WO2019031604A1

WO2019031604A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using liquid crystal alignment film

Info

Publication number: WO2019031604A1
Application number: PCT/JP2018/030083
Authority: WO
Inventors: 隆志岩田; 十南田尻
Original assignee: Jnc株式会社; Jnc石油化学株式会社
Priority date: 2017-08-10
Filing date: 2018-08-10
Publication date: 2019-02-14
Also published as: JP7255482B2; TW201920365A; JPWO2019031604A1; CN110998424B; CN110998424A; TWI788401B; KR20200039671A

Abstract

[Problem] To provide a liquid crystal alignment agent that makes it possible to form a liquid crystal alignment film that gives a liquid crystal display element that has favorable viewing angle characteristics and afterimage characteristics. [Solution] A liquid crystal alignment agent that contains a polymer that is the product of reacting starting materials that include a tetracarboxylic acid dianhydride and a diamine. The starting materials used to synthesize the polymer include at least one compound selected from compounds represented by formulas (1)–(3) and also include compounds represented by formulas (A)–(C) and at least one compound selected from compounds represented by formula (D), provided that, when m in formula (1) is 8, no compound represented by formulas (A)–(C) need be included in the diamine, and the tetracarboxylic acid dianhydride need not be a compound represented by formula (D).

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device using the same

The present invention relates to a liquid crystal alignment agent for forming a liquid crystal alignment film, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display device having the liquid crystal alignment film.

As liquid crystal display elements, in addition to liquid crystal display elements of vertical electric field mode such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type, IPS (In-Plane Switching) type and FFS (FPS) 2. Description of the Related Art There is known a horizontal electric field liquid crystal display device in which an electrode is formed only on one side of a pair of oppositely arranged substrates such as a Fringe Field Switching) type to generate an electric field in a direction parallel to the substrates. Among them, liquid crystal display elements of lateral electric field type represented by IPS type and FFS type are excellent in viewing angle characteristics and color reproducibility, and are used for various liquid crystal display elements such as televisions, tablets, and smartphones (patented) Literature 1).

The liquid crystal aligning film which is one of the structural members used for a liquid crystal display element is an important member in connection with a display quality. In recent years, the performance required for the liquid crystal alignment film is diversified and advanced with the improvement of the quality of liquid crystal display elements. In particular, in a liquid crystal display element of a lateral electric field type, in order to further improve the viewing angle characteristics and color reproducibility in black display, it is further required to suppress the pretilt angle of liquid crystal low, and further after applying a voltage. There is a need for a liquid crystal alignment film that gives a liquid crystal display element that does not generate an afterimage after the voltage is turned off, that is, has a small amount of residual DC accumulation and quick relaxation of charge (Patent Documents 2 and 3).

International Publication No. 1998/027454 WO 2015/080185 WO 2015/050135

Although the liquid crystal aligning film which has each performance was proposed until now like patent document 2 and 3, this inventor is about the liquid crystal aligning agent which forms the liquid crystal aligning film which has these two performances. Found that it was not proposed.

Therefore, according to the present invention, it is possible to form a liquid crystal alignment film giving a liquid crystal display element capable of suppressing the pretilt angle of liquid crystal to a low level and having a small amount of residual DC accumulation and quick relaxation of electric charge. It is an object of the present invention to provide a liquid crystal aligning agent capable of Another object of the present invention is to provide a liquid crystal display device having the liquid crystal alignment film and having excellent viewing angle characteristics and afterimage characteristics.

The present inventors include at least one selected from the compounds represented by the following formulas (1) to (3) as one of the raw materials used for the synthesis, and the following formula (A) A liquid crystal aligning agent containing a polymer containing at least one selected from a compound represented by the formula (C) and a compound represented by the following formula (D) can suppress the pretilt angle of liquid crystal to a low level. And, it has been found that it is possible to form a liquid crystal alignment film which gives a liquid crystal display element in which the accumulation of residual DC is small and the relaxation of charges is fast. Moreover, the liquid crystal display element which has this liquid crystal aligning film discovered that a viewing angle characteristic and an afterimage characteristic were favorable, and came to this invention.

In the formula (1), m is an integer of 3 to 8, and in the formula (3), n is an integer of 1 to 3, and in the formulas (1) to (3), any carbon constituting a ring A group whose bonding position is not fixed to an atom indicates that the bonding position in the ring is arbitrary, and in the formula (A), A ¹ is nitrogen or a nitrogen-containing heterocycle, and W ¹ is independently , Alkylene of 1 to 5 carbons, and optional -CH ₂ -may be replaced by -CO-, 1,4-phenylene, or 1,3-phenylene, Z ¹ is hydrogen, hydrogen by heat A protecting group replacing an atom, or alkyl having 1 to 5 carbon atoms, a is independently 0 or 1, and in the formula (B), A ² is independently a nitrogen or nitrogen-containing heterocycle , ^{W 2} and ^{W 3} independently an alkylene having 1 to 5 carbon atoms Ri, arbitrary _-CH 2 -, -CO-, 1,4-phenylene, or may be replaced by 1,3-phenylene, ^{Z 2} is independently hydrogen, thermal by a protecting group to replace the hydrogen atom, Or a C 1-5 alkyl, a is independently 0 or 1, and in formula (C), Z ³ is a monovalent organic group containing at least one of a secondary or tertiary amino group. And in the formula (D), T is a divalent unsaturated bond-containing group containing 1 to 2 carbon-carbon double bonds or 1 to 2 carbon-carbon triple bonds, and 1) In the formula (3) and the formulas (A) to (C), a group whose bonding position is not fixed to any carbon atom constituting the ring has an arbitrary bonding position in the ring. When the m is 8 in the formula (1), the diamine And none of the compounds represented by the formulas (A) to (C) may be included, and the tetracarboxylic acid dianhydride may not be a compound represented by the following formula (D) .

By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film capable of suppressing the pretilt angle of liquid crystal to a low level, providing a liquid crystal display element having a small residual DC accumulation and fast charge relaxation. Moreover, the liquid crystal display element which has this liquid crystal aligning film has a favorable viewing angle characteristic and a residual image characteristic.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments. In the present specification, unless otherwise specified, measurements of operations and physical properties are performed under the conditions of room temperature (20 ° C. or more and 25 ° C. or less) / relative humidity 40% RH or more and 50% RH or less.

The liquid crystal aligning agent of the present invention contains at least one selected from the compounds represented by the following formulas (1) to (3) as one of the raw materials used for the synthesis, and A) a polymer represented by the formula (C), and a polymer comprising at least one selected from the compounds represented by the following formula (D) (hereinafter simply referred to as “polymer”, “polymer” according to the present invention It may be referred to as a liquid crystal aligning agent containing

In the formula (1), m is an integer of 3 to 8, and in the formula (3), n is an integer of 1 to 3, and in the formulas (1) to (3), any carbon constituting a ring A group whose bonding position is not fixed to an atom indicates that the bonding position in the ring is arbitrary, and in the formula (A), A ¹ is nitrogen or a nitrogen-containing heterocycle, and W ¹ is independently , Alkylene of 1 to 5 carbons, and optional -CH ₂ -may be replaced by -CO-, 1,4-phenylene, or 1,3-phenylene, Z ¹ is hydrogen, hydrogen by heat A protecting group replacing an atom, or an alkyl having 1 to 5 carbon atoms, r is an arbitrary integer of 0 or more, a is independently 0 or 1, and in the formula (B), A ² is independently Te, nitrogen or a nitrogen-containing heterocycle,, ^{W 2} and ^{W 3} are independently Te alkylene having 1 to 5 carbon atoms, arbitrary _-CH 2 -, -CO-, 1,4-phenylene, or may be replaced by 1,3-phenylene, ^{Z 2} is independently hydrogen, A protecting group which is substituted by a hydrogen atom by heat, or an alkyl having 1 to 5 carbon atoms, r is an arbitrary integer of 0 or more, a is independently 0 or 1, and in the formula (C), Z ^{3 is} Is a monovalent organic group containing at least one of a secondary or tertiary amino group, and in formula (D), T is a 1 to 2 carbon-carbon double bond or a 1 to 2 carbon- A divalent unsaturated bond-containing group containing a carbon triple bond, and which is bonded to any carbon atom constituting a ring in formulas (1) to (3) and formulas (A) to (C) A group whose position is not fixed indicates that the bonding position in the ring is arbitrary. However, when m is 8 in the formula (1), the diamine may not contain any of the compounds represented by the formulas (A) to (C), and the tetracarboxylic acid The anhydride may not be the compound represented by the formula (D). By having such a configuration, it is possible to suppress the pretilt angle of the liquid crystal to a low level, and to provide a liquid crystal alignment film in which the accumulation of residual DC is small and the relaxation of charges is fast.

In the embodiment of the present invention, it is a liquid crystal aligning agent containing at least one of polymers containing constituent units derived from the following raw materials, and the raw materials are represented by the above formulas (1) to (3) At least one selected from the group consisting of compounds, and at least one selected from the group consisting of said formula (A), said formula (B), said formula (C) and said formula (D); When m is 8 in the formula (1), the diamine may not contain any of the compounds represented by the formulas (A) to (C), and the tetracarboxylic acid dianhydride is The liquid crystal aligning agent which does not need to be a compound represented by said Formula (D) is provided. In the embodiment, the polymer is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide. However, when m is 8 in the formula (1), the diamine may not contain any of the compounds represented by the formulas (A) to (C), and the tetracarboxylic acid dianhydride The substance may not be the compound represented by the formula (D). In the present specification, "a polymer which is a reaction product from a raw material containing ..." may be a "polymer containing a structural unit derived from a raw material".

In the embodiment of the present invention, it is a method for producing a liquid crystal aligning agent containing at least one of a polymer which is a reaction product from a raw material containing tetracarboxylic acid dianhydride and a diamine, and the polymer is synthesized. And at least one selected from the group of compounds represented by the above-mentioned formulas (1) to (3), the group of compounds represented by the above-mentioned formulas (A) to (C), and And at least one selected from the compounds represented by formula (D), wherein the polymer is a polyamic acid, a polyimide, a partial polyimide, a polyamic acid ester, a polyamic acid-polyamide copolymer, and a polyamideimide At least one member selected from the group consisting of, provided that m is 8 in the above formula (1), And none of the compounds represented by the formulas (A) to (C) may be included, and the tetracarboxylic acid dianhydride may not be a compound represented by the following formula (D) , A manufacturing method is provided.

In the embodiment of the present invention, the use (application) of the polymer according to the present invention as a liquid crystal aligning agent is also provided.

In the present specification, the state in which the polymer is dissolved in an organic solvent is referred to as a varnish. There is no particular limitation on the method of producing the varnish, and a mixture of a polymer obtained by reacting a mixture of raw materials containing tetracarboxylic acid dianhydride (including its derivative) and diamine (including dihydrazide) in an organic solvent and an organic solvent May be used as a varnish as it is in the production of a liquid crystal aligning agent. In addition, a polymer may be recovered from the reaction mixture, and the polymer redissolved in an organic solvent may be used as a varnish in the production of a liquid crystal aligning agent. The liquid crystal aligning agent of the present invention is mainly composed of a varnish obtained by dissolving a polymer selected from the group of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide in an organic solvent. It is a solution, and two or more kinds of varnish may be used. In a preferred embodiment of the present invention, the liquid crystal aligning agent is applied to a substrate, and then film formation is performed by means such as heating to form a polyimide liquid crystal alignment film.

