WO2019103044A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent with excellent filtering and printing properties, a liquid crystal alignment film with excellent liquid crystal alignment properties obtained from said liquid crystal aligning agent, and a liquid crystal display element provided with said liquid crystal alignment film are provided. This liquid crystal aligning agent is characterized by containing: at least one polymer selected from the group consisting of polyamic acid or polyamic acid ester having the structure of formula [1], and a polyimide that is an imide compound thereof; and a solvent containing at least one solvent A selected from the group consisting of formulae (d-1) to (d-5) and formula (e) and at least one solvent B selected from the group consisting of formulae (B-1) to (B-4).

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display device

The present invention relates to a liquid crystal aligning agent excellent in filterability and printability, a liquid crystal alignment film excellent in liquid crystal alignment obtained from the liquid crystal aligning agent, a method for producing the same, and a liquid crystal display element.

As a liquid crystal alignment film of a liquid crystal display element, a so-called polyimide-based liquid crystal alignment film is widely used, which is obtained by applying and baking a liquid crystal aligning agent containing a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide as a main component It is done. In the production of such a liquid crystal aligning agent, in order to remove foreign substances contained in a solution of the liquid crystal aligning agent, a method of performing filtration using a filter for filtration in a state where a polyimide precursor or polyimide is dissolved in a solvent is conventionally used. (Patent Document 1).

Japanese Patent Application Laid-Open No. 08-262450

In the field of liquid crystal alignment film, a thin film of about several hundreds of nm is conventionally used, and the mixture of minute foreign substances in the liquid crystal alignment agent has not become a major problem. However, in recent years, the need for further thin films has increased, and at the same time, it has become necessary to remove smaller foreign substances than ever before. This can be achieved by filtering with a filter with a small pore size in order to remove minute foreign substances in the solution, but when the quantity of foreign substances is large, if it is manufactured on a large scale, it takes time for filtration, causing problems in manufacturing Become. Further, the demand for improvement in display quality has become more severe, and in addition to liquid crystal aligning agents with less pinholes and repelling, liquid crystal alignment films having characteristics more than ever for liquid crystal alignment are also required.

In view of the above problems, an object of the present invention is to provide a liquid crystal aligning agent having excellent filterability and printability, a liquid crystal aligning film having excellent liquid crystal alignment obtained from the liquid crystal aligning agent, and a liquid crystal display device comprising the liquid crystal aligning film. To provide.

As a result of intensive studies to solve the above problems, the present inventors simultaneously improve various properties by combining a polymer having a specific structure and a solvent containing a specific solvent. I found out.
The present invention is based on such findings and has the following gist.
Polyamic acid having a structure of the following formula [1], polyamic acid ester (hereinafter, polyamic acid and polyamic acid ester are also generically referred to as a polyimide precursor), and at least one selected from polyimides that are imidized products thereof A liquid crystal aligning agent containing a polymer and a solvent, wherein the solvent is at least one solvent A selected from the group consisting of the following formulas (d-1) to (d-5) and the following formula (e) And a solvent comprising at least one solvent B selected from the group consisting of the following formulas (B-1) to (B-4):

X is a single _{bond, -O -, - C (CH} 3) 2 -, - NH -, - CO -, - NHCO -, - COO -, - (CH 2) m -, - SO 2 -, - O _{- (CH 2) m -O -} , - O-C (CH 3) 2 -, - CO- (CH 2) m -, - NH- (CH 2) m -, - SO 2 - (CH 2) m -Represents a divalent organic group selected from the group consisting of-, -CONH- (CH ₂ ) _m- , -CONH- (CH ₂ ) _m -NHCO- and -COO- (CH ₂ ) _m -OCO-, m is an integer of 1 to 8; Two Y independently represent a side chain structure selected from the following formulas [S1] to [S3] or a structure derived from tocopherol.

X ¹ and X ² are independently a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )-, -NH -, -O-, -COO-, -OCO-, or ((CH ₂ ) _a1 -A ₁ ) _m1- (plurality of a1 independently represents an integer of 1 to 15, multiple A ₁ of And represents an oxygen atom, -COO or OCO, and m ₁ represents 1 to 2.), and G ¹ and G ² independently represent a divalent aromatic group having 6 to 12 carbon atoms or 3 carbon atoms. A divalent cyclic group selected from a divalent alicyclic group of 8 to 8, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, It may be substituted by a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, And n is an independently integers of from 0 to 3, their sum is 1 - 4, ^{R 1} is alkyl having 1 to 20 carbon atoms, from 1 to 20 carbon atoms alkoxy, or 2 to 20 carbon atoms And any hydrogen in these groups may be replaced by a fluorine atom.
X ³ represents a single bond, -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or OCO-, and R ² represents carbon The alkyl is an alkyl of 1 to 20 or an alkoxyalkyl of 2 to 20 carbons, and any hydrogen in these groups may be replaced by a fluorine atom.
X ⁴ represents —CONH—, —NHCO—, —O—, —COO— or OCO—, and R ³ represents a structure having a steroid skeleton.

