JP2020129059A - Liquid crystal photo-aligning agent, liquid crystal alignment film, liquid crystal display element using the same, and diamine, (meth)acrylate, and polymer - Google Patents

Abstract

To provide a liquid crystal alignment film which allows for imparting anisotropy by a photo-alignment method and has a high transmittance, and to provide a liquid crystal display element.SOLUTION: A liquid crystal photo-aligning agent is used, containing a polymer having a constituent unit with an azobenzene derivative on a side chain. Heating the liquid crystal photo-aligning agent causes chemical reaction of the constituent unit containing the azobenzene derivative.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display device using the same. Specifically, a liquid crystal alignment agent for forming a liquid crystal alignment film of a photo-alignment system (hereinafter sometimes abbreviated as a photo alignment film), and a liquid crystal alignment film of a photo-alignment system formed by using the liquid crystal alignment agent. And a liquid crystal display device having this liquid crystal alignment film. Further, the present invention relates to polymers such as polyamic acid, polyimide, poly(meth)acrylate used for the liquid crystal aligning agent, and diamine and (meth)acrylate as raw materials thereof.

Liquid crystal display devices include TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, IPS (In-Plane Switching) mode, FFS (Fringe Field Switching) mode, and vertical alignment type VA (Multi-domain Vertical Alignment) mode. Various driving methods are known. These liquid crystal display elements are applied to image display devices of various electronic devices such as televisions and mobile phones, and are being developed with the aim of further improving the display quality. Specifically, the improvement of the performance of the liquid crystal display device is achieved not only by the improvement of the driving method and the device structure but also by the constituent members used for the device. Among the components used for the liquid crystal display element, the liquid crystal alignment film is one of the important materials related to the display quality, and in order to meet the demand for high quality of the liquid crystal display element, the liquid crystal alignment film is required. Is also actively researched.

Here, the liquid crystal alignment film is provided on a pair of substrates provided on both sides of the liquid crystal layer of the liquid crystal display element so as to be in contact with the liquid crystal layer, and liquid crystal molecules constituting the liquid crystal layer are fixed to the substrate at a certain level. It has the function of aligning with regularity. By using a liquid crystal alignment film having a high liquid crystal alignment property, it is possible to realize a liquid crystal display element having high contrast and improved afterimage characteristics (for example, see Patent Documents 1 and 2).
In order to form such a liquid crystal alignment film, a solution (varnish) in which polyamic acid, soluble polyimide, polyamic acid ester or poly(meth)acrylate is dissolved in an organic solvent is mainly used at present. To form a liquid crystal alignment film with these varnishes, after applying the varnish to the substrate, the coating film is solidified by heating or the like to form a liquid crystal alignment film, and if necessary, an alignment treatment suitable for the above-mentioned display mode is performed. Give. The alignment treatment method includes rubbing the surface of the alignment film by rubbing the surface of the alignment film with a cloth to adjust the direction of the polymer molecules, and irradiating the alignment film with linearly polarized ultraviolet rays to cause photoisomerization or dimerization of the polymer molecules. A photo-alignment method that causes photochemical change to impart anisotropy to the film is known. Among them, the photo-alignment method has higher alignment uniformity than the rubbing method, and a non-contact alignment treatment method. Therefore, there are advantages that the film is not scratched and that the cause of display failure of the liquid crystal display element such as dust generation and static electricity can be reduced.

As a liquid crystal alignment film using such a photo-alignment method, for example, in Patent Documents 1 to 6, a photo-alignment film having a large anchoring energy and a good liquid crystal alignment property is obtained by applying a photoisomerization technique. It is described.

JP, 2010-197999, A International publication 2013/1574643 JP, 2005-275364, A JP, 2007-248637, A Japanese Patent Laid-Open No. 2009-069493 Japanese Patent Laid-Open No. 8-328005

As described above, the liquid crystal alignment film formed by performing the alignment treatment by the photo-alignment method is known. In order to impart anisotropy to the film, a photoreactive structure that causes a photochemical reaction such as photoisomerization or dimerization in the polymer molecule is used. For example, Patent Document 6 describes that good alignment can be obtained by producing a liquid crystal cell with a liquid crystal alignment film using an azobenzene derivative as a photoreactive structure. However, there is a problem that the transmittance of the liquid crystal alignment film is lowered due to the absorption in the visible light region peculiar to the azobenzene derivative.

Therefore, in order to solve the problems of the conventional art, the inventors of the present invention can impart anisotropy by a photo-alignment method and have a high transmittance, and a liquid crystal alignment film such as this. The present inventors have conducted intensive studies for the purpose of providing a liquid crystal aligning agent capable of forming an alignment film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polymer having a constitutional unit containing an azobenzene derivative, and a constitutional unit containing the azobenzene derivative undergoes a chemical reaction when heated by a liquid crystal. By using it as an aligning agent, it is possible to change its constitutional unit to a structure that does not contain an azobenzene derivative in the heating/baking process after the photo-alignment treatment of the coating film of the liquid crystal aligning agent. We have come to the knowledge that a high-quality liquid crystal alignment film can be realized. The present invention has been proposed on the basis of such findings, and specifically has the following configurations.

[1] A liquid crystal aligning agent for photo-alignment containing a polymer having a constitutional unit containing a photoreactive structure in a side chain, wherein the constitutional unit containing the photoreactive structure causes a chemical reaction by heating. Liquid crystal aligning agent.
[2] The liquid crystal aligning agent for photo-alignment according to [1], wherein the chemical reaction is a cyclization reaction.
[3] The photo-alignment according to [1] or [2], wherein the structural unit containing the photoreactive structure contains a structure represented by the following formula (a-1) or the following formula (a-2). Liquid crystal aligning agent;

[In the formula (a-1), R ^a represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
In formula (a-2), R ^b and R ^c each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. ;
In formula (a-1) and formula (a-2), * represents the bonding position with the photoreactive group. ]
[4] The liquid crystal aligning agent for photoalignment according to any one of [1] to [3], wherein the photoreactive structure is a photoisomerization structure or a structure that causes photo-Fries rearrangement.
[5] The liquid crystal aligning agent for photoalignment according to any one of [1] to [4], wherein the photoreactive structure has a structure represented by the following formula (1A).

[In Formula (1A), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
* Represents a bond position in the benzene ring, and is any position which can be replaced with a hydrogen atom in one benzene ring and any position which can be replaced with a hydrogen atom in the other benzene ring;
The hydrogen atom of the benzene ring may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (1A). ]
[6] The polymer contains a polymer which is a reaction product from a raw material containing tetracarboxylic dianhydride and diamine;
The reaction product is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide,
The said diamine is the liquid crystal aligning agent for optical alignment in any one of [1]-[5] containing at least 1 of the diamine represented by following formula (2).

[In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O-CO-CH=CH- represents and the number of ^R3r is 2, ^R3r may be the same or different, and ^R3q and ^R3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cycloaliphatic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of combinations thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ]
[7] The liquid crystal aligning agent for optical alignment according to [6], wherein the diamine represented by the formula (2) is a diamine represented by the following formula (3).

[In Formula (3), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a linear alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one or —CH ₂ — of the linear alkylene group or two non-adjacent ones is replaced by —O—. May;
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ]
[8] The liquid crystal for optical alignment according to [6] or [7], wherein the diamine represented by the formula (3) is a diamine represented by any of the following formulas (4) to (6). Alignment agent.

[In the formulas (4) to (6), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
n represents a positive integer of 1 to 12. ]
[9] The diamine is the following formula (4-1-1), formula (4-1-2), formula (4-2-1), formula (4-2-2) or formula (5-1-1). ), formula (5-1-2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6-1-2), formula (6 2-1) and the liquid crystal aligning agent for optical alignment according to any one of [6] to [8], which is a diamine represented by any of the formulas (6-2-2).

[Formula (4-1-1), Formula (4-1-2), Formula (4-2-1), Formula (4-2-2), Formula (5-1-1), Formula (5- 1-2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6-1-2), formula (6-2-1), In the formula (6-2-2), n represents a positive integer of 1-12. ]
[10] In any one of [1] to [5], containing poly(meth)acrylate which is a reaction product from a raw material containing (meth)acrylate represented by the following formula (7) as the polymer. The liquid crystal aligning agent for optical alignment as described above.

[In formula (7), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O-CO-CH=CH- represents and the number of ^R3r is 2, ^R3r may be the same or different, and ^R3q and ^R3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cycloaliphatic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of combinations thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (7). ]
[11] The liquid crystal aligning agent for optical alignment according to [10], wherein the (meth)acrylate represented by the formula (7) is a (meth)acrylate represented by the following formula (8).

[In formula (8), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a straight chain alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one of —CH ₂ — of the straight chain alkylene group or two non-adjacent groups is replaced with —O—, May be listed;
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (8). ]
[12] The (meth)acrylate represented by the formula (8) is the (meth)acrylate represented by any of the following formulas (9) to (11), [10] or [11]. , A liquid crystal aligning agent for photo-alignment.

[In the formulas (9) to (11), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
R ⁹ represents a hydrogen atom or a methyl group;
n represents a positive integer of 1 to 12. ]
[13] The (meth)acrylate is represented by the following formula (9-1-1), formula (9-1-2), formula (9-2-1), formula (9-2-2), formula (10- 1-1), formula (10-1-2), formula (10-2-1), formula (10-2-2), formula (11-1-1), formula (11-1-2), The liquid crystal alignment for optical alignment according to any one of [10] to [12], which is a (meth)acrylate represented by any of formula (11-2-1) and formula (11-2-2). Agent.

[Formula (9-1-1), Formula (9-1-2), Formula (9-2-1), Formula (9-2-2), Formula (10-1-1), Formula (10- 1-2), formula (10-2-1), formula (10-2-2), formula (11-1-1), formula (11-1-2), formula (11-2-1), In and (11-2-2), n represents a positive integer of 1-12. ]
[14] A liquid crystal alignment film formed by the liquid crystal alignment agent for optical alignment according to any one of [1] to [13].
[15] A liquid crystal display device having the liquid crystal alignment film according to [14].
[16] A diamine represented by the following formula (2).

[In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O 3 is 2 and the number of R ^3r is 2, R ^3r may be the same or different, and R ^3q and R ^3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ]
[17] The diamine according to [16], which is represented by the following formula (3).

[In Formula (3), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a linear alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one or —CH ₂ — of the linear alkylene group or two non-adjacent ones is replaced by —O—. May;
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ]
[18] The diamine according to [17] represented by any of the following formulas (4) to (6).

[In the formulas (4) to (6), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
n represents a positive integer of 1 to 12. ]
[19] Formula (4-1-1), Formula (4-1-2), Formula (4-2-1), Formula (4-2-2), Formula (5-1-1), Formula (5-1-2), Formula (5-2-1), Formula (5-2-2), Formula (6-1-1), Formula (6-1-2), Formula (6-2- 1) and the diamine as described in [17] represented by Formula (6-2-2).

[Formula (4-1-1), Formula (4-1-2), Formula (4-2-1), Formula (4-2-2), Formula (5-1-1), Formula (5- 1-2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6-1-2), formula (6-2-1), In the formula (6-2-2), n represents a positive integer of 1-12. ]
[20] A (meth)acrylate represented by the following formula (7).

[In formula (7), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O-CO-CH=CH- represents and the number of ^R3r is 2, ^R3r may be the same or different, and ^R3q and ^R3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cycloaliphatic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of combinations thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (7). ]
[21] The (meth)acrylate according to [20] represented by the following formula (8).

[In formula (8), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a straight chain alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one of —CH ₂ — of the straight chain alkylene group or two non-adjacent groups is replaced with —O—, May be listed;
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (8). ]
[22] The (meth)acrylate according to [21] represented by any of the following formulas (9) to (11).

[In the formulas (9) to (11), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
R ⁹ represents a hydrogen atom or a methyl group;
n represents a positive integer of 1 to 12. ]
[23] A polymer which is a reaction product from a raw material containing tetracarboxylic dianhydride and diamine;
The reaction product is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide,
The diamine is a polymer containing at least one diamine represented by the following formula (2).

[In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O-CO-CH=CH- represents and the number of ^R3r is 2, ^R3r may be the same or different, and ^R3q and ^R3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cycloaliphatic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of combinations thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]

[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ]
[24] A poly(meth)acrylate which is a reaction product from a raw material containing a (meth)acrylate represented by the following formula (7).

[In formula (7), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O-CO-CH=CH- represents and the number of ^R3r is 2, ^R3r may be the same or different, and ^R3q and ^R3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a cycloaliphatic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of combinations thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent.

According to the liquid crystal aligning agent for photo-alignment of the present invention, anisotropy can be imparted by the photo-alignment method and a liquid crystal aligning film having high transmittance can be formed. Further, by using the liquid crystal alignment film formed of the liquid crystal alignment agent for optical alignment of the present invention, it is possible to realize a liquid crystal display device in which the liquid crystal layer is highly aligned and excellent in afterimage characteristics.

Hereinafter, the present invention will be described in detail. The description of the constituents described below may be made based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. Further, the “liquid crystal aligning agent for photo-alignment” in the present invention means a liquid crystal aligning agent capable of imparting anisotropy by irradiating polarized light when the film is formed on a substrate. In the writing, it may be simply referred to as "liquid crystal aligning agent". In the present specification, “(meth)acrylate” means “either one or both of acrylate and methacrylate”. Similarly, "poly(meth)acrylate" means "one or both of polyacrylate and polymethacrylate", and "(meth)acryloyloxy group" means "any one or both of acryloyloxy group and methacryloyloxy group". means.

Liquid Crystal Alignment Agent for Photo Alignment The liquid crystal alignment agent for photo alignment of the present invention contains a polymer having a constitutional unit having a photoreactive structure in a side chain and having a constitutional unit that causes a chemical reaction by heating. According to the liquid crystal aligning agent of the present invention, the alignment property can be imparted by the photo-alignment method.
In the present specification, the “photoreactive structure” means an atomic group whose structure is changed by irradiation with light. Such a photoreactive structure usually has a specific site (photoreactive group) that absorbs light and causes a chemical change, and the structure changes due to the chemical change of the photoreactive group. In the following description, the chemical reaction of the photoreactive structure caused by such light absorption is called “photochemical reaction”, and the structural change caused by the photochemical reaction is called photochemical change. The photochemical reaction is a chemical reaction caused by electrons being excited by absorbing light, and is distinguished from a chemical reaction caused by heating. Specific examples of photochemical changes include photoisomerization and photo-Fries rearrangement. The wavelength of light that causes a structural change in the photoreactive structure is not particularly limited, but is preferably 150 to 800 nm, more preferably 200 to 400 nm, and further preferably 300 to 400 nm. Further, the light irradiation intensity required to cause a structural change in the photoreactive structure is preferably 0.05 to 20 J/cm ² .

In the present specification, the “structural unit containing a photoreactive structure” is a structural unit that constitutes a polymer and means a structural unit including a photoreactive structure as described above. The structural unit containing a photoreactive structure in the polymer contained in the liquid crystal aligning agent for photoalignment of the present invention is one that further causes a chemical reaction by heating. In the following description, a constitutional unit containing a photoreactive structure that causes a chemical reaction by heating may be referred to as a “constitutional unit containing a thermoreactive photoreactive structure”. The chemical reaction caused by heating is not particularly limited, but it is preferably a reaction for converting a photoreactive group having a photoreactive structure into a structure having no photoreactive property, such as cyclization of the photoreactive group and another group. The reaction is particularly preferable. As a result, the linearity of the polymer is increased, and a liquid crystal alignment film with higher alignment can be obtained. The heating temperature for causing the chemical reaction is preferably 40 to 300°C, more preferably 100 to 300°C, and further preferably 150 to 280°C. The heating time is preferably 1 minute to 3 hours, more preferably 5 minutes to 1 hour, and further preferably 15 minutes to 45 minutes. Regarding the heating temperature and the heating time for causing the chemical reaction, the heating time is preferably 10 minutes to 3 hours when the heating temperature is 40 to 180°C, and the heating time is preferably when the heating temperature is 180 to 300°C. It is preferably 1 minute to 1 hour. Above all, it is more preferable that the heating temperature is 150 to 280° C. and the heating time is 10 minutes to 1 hour from the viewpoint that the reaction efficiency can be increased.

The liquid crystal aligning agent for liquid crystal alignment (liquid crystal aligning agent) of the present invention is used for forming a liquid crystal aligning film. To form a liquid crystal alignment film with the liquid crystal aligning agent of the present invention, for example, a liquid crystal aligning agent is applied to a substrate to form a film, and then polarized light for optical alignment is irradiated. As a result, the photoreactive structure of the polymer side chain, which is approximately parallel to the polarization direction, selectively undergoes a photochemical reaction to change the structure, and the polymer side chain component (structure change) As a result, the component oriented in a specific direction) becomes dominant. After that, the photo-aligned film is heated and baked to form a solid liquid crystal alignment film. At this time, in the polymer used in the present invention, the structural unit having a photoreactive structure undergoes a chemical reaction by heating, the photoreactive group disappears, and the number of photoreactive groups decreases in the entire film. Or the photoreactive group is absent. Therefore, when the photoreactive group includes or is a part of a structure that absorbs light in the visible light region such as azobenzene, the number of photoreactive groups is reduced to form a liquid crystal alignment film with high transmittance. It can be a possible liquid crystal aligning agent.
For the detailed conditions for forming the liquid crystal alignment film, the description in the column of the liquid crystal alignment film can be referred to.
The polymer having a constitutional unit containing a heat-reactive photoreactive structure contained in the liquid crystal aligning agent of the present invention will be described below. In the following description, the “polymer having a constitutional unit containing a heat-reactive photoreactive structure” may be referred to as a “polymer containing a heat-reactive photoreactive structure”.

[Polymer having a structural unit containing a thermoreactive photoreactive structure]
The liquid crystal aligning agent of the present invention contains a polymer having a side chain of a structural unit containing a photoreactive structure that causes a chemical reaction by heating. Since the polymer having a structural unit containing a heat-reactive photoreactive structure used in the present invention has a photoreactive structure in the side chain, when a liquid crystal alignment film is formed by selecting the side chain linking group described below. The pretilt angle can be adjusted to any value.