More specifically, the liquid crystal aligning agent of the present invention is at least one selected from the compounds represented by Formula (1) to Formula (3) as a raw material used for synthesis, and the above-mentioned Formula (A) A compound represented by the formula (C), and at least one polymer obtained by reacting at least one selected from the compounds represented by the formula (D), provided that the formula (1) is When m is 8 in the above, the diamine may not contain any of the compounds represented by the formulas (A) to (C), and the tetracarboxylic acid dianhydride may have the formula (D) It does not have to be a compound represented by). In addition, in an embodiment of the present invention, a liquid crystal aligning agent containing at least one of a polymer which is a reaction product from a raw material containing tetracarboxylic acid dianhydride and a diamine, which is used to synthesize the polymer Raw materials containing at least one selected from the group of compounds represented by the formulas (1) to (3) and at least one selected from the group of compounds represented by the formulas (A) to (C) And at least one selected from the compounds represented by the above-mentioned formula (D). Further, in the embodiment of the present invention, the liquid crystal aligning agent contains one polymer which is a reaction product from a raw material containing tetracarboxylic acid dianhydride and diamine, and more specifically, the embodiment of the present invention The liquid crystal aligning agent in the above includes at least one selected from the group of compounds represented by the formulas (1) to (3), and a group of compounds represented by the formulas (A) to (C). And one polymer using a raw material containing at least one selected from the compounds represented by the above-mentioned formula (D) (in an embodiment, it is in the form of being laminated one layer on the substrate, “ It can also be called "monolayer system". That is, in the embodiment of the present invention, one polymer is contained. Moreover, in the embodiment of the present invention, two or more of the polymers are contained (in an embodiment, two or more layers are laminated on the substrate, and therefore, they may be called “blend systems”). Moreover, the liquid crystal aligning agent of embodiment of this invention contains polymer (P) and polymer (Q) as a raw material used to synthesize | combine. That is, in an embodiment of the present invention, the polymer contains at least two, and the at least two polymers include a polymer (P) and a polymer (Q); used to synthesize the polymer (P) The raw material contains at least one selected from the group of compounds represented by the formulas (1) to (3); and the raw material used to synthesize the polymer (Q) is the compound represented by the formula (A) And at least one selected from the group of compounds represented by formula (C), and the compounds represented by formula (D).

In the present invention, the polymer is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide. Also, as used herein, these include their derivatives. For example, the polymer is a polyamic acid or a derivative thereof.

The compounds represented by the formulas (1) to (3) will be described.

In the formula (1), m is an integer of 3 to 8, and more specifically, m is 3, 4, 5, 6, 7 or 8. Here, it is preferable that m is 8 in particular because the effect of suppressing the pretilt angle can be exhibited. Moreover, it is suitable also from the point which shows especially favorable liquid-crystal orientation as m is 3.

In the formula (3), n is an integer of 1 to 3.

In formulas (1) to (3), a group whose bonding position is not fixed to any carbon atom constituting a ring means that the bonding position on the ring is arbitrary. In the embodiment of the present invention, the bonding position of the amino group to the ring is preferably in the meta or para position in order to ensure the following linearity.

By using at least one of the compounds represented by the above formulas (1), (2) and (3) as a raw material used for the synthesis, the stable conformation of the obtained polymer is very linear. Therefore, it is considered that the pretilt angle of the liquid crystal can be suppressed low.

Preferred specific examples of the compounds represented by Formula (1) to Formula (3) are shown below.

Among them, the compounds represented by Formula (1-1), Formula (1-4), Formula (2-1), and Formula (3-1) exhibit high liquid crystal alignment, and the pretilt angle of the liquid crystal is further increased. It is preferable because it can be kept low. In particular, at least one of the formula (1-1) and the formula (1-4) is preferable because the solubility in an organic solvent is excellent. As described above, in the present invention, there is also provided a diamine represented by the above formula (1-4). By using a diamine represented by the above formula (1-4) as a diamine raw material among raw materials used to synthesize a polymer used for a liquid crystal aligning agent, the pretilt angle of liquid crystal can be specifically suppressed low. And, it is possible to form a liquid crystal alignment film which gives a liquid crystal display element in which the accumulation of residual DC is small and the relaxation of charges is fast. In addition, by using only the diamine represented by the above formula (1-4) as a diamine raw material among the raw materials used to synthesize the polymer used for the liquid crystal aligning agent, the pretilt angle of the liquid crystal is specifically suppressed low. be able to. Therefore, in the present invention, it is a liquid crystal aligning agent containing at least one of a polymer which is a reaction product from a raw material containing tetracarboxylic acid dianhydride and a diamine, and the diamine is a compound of the above formula (1-4) The liquid crystal aligning agent which consists only of the diamine shown by these is also provided. In addition, when using the diamine shown by said Formula (1-4) as a diamine raw material among the raw materials used to synthesize | combine the polymer used for a liquid crystal aligning agent, an acid dianhydride is not restrict | limited in particular. In addition, as a method for synthesizing the diamine represented by the formula (1-4), the method described in the section of the Examples can be mentioned as an example, but it is not limited thereto.

Subsequently, the compounds represented by the formulas (A) to (D) will be described.

In formula (A), A ¹ is nitrogen or a nitrogen-containing heterocycle, W ¹ is independently alkylene having 1 to 5 carbon atoms, and arbitrary —CH ₂ — is —CO—, 1, It may be replaced by 4-phenylene or 1,3-phenylene, Z ¹ is hydrogen, a protecting group which is replaced with heat by a hydrogen atom, or alkyl having 1 to 5 carbon atoms, r is any integer of 0 or more And a is independently 0 or 1. Here, the nitrogen-containing heterocycle in the present specification is a concept including a nitrogen-containing heterocycle and a nitrogen-containing aliphatic ring. In addition to the nitrogen atom, the nitrogen-containing heterocycle may contain a heteroatom such as an oxygen atom or a sulfur atom. Further, in the present specification, an arbitrary integer of r means that when A ¹ is a nitrogen-containing heterocycle, the number may vary depending on the number of rings to be fused, the nitrogen atom contained, and the number of heteroatoms. For example, it can be an integer of 1 to 10. In the present specification, “a protective group which replaces a hydrogen atom by heat” is not particularly limited as long as it replaces a hydrogen atom by heat, but preferably, Boc (abbreviation of t-butoxycarbonyl group), benzyl Carbamate protecting groups such as oxycarbonyl group, 9-fluorenylmethyl oxycarbonyl group, allyloxycarbonyl group and the like can be mentioned.

In formula (B), A ² is independently nitrogen or a nitrogen-containing heterocycle, W ² and W ³ are independently alkylene having 1 to 5 carbon atoms, and arbitrary —CH ₂ — is -CO-, 1,4-phenylene, or 1,3-phenylene may be replaced, and Z ² is independently hydrogen, a protecting group which is substituted for hydrogen by heat, or alkyl having 1 to 5 carbon atoms, , R is any integer of 0 or more, and a is independently 0 or 1.

In formula (C), Z ³ is a monovalent organic group containing at least one secondary or tertiary amino group.

In the formula (D), T is a divalent unsaturated bond-containing group containing 1 to 2 carbon-carbon double bonds or 1 to 2 carbon-carbon triple bonds. In an embodiment of the present invention, T contains an arylene group having 6 to 12 carbon atoms. When m is 8 in the formula (1), T may be an alkylene group, and the alkylene group preferably has 2 to 16 carbon atoms, more preferably 2 to 8 carbon atoms, and 4 to 6 carbon atoms. More preferably, it is 8.

Further, in the formulas (1) to (3) and the formulas (A) to (C), in the group where the bonding position is not fixed to any carbon atom constituting the ring, the bonding position in the ring is arbitrary. To indicate that

In the embodiment of the present invention, the compounds represented by Formula (A) to Formula (C) have nitrogen (in particular, a secondary amino group, a tertiary amino group), or a nitrogen-containing heterocycle. These groups act as groups promoting transfer of charge in the liquid crystal alignment film, and are considered to play a role of quickly relieving the accumulated charge. Further, in the compound represented by the formula (D), a π electron cloud is spread throughout the molecule. Therefore, the polymer obtained by reacting the compounds represented by the formulas (A) to (C) with the compound represented by the formula (D) has a high degree of conjugation, so that it can be used as a liquid crystal alignment film. It is thought that when it is used, the volume resistance value is lowered, the residual DC pool is reduced, and it contributes to the quick relaxation of charge. However, when m is 8 in the formula (1), the compounds represented by the formulas (A) to (D) are not essential as a diamine, and the effect of being able to remarkably reduce the pretilt angle is exerted. There is also no particular limitation on the acid dianhydride to be reacted, and it may be, for example, a compound represented by the formula (D) or any one of (AN-1) to (AN-18). Or other known ones.

Specific examples of the compounds represented by the formulas (A) to (D) are shown below.

In formulas (A-1) to (A-11), a group whose bonding position is not fixed to any carbon atom constituting a ring means that the bonding position in the ring is arbitrary. In formula (B-3), k is an integer of 1 to 5, and more specifically 1, 2, 3, 4 or 5. In the formula (B-4), n is an integer of 1 to 3, and more specifically 1, 2 or 3.

Among them, the above formula (A-12), formula (A-14), formula (A-15), formula (A-16), formula (A-17), formula (A-19) and formula (B-3) And at least one of Formula (B-5), Formula (C-2), Formula (C-3), Formula (D-2), and Formula (D-3). In particular, Formula (B-3) and Formula (D-2) are preferable because they reduce residual DC accumulation and charge relaxation is particularly fast. Further, the formula (A-15) is more preferable because it reduces the accumulation of residual DC, not only the relaxation of charges is fast, but also the voltage holding ratio is good. Here, in the formula (B-3), it is more preferable that k = 2.

According to an embodiment of the present invention, the compounds represented by the formulas (1) to (3) are compounds represented by the formulas (1) to (3); At least one selected from the group of compounds represented by formula (1-4), formula (2-1), formula (2-2), and formulas (3-1) to formula (3-6) Compounds represented by the above formulas (A) to (C) are the above formulas (A-1) to (A to 20), formulas (B-1) to (B-8), and And at least one selected from the group of compounds represented by Formula (C-1) to Formula (C-3); and the compound represented by Formula (D) is a compound represented by Formula (D-1) to At least one selected from the group of compounds represented by formula (D-4). According to such an embodiment, the intended effects of the present invention can be produced efficiently.

Further, in the embodiment of the present invention, the compounds represented by the formulas (1) to (3) are the compounds represented by the formulas (1-1), (1-4), (2-1), and (2-1). At least one selected from the group of compounds represented by formula (3-1); the compounds represented by formulas (A) to (C) are compounds represented by formulas (A-12) and (A) -14), formula (A-15), formula (A-16), formula (A-17), formula (A-19), formula (A-20), formula (B-3), formula (B-) 5) at least one selected from the group of compounds represented by formula (C-2) and formula (C-3); and the compound represented by formula (D) is a compound represented by formula (D-) 2) and at least one selected from the group of compounds represented by formula (D-3). According to such an embodiment, the intended effects of the present invention can be produced efficiently.

In the embodiment of the present invention, at least at least one of the compounds represented by the formulas (A) to (C) is obtained in order to obtain a liquid crystal display element having excellent residual image characteristics and having small residual DC accumulation and quick relaxation of charges. It is also preferable to use one and at least one of the compounds represented by formula (D) in combination. Therefore, according to an embodiment of the present invention, the raw material used to synthesize the polymer contains at least one selected from the group of compounds represented by the formulas (1) to (3), and the formula It includes at least one selected from the group of compounds represented by (A) to formula (C), and includes at least one selected from the compounds represented by formula (D).

In the present invention, in a form including at least one selected from the group of compounds represented by formulas (1) to (3) and a compound represented by formula (B) as a raw material for synthesizing the polymer, The content of the compound represented by the formula (C) relative to the total amount of diamine is preferably significantly reduced, preferably less than 30 mol%, and less than 20 mol% with respect to the total amount of diamine used. Is more preferably, it is more preferably less than 10 mol%, still more preferably less than 5 mol%, still more preferably less than 4 mol%, still more preferably less than 3 mol% It is further more preferable that it is less than 2 mol%, still more preferable to be less than 1 mol%, and even more preferable not to be substantially contained. Here, "substantially free of" means less than 0.1 mol% with respect to the total amount of diamine used. Here, if 30 mol% or more is contained, there is a possibility that the characteristics of the DC afterimage may be deteriorated.

In the embodiment of the present invention, in the case where one type of the polymer is contained, at least one selected from the group of compounds represented by formulas (1) to (3) as a raw material for synthesizing the polymer In a form including the compound represented by C), at least one of the compound represented by the formula (A) and the compound represented by the formula (B) (in particular, represented by the formula (A) It is preferred to further combine the compounds). Here, when at least one of the compound represented by the formula (A) and the compound represented by the formula (B) (in particular, the compound represented by the formula (A)) is not used, the orientation is deteriorated. There is a risk of In the embodiment of the present invention, when the compound represented by the formula (C) is added, the compound represented by the formula (A) is also used in combination to have a technical effect of improving the characteristics of the DC afterimage. .

