compound or other polymerizable compound (particularly, liquid crystal compound) without blending the above-mentioned specific compound. If it is a film, it is not particularly limited.
Here, in general, liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type according to their shapes. In addition, there are small molecule and high molecular types, respectively. A polymer generally refers to a molecule having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound). Two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of disk-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound may be used. For the immobilization of the above-mentioned liquid crystal compound, it is more preferable to form a rod-shaped liquid crystal compound having a polymerizable group or a disk-shaped liquid crystal compound, and the liquid crystal compound may have two or more polymerizable groups in one molecule. More preferred. When the liquid crystal compound is a mixture of two or more kinds, it is preferable that at least one kind of liquid crystal compound has two or more polymerizable groups in one molecule.
As the rod-shaped liquid crystal compound, for example, those described in claim 1 of JP-A No. 11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and discotics can be used. 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. However, it is not limited to these.

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

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

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

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

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

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

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

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

[Organic EL display device]
The organic EL display device, which is an example of the image display device of the present invention, includes, for example, a λ / 4 plate (positive A plate) made of a polarizing element, an optically anisotropic film of the present invention, and an organic EL from the viewing side. A mode having a display panel in this order is preferably mentioned.
Further, the organic EL display panel is a display panel configured by using an organic EL element formed by sandwiching an organic light emitting layer (organic electroluminescence layer) between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Example 1]
[Manufacturing of optical film]
A polymerizable liquid crystal composition having the following composition was prepared and applied to a glass substrate with a rubbing-treated polyimide alignment film (SE-150 manufactured by Nissan Chemical Industry Co., Ltd.) by spin coating.
The coating film was oriented at the temperatures shown in Table 4 below to form a liquid crystal layer.
Then, the film was cooled to the exposure temperature shown in Table 4 below, and the orientation was fixed by irradiation with ultraviolet rays of 1000 mJ / cm ² , to form an optically anisotropic film, and an optical film was produced.

―――――――――――――――――――――――――――――――――
Polymerizable liquid crystal composition ――――――――――――――――――――――――――――――――――
-The following polymerizable liquid crystal compound (II-1) 10.8 parts by mass-The following specific compound (I-1-1) 13.2 parts by mass-Photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass・ The following fluorine-containing compound A 0.02 parts by mass ・ chloroform 120.00 parts by mass ―――――――――――――――――――――――――――――――― ―

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 the specific compound was changed to the compound shown in Table 4 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 the specific compound was changed to the compounds shown in Table 4 below and parts by mass.

<Letteration>
With respect to the produced optical film, a retardation value (Re (450)) having a wavelength of 450 nm and a retardation value (Re (550)) having a wavelength of 550 nm were obtained using Axo Scan (OPMF-1, manufactured by Optoscience). It was measured and Re (450) / Re (550) was calculated. These results are shown in Table 4 below.
Further, the optically anisotropic layer produced by the above-mentioned method using the polymerizable liquid crystal compound used in Examples and Comparative Examples also has a retardation value (Re (450)) having a wavelength of 450 nm and a retardation having a wavelength of 550 nm. The value (Re (550)) was measured, and Re (450) / Re (550) was calculated. These results are shown in Table 4 below.

<Moist heat durability>
As the test conditions for moist heat durability, a test was conducted in which the mixture was left in an environment of 85 ° C. and a relative humidity of 85% for 500 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 wet and heat durability was evaluated according to the following criteria. The results are shown in Table 4 below.
A: The amount of change in Re (550) after the test with respect to Re (550) before the test is less than 10% of Re (550) before the test. B: Re (550) after the test with respect to Re (550) before the test. The amount of change is 10% or more and less than 30% of Re (550) before the test. C: The amount of change of Re (550) after the test with respect to Re (550) before the test is 30% or more of Re (550) before the test.

<Amine resistance>
As the test conditions for amine resistance, a 2 mol% solution of NH ₃ / MeOH was placed in a vial, an optical film was placed at the outlet, and the mixture 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 4 below.
A: The amount of change in Re (550) after the test with respect to Re (550) before the test is less than 10% of Re (550) before the test. B: Re (550) after the test with respect to Re (550) before the test. The amount of change is 10% or more and less than 30% of Re (550) before the test. C: The amount of change of Re (550) after the test with respect to Re (550) before the test is 30% or more of Re (550) before the test.