R _1a represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group, and R _2a and R _2b are independently Is an alkyl group having 1 to 6 carbon atoms, R _3a is a methyl group or an ethyl group, R _5a is an alkyl group having 1 to 6 carbon atoms, and R _5b and R _5c are independently hydrogen atoms , A monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds of the hydrocarbon group, and r _1a and r _1b are independently And hydrogen is an alkyl group having 1 to 6 carbon atoms, m is an integer of 2 to 6, and n is 1 or 2.

A _p1 and A _p2 independently represent an alkyl group having 1 to 6 carbon atoms, A _p5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A _q1 represents -O- or -COO- , A _q2 represents a single bond or a carbonyl group, A _q3 represents -O-, A _k1 , A _k2 and A _k6 independently represent an alkanediyl group having 2 to 4 carbon atoms, and n1 is 1 to 3 is shown. A _p3 and A _{p4 each} represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A _x represents -C (OH) R _a- , -CHR _b- (R _a , R _b is independently hydrogen; , a methyl group or an ethyl group), -. CO- or -COO -. * (where * indicates a) that indicates the bonding position to _{a k4, a k4, a k5} is carbon independently 1ア ル キ ル 4 represents an alkyl group, m represents 0 to 1, and n4 represents 1 to 3. However, the case where n 4 is 1, A _{k 6} is an alkanediyl group having 2 carbon atoms, and _{Ap 5} is an alkyl group having 4 carbon atoms is excluded. However, the case where n 4 is 1 and Ak 6 is an alkanediyl group having 2 carbon atoms and Ap 5 is an alkyl group having 4 carbon atoms is excluded.

According to the present invention, a liquid crystal aligning agent excellent in filterability and printability, a liquid crystal alignment film excellent in liquid crystal alignment obtained from the liquid crystal aligning agent, and a liquid crystal display element provided with the liquid crystal alignment film can be obtained.

The liquid crystal aligning agent of the present invention comprises at least one polymer (hereinafter also referred to as a specific polymer) selected from the group consisting of a polyimide precursor having a structure of the following formula [1] and a polyimide which is an imidized product thereof. contains.

<Specific polymer>
It is preferable that a specific polymer has a structure of Formula [1] in the principal chain of a polymer, among others, from easiness of synthesis. Here, the main chain of the polymer refers to a portion composed of the longest chain of atoms in the polymer. Moreover, it does not exclude that the structure of said Formula [1] also exists in parts (For example, part of the side chain of a polymer) other than a principal chain in a specific polymer.

X in the formula [1] is as defined above.
Among them, X is preferably a single bond, -O-, -NH- or -O- (CH ₂ ) _m -O-.

Y in the formula [1] has a side chain structure selected from the following formulas [S1] to [S3] or a structure having a tocopherol skeleton.

X ¹ and X ² in the formula [S1] are as defined above. Among them, from the viewpoint of availability of raw materials and ease of synthesis, a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O- COO- is preferred. More preferably, it is a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 10), -O-, -CH ₂ O- or COO-.

G ¹ and G ² are as defined above.
Examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, biphenylene and naphthalene. Further, examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropylene and cyclohexylene.

Preferred specific examples of the formula [S1] include structures of the following formulas [S1-x1] to [S1-x7].

In formulas [S1-x1] to [S1-x7], R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. X ^p is-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-. A ₁ is an oxygen atom or -COO- * (wherein a bond with * is bonded to (CH ₂ ) a ₂ ), and A ₂ is an oxygen atom or * -COO- (with "*" The attached bond is (CH ₂ ) _a2 ). a ₁ and a ₃ are independently an integer of 0 or 1, and a ₂ is an integer of 1 to 10. Cy is a 1,4-cyclohexylene group or a 1,4-phenylene group.

X ³ in the formula [S2] is as defined above. Among them, -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or OCO- is preferable from the viewpoint of liquid crystal alignment.
R ² is as defined above. Among them, alkyl having 3 to 20 carbons or alkoxyalkyl having 2 to 20 carbons is preferable from the viewpoint of liquid crystal alignment.
As preferred specific examples of the formula [S2], -CONH- (CH ₂ ) _n -CH ₃ (n = 2 to 17), -NHCO- (CH ₂ ) _n -CH ₃ (n = 2 to 17), -O -(CH ₂ ) _n -CH ₃ (n = 2 to 17), -COO- (CH ₂ ) _n -CH ₃ (n = 2 to 17), -CH ₂ O- (CH ₂ ) _n -CH ₃ ( n = 2 to 17).