In the embodiment of the present invention, when one of the polymers is contained, a compound represented by Formula (1-1) and a compound represented by Formula (B-3) are used as raw materials for synthesizing the polymer. In the combined embodiment, the content of the compound represented by the formula (1-1) with respect to the total amount of diamine used is 90 with respect to the total amount of diamine used to synthesize the polymer in order to suppress the pretilt angle of the liquid crystal low. It is preferable to use more than mol%, it is more preferable to use 92 mol% or more, and it is further preferable to use 95 mol% or more. If it is important to make the charge relaxation faster by reducing the amount of residual DC accumulation while maintaining the electrical characteristics such as the voltage holding ratio, it is preferable that the amount is not too large, specifically 90 moles. % Is preferable, 88 mol% or less is more preferable, 86 mol% or less is further preferable, 84 mol% or less is further preferable, and 82 mol% or less is further preferable. It is more preferably 80 mol% or less, and may be 78 mol% or less, 76 mol% or less, 74 mol% or less, or 72 mol% or less.

In the embodiment of the present invention, when one of the polymers is contained, the raw material used to synthesize the polymer is represented by Formula (A-12), Formula (A-14), Formula (A-15), Formula Table (A-16), Formula (A-17), Formula (A-19), Formula (B-3), Formula (B-5), Formula (C-2), and Formula (C-3) (In combination) with at least one selected from the group of compounds listed above; and at least one selected from the group of compounds represented by Formula (D-2) and Formula (D-3). Further, according to an embodiment of the present invention, the raw material used to synthesize the polymer is at least one selected from the compounds represented by Formula (A-15) and Formula (B-3); Is more preferably (used in combination) with the compound represented by D-2), and in the formula (B-3), k = 2 is more preferable.

In the embodiment of the present invention, at least one selected from the compounds represented by the above formulas (1) to (3) as raw materials used for the synthesis; and in the above formulas (A) to (C) A liquid crystal aligning agent comprising: a compound represented by the formula: and at least one polymer obtained by reacting at least one selected from the compounds represented by the formula (D); used for synthesizing the polymer The amount of the compounds represented by the formulas (1) to (3) is the total amount of diamine used to synthesize the polymer (in the liquid crystal aligning agent, two or more kinds of polymers are used to control the pretilt angle of the liquid crystal). When it is contained, it is preferably used at 27 mol% or more, more preferably 28 mol% or more, and still more preferably 29 mol% or more, based on the total amount (100 mol%) of total diamines. It is more preferable to use 30 mol% or more, more preferably 31 mol% or more, still more preferably 32 mol% or more, still more preferably 33 mol% or more, and 34 mol% or more Is more preferable, and it is even more preferable to use 35 mol% or more. Further, for the purpose of reducing volume resistance, it is preferable to use 99 mol% or less, 98 mol% or less, 96 mol% or less, or 94 mol% or less. , 92 mol% or less, 90 mol% or less, 88 mol% or less, 86 mol% or less, or 84 mol% or less It may be 82 mol% or less. Further, in the embodiment of the present invention, the amounts of the compounds represented by the formulas (A) to (C) reduce the accumulation of residual DC while maintaining the electric characteristics such as the voltage holding ratio, The total amount of diamine used to synthesize the polymer (in the case where the liquid crystal aligning agent contains two or more polymers, 0 mol% relative to the total amount of diamine (100 mol%) of the total diamine) in order to accelerate relaxation of The above is preferable, more than 0 mol% is more preferable, 1 mol% or more is more preferable, 2 mol% or more is further more preferable, 3 mol% or more is further more preferable, 4 mol% or more is further more preferable, 5 mol% The above is more preferable, and 6 mol% or more is still more preferable. Further, for the purpose of improving liquid crystal alignment, less than 50 mol% is preferable, 46 mol% or less is more preferable, 44 mol% or less is more preferable, 42 mol% or less is more preferable, 38 mol% or less is more preferable , 36 mol% or less is more preferable, 34 mol% or less is further more preferable, 32 mol% or less is still more preferable, 30 mol% or less is still more preferable, 28 mol% or less is even more preferable, 26 mol% or less Is more preferable, 24 mol% or less is even more preferable, and 22 mol% or less is even more preferable.

In the embodiment of the present invention, when one of the polymers is contained, the above formulas (1) to (3) are used with respect to the total amount of diamine used to synthesize the polymer in order to suppress the pretilt angle of the liquid crystal. It is preferable that the ratio of the compounds represented by (total of two or more types thereof) is more than 50 mol%, more preferably 54 mol% or more, with respect to the total amount of diamine to be used, 60 mol % Or more, more preferably 60% or more, still more preferably 65% or more, still more preferably 66% or more, and even more preferably 67% or more. Even more preferably 68 mol% or more, still more preferably 69 mol% or more, 70 mol% or more There is more preferably more. Further, it is preferably 99 mol% or less, may be 98 mol% or less, may be 96 mol% or less, may be 94 mol% or less, or 90 mol% or less. It may well be less than 90 mol%. However, when m is 8 in the formula (1), it is preferably 100 mol%, and the pretilt angle can be surprisingly lowered when it is 100 mol%.

Further, in the present embodiment (in the case where one type of the polymer is contained), the ratio of the compounds represented by the above formulas (A) to (C) (the total amount if two or more types are contained) The amount is preferably 0.5 mol% or more, more preferably 0.8 mol% or more, still more preferably 1 mol% or more, and may be 4 mol% or more. It may be mol% or more. Further, in the present embodiment (in the case where one type of the polymer is contained), the ratio of the compounds represented by the above formulas (A) to (C) (the total of two or more types) is the total amount of diamine used On the other hand, for the purpose of improving the liquid crystal alignment, less than 50 mol% is preferable, 46 mol% or less is more preferable, 44 mol% or less is more preferable, 42 mol% or less is still more preferable, 40 mol% or less It is more preferable, 38 mol% or less is further more preferable, 36 mol% or less is further more preferable, 34 mol% or less is still more preferable, 32 mol% or less is still more preferable, 30 mol% or less is further more preferable, 28 mol % Or less is more preferable, 26 mol% or less is further more preferable, 24 mol% or less is still more preferable, 22 mol% or less is more preferable Preferred. However, in order to reduce the pretilt angle, the formula (B-3) (for example, k = 2), the formula (B-5), the formula (B-8), the formula (C-1) to the formula (C-3) 40 mol% or less is preferable, less than 40 mol% is more preferable, 30 mol% or less is further more preferable, and less than 30 mol% is still more preferable. In particular, the use amount of the formulas (C-1) to (C-3) is more preferably 10 mol% or less, and even more preferably less than 10 mol%.

Therefore, in the present embodiment (in the case where one type of the polymer is contained), the ratio of the compounds represented by the formulas (1) to (3) (the total of two or more types) is the total amount of diamine used On the other hand, the ratio of the compounds represented by the formulas (A) to (C) is 70% by mole or more, and is 1 to 30% by mole relative to the total amount of the diamine to be used.

Moreover, in the present embodiment, when the compound represented by the formula (D) is used, the amount of the compound represented by the formula (D) is not particularly limited, but the retention rate of alignment voltage It may be 10 mol% or more based on the total amount of tetracarboxylic acid dianhydride used to synthesize the polymer in order to reduce residual DC accumulation and accelerate charge relaxation while maintaining the electrical properties. 20 mol% or more may be sufficient, and 30 mol% or more may be sufficient. Moreover, 60 mol% or less is preferable and 50 mol% or less is more preferable.

The liquid crystal aligning agent of the present invention preferably contains at least two polymers of polymer (P) and polymer (Q). Thus, containing at least two of said polymers, said at least two polymers comprising a polymer (P) and a polymer (Q); the raw materials used to synthesize said polymer (P) have the formula (1) And at least one selected from the group of compounds represented by (3); and the raw material used to synthesize the polymer (Q) is a compound represented by the above formulas (A) to (C). And at least one selected from the group of compounds represented by the formula (D) and a compound represented by the formula (D).

The liquid crystal aligning agent containing a polymer (P) and a polymer (Q) WHEREIN: The usage-amount (2 types) of the compound represented by Formula (1)-Formula (3) as a raw material used to synthesize | combine a polymer (P) If the total content is more than 50 mol%, preferably 54 mol% or more, based on the total amount of diamine used to synthesize the polymer (P), in order to keep the pretilt angle of the liquid crystal low. Is more preferably 56 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, and still more preferably 75 mol% or more It is still more preferable to use 80 mol% or more, even more preferable to use 82 mol% or more, and even more preferable to use 84 mol% or more. It is more preferable to use mol% or more, more preferably 86 mol% or more, still more preferably 87 mol% or more, still more preferably 88 mol% or more, and 89 mol% or more It is even more preferable to use 90 mol% or more. Here, it is considered that the compound represented by the formula (1-4) as a raw material used to synthesize the polymer (P) is a compound that increases surface energy as a raw material used to synthesize the polymer (Q) When the compound represented by the formula (E-5) is used, it is also preferable to reduce the amount of the compound represented by the formula (1-4) used for the polymer (P). The upper limit is not particularly limited, and may be 100 mol%, 95 mol% or less, 85 mol% or less, or 75 mol% or less. Good. In addition, the amounts of the compounds represented by the formulas (A) to (C) used to synthesize the polymer (Q) (the total of two or more kinds thereof) are electric characteristics such as voltage holding ratio In order to reduce residual DC accumulation and accelerate charge relaxation while maintaining the above, it is preferable to be more than 0 mol%, preferably 5 mol% or more based on the total amount of diamine used to synthesize the polymer. Is more preferably 10 mol% or more, still more preferably 20 mol% or more, still more preferably 25 mol% or more, still more preferably 30 mol% or more preferable. Moreover, in order to maintain liquid crystal alignment, it is preferably 60 mol% or less, more preferably 55 mol% or less, and still more preferably 50 mol% or less. However, in order to reduce the pretilt angle, the formula (B-3) (for example, k = 2), the formula (B-5), the formula (B-8), the formula (C-1) to the formula (C-3) 30 mol% or less is preferable and, as for the usage-amount of), less than 30 mol% is more preferable. The amount of the compounds represented by the formulas (A) to (C) used to synthesize the polymer (Q) is preferably 10 to 50 mol%, more preferably 30 to 50 mol%.

In addition, the amount of the compound represented by the formula (D) is such that the polymer (Q) can be reduced in order to reduce the accumulation of residual DC and accelerate the charge relaxation while maintaining the electrical characteristics such as the voltage holding ratio. The amount is preferably 20 to 50% by mole, and more preferably 20 to 30% by mole, relative to the total amount of tetracarboxylic acid dianhydride used for the synthesis.

Therefore, in the embodiment of the present invention, in the polymer (P), the ratio of the compounds represented by the formulas (1) to (3) is 70 mol% or more with respect to the total amount of diamine used; In the polymer (Q), the ratio of the compounds represented by the formulas (A) to (C) is 10 to 50 mol% with respect to the total amount of diamine used.

In the polymer (P), the ratio of the compounds represented by the formulas (1) to (3) is 90 mol% or more based on the total amount of diamine used; in the polymer (Q), The ratio of the compounds represented by the formulas (A) to (C) is 30 to 50 mol% with respect to the total amount of diamine used. In the embodiment of the present invention, in the polymer (P), the ratio of the compounds represented by the above formulas (1) to (3) is 70 mol% or more, preferably 90 mol% with respect to the total amount of diamine used. In the polymer (Q), the proportion of the compound represented by the formula (D) is 20 to 50 mol% with respect to the total amount of tetracarboxylic acid dianhydride used.

In the present invention, known tetracarboxylic acid dianhydrides (including their derivatives) and diamines (including dihydrazides) can be further used as raw materials used to synthesize polymers.

The tetracarboxylic acid dianhydride used in the present invention can be selected without limitation from known tetracarboxylic acid dianhydrides. Known tetracarboxylic acid dianhydrides are aromatic systems (including heteroaromatic ring systems) in which a dicarboxylic acid anhydride is directly bonded to the aromatic ring, and aliphatic systems in which the dicarboxylic acid anhydride is not directly bonded to the aromatic ring It may belong to any group (including heterocyclic ring systems). For example, tetracarboxylic acid dianhydrides disclosed in JP-A-2016-029447 and JP-A-2016-041683 can be used. Preferred examples are shown below.