<Light resistance>
For the produced optical film, set the glass substrate on a xenon irradiator (SX75 manufactured by Suga Test Instruments Co., Ltd.) so that the coating film of the polymerizable liquid crystal composition serves as the irradiation surface, and use a # 275 filter for 200 hours. An irradiation test was conducted.
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 4 below.
A: The amount of change in Re (550) after the test with respect to Re (550) before the test is less than 5% of Re (550) before the test. B: Re (550) after the test with respect to Re (550) before the test. The amount of change is 5% or more and less than 15% of Re (550) before the test. C: The amount of change of Re (550) after the test with respect to Re (550) before the test is 15% or more of Re (550) before the test.

The structures of the polymerizable liquid crystal compounds and the like in Table 4 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)

Polymerizable Liquid Crystal Compound (II-6: LC242 described in Example 1 of Japanese Patent No. 5453798) [Comparative Compound]

Polymerizable liquid crystal compound (II-7: Mother liquid crystal of Example 31 of JP-A-2018-145192) (X-1 (50%), X-2 (30%), X-3 (20%)) [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: vi-1-5 described in Example 1 of Japanese Patent No. 5453798) [Comparative Compound]

Specific Compound (I-1-6: Compound (I-9) described in Example 31 of JP-A-2018-145192) [Comparative compound]

From the results shown in Table 4 above, when the content of the specific compound is 45% by mass with respect to the total mass of the low wavelength dispersible liquid crystal compound and the specific compound, the inverse wavelength dispersibility of the optically anisotropic film formed. It was found that the wet heat durability and the amine resistance were both inferior, and the light resistance was also inferior (Comparative Example 1).
Further, when the content of the specific compound is 40% by mass with respect to the total mass of the low wavelength dispersible liquid crystal compound and the specific compound, the optically anisotropic film formed has wet heat durability, amine resistance, and light resistance. Although the properties were good, it was found that the inverse wavelength dispersibility did not occur (Comparative Example 2).
On the other hand, it contains a low wavelength dispersible liquid crystal compound and a specific compound, and the content of the specific compound is more than 50% by mass and 90% by mass or less with respect to the total mass of the low wavelength dispersible liquid crystal compound and the specific compound. It was found that when compounded in, an optically anisotropic film having excellent anti-wavelength dispersibility, wet heat durability, amine resistance and light resistance can be formed (Examples 1 to 10). It can be said that this result is an unexpected effect in consideration of the comparison between Example 10 and Comparative Example 1.
In particular, from the comparison between Examples 1, 7 and 8 and Example 9, when the transparent point of the low wavelength dispersible liquid crystal compound is 160 to 350 ° C., the inverse wavelength dispersibility of the formed optically anisotropic film is high. It was found to be better, with better wet and heat durability and better amine resistance.

Claims (12)

It contains a polymerizable liquid crystal compound and a compound represented by the following formula (I-1).
The optically anisotropic layer produced by using the polymerizable liquid crystal compound satisfies the following formula (A).
The content of the compound represented by the formula (I-1) is more than 50% by mass and 90% by mass or less with respect to the total mass of the polymerizable liquid crystal compound and the compound represented by the formula (I-1). A polymerizable liquid crystal composition.
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 surface of the optically anisotropic layer at a wavelength of 550 nm. Represents an internal lettering.

Here, in the above formula (I-1),
Ar ¹ and Ar ² each independently represent any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-7).
D ¹ is a single bond, or -CO-, -O-, -S-, -C (= S)-, -CR ¹ R ^2- , -CR ³ = CR ^4- , -NR ^5- , or , Representing a divalent linking group consisting of a combination of two or more of these, and R ¹ to R ⁵ 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 independently represent -O-, -S-, -CO-, -CO-NR ^6- , or a single bond, and R ⁶ independently represents a hydrogen atom and a fluorine atom, respectively. , Or an alkyl group having 1 to 4 carbon atoms.
L ¹ and L ² each independently represent an alkylene group represented by the following formula (I-2).
Mes ¹ and Mes ² independently represent a polymerizable group-containing group represented by the following formula (I-3).

Here, in the above equations (Ar-1) to (Ar-7),
* Represents the bond position with X ¹ or D ¹ for Ar ¹ , and represents the bond position with D ¹ or X ² for Ar ² .
Q ¹ represents N or CH.
^Q2 represents -S-, -O-, or -N (R ⁷ )-, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
Z ¹ , Z ² and Z ³ independently have a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a carbon number of carbon atoms. Represents 6 to 20 monovalent aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -OR ⁸ , -NR ⁹ R ¹⁰ or -SR ¹¹ , where R ⁸ to R ¹¹ are independent of each other. , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.
A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -N (R ¹² )-, -S-, and -CO-, where R ¹² is a hydrogen atom or Represents a substituent.
X represents a Group 14-16 non-metal atom to which a hydrogen atom or a substituent may be attached.
D ⁴ and D ⁵ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR ¹ R ^2- , -CR ³ = CR ^4- , -NR ^5- , or a divalent linking group consisting of two or more of these, and R ¹ to R ⁵ are independently hydrogen atoms, fluorine atoms, or carbon atoms 1 to 4, respectively. Represents an alkyl group.
SP ¹ and SP ² independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -CH _2- represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where Q is a substituent. Represents.
L ³ and L ⁴ each independently represent a monovalent organic group.
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
Ay has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , Represents an organic group having 2 to 30 carbon atoms.
The aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
^Q3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