X ⁴ in the formula [S3] is as defined above. Among them, -O-, -COO- or -OCO- is preferable from the viewpoint of liquid crystal alignment.
As a structure having a steroid skeleton, a structure in which a hydroxy group is removed from a compound such as β-sitosterol or ergosterol, a structure in which a hydroxy group is removed from a steroid compound described in [0024] of JP-A-4-281427, [0030] ] The structure which removed the acid chloride group from the steroid compound as described in, the structure which remove | eliminated the amino group from the steroid compound as described in [0038], the structure as which the halogen group was remove | excluded from the steroid compound, And structures described in [0018] to [0022] of JP-146421.

The following formula [S3-x] is given as a preferred specific example of the formula [S3]. Further, the definitions of X, Col and G in the formula [S3-x] are as follows.

(In the formula, * indicates a bonding position)

More preferable structures of the formula [S3] include structures represented by the following formulas [S3-1] to [S3-6].

(In the formula, * indicates a bonding position)

Examples of the structure having a tocopherol skeleton in the formula [1] include structures derived from compounds such as α-tocopherol, β-tocopherol, γ-tocopherol and δ-tocopherol. Specific examples of the structure having a tocopherol skeleton include a structure represented by the following formula [T]. In addition, "*" shows a coupling | bonding position.

The specific polymer contained in the liquid crystal aligning agent of the present invention is selected from the group consisting of a polyimide precursor having a divalent group represented by the formula [1] and a polyimide which is an imidized product of the polyimide precursor. As long as it is at least one or more polymers, it may be synthesized by any method.
Among them, the specific polymer is a tetracarboxylic acid dianhydride having the structure of the formula [1] or a derivative thereof (hereinafter, also referred to as a specific tetracarboxylic acid compound), or a tetracarboxylic acid containing the specific tetracarboxylic acid compound A polyimide precursor obtained by reacting an acid component and a diamine component; a polyimide which is an imidized product of the polyimide precursor; a diamine having the structure of the above-mentioned tetracarboxylic acid component and the formula [1] (hereinafter, specific diamine Or at least one selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a specific diamine; and a polyimide which is an imidized product of the polyimide precursor.

[Tetracarboxylic acid component]
The tetracarboxylic acid component used to synthesize the specific polymer contains either a specific tetracarboxylic acid compound, another tetracarboxylic acid compound, or both.
<Specific tetracarboxylic acid compound>
The specific tetracarboxylic acid compound is a tetracarboxylic acid compound having a structure of the above formula [1], and examples thereof include a compound represented by the following formula [T], or a derivative thereof.

In formula [T], A represents a trivalent group, and two A may be the same or different. Examples of A include a trivalent organic group having at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, a benzene ring structure and the following formula (A-1). P represents a divalent organic group having a structure of Formula [1].

Examples of the derivative of the tetracarboxylic acid compound include tetracarboxylic acid dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dihalide.

<Other tetracarboxylic acid compounds>
Other tetracarboxylic acid compounds include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3, 3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenone Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,1 3,3,3-Hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxylic acid) Ruboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid Acid dianhydride obtained from tetracarboxylic acid such as acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, Or a derivative thereof, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound which is a derivative thereof.

Among these, from the viewpoint of high solubility of the polymer, at least one or more of tetracarboxylic dianhydride having a structure represented by the formula [4] and its tetracarboxylic acid derivative are preferable.

Z represents a structure selected from the following [4a] to [4k].

(* 1 is a bonding position for bonding to one acid anhydride group, and * 2 is a bonding position for bonding to the other acid anhydride group.)

In the formula [4a], Z ¹ to Z ⁴ independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring. Preferred examples of Z ¹ to Z ⁴ include structures of the following formulas [4a-1] and [4a-2].

(* 1 and * 2 are as defined above.)

Wherein [4g], ^{Z 5} and ^{Z 6} are independently a hydrogen atom or a methyl group.
Among Z in the formula [4], in view of easiness of synthesis and easiness of polymerization reactivity at the time of producing a polymer, formula [4a], formula [4c] to formula [4 g] or formula [4] 4k] is preferred. Formula [4a] or Formula [4e] to Formula [4g] are more preferable, and [4a], Formula [4e] or Formula [4f] is particularly preferable. Preferred examples thereof include tetracarboxylic acid dianhydrides having a structure represented by [4a-1], Formula [4a-2], Formula [4e] and Formula [4f] or derivatives thereof.

The tetracarboxylic acid compound represented by the formula [4] in the polymer of the present invention is preferably 1 mol% or more in 100 mol% of all tetracarboxylic acid compounds from the viewpoint of enhancing the solubility of the polymer. Among them, 5 mol% or more is preferable, and 10 mol% or more is more preferable.
The tetracarboxylic acid compound is selected depending on the solubility of the polymer of the present invention in the solvent, the coating property of the liquid crystal aligning agent, and the liquid crystal alignment property in the liquid crystal aligning film, the voltage holding ratio, and the accumulated charge. One kind or two or more kinds can be mixed and used.

[Diamine component]
The diamine used to synthesize a specific polymer contains a specific diamine. A specific diamine is a diamine which has a structure of said Formula [1], for example, the compound represented by following formula [2] is mentioned.
<Specific diamine>
The specific diamine used for the liquid crystal aligning agent of this invention is represented by following formula [2].