In Formula (AN-2) and Formula (AN-8), m is independently an integer of 1 to 12.

In the above-mentioned tetracarboxylic acid dianhydride, preferred materials for improving each property will be described.

When importance is given to improving the orientation of the liquid crystal, compounds represented by Formula (AN-2), Formula (AN-7), and Formula (AN-8) are preferable.

When importance is given to improving the transmittance of the liquid crystal display element, Formula (AN-1), Formula (AN-5), Formula (AN-4), Formula (AN-11), and Formula (AN-12). Formula (AN-13), Formula (AN-14), Formula (AN-17), and Formula (AN-18) are preferable.

When emphasis is placed on improving the VHR (voltage holding ratio) of the liquid crystal display element, Formula (AN-1), Formula (AN-4), Formula (AN-5), Formula (AN-11), Formula (AN-11) (AN-13), formula (AN-14), formula (AN-16), formula (AN-17), and formula (AN-18) are preferred.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, the formula (AN-3), the formula (AN-6), the formula (AN-7), the formula (AN-9), the formula (AN-10) and the formula (AN-11) And formula (AN-15) is preferred.

In the present invention, as a raw material used to synthesize a polymer, nitrogen (in particular, a secondary amino group, a tertiary amino group), or a tetracarboxylic acid dianhydride having a nitrogen-containing heterocycle (for example, By using AN-3) and the above equation (AN-11)), it is considered that the accumulation of residual DC can be further reduced and the relaxation rate can be improved. It is preferable to use 1 to 40% by mole, more preferably 1 to 15% by mole, and even more preferably 1 to 10% by mole relative to the total amount of tetracarboxylic acid dianhydride used to synthesize the polymer.

In an embodiment of the present invention, at least one selected from the group of compounds represented by formulas (1) to (3) and at least one selected from the group of compounds represented by formulas (A) to (C). In the form including one, it is preferable to use three or more tetracarboxylic acid dianhydrides in combination. When the tetracarboxylic dianhydride is a combination of two or less in the present embodiment, the liquid crystal alignment may be deteriorated. Here, as preferable examples of three or more specific combinations, in addition to the combinations listed in the examples of the present application, (AN-2), (AN-4) and (AN-6); -4), (AN-7) and (AN-9); (AN-4), (AN-6) and (AN-11), etc. are preferable. With such a combination, the intended effects of the present invention can be produced efficiently.

In embodiments of the present invention it is preferred to use the formula (AN-8) as the acid dianhydride. Further, in the case where the formula (1-1) and the formula (B) are combined, it is preferable to use the formula (AN-8) as the acid dianhydride. According to this embodiment, it is possible to reduce the pretilt angle, to reduce the accumulation of residual DC, to improve the relaxation rate, and to further increase the liquid crystal alignment. In the embodiment of the present invention, the ratio of the compound represented by Formula (1-1), which is a case where the compound represented by Formula (1-1) and the compound represented by Formula (B) are combined It is particularly preferable to use the formula (AN-8) as the acid dianhydride when it is 90 mol% or more based on the total amount of diamine used. According to this embodiment, it is possible to reduce the pretilt angle, to reduce the accumulation of residual DC, to improve the relaxation rate, and to further increase the liquid crystal alignment.

In the present invention, in a form containing at least two polymers of polymer (P) and polymer (Q), at least one selected from the compounds represented by the above-mentioned formula (D) as a raw material used for polymer (P) One may be used.

As a compound used for a polymer (P), Formula (AN-1), Formula (AN-3), Formula (AN-4), Formula (AN-6), Formula (AN-8), and Formula (AN-) 9) is preferable, and in the formula (AN-8), m = 4 or 8 is more preferable. Equation (AN-4), Equation (AN-6), and Equation (AN-8) are used in combination to show high characteristics with good balance in each characteristic of electric characteristics such as liquid crystal alignment and voltage holding ratio. Is preferred, and in the formula (AN-8), m = 4 or 8 is more preferred.

The diamines (including dihydrazides) used in the present invention can be selected without limitation from known diamines and dihydrazides. For example, diamines and dihydrazides disclosed in JP-A-2016-029447 and JP-A-2016-041683 can be used. Preferred examples are shown below.

In the formulas (DI-3), (DI-6) and (DI-7), m is an integer of 1 to 12.

In an embodiment of the present invention, the raw material used to synthesize the polymer further contains at least one selected from compounds represented by the following formula (E).

In the above formula (E), W ⁴ is alkylene having 1 to 6 carbon atoms, 1,3-phenylene or 1,4-phenylene; and W ⁵ is independently a single bond, —NHCO—, or It is -CONH-. In particular, phase separation can be efficiently caused by including the compound represented by the formula (E) in the form of a two-layer system (blend system). In the embodiment of the present invention, the raw material used for the synthesis of the polymer (Q) includes at least one selected from the compounds represented by the formula (E).

In formula (E), W ⁴ is alkylene having 1 to 6 carbons, 1,3-phenylene, or 1,4-phenylene, and W ⁵ is independently a single bond, —NHCO—, or — It is CONH-.

Examples of the compound represented by the formula (E) include the following formulas (E-1) to (E-8). That is, the compound represented by the formula (E) is at least one selected from the compounds represented by the following formulas (E-1) to (E-8).

In Formula (E-5) and Formula (E-8), p is each independently an integer of 1 to 6.

Further, in the embodiment of the present invention, the compounds represented by the formulas (1) to (3) are compounds represented by the formulas (1-1) to (1-4), (2-1), and 2-2) at least one member selected from the group of compounds represented by formula (3-1); compounds represented by formulas (A) to (C) are compounds represented by formula (A-12): ), Formula (A-14), formula (A-15), formula (A-16), formula (A-17), formula (B-3), formula (C-2), and formula (C-3) And at least one compound selected from the group of compounds represented by formula (D); compounds represented by formula (D-2) and formula (D-3) represented by formula (D): At least one compound selected from the group consisting of: at least one compound selected from the group of compounds represented by Formula (E-5) to Formula (E-7): is there. In the embodiment of the present invention, the compounds represented by the formulas (1) to (3) are at least one selected from the formula (1-1) and the formula (1-4); The compounds represented by the formulas (A) to (C) are at least one selected from the formulas (A-15) and (B-3); and the compounds represented by the formula (D) are A compound represented by the formula (D-2); and a compound represented by the formula (E) is a compound represented by the formula (E-5).

In the above-mentioned diamine (including dihydrazide), preferred materials for improving each property are described.

When it is important to further improve the alignment of the liquid crystal, among the above diamines (including dihydrazide), the formula (DI-3), the formula (DI-6), the formula (DI-7) and the formula DI-9), formula (DI-10), formula (E-1) and formula (E-8) are preferred. Formula (DI-3), Formula (DI-6), Formula (DI-7), and Formula (E-1) are more preferable. In formula (DI-3), m = 1, 2, 4 or 6 is preferable, and m = 2, 4 is more preferable. In the formula (DI-6), m = 2 to 6 is preferable, and m = 2 or 5 is more preferable. In formula (DI-7), m = 1 or 2 is preferable, and m = 1 is more preferable. The above diamines may be used alone or in combination of two or more.

When importance is given to improving the transmittance, among the above-mentioned diamines (including dihydrazide), Formula (DI-1), Formula (DI-3), Formula (DI-8), and Formula (E-). 8) is preferable, and (DI-1) is more preferable. In Formula (DI-3), m = 1, 2, 4 or 6 is preferable, and m = 1 or 2 is more preferable.

When importance is given to improving the VHR of the liquid crystal display element, among the above diamines (including dihydrazide), the formula (DI-1), the formula (DI-3), the formula (E-1), and the formula (E-2) is preferred, and formulas (DI-1) and (DI-3) are more preferred. In the formula (DI-3), m = 1 is preferable.

It is effective to improve the relaxation rate of the residual charge (residual DC) in the liquid crystal alignment film by reducing the volume resistivity of the liquid crystal alignment film as one of the methods for preventing the image sticking. When the purpose is emphasized, among the above-mentioned diamines (including dihydrazide), Formula (DI-3), Formula (DI-6), Formula (DI-7), and Formula (E-1) to Formula (E-6) is preferable, and formulas (DI-3), (DI-7), (E-1), (E-5), and (E-6) are more preferable. In formula (DI-3), m = 1, 2, 4 or 6 is preferable, and m = 1 or 2 is more preferable. In the formula (DI-6), m = 2 to 6 is preferable, and m = 2 or 5 is more preferable. In formula (DI-7), m = 1 or 2 is preferable, and m = 1 is more preferable. In formula (E-5), p = 4 is preferable.

In a liquid crystal aligning agent containing a polymer (P) and a polymer (Q) according to an embodiment of the present invention, as a raw material used for the polymer (P), it is selected from the compounds represented by the above formulas (A) to (C) Or at least one selected from the compounds represented by formulas (1) to (3) may be used as the raw material used for the polymer (Q). In the embodiment, in the raw material used for the polymer (P), the nitrogen-containing heterocycle is preferably a nitrogen-containing cycloalkane, and examples thereof include, for example, Formula (A-15), Formula (A-16) and Formula (A-17) Etc. are preferred.

As a compound used for a polymer (P), Formula (DI-3), Formula (DI-5), Formula (A-15), and Formula (C-3) are preferable. Here, in the formula (DI-3), m = 1 or 4 is preferable, and 1 is more preferable. In addition, as compounds used for the polymer (Q), compounds represented by Formula (DI-3), Formula (DI-5), Formula (DI-6), Formula (DI-9), and Formula (E) It is preferable to use at least one selected. Here, in the formula (DI-3), m = 1, 2 or 4 is preferable, and 1 or 2 is more preferable. Here, in the formula (DI-6), m = 2 or 5 is preferable, and 2 is more preferable.

In the embodiment of the present invention, in order to suppress the pretilt angle of the liquid crystal to a lower level, to reduce the accumulation of residual DC and to accelerate the relaxation, a polymer (P) having a role to suppress the liquid crystal pretilt angle to a lower layer On the layer side, it is important to segregate the polymer (Q), which plays a role in giving a liquid crystal display element having a small amount of residual DC accumulation and quick relaxation of charges, to a lower layer (to the substrate side). The use of a compound that increases the surface energy for the polymer (Q) is considered to make the two polymers more susceptible to segregation. Therefore, in the embodiment of the present invention, the liquid crystal alignment film used to align the liquid crystal layer is a coating film derived from the liquid crystal alignment agent located on the substrate, and the coating film is a polymer (P) and a polymer ( Q), the polymer (P) is located on the liquid crystal layer side, and the polymer (Q) is located on the substrate side.

In the embodiment of the present invention, as a raw material used for the polymer (Q), it is preferable to use a compound represented by the formula (E), which is considered to be a compound that increases surface energy. As specific compounds, formulas (E-1) to (E-8) are preferable, and formulas (E-1), (E-3), (E-4), and (E-5) are preferable. Formula (E-6) is more preferable, Formula (E-3), Formula (E-4), Formula (E-5), and Formula (E-6) are more preferable, and (E-5), (E-5) It is still more preferable to use -6), (E-5) is even more preferable, and in the formula (E-5), p = 4 is preferable. In the embodiment of the present invention, the amount of the compound represented by the formula (E) used to synthesize the polymer (Q) is relative to the total amount of diamine used to synthesize the polymer (Q) And 50 to 70 mol% are preferable. Therefore, in the polymer (Q), the proportion of the compound represented by the formula (E) is 50 to 70 mol% with respect to the total amount of diamine used.

In an embodiment of the present invention, in each diamine, a part of the diamine may be replaced by a monoamine in the range of 40 mol% or less of the ratio of monoamine to diamine. Such substitution can cause termination of the polymerization reaction when forming the polymer (for example, polyamic acid), and can suppress the progress of further polymerization reactions. Then, the weight average molecular weight (hereinafter also referred to as Mw) of the obtained polymer (for example, polyamic acid, polyamic acid ester or polyimide) can be easily controlled, and for example, the liquid crystal can be obtained without losing the effect of the present invention. The coating properties of the alignment agent can be improved. The diamine to be replaced by the monoamine may be one or more, as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Can be mentioned.