The structural units constituting the polymer may be all structural units containing a heat-reactive photoreactive structure, or some of them may be a structural unit containing a heat-reactive photoreactive structure and the rest may be a thermal reaction. It may be a constitutional unit containing no photoreactive structure. The number of structural units containing a thermoreactive photoreactive structure in the polymer is not particularly limited, but is preferably 3 to 500, more preferably 5 to 400, and more preferably 5 to 400 per 1 molecule of the polymer. It is more preferable that the number is 300. When the polymer has two or more constitutional units containing a thermally reactive photoreactive structure, the plural constitutional units may be the same or different from each other.

(Structural unit containing a heat-reactive photoreactive structure)
The structural unit containing a heat-reactive photoreactive structure in the polymer contained in the liquid crystal aligning agent of the present invention contains a photoreactive structure whose structure is changed by irradiation of light, and causes a chemical reaction by heating. is there.
The constitutional unit containing the heat-reactive photoreactive structure may be composed of only the heat-reactive photoreactive structure, or may include other structures. The number of heat-reactive photoreactive structures contained in the structural unit may be one or two or more. When the structural unit includes two or more thermoreactive photoreactive structures, these thermoreactive photoreactive structures may be the same or different from each other.

The constitutional unit containing a heat-reactive photoreactive structure preferably contains at least one of the structure represented by the following formula (a-1) and the structure represented by the following formula (a-2). In the structural unit having such a structure, when the coating film of the liquid crystal aligning agent is heated, the substituent of the benzene ring in each formula and the photoreactive group undergo a cyclization reaction to eliminate the photoreactive group, and thus the entire film is formed. The number of photoreactive groups is reduced or the photoreactive groups are absent. As a result, a liquid crystal alignment film that is stable to light can be formed.
Here, the structural unit may include only the structure represented by the formula (a-1) or may include only the structure represented by the formula (a-2). Both the structure represented by and the structure represented by formula (a-2) may be included. Further, the number of structures represented by the formula (a-1) and the number of structures represented by the formula (a-2) contained in the structural unit are each 1 or 2 or more. Good. When the structural unit includes two or more structures represented by formula (a-1), these structures may be the same or different from each other, and the structural unit is represented by formula (a-2). When two or more of the structures described above are included, these structures may be the same or different from each other.

In formula (a-1), R ^a represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. In formula (a-2), R ^b and R ^c each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. .. R ^b and R ^c may be the same or different from each other. In Formula (a-1) and Formula (a-2), * is a bonding position with the photoreactive group. * May be directly bonded to the photoreactive group, or may be linked to the photoreactive group via a divalent group.

In formula (a-1), the alkyl group for R ^a may be linear, branched, or cyclic. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1 Examples thereof include a methylbutyl group, a 1-ethylpropyl group, a hexyl group, an isohexyl group, a 1-methylpentyl group and a 1-ethylbutyl group.
The alkanoyl group for R ^a may be linear, branched or cyclic. The alkanoyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 2 carbon atoms, and even more preferably 1 carbon atom. Specific examples of the alkanoyl group include a methanoyl group, an ethanoyl group, a propanoyl group, an isopropanoyl group, a butanoyl group, an isobutanoyl group, a sec-butanoyl group, a tert-butanoyl group, a pentanoyl group, an isopentanoyl group, a neopentanoyl group, Examples thereof include a tert-pentanoyl group, a 1-methylbutanoyl group, a 1-ethylpropanoyl group, a hexanoyl group, an isohexanoyl group, a 1-methylpentanoyl group and a 1-ethylbutanoyl group.
The aryl group of the arylcarbonyl group for R ^a may be either a single ring or a condensed ring. The aryl group has preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and further preferably 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like. Specific examples of the arylcarbonyl group include a phenylcarbonyl group and a 1-naphthylcarbonyl group.
The alkyl group, alkanoyl group and arylcarbonyl group for R ^a may each be substituted with a substituent. Examples of the substituent include a hydroxyl group, an amino group, a halogeno group and the like.
Of these, R ^a is preferably ^a methyl group, an ethyl group, a propyl group, a hydrogen atom, a methanoyl group, or a phenyl group from the viewpoint that the performance of the finally produced liquid crystal alignment film can be improved.

In formula (a-2), the alkyl group, alkanoyl group, arylcarbonyl group for R ^b and R ^c , and the substituents that may be substituted on these groups, the preferred ranges, and specific examples are as described above in formula (a- Reference can be made to the description, preferred ranges, and specific examples of the alkyl group, alkanoyl group, arylcarbonyl group and substituents that can be substituted on these groups in R ^a of 1).

In the formula (a-1) and the formula (a-2), the photoreactive group bonded to * is not particularly limited, but an azo group, a 1,2-ethenediyl group, a 1,2-ethynediyl group, an imino group, Examples thereof include a carbonyl group and an oxycarbonyl group.
The hydrogen atom of each benzene ring in formula (a-1) and formula (a-2) may be substituted with a substituent. Regarding the preferred range and specific examples of the substituent, the preferred range and specific examples of the substituent capable of substituting on the benzene ring in the following formula (1A) can be referred to.

Examples of the photoreactive structure contained in the structural unit include a photoisomerization structure such as an azobenzene structure, a stilbene structure, and an acylhydrazone structure, and a photofries rearrangement structure such as a phenyl ester structure. The photoreactive structure contained in the structural unit of the polymer used in the present invention is preferably a photoisomerization structure such as an azobenzene structure, a stilbene structure, an acylhydrazone structure, and among them, an azobenzene structure is particularly preferable.

As a preferable example of the heat-reactive photoreactive structure having an azobenzene structure, a structure represented by the following formula (1A) can be mentioned. When the structure represented by the following formula (1A) is irradiated with polarized ultraviolet light, trans-cis isomerization of the azo group occurs and a component is directed in a specific direction (as a result of the change in structure, the component is directed in a specific direction). Component) becomes dominant. Thereby, a liquid crystal alignment film oriented in a specific direction can be obtained.

In formula (1A), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least one of R ¹ and R ² . Is a group represented by formula (1-1) or formula (1-2). One of R ¹ and R ² which is a group represented by formula (1-1) or formula (1-2) may be either ^one or both of R ¹ and R ^2. .. When both R ¹ and R ² are groups represented by formula (1-1) or formula (1-2), those groups may be the same or different from each other.
* Represents a bonding position of the structure represented by the formula (1A) to the linking group, and can be substituted with a hydrogen atom in the benzene ring, or with a hydrogen atom in the other benzene ring. It is one of the positions.

In formula (1-1), R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. In formula (1-2), R ⁴ and R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. .. R ⁴ and R ⁵ may be the same or different from each other. In formulas (1-1) and (1-2), * represents a bonding position to each benzene ring in formula (1A). The description and preferable ranges of the alkyl group, alkanoyl group, arylcarbonyl group and the substituents which can be substituted on these groups in R ⁴ and R ⁵ , and specific examples are the alkyl group in R ^a of the above formula (a-1). , The alkanoyl group, the arylcarbonyl group and the substituents which may be substituted on these groups, the preferred ranges, and the specific examples can be referred to.

The hydrogen atom of the benzene ring in formula (1A) may be substituted with a substituent. Preferable examples of the substituent include an alkyl group, an alkoxy group, a halogenated alkyl group, a halogeno group and a carboxyalkyl group. The alkyl group may be linear, branched or cyclic. The alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The alkoxy group preferably has 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. A trifluoromethyl group etc. can be illustrated as a specific example of a halogenated alkyl group. Specific examples of the halogeno group include a fluoro group, a chloro group, a bromo group, an iodo group and the like. Specific examples of the carboxyalkyl group include a carboxymethyl group and a carboxyethyl group.

(Chemical reaction by heating a structural unit having a thermoreactive photoreactive structure)
The polymer containing a heat-reactive photoreactive structure used for the liquid crystal aligning agent in the present invention is characterized in that a structural unit having a photoreactive structure causes a chemical reaction by heating. As a result, in this polymer, after the anisotropy is imparted by the photo-alignment method (after the structure is changed in the photo-reactive structure by light irradiation), the photo-reaction of the photo-reactive structure is caused by heating. It can be converted into a structure that is stable to light by eliminating the property.
Hereinafter, the mechanism of disappearance of the photoreactive group by a chemical reaction by heating will be described with respect to a constitutional unit having a thermoreactive photoreactive structure which is an azobenzene structure, an acylhydrazone structure, a phenyl ester structure or an N-benzylideneaniline structure. ..

(A) Cyclization Reaction of Azobenzene Structure: 5-Membered Ring Formation An azobenzene structure having a substituent R ^1A at the ortho position with respect to the azo group of one benzene ring, that is, an azobenzene structure represented by the following formula (A-1) In the structural unit which has, as shown in the following reaction formula, by heating, the azo group reacts with the substituent R ^{1A of the} benzene ring to form an indazole ring, and the azo group disappears. For details of this reaction, reference can be made to New J. chem., 1999, 23, 1223-1230.

In formula (A-1), R ^1A represents a group represented by formula (A-1-1) or formula (A-1-2). In formula (A-1-1) and formula (A-1-2), R ^4A and R ^5A are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, Alternatively, it represents a substituted or unsubstituted arylcarbonyl group. For the description and preferred ranges of R ^4A and R ^5A , and specific examples, the description of the alkyl group, alkanoyl group, arylcarbonyl group and the substituents which may be substituted on these groups in R ^a of the above formula (a-1). The preferred range and specific examples can be referred to.

(B) Cyclization reaction of azobenzene structure: 6-membered ring formation An azobenzene structure having a substituent (—CH ₂ COOR ^1B ) at the ortho position with respect to the azo group of one benzene ring, that is, represented by the following formula (B-1) In the constitutional unit having an azobenzene structure, as shown in the following reaction formula, the azo group reacts with the substituent (—CH ₂ COOR ^1B ) of the benzene ring by heating to form a cyclic structure, and the azo group disappears. To do.

In formula (B-1), R ^1B represents a hydrogen atom or a substituted or unsubstituted alkyl group. The description and preferred ranges, specific examples of the alkyl group and the substituents that can be substituted on the alkyl group are as described above, the description and the preferred range, specific examples of the alkyl group and its substituent in R ^a of the above formula (a-1). Can be referenced.

(C) Cyclization Reaction of Acylhydrazone Structure: 5-Membered Ring Formation An acylhydrazone structure having a substituent R ^1C at the ortho position to the imino group in the benzene ring, that is, an acylhydrazone structure represented by the formula (C-1) In the structural unit which has, as shown in the following reaction formula, by heating, the imino group (=NR) reacts with the substituent R ^{1C of the} benzene ring to form a cyclic structure, and the imino group disappears.

In formula (C-1), R ^1C represents a group represented by formula (C-1-1) or formula (C-1-2). In formula (C-1), formula (C-1-1) and formula (C-1-2), R ^2C , R ^4C and R ^5C are each independently a hydrogen atom, a substituted or unsubstituted alkyl group. Represents a group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. The explanations and preferred ranges of the alkyl group, alkanoyl group, arylcarbonyl group and substituents which can be substituted on these groups in R ^2C , R ^4C and R ^5C , and specific examples thereof are given by R ^{a of the} above formula (a-1). For the alkyl group, alkanoyl group, arylcarbonyl group and the substituents which may be substituted on these groups, preferred ranges, and specific examples can be referred to.

(D) Cyclization reaction after Fries rearrangement: 5-membered ring formation A phenyl ester structure having a substituent (—CH ₂ NHR ^1D ) at the ortho position to the ester bond site of the benzene ring, that is, represented by the following formula (D-1) As shown in the following reaction formula, the phenyl ester structure is subjected to Fries rearrangement, and then the carbonyl group reacts with the substituent (—CH ₂ NHR ^1D ) on the benzene ring to form a cyclic structure, and the carbonyl group disappears. To do.

In formula (D-1), R ^1D represents a substituted or unsubstituted alkyl group. The description and preferred ranges and specific examples of the alkyl group and the substituents that may be substituted on the alkyl group are as described above, the description and the preferred ranges, and specific examples of the alkyl group and its substituent in R ^a of the above formula (a-1). Can be referenced.

(E) Cyclization reaction of N-benzylideneaniline structure: 5-membered ring formation N-benzylideneaniline structure having a substituent R ^1E in the ortho position to the imino group in the benzene ring, that is, represented by formula (E-1) In the structural unit having an N-benzylideneaniline structure, as shown in the following reaction formula, the imino group (=NR) reacts with the substituent R ^{1E of the} benzene ring to form a cyclic structure by heating, and the imino group disappears. To do.

In formula (E-1), R ^1E represents a group represented by formula (E-1-1) or formula (E-1-2). In formula (E-1-1) and formula (E-1-2), R ^4E and R ^5E are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, Alternatively, it represents a substituted or unsubstituted arylcarbonyl group. The description and preferable ranges of the alkyl group, alkanoyl group, arylcarbonyl group and substituents which can be substituted on these groups in R ^4E and R ^5E , and specific examples are the alkyl group in R ^a of the above formula (a-1). , The alkanoyl group, the arylcarbonyl group and the substituents which may be substituted on these groups, the preferred ranges and specific examples can be referred to.

Whether a structural unit containing a photoreactive structure has undergone a chemical reaction by heating can be confirmed by an ultraviolet-visible absorption spectrum (transmittance), a nuclear magnetic resonance (NMR) spectrum, and an infrared spectroscopy (IR) spectrum. .. For example, when the photoreactive structure is an azobenzene structure, it can be confirmed that the above-mentioned cyclization reaction occurs by increasing the transmittance at 365 nm, which is the absorption wavelength of azobenzene. Here, in a liquid crystal aligning agent containing an azobenzene structure as a constitutional unit of a polymer, it is preferable that the transmittance at 365 nm be increased by 25% or more by a chemical reaction by heating. Specifically, when a film made of a liquid crystal aligning agent for photo-alignment is heated and baked at 230° C. for 30 minutes, the transmittance of the film at 365 nm increases by 25% or more from the transmittance of the film before heating and baking at 365 nm. It is preferable. With such a liquid crystal aligning agent for photoalignment, the photoreactivity of the azobenzene structure can be reliably reduced by heating, and a liquid crystal aligning film having high transmittance and exhibiting good liquid crystal aligning property can be formed.

(Side chain linking group)
The constitutional unit containing the heat-reactive photoreactive structure is contained in the side chain of the polymer. The method of introducing the structural unit containing the heat-reactive photoreactive structure into the side chain of the polymer is not limited, but may be, for example, bonded to the main chain of the polymer via a linking group. Examples of the linking group that connects the structural unit containing the heat-reactive photoreactive structure and the polymer main chain include a linking group represented by the following formula (S).

In the formula (S), R ^o represents a single bond, —COO—, —OCO— or —O—. R ^p and R ^t are each independently a single bond, —O—, an alkylene group having 1 to 12 carbon atoms, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO. It represents -O- or -O-CO-CH=CH-, and the hydrogen atom bonded to them may be replaced with a halogen group. R ^r is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH. =CH-, and when the number of R ^r is 2, R ^r may be the same or different. R ^q and R ^s are each independently a group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. Represents a selected group. However, when R ^r is —CH═CH—CO—O— or —O—CO—CH═CH—, R ^q or R ^s on the side to which —CH═CH— is bonded is an aromatic ring. R ^u is a single bond, an alkylene group having 1 to 12 carbon atoms, —COO—, —OCO— or —O—, and the hydrogen atom bonded to them may be replaced with a halogen group. s1 is 0 or 1. s2 is an integer of 0-2. When s2 is 0, when R ^u is a single bond, R ^p also represents a single bond. When s1 is 1 and s2 is an integer of 1 to 2, when R ^u is a single bond, R ^t also represents a single bond. *A is a bonding position with the polymer main chain, *b is a structural unit containing a heat-reactive photoreactive structure (heat-reactive photoreactive structure; for example, a structure represented by formula (1A)) Is the binding position of.

In formula (S):
R ^o is a single bond or —O—, R ^p is an alkylene group having 1 to 12 carbon atoms, s2 is 0, and R ^u is —O—;
R ^o is a single bond or —O—, R ^p is an alkylene group having 1 to 12 carbon atoms, and R ^q is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, or carbon number. 5 to 8 alicyclic hydrocarbon, and a group selected from the group consisting of combinations thereof, s1 is 0, s2 is 1 to 2, and R ^t is an alkylene group having 1 to 12 carbon atoms. And R ^u is —O—;
R ^o is a single bond, R ^p is —OCO— or —COO—, and R ^q is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic ring having 5 to 8 carbon atoms. Is a group selected from the group consisting of formula hydrocarbons and combinations thereof, s1 is 0, s2 is 1 to 2, R ^t is an alkylene group having 1 to 12 carbon atoms, and R ^u is -O-;
R ^o is a single bond, R ^p is a single bond, s2 is 0, and R ^u is —COO— or —OCO—;
R ^o is —COO—, —OCO— or —O—, R ^p is an alkylene group having 1 to 12 carbon atoms, s2 is 0, and R ^u is —COO—, —OCO— or —. O-;
R ^o is a single bond or —O—, R ^p is an alkylene group having 1 to 12 carbon atoms, and R ^q is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, or carbon number. A group selected from the group consisting of 5 to 8 alicyclic hydrocarbons, and a combination thereof, s1 is 0, s2 is 1 to 2, R ^t is —COO—, and R ^u Is a single bond; or
R ^o is a single bond, R ^p is —OCO— or —COO—, and R ^q is a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, a C 5-8 aliphatic resin. A group selected from the group consisting of cyclic hydrocarbons and combinations thereof, wherein s1 is 0, s2 is 1-2, R ^t is -COO-, and R ^u is a single bond. It is preferable.

Specific examples include connecting groups represented by the following formulas (1S) to (12S).
In formulas (1S) to (12S), m is an integer of 1 to 12.

