JP7042761B2 - Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device - Google Patents

Description

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

Optical films such as optical compensation sheets and retardation films are used in various image display devices from the viewpoints of eliminating image coloring and expanding the viewing angle.
A stretched birefringence film has been used as the optical film, but in recent years, an optically anisotropic film formed by using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound has been used instead of the stretched birefringence film. (See, for example, Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 2010-031223 International Publication No. 2014/010325 Japanese Unexamined Patent Publication No. 2016-081035

As a result of examining the compositions described in Patent Documents 1 to 3, the present inventors have clarified that the filtration pressure increases with time, and in particular, a problem becomes apparent during the production of an optically anisotropic film. Was clarified.

Therefore, it is an object of the present invention to provide a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device capable of suppressing an increase in filtration pressure.

As a result of diligent studies to achieve the above problems, the present inventors have found that an increase in filtration pressure can be suppressed by using a polymerizable liquid crystal composition containing a specific amine compound together with the polymerizable liquid crystal compound. The present invention has been completed.
That is, it was found that the above problem can be achieved by the following configuration.

[1] A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and an amine compound represented by the formula (1) or (2) described later.
[2] The polymerizable liquid crystal composition according to [1], wherein R ⁷ in the formulas (1) and (2) described later represents an alkyl group which may have a substituent.
[3] The polymerizable liquid crystal composition according to [1] or [2], wherein the polymerizable liquid crystal compound is a compound represented by the formula (I) described later.

[4] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [3].
[5] The optically anisotropic film according to [4], which satisfies the following formula (II).
0.50 <Re (450) / Re (550) <1.00 ... (II)
Here, in the formula (II), 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.
[6] An optical film having the optically anisotropic film according to [4] or [5].
[7] A polarizing plate having the optical film according to [6] and a polarizing element.
[8] An image display device having the optical film according to [6] or the polarizing plate according to [7].

According to the present invention, it is possible to provide a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device capable of suppressing an increase in filtration pressure.

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, the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited unless the bonding position is specified, and for example, the formula described later (for example) When D ¹ in I) is -CO-O-, assuming that the position bonded to the Ar side is * 1 and the position bonded to the G ¹ side is * 2, D ¹ is * 1-. It may be CO-O- * 2 or * 1-O-CO- * 2.

[Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound and an amine compound represented by the formula (1) or (2) described later (hereinafter, also abbreviated as "specific amine compound"). It is a sex liquid crystal composition.

In the present invention, as described above, by using the polymerizable liquid crystal composition containing the specific amine compound together with the polymerizable liquid crystal compound, it is possible to suppress an increase in the filtration pressure over time.
This is not clear in detail, but the present inventors speculate as follows.
First, with respect to the known polymerizable liquid crystal compositions described in Patent Documents 1 to 3, etc., the present inventors have increased the filtration pressure over time due to peroxides contained in solvents and additives, and trace amounts. It is speculated that the cause is that the presence of the acid promotes the polymerization reaction of the polymerizable liquid crystal compound.
Therefore, in the present invention, the specific amine compound can neutralize the acid that may exist in the system and suppress the promotion of the unintended polymerization reaction of the polymerizable liquid crystal compound, and as a result, the filtration pressure with time increases. It is probable that it was possible to suppress.
Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.

[Polymerizable liquid crystal compound]
The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention is not particularly limited as long as it is a liquid crystal compound having a polymerizable group.
Here, the type of the polymerizable group of the polymerizable liquid crystal 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.

The type of the polymerizable liquid crystal compound is not particularly limited, but can be classified into a rod-shaped type (rod-shaped liquid crystal compound) and a disk-shaped type (disk-shaped liquid crystal compound) according to its shape. Furthermore, there are a small molecule type and a high molecular type, 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. 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.

The polymerizable liquid crystal compound is preferably a liquid crystal compound exhibiting reverse wavelength dispersibility.
Here, the "liquid crystal compound exhibiting reverse wavelength dispersibility" is a retardation film produced using this, when the in-plane retardation (Re) value at a specific wavelength (visible light range) is measured. It means that the Re value becomes equal or higher as the measurement wavelength becomes larger.