Each of X and Y in the formula [2] has the same meaning as in the above-mentioned formula [1].

Preferably, X is a single bond, —O—, —NH— or —O— (CH ₂ ) _m —O—, from the viewpoint of easy synthesis of a specific diamine. m is an integer of 1 to 8;
In formula [2], Y may be a meta position or an ortho position from the position of X, but is preferably an ortho position from the viewpoint of high reactivity of a specific diamine. Specifically, formula [2] is preferably the following formula [2 '].

The above formula [2] is preferably a structure of any of the following formulas from the viewpoint of high reactivity of the specific diamine, and a structure represented by the formula [2] -a1-1 is more preferred.

As a preferable form of Y in the said Formula [2], the preferable form of Y in said Formula [1] can be applied. Among them, a structure selected from the above formulas [S1-x3] to [S1-x4], [S1-x6] and formula [S3-x] is preferable from the viewpoint of enhancing the liquid crystal alignment. The structures of W-1] to [W-6] can be mentioned.

In the formula, X ^p1 to X ^p8 are independently-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )-, -NH -, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-. X ^s1 to X ^s4 independently represent -O-, -COO- or -OCO-. X _a to X _{f each} represents a single bond, —O—, —NH— or —O— (CH ₂ ) _m —O—. R ^1a to R ^1h independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. m is an integer of 1 to 8;
Specific diamines are 1 according to the ink jet coatability of the liquid crystal alignment agent, the liquid crystal alignment when used as a liquid crystal alignment film, voltage holding characteristics, characteristics such as accumulated charge, and the response speed of liquid crystal when used as a liquid crystal display element. The species or two or more species can be mixed and used.

The specific diamine is preferably used in an amount of 1 to 100% by mole, more preferably 2 to 100% by mole, and particularly preferably 5 to 90% by mole, of the diamine component used for the synthesis of the specific polymer.
As a diamine for synthesizing a polyamic acid or a polyamic acid ester, only a specific diamine may be used, or other diamine may be used in combination with the specific diamine. Here, as the other diamine, for example, a diamine having a pretilt angle developing property other than the above (2), a diamine having a function of generating polymerization or radical upon irradiation with light, WO [International Publication WO 2015/046374] Of the diamine described in [0171] to [0172], a diamine having the nitrogen-containing heterocycle described in [0173] to [0188], or the diamine of JP-A-2016-218149. Diamines having the nitrogen-containing structure described in [0050], 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl)- And organosiloxane-containing diamines such as 1,1,3,3-tetramethyldisiloxane. Among them, in a liquid crystal display element of a PSA (Polymer Sustained Alignment) system, a diamine having a function of generating polymerization or generating a radical by light irradiation is preferable from the viewpoint of enhancing the response speed.

Preferred specific examples of other diamines include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-difluoro-4 4,4'-Diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, 4,4'- Diaminobenzophenone, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4 -Aminophenyl) butane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-amino) Phenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1 1,4-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzamido), N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 2,2′-bis [4- (4-aminophenoxy) ) Phenyl] propane, 2,2'-bis (4-aminophenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1, 9-bis (4-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, bis (4-aminocyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5- Diaminopentane, 1,6-diaminohexane, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diamino Phenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-Diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4, 4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid, 2,6 -Diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diamide Carbazole, 1,4-bis- (4-aminophenyl) -piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N ' -Bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, the following formula (D-2-1) to formula (D-2-8) A compound represented by each of

Furthermore, there may be mentioned diamine compounds in which these amino groups are secondary amino groups.

Examples of the diamine having a pretilt angle developing property other than the above formula (2) include diamines represented by the structural formulas of the following formulas [V-1] to [V-7].

In the above formulae, X ^v1 to X ^v4 are independently-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )-,- _{NH -, - O -, -} CH 2 O -, - CH 2 OCO -, - COO-, or -OCO- shows a. X ^v5 represents -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-. X ^V6 to X ^V7 independently represent -O-, -COO- or -OCO-.
Examples of the diamine having a function of polymerizing by light irradiation include diamines in which the structures represented by the following formulas [p1] to [p7] are directly or linked to an aromatic ring such as a benzene ring via a linking group. Be

Specific examples thereof include diamines represented by the following formula [Pa] or [P-b].

The bonding position of the _two amino groups (-NH ₂ ) in the formula [Pa] and the formula [P-b] is not limited, but from the viewpoint of the reactivity of the diamine, the positions 2, 4 and 5, 2, 5 Or the positions of 3, 5 are preferred. In consideration of the ease of synthesis of the diamine, the positions 2, 4 or 3, 5 are more preferable.