(Type of polymer)
Used in the liquid crystal aligning agent in the present invention, the polymer containing a heat-reactive photoreactive structure may have a side chain a structural unit containing a heat-reactive photoreactive structure as described above, The type of polymer serving as the main chain is not particularly limited. Further, the type of the polymer containing the heat-reactive photoreactive structure used for the liquid crystal aligning agent may be one type or two or more types. That is, the liquid crystal aligning agent of the present invention may contain a polymer containing two or more kinds of thermally reactive photoreactive structures.
Examples of the polymer having a heat-reactive photoreactive structure include, for example, a polymer in which a structure represented by the formula (1A) is easily introduced into a side chain, such as polyamic acid, polyamic acid derivative, polyester, polyamide, polysiloxane, and cellulose. Derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, polyitaconates, polyfumarates, polymaleates, poly α-methylene-γ-butyrolactones, polystyrenes, polyvinyls, polymaleimides, polynorbornenes, etc. Among them, the polymer containing the heat-reactive photoreactive structure is preferably polyamic acid, polyamic acid derivative or poly(meth)acrylate, and polyamic acid or poly(meth)acrylate. Is more preferable.

Hereinafter, polyamic acid and its derivative, and poly(meth)acrylate will be described in detail as preferred examples of the polymer containing a heat-reactive photoreactive structure used for the liquid crystal aligning agent in the present invention.

(Polyamic acid and its derivatives)
The polyamic acid is a polymer synthesized by a polymerization reaction of a diamine represented by the formula (DI) and a tetracarboxylic dianhydride represented by the formula (AN), and a repeating unit represented by the formula (PAA). Have. By dehydrating and ring-closing the polyamic acid, a polyimide liquid crystal alignment film having a repeating unit represented by the formula (PI) can be formed. By using a compound having a constitutional unit containing a heat-reactive photoreactive structure as the diamine, the constitutional unit containing a heat-reactive photoreactive structure can be easily introduced into the side chain. For example, as the diamine represented by the formula (DI), a compound having a structure in which a diamine structural unit is linked to the bonding position * of the structure represented by the formula (1A) can be used. The diamine structural unit may be linked to the bonding position * of the structure represented by the formula (1A) via a linking group (for example, the above side chain linking group). Here, an example of the diamine structural unit is obtained by removing a hydrogen atom (excluding a hydrogen atom in an amino group) from a compound represented by any one of formulas (DI-1) to (DI-16) described later. A structural unit obtained by removing a hydrogen atom (excluding a hydrogen atom in an amino group) from (DI-4) is preferable, and a hydrogen atom (a hydrogen atom in an amino group is a Structural units obtained by removing (excluding) are more preferable. For example, by substituting the structure represented by formula (1A) for the diamine structural unit, the structure represented by formula (1A) can be obtained in the side chain of the diamine.

In Formula (AN), Formula (PAA), and Formula (PI), X ¹ represents a tetravalent organic group. In Formula (DI), Formula (PAA), and Formula (PI), X ² represents a divalent organic group. For the preferred range and specific examples of the tetravalent organic group in X ¹ , the corresponding structure of tetracarboxylic dianhydride described in the section of tetracarboxylic dianhydride below can be referred to. Regarding the preferred range and specific examples of the divalent organic group in X ^2, the diamine having a structure represented by the formula (1A) described below, or the known diamine below, the corresponding diamine or dihydrazide described in the column of dihydrazide The description of the structure can be referred to. In the production of polyamic acid and its derivative having a constitutional unit containing a heat-reactive photoreactive structure, the diamine represented by the formula (DI) is the only diamine containing a constitutional unit containing a heat-reactive photoreactive structure. And a diamine containing a constitutional unit containing a heat-reactive photoreactive structure and a diamine not containing a constitutional unit containing a heat-reactive photoreactive structure (for example, represented by the formula (1A) described below). A mixture of diamines other than the diamine having the structure

The polyamic acid derivative is a compound in which a part of the polyamic acid is replaced with another atom or atomic group to modify the characteristics, and particularly, a compound having high solubility in a solvent used for a liquid crystal aligning agent is preferable. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides. More specifically, 1) all amino groups and carboxyl groups of polyamic acid undergo a dehydration ring closure reaction. Polyimide, 2) Partial polyimide partially dehydrated and ring-closed, 3) Polyamic acid ester in which carboxyl group of polyamic acid is converted to ester, 4) Part of acid dianhydride contained in tetracarboxylic dianhydride compound And a polyamic acid-polyamide copolymer obtained by substituting organic dicarboxylic acid for reaction, and 5) a polyamide-imide obtained by subjecting part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction. Among these derivatives, for example, polyimide can include those having a structural unit represented by the above formula (PI), and polyamic acid ester can have a structural unit represented by the following formula (PAE). I can list things.

In formula (PAE), X ¹ represents a tetravalent organic group, X ² represents a divalent organic group, and Y represents an alkyl group. The preferred ranges and examples of X ^1, X ^2, can be referred to for X ^1, X ² in the formula (PAA). For the description and preferred ranges and specific examples of Y, reference can be made to the description and preferred ranges and specific examples for the alkyl group in ^Ra in formula (a-1) above.

In the present invention, preferred examples of the polyamic acid and its derivative used as the polymer containing a heat-reactive photoreactive structure include those having a constitutional unit containing a structure represented by formula (1A) in a side chain. For example, a polyamic acid is a reaction of a diamine having a structure in which a diamine structural unit is linked to a bonding position * of a structure represented by the formula (1A) via a linking group, and a polymerization reaction of a tetracarboxylic dianhydride. It can be obtained as a product. In the following description, a diamine having a structure in which a diamine structural unit is linked to a bonding position * of a structure represented by the formula (1A) via a linking group is referred to as “a diamine having a structure represented by the formula (1A)”. Say. As the diamine having the structure represented by the formula (1A), the diamine represented by the formula (2) described later can be preferably used. For the description, preferable ranges, and specific examples, the description regarding the diamine represented by the formula (2) described below can be referred to. Further, for the description and preferable range of the tetracarboxylic dianhydride and specific examples, the description in the section of the tetracarboxylic dianhydride below can be referred to. The diamine and the tetracarboxylic dianhydride having the structure represented by the formula (1A) used for the synthesis of the polyamic acid may be one kind or two or more kinds, respectively. Further, in addition to the diamine having the structure represented by the formula (1A) and the tetracarboxylic dianhydride, other monomer may be used in combination, and the constituent unit derived from the monomer may be introduced into the polyamic acid. Examples of other monomers include diamines and dihydrazides other than the diamine having the structure represented by the formula (1A). For the description, preferred ranges, and specific examples, the columns of diamine other than the diamine having the structure represented by the formula (1A) and other monomers can be referred to.

The polyamic acid or its derivative having the structure represented by the formula (1A) can be produced in the same manner as the known polyamic acid or its derivative used for forming a polyimide film.
For example, the total charged amount of tetracarboxylic dianhydride is preferably 0.9 to 1.1 mol based on 1 mol of the total amount of diamine.

Further, when the polyamic acid having the structure represented by the formula (1A) is a polyimide having the structure represented by the formula (1A) which is a polyamic acid derivative, the obtained polyamic acid solution is dehydrated. By reacting with an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride as a reagent and a tertiary amine such as triethylamine, pyridine and collidine as a dehydration ring-closing catalyst at a temperature of 20 to 150° C. , Polyimide can be obtained. Alternatively, a large amount of a poor solvent (methanol, ethanol, an alcohol solvent such as isopropanol or a glycol solvent) from the obtained polyamic acid solution is used to precipitate the polyamic acid, and the precipitated polyamic acid is treated with toluene, xylene, or the like. A polyimide can also be obtained by carrying out an imidization reaction at a temperature of 20 to 150° C. together with the above dehydrating agent and dehydration ring-closing catalyst in a solvent.

In the imidization reaction, the ratio of the dehydrating agent to the dehydrating ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount of the dehydrating agent and the dehydration ring-closing catalyst used is preferably 1.5 to 10 times the molar amount of the total molar amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid. By adjusting the dehydrating agent used in this imidization reaction, the amount of catalyst, the reaction temperature and the reaction time, the degree of imidization can be controlled, whereby a partial polyimide in which only part of the polyamic acid is imidized is obtained. be able to. The obtained polyimide can be separated from the solvent used for the reaction and redissolved in another solvent to be used as a liquid crystal aligning agent, or can be used as a liquid crystal aligning agent without separating from the solvent. ..

The polyamic acid ester having the structure represented by the formula (1A) is obtained by reacting the polyamic acid having the structure represented by the above formula (1A) with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound or the like. Obtained by a method of synthesis or a method of synthesis by reacting a tetracarboxylic acid diester or tetracarboxylic acid diester dichloride derived from tetracarboxylic acid dianhydride with a diamine having a structure represented by formula (1A) be able to. A tetracarboxylic acid diester derived from tetracarboxylic acid dianhydride can be obtained, for example, by reacting tetracarboxylic acid dianhydride with 2 equivalents of an alcohol to open the ring, and tetracarboxylic acid diester dichloride is tetracarboxylic acid. It can be obtained by reacting a diester with 2 equivalents of a chlorinating agent such as thionyl chloride. The polyamic acid ester may have only an amic acid ester structure, or may be a partial esterified product in which an amic acid structure and an amic acid ester structure coexist.

The liquid crystal aligning agent for optical alignment of the present invention may contain only one kind of these polyamic acids, polyamic acid esters and polyimides obtained by imidizing these, or may contain two or more kinds.

The molecular weight of the polyamic acid having the structure represented by the formula (1A) or its derivative is preferably 5,000 to 500,000 in terms of polystyrene equivalent weight average molecular weight (Mw), and 7,000 to 200, It is more preferably 000. The molecular weight of the polyamic acid or its derivative can be determined by measurement by gel permeation chromatography (GPC) method.

The polyamic acid having a structure represented by the formula (1A) or its derivative is obtained by precipitating with a large amount of a poor solvent, and analyzing the solid content by IR (infrared spectroscopy) or NMR (nuclear magnetic resonance analysis) The existence can be confirmed by. In addition, an extract of an organic solvent of a decomposed product of the polyamic acid or its derivative with an aqueous solution of a strong alkali such as KOH or NaOH is used for GC (gas chromatography), HPLC (high performance liquid chromatography) or GC-MS (gas chromatography mass spectrometry). It is possible to confirm the monomer used by analyzing in.

(Poly(meth)acrylate)
Poly(meth)acrylate is a polymer synthesized by a polymerization reaction of a (meth)acrylate represented by the formula (ACR), and has a repeating unit represented by the formula (PACR). By using a compound having a constitutional unit containing a heat-reactive photoreactive structure as the (meth)acrylate, a constitutional unit containing a heat-reactive photoreactive structure can be easily introduced into the side chain. For example, a compound having a structure in which a (meth)acryloyloxy group is linked to the bonding position * of the structure represented by the formula (1A) can be used. The (meth)acryloyloxy group may be linked to the bonding position * of the structure represented by the formula (1A) via a linking group (for example, the above side chain linking group).

In formula (ACR) and formula (PACR), X ³ represents a monovalent organic group, and Z represents a hydrogen atom or a methyl group. For the preferred range and specific examples of X ³ , reference can be made to the corresponding structure of (meth)acrylate described as a monomer used in the production of poly(meth)acrylate below. In the production of a poly(meth)acrylate having a constitutional unit containing a heat-reactive photoreactive structure, the (meth)acrylate represented by the formula (ACR) includes a constitutional unit containing a heat-reactive photoreactive structure. (Meth)acrylate containing a constitutional unit containing a thermoreactive photoreactive structure and (meth)acrylate not containing a constitutional unit containing a thermoreactive photoreactive structure (For example, it may be a mixture of (meth)acrylates other than the (meth)acrylate having the structure represented by the formula (1A) described later).

In the present invention, a preferable example of the poly(meth)acrylate used as the polymer containing the heat-reactive photoreactive structure is one having a structural unit containing the structure represented by the formula (1A) in the side chain. For example, poly(meth)acrylate is a reaction product of a polymerization reaction of a (meth)acrylate in which a (meth)acryloyloxy group is linked to a bonding position * of a structure represented by the formula (1A) via a linking group. Obtainable. In the following description, a (meth)acrylate having a structure in which a (meth)acryloyloxy group is linked to the bonding position * of the structure represented by the formula (1A) via a linking group is represented by “the formula (1A)”. (Meth)acrylate having a structure that The (meth)acryloyloxy group in this (meth)acrylate may be linked to the bonding position * of the structure represented by the formula (1A) via a linking group.

As the (meth)acrylate having the structure represented by the formula (1A), the (meth)acrylate represented by the formula (7) described later can be preferably used. For the description, preferred ranges, and specific examples, the description of the (meth)acrylate represented by the formula (7) can be referred to. The (meth)acrylate having the structure represented by the formula (1A) used for synthesizing the poly(meth)acrylate may be one kind or two or more kinds. Further, in addition to the (meth)acrylate having the structure represented by the formula (1A), other (meth)acrylate is used in combination, and a constitutional unit derived from the (meth)acrylate is introduced into the poly(meth)acrylate. May be. Examples of other (meth)acrylates include (meth)acrylates other than the (meth)acrylate having the structure represented by the formula (1A). For the explanations, preferred ranges, and specific examples thereof, the section of (meth)acrylate other than the (meth)acrylate having the structure represented by the formula (1A) can be referred to.
The poly(meth)acrylate having the structure represented by the formula (1A) can be produced in the same manner as the known poly(meth)acrylate used for forming a film of poly(meth)acrylate.

The polymerization reaction of (meth)acrylate is not particularly limited, and a general-purpose method industrially used can be used. Specifically, it can be polymerized by cationic polymerization, radical polymerization or anionic polymerization using a vinyl group of (meth)acrylate. Of these, radical polymerization is particularly preferable from the viewpoint of easy reaction control.

As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible irreversible chain transfer (RAFT) polymerization reagents can be used. For example, the radical polymerization initiator described in WO2014/054785 may be mentioned.

The organic solvent used in the polymerization reaction is not particularly limited as long as it can dissolve the produced polymer. For example, the organic solvent described in WO2014/054785 may be mentioned.

The polymerization temperature in the radical polymerization is not limited as long as it is within the temperature range in which the polymerization reaction proceeds, but the chemical reaction of the structural unit having a thermally reactive photoreactive structure (for example, a cyclization reaction of an azobenzene structure) It is preferred to carry out at a temperature below that which occurs. For example, the temperature is preferably 5° C. or lower, and more preferably 10° C. or lower, lower than the lower limit temperature at which a chemical reaction due to heating occurs. Specifically, radical polymerization can be performed at 30°C to 150°C, preferably 50°C to 100°C. The reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high-molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by weight to 50% by weight, more preferably 5% by weight to 30% by weight. The reaction can be performed at a high concentration in the initial stage, and then an organic solvent can be added.

In the above radical polymerization reaction, when the ratio of the radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained high molecular weight becomes small, and when the ratio of the radical polymerization initiator is small, the obtained high molecular weight becomes large. It is preferably 0.1 mol% to 10 mol% with respect to the monomer. Further, various monomer components, solvents, initiators, etc. can be added during the polymerization.

When recovering solid poly(meth)acrylate from the poly(meth)acrylate solution obtained by the above reaction, the reaction solution may be poured into a poor solvent to cause precipitation. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like. The polymer precipitated by pouring it into a poor solvent can be collected by filtration and then dried at room temperature or under normal pressure or reduced pressure by heating.

The poly(meth)acrylate obtained by the above operation is preferably prepared as a coating liquid so as to be suitable for forming a liquid crystal alignment film. That is, it is preferably prepared as a solution in which poly(meth)acrylate is dissolved in a solvent. As the solvent, the organic solvent described later can be preferably used.

The molecular weight of the poly(meth)acrylate having the structure represented by the formula (1A) is preferably 7,000 to 500,000 in terms of polystyrene equivalent weight average molecular weight (Mw), and 10,000 to 200, It is more preferably 000. The molecular weight of poly(meth)acrylate can be determined by measurement by gel permeation chromatography (GPC) method.

The poly(meth)acrylate having the structure represented by the formula (1A) is obtained by precipitating with a large amount of a poor solvent to analyze the solid content by IR (infrared spectroscopy) and NMR (nuclear magnetic resonance analysis). The existence can be confirmed by.

[Other ingredients]
The liquid crystal aligning agent for photo-alignment of the present invention may be composed only of a polymer containing a heat-reactive photoreactive structure, or may contain other components. Other components may include a polymer containing no heat-reactive photoreactive structure and a solvent for dissolving the polymer.

(Monomer used for producing polyamic acid and its derivative: diamine having a structure represented by the formula (1A))
The diamine having the structure represented by the formula (1A) is a diamine having a structure in which a diamine structural unit is linked to the bonding position * of the structure represented by the formula (1A) via a linking group, and includes, for example, the formula (1 Any material having a structure represented by 2) may be used.
The diamine represented by the formula (2) can be obtained by synthesizing a polymer such as a polyamic acid, a polyimide, a polyamide, a partial polyimide, a polyamic acid ester, a polyamic acid-polyamide copolymer, and a polyamideimide by using the diamine as a monomer. A polymer having a constitutional unit containing the structure represented by (1A) in its side chain can be obtained. Therefore, the diamine represented by the formula (2) is highly useful as a raw material of the polymer used in the liquid crystal aligning agent of the present invention. In addition to the liquid crystal alignment film, the polymer synthesized by using the diamine represented by the formula (2) as a monomer is an optically anisotropic substance, a retardation film, an optical compensation film, an antireflection film, various films, or It can also be used as an optical member or the like.

In formula (2), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least 1 of R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2). R ^3o , R ^3p , R ^3q , R ^3r , R ^3s , R ^3t , R ^3u , s1 and s2 are R ^o , R ^p , R ^q , R ^r , R ^s , R ^t , and R in formula (S). Reference can be made to the description of ^u , s1 and s2, their preferred ranges, and specific examples. The two —NH ₂ are bonded to the benzene ring to which R ^3o is directly bonded, and the bonding positions are any two positions that can be substituted with a hydrogen atom in the benzene ring. The two —NH ₂ may be ortho, meta or para with respect to each other. Two —NH ₂ is preferably bonded to the 3 and 4 positions, or the 3 and 5 positions when R ^3o is the 1 position, and more preferably bonded to the 3 and 5 positions. preferable. The remaining substitutable positions of the three benzene rings may be unsubstituted or may be substituted with a substituent. For the preferred range and specific examples of the substituent, the preferred range and specific examples of the substituent capable of substituting on the benzene ring in the above formula (1A) can be referred to.

In formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents a substituted arylcarbonyl group. * Represents the bonding position to the benzene ring in formula (2). Equation (1-1), R ^4, R ⁵ in (1-2), the description of the * formula in the formula (1A) (1-1), R 4, R 5 in (1-2), * Can be referred to.

The diamine represented by the formula (2) is represented by the following formula (3) because of its ease of synthesis and availability of raw materials, and when it is used as a raw material for a liquid crystal aligning agent, its high liquid crystal aligning property. It is preferable to be a diamine.

In formula (3), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least 1 of R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2). R ⁶ represents a straight chain alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one of —CH ₂ — of the straight chain alkylene group or two non-adjacent groups is replaced with —O—, May be. The two —NH ₂ are bonded to the terminal benzene ring to which R ⁶ is directly bonded, and the bonding position is any position in the benzene ring that is substitutable with a hydrogen atom. The remaining substitutable positions of the three benzene rings may be unsubstituted or may be substituted with a substituent. For the preferred range and specific examples of the substituent, the preferred range and specific examples of the substituent capable of substituting on the benzene ring in the above formula (1A) can be referred to.

In formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents a substituted arylcarbonyl group. * Represents the bonding position to the benzene ring in formula (3). Equation (1-1), R ^4, R ⁵ in (1-2), the description of the * formula in the formula (1A) (1-1), R 4, R 5 in (1-2), * Can be referred to.

The diamine represented by the formula (3) is more preferably the diamine represented by the following formulas (4) to (6).

In formulas (4) to (6), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. For preferred ranges and specific examples of the substituents of R ⁷ and R ⁸ , the preferred range and specific examples of the alkyl group of R ^{4 in} the above formula (1A) can be referred to. n represents a positive integer of 1 to 12.

The diamines represented by the formulas (4) to (6) include the following formulas (4-1-1), formulas (4-1-2), formulas (4-2-1) and formulas (4-2-2). ), formula (5-1-1), formula (5-1-2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6 -1-2), the formula (6-2-1), and the formula (6-2-2) are more preferred.

Formula (4-1-1), Formula (4-1-2), Formula (4-2-1), Formula (4-2-2), Formula (5-1-1), Formula (5-1) -2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6-1-2), formula (6-2-1), and In Formula (6-2-2), n represents a positive integer of 1-12.

(Monomer used for producing polyamic acid and its derivative: tetracarboxylic dianhydride)
The tetracarboxylic dianhydride used as the raw material of the polymer of the present invention can be selected from known tetracarboxylic dianhydrides without any limitation. Such a tetracarboxylic dianhydride is an aromatic system in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring (including a heteroaromatic ring system) and an aliphatic system in which a dicarboxylic acid anhydride is not directly bonded to an aromatic ring. It may belong to any group of the system (including the heterocyclic system).

Preferable examples of such tetracarboxylic acid dianhydrides are represented by the following formulas (AN-I) to (AN-V) from the viewpoint of easy availability of raw materials, ease of polymer production, and electric properties of the film. The tetracarboxylic dianhydride represented by either is mentioned.

Formula (AN-I), in formula (AN-IV) and formula (AN-V), X is independently a single bond or -CH ₂ - represents a. In the formula (AN-II), G represents a single bond, an alkylene group having 1 to 20 carbon atoms, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, - C (CF _{3) 2} -, or a divalent group represented by the following formula (G13-1), -CH ₂ - is, -O -, - CO -, - NH- may be replaced by.

In formula (G13-1), G ^13a and G ^13b each independently represent a single bond or a divalent group selected from —O—, —CONH— or —NHCO—. The phenylene group is preferably a 1,4-phenylene group or a 1,3-phenylene group.
In formulas (AN-II) to (AN-IV), Y independently represents one selected from the group of the following trivalent groups. Each bond of the trivalent group is linked to any carbon atom, and at least one hydrogen atom of the trivalent group may be substituted with a methyl group, an ethyl group or a phenyl group.

In formulas (AN-III) to (AN-V), ring A ¹⁰ is a cyclic group obtained by removing hydrogen atoms from a monocyclic hydrocarbon having 3 to ¹⁰ carbon atoms by the number of bonds, or a ring group having 6 to 30 carbon atoms. It represents a cyclic group obtained by removing hydrogen atoms from a condensed polycyclic hydrocarbon by the number of bonds. At least one hydrogen atom in each cyclic group may be substituted with a methyl group, an ethyl group or a phenyl group. In addition, the bond hanging on each ring is linked to any carbon constituting the ring, and two bonds may be bonded to the same carbon atom.

Furthermore, as tetracarboxylic dianhydride, the following formula (AN-1)-formula (AN-12), formula (AN-15), and formula (AN-16-1)-formula (AN-16-15). ) Is included.

In formula (AN-1), G ¹¹ represents a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group, or a 1,4-cyclohexylene group. X ¹¹ independently represents a single bond or —CH ₂ —. G ¹² independently represents any of the following trivalent groups.

When G ¹² is >CH—, the hydrogen atom of >CH— may be substituted with a methyl group. When G ¹² is> N-, G ¹¹ represents a single bond and -CH ₂ - that they are not, X ¹¹ is not a single bond. R ¹¹ represents a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula.

In formulas (AN-1-2) and (AN-1-14), m is independently an integer of 1 to 12.

In formula (AN-2), R ⁶¹ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formula.

In formula (AN-3), ring A ¹¹ represents a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas.

In the formula (AN-4), G ¹³ represents a single _{bond, - (CH 2) m -} , - O -, - S -, - C (CH 3) 2 -, - SO 2 -, - CO -, - C (CF _{3) 2} -, or a divalent group represented by the following formula (G13-1), m is an integer from 1 to 12. Rings A ¹¹ each independently represent a cyclohexane ring or a benzene ring. G ¹³ may be attached at any position on ring A ¹¹ .

In Formula (G13-1), G ^13a and G ^13b each independently represent a single bond, a divalent group represented by —O—, —CONH—, or —NHCO—. The phenylene group is preferably a 1,4-phenylene group or a 1,3-phenylene group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas.

In the formula (AN-4-17), m is an integer of 1-12.

In formula (AN-5), R ¹¹ independently represents a hydrogen atom or a methyl group. Of the two R ¹¹ , R ¹¹ in the benzene ring is bonded to any substitutable position of the benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-5) include compounds represented by the following formulas.

In formula (AN-6), X ¹¹ independently represents a single bond or —CH ₂ —. X ¹² is _{-CH 2 -, - CH 2 CH} 2 - or represents a -CH = CH-. n is 1 or 2. When n is 2, two X ^12's may be the same or different from each other.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulas.

In formula (AN-7), X ¹¹ represents a single bond or —CH ₂ —.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulas.

In formula (AN-8), X ¹¹ represents a single bond or —CH ₂ —. R ¹² represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. Ring A ¹² represents a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulas.

In formula (AN-9), r is 0 or 1 each independently.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.

In formula (AN-11), ring A ¹¹ independently represents a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulas.

In formula (AN-12), each ring A ¹¹ independently represents a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formula.

In formula (AN-15), w is an integer of 1 to 10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulas.

Examples of the tetracarboxylic dianhydride other than the above include the following compounds.

In the above tetracarboxylic acid dianhydride, suitable materials for improving each property of the liquid crystal alignment film described later will be described. When it is important to improve the orientation of the liquid crystal, compounds represented by formula (AN-1), formula (AN-3) and formula (AN-4) are preferable, and compounds represented by formula (AN-1- 2), the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-17), and the compound represented by the formula (AN-4-29) are more preferable, and the formula (AN-4-29) In AN-1-2), m=4 or 8 is preferable, in formula (AN-4-17), m=4 or 8 is preferable, and m=8 is more preferable.

When importance is attached to improving the transmittance of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1), and the formula (AN-4-). 17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-16-3), formula ( AN-16-4) and compounds represented by formula (AN-2-1) are preferable, and in formula (AN-1-2), m=4 or 8 is preferable, and formula (AN-4-). In 17), m=4 or 8 is preferable, and m=8 is more preferable.

When importance is placed on improving the VHR of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1), and the formula (AN-4-17). ), formula (AN-4-30), formula (AN-7-2), formula (AN-10-1), formula (AN-16-3), formula (AN-16-4), and formula (AN-16-4). A compound represented by AN-2-1) is preferable, in the formula (AN-1-2), m=4 or 8 is preferable, and in the formula (AN-4-17), m=4 or 8 Is preferred, and m=8 is more preferred.

Improving the relaxation rate of the residual charge (residual DC) in the liquid crystal alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29), and the formula (AN- The compound represented by 11-3) is preferable.

(Monomer used for production of polyamic acid and its derivative: diamine other than diamine having structure represented by formula (1A) and other monomer)
The raw material of the polymer of the present invention may contain a diamine other than the diamine having the structure represented by the formula (1A) (diamine represented by the formula (2)) and other monomers. Examples of the other monomer include dihydrazide. This makes it possible to introduce the structural units derived from these monomers into the polymer and control the properties of the polymer.
The diamine and dihydrazide other than the diamine having the structure represented by the formula (1A) can be selected from known diamines and dihydrazides without limitation.

Diamines can be divided into two types depending on their structure. That is, when a skeleton connecting two amino groups is viewed as a main chain, it is a diamine having a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. A diamine having no such side chain group may be referred to as a non-side chain type diamine. This side chain group is a group having an effect of increasing the pretilt angle.
By properly using the non-side chain type diamine and the side chain type diamine, it is possible to correspond to the respective pretilt angles required.

The side chain type diamine is preferably used in combination to the extent that the characteristics of the present invention are not impaired. Further, it is preferable to select and use the side chain type diamine and the non-side chain type diamine for the purpose of improving vertical alignment property to liquid crystal, VHR, burn-in property and alignment property.

The known diamines and dihydrazides are shown below.

In the above formula (DI-1), G ²⁰ represents a group represented by —CH ₂ — or a formula (DI-1-a). When G ²⁰ is —CH ₂ —, at least one of m —CH ₂ — may be replaced by —NH—, —O—, and at least one hydrogen atom of m —CH ₂ —. May be substituted with a hydroxyl group. m is an integer of 1-12. When m in DI-1 is 2 or more, a plurality of G ^20's may be the same or different. However, when G ²⁰ is a group represented by the formula (DI-1-a), m is 1.

In formula (DI-1-a), v is each independently an integer of 1 to 6.

In formula (DI-3), formula (DI-6) and formula (DI-7), G ²¹ is independently a single bond, —NH—, —NCH ₃ —, —O—, —S—, —S. _{-S -, - SO 2 -,} - CO -, - COO -, - CONCH 3 -, - CONH -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m _{-, - O- (CH 2)} m -O -, - N (CH 3) - (CH 2) k -N (CH 3) -, - (O-C 2 H 4) m -O -, - O _{-CH 2 -C (CF 3) 2} -CH 2 -O -, - O-CO- (CH 2) m -CO-O -, - CO-O- (CH 2) m -O-CO -, - _{(CH 2) m -NH- (CH} 2) m -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO _{-C 3 H 6 - (NH-} C 3 H 6) n -CO-, or -S- (CH _{2) m} -S- and represents, m is an integer from 1 to 12 independently, k is 1 Is an integer of 5 and n is 1 or 2. In formula (DI-4), s is independently an integer of 0-2.

In formula (DI-5), G ³³ represents a single bond, —NH—, —NCH ₃ —, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —COO—, _{-CONCH 3 -, - CONH -,} - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O -, - N ( _{CH 3) - (CH 2)} k -N (CH 3) -, - (O-C 2 H 4) m -O -, - O-CH 2 -C (CF 3) 2 -CH 2 -O-, _{-O-CO- (CH 2) m} -CO-O -, - CO-O- (CH 2) m -O-CO -, - (CH 2) m -NH- (CH 2) m -, - CO _{- (CH 2) k -NH- (} CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO-C 3 H 6 - (NH-C 3 H 6) n -CO -, or _{-S- (CH 2) m -S -} , - N (Boc) - (CH 2) e -N (Boc) -, - NH- (CH 2) e -N (Boc) -, - N _{(Boc) - (CH 2)} e -, - (CH 2) m -N (Boc) -CONH- (CH 2) m -, - (CH 2) m -N (Boc) - (CH 2) m - , A group represented by the following formula (DI-5-a) or the following formula (DI-5-b), m is independently an integer of 1 to 12, and k is an integer of 1 to 5. , E is an integer of 2 to 10, and n is 1 or 2. Boc is a t-butoxycarbonyl group.

In formula (DI-6) and formula (DI-7), G ²² are independently a single bond, -O -, - S -, - CO -, - C (CH 3) 2 -, - C (CF 3 ) ₂ -, or an alkylene group having 1 to 10 carbon atoms.

Formula (DI-2) at least one hydrogen atom of the cyclohexane ring and benzene ring in ~ (DI-7) is, -F, -Cl, alkylene group having 1 to 3 carbon atoms, -OCH _3, -OH, - _{CF 3, -CO 2 H, -CONH} 2, -NHC 6 H 5, may be substituted with a phenyl group or benzyl group, in the addition formula (DI-4), at least one cyclohexane ring and benzene ring One hydrogen atom may be substituted with one selected from the group of groups represented by any of the following formulas (DI-4-a) to (DI-4-i). In ), when G ³³ is a single bond, at least one hydrogen atom of the cyclohexane ring and the benzene ring may be replaced with NHBoc or N(Boc) ₂ .

A group in which the bonding position is not fixed to the carbon atoms forming the ring indicates that the bonding position in the ring is arbitrary. The bonding position of —NH ₂ to the cyclohexane ring or the benzene ring is any position except the bonding position of G ²¹ , G ²² or G ³³ .

In formula (DI-4-a) and formula (DI-4-b), R 20 represents a hydrogen atom or -CH ₃ independently. In formula (DI-4-f) and formula (DI-4-g), m is each independently an integer of 0 to 12, and Boc is a t-butoxycarbonyl group.

In formula (DI-5-a), q is independently an integer of 0 to 6. ^R44 represents a hydrogen atom, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

In the formula (DI-11), r is 0 or 1. In formulas (DI-8) to (DI-11), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

In formula (DI-12), R ²¹ and R ²² each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ²³ is independently an alkylene group having 1 to 6 carbon atoms or a phenylene group. Alternatively, it represents a phenylene group substituted with an alkyl group, and w is an integer of 1 to 10.

In formula (DI-13), R ²³ independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or —Cl, and p is independently an integer of 0 to 3, q is an integer of 0-4.

In formula (DI-14), ring B represents a monocyclic heterocyclic aromatic group, R ²⁴ represents a hydrogen atom, —F, —Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an alkenyl group, Represents an alkynyl group, and q is independently an integer of 0-4. When q is 2 or more, a plurality of R ²⁴ may be the same as or different from each other. In formula (DI-15), ring C represents a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ represents a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1. Then, a group in which the bonding position is not fixed to the carbon atoms forming the ring indicates that the bonding position in the ring is arbitrary. In formulas (DI-13) to (DI-16), the bonding position of —NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) can be given as the diamines having no side chains of the above formulas (DI-1) to (DI-16). ..

Examples of the diamine represented by the formula (DI-1) are shown below.

In Formula (DI-1-7) and Formula (DI-1-8), k is an integer of 1-3 each independently. In formula (DI-1-9), v is each independently an integer of 1 to 6.

Examples of the diamines represented by the formulas (DI-2) to (DI-3) are shown below.

Examples of the diamine represented by the formula (DI-4) are shown below.

In formulas (DI-4-20) and (DI-4-21), m is independently an integer of 1 to 12.

Examples of the diamine represented by the formula (DI-5) are shown below.
In the formula (DI-5-1), m is an integer of 1-12.

In formula (DI-5-12) and formula (DI-5-13), m is independently an integer of 1 to 12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

In formulas (DI-5-35) to (DI-5-37) and formulas (DI-5-39), m are each independently an integer of 1 to 12, and formula (DI-5-38). ) And formula (DI-5-39), k is independently an integer of 1 to 5, and in formula (DI-5-40), n is an integer of 1 or 2.

In formula (DI-5-42) ~ formula (DI-5-44), e is independently a 2-10 integer, R ⁴³ in formula (DI-5-45) is a hydrogen atom, -NHBoc , Or -N(Boc) ₂ . In formulas (DI-5-42) to (DI-5-44), Boc is a t-butoxycarbonyl group.

Examples of the diamine represented by the formula (DI-6) are shown below.

Examples of the diamine represented by the formula (DI-7) are shown below.
In formula (DI-7-3) and formula (DI-7-4), m is independently an integer of 1 to 12, and n is independently 1 or 2.

Examples of the diamine represented by the formula (DI-8) are shown below.

Examples of the diamine represented by the formula (DI-9) are shown below.

Examples of the diamine represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of the diamine represented by the formula (DI-12) are shown below.

Examples of the diamine represented by the formula (DI-13) are shown below.

Examples of the diamine represented by the formula (DI-14) are shown below.

Examples of the diamine represented by the formula (DI-15) are shown below.

Examples of the diamine represented by the formula (DI-16) are shown below.

Next, dihydrazide will be described. Examples of the known dihydrazide having no side chain include compounds represented by any of the following formulas (DIH-1) to (DIH-3).

In formula (DIH-1), G ²⁵ is a single bond, an alkylene group having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO ₂ —, —C(CH ₃ ) ₂ —, or -C (CF _{3) 2} - represents a.
In formula (DIH-2), ring D represents a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen atom of this group may be substituted with a methyl group, an ethyl group or a phenyl group. In formula (DIH-3), each ring E independently represents a cyclohexane ring or a benzene ring, and at least one hydrogen atom of this group may be substituted with a methyl group, an ethyl group, or a phenyl group. The plurality of E's may be the same as or different from each other. Y represents a single bond, an alkylene having 1 to 20 carbon atoms, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 -, or -C (CF _{3) 2} - represents a .. In formula (DIH-2) and formula (DIH-3), the bonding position of —CONHNH ₂ bonded to the ring is an arbitrary position.