In the present invention, the polymerizable liquid crystal compound is preferably a compound represented by the following formula (I) because it is more excellent in reverse wavelength dispersibility.
L ¹ -SP ¹ -D ^5- (A ¹ ) _a1 -D ^3- (G ¹ ) _g1 -D ¹ -Ar-D ^2- (G ² ) _g2 -D ^4- (A ² ) _a2 -D ^6- SP ² -L ² ... (I)

In the above formula (I), a1, a2, g1 and g2 independently represent 0 or 1, respectively. However, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.
Further, in the above formula (I), D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are independently single-bonded or -CO-, -O-, -S-,-, respectively. C (= S)-, -CR ¹ R ^2- , -CR ³ = CR ^4- , -NR ^5- , or a divalent linking group 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.
Further, in the above formula (I), 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 alicyclic. One or more of -CH _2- constituting the hydrocarbon group may be substituted with -O-, -S- or -NH-.
Further, in the above formula (I), A ¹ and A ² 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 (I), SP ¹ and SP ² 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 (I), L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar is an aromatic ring represented by the following formula (Ar- ³ ), at ^{least one} of L1 and L2 and L3 and L4 in the following formula (Ar- ³ ) is a polymerizable group. Represents.

In the above formula (I), a1, a2, g1 and g2 are all preferably 1.

In the above formula (I), as the divalent linking group represented by D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ , for example, —CO—, —O—, —CO—O—, -C (= S) O-, -CR ^{1 R 2-, -CR 1 R 2-CR 1 R 2-, -O-CR 1 R 2- , -CR 1 R 2 -} O ^- CR ¹ R ^2- , -CO-O-CR ¹ R ^2- , -O-CO-CR ¹ R ^2- , -CR ¹ R ² -O-CO-CR ¹ R ^2- , -CR ¹ R ² -CO-O-CR Examples thereof include ¹ R ^2- , -NR ⁵ -CR ¹ R ^2- , and -CO-NR ^5- . 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), 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 (I), for G ¹ and G ² , examples of the substituent that the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms may have include an alkyl group and an alkoxy group. , Halogen atoms and the like.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or an isopropyl group) is preferable. , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is used. Is particularly preferable.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and carbon is more preferable. It is more preferably an alkoxy group having the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.

In the above formula (I), examples of the aromatic ring having 6 or more carbon atoms represented by A ¹ and A ² 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 (I), examples of the cycloalkane ring having 6 or more carbon atoms represented by A ¹ and A ² 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 ¹ and A ² , G ¹ and G ² in the above formula (I) are examples of substituents that the aromatic ring having 6 or more carbon atoms or the cycloalkane ring having 6 or more carbon atoms may have. Examples include the same substituents that may have.

In the above formula (I), examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ¹ and SP ² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene. Preferred examples include a group, a methylhexylene group, a heptylene group and the like. As described above, in SP ¹ and SP ² , one or more of -CH _2- constituting a linear or branched alkylene group having 1 to 12 carbon atoms are -O-, -S-, and -NH. It may be a divalent linking group substituted with −, −N (Q) − or —CO—, and the substituent represented by Q includes G1 and G in the above formula ( ^I ). Examples thereof include the same substituents that ² may have.

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

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

In the above formula (I), for the reason that the durability is good, it is preferable that both L ¹ and L ² in the above formula (I) are polymerizable groups, and it is preferable that they are acryloyl group or methacryloyl group. More preferred.

On the other hand, in the above formula (I), Ar represents any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-5). In the following formulas (Ar-1) to (Ar-5), * represents the bonding position with D ¹ or D ² in the above formula (I).

In the above formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N (R ⁶ )-, and R ⁶ is 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 ⁶ 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.
Further, examples of the substituent that Y ¹ may have include the same substituents that G ¹ and G ² in the above formula (I) may have.

Further, in the above formulas (Ar-1) to (Ar-5), 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 ⁷ , -NR ⁸ R ⁹ , or , -SR ¹⁰ and R ⁷ to R ¹⁰ 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 R ⁷ to R ¹⁰ , specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group. Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.