In the formula [Pa], R ⁸ is a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, which is a single bond, -O-, -COO-, -NHCO-, or -CONH- from the easiness of synthesis Is preferred.
R ⁹ represents a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, a divalent group selected from an aromatic ring having 6 to 12 carbon atoms such as a benzene ring and a naphthalene ring, and cyclohexane Ring or other divalent alicyclic group having 3 to 8 carbon atoms, such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, pyrazine, pyridazine, triazine, indole, quinoline, carbazole, thiazole, purine, tetrahydrofuran, thiophene, etc. And a divalent cyclic group selected from the heterocycles of Here, the —CH ₂ — of the alkylene group may be optionally substituted by —CF ₂ — or —CH = CH—. From the ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferred. k is an integer of 0 to 4;

R ¹⁰ represents a structure selected from the above formulas [p1] to [p7]. From the viewpoint of photoreactivity, [p1], [p2] and [p4] are preferable.
In the formula [P-b], Y ₁ and Y ₃ independently represent -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO Represents-. Y ₂ and Y ₅ are independently synonymous with R ₉ in the above [Pa]. Y ₄ represents a cinnamoyl group. Y ₆ represents a structure selected from the above formulas [p1] to [p7]. From the viewpoint of photoreactivity, [p1], [p2] and [p4] are preferable. m represents 0 or 1;
The diamine having a function of polymerizing by light irradiation is determined according to the liquid crystal alignment property when formed into a liquid crystal alignment film, the pretilt angle, the voltage holding property, the characteristics such as accumulated charge, and the response speed of the liquid crystal when formed into a liquid crystal display element. , 1 type, or 2 or more types can be mixed and used.

It is preferable to use 10 to 70% by mole, more preferably 10 to 60% by mole, and particularly preferably 10 to 50% by mole of the diamine component used for the synthesis of the specific polymer, as the diamine having a function of polymerizing by light irradiation. is there.
Examples of diamines having a function of generating radicals by light irradiation include diamines having a moiety having a radical generating structure which is decomposed by ultraviolet irradiation to generate radicals in the side chain, for example, diamines represented by the following formula (R) Can be mentioned.

Ar, R ₁ , R ₂ , T ₁ , T ₂ , S and Q in the above formula (R) have the following definitions.
That is, Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene and biphenylene, to which an organic group may be substituted, and a hydrogen atom may be substituted by a halogen atom.
R ₁ and R ₂ are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group.
T _{1, T 2} are independently a single bond or -O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH -, - CH 2 O -, - N (CH 3) - And -CON (CH ₃ )-and -N (CH ₃ ) CO-.
S has the same meaning as R ⁹ in the above [Pa].

Q is a structure selected from the following formulas [q-1] to [q-4] (in the structural formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ represents —CH ₂ —, — NR—, —O—, or —S— is shown.

(In the formula, * indicates a bonding position.)
In the above-mentioned formula (R), from the viewpoint of efficient absorption of ultraviolet light, Ar to which a carbonyl is bonded is preferably a structure having a long conjugation length such as naphthylene or biphenylene. Further, Ar may have a substituent, and such a substituent is preferably an electron donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, an amino group and the like. If the wavelength of ultraviolet light is in the range of 250 to 380 nm, sufficient characteristics can be obtained even with a phenyl group, so a phenyl group is most preferable.

R ₁ and R _{2 each} independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group, and in the case of an alkyl group or an alkoxy group, a ring is formed by R ₁ and R ₂ It may be done.
From the viewpoint of easily producing a specific polymer, Q is more preferably a hydroxyl group or an alkoxyl group.
The diaminobenzene in the formula (R) may be any structure of o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, but m-phenylenediamine, in that it has high reactivity with the tetracarboxylic acid component. Or p-phenylenediamine is preferred.

Specifically, structures represented by the following formulas [R-1] to [R-4] are most preferable in terms of easiness of synthesis, high degree of versatility, and properties. In the formula, n is an integer of 2 to 8.

It is preferable to use 5 to 70 mol% of the diamine component used for the synthesis of the specific polymer, and more preferably 10 to 60 mol% from the viewpoint of maintaining liquid crystal alignment, as the diamine having the function of generating radicals upon light irradiation. And particularly preferably 10 to 50 mol%.

<Synthesis of specified polymer>
The specific polymer is obtained by reacting a diamine and a tetracarboxylic acid compound as described above. As a method of obtaining a polyamic acid, a method of polycondensation of tetracarboxylic acid dianhydride and diamine to obtain a polyamic acid or a method of polycondensation of a tetracarboxylic acid dihalide compound and a diamine compound to obtain a polyamic acid can be mentioned. .
The specific polymer can be obtained by reacting with a molecular weight modifier as needed. Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate It can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the tetracarboxylic acid compound and diamine used.

As a method of obtaining a polyamic acid ester, a method of polycondensing a diamine with a tetracarboxylic acid dialkyl ester compound in which a carboxylic acid group is dialkylesterified, a tetracarboxylic acid dialkyl ester dihalide in which a carboxylic acid group is dialkylesterified and dihalified. Examples thereof include a method of polycondensation of a compound and a primary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester.
As a method of obtaining a polyimide, the method of making said polyimide precursor ring-closing and making it a polyimide is mentioned.