Examples of compounds represented by any of the formulas (DIH-1) to (DIH-3) are shown below.
In the formula (DIH-1-2), m is an integer of 1-12.

The diamine and dihydrazide as described above are effective in improving the electrical characteristics such as lowering the ion density of the liquid crystal display device.

A diamine suitable for the purpose of increasing the pretilt angle will be described. Examples of the diamine having a side chain group suitable for the purpose of increasing the pretilt angle include any of the formulas (DI-31) to (DI-35) and the formulas (DI-36-1) to (DI-36-8). The diamine represented by
In formula (DI-31), G ²⁶ represents a single bond, -O -, - COO -, - OCO -, - CO -, - CONH -, - CH 2 O -, - OCH 2 -, - CF 2 O- , -OCF ₂ -, or - (CH _{2) ma} - represents, ma is an integer from 1 to 12. Preferred examples of G ²⁶ are a single bond, —O—, —COO—, —OCO—, —CH ₂ O—, and an alkylene group having 1 to 3 carbon atoms, and particularly preferred examples are a single bond, —O—, -COO -, - OCO -, - CH 2 O -, - CH 2 - and -CH ₂ CH ₂ -. R ²⁵ represents an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl group, at least one hydrogen atom may be replaced by -F, and at least one -CH ₂ - is -O -, - CH = CH- or -C≡C- also be substituted by Good. Hydrogen atoms of the phenyl group, a substituted _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF3, an alkoxy group an alkyl group or a C3-30 having 3 to 30 carbon atoms It may have been done. The bonding position of —NH ₂ bonded to the benzene ring is shown as an arbitrary position in the ring, but the bonding position is preferably the meta position or the para position. That is, when the bonding position of the group “R ²⁵ —G ²⁶ —” is the 1-position, the two bonding positions are preferably the 3-position and the 5-position, or the 2-position and the 5-position.
In formula (DI-31-a), G ²⁷ , G ^28, and G ²⁹ are bond groups, which are each independently a single bond or an alkylene group having 1 to 12 carbon atoms. one or more -CH ₂ - may, -O -, - COO -, - OCO -, - CONH -, - CH = CH- may be substituted with. Ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, A pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group, a naphthalene-1,5-diyl group, a naphthalene-2,7-diyl group or an anthracene-9,10-diyl group, and a ring B ²¹ , Ring B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen atom may be substituted with —F or —CH ₃ , and s, t and u are each independently an integer of 0 to 2. Where the sum of these is from 1 to 5 and when s, t or u is 2, the two linking groups within each bracket may be the same or different, and the two rings are It may be the same or different. R ²⁶ is a hydrogen atom, -F, -OH, alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, - OCHF _2, or represents -OCF _3, at least one -CH ₂ in the alkyl group of the carbon number of 1 to 30 - is substituted by a divalent group represented by the following formula (DI-31-b) Good.
In formula (DI-31-b), R ²⁷ and R ²⁸ are each independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferred examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

In formula (DI-32) and formula (DI-33), G ³⁰ independently represents a single bond, —CO— or —CH ₂ —, R ²⁹ independently represents a hydrogen atom or —CH ₃ , R ³⁰ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. At least one hydrogen atom of the benzene ring in formula (DI-33) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group. Then, a group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. Formula (DI-32) in two groups - one of the "phenylene -G ³⁰ -O-" is attached to the 3 position of the steroid nucleus, it is preferable that the other is bound to 6-position of the steroid nucleus. The bonding positions of the two groups “-phenylene-G ³⁰ —O—” in the formula (DI-33) to the benzene ring are preferably meta or para to the bonding position of the steroid nucleus. In formula (DI-32) and formula (DI-33), —NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

In formula (DI-34) and formula (DI-35), G ³¹ independently represents —O— or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms. Represents. R ³¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and at least one —CH ₂ — of this alkyl group may be replaced by —O—, —CH═CH— or —C≡C—. Good. R ³² represents an alkyl group having 6 to 22 carbon atoms, and R ³³ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. Ring B ²⁵ is a 1,4-phenylene group or 1,4-cyclohexylene group, and r is 0 or 1. And -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferably independently in the meta position or the para position with respect to the bonding position of G ³¹ .

Examples of the compound represented by the formula (DI-31) are shown below.
In formulas (DI-31-1) to (DI-31-11), each R ³⁴ independently represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably 5 carbon atoms. Is an alkyl group having 25 to 25 carbon atoms or an alkoxy group having 5 to 25 carbon atoms. R ^35's each independently represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In formulas (DI-31-12) to (DI-31-17), each R ³⁶ independently represents an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R ³⁷ independently represents an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms.

In formulas (DI-31-18) to (DI-31-43), each R ³⁸ independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably 3 carbon atoms. Is an alkyl group having 20 to 20 carbon atoms or an alkoxy group having 3 to 20 carbon atoms. Each R ³⁹ independently represents a hydrogen atom, —F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , and preferably Is an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. G ³³ represents an alkylene group having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-32) are shown below.

Examples of the compound represented by the formula (DI-33) are shown below.

Examples of the compound represented by the formula (DI-34) are shown below.

In formulas (DI-34-1) to (DI-34-12), each R ⁴⁰ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or alkyl group having 1 to 10 carbon atoms. And R ⁴¹ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Examples of the compound represented by the formula (DI-35) are shown below.
In formulas (DI-35-1) to (DI-35-3), each R ³⁷ independently represents an alkyl group having 6 to 30 carbon atoms, and R ⁴¹ each independently represents a hydrogen atom or a carbon atom 1 to 1 Represents 12 alkyl groups.

The compounds represented by formulas (DI-36-1) to (DI-36-8) are shown below.
In formulas (DI-36-1) to (DI-36-8), R ^42's each independently represent an alkyl group having 3 to 30 carbon atoms.

With respect to the above-mentioned diamine and dihydrazide, suitable materials for improving each property of the liquid crystal alignment film described later will be described. When it is important to further improve the orientation of the liquid crystal, formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9). ), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3), and formula (DI-7-5). It is preferable to use the compound represented by DI-11-2). In the formula (DI-5-1), m=2, 4 or 6 is preferable, and m=4 is more preferable. In Formula (DI-5-12), m=2 to 6 is preferable, and m=5 is more preferable. In Formula (DI-5-13), m=1 or 2 is preferable, and m=1 is more preferable.

When it is important to improve the transmittance, the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula (DI-5-5), the formula It is preferable to use the diamine represented by (DI-5-24) and the formula (DI-7-3), and more preferably the compound represented by the formula (DI-2-1). In formula (DI-5-1), m=2, 4 or 6 is preferable, and m=4 is more preferable. In the formula (DI-7-3), m=2 or 3, and n=1 or 2 are preferable, and m=3 and n=1 are more preferable.

When importance is placed on improving the VHR of the liquid crystal display element, formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10). ), formula (DI-4-15), formula (DI-4-22), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1). It is preferable to use a compound represented by formula (DI-2-1), formula (DI-5-1), and formula (DI-13-1). In the formula (DI-5-1), m=1 is preferable. In the formula (DI-5-30), k=2 is preferable.

Improving the relaxation rate of the residual charge (residual DC) in the liquid crystal alignment film by lowering the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing image sticking. When this purpose is emphasized, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5). -1), Formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-28), Formula (DI-4-20), Formula (DI-4-21), Formula It is preferable to use the compounds represented by (DI-7-12) and formula (DI-16-1), and formula (DI-4-1), formula (DI-5-1), and formula (DI A compound represented by -5-13) is more preferable. In formula (DI-5-1), m=2, 4 or 6 is preferable, and m=4 is more preferable. In Formula (DI-5-12), m=2 to 6 is preferable, and m=5 is more preferable. In Formula (DI-5-13), m=1 or 2 is preferable, and m=1 is more preferable. In the formula (DI-7-12), m=3 or 4 is preferable, and m=4 is more preferable.

In each diamine, a part of the diamine may be replaced with the monoamine in the range where the ratio of the monoamine to the diamine is 40 mol% or less. Such replacement can cause termination of the polymerization reaction when producing the polyamic acid, and can suppress the further progress of the polymerization reaction. Therefore, by such replacement, the molecular weight of the obtained polymer (polyamic acid or its derivative) can be easily controlled, and for example, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. You can The diamine to be replaced with the monoamine may be one type or two or more types unless the effects of the present invention are impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Is mentioned.

The raw material of the polyamic acid or its derivative may further contain a monoisocyanate compound as a monomer. By including the monoisocyanate compound in the monomer, the terminal of the obtained polyamic acid or its derivative is modified and the molecular weight is adjusted. By using this end-modified polyamic acid or its derivative, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% with respect to the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

(Amount of diamine having structure represented by formula (1A) in raw material of polyamic acid and its derivative)
In the raw material of the polyamic acid and its derivative, the diamine having a structure represented by the formula (1A) (preferably, the diamine represented by the formula (2)) is 20 to 100 mol% with respect to the total amount of the diamine. It is preferably 50 to 100 mol %.

(Monomer used for producing poly(meth)acrylate: (meth)acrylate having a structure represented by the formula (1A))
The (meth)acrylate having a structure represented by the formula (1A) has a structure in which a (meth)acryloyloxy group is linked to the bonding position * of the structure represented by the formula (1A) via a linking group (meth ) An acrylate, for example, any one having a structure represented by the formula (7) may be used.
The (meth)acrylate represented by the formula (7) is, for example, a polymer having a constitutional unit containing a structure represented by the formula (1A) in a side chain by synthesizing a poly(meth)acrylate using this as a monomer. Can be obtained. Therefore, the (meth)acrylate represented by the formula (7) is highly useful as a raw material for the polymer used in the liquid crystal aligning agent of the present invention. Further, the polymer synthesized by using the (meth)acrylate represented by the formula (7) as a monomer is, in addition to the liquid crystal alignment film, an optically anisotropic substance, a retardation film, an optical compensation film, an antireflection film, various types. It can also be used as a film or an optical member.

In formula (7), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least 1 of R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2). R ^3o , R ^3p , R ^3q , R ^3r , R ^3s , R ^3t , R ^3u , s1 and s2 are R ^o , R ^p , R ^q , R ^r , R ^s , R ^t , and R in formula (S). Reference can be made to the description of ^u , s1 and s2, their preferred ranges, and specific examples. R ⁹ represents a hydrogen atom or a methyl group. The hydrogen atom of the benzene ring in formula (7) may be substituted with a substituent. For the preferred range and specific examples of the substituent, the preferred range and specific examples of the substituent capable of substituting on the benzene ring in the above formula (1A) can be referred to.

In formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents a substituted arylcarbonyl group. * Represents the bonding position to the benzene ring in formula (7). Equation (1-1), R ^4, R ⁵ in (1-2), the description of the * formula in the formula (1A) (1-1), R 4, R 5 in (1-2), * Can be referred to.

The (meth)acrylate represented by the formula (7) has the following formula (8) because of its ease of synthesis and availability of raw materials, and when it is used as a raw material of a liquid crystal aligning agent, its liquid crystal aligning property is high. The (meth)acrylate represented by is preferable.

In formula (8), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least 1 of R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2). R ⁶ represents a straight chain alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one of —CH ₂ — of the straight chain alkylene group or two non-adjacent groups is replaced with —O—, May be. R ⁹ represents a hydrogen atom or a methyl group. The hydrogen atoms of the two benzene rings in formula (8) may be substituted with a substituent. For the preferred range and specific examples of the substituent, the preferred range and specific examples of the substituent capable of substituting on the benzene ring in the above formula (1A) can be referred to.

In formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents a substituted arylcarbonyl group. * Represents the bonding position to the benzene ring in formula (9). Equation (1-1), R ^4, R ⁵ in (1-2), the description of the * formula in the formula (1A) (1-1), R 4, R 5 in (1-2), * Can be referred to.

The (meth)acrylate represented by the formula (8) is more preferably the (meth)acrylate represented by the following formulas (9) to (11).

In formulas (9) to (11), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. For preferred ranges and specific examples of the substituents of R ⁷ and R ⁸ , the preferred range and specific examples of the alkyl group of R ^{4 in} the above formula (1A) can be referred to. R ⁹ represents a hydrogen atom or a methyl group. n represents a positive integer of 1 to 12.

The (meth)acrylates represented by the following formulas (9) to (11) are represented by the following formula (9-1-1), formula (9-1-2), formula (9-2-1) and formula (9). -2-2), formula (10-1-1), formula (10-1-2), formula (10-2-1), formula (10-2-2), formula (11-1-1). Are more preferably (meth)acrylates represented by formula (11-1-2), formula (11-2-1), and formula (11-2-2).

Formula (9-1-1), Formula (9-1-2), Formula (9-2-1), Formula (9-2-2), Formula (10-1-1), Formula (10-1) -2), formula (10-2-1), formula (10-2-2), formula (11-1-1), formula (11-1-2), formula (11-2-1), and In the formula (11-2-2), n represents a positive integer of 1-12.

(Monomer used for producing poly(meth)acrylate: (meth)acrylate other than (meth)acrylate having a structure represented by the formula (1A))
The raw material of poly(meth)acrylate may contain (meth)acrylate other than the (meth)acrylate having the structure represented by the formula (1A). This makes it possible to introduce the structural units derived from these monomers into the polymer and control the properties of the polymer. As the (meth)acrylate other than the (meth)acrylate having the structure represented by the formula (1A), any known (meth)acrylate, particularly monofunctional (meth)acrylate can be used. Examples of (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert. -Butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate , Hexadecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate , Dicyclopentanyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-chloro-2 -Hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2- Methoxyethyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, methoxy-triethylene glycol (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, methoxy-polyethylene glycol (meth)acrylate, nonylphenoxy-polyethylene glycol (Meth)acrylate, methoxydipropylene glycol (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-dicyclopentenyloxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate , Glycidyl (meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, naphthylmethyl (meth)acrylate, anthrylmethyl (meth)acrylate, 2-hydr Roxy-3-phenoxypropyl (meth)acrylate, 2-succinate ethyl (meth)acrylate, 2-hexahydrophthalate ethyl (meth)acrylate, 2-phthalate ethyl (meth)acrylate, 2,2-dimethyl- 3-benzoatepropyl(meth)acrylate, 2-(dimethylamino)ethyl(meth)acrylate, pentamethylpiperidinyl(meth)acrylate, tetramethylpiperidinyl(meth)acrylate, 3-(trimethoxysilyl)propyl( (Meth)acrylate, phenyl(meth)acrylate, naphthyl(meth)acrylate, anthracene(meth)acrylate, furfuryl(meth)acrylate, 4-(6-(meth)acryloyloxyhexyl)oxybenzoic acid, and (E)-3. -(4-(6-(meth)acryloyloxyhexyl)oxyphenyl)acrylic acid can be mentioned. Other examples include (meth)acrylates described in WO2014/054785 (particularly paragraphs 0220 to 0222).

When it is important to further improve the orientation of the liquid crystal, methyl(meth)acrylate, ethyl(meth)acrylate, glycidyl(meth)acrylate, 4-glycidyloxybutyl(meth)acrylate, 4-(6-( It is preferable to use (meth)acryloyloxyhexyl)oxybenzoic acid and (E)-3-(4-(6-(meth)acryloyloxyhexyl)oxyphenyl)acrylic acid.

[Preparation of liquid crystal aligning agent]
The liquid crystal aligning agent may be composed of one type of polymer having a constitutional unit containing a heat-reactive photoreactive structure, and two or more types of polymers having a constitutional unit containing a heat-reactive photoreactive structure are mixed. It may have been done. Further, a polymer other than the polymer having a structural unit containing a thermally reactive photoreactive structure may be contained. In the present specification, a liquid crystal aligning agent composed of one type of polymer may be referred to as a single-layer type liquid crystal aligning agent. A liquid crystal aligning agent in which two or more polymers are mixed may be referred to as a blend type liquid crystal aligning agent.

When importance is attached to the liquid crystal alignment property of the liquid crystal alignment film, it is preferable to prepare a liquid crystal aligning agent by mixing polyamic acid or its derivative as a polymer having a constitutional unit containing a thermally reactive photoreactive structure. Further, when importance is attached to storage stability, it is preferable to prepare a liquid crystal aligning agent using poly(meth)acrylate as a polymer having a structural unit containing a thermoreactive photoreactive structure.

The case of using polyamic acid and its derivative as the liquid crystal aligning agent of the present invention will be described in detail. A blend type liquid crystal aligning agent is preferable when the balance between the storage stability of the liquid crystal aligning agent, the printability of the liquid crystal aligning agent on the display element substrate, and the characteristics of the liquid crystal aligning film to be formed is important. Specifically, a diamic acid having a structure represented by formula (1A) (preferably a diamine represented by formula (2)) is used as a monomer, and a mixture of polyamic acid and its derivative, or a formula ( 1A) by mixing with a polyamic acid or a derivative thereof prepared using a diamine having a structure represented by formula (1A) and a polyamic acid or a derivative thereof not using the diamine having a structure represented by formula (1A) as a raw material The resulting liquid crystal aligning agent is preferred.

In order to produce a polyamic acid and its derivative which do not use a diamine having a structure represented by the formula (1A) as a raw material, a diamine other than the diamine having a structure represented by the formula (1A), a dihydrazide, and a tetracarboxylic acid diamine. Anhydrous is preferably used.

When such a two-component polymer is used, for example, a polymer having excellent performance in aligning liquid crystal is selected on one side, and a polymer having excellent performance on improving electrical characteristics of the liquid crystal display device is selected on the other side. There is an aspect of selecting the polymer. In this case, by controlling the structure and molecular weight of each polymer, in the process of applying a liquid crystal aligning agent obtained by dissolving these polymers in a solvent to a substrate and performing preliminary drying to form a thin film, as described later. It is possible to segregate a polymer having excellent liquid crystal alignment ability in the upper layer of the thin film and a polymer having excellent performance in improving the electrical characteristics of the liquid crystal display device in the lower layer of the thin film. For this purpose, it is possible to apply a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer in mixed polymers. The confirmation of such layer separation is made such that the surface energy of the formed liquid crystal alignment film is the same as or close to the surface energy of the film formed by the liquid crystal alignment agent containing only the polymer intended to segregate in the upper layer. It can be confirmed by the value.