Further, in the above formulas (Ar-2) and (Ar ^{- 3} ), A3 and A4 are independently derived from -O-, -N ( ^R11 )-, -S-, and -CO-, respectively. Represents a group selected from the group, where R ¹¹ represents a hydrogen atom or substituent.
Examples of the substituent represented by R ¹¹ include the same substituents that G ¹ and G ² in the above formula (I) may have.

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

Further, in the above formula (Ar-3), D ⁷ and D ⁸ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR ¹ respectively. R ^2- , -CR ³ = CR ^4- , -NR ^5- , or a divalent linking group 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 those described in D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ in the above formula (I).

Further, in the above formula (Ar-3), SP ³ and SP ⁴ 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 G ¹ and G ² in the above formula (I) may have.
Here, examples of the alkylene group include the same groups as those described in SP ¹ and SP ² in the above formula (I).

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

Further, in the above formulas (Ar-4) to (Ar-5), 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-5), Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic. Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, ^Q3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of Patent Document 2 (International Publication No. 2014/010325).
Specific examples of the alkyl group having 1 to 6 carbon atoms indicated by ^Q3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert. -Butyl group, n-pentyl group, n-hexyl group and the like can be mentioned, and the substituents are the same as the substituents that G ¹ and G ² in the above formula (I) may have. Can be mentioned.

Specific examples of the dedispersible liquid crystal compound represented by the above formula (I) include the compound represented by the general formula (I) described in JP-A-2008-297210 (particularly, paragraph number []. 0034] to [0039], compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, compounds described in paragraph numbers [0067] to [0073]). Compounds represented by the general formula (II) described in JP-A-2016-053709 (particularly, compounds described in paragraph numbers [0036] to [0043]), and general documents described in JP-A-2016-081035. Examples thereof include compounds represented by the formula (1) (particularly, compounds described in paragraph numbers [0043] to [0055]).

In the present invention, A ¹ and A ² in the above formula (I) independently form a cycloalkane ring having 6 or more carbon atoms for the reason that the effect of the present invention for suppressing an increase in filtration pressure becomes apparent. It is preferably a polymerizable liquid crystal compound to be represented, and A ¹ and A ² in the above formula (I) each independently represent a cycloalkane ring having 6 or more carbon atoms, and D in the above formula (I). It is more preferable that ³ and D ⁴ are both polymerizable liquid crystal compounds representing a single bond.
Examples of such a polymerizable liquid crystal compound preferably include compounds represented by the following formulas (1) to (12), and specifically, K (specifically, K (1) to (12) in the following formulas (1) to (12). Examples of the side chain structure) include compounds having the side chain structures shown in Tables 1 and 2 below.
In Tables 1 and 2 below, "*" shown in the side chain structure of K represents the bonding position with the aromatic ring.
Further, in the side chain structure represented by 1-2 in Table 1 below and 2-2 in Table 2 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.

[Specific amine compound]
The specific amine compound contained in the polymerizable liquid crystal composition of the present invention is an amine compound represented by the following formula (1) or (2).

In the above formulas (1) and (2), R ¹ to R ⁶ each independently represent an alkyl group which may have a hydrogen atom or a substituent, and R ¹ and R ⁶ are bonded to each other. A ring may be formed.
Further, in the above formulas (1) and (2), R ⁷ represents an alkyl group which may have a hydrogen atom, a hydroxy group, an alkoxy group, or a substituent.
Further, in the above equation (2), m represents an integer of 2 to 4, and each symbol that is present in a plurality in the above equation (2) is different even if they are the same. May be good.
Further, in the above formula (2), X represents a linking group having an m-value.

Here, in the above formulas (1) and ( ² ), as the alkyl group represented by one aspect of ^R1 to R6, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable. Alkyl groups having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable. Alkyl groups of numbers 1 to 4 are more preferable, and methyl groups or ethyl groups are particularly preferable.
Examples of the substituent that the alkyl group may have include the same substituents that G ¹ and G ² in the formula (I) may have.