The reaction of the diamine with the tetracarboxylic acid compound is preferably carried out in a solvent. The solvent is not particularly limited as long as it can dissolve the produced polymer. Although the example of a solvent is given to the following, it is not limited to these examples.
For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-2-imidazolidinone Can be mentioned. Further, when the solvent solubility of the polymer is high, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D-1] to [D-3] Solvents can be used.

(In the formula [D-1], D ¹ represents an alkylene group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkylene group having 1 to 3 carbon atoms; In the above, D ³ represents an alkylene group having 1 to 4 carbon atoms).
These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polymer, it may be mixed and used for the said solvent in the range which the produced | generated polymer does not precipitate. In addition, since water in the solvent inhibits the polymerization reaction and causes hydrolysis of the formed polymer, it is preferable to use the solvent which has been dehydrated and dried.

When the diamine and the tetracarboxylic acid compound are reacted in a solvent, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer of high molecular weight, and the concentration is too high And the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction may be performed at high concentration, and then solvent may be added.
In the polycondensation reaction, the ratio of the total number of moles of diamine to the total number of moles of the tetracarboxylic acid compound is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the specific polymer to be produced increases as the molar ratio approaches 1.0.
The polyimide is a polyimide obtained by ring-closing the polyimide precursor, and in this polyimide, the ring-closing rate (also referred to as imidation rate) of the amic acid group does not necessarily have to be 100%, depending on the application and purpose. It can be adjusted arbitrarily.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which the catalyst is added to the solution of the polyimide precursor.
The temperature for thermally imidizing the polyimide precursor in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction out of the system.
Catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 ° C to 250 ° C, preferably 0 to 180 ° C. . The amount of basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid group, and the amount of acid anhydride is 1 to 50 moles, preferably 3 to 30 moles of the amic acid group. It is a double. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferable because it has a suitable basicity to allow the reaction to proceed. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned, and it is particularly preferable to use acetic anhydride because purification after completion of the reaction becomes easy. The imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When the produced polyimide precursor or polyimide is recovered from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be introduced into a solvent and precipitated. As a solvent used for precipitation, methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like can be mentioned. The polymer precipitated by charging in a solvent can be recovered by filtration and then dried by heating at normal temperature or under normal pressure or reduced pressure. Further, by repeating the operation of re-dissolving and collecting the precipitated and recovered polymer in a solvent and re-precipitating and collecting 2 to 10 times, impurities in the polymer can be reduced. As the solvent in this case, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and it is preferable to use three or more solvents selected from these, since the efficiency of purification is further improved.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyimide precursor and the polyimide is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. It is. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in such a molecular weight range, good orientation of the liquid crystal display element can be secured.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of the present invention is constituted by dissolving, in a solvent, at least one polymer selected from the group consisting of a polyimide precursor as described above and a polyimide and optionally added components used as needed. .
The solvent used for the liquid crystal aligning agent of the present invention is, as described above, at least one solvent A selected from the group consisting of the above formulas (d-1) to (d-5) and (e), and B-1) to at least one solvent B selected from the group consisting of (B-3).
By containing the solvent A, the specific polymer is easily dissolved in the solvent, and a liquid crystal aligning agent excellent in filterability and printability can be obtained. Moreover, since the pinhole and repelling at the time of apply | coating a liquid crystal aligning agent to a board | substrate can be suppressed by containing the solvent B, the liquid crystal aligning agent excellent in printability is obtained. Further, by containing the solvent A and the solvent B in combination, when the coating film of the liquid crystal aligning agent is dried, aggregation does not occur between the side chain components of the specific polymer, so the in-plane uniformity of the alignment component As a result, a liquid crystal alignment film excellent in liquid crystal alignment can be obtained. Moreover, even if the monomer component contained in a specific polymer will become multiple types by combining 2 or more types, the liquid crystal aligning film excellent in the liquid crystal aligning agent excellent in filterability and printability, and liquid crystal orientation is obtained.

The solvent preferably contains three or more kinds of one or more kinds of solvent A and one or more kinds of solvent B from the viewpoint of further enhancing the printability, and more preferably four or more kinds, It is particularly preferred to contain more than species.
In Formula (d-1), examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms of R _1a include a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include a chain having 1 to 8 carbon atoms Examples thereof include an alkyl group and a cycloalkyl group having 3 to 8 carbon atoms. Further, examples of the monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group include, for example, alkoxyalkyl groups having 2 to 8 carbon atoms.
As specific examples of these, examples of the chain alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Examples of the alkoxyalkyl group having 2 to 8 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group and an ethoxyethyl group. These groups may be linear or branched.