As a method of expressing the layer separation, it is also possible to reduce the molecular weight of the polymer to be segregated in the upper layer.

In a liquid crystal aligning agent composed of a mixture of polyamic acids, layer separation can be achieved by using polyimide as the polymer to be segregated in the upper layer.

The diamine having the structure represented by the formula (1A) may be used as a raw material monomer of the polymer segregated in the upper layer of the thin film or may be used as a raw material monomer of the polymer segregated in the lower layer of the thin film. It may also be used as a raw material monomer for both polymers.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film may be selected from the known tetracarboxylic dianhydrides exemplified above without any limitation. it can.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film is represented by the formula (AN-1-1), the formula (AN-2-1) and the formula (AN-3-). 1), a formula (AN-4-5), and a compound represented by a formula (AN-4-17) are preferable, and a formula (AN-4-17) is more preferable. In formula (AN-4-17), m=4 or 8 is preferable, and m=8 is more preferable.

The diamine and dihydrazide used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film can be selected from the known diamines exemplified above without any limitation.

As the diamine and dihydrazide other than the diamine represented by the formula (2) used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film, the formula (DI-4-1) and the formula (DI-4- It is preferable to use the compounds represented by 13), formula (DI-4-15), formula (DI-5-1), formula (DI-7-3), and formula (DI-13-1). Especially, it is more preferable to use the compounds represented by formula (DI-4-13), formula (DI-4-15), formula (DI-5-1), and formula (DI-13-1). In formula (DI-5-1), m=1, 2 or 4 is preferable, and m=4 is more preferable. In the formula (DI-7-3), m=3 and n=1 are preferable.

The non-photosensitive diamine used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film preferably contains 30 mol% or more of aromatic diamine in the total amount of the non-photosensitive diamine, and 50 mol% or more. It is more preferable to include.

The above-mentioned acid dianhydride and diamine having a photoisomerization structure are preferably used for synthesizing a polyamic acid or its derivative segregated in the upper layer of a thin film.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film can be selected without limitation from the known tetracarboxylic dianhydrides exemplified above. ..

Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film include formula (AN-1-1), formula (AN-1-13), and formula (AN-2). -1), a compound represented by formula (AN-3-2), and a formula (AN-4-21) are preferable, and a formula (AN-1-1), a formula (AN-2-1), and a formula (AN-3-2) is more preferable.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film should contain 10 mol% or more of aromatic tetracarboxylic dianhydride in the total amount of tetracarboxylic dianhydride. Is preferable, and it is more preferable to contain 30 mol% or more.

The diamine and dihydrazide used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film can be selected from the known diamines exemplified above without any limitation.

Examples of the diamine and dihydrazide used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film include formula (DI-4-1), formula (DI-4-2), and formula (DI-4-10). , Formula (DI-4-18), formula (DI-4-19), formula (DI-5-9), formula (DI-5-28), formula (DI-5-30), formula (DI- 13-1) and the compound represented by Formula (DIH-2-1) are preferable. Among them, represented by formula (DI-4-1), formula (DI-4-18), formula (DI-4-19), formula (DI-5-9), and formula (DI-13-1). Are more preferred. In the formula (DI-5-30), diamines with k=2 are preferred.

The diamine used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film preferably contains the aromatic diamine in an amount of 30 mol% or more, and preferably 50 mol% or more, based on all diamines. More preferable.

The polyamic acid or its derivative segregated in the upper layer of the thin film, and the polyamic acid or its derivative segregated in the lower layer of the thin film are both the following as a synthesis method of polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention. It can be synthesized according to the method described in.

The proportion of the polyamic acid or its derivative segregated in the upper layer of the thin film and the ratio of the polyamic acid or its derivative segregated in the upper layer of the thin film to the total amount of the polyamic acid or its derivative segregated in the lower layer of the thin film is from 5% by weight to 50% by weight. % Is preferable, and 10% by weight to 40% by weight is more preferable.

(solvent)
Further, for example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of adjusting the coating property of the liquid crystal aligning agent and the concentration of the polymer having a structural unit containing a thermally reactive photoreactive structure. .. The solvent can be applied without particular limitation as long as it is a solvent capable of dissolving a polymer component. The solvent includes a wide range of solvents that are commonly used in the manufacturing process and application of polymer components such as polyamic acid, soluble polyimide, and poly(meth)acrylate, and can be appropriately selected according to the purpose of use. The solvent may be one kind or a mixed solvent of two or more kinds.

Examples of the solvent include a solvent that is a hydrophilic solvent for a polymer having a structural unit containing a heat-reactive photoreactive structure, and another solvent for improving the coating property.

Examples of the aprotic polar organic solvent which is a hydrophilic solvent for polyamic acid, its derivative or (meth)acrylate include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N , N-dimethylacetamide, dimethylsulfoxide, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, N,N-dimethylisobutyramide, γ-butyrolactone and γ-valerolactone.

Examples of other solvents for improving coating properties include diisobutyl ketone, alkyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, 4-methyl-2-pentanol, diisobutylcarbinol, tetralin, Isophorone, ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ether such as diethylene glycol butyl methyl ether, ethylene glycol monoalkyl or phenyl Acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoalkyl ether such as 1-butoxy-2-propanol, dialkyl malonate such as diethyl malonate, dipropylene glycol monoalkyl such as dipropylene glycol monomethyl ether Examples thereof include ethers and ester compounds such as acetates.

Among these, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, γ-valerolactone, diisobutyl ketone, 4-methyl-2-pentanol, diisobutylcarbinol, ethylene glycol mono Butyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, 1-butoxy-2-propanol, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, butyl cellosolve acetate are more preferable.

The polymer concentration in the liquid crystal aligning agent of the present invention is preferably 0.1 to 40% by weight. When the liquid crystal aligning agent is applied to the substrate, an operation of previously diluting the contained polymer with a solvent may be required in order to adjust the film thickness.

The solid content concentration in the liquid crystal aligning agent of the present invention is not particularly limited, and an optimum value may be selected according to various coating methods described below. Usually, it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the varnish in order to suppress unevenness and pinholes during coating.

The preferred range of the viscosity of the liquid crystal aligning agent of the present invention varies depending on the coating method, the concentration of the polymer, the type of polymer used, the type and ratio of the solvent. For example, in the case of coating with a printing machine, it is 5 to 100 mPa·s (more preferably 10 to 80 mPa·s). If it is less than 5 mPa·s, it may be difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa·s, printing unevenness may increase. In the case of coating by spin coating, 5 to 200 mPa·s (more preferably 10 to 100 mPa·s) is suitable. When coating using an inkjet coating device, 5 to 50 mPa·s (more preferably 5 to 20 mPa·s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measuring method, for example, using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo) (measurement temperature: 25° C.).

The liquid crystal aligning agent of the present invention may further contain an additive. For example, JP-A-2007-28659, JP-A-2008-096979, JP-A-2009-109987, JP-A-2009-175715, JP-A-2010-054872, JP-A-2015-212807, Examples thereof include alkenyl-substituted nadimide compounds, oxazine compounds, compounds having a radical-polymerizable unsaturated double bond, epoxy compounds, oxazole compounds, and silane compounds described in JP-A-2016-170409.

Liquid Crystal Alignment Film Next, the liquid crystal alignment film of the present invention will be described.
The liquid crystal alignment film of the present invention is formed by the liquid crystal alignment agent for optical alignment of the present invention.
Hereinafter, a method for forming a liquid crystal alignment film using the liquid crystal alignment agent for optical alignment of the present invention will be described. The liquid crystal aligning agent for photo-alignment of the present invention can form a liquid crystal aligning film by causing a chemical reaction of constitutional units having a heat-reactive photoreactive structure in the step of heating and baking. When the polymer of the present invention is polyamic acid or a derivative thereof, an imidization reaction can be further caused to form a liquid crystal alignment film.

The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent for photo-alignment. The liquid crystal alignment film of the present invention comprises, for example, a step of forming a coating film of the liquid crystal alignment agent for photo-alignment of the present invention, a step of heating and drying the coating film to form a film of the liquid crystal alignment agent, It can be obtained by going through a step of irradiating the film with light to give anisotropy and a step of heating and baking the film of the liquid crystal aligning agent having anisotropy. During the heating and firing, in the liquid crystal aligning agent for photo-alignment according to the present invention, the structural unit having a photo-reactive structure undergoes a chemical reaction to reduce or eliminate the photo-reactive group. For this reason, it is preferable that the liquid crystal alignment film of the present invention is irradiated with light to impart anisotropy after the coating step and the heating and drying step, and then subjected to the heating and firing step. In the present specification, the disappearance of the photoreactive group of the photoreactive structure may be referred to as making the photoreactive structure a photoreactive structure.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display device, as in the case of producing a normal liquid crystal aligning film. As the substrate, glass such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ —ZnO), electrodes such as IGZO (In—Ga—ZnO ₄ ) electrodes and a color filter may be provided, glass, silicon nitride, Substrates made of acrylic, polycarbonate, polyimide, etc. may be mentioned.

The spinner method, the printing method, the dipping method, the dropping method, the inkjet method and the like are generally known as methods for applying the liquid crystal aligning agent to the substrate. These methods are also applicable to the present invention.

In the heat drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, etc. are generally known. The heating and drying step is preferably carried out at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heating and baking step. Specifically, the heating and drying temperature is preferably in the range of 30°C to 150°C, and more preferably in the range of 50°C to 120°C.

As the heating and firing step, a method of performing heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, etc. are generally known. These methods are also applicable to the present invention. It may be carried out under the condition that a structural unit having a heat-reactive photoreactive structure can cause a chemical reaction. When a liquid crystal aligning agent for alignment containing a polyamic acid or its derivative is used, it can be carried out under the conditions necessary for exhibiting a dehydration/ring-closing reaction. When a liquid crystal aligning agent for alignment containing poly(meth)acrylate is used, it is generally preferably carried out at a temperature of about 50 to 300° C. for 1 minute to 3 hours, more preferably 80 to 200° C.
Generally, it is preferably carried out at a temperature of about 100 to 300° C. for 1 minute to 3 hours, more preferably 120 to 280° C., further preferably 150 to 250° C. In addition, heating and baking can be performed at different temperatures a plurality of times. A plurality of heating devices set to different temperatures may be used, or one heating device may be used while sequentially changing to different temperatures. When the heating and firing are performed twice at different temperatures, it is preferable that the first heating is performed at 90 to 180° C. and the second heating is performed at a temperature of 185° C. or higher. Further, the temperature can be changed from low temperature to high temperature for firing. When firing is performed while changing the temperature, the initial temperature is preferably 90 to 180°C. The final temperature is preferably 185 to 300°C, more preferably 190 to 230°C.

In the method for forming a liquid crystal alignment film of the present invention, a known photo-alignment method is preferably used as a means for imparting anisotropy to a thin film in order to align the liquid crystal in one direction with respect to the horizontal and/or vertical direction. be able to.

The method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method, the thin film after heating and drying the coating film is irradiated with linearly polarized light or non-polarized light to impart anisotropy to the thin film, It can be formed by heating and baking. Alternatively, it can be formed by heating and drying the coating film, baking it by heating, and then irradiating the thin film with linearly polarized light or unpolarized light. From the viewpoint of orientation, the radiation irradiation step is preferably performed before the heating and firing step.

Further, in order to improve the liquid crystal aligning ability of the liquid crystal aligning film, it is possible to irradiate the film with linearly polarized light or unpolarized light while heating the coating film. The irradiation of radiation may be performed in the step of heating and drying the coating film, or in the step of heating and baking, or may be performed between the heating and drying step and the heating and baking step. The heating and drying temperature in the step is preferably in the range of 30°C to 150°C, more preferably 50°C to 120°C. The heating and firing temperature in this step is preferably in the range of 30°C to 300°C, and more preferably in the range of 50°C to 250°C.

As the radiation, for example, ultraviolet rays containing light with a wavelength of 150 to 800 nm or visible light can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferable. Further, linearly polarized light or non-polarized light can be used. The light is not particularly limited as long as it can impart liquid crystal aligning ability to the thin film, but linear polarization is preferable when it is desired to exert a strong alignment regulating force on the liquid crystal.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even when irradiated with low energy light. Dose of linearly polarized light in the irradiation step is preferably from 0.01~20J / cm ^2, more preferably 0.03~10J / cm ^2. The wavelength of linearly polarized light is preferably 200 to 400 nm, more preferably 300 to 400 nm. The irradiation angle of the linearly polarized light with respect to the film surface is not particularly limited, but when it is desired to exert a strong alignment regulating force on the liquid crystal, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. Further, the liquid crystal alignment film of the present invention can align the liquid crystal in a direction perpendicular to the polarization direction of the linearly polarized light by irradiating the liquid crystal with the linearly polarized light.

Light sources used in the process of irradiating linearly polarized or non-polarized radiation include ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, deep UV lamp, halogen lamp, metal halide lamp, high power metal halide lamp, xenon lamp, mercury. A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excitation electrodeless lamp, or the like can be used without limitation.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further including steps other than the steps described above. For example, the liquid crystal alignment film of the present invention does not require a step of cleaning the film after baking or irradiation with radiation with a cleaning liquid, but a cleaning step can be provided for the convenience of other steps.

Examples of the cleaning method using a cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning and the like. These methods may be used alone or in combination. As the cleaning liquid, pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, ketones such as acetone and methyl ethyl ketone are used. It can be used, but is not limited thereto. Of course, as these cleaning liquids, those which are sufficiently purified and contain few impurities are used. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal aligning ability of the liquid crystal aligning film of the present invention, an annealing treatment by heat or light can be used before and after the heating/baking step or before and after irradiation with polarized or unpolarized radiation. In the annealing treatment, the annealing temperature is 30 to 180° C., preferably 50 to 150° C., and the time is preferably 1 minute to 2 hours. Further, the annealing light used for the annealing treatment includes a UV lamp, a fluorescent lamp, an LED lamp and the like. The light irradiation amount is preferably 0.3 to 10 J/cm ² .

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, more preferably 30 to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having a particularly large anisotropy of alignment. The magnitude of such anisotropy can be evaluated by the method using polarized IR described in JP-A-2005-275364. It can also be evaluated by a method using ellipsometry. Specifically, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, a polymer film having a large retardation value has a large degree of alignment, and when used as a liquid crystal alignment film, a liquid crystal alignment film having a larger anisotropy is considered to have a large alignment regulating force with respect to the liquid crystal composition. To be

The liquid crystal alignment film of the present invention can be used for controlling the alignment of a liquid crystal composition for liquid crystal displays such as smartphones, tablets, in-vehicle monitors, and televisions. In addition to the application of the liquid crystal composition for liquid crystal displays, it can be used for the alignment control of optical compensators and all other liquid crystal materials. Further, since the liquid crystal alignment film of the present invention has a large anisotropy, it can be used alone as an optical compensator.

Liquid Crystal Display Element Next, the liquid crystal display element of the present invention will be described.
The liquid crystal display element of the present invention is characterized in that it has the liquid crystal alignment film of the present invention.
The liquid crystal display device of the present invention can maintain a high voltage holding ratio and realize a high display quality even when a high-intensity backlight is mounted.
The liquid crystal display element of the present invention will be described in detail. According to the present invention, a pair of substrates arranged to face each other, an electrode formed on one or both of the facing surfaces of each of the pair of substrates, and an electrode formed on each of the facing surfaces of the pair of substrates. A liquid crystal alignment film, a liquid crystal layer formed between the pair of substrates, a pair of polarizing films installed so as to sandwich the counter substrate, a backlight and a driving device, wherein: The liquid crystal alignment film is composed of the liquid crystal alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include an ITO film and a metal vapor deposition film. Further, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired patterned shape, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The form of formation of the electrodes differs depending on the type of liquid crystal display element. For example, in the case of an IPS type liquid crystal display element (horizontal electric field type liquid crystal display element), the electrodes are arranged on one of the pair of substrates, and the other liquid crystal display element. In this case, electrodes are arranged on both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

In the case of a homogeneously aligned liquid crystal display element (for example, IPS, FFS, etc.), at least a backlight, a first polarizing film, a first substrate, a first liquid crystal alignment film, a liquid crystal layer, and The second substrate, having a second polarizing film, the polarizing axis of the polarizing film, the polarizing axis of the first polarizing film (direction of polarization absorption) and the polarizing axis of the second polarizing film intersect (preferably (Orthogonal) to be installed. At this time, the liquid crystal can be installed so that the polarization axis of the first polarizing film and the liquid crystal alignment direction are parallel or orthogonal to each other. The liquid crystal display device installed so that the polarization axis of the first polarizing film and the liquid crystal alignment direction are parallel to each other is referred to as O-mode, and the liquid crystal display device installed so as to be orthogonal to each other is referred to as E-mode. The liquid crystal alignment film of the present invention can be applied to both O-mode and E-mode and can be selected according to the purpose.

A compound having dichroism is used for many photoisomerizable materials. Therefore, the polarization axis of the polarized light irradiated to add anisotropy to the liquid crystal aligning agent is aligned parallel to the polarization axis of the polarized light from the polarizing film arranged on the backlight side (the liquid crystal aligning agent of the present invention is When it is used, the transmittance of the liquid crystal alignment film in the light absorption wavelength region is increased by setting the O-mode). Therefore, the transmittance of the liquid crystal display device can be further improved.

The liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates whose surfaces on which the liquid crystal alignment film is formed face each other. In the formation of the liquid crystal layer, spacers such as fine particles and a resin sheet that intervene between the pair of substrates and form an appropriate interval can be used as necessary.

As a method for forming the liquid crystal layer, a vacuum injection method and an ODF (One Drop Fill) method are known.