In the embodiment of the present invention, the polymer may further contain a monoisocyanate compound as its raw material. By including the monoisocyanate compound as a raw material, the end of the resulting polymer (for example, polyamic acid (including its derivative)) is modified to adjust Mw. By using this end-modified type polymer (for example, polyamic acid (including its derivative)), the coating properties of the liquid crystal aligning agent can be improved, for example, without impairing the effects of the present invention. From the above viewpoint, the content of the monoisocyanate compound in the raw material is preferably 1 to 10 mol% with respect to the total amount of diamine and tetracarboxylic acid dianhydride in the raw material. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

In an embodiment of the present invention, the polymer is obtained by reacting a mixture of tetracarboxylic dianhydride and diamine in an organic solvent. In this synthesis reaction, special conditions are not necessary other than the selection of the raw materials, and the conditions in the usual polymer (for example, polyamic acid) synthesis can be applied as they are. The solvent which can be used is mentioned later.

In the embodiment of the present invention, the liquid crystal aligning agent may further contain other components other than the polymer. One or more other components may be used. Other components include, for example, other polymers and compounds described later.

Other polymers include polyamic acids other than the polymer (P) and the polymer (Q), polyamic acid esters, or polyimides (hereinafter referred to as "other polyamic acids or derivatives thereof"), polyesters, polyamides, polysiloxanes, Cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like can be mentioned. These may be one kind or two or more kinds. Among these, other polyamic acids or derivatives thereof and polysiloxanes are preferable, and other polyamic acids or derivatives thereof are more preferable.

The diamine used to synthesize other polyamic acids or derivatives thereof preferably contains 30 mol% or more, more preferably 50 mol% or more of aromatic diamine based on all diamines.

The other polyamic acids or their derivatives can be synthesized according to the method described below as a method of synthesizing polyamic acids or their derivatives which are essential components of the liquid crystal aligning agent of the present invention.

As mentioned above, one of the preferred embodiments of the liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing at least two polymers of polymer (P) and polymer (Q). It is known that in the process of forming a coating film (especially a thin film) using a liquid crystal alignment agent containing two polymers, a polymer with small surface energy separates in the upper layer and a polymer with large surface energy separates in the lower layer . In the present invention, a polymer (P) which plays a role of suppressing the pretilt angle of liquid crystal to a lower layer, and a polymer (Q) which plays a role of giving a liquid crystal display element having a small residual DC accumulation and a fast charge relaxation. By segregating, it is possible to form a liquid crystal alignment film exhibiting the above two properties. In an embodiment of the present invention, at least two polymers of polymer (P) and polymer (Q) have different surface energy from each other, and the surface energy of polymer (Q) is larger than that of polymer (P) .

The confirmation as to whether or not the liquid crystal alignment film is separated into layers is, for example, the surface energy of the formed film is measured and the same as the value of the surface energy of the film formed by the liquid crystal alignment agent containing only the polymer (P). It can be confirmed by having a value close to it.

In order to exhibit good liquid crystal alignment and low pretilt angle characteristics as described above, the content of the polymer (P) in the liquid crystal aligning agent of the present invention is 20% by weight based on 100% by weight of the total contained polymer It is preferable that it is more than, and it is preferable that it is 30 weight% or more. Moreover, it is preferable that it is 80 weight% or less, and it is more preferable that it is 70 weight% or less. However, the preferable content of the polymer (P) described here is one guideline, and may vary depending on the combination of tetracarboxylic acid dianhydride or diamine used as a raw material.

In the present invention, in the embodiment containing one polymer, the Mw of the polymer is preferably 20,000 to 160,000, more preferably 40,000 to 80,000, and further 45,000 to 70,000. preferable. Also in at least two polymers of polymer (P) and polymer (Q), Mw is preferably independently 20,000 to 160,000, and more preferably 40,000 to 80,000. The Mw of the polymer can be measured by the method described in the examples. The Mw of the polymer can be adjusted, for example, by the time for which the tetracarboxylic acid dianhydride and the diamine are reacted. The end point of the reaction can be determined by collecting a small amount of the reaction solution in the polymerization reaction, determining the Mw of the polymer contained therein by measurement by gel permeation chromatography (GPC), and measuring the value. There is also well known a method of controlling Mw by causing termination of a polymerization reaction by replacing a considerable amount of tetracarboxylic acid dianhydride and diamine at the start of the reaction with a monocarboxylic acid or a monoamine.

As said polysiloxane, Unexamined-Japanese-Patent 2009-036966, 2010-185001, 2011-102963, 2011-253175, 2012-159825, the international publication 2008 are mentioned. WO 04/044, WO 2009/148099, WO 2010/074261, WO 2010/074264, WO 2010/126108, WO 2011/068123, It can further contain the polysiloxane disclosed in WO 2011/068127, WO 2011/068128, WO 2012/115157, WO 2012/165354, etc. .

In an embodiment of the present invention, the composition further contains at least one selected from the group consisting of an alkenyl substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound.

<Alkenyl substituted nadiimide compound>
For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadiimide compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element over a long period of time. The alkenyl-substituted nadiimide compounds may be used alone or in combination of two or more. The content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, and preferably 1 to 70% by weight with respect to the polymer (for example, polyamic acid (including its derivatives)), for the above purpose. More preferably, it is more preferably 1 to 50% by weight.

The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polymer (for example, polyamic acid (including its derivative)) used in the present invention. As such an alkenyl substituted nadiimide compound, for example, an alkenyl substituted nadiimide compound disclosed in JP 2013-242526 A and the like can be mentioned. Preferred alkenyl-substituted nadiimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, N, N'-m-xylylene-bis (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene- And 2,3-dicarboximide).

<Compound Having Radically Polymerizable Unsaturated Double Bond>
For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long time. The compound having a radically polymerizable unsaturated double bond may be one type of compound or two or more types of compounds. In addition, the alkenyl substituted nadiimide compound is not contained in the compound which has a radically polymerizable unsaturated double bond. The content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight with respect to the polymer (for example, polyamic acid (including its derivatives)), for the above-mentioned purpose. It is more preferably 70% by weight, further preferably 1 to 50% by weight.

The ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound reduces the ion density of the liquid crystal display element, suppresses the temporal increase of the ion density, and further suppresses the generation of a residual image. For this reason, the weight ratio of the compound having a radically polymerizable unsaturated double bond / the alkenyl substituted nadiimide compound is preferably 0.1 to 10, and more preferably 0.5 to 5.

As a compound which has a preferable radically polymerizable unsaturated double bond, the compound which has a radically polymerizable unsaturated double bond currently indicated by Unexamined-Japanese-Patent No. 2013-242526 etc. can be mentioned, for example.

<Oxazine Compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electric properties of the liquid crystal display element for a long time. The oxazine compound may be one type of compound or two or more types of compounds. The content of the oxazine compound is preferably 0.1 to 50% by weight, and preferably 1 to 40% by weight with respect to the polymer (for example, polyamic acid (including its derivative)), for the above purpose. More preferably, it is more preferably 1 to 20% by weight.

The oxazine compound is soluble in an organic solvent in which a polymer (for example, a polyamic acid (including its derivative)) is dissolved, and in addition, an oxazine compound having ring-opening polymerization is preferable. Preferred oxazine compounds include, for example, oxazine compounds represented by Formula (OX-3-1) and Formula (OX-3-9), and oxazine compounds disclosed in JP-A-2013-242526 and the like. be able to.

<Oxazoline compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long time. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one type of compound or two or more types of compounds. The content of the oxazoline compound is preferably 0.1 to 50% by weight, and preferably 1 to 40% by weight with respect to the polymer (for example, polyamic acid (including its derivative)), for the above purpose. More preferably, it is preferably 1 to 20% by weight. Alternatively, when the oxazoline structure in the oxazoline compound is converted to oxazoline, the content of the oxazoline compound is 0.1 to 40% by weight with respect to the polymer (for example, polyamic acid (including its derivative)) , Preferred from the above purpose.

As an oxazoline compound, the oxazoline compound currently disclosed by Unexamined-Japanese-Patent No. 2013-242526 etc. can be mentioned, for example. Preferred oxazoline compounds include 1,3-bis (4,5-dihydro-2-oxazolyl) benzene.

<Epoxy compound>
For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long time. The epoxy compound may be one type of compound or two or more types of compounds. The content of the epoxy compound is preferably 0.1 to 50% by weight, and preferably 1 to 40% by weight with respect to the polymer (for example, polyamic acid (including its derivative)), for the above purpose. More preferably, it is more preferably 1 to 20% by weight.

As an epoxy compound, the epoxy compound currently disclosed by Unexamined-Japanese-Patent No. 2013-242526 etc. can be mentioned, for example. Preferred epoxy compounds include N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy And silanes, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (3,3 ', 4,4'-diepoxy) bicyclohexyl.

For example, the liquid crystal aligning agent of the present invention may further contain various additives. As various additives, for example, high molecular compounds other than polymers (for example, polyamic acid (including its derivatives)) and low molecular compounds can be mentioned, and they can be selected and used according to the respective purposes. The addition of the additive has the technical effect of enhancing the hardness of the film, and in particular, the resistance to rubbing treatment is enhanced, and thus the reliability as an alignment film is enhanced. Although the addition of additives tends to increase the pretilt angle, the embodiment of the present invention has the effect that the addition of such additives can significantly reduce the pretilt angle.

For example, examples of the polymer compound include polymer compounds soluble in organic solvents. It is preferable to add such a polymer compound to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical properties and the alignment of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone-modified polyurethanes, and silicone-modified polyesters.

Further, as the low molecular weight compound, for example, 1) when it is desired to improve the coating property, 2) surfactant according to the purpose, 2) when it is necessary to improve antistatic, 3) adhesion to the substrate When it is desired to improve the properties, silane coupling agents and titanium-based coupling agents may be mentioned, and 4) an imidation catalyst may be mentioned if the imidation is allowed to proceed at a low temperature.

As a silane coupling agent, the silane coupling agent currently disclosed by Unexamined-Japanese-Patent No. 2013-242526 etc. can be mentioned, for example. Preferred silane coupling agents include 3-aminopropyltriethoxysilane. Further, examples of the imidization catalyst include imidization catalysts disclosed in JP-A-2013-242526 and the like.

The amount of the silane coupling agent to be added is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polymer (eg, polyamic acid (including its derivative)).

The addition amount of the imidization catalyst is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, with respect to the carbonyl group of the polymer (eg, polyamic acid (including its derivative)).

The amount of other additives added varies depending on the application, but is usually 0 to 100% by weight of the total weight of the polymer (for example, polyamic acid (including its derivatives)), and 0.1 to 50% % Is preferred.

Also, for example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of the coatability of the liquid crystal aligning agent and the adjustment of the concentration of the polymer (for example, polyamic acid (including its derivative)). The solvent can be applied without particular limitation as long as the solvent has the ability to dissolve the polymer component. The solvent widely includes solvents generally used in the production process of the polymer component such as a polymer (for example, polyamic acid, soluble polyimide and the like) and the application, and can be appropriately selected according to the purpose of use. The solvent may be one or a mixture of two or more.

As the solvent, a parent solvent of the polymer (for example, a polyamic acid (including a derivative thereof)) and other solvents for the purpose of improving the coating property can be mentioned.

Examples of the aprotic polar organic solvent which is a parent solvent for polymers (for example, polyamic acid (including its derivatives)) include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N Lactones such as -methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, γ-butyrolactone and the like .

Examples of other solvents for the purpose of improving coating properties include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as phenyl acetate, ethylene glycol monobutyl ether, and diethylene glycol monoethyl. Diethylene glycol monoalkyl ether such as ether, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene such as dipropylene glycol monomethyl ether Glycol monoalkyl ether, ester compounds such as these acetates, diisobutyl ketone etc. Tons of compounds and the like.

Among these, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether Dipropylene glycol monomethyl ether and diisobutyl ketone are particularly preferred.

The concentration of the polymer (for example, polyamic acid) in the liquid crystal aligning agent of the present invention is preferably 0.1 to 40% by weight, more preferably 1 to 20% by weight, and 1.5 to 8% by weight It is further preferred that When the alignment agent is applied to a substrate, an operation of previously diluting the contained polymer (eg, polyamic acid) with a solvent may be required to adjust the film thickness.