In the formulas (d-2), (d-5) and the formula (e), examples of the alkyl group having 1 to 6 carbon atoms as R _2a , R _2b , R _5a , r _1a and r _1b include methyl and ethyl And a propyl group, a butyl group, a pentyl group, a hexyl group and the like, which may be linear or branched.
In formula (d-3), R _3a represents a methyl group or an ethyl group.
In the formula (d-5), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms of R _5b and R _5c include a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include 1 to 6 carbon atoms And a linear alkyl group, a cycloalkyl group having 3 to 6 carbon atoms, and the like. The monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group includes, for example, an alkoxyalkyl group having 1 to 6 carbon atoms. As specific examples of these, as a linear alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like can be mentioned; , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

Specific examples of the formula (d-1) include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (N-butyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (n-hexyl) -2-pyrrolidone, N-cyclohexyl- Examples thereof include 2-pyrrolidone, N- (n-octyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone and the like. Among them, from the viewpoint of enhancing the filterability of the liquid crystal aligning agent, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N- (n- (n) Particularly preferred are -butyl) -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N- (n-hexyl) -2-pyrrolidone and N-methoxypropyl-2-pyrrolidone.

Specific examples of the formula (d-2) include 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as symbol DMI), 1,3-diethyl-2-imidazolidinone, and 1,3-diethyl-2-imidazolidinone. Dipropyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone and the like can be mentioned. DMI is preferable from the viewpoint of enhancing the filterability of the liquid crystal aligning agent.
Specific examples of the formula (d-5) include 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, iso Propoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like. Among them, 3-butoxy-N, N-dimethylpropanamide or 3-methoxy-N, N-dimethylpropanamide is preferable from the viewpoint of enhancing the filterability of the liquid crystal aligning agent.

Specific examples of the formula (e) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate, 2-methyl-1,3-propylene carbonate, and 2,2-dimethyl-1,3-propylene carbonate Etc. Among these, propylene carbonate, ethylene carbonate, or butylene carbonate is preferable from the viewpoint of enhancing the filterability of the liquid crystal aligning agent.
Among the solvents A, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-cyclohexyl-2 from the viewpoint of enhancing liquid crystal alignment and filterability. -Pyrrolidone, N- (n-hexyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone Preferred is at least one selected from the group consisting of 3-butoxy-N, N-dimethylpropanamide and 3-methoxy-N, N-dimethylpropanamide.

From the viewpoint of enhancing filterability, the content ratio of the solvent A in the solvent is preferably 5 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 20 to 90% by mass with respect to the entire solvent contained in the liquid crystal aligning agent. % Is more preferred.
Alkyl group _{A p1} and _{A p2} of the formula (B-1), and alkyl group of _{A p3} and _{A p4} of the formula (B-2), the alkyl group of _{A p5} of the above formula (B-4) is And a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and the like.
The alkanediyl group of A _k1 , A _k2 and A _k6 may be linear or branched and, for example, methylene, ethylene, 1,3-propanediyl, 1,2-propanediyl, 1,4- Examples include butanediyl group and 1,3-butanediyl group. A _k1 is preferably ethylene, 1,3-propanediyl or 1,4-butanediyl. n is preferably 1 or 2. Examples of the alkyl group of _Ak4 and _{Ak5 in} the above formula (B-3) include a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, and the like.

Preferred examples of the compound represented by the above formula (B-1) include ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol diethyl ether, diethylene glycol ethyl propyl ether, diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol Acetate, ethylene glycol, 1,4-butane diol.

Examples of the compound represented by the above formula (B-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, n-butyl lactate, isoamyl lactate, ethyl 3-ethoxypropionate and the like .
Examples of the compound represented by the above formula (B-3) include diacetone alcohol, acetylacetone, ethyl acetoacetate, diisobutyl ketone, 4,6-dimethyl-2-heptanone, diisobutyl carbinol and the like.
Examples of the compound represented by the above formula (B-4) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol i-propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether and the like can be mentioned.

Among the solvents B, diisobutyl ketone, diisobutyl carbinol, 4,6-dimethyl-2-heptanone, diacetone alcohol, n-butyl lactate, isoamyl lactate, butyl glycolate, from the viewpoint of achieving both printability and filterability. Ethyl 3-ethoxypropionate, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl propyl ether, diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, dipropylene glycol monomethyl ether Propylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate and pro It is preferably at least one selected from alkylene glycol diacetate.
The content ratio of the solvent B in the solvent is preferably 1 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 20 to 90% by mass with respect to the entire solvent contained in the liquid crystal aligning agent.