Further, in the above formulas (1) and (2), as the alkoxy group represented by one aspect of ^R7 , for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, methoxy) is preferable. Groups, ethoxy groups, n-butoxy groups, methoxyethoxy groups, etc.) are more preferable, alkoxy groups having 1 to 4 carbon atoms are further preferable, and methoxy groups or ethoxy groups are particularly preferable.
Further, as the alkyl group shown in one aspect of R ⁷ , for example, the same as the alkyl group shown in one aspect of R ¹ to R ⁶ can be mentioned. Examples of the substituent that the alkyl group may have include the same substituents that G ¹ and G ² in the above formula (I) may have.

In the present invention, R ⁷ in the above formulas (1) and (2) may represent an alkyl group which may have a substituent for the reason that the increase in filtration pressure over time can be further suppressed. preferable.

Further, in the above formula (2), m represents an integer of 2 to 4, but is preferably 2 or 3.

Further, in the above formula (2), among the m-valent linking groups represented by X, the divalent linking group includes, for example, a linear or branched alkylene group having 1 to 12 carbon atoms; a substituent. Examples thereof include a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent; and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. In addition, one or more of -CH _2- which constitutes an alkylene group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group may be -O-, -S-, -NH-, -N (Q)-, or -N (Q)-. , -CO- may be substituted.
Specific 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. Groups and the like are preferably mentioned.
Specific preferred examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include a cyclopentanediyl group, a cyclohexanediyl group, a cyclohexenediyl group, a norbornanediyl group, and a norbornenediyl group. Be done.
As the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, specifically, for example, a benzenediyl group (phenylene group), a toluenediyl group, a xylene diyl group, a naphthalene diyl group, an anthrasendiyl group and the like are preferable. Listed in.
The substituents that the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have are the same as the substituents that G ¹ and G ² in the above formula (I) may have. Things can be mentioned.

Further, in the above formula (2), among the m-valent linking groups represented by X, the trivalent linking group includes, for example, a trivalent cycloalkyl group, a trivalent aryl group, and a trivalent heteroaryl group. Examples include groups represented by the following formulas. In the following formula, * represents the bond position with the piperidine ring, and R ⁸ represents a hydrogen atom, an alkyl group or an aryl group.

Further, in the above formula (2), among the m-valent linking groups represented by X, examples of the tetravalent linking group include a tetravalent arylene group and a group represented by the following formula. In the following formula, * represents the bonding position with the piperidine ring.

In the present invention, in the above formula (1), R ¹ and R ⁶ may be bonded to each other to form a ring as described above.
Here, the ring formed is not particularly limited as long as it is a ring having four or more members including a nitrogen atom, and examples of the amine compound having such a ring structure include the following formula (1-1). Examples thereof include an amine compound having a ring structure represented by.

In the above formula (1-1), R ² to R ⁵ each independently have an alkyl group which may have a hydrogen atom or a substituent, as in the case of R ² to R ⁵ in the above formula (1). show.
Further, in the above formula (1-1), R ⁷ is an alkyl group which may have a hydrogen atom, a hydroxy group, an alkoxy group, or a substituent, like R ⁷ in the above formula (1). show.
Further, in the above formula (1-1), R ¹⁰ represents a hydrogen atom or a substituent.
Examples of the substituent indicated by R ¹⁰ include an alkyl group and a substituent that binds to the piperidine ring at a nitrogen atom or an oxygen atom. Examples of the substituent that binds to the piperidin ring at the nitrogen atom or the oxygen atom include an amino group, an acylamino group, a hydroxy group, an alkoxy group, an aryloxy group or an acyloxy group. In addition, these groups may further have a substituent.
Of these, the substituent indicated by R ¹⁰ is preferably an alkyl group, an amino group (particularly, an amino group having an aryl group or a heterocyclic group), a hydroxy group, an alkoxy group or an acyloxy group.

Specific examples of the compound represented by the above formula (1) include N, N-diisopropylethylamine (DIPEA) and examples of the compound represented by the above formula (1-1) described later. Can be mentioned.

Specific examples of the compound represented by the above formula (1-1) include 4-hydroxy-2,2,6,6-tetramethylpiperidine and 4-stearoyloxy-2,2,6,6. -Tetramethylpiperidine, 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 1,2 , 2,6,6-pentamethylpiperidine-4-yl-β (3,5-di-t-butyl-4-hydroxyphenyl) -propionate and the like.