The viscosity of the liquid crystal aligning agent of the present invention can be determined by the method of application, concentration of polymer (eg, polyamic acid (including its derivative)), type of polymer (eg, polyamic acid (including its derivative)), solvent The preferred range differs depending on the type and ratio. For example, in the case of coating by a printing machine, a range of 5 to 100 mPa · s is preferable because a sufficient film thickness can be obtained, and large printing unevenness can be prevented, and it is preferably 10 to 80 mPa · s. Is more preferred. In the case of coating by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an ink jet coating apparatus, 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 rotational viscosity measurement, and is measured (measurement temperature: 25 ° C.) using, for example, a rotational viscometer (type TVE-20L manufactured by Toki Sangyo Co., Ltd.). In the examples of the present application, the viscosity was about 5 to 15 mPa · s.

<Liquid crystal alignment film>
According to the embodiment of the present invention, there is provided a liquid crystal alignment film formed by the liquid crystal alignment agent. The details will be described below. In the embodiment of the present invention, the liquid crystal alignment film is a film formed by heating a coating of the liquid crystal alignment agent. The liquid crystal aligning film of this invention can be obtained by the normal method of producing a liquid crystal aligning film from a liquid crystal aligning agent. For example, the liquid crystal aligning film of this invention can be obtained by passing through the process of forming the coating film of the liquid crystal aligning agent of this invention, the process of heat-drying, and the process of heat-baking. With respect to the liquid crystal alignment film of the present invention, the film obtained through the heating and drying process and the heating and baking process may be rubbed to impart anisotropy, as described later, as necessary. Alternatively, if necessary, light may be irradiated after the coating step and the heating and drying step, or light may be irradiated after the heating and baking step to impart anisotropy.

A coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to preparation of a normal liquid crystal aligning film. The substrate may be provided with an electrode such as ITO (IndiumTin Oxide), IZO (In ₂ O ₃ -ZnO), IGZO (In-Ga-ZnO ₄ ) electrode, a color filter, etc. glass, silicon nitride, Substrates made of acrylic, polycarbonate, polyimide and the like can be mentioned. In addition, ITO was used in the Example of this application.

Generally as a method of apply | coating a liquid crystal aligning agent to a board | substrate, a spinner method, the printing method, the dipping method, the dripping method, the inkjet method etc. are known. These methods are equally applicable to the present invention.

As the heating and drying step (pre-baking step), a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. It is preferable to carry out the heating and drying step at a temperature within the range where evaporation of the solvent is possible, and it is more preferable to carry out the heating and drying step at a temperature relatively lower than the temperature in the heating and baking step. Specifically, the heat 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. Also, the time is not particularly limited, but for example, 1 to 10 minutes, and further 1 to 5 minutes is preferable.

The heating and calcining step can be performed, for example, under the conditions necessary for the polyamic acid or a derivative thereof to exhibit a dehydration and ring closure reaction. As the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. In general, a temperature of about 100 to 300 ° C. is preferable, 120 to 280 ° C. is more preferable, and 150 to 250 ° C. is more preferable. The time is preferably 1 minute to 3 hours. In addition, heating and firing can be performed multiple times at different temperatures. 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. In the case of performing heating and baking twice at different temperatures, it is preferable to carry out the heat treatment at a temperature of 90 to 180 ° C. for the first time and a temperature of 185 ° C. or more for the second time. In addition, the temperature can be changed from low temperature to high temperature for firing. When firing is carried out by changing the temperature, the initial temperature is preferably 90 to 180.degree. The final temperature is preferably 185 to 300 ° C., more preferably 190 to 230 ° C.

In the method of forming a liquid crystal alignment film of the present invention, in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical directions, known methods such as rubbing method and photo alignment method are provided as means for imparting anisotropy to the alignment film. The formation method of can be used suitably. The material of the rubbing cloth may, for example, be cotton, rayon or nylon.

In the embodiment of the present invention using the rubbing method, the liquid crystal alignment film is formed by applying the liquid crystal alignment agent to a substrate, heating and drying the substrate coated with the liquid crystal alignment agent, and producing a film The film can be formed through the steps of heating and baking the film and rubbing the film after the heating and baking.

The rubbing treatment can be carried out in the same manner as the rubbing treatment for alignment treatment of a normal liquid crystal alignment film, as long as sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. A preferable condition is a hair-foot pushing amount of 0.2 to 0.8 mm. The stage moving speed is 5 to 250 mm / sec. The roller rotation speed is 500 to 2,000 rpm.

In the embodiment of the present invention, the liquid crystal alignment film is suitably obtained by a method further including other steps other than the steps described above. For example, you may provide the process of wash | cleaning the produced film with a washing | cleaning liquid as a part of process for producing a liquid crystal aligning film. Of course, in the liquid crystal alignment film of the present invention, the step of washing the film after firing or irradiation with a washing solution is not essential. Moreover, although it is not essential also in other processes, a cleaning process can be provided as needed.

Examples of the cleaning method using a cleaning solution include brushing, jet spray, steam cleaning, ultrasonic cleaning and the like. These methods may be performed alone or in combination. As the cleaning solution, pure water (preferably ultrapure 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, acetone Although ketones, such as methyl ethyl ketone, can be used, it is not limited to these. Of course, as these cleaning solutions, those which are sufficiently purified and low in impurities are used. Such a cleaning method can be applied to the above-mentioned cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment with heat or light can be used before and after the heating and baking step and before and after the rubbing step. 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, and more preferably 10 minutes to 1 hour. Further, as the annealing light used for the annealing treatment, a UV lamp, a fluorescent lamp, an LED lamp and the like can be mentioned. The light irradiation dose 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, and 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 gauge or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having 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 or the like. It can also be evaluated by a method using ellipsometry as described below. 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, those having a large retardation value have a large degree of orientation. Therefore, when it is used as a liquid crystal aligning film, since the said liquid crystal aligning film has larger anisotropy, it is thought that alignment control of a liquid crystal composition can be carried out large.

The liquid crystal alignment film of the present invention can be suitably used for a transverse electric field liquid crystal display element. When it is used for a liquid crystal display device of a transverse electric field system, the smaller the pretilt (Pt) angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state, and the contrast is improved. The pretilt (Pt) angle is preferably 1.5 ° or less, more preferably 1.2 ° or less. Therefore, according to the embodiment of the present invention, the liquid crystal aligning agent is used in the manufacture of a lateral electric field liquid crystal display device. Further, according to the embodiment of the present invention, there is provided a lateral electric field liquid crystal display device having the liquid crystal alignment film.

The liquid crystal alignment film of the present invention can be used to control the alignment of liquid crystal compositions for liquid crystal displays such as smartphones, tablets, in-vehicle monitors, and televisions. Besides the alignment application of the liquid crystal composition for liquid crystal display, it can be used for the alignment control of an optical compensation material and all other liquid crystal materials. In addition, since the alignment film of the present invention has large anisotropy, it can be used alone as an optical compensatory material. Moreover, according to the embodiment of the present invention, there is provided a liquid crystal display device having the liquid crystal alignment film.

<Liquid crystal display element>
The liquid crystal display element of the present invention will be described in detail. The present invention is formed on a pair of oppositely disposed substrates, an electrode formed on one or both of opposing surfaces of the pair of substrates, and an opposed surface of the pair of substrates. The liquid crystal display element which has the liquid crystal aligning film and the liquid crystal layer formed between a pair of board | substrates, Comprising: The said liquid crystal aligning film provides the liquid crystal display element which is an alignment film of this invention.

The said electrode will not be specifically limited if it is an electrode formed in one surface of a board | substrate. Examples of such an electrode include a deposited film of ITO or metal, and the like. The electrode may be formed on the entire surface of one side of the substrate, or may be formed, for example, in a desired shape which is patterned. The desired shape of the electrode includes, for example, a comb or zigzag structure. The electrode may be formed on one of the pair of substrates or may be formed on both of the 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, the electrode is disposed on one of the pair of substrates, and in the case of the other liquid crystal display elements Electrodes are disposed on both sides. The liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed in such a manner that a liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, it is possible to use a spacer, such as fine particles or a resin sheet, which is interposed between the pair of substrates to form an appropriate distance.

As a method of forming the liquid crystal layer, for example, a vacuum injection method or an ODF (One Drop Fill) method can be used. As a sealing agent used for bonding of a board | substrate, UV curing type and a thermosetting type sealing agent can be used, for example. For example, screen printing can be used for printing the sealing agent.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application No. 5-501735, Japanese Patent Nos. 8-157826 and 8-21960. JP, 9-241644 (EP8852722A1), JP-A-9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255956 JP-A-9-241643 (EP885271A1), JP-A-10-204016 (EP844229A1), JP-A-10-204436, JP-A-10-231482, JP-A2000-087040, JP-A-2001 No. -48822 is disclosed Crystal compositions.

As preferable examples of the liquid crystal composition having the negative dielectric anisotropy, there are disclosed JP-A-57-114532, JP-A-2-24725, JP-A-4-224885 and JP-A-8-40953. JP-A-8-104869, JP-A-10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, and the like. Japanese Patent Application Laid-Open Nos. 10-236993, 10-236994, 10-237000, 10-237004, 10-237024, 10-237035, 10 -237075, JP-A-10-237076, JP-A-10-237448 (EP 9672) 1A1), JP-A-10-287874, JP-A-10-287875, JP-A-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, WO 2011/024666, WO 2010/072370 The liquid crystal compositions disclosed in JP-A-2010-537010, JP-A-2012-077201, JP-A-2009-084362, etc. can be mentioned. It is also acceptable to use one or more optically active compounds added to a liquid crystal composition having positive or negative dielectric anisotropy.

For example, an additive may be further added to the liquid crystal composition used for the liquid crystal display element of the present invention, for example, from the viewpoint of improving the orientation. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet light absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors and the like. Preferred photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet light absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors include compounds disclosed in WO 2015/146330 and the like. Can be mentioned.

A polymerizable compound may be mixed into the liquid crystal composition to be compatible with a liquid crystal display device in a 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), vinyl ketone and the like. Preferred compounds include the compounds disclosed in WO 2015/146330 and the like.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. The evaluation methods and compounds used in the examples are as follows.

1. Weight average molecular weight (Mw)
The weight average molecular weight of the polyamic acid was measured by GPC method using a 2695 separation module · 2414 differential refractometer (manufactured by Waters), and determined by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. As the column, HSPgel RT MB-M (manufactured by Waters) was used, and the measurement was performed under the conditions of a column temperature of 50 ° C. and a flow rate of 0.40 mL / min using the mixed solution as a developing agent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corp. was used.

2. Pretilt angle (Pt angle)
It was measured at room temperature with a liquid crystal evaluation apparatus (OMS-CA3) manufactured by Chuo Seiki Co., Ltd. In order to obtain a wide viewing angle, 1.5 degrees or less is desirable, and 1.2 degrees or less is more desirable.

3. DC Persistence Evaluation After applying a rectangular wave of 30 Hz and 3 V for 10 minutes, a DC voltage of 0.3 V was superimposed for 20 minutes. After the DC voltage was set to 0 V, a 3 V rectangular wave was applied again for 20 minutes. As the charge absorption at the time of DC voltage superposition is quicker, the residual DC in the asymmetrical AC drive becomes smaller and the DC residual image is less likely to occur, so flicker elimination is performed 20 minutes after the DC voltage is superimposed. When the voltage became 0.15 V or less, the DC afterimage was defined as “○” when the DC afterimage became “○”, 0.1 V or less. When the flicker erase voltage did not become 0.15 V or less by 20 minutes after superimposing the DC voltage, the DC afterimage was defined as “×” and evaluated.

4. Voltage holding ratio It carried out by the method as described in "Mizushima et al., Proceedings of the 14th Liquid Crystal Display Symposium p78 (1988)". The measurement was performed by applying a rectangular wave with a frequency of 30 Hz and a wave height of ± 5 V to the cell. The measurement was performed at 60 ° C. This value is an index showing how much the applied voltage is held after the frame period, and if this value is 100%, it indicates that all charges are held. When the value is 99.5% or more, the liquid crystal display element with good display quality is obtained.

<Solvent>
NMP: N-methyl-2-pyrrolidone BC: butyl cellosolve (ethylene glycol monobutyl ether)
GBL: γ-butyrolactone.