In the vacuum injection method, a seal is printed and a substrate is attached by providing a gap (cell gap) so that the liquid crystal alignment film surfaces face each other and leaving the liquid crystal injection port. Liquid crystal is injected and filled into the cell gap defined by the substrate surface and the sealant by utilizing a vacuum differential pressure, and then the injection port is sealed to manufacture a liquid crystal display element.

In the ODF method, a sealant is printed on the outer periphery of the liquid crystal alignment film surface of one of a pair of substrates, liquid crystal is dropped on the area inside the sealant, and then the other substrate is placed so that the liquid crystal alignment film surfaces face each other. Stick together. Then, the liquid crystal is spread over the front surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal display element.

In addition to the UV curable type, a thermosetting type is also known as a sealing agent used for bonding substrates. Printing of the sealant can be performed by, for example, a screen printing method.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include JP3086228, JP2635435, JP-A-5-501735, JP-A-8-157826, JP-A-8-231960, JP-A-9-241644 (EP885272A1), and JP Kaihei 9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-2559596, JP-A-9-241643 (EP885271A1), JP-A-10-201416 (EP844229A1), JP-A-10-1998. -204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822 and the like are mentioned.

Preferable examples of the liquid crystal composition having the negative dielectric anisotropy include JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, and JP-A-8-104869. Kaihei 10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237000. -237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076, JP-A-10-237448 (EP9672661A1), JP-A-10-287874, JP-A-10-287875, and JP-A-10-287875. 10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, JP-A-2010-037428, International Publication 2011/ The liquid crystal compositions disclosed in 024666, International Publication 2010/072370, Japanese Patent Laid-Open No. 2010-5370010, JP 2012-077201, JP 2009-084362 and the like can be mentioned.

There is no problem in using one or more optically active compounds added to a liquid crystal composition having a positive or negative dielectric anisotropy.

In addition, for example, the liquid crystal composition used for the liquid crystal display element of the present invention may further contain an additive from the viewpoint of improving the orientation, for example. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerization initiators, polymerization inhibitors and the like. Preferred photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerization initiators and polymerization inhibitors include compounds disclosed in International Publication 2015/146330 and the like. ..

A polymerizable compound can be mixed with the liquid crystal composition in order to adapt to a liquid crystal display device of PSA (polymer sustained alignment) mode. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane) and vinyl ketone. Preferred compounds include compounds disclosed in WO 2015/146330 and the like.

Hereinafter, the features of the present invention will be described more specifically with reference to Examples and Comparative Examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.
The evaluation methods and compounds used in the examples are as follows.

[Weight average molecular weight (Mw)]
The weight average molecular weight of the polymer was determined by measuring with a GPC method using a 2695 separation module/2414 differential refractometer (manufactured by Waters) and converting into polystyrene. The obtained polymer was diluted with a phosphoric acid-dimethylformamide (DMF) mixed solution (phosphoric acid/DMF=0.6/100:weight ratio) so that the polymer concentration was about 2% by weight. HSPgel RT MB-M (manufactured by Waters) was used as a column, and the mixed solution was used as a developing agent, and the measurement was carried out at a column temperature of 50° C. and a flow rate of 0.40 mL/min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

[Transmittance]
A liquid crystal alignment film is formed on a transparent glass substrate, a transmittance of 330 nm to 480 nm is measured with an ultraviolet-visible spectrophotometer V-660 (manufactured by JASCO Corporation), and the average value of the transmittance at 380 nm to 430 nm is calculated. I asked. The average value of this transmittance was made relative to the transmittance of the transparent glass substrate on which the liquid crystal alignment film was not formed as 100%. It can be said that if the average transmittance is 80% or more, it has good transparency, and if it is 85% or more, it has excellent transparency.

[AC afterimage (evaluation of liquid crystal orientation)]
The AC afterimage was measured according to the method described in International Publication No. 2000/43833.
Specifically, the brightness-voltage characteristics (B-V characteristics) of the manufactured liquid crystal cell were measured, and this was taken as the brightness-voltage characteristics before stress application: B(before). Next, an alternating current of 4.5 V and 60 Hz was applied to the liquid crystal cell for 20 minutes, short-circuited for 1 second, and the luminance-voltage characteristic (B-V characteristic) was measured again. This was defined as the luminance-voltage characteristic after stress application: B (after). Then, using the measured brightness at a voltage of 1.3 V of each BV characteristic, a brightness change rate ΔB (%) was obtained by the following formula. The smaller the value of ΔB(%), the more the occurrence of AC afterimage can be suppressed, that is, the better the liquid crystal alignment.
ΔB(%)=[B(after) _1.3 −B(before) _1.3 ]/B(before) _1.3
In the formula, B(before) _1.3 shows the brightness at 1.3 V in the B-V characteristic before stress application, and B(after) _1.3 shows the brightness at _1.3 V in the B-V characteristic after stress application. ..
The brightness change rate ΔB was evaluated according to the following criteria.
ΔB (%) is less than 2.0%: ◎
ΔB(%) is 2.0% or more and less than 4.0%: ○ ΔB(%) is 4.0% or more and less than 8.0%: Δ
ΔB (%) is 8.0% or more: ×

The compounds used in Examples and Comparative Examples are shown below.
[Diamine represented by formula (2)]
The diamine represented by the formula (2) used for preparing the varnish in this example is shown below.

[Tetracarboxylic acid dianhydride]
The tetracarboxylic dianhydride used for the preparation of the varnish in this example is shown below.

[Diamine other than the diamine represented by the formula (2)]
The diamines other than the diamine represented by the formula (2) used for preparing the varnish in this example are shown below.

[(Meth)Acrylate Represented by Formula (7)]
The (meth)acrylate represented by the formula (7) used for preparing the varnish in this example is shown below.

[(Meth)acrylate other than (meth)acrylate represented by Formula (7)]
The (meth)acrylates other than the (meth)acrylate represented by the formula (7) used for preparing the varnish in this example are shown below.

[solvent]
The solvents used in the preparation of the liquid crystal aligning agent in this example are shown below.
N-methyl-2-pyrrolidone butyl cellosolve (ethylene glycol monobutyl ether)
γ-butyrolactone diisobutyl ketone

The diamine represented by the formula (2) used in this example was synthesized by the following procedure.
[Synthesis Example 1] Synthesis of diamine (4-2-1, n=2) <First step: ether synthesis>
Sodium ethoxide (25.2 g, 351.2 mmol) and ethanol (500 mL) were added to a 2000 mL three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer, and a nitrogen introducing tube, and the mixture was ice bathed. 3-Methoxybenzyl chloride (50.0 g, 319.3 mmol) and ethanol (250 mL) were added dropwise, then the solution was stirred at reflux under a nitrogen atmosphere for 5 hours. The solvent was distilled off under reduced pressure, ethyl acetate (500 mL) was added, and the mixture was washed with water (500 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (amount 51.5 g, yield 97%).

<Second stage: protection>
4-Nitrophenol (60.0 g, 431.3 mmol) and acetone (1500 mL) were added to a 3000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube. Then potassium carbonate (70.4 g, 1035.2 mmol) and 4-methoxybenzyl chloride (74.3 g, 474.4 mmol) were added. Then, the solution was stirred under reflux for 7 hours under a nitrogen atmosphere. After cooling the reaction solution, it was filtered and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 111.8 g, quantitative).

<Third stage: reduction>
In a 2000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, the compound (111.8 g, 431.2 mmol) obtained in the second step, iron (48.2 g, 862.5 mmol), ammonium chloride (46 0.1 g, 862.5 mmol), ethanol (600 mL) and water (300 mL) were added, and the solution was stirred under reflux for 8 hours under a nitrogen atmosphere. The reaction solution was cooled, filtered, and the solvent was distilled off under reduced pressure. Then, toluene (500 mL) and a 1M aqueous sodium hydroxide solution were added until the pH reached 9, and a liquid separation operation was performed. Then, the organic layer was washed with water (500 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 91.0 g, yield 92%).

<Fourth stage: diazo coupling>
The compound (69.0 g, 300.8 mmol) obtained in the third step and 6 mol/L hydrochloric acid (170 mL) were added to a 500 mL three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introducing tube, and the mixture was ice-bathed. Sodium nitrite (24.9 g, 361.0 mmol) and water (125 mL) were added dropwise, and then the solution was stirred in an ice bath for 1 hour under a nitrogen atmosphere to obtain a diazonium salt solution. The compound (50.0 g, 300.8 mmol) obtained in the first step, water (1000 mL) and ethanol (100 mL) were added to a separately prepared thermometer and a 3000 mL three-necked flask equipped with a nitrogen introduction tube, and the mixture was ice-cooled. .. After the above diazonium salt solution was added, the solution was stirred in an ice bath for 1 hour under nitrogen atmosphere. After completion of the reaction, filtration was performed to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 89.5 g, yield 61%).

<Fifth stage: Deprotection>
The compound (89.5 g, 220.2 mmol) obtained in the fourth step, dichloromethane (1800 mL) and water (250 mL) were added to a 3000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introducing tube. DDQ (100.0 g, 440.4 mmol) was then added and the solution was stirred for 2 hours at room temperature under nitrogen atmosphere. After completion of the reaction, the reaction solution was filtered, dichloromethane (200 mL) was added, and the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (1500 mL×2 times) and water (1500 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 29.6 g, yield 47%).

<Sixth stage: etherification>
In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, the compound (29.6 g, 103.5 mmol) obtained in the fifth step, potassium carbonate (7.8 g, 113.8 mmol), and DMF( 300 mL) was added. Then, 1-(2-bromoethoxy)-3,5-dinitrobenzene (synthesized by the method described in JP 2000-281783 A, 31.6 g, 108.7 mmol) was added. Then, the solution was stirred at 100° C. under a nitrogen atmosphere for 10 hours. After cooling the reaction solution, it was poured into water (1000 mL), ethyl acetate (1000 mL) was added, and liquid separation operation was performed. Then, the organic layer was washed with water (1000 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 32.4 g, 63%).

<Seventh stage: Reduction>
In a 2000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, the compound obtained in the sixth step (32.4 g, 65.2 mmol), sodium sulfide nonahydrate (62.6 g, 260. 7 mmol), ethanol (500 mL), and water (150 mL) were added, and the mixture was stirred under reflux for 1 hour under a nitrogen atmosphere. The solvent was distilled off from this reaction solution under reduced pressure, and then water (400 mL) and ethyl acetate (500 mL) were added for extraction. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product. This crude product was purified by silica gel chromatography to obtain 10.0 g of a diamine (4-2-1, n=2) represented by the following formula in a yield of 35%.

[Synthesis Example 2] Synthesis of compound (5-2-1, n=2) <First step: protection>
3-Hydroxybenzyl alcohol (30.0 g, 241.7 mmol) and acetone (750 mL) were added to a 2000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube. Then potassium carbonate (39.5 g, 580.0 mmol) and 4-methoxybenzyl chloride (41.6 g, 265.8 mmol) were added. Then, the solution was stirred under reflux for 7 hours under a nitrogen atmosphere. After cooling the reaction solution, it was filtered and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 59.0 g, quantitative).

<Second stage: Chlorination>
In a 1000 mL three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introducing tube, the compound (59.0 g, 241.6 mmol) obtained in the first step, dichloromethane (300 mL), and triethylamine (40.4 mL, 290.0 mmol). ) Was added and the mixture was bathed in ice. Methanesulfonyl chloride (22.4 mL, 290.0 mmol) was then added dropwise and the solution was stirred for 48 hours at room temperature under nitrogen atmosphere. After completion of the reaction, dichloromethane (200 mL) was added, and the mixture was washed with water (500 mL x 2 times). After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 60.9 g, 96%).

<Third stage: ether synthesis>
Sodium ethoxide (18.3 g, 255.1 mmol) and ethanol (300 mL) were added to a 2000 mL three-necked flask equipped with a reflux tube, a dropping funnel, a thermometer, and a nitrogen introducing tube, and the mixture was ice-bathed. An ethanol solution (600 mL) of the compound (60.9 g, 231.9 mmol) obtained in the second step was added dropwise, and then the solution was stirred under reflux for 5 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, ethyl acetate (500 mL) was added, and the mixture was washed with water (500 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 61.9 g, yield 98%).

<Fourth stage: diazo coupling>
4-Methoxyaniline (22.6 g, 183.6 mmol) and 6 mol/L hydrochloric acid (100 mL) were added to a 500 mL three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introducing tube, and the mixture was ice-bathed. Sodium nitrite (15.2 g, 220.3 mmol) and water (75 mL) were added dropwise, and then the solution was stirred in an ice bath for 1 hour under a nitrogen atmosphere to obtain a diazonium salt solution. The compound (50.0 g, 183.6 mmol) obtained in the third step, water (1000 mL) and ethanol (100 mL) were added to a separately prepared thermometer and a 3000 mL three-necked flask equipped with a nitrogen introduction tube, and the mixture was ice-bathed. .. After the above diazonium salt solution was added, the solution was stirred in an ice bath for 1 hour under nitrogen atmosphere. After completion of the reaction, filtration was performed to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 57.3 g, yield 64%).

<Fifth stage: Deprotection>
The compound (57.3 g, 141.0 mmol) obtained in the fourth step, dichloromethane (1200 mL) and water (200 mL) were added to a 3000 mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introducing tube. DDQ (64.0 g, 281.9 mmol) was then added and the solution was stirred for 2 hours at room temperature under nitrogen atmosphere. After completion of the reaction, the reaction solution was filtered, dichloromethane (200 mL) was added, and the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (1000 mL x 2 times) and water (1000 mL x 2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 20.2 g, yield 50%).

<Sixth stage: etherification>
In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introducing tube, the compound (20.2 g, 70.5 mmol) obtained in the fifth step, potassium carbonate (5.3 g, 77.6 mmol), and DMF( 200 mL) was added. Then 1-(2-bromoethoxy)-3,5-dinitrobenzene (21.6 g, 74.1 mmol) was added. Then, the solution was stirred at 100° C. under a nitrogen atmosphere for 10 hours. After cooling the reaction solution, it was poured into water (1000 mL), ethyl acetate (1000 mL) was added, and liquid separation operation was performed. Then, the organic layer was washed with water (1000 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 25.2 g, 72%).

<Seventh stage: Reduction>
In a 2000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introducing tube, the compound (25.2 g, 50.8 mmol) obtained in the sixth step, sodium sulfide nonahydrate (48.8 g, 203. 0 mmol), ethanol (400 mL), and water (120 mL) were added, and the mixture was stirred under reflux for 1 hour under a nitrogen atmosphere. The solvent was distilled off from this reaction solution under reduced pressure, and then water (400 mL) and ethyl acetate (500 mL) were added for extraction. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product. This crude product was purified by silica gel chromatography to obtain a diamine (5-2-1, n=2) represented by the following formula in an amount of 8.2 g and a yield of 37%.

The (meth)acrylate represented by the formula (7) used in this example was synthesized by the following procedure.
[Synthesis Example 3] Synthesis of (meth)acrylate (9-2-1, n=6) <First step: etherification>
In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introducing tube, the compound (15.3 g, 53.4 mmol) obtained in the fifth step of Synthesis Example 1, potassium carbonate (4.0 g, 58.8 mmol). , And DMF (150 mL) were added. Then 6-chlorohexanol (7.67 g, 56.1 mmol) was added. Then, the solution was stirred at 100° C. under a nitrogen atmosphere for 10 hours. After cooling the reaction solution, it was poured into water (500 mL), ethyl acetate (500 mL) was added, and a liquid separation operation was performed. Then, the organic layer was washed with water (1000 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 16.9 g, 81%).

<Second stage: esterification>
In a 300 mL three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introducing tube, the compound (16.9 g, 43.3 mmol) obtained in the first step, triethylamine (7.2 mL, 51.9 mmol), and tetrahydrofuran (THF) ) (100 mL) was added and the mixture was ice-bathed. Then methacryloyl chloride (5.43 g, 51.9 mmol) was added dropwise, after which the solution was stirred at room temperature under a nitrogen atmosphere for 3 hours. After cooling the reaction solution, it was poured into water (300 mL) and the precipitated solid was filtered to obtain a crude product. The crude product was purified by silica gel chromatography to obtain compound (9-2-1, n=6) (yield 17.7 g, 90%).

[Synthesis Example 4] Synthesis of (meth)acrylate (10-2-1, n=6) <First step: etherification>
In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, the compound obtained in the fifth step of Synthesis Example 2 (9.8 g, 34.2 mmol), potassium carbonate (2.6 g, 37.6 mmol) _. , And DMF (100 mL) were added. Then 6-chlorohexanol (4.9 g, 35.9 mmol) was added. Then, the solution was stirred at 100° C. under a nitrogen atmosphere for 10 hours. After cooling the reaction solution, it was poured into water (500 mL), ethyl acetate (500 mL) was added, and a liquid separation operation was performed. Then, the organic layer was washed with water (500 mL×2 times). The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield 11.1 g, 83%).

<Second stage: esterification>
In a 300 mL three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introducing tube, the compound (11.1 g, 28.5 mmol) obtained in the first step, triethylamine (4.8 mL, 34.2 mmol), and THF (60 mL). ) Was added and the mixture was bathed in ice. Then methacryloyl chloride (3.6 g, 34.2 mmol) was added dropwise, after which the solution was stirred at room temperature under a nitrogen atmosphere for 3 hours. After cooling the reaction solution, it was poured into water (300 mL) and the precipitated solid was filtered to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the compound (10-2-1, n=6) (yield 11.3 g, 87%).

[Polymerization Example 1] Polymer synthesis In a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introducing tube, 2.9464 g of formula (4-2-1, n=2) and formula (DI-5-1, m 0.3346 g of (1) was added, and N-methyl-2-pyrrolidone (74.0 g) was added. To this solution, 2.7188 g of formula (AN-4-26) was added as tetracarboxylic dianhydride, and the mixture was stirred at room temperature for 24 hours. Γ-Butyrolactone (10.0 g) and butyl cellosolve (10.0 g) were added to this reaction solution, and the mixture was heated and stirred at 80° C. until the produced polymer had a desired weight average molecular weight. As a result, a varnish 1 having a polymer weight average molecular weight of 15,000 and a resin content concentration (polymer concentration as solid content) of 6% by weight was obtained.