On the other hand, as the compound represented by the above formula (2), specifically, for example,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylic acid (ADEKA STAB LA-52, manufactured by ADEKA);
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylic acid (ADEKA STAB LA-57, manufactured by ADEKA);
1,2,3,4-butanetetracarboxylic acid tetramethylester, 1,2,2,6,6-pentamethyl-4-piperidinol, β, β, β', β'-tetramethyl-2,4 , 8,10-Tetraoxaspiro [5.5] Undecane-3,9-Reaction mixture with diethanol (ADEKA STAB LA-63P, manufactured by ADEKA);
1,2,3,4-Butanetetracarboxylic acid tetramethyl ester, 2,2,6,6-tetramethyl-4-piperidinol, β, β, β', β'-tetramethyl-2,4 Reaction mixture with 8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol (ADEKA STAB LA-68, manufactured by ADEKA);
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacic acid (ADEKA STAB LA-72, manufactured by ADEKA);
Bis (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacic acid;
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacic acid (ADEKA STAB LA-77Y / ADEKA STAB LA-77G, manufactured by ADEKA);
Bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81, manufactured by ADEKA);
1,2,2,6,6-pentamethyl-4-piperidylmethacrylate (ADEKA STAB LA-82, manufactured by ADEKA);
2,2,6,6-Tetramethyl-4-piperidylmethacrylate (ADEKA STAB LA-87, manufactured by ADEKA);
Trimeritoic acid-tris (2,2,6,6-tetramethylpiperidin-4-yl) ester;
Dibutyl malonic acid-bis (1,2,2,6,6-pentamethyl-piperidine-4-yl) ester;
Dibenzylmalonic acid-bis (1,2,3,6-tetramethyl-2,6-diethyl-piperidine-4-yl) ester;
Dimethyl-bis (2,2,6,6-tetramethylpiperidin-4-yloxy) -silane;
Tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosfit;
Tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphate;
N, N'-bis (2,2,6,6-tetramethylpiperidine-4-yl) -hexamethylene-1,6-diamine;
N, N'-bis- (2,2,6,6-tetramethylpiperidine-4-yl) -hexamethylene-1,6-diacetamide;
4-Benzylamino-2,2,6,6-tetramethylpiperidine, N, N'-bis- (2,2,6,6-tetramethylpiperidine-4-yl) -N, N'-dibutyl-adipamide ;
N, N'-bis (2,2,6,6-tetramethylpiperidine-4-yl) -N, N'-dicyclohexyl- (2-hydroxy) propyleneindiamine;
N, N'-bis- (2,2,6,6-tetramethylpiperidine-4-yl) -p-xylylene-diamine;
4-Bis (2-hydroxyethyl) amino-1,2,2,6,6-pentamethylpiperidine;
4-Methacrylamide-1,2,2,6,6-pentamethylpiperidine;
α-cyano-β-methyl-β- [N- (2,2,6,6-tetramethylpiperidin-4-yl)]-amino-acrylic acid methyl ester;
And so on.

In the present invention, the content of the specific amine compound is preferably 0.001 to 1.0 part by mass, preferably 0.01 to 0.8 part by mass with respect to 100 parts by mass of the above-mentioned polymerizable liquid crystal compound. Is more preferable, and 0.05 to 0.5 parts by mass is further preferable.

[Other polymerizable compounds]
In addition to the above-mentioned polymerizable liquid crystal compound, the polymerizable liquid crystal composition of the present invention may contain other polymerizable compounds having one or more polymerizable groups.
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.

The other polymerizable compound is preferably another polymerizable compound having 1 to 4 polymerizable groups because the durability of the formed optically anisotropic film is improved, and the polymerizable group is preferably used. More preferably, it is another polymerizable compound having two.

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 other polymerizable compounds are contained, the content is preferably less than 50% by mass, more preferably 40% by mass or less, based on the mass of the above-mentioned polymerizable liquid crystal compound. It is more preferably 2 to 30% by mass.