<Additives>
Additive (Ad1): 1,3-bis (4,5-dihydro-2-oxazolyl) benzene Additive (Ad2): 3-aminopropyltriethoxysilane Additive (Ad3): 2- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane.

Synthesis Example 1a Synthesis of Compound (1-4) A commercial product of the reagent used for synthesis was used as it was without purification.

<First stage>
In a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 50.0 g (236.9 mmol) of suberoyl chloride was placed, and 250 mL of dichloromethane was added. The solution was cooled to 5 ° C., and 75.8 g (568.6 mmol, 2.4 eq.) Of aluminum (III) chloride was added. The solution was kept at 5 ° C. and stirred for 30 minutes, and then a solution of 38.9 g (497.5 mmol, 2.1 eq.) Of benzene in 250 mL of dichloromethane was added dropwise. After the addition was over, cooling of the solution was stopped, the temperature was raised to room temperature, and this solution was stirred at room temperature for a further 12 hours. This series of reactions was performed under a nitrogen atmosphere. The reaction solution was poured into 1500 mL of 3N HCl, the organic layer was recovered, and the organic layer was washed three times with 500 mL of pure water. After washing, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain crude crystals. The obtained crude crystals were recrystallized from toluene, and the obtained crystals were vacuum dried at 80 ° C. for 12 hours to obtain 1,8-diphenyloctane-1,8-dione (yield: 61.4 g, yield) 88%).

Second stage
In a 1 L 3-neck flask equipped with a dropping funnel and a thermometer, 50.0 g (170.0 mmol) of 1,8-diphenyloctane-1,8-dione obtained in the first step was placed, and 500 mL of dichloromethane was added. The solution was cooled to 5 ° C., and 70.9 g (374.0 mmol, 2.2 eq.) Of titanium (IV) tetrachloride was added dropwise. The solution was kept at 5 ° C. and stirred for 1 hour, and then 59.3 g (510.0 mmol, 3.0 eq.) Of triethylsilane was further added dropwise. The solution was kept at 5 ° C. and stirred for 6 hours. This series of reactions was performed under a nitrogen atmosphere. The reaction solution was poured into 1 L of pure water, the organic layer was recovered, and the organic layer was washed with 500 mL of saturated aqueous sodium bicarbonate three times and then with 500 mL of pure water three times. After washing, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. The obtained crude product was separated and purified by column chromatography (filler; silica gel, developing solvent; toluene: heptane = 2: 1) to obtain 1,8-diphenyloctane (yield: 42.6 g, yield) 94%).

In a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 50.1 g (270.2 mmol, 2.4 eq.) Of 4-nitrobenzoyl chloride was placed, and 250 mL of dichloromethane was added. The solution was cooled to 5 ° C., and 45.0 g (337.8 mmol, 3.0 eq.) Of aluminum (III) chloride was added. The solution was kept at 5 ° C. and stirred for 30 minutes, and then a solution of 30.0 g (112.6 mmol) of 1,8-diphenyloctane obtained in the second step in 150 mL of dichloromethane was added dropwise. After the addition was over, cooling of the solution was stopped, the temperature was raised to room temperature, and this solution was stirred at room temperature for a further 12 hours. This series of reactions was performed under a nitrogen atmosphere. The reaction solution was poured into 1500 mL of 3N HCl, the organic layer was recovered, and the organic layer was washed three times with 500 mL of pure water. After washing, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. The obtained crude product was separated and purified by column chromatography (packing agent: silica gel, developing solvent: dichloromethane) to obtain compound (1-4) -NK (yield: 52.1 g, 82%) .

Stage 4

In a 1 L 3-neck flask equipped with a dropping funnel and a thermometer, 50.0 g (88.6 mmol) of the compound (1-4) -NK obtained in the third step was placed, and 500 mL of dichloromethane was added. The solution was cooled to 5 ° C., and 37.0 g (194.9 mmol, 2.2 eq.) Of titanium (IV) tetrachloride was added dropwise thereto. The solution was kept at 5 ° C. and stirred for 1 hour, and then 30.9 g (265.8 mmol, 3.0 eq.) Of triethylsilane was added dropwise thereto. The solution was kept at 5 ° C. and stirred for 4 hours. This series of reactions was performed under a nitrogen atmosphere. The reaction solution was poured into 1 L of pure water, the organic layer was recovered, and the organic layer was washed three times with 500 mL of saturated aqueous sodium bicarbonate solution and then three times with 500 mL of pure water. After washing, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain a crude product. The obtained crude product was separated and purified by column chromatography (packing agent: silica gel, developing solvent: tetrahydrofuran) to obtain compound (1-4) -N (yield: 41.7 g, 88%) .

<Step 5>
In a 3 L autoclave reaction tube made of SUS316, 40.0 g (74.5 mmol) of the compound (1-4) -N obtained in the fourth step and 4.0 g of 5% Pd / C powder (E type) were placed, and 800 mL of tetrahydrofuran was added. . The solution is stirred at 60 ° C. for 18 hours under a hydrogen atmosphere (hydrogen pressure; 0.6 MPa), allowed to cool, and after removing the Pd / C powder by filtration, the solvent is evaporated under reduced pressure and the compound (1- The crude product of 4) was obtained. The obtained crude product is separated and purified by column chromatography (packing agent: silica gel, developing solvent: tetrahydrofuran) and then recrystallized from a mixed solvent of ethanol: toluene = 2: 1 (volume ratio) to obtain crystals The residue was vacuum dried at 80 ° C. for 12 hours to give compound (1-4) (yield: 32.0 g, yield: 90%).

The melting point of the obtained compound (1-4) was 113.3 to 114.7 ° C. The melting point was measured using an automatic melting point measurement system MP-70 manufactured by METTLER TOLEDO.

Synthesis Example 1 Synthesis of Varnish 4.001 g of a compound represented by the formula (1-1) was placed in a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, and 54.0 g of NMP was added. The solution is ice-cooled to a solution temperature of 5 ° C., and then 0.390 g of the compound represented by the formula (AN-1), 0.965 g of the compound represented by the formula (AN-4), the formula (AN-6) The compound represented by 0.64g and NMP20.0g were added, and it stirred at room temperature for 12 hours. Thereto, 20.0 g of BC was added, and the solution was heated and stirred at 70 ° C. until the weight average molecular weight of the polymer of the solute reached a desired weight average molecular weight, to obtain Varnish 1 having a solid content of 6 wt%. The weight average molecular weight (Mw) of the polymer contained in this varnish 1 was 60,000.

Synthesis Examples 2 to 55
Varnishes 2 to 55 were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed, and the solid concentration of the polymer was 6% by weight. The composition and weight average molecular weight (Mw) of the obtained varnish are shown in Tables 1 to 5. Synthesis Example 1 is also shown again. The inside of [] represents the molar ratio of each of the tetracarboxylic acid compound group and the diamine compound group.

[Example 1] Preparation of liquid crystal aligning agent, preparation of liquid crystal cell for DC residual image and pretilt angle measurement, DC residual image measurement, and pretilt angle measurement Synthesized in Synthesis Example 1 in a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introducing pipe. 3.0 g of Varnish 1 and 7.0 g of Varnish 27 synthesized in Synthesis Example 27 were weighed out, 4.0 g of NMP, 3.0 g of GBL and 3.0 g of BC were added thereto, and the mixture was stirred at room temperature for 1 hour to obtain a resin content of 3% by weight The liquid crystal aligning agent 1 was obtained. The liquid crystal aligning agent 1 was applied to a glass substrate with an FFS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After pre-baking at 80 ° C. for about 3 minutes after coating, baking was carried out at 230 ° C. for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The obtained liquid crystal alignment film was rubbed by a rubbing cloth (hair length 2.8 mm: cotton) by using a rubbing apparatus manufactured by Iinuma Gauge Mfg. Co., Ltd., and the stage moving speed was 20 mm / sec, Rubbing was performed at a roller rotational speed of 1000 rpm. The surface of the obtained substrate was washed with ultrapure water and then dried in an oven at 120 ° C. for 30 minutes. Next, two substrates on which these liquid crystal alignment films are formed are opposed to each other on the side on which the liquid crystal alignment film is formed, and a gap for injecting a liquid crystal composition is provided between the opposed liquid crystal alignment films. I put it together. At this time, the rubbing directions of the respective liquid crystal alignment films were made parallel. The positive type liquid crystal composition A was vacuum-injected into these cells, and the inlet was sealed with a photo-curing agent to produce a liquid crystal cell (liquid crystal display element) having a cell thickness of 4 μm.

Physical property values: NI 100.1 ° C .; Δε 5.1; Δn 0.093; η 25.6 mPa · s.
When the DC afterimage of the liquid crystal cell was measured, it was "◎". Moreover, when the pretilt angle was measured, the value was 0.7 °. Furthermore, the voltage holding ratio of this liquid crystal cell was 99.8% at 5V-30 Hz. The cell was placed on a backlight tester (FujiCOLOR LED Viewer Pro HR-2 manufactured by Fujifilm Corp .; luminance 2,700 cd / m ² ) for 500 hours to conduct a reliability test. The voltage holding ratio of the measuring cell after the reliability test was 99.7%.

[Examples 2 to 23 and Comparative Examples 1 to 3]
A liquid crystal cell was prepared according to Example 1 except that the varnish used was changed, and DC afterimage, pretilt angle and voltage holding ratio were measured. The varnishes used and the measurement results are shown in Table 6 together with Example 1. Here, the varnish P is a varnish composition in the state which melt | dissolved the polymer (P) component in the solvent. The varnish Q is a varnish composition in which the polymer (Q) component is dissolved in a solvent.

In all of Examples 1 to 23, DC afterimages were “○” and “◎”. In addition, the pretilt angle was 1.2 ° or less, and the voltage holding ratio was 99.5% or more. In Comparative Example 1, the DC afterimage was “◎”, but the pretilt angle was as high as 2.3 °. In the comparative example 2, although the pretilt angle was 1.5 degrees or less and was favorable, DC afterimage was "x". In Comparative Example 3, the DC afterimage was “◎”, but the pretilt angle was as high as 2.2 °.

[Example 24]
The procedure was carried out except that “3.0 g of Varnish 1 synthesized in Synthesis Example 1 and 7.0 g of Varnish 27 synthesized in Synthesis Example 27 were changed to“ 10.0 g of Varnish 3 synthesized in Synthesis Example 3 ”. The liquid crystal aligning agent 27 was obtained according to Example 1. Using the obtained liquid crystal aligning agent 27, a liquid crystal cell was produced according to the method described in Example 1, and DC afterimage, pretilt angle and voltage retention were measured. The DC afterimage of the liquid crystal cell was “○”, and the pretilt angle was 0.6 °. The initial voltage holding ratio was 99.8%, and the voltage holding ratio of the measuring cell after the reliability test was 99.7%.

[Examples 25 to 45, Comparative Examples 4 to 6 and Reference Examples 1 to 2]
A liquid crystal cell was prepared according to Example 24 except that the varnish used was changed, and DC afterimage, pretilt angle and voltage holding ratio were measured. The varnishes used and the measurement results are shown in Table 7 together with Example 24.

In all of Examples 24 to 45, the DC afterimage was “」 ”or“ ◎ ”. Moreover, the pretilt angle was 1.5 degrees or less, and the voltage retention was 99.5% or more. In the comparative example 4, although the pretilt angle was 1.5 degrees or less and was favorable, DC afterimage was "x". In Comparative Example 5, the DC afterimage was “◎”, but the pretilt angle was as high as 2.1 °, and a low pretilt angle could not be expressed. In Comparative Example 6, although the DC afterimage was “◎”, the pretilt angle was as high as 2.0 °, and a low pretilt angle could not be expressed. In Reference Example 1, the DC afterimage was “x”, but the pretilt angle was 0.3 ° and was surprisingly low. Also in Reference Example 2, the DC afterimage was “x”, but the pretilt angle was 0.2 ° and was surprisingly low. The liquid crystal aligning agent which the said diamine in the polymer which is a reaction product from the raw material containing tetracarboxylic dianhydride and a diamine in embodiment containing 1 type of polymer in a liquid crystal aligning agent consists only of Formula (1-4) is It has been found that the pretilt angle can be surprisingly lowered.