Here, in the above formula (I-2),
* Represents the bond position with Mes ¹ or X ¹ for L ¹ , and represents the bond position with Mes ² or X ² for L ² .
m represents an integer of 1 or more.
However, the hydrogen atom contained in the alkylene 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 1 to 20 carbon atoms. It may be substituted with an alkyl group of.
Further, of -CH ₂ -that constitutes the alkylene group and is not directly bonded to X ¹ or X ² , one or two or more -CH ₂ -that are not adjacent to each other are -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, or It may be replaced with -C≡C-.

Here, in the above formula (I-3),
* Represents the bond position with L ¹ for Mes ¹ and the bond position with L ² for Mes ² .
M is a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4. -Represents a diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group. However, the hydrogen atom contained in these groups 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 1 to 20 carbon atoms. It may be substituted with an alkyl group of.
D ² and D ³ are independently -O-, -S-, -OCH _2- , -CH ₂ CH _2- , -CO-, -COO-, -CO-S-, -OCO-O-, respectively. , -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 a single bond.
The SP is one or more of -CH _2- constituting 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 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, a plurality of Ms may be the same or different, a plurality of D ^2s may be the same or different, and a plurality of D ^3s may be the same or different. , Each may be the same or different, and the plurality of SPs may be the same or different. The polymerizable liquid crystal composition according to claim 1, wherein the transparent point of the polymerizable liquid crystal compound is 160 to 350 ° C. The polymerizable liquid crystal composition according to claim 1 or 2, 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 above formula (II),
a1, a2, g1 and g2 independently represent 0 or 1, respectively. However, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.
q represents 1 or 2.
D ⁶ , D ⁷ , D ⁸ , D ⁹ , D ¹⁰ and D ¹¹ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR. ¹ R ^2- , -CR ³ = CR ^4- , -NR ^5- , or a divalent linking group consisting of a combination of two or more of these, and R ¹ to R ⁵ are independent hydrogen atoms. , A hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. However, when q is 2, the plurality of D ^7s may be the same or different.
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 constitute an alicyclic hydrocarbon group-CH ₂ . One or more of-may be substituted with -O-, -S- or -NH-.
A ³ and A ⁴ independently represent an aromatic ring having 6 or more carbon atoms which may have a substituent or a cycloalkane ring having 6 or more carbon atoms which may have a substituent.
SP ³ and SP ⁴ independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -CH _2- represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where Q is a substituent. Represents.
L ⁵ and L ⁶ each independently represent a monovalent organic group, and at least one of L ⁵ and L ⁶ represents a polymerizable group.
Ar ³ represents an aromatic ring which may have a substituent. However, when q is 2, the plurality of Ar ^3s may be the same or different. The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound is a compound having four or more ring structures. X in the formula (Ar-2) represents a non-metal atom of Group 14 to 16 to which a substituent may be bonded.
When the substituent is bonded to the non-metal 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. The polymerizable liquid crystal composition according to any one of claims 1 to 4, which comprises only at least one substituent selected from the group consisting of a sulfo group and a hydroxyl group. The polymerizable liquid crystal composition according to any one of claims 1 to 5, wherein X ¹ and X ² in the formula (I-1) represent a linking group represented by —O—. Claims 1 to 1, wherein P in the formula (I-3) represents any polymerizable group selected from the group consisting of the groups represented by the following formulas (P-1) to (P-20). 6. The polymerizable liquid crystal composition according to any one of 6.

Here, in the above equations (P-1) to (P-20), * represents a bonding position with SP. An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 7. The optically anisotropic film according to claim 8, which satisfies the following formula (III).
0.50 <Re (450) / Re (550) <1.00 ... (III)
Here, in the 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 letteration. An optical film having the optically anisotropic film according to claim 8 or 9. A polarizing plate having the optical film according to claim 10 and a polarizing element. An image display device having the optical film according to claim 10 or the polarizing plate according to claim 11.

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