[Polymer initiator]
The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-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 Application Laid-Open No. 63-40799, Japanese Patent Application Laid-Open No. 5-29234, Japanese Patent Application Laid-Open No. 10-95788, Japanese Patent Application Laid-Open No. 10-29997) and the like.
Further, in the present invention, 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 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, 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. Examples thereof include agents and cross-linking agents.

[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 film of the present invention preferably satisfies the following formula (II).
0.50 <Re (450) / Re (550) <1.00 ... (II)
Here, in the above formula (II), 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.
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).

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 phase axial direction (the direction in which the refractive index in the plane is maximized) in the film plane is nx, the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny, and the refraction in the thickness direction. When the rate is nz, the positive A plate satisfies the relation of the formula (A1), 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) x d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in "ny≈nz", and when (nx-nz) xd is -10 to 10 nm, preferably -5 to 5 nm, it is also included in "nx≈nz". Further, in the positive C plate, for example, when (nx-ny) × d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, it is also included in “nx≈ny”.

When the optically anisotropic 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 hardcoat 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 membranes]
The optical film of the present invention may have another optically anisotropic film in addition to the optically anisotropic film of the present invention.
That is, the optical film of the present invention may have a laminated structure of the optically anisotropic film of the present invention and another optically anisotropic film.
Such other optically anisotropic films are particularly good as long as they are optically anisotropic films obtained by using the above-mentioned other polymerizable compounds (particularly, liquid crystal compounds) without blending the above-mentioned polymerizable liquid crystal compound. Not 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, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 (all manufactured by BASF) and the like can be used.

[Polarizer]
The polarizing plate of the present invention has the above-mentioned optical film of the present invention and a 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, a polyvinyl alcohol-based resin (a polymer containing _-CH2 -CHOH- as a repeating unit. In particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers) is excellent in adhesion. It is preferable that the polymer contains one).

In the present invention, the thickness of the polarizing element is not particularly limited, but is preferably 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 preferably a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. Not limited to.
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, from the viewing side, a λ / 4 plate (positive A plate) made of a polarizing element, an optically anisotropic film of the present invention, and an organic EL. 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]
10.2 g of cyclopentanone is added to 1.8 g of the following polymerizable liquid crystal compound L-1 and 3.0 mg of the following N, N-diisopropylethylamine (DIPEA), and the mixture is stirred at room temperature (23 ° C.) for 1 hour. Then, the polymerized liquid crystal composition was prepared by heating at 60 ° C. for 10 minutes to dissolve the mixture.
Then, the prepared polymerizable liquid crystal composition was filtered through a 0.45 μm filter and then allowed to stand at room temperature for 5 days.
Then, 5 mL of the solution was taken in a 6 cc syringe and a weight of 6 kg was applied with a 0.45 μm filter. As a result, the liquid flow volume after 180 seconds was 3.1 mL.

Polymerizable liquid crystal compound L-1

N, N-diisopropylethylamine (DIPEA)

[Example 2]
Examples except that bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacic acid (ADEKA STAB LA-72, manufactured by ADEKA) represented by the following formula was used instead of DIPEA. The same operation as in 1 was performed. As a result, the liquid flow volume after 180 seconds was 3.7 mL.

[Example 3]
The same operation as in Example 1 was performed except that Tinuvin 123 (manufactured by BASF) represented by the following formula was used instead of DIPEA. As a result, the liquid flow volume after 180 seconds was 2.6 mL.

[Comparative Example 1]
The same operation as in Example 1 was performed except that Teklan DO was not added. As a result, the liquid flow volume after 180 seconds was 0.8 mL.

[Comparative Example 2]
The same operation as in Example 1 was performed except that TEMPO represented by the following formula was used instead of DIPEA. As a result, the liquid flow volume after 180 seconds was 1.0 mL.

Table 3 below shows the blending amounts of the polymerizable liquid crystal compounds and the like in Examples 1 to 3 and Comparative Examples 1 and 2, and the amount of liquid passing 180 seconds after being allowed to stand for 5 days.