[Example 46]
A resin component concentration of 3% by weight in accordance with Example 1 except that 6 mg of additive (Ad1) was further added to “NMP 4.0 g, GBL 3.0 g and BC 3.0 g” in Example 1. The additive concentration was 1 part by weight of the liquid crystal aligning agent 54 per 100 parts by weight of the resin component. Using the obtained liquid crystal aligning agent 54, a liquid crystal cell was produced according to the method described in Example 1, and DC afterimage, pretilt angle and voltage retention were measured. The DC afterimage of the liquid crystal cell was “◎”, and the pretilt angle was 0.9 °. The initial voltage holding ratio was 99.8%, and the voltage holding ratio of the measuring cell after the reliability test was 99.6%.

[Examples 47 to 60 and Comparative Examples 7 to 9]
A liquid crystal cell was produced according to Example 46 except that the varnish and the additive used were changed, and the DC afterimage, pretilt angle and voltage retention were measured. The varnishes, additives and measurement results used are shown in Table 8 together with Example 46.

In all of Examples 46 to 60, the DC afterimage was “60”. Moreover, the pretilt angle was 1.5 degrees or less, and the voltage retention was 99.5% or more. In Comparative Example 7, the DC afterimage was “◎”, but the pretilt angle was as high as 2.4 °. In the comparative example 8, although the pretilt angle was 1.5 degrees or less and was favorable, DC afterimage was "x". In Comparative Example 9, the DC afterimage was “◎” but the pretilt angle was as high as 2.3 °.

[Example 61]
A resin component concentration of 3% by weight in accordance with Example 1 except that 6 mg of additive (Ad1) is further added to “NMP 4.0 g, GBL 3.0 g and BC 3.0 g” in Example 24 The additive concentration was 1 part by weight of the liquid crystal aligning agent 72 per 100 parts by weight of the resin component. Using the obtained liquid crystal alignment agent 72, a liquid crystal cell was produced according to the method described in Example 1, and DC afterimage, pretilt angle and voltage retention were measured. The DC afterimage of the liquid crystal cell was “○”, and the pretilt angle was 0.8 °. The initial voltage holding ratio was 99.7%, and the voltage holding ratio of the measuring cell after the reliability test was 99.6%.

[Examples 62 to 82, Comparative Examples 10 to 12 and Reference Examples 3 to 4]
A liquid crystal cell was produced according to Example 61 except that the varnish and the additive used were changed, and the DC afterimage, pretilt angle and voltage retention were measured. The varnish used, additives and measurement results are shown in Table 9 together with Example 61.

In all of Examples 61 to 82, the DC afterimage was “○” or “◎”. Moreover, the pretilt angle was 1.5 degrees or less, and the voltage retention was 99.5% or more. In the comparative example 10, although the pretilt angle was 1.5 degrees or less and was favorable, DC afterimage was "x". In Comparative Example 11, the DC afterimage was “◎”, but the pretilt angle was as high as 2.2 °, and a low pretilt angle could not be expressed. In Comparative Example 12, the DC afterimage was “◎”, but the pretilt angle was as high as 2.2 °, and a low pretilt angle could not be expressed. In Reference Example 3, the DC afterimage was “x”, but the pretilt angle was 0.4 ° and was surprisingly low. Also in Reference Example 4, the DC afterimage was “x”, but the pretilt angle was 0.3 ° and was surprisingly low. The liquid crystal aligning agent which the said diamine in the polymer which is a reaction product from the raw material containing tetracarboxylic dianhydride and a diamine in embodiment containing 1 type of polymer in a liquid crystal aligning agent consists only of Formula (1-4) is It has been found that even when the additive is added, the pretilt angle can be significantly reduced.

By using the liquid crystal aligning agent of the present invention, it is possible to form a liquid crystal alignment film which can suppress the pretilt angle of liquid crystal to a low level, give a liquid crystal display element having a small residual DC accumulation and quick relaxation of charges. The liquid crystal aligning agent of the present invention can be suitably applied to a transverse electric field liquid crystal display device.

Claims

A liquid crystal aligning agent containing at least one of a polymer which is a reaction product from a raw material containing tetracarboxylic acid dianhydride and a diamine;
The raw material used to synthesize the polymer contains at least one selected from the group of compounds represented by the following formulas (1) to (3), and
A liquid crystal aligning agent comprising at least one selected from a group of compounds represented by the following formulas (A) to (C) and a compound represented by the following formula (D);
Here, the polymer is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide;

In formula (1), m is an integer of 3 to 8;
In formula (3), n is an integer of 1 to 3;
In formulas (1) to (3), a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary;
In formula (A), A 1 is nitrogen or a nitrogen-containing heterocycle, W 1 is independently alkylene having 1 to 5 carbon atoms, and arbitrary —CH 2 — is —CO—, 1, It may be replaced by 4-phenylene or 1,3-phenylene, Z 1 is hydrogen, a protecting group which is replaced with heat by a hydrogen atom, or alkyl having 1 to 5 carbon atoms, r is any integer of 0 or more And a is independently 0 or 1;
In formula (B), A 2 is independently nitrogen or a nitrogen-containing heterocycle, W 2 and W 3 are independently alkylene having 1 to 5 carbon atoms, and any —CH 2 — And -CO-, 1,4-phenylene, or 1,3-phenylene may be replaced, and Z 2 is independently hydrogen, a protecting group which replaces a hydrogen atom by heat, or an alkyl having 1 to 5 carbon atoms And r is independently any integer of 0 or more, and a is independently 0 or 1;
In formula (C), Z 3 is a monovalent organic group containing at least one of a secondary or tertiary amino group;
In Formula (D), T is a divalent unsaturated bond-containing group containing 1 to 2 carbon-carbon double bonds or 1 to 2 carbon-carbon triple bonds;
In the formulas (1) to (3) and the formulas (A) to (C), a group whose bonding position is not fixed to any carbon atom constituting the ring has an arbitrary bonding position in the ring. However, when m is 8 in the formula (1), the diamine may not contain any of the compounds represented by the formulas (A) to (C); The carboxylic acid dianhydride may not be the compound represented by the above formula (D).
The liquid crystal aligning agent of Claim 1 which contains one said polymer.
The ratio of the compounds represented by the formulas (1) to (3) is 70 mol% or more with respect to the total amount of diamine used, and the compounds represented by the formulas (A) to (C) The liquid crystal aligning agent according to claim 2, wherein the proportion is 1 to 30 mol% with respect to the total amount of diamine used.
Containing at least two of said polymers,
The at least two polymers comprise a polymer (P) and a polymer (Q);
The raw material used to synthesize the polymer (P) contains at least one selected from the group of compounds represented by the formulas (1) to (3);
The raw materials used to synthesize the polymer (Q) are at least one selected from the group of compounds represented by the above formulas (A) to (C) and the compounds represented by the above formula (D) The liquid crystal aligning agent of Claim 1 containing B.
The compounds represented by the formulas (1) to (3) have the following formulas (1-1) to (1-4), (2-1), (2-2), and 3-1) to at least one selected from the group of compounds represented by formula (3-6);
The compounds represented by the formulas (A) to (C) are represented by the following formulas (A-1) to (A to 20), formulas (B-1) to (B-8), and C-1) to at least one selected from the group of compounds represented by formula (C-3);
The compound represented by said Formula (D) is at least one selected from the group of the compound represented by following formula (D-1)-formula (D-4). The liquid crystal aligning agent of 1 item.

In formulas (A-1) to (A-11), a group whose bonding position is not fixed to any carbon atom constituting a ring means that the bonding position on the ring is arbitrary;
In formula (B-3), k is an integer of 1 to 5; and
In formula (B-4), n is an integer of 1 to 3.
The compounds represented by the formulas (1) to (3) are represented by the formulas (1-1), (1-4), (2-1), and (3-1). At least one selected from the group of compounds;
The compounds represented by the formulas (A) to (C) are the compounds represented by the formulas (A-12), (A-14), (A-15), (A-16), and (A-). 17) Compounds represented by Formula (A-19), Formula (A-20), Formula (B-3), Formula (B-5), Formula (C-2), and Formula (C-3) At least one selected from the group of
The liquid crystal according to claim 5, wherein the compound represented by the formula (D) is at least one selected from the group of compounds represented by the formula (D-2) and the formula (D-3). Alignment agent.
The liquid crystal aligning agent according to any one of claims 1 to 6, further comprising at least one selected from a compound represented by the following formula (E) as a raw material used to synthesize the polymer:

In the formula (E), W 4 is alkylene having 1 to 6 carbon atoms, 1,3-phenylene or 1,4-phenylene;
W 5 is independently a single bond, -NHCO-, or -CONH-.
The liquid crystal aligning agent according to claim 7, wherein the compound represented by the formula (E) is at least one selected from compounds represented by the following formulas (E-1) to (E-8);

In Formula (E-5) and Formula (E-8), p is each independently an integer of 1 to 6.
The liquid crystal aligning agent of Claim 7 or 8 containing at least 1 chosen from the compound represented by the said Formula (E) as a raw material used for the synthesis | combination of the said polymer (Q).
The compounds represented by the formulas (1) to (3) can be represented by the formulas (1-1) to (1-4), (2-1), (2-2), and (3-). At least one selected from the group of compounds represented by 1);
The compounds represented by the formulas (A) to (C) are the compounds represented by the formulas (A-12), (A-14), (A-15), (A-16), and (A-). 17) at least one selected from the group of compounds represented by Formula (B-3), Formula (C-2), and Formula (C-3);
The compound represented by the formula (D) is at least one selected from the group of compounds represented by the formula (D-2) and the formula (D-3);
10. The compound according to any one of claims 1 to 9, wherein the compound represented by the formula (E) is at least one selected from the group of compounds represented by the formulas (E-5) to (E-7). The liquid crystal aligning agent of 1 item.
The compounds represented by the formulas (1) to (3) are at least one selected from the formulas (1-1) and (1-4);
The compounds represented by the above formulas (A) to (C) are at least one selected from the above formulas (A-15) and (B-3);
The compound represented by the formula (D) is a compound represented by the formula (D-2);
The liquid crystal aligning agent of Claim 10 whose compound represented by said Formula (E) is a compound represented by said Formula (E-5).
In the polymer (P), the ratio of the compounds represented by the formulas (1) to (3) is 70 mol% or more with respect to the total amount of diamine used;
12. The polymer (Q) according to any one of claims 4 to 11, wherein the ratio of the compounds represented by the formulas (A) to (C) is 10 to 50 mol% with respect to the total amount of diamine used. The liquid crystal aligning agent as described in a term.
In the polymer (P), the ratio of the compounds represented by the formulas (1) to (3) is 70 mol% or more with respect to the total amount of diamine used;
12. The polymer (Q) according to any one of claims 4 to 11, wherein the ratio of the compound represented by the formula (D) is 20 to 50 mol% with respect to the total amount of tetracarboxylic acid dianhydride used. The liquid crystal aligning agent as described in a term.
In the polymer (P), the ratio of the compounds represented by the formulas (1) to (3) is 90 mol% or more with respect to the total amount of diamine used;
The liquid crystal aligning agent according to claim 12, wherein in the polymer (Q), the ratio of the compounds represented by the formulas (A) to (C) is 30 to 50 mol% with respect to the total amount of diamine used. .
The liquid crystal aligning agent according to claim 13, wherein in the polymer (P), the ratio of the compounds represented by the formulas (1) to (3) is 90% by mole or more based on the total amount of the diamine to be used.
The liquid crystal according to any one of claims 7 to 15, wherein the proportion of the compound represented by the formula (E) in the polymer (Q) is 50 to 70 mol% with respect to the total amount of diamine used. Alignment agent.
The compound according to any one of claims 1 to 16, further comprising at least one selected from the group consisting of an alkenyl substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. The liquid crystal aligning agent for photo alignment as described in 1 item.
The liquid crystal aligning agent according to any one of claims 1 to 17, which is used for the production of an in-plane switching liquid crystal display device.
A diamine represented by the above formula (1-4).
It is a liquid crystal aligning agent containing at least one of a polymer which is a reaction product from a raw material containing tetracarboxylic acid dianhydride and a diamine,
The liquid crystal aligning agent which consists of only the said diamine shown by the said Formula (1-4) of Claim 19.
A liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of claims 1 to 20.
The liquid crystal display element which has a liquid crystal aligning film of Claim 21.
A lateral electric field liquid crystal display device comprising the liquid crystal alignment film according to claim 21.