[Polymerization Examples 2 to 7]
Varnishes 2 to 7 having a resin content of 6% by weight were prepared in the same manner as in Polymerization Example 1 except that the compounds used as the diamine and the tetracarboxylic dianhydride were changed as shown in Table 1. At this time, the polymer synthesis conditions were adjusted so that the weight average molecular weight was in the range of 5,000 to 20,000. Table 1 shows the weight average molecular weight of the produced polymer. In Table 1, in Preparation Examples in which two or more compounds are listed as diamines, it means that all of the compounds are used as diamines, and two or more compounds are listed as tetracarboxylic dianhydrides. In the preparations given, it means that all the compounds were combined and used as tetracarboxylic dianhydride. The numerical value in square brackets represents the compounding ratio (mol %). The same applies to Tables 2 to 4 below.

[Comparative Polymerization Examples 1 and 2]
Comparative varnishes 1 and 2 having a resin content of 6% by weight were prepared in the same manner as in Polymerization Example 1 except that the compounds used as the diamine and the tetracarboxylic dianhydride were changed as shown in Table 2. The weight average molecular weight of the produced polymer is shown in Table 2.

[Polymerization Example 8] Polymer synthesis A compound (14.8 g, 32.6 mmol) represented by the formula (9-2-1, n=6) was put into a 200 mL three-necked flask equipped with a stirring blade and a nitrogen introducing tube. , THF (85.2 g) was added. Next, 2,2'-azobisisobutyronitrile (0.27 g, 1.6 mmol) was added, deaeration was performed, and then the mixture was reacted at 60°C for 20 hours. The reaction solution was poured into methanol (500 mL), and the precipitated solid was filtered and dried to obtain polymer powder 1. The weight average molecular weight of this polymer was 126,000.
[Polymerization Examples 9 to 13]
Polymer powders 2 to 6 were prepared in the same manner as in Polymerization Example 8 except that the compound used as the (meth)acrylate was changed as shown in Table 3. In addition, in Table 3, in the preparation example in which two or more compounds are listed as (meth)acrylate, it means that all of the compounds are used together as (meth)acrylate. The numerical value in square brackets represents the compounding ratio (mol %).

[Comparative Polymerization Example 3]
Comparative Polymer Powder 1 was obtained according to Polymerization Example 8 except that the (meth)acrylate was changed. Table 4 shows the (meth)acrylate used and the weight average molecular weight of the obtained polymer.

Example 1 Preparation of Orienting Agent 1 Varnish 1 (10.0 g) was weighed and put into a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introducing tube, and N-methyl-2-pyrrolidone (1 0.0 g), butyl cellosolve (0.5 g) and diisobutyl ketone (0.5 g) were added, and the mixture was stirred at room temperature for 1 hour to obtain an aligning agent 1 having a resin content concentration of 5% by weight.

[Examples 2 to 7] Preparation of aligning agents 2 to 7 Aligning agents 2 to 7 were prepared in the same manner as in Example 1 except that the varnishes 2 to 7 were used instead of the varnish 1. Table 5 shows the varnish used for the preparation of the liquid crystal aligning agent in each example.

[Comparative Examples 1 and 2] Preparation of comparative aligning agents 1 and 2 Comparative aligning agents 1 and 2 were prepared in the same manner as in Example 1 except that comparative varnishes 1 and 2 were used instead of varnish 1. Table 6 shows comparative varnishes used for the preparation of the liquid crystal aligning agent in each comparative example.

[Example 8] Preparation of Orienting agent 8 Polymer powder 1 (0.6 g) was weighed and put into a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introducing tube, and N-methyl-2-pyrrolidone ( 8.4 g), butyl cellosolve (2.0 g) and diisobutyl ketone (1.0 g) were added, and the mixture was stirred at room temperature for 1 hour to obtain an aligning agent 8 having a resin content concentration of 5% by weight.

[Examples 9 to 13] Preparation of aligning agents 9 to 13 Aligning agents 9 to 13 were prepared in the same manner as in Example 8 except that the polymer powders 2 to 6 were used instead of the polymer powder 1. Table 7 shows the polymer powder used in the preparation of the liquid crystal aligning agent in each example.

Comparative Example 3 Preparation of Comparative Orientation Agent 3 Comparative Orientation Agent 3 was prepared in the same manner as in Example 8 except that Comparative Polymer Powder 1 was used instead of Polymer Powder 1. Table 8 shows comparative polymer powders used for the preparation of the liquid crystal aligning agent in each comparative example.

[Examples 1 to 7] Formation of liquid crystal alignment film and evaluation of transmittance The liquid crystal aligning agent prepared in Examples 1 to 7 was dropped on a glass substrate and spin-coated. After coating, the substrate was heated at 60° C. for 1 minute to evaporate the solvent and form a film of the liquid crystal aligning agent. Ushio Electric Co., Ltd. Multi Light ML-501C/B was used for the film of this liquid crystal aligning agent, and ultraviolet linear polarization of wavelength 365 nm was 2.0 J/cm ² from the vertical direction to the substrate through a polarizing plate. And subjected to photo-alignment treatment. The film of the liquid crystal aligning agent subjected to this photo-alignment treatment was heated and baked at 230° C. for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. Using this substrate, the average transmittance was determined by the method described above. The results are shown in Table 9.

[Comparative Examples 1 and 2] Formation of Liquid Crystal Alignment Film and Evaluation of Transmittance The average transmittance was evaluated in the same manner as in Examples 1 to 7 except that Comparative Alignment Agents 1 and 2 were used instead of Alignment Agents 1 to 7. I asked. The results are shown in Table 10.

[Examples 8 to 13] Formation of liquid crystal alignment film and evaluation of transmittance The liquid crystal alignment agent prepared in Examples 8 to 13 was dropped on a glass substrate and spin-coated. After coating, the substrate was heated at 60° C. for 1 minute to evaporate the solvent and form a film of the liquid crystal aligning agent. The film of this liquid crystal aligning agent was irradiated with UV linearly polarized light having a wavelength of 365 nm at 50 mJ/cm ² through a polarizing plate from the vertical direction on the substrate using Multilight ML-501C/B manufactured by USHIO INC. Then, photo-alignment treatment was performed. The film of the liquid crystal aligning agent subjected to this photo-alignment treatment was heated and baked at 180° C. for 60 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. Using this substrate, the average transmittance was determined by the method described above. The results are shown in Table 11.

[Comparative Examples 1 and 2] Formation of Liquid Crystal Alignment Film and Evaluation of Transmittance The average transmittance was determined in the same manner as in Examples 8 to 13 except that Comparative Alignment Agent 3 was used instead of Alignment Agents 8 to 13. .. The results are shown in Table 12.

As shown in Tables 9 and 11, an aligning agent 1 containing varnishes 1 to 13 prepared by using a diamine represented by the formula (2) or a (meth)acrylate represented by the formula (7). It was confirmed that the liquid crystal alignment film formed using No. 13 had a high average transmittance. It is considered that this is because a part of the azobenzene structure formed an indazole ring by the heating and baking treatment, and the azobenzene structure was reduced. On the other hand, the liquid crystal alignment film formed using the comparative alignment agents 1 to 3 containing the comparative varnishes 1 to 3 had a low average transmittance. It is considered that the reason why the average transmittance is low is that the azobenzene structure does not form an indazole ring and remains as an azobenzene structure as it is even after the heating and baking treatment.

[Evaluation of AC afterimage characteristics (evaluation of liquid crystal orientation)]
Using the liquid crystal aligning agents prepared in Examples 1 to 13, a 100 nm-thick liquid crystal aligning film was formed on a glass substrate with an FFS electrode and a glass substrate with a column spacer under the same conditions as in the evaluation of transmittance. The two substrates on which the liquid crystal alignment film is formed are made to face each other on the surfaces on which the liquid crystal alignment film is formed, and a space for injecting the liquid crystal composition is formed between the opposed liquid crystal alignment films. Stuck together. At this time, the substrates were oriented so that the polarization directions of the linearly polarized light with which the liquid crystal alignment films were irradiated during the photo-alignment treatment were parallel to each other. A negative type liquid crystal composition A having the following composition was injected into the space between the bonded substrates, and the injection port was sealed with a photocuring agent to prepare a liquid crystal cell (liquid crystal display element) having a cell thickness of 4 μm. With respect to the obtained liquid crystal cell, the luminance change rate ΔB before and after the stress application at 1.3 V was measured, and the AC residual property was evaluated according to the above criteria. The results are shown in Tables 13 and 14.

<Negative liquid crystal composition A>

As shown in Tables 13 and 14, an aligning agent 1 containing varnishes 1 to 13 prepared using a diamine represented by the formula (2) or a (meth)acrylate represented by the formula (7). Each of the liquid crystal cells using No. 13 had a rate of change in brightness ΔB due to stress application of less than 4.0% (∘ to ⊚) and exhibited good AC residual characteristics.
From the above results, when the varnish prepared by using the diamine represented by the formula (2) or the (meth)acrylate represented by the formula (7) is used as the liquid crystal aligning agent, the transmittance of the liquid crystal aligning film is increased. It was found that the liquid crystal cell to which the liquid crystal alignment film was applied had excellent AC afterimage characteristics.

Use of the liquid crystal aligning agent for optical alignment of the present invention can provide a liquid crystal display device having high transmittance.

Claims (24)

A liquid crystal aligning agent for photo-alignment containing a polymer having a constitutional unit containing a photoreactive structure in a side chain,
A liquid crystal aligning agent for photoalignment, in which a constitutional unit containing the photoreactive structure causes a chemical reaction by heating. The liquid crystal aligning agent for photo-alignment according to claim 1, wherein the chemical reaction is a cyclization reaction. The liquid crystal aligning agent for photo-alignment according to claim 1 or 2, wherein the structural unit containing the photoreactive structure contains a structure represented by the following formula (a-1) or the following formula (a-2):
[In the formula (a-1), R ^a represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
In formula (a-2), R ^b and R ^c each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group. ;
In formula (a-1) and formula (a-2), * represents the bonding position with the photoreactive group. ] The liquid crystal aligning agent for photo-alignment according to any one of claims 1 to 3, wherein the photoreactive structure is a photoisomerization structure or a structure that causes photo-Fries rearrangement. The liquid crystal aligning agent for photo-alignment according to claim 1, wherein the photoreactive structure has a structure represented by the following formula (1A).
[In Formula (1A), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
* Represents a bond position in the benzene ring, and is any position which can be replaced with a hydrogen atom in one benzene ring and any position which can be replaced with a hydrogen atom in the other benzene ring;
The hydrogen atom of the benzene ring may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (1A). ] The polymer contains a polymer which is a reaction product from a raw material containing tetracarboxylic dianhydride and diamine;
The reaction product is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide,
The said diamine is the liquid crystal aligning agent for optical alignments of any one of Claims 1-5 containing at least 1 of the diamine represented by following formula (2).
[In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O 3 is 2 and the number of R ^3r is 2, R ^3r may be the same or different, and R ^3q and R ^3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ] The liquid crystal aligning agent for optical alignment according to claim 6, wherein the diamine represented by the formula (2) is a diamine represented by the following formula (3).
[In Formula (3), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a linear alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one or —CH ₂ — of the linear alkylene group or two non-adjacent ones is replaced by —O—. May;
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ] The liquid crystal aligning agent for optical alignment according to claim 6 or 7, wherein the diamine represented by the formula (3) is a diamine represented by any of the following formulas (4) to (6).
[In the formulas (4) to (6), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
n represents a positive integer of 1 to 12. ] The diamine is the following formula (4-1-1), formula (4-1-2), formula (4-2-1), formula (4-2-2), formula (5-1-1), formula (5-1-2), Formula (5-2-1), Formula (5-2-2), Formula (6-1-1), Formula (6-1-2), Formula (6-2- 1) and the diamine represented by any one of Formula (6-2-2), The liquid crystal aligning agent for optical alignments of any one of Claims 6-8.
[Formula (4-1-1), Formula (4-1-2), Formula (4-2-1), Formula (4-2-2), Formula (5-1-1), Formula (5- 1-2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6-1-2), formula (6-2-1), In the formula (6-2-2), n represents a positive integer of 1-12. ] The light according to any one of claims 1 to 5, which contains, as the polymer, poly(meth)acrylate which is a reaction product from a raw material containing a (meth)acrylate represented by the following formula (7). Liquid crystal aligning agent for alignment.
[In formula (7), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O 3 is 2 and the number of R ^3r is 2, R ^3r may be the same or different, and R ^3q and R ^3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (7). ] The liquid crystal aligning agent for optical alignment according to claim 10, wherein the (meth)acrylate represented by the formula (7) is a (meth)acrylate represented by the following formula (8).
[In formula (8), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a straight chain alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one of —CH ₂ — of the straight chain alkylene group or two non-adjacent groups is replaced with —O—, May be listed;
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (8). ] The (meth)acrylate represented by the formula (8) is a (meth)acrylate represented by any of the following formulas (9) to (11), for optical alignment according to claim 10 or 11. Liquid crystal aligning agent.
[In the formulas (9) to (11), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
R ⁹ represents a hydrogen atom or a methyl group;
n represents a positive integer of 1 to 12. ] The (meth)acrylate is represented by the following formula (9-1-1), formula (9-1-2), formula (9-2-1), formula (9-2-2), formula (10-1-1). ), formula (10-1-2), formula (10-2-1), formula (10-2-2), formula (11-1-1), formula (11-1-2), formula (11) 2-1) and the liquid crystal aligning agent for optical alignment according to any one of claims 10 to 12, which is a (meth)acrylate represented by any one of the formulas (11-2-2).
[Formula (9-1-1), Formula (9-1-2), Formula (9-2-1), Formula (9-2-2), Formula (10-1-1), Formula (10- 1-2), formula (10-2-1), formula (10-2-2), formula (11-1-1), formula (11-1-2), formula (11-2-1), In and (11-2-2), n represents a positive integer of 1-12. ] A liquid crystal alignment film formed by the liquid crystal alignment agent for optical alignment according to claim 1. A liquid crystal display device comprising the liquid crystal alignment film according to claim 14. A diamine represented by the following formula (2).
[In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O 3 is 2 and the number of R ^3r is 2, R ^3r may be the same or different, and R ^3q and R ^3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ] The diamine according to claim 16, which is represented by the following formula (3).
[In Formula (3), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a linear alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one or —CH ₂ — of the linear alkylene group or two non-adjacent ones is replaced by —O—. May;
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ] The diamine according to claim 17, which is represented by any one of the following formulas (4) to (6).
[In the formulas (4) to (6), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
n represents a positive integer of 1 to 12. ] Formula (4-1-1), Formula (4-1-2), Formula (4-2-1), Formula (4-2-2), Formula (5-1-1), Formula (5- 1-2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6-1-2), formula (6-2-1), The diamine according to claim 17, which is represented by any one of Formula (6-2-2) and Formula (6-2-2).
[Formula (4-1-1), Formula (4-1-2), Formula (4-2-1), Formula (4-2-2), Formula (5-1-1), Formula (5- 1-2), formula (5-2-1), formula (5-2-2), formula (6-1-1), formula (6-1-2), formula (6-2-1), In the formula (6-2-2), n represents a positive integer of 1-12. ] (Meth)acrylate represented by the following formula (7).
[In formula (7), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O 3 is 2 and the number of R ^3r is 2, R ^3r may be the same or different, and R ^3q and R ^3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (7). ] The (meth)acrylate according to claim 20, which is represented by the following formula (8).
[In formula (8), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ⁶ represents a straight chain alkylene group having 1 to 12 carbon atoms or a single bond, and in R ⁶ , one of —CH ₂ — of the straight chain alkylene group or two non-adjacent groups is replaced with —O—, May be listed;
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (8). ] The (meth)acrylate according to claim 21, which is represented by any of the following formulas (9) to (11).
[In the formulas (9) to (11), R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ⁷ and R ⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted arylcarbonyl group;
R ⁹ represents a hydrogen atom or a methyl group;
n represents a positive integer of 1 to 12. ] A polymer which is a reaction product from a raw material containing tetracarboxylic dianhydride and diamine;
The reaction product is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide,
The diamine is a polymer containing at least one diamine represented by the following formula (2).
[In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a group represented by Formula (1-1) or Formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O 3 is 2 and the number of R ^3r is 2, R ^3r may be the same or different, and R ^3q and R ^3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
Hydrogen atoms in the three benzene rings may be substituted with a substituent. ]
[In Formulas (1-1) and (1-2), R ⁴ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, or a substituted or unsubstituted Represents an unsubstituted arylcarbonyl group;
* Represents the bonding position to the benzene ring in formula (2). ] A poly(meth)acrylate which is a reaction product from a raw material containing a (meth)acrylate represented by the following formula (7).
[In formula (7), R ¹ and R ² each independently represent a hydrogen atom, a group represented by formula (1-1) or formula (1-2), and at least R ¹ and R ² One is a group represented by formula (1-1) or formula (1-2);
R ^3o represents a single bond, —COO—, —OCO— or —O—, and R ^3p and R ^3t each independently represent a single bond, —O—, an alkylene group having 1 to 12 carbons, and —COO—. , -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-, and the hydrogen atom bonded to them is replaced with a halogen group. ^R3r may be a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -. When O 3 is 2 and the number of R ^3r is 2, R ^3r may be the same or different, and R ^3q and R ^3s are each independently a divalent benzene ring. , A naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination thereof, provided that R ^3r is —CH═CH—. CO-O -, - O- CO-CH = CH- case is, the side of the R ^3q or R ^3s that -CH = CH- are attached is an aromatic ring, R ^3u is a single bond, 1 to carbon atoms 12 alkylene groups, -COO-, -OCO- or -O-, the hydrogen atom bonded to them may be replaced by a halogen group, s1 is 0 or 1, s2 is 0-2. Is an integer, s2 is 0, when R ^3u is a single bond, R ^3p also represents a single bond, and when s1 is 1 and s2 is an integer of 1 to 2, R ^3u is a single bond. And R ^3t also represents a single bond,
R ⁹ is a hydrogen atom or a methyl group;
Hydrogen atoms in the two benzene rings may be substituted with a substituent.