From the results shown in Table 3 above, it was found that when the amine compound was not blended, the amount of liquid flowing after standing for 5 days decreased and the filtration pressure increased (Comparative Example 1).
Further, it was found that when another amine compound not corresponding to the specific amine compound was blended, the amount of liquid passing through after standing for 5 days decreased and the filtration pressure increased as in Comparative Example 1 (comparison). Example 2).
On the other hand, it was found that when the specific amine compound was blended, the amount of liquid flowing was large even after being allowed to stand for 5 days, and the increase in the filtration pressure could be suppressed (Examples 1 to 3).
In particular, from the comparison between Examples 1 and 2 and Example 3, when an amine compound in which ^R7 in the above formulas (1) and (2) represents an alkyl group which may have a substituent is used, it can be used. It was found that the increase in filtration pressure over time can be further suppressed.

10 Optical film 12 Optical anisotropic film 14 Alignment film 16 Support 18 Hardcourt layer

Claims (7)

A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound which is a compound represented by the following formula (I) and an amine compound represented by the following formula (1) or (2).
L ¹ - SP ¹ - D ^5- (A ¹ ) _a1 - D ^3- (G ¹ ) _g1 - D ¹ -Ar-D ^2- (G ² ) _g2 - D ^4- (A ² ) _a2 - D ^6- SP ² -L ² ... (I)

Here, in the above equations (1) and (2),
R ¹ to R ⁶ each independently represent an alkyl group which may have a hydrogen atom or a substituent, and R ¹ and R ⁶ may be bonded to each other to form a ring.
R ⁷ represents an alkyl group which may have a hydrogen atom, a hydroxy group, an alkoxy group, or a substituent.
m represents an integer of 2 to 4, and each symbol that is present in a plurality in the equation (2) may be the same or different.
X represents a linking group having an m-value.
In the formula (I),
a1, a2, g1 and g2 independently represent 0 or 1, respectively. However, at least one of a1 and g1 represents 1, and at least one of a2 and g2 represents 1.
D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are independently single-bonded or -CO-, -O-, -S-, -C (= S)-, -CR. ¹ R ^2- , -CR ³ = CR ^4- , -NR ^5- , or a divalent linking group 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.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, and constitutes the alicyclic hydrocarbon group-CH. One or more of _2- may be substituted with -O-, -S- or -NH-.
A ¹ and A ² each independently represent a cycloalkane ring having 6 or more carbon atoms.
SP ¹ and SP ² independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -CH _2- represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where Q is a substituent. Represents.
L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar is an aromatic ring represented by the following formula (Ar- ³ ), at ^{least one} of L1 and L2 and L3 and L4 in the following formula (Ar-3) ^is a polymerizable group. Represents.
Ar represents any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-5).

Here, in the above equations (Ar-1) to (Ar-5),
* Represents the bonding position with D ¹ or D ² .
Q ¹ represents N or CH.
Q2 represents -S-, -O-, or -N (R ⁶ )-, and R 6 represents ^a hydrogen atom or an alkyl group having 1 to ⁶ carbon atoms.
Y ¹ 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 ⁷ , -NR ⁸ R ⁹ , or -SR ¹⁰ , where R ⁷ to R ¹⁰ 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 ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N (R ¹¹ )-, -S-, and -CO-, where R ¹¹ is a hydrogen atom or Represents a substituent.
X represents a group 14-16 non-metal atom to which a hydrogen atom or a substituent may be bonded.
D ⁷ and D ⁸ 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 ³ and SP ⁴ independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -CH _2- represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, where Q is a substituent. Represents.
L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ and L ² in the above formula (I) represents a polymerizable group.
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
Ay has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , Represents an organic group having 2 to 30 carbon atoms.
The aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Q3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent ^. The polymerizable liquid crystal composition according to claim 1, wherein R ⁷ in the formulas (1) and (2) represents an alkyl group which may have a substituent. An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to claim 1 or 2 . The optically anisotropic film according to claim 3 , which satisfies the following formula (II).
0.50 <Re (450) / Re (550) <1.00 ... (II)
Here, in the formula (II), 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 3 or 4 . A polarizing plate having the optical film according to claim 5 and a polarizing element. An image display device having the optical film according to claim 5 or the polarizing plate according to claim 6 .

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