The solvent contained in the liquid crystal aligning agent of the present invention preferably contains one combination selected from the following ms1 to ms10, from the viewpoint of achieving both the printability and the filterability of the liquid crystal aligning agent, and MS1 to MS29 More preferably, it comprises one selected combination.
Ms1: N-methyl-2-pyrrolidone and propylene glycol monobutyl ether ms2: N-methyl-2-pyrrolidone and dipropylene glycol monomethyl ether ms3: N-methyl-2-pyrrolidone and dipropylene glycol dimethyl ether ms4: N -Methyl-2-pyrrolidone and propylene glycol monomethyl ether-ms5: N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether-ms6: N-ethyl-2-pyrrolidone and dipropylene glycol monomethyl ether-ms 7: N-ethyl-2 -Pyrrolidone and dipropylene glycol dimethyl ether · ms 8: N-ethyl 2-pyrrolidone and propylene glycol monomethyl ether · ms 9: N-methyl 2-pyrrolidone and isoamyl lactate s10: N-methyl-2-pyrrolidone and diacetone alcohol · ms11: .gamma.-butyrolactone and ethyl-3-ethoxypropionate · MS 12: N-ethyl-2-pyrrolidone and diisobutyl ketone

・ MS1: N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether ・ MS2: N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol monomethyl ether ・ MS3: N-methyl-2-pyrrolidone γ-butyrolactone and dipropylene glycol dimethyl ether · MS4: N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether · MS5: N-ethyl 2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether · MS 6: N -Ethyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol monomethyl ether · MS 7: N-ethyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether Tel · MS8: N-ethyl-2-pyrrolidone and γ- butyrolactone and propylene glycol monomethyl ether

MS9: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and propylene glycol monobutyl ether MS10: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and dipropylene glycol monomethyl ether MS11: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and dipropylene glycol dimethyl ether MS12: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether MS13: N-Methyl-2-pyrrolidone, diacetone alcohol and diethylene glycol diethyl ether MS14: N-Methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether M 15: N- methyl-2-pyrrolidone and N- ethyl-2-pyrrolidone and diisobutyl carbinol · MS 16: N- ethyl-2-pyrrolidone and propylene glycol monobutyl ether and diisobutyl ketone

MS17: N-ethyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate and dipropylene glycol monomethyl ether MS18: N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and diacetone alcohol, MS19: γ-butyrolactone And 1,3-dimethyl-2-imidazolidinone and ethyl-3-ethoxypropionate MS20: N-methyl-2-pyrrolidone and 3-methoxy-N, N-dimethylpropanamide and diacetone alcohol MS21: N-methyl-2-pyrrolidone, propylene carbonate and diacetone alcohol MS22: N-methyl-2-pyrrolidone, butyl glycolate and dipropylene glycol dimethyl ether

MS23: N-ethyl-2-pyrrolidone, diacetone alcohol and propylene glycol monobutyl ether MS24: N-ethyl-2-pyrrolidone, diacetone alcohol and ethyl 3-ethoxypropionate MS25: γ-valerolactone γ-butyrolactone and ethyl-3-ethoxypropionate MS26: N-methyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether MS27: N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and diethylene glycol butyl Methylether MS28: N-ethyl-2-pyrrolidone, diethylene glycol ethyl methylether and diisobutyl ketone MS29: N-methyl-2-pyrrolidone and diaceto Alcohol and propylene glycol diacetate

The liquid crystal aligning agent of the present invention may be used in combination with other solvents as the solvent. Other solvents which can be used here include, for example, N, N-dimethylpropyleneurea, N, N, 2-trimethylpropionamide, ethylene glycol monobutyl ether (butyl cellosolve), methyl methoxypropionate, isoamyl propio And solvents having a low surface tension as described in [0203] of WO2011 / 132751, and salts thereof. Isoamyl isobutyrate, diisopentyl ether, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, methyl 2-hydroxyisobutyrate, WO2011 / 132751 However, it is not limited to these.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is selected in consideration of viscosity, volatility, etc. However, the range of the solid content concentration which is particularly preferable depends on the method used when applying the liquid crystal aligning agent to the substrate. For example, in the case of the flexographic printing method, it is particularly preferable to set the solid concentration in the range of 3 to 9% by weight and thereby to set the solution viscosity in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by weight and thereby to set the solution viscosity in the range of 3 to 15 mPa · s.
The liquid crystal aligning agent of the present invention is a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslink having at least one substituent selected from a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. Or a crosslinkable compound having a polymerizable unsaturated bond may be introduced. The crosslinkable compound preferably has two or more of these substituents and polymerizable unsaturated bonds.

As a crosslinkable compound which has an epoxy group or an isocyanate group, the compound as described in [0087] of WO2015 / 008846 etc. are mentioned, for example.
Specific examples of the crosslinkable compound having an oxetane group include the crosslinkable compounds represented by Formula [4a] to Formula [4k] listed on pages 58 to 59 of WO2011 / 132751. More preferable specific examples include compounds of the formula [4b], the formula [4d] and the formula [4k] and n = 5.
Specific examples of the crosslinkable compound having a cyclocarbonate group include the crosslinkable compounds represented by Formula [5-1] to Formula [5-42] listed on pages 76 to 82 of WO 2012/014898. .

As a crosslinkable compound having at least one type of substituent selected from the group consisting of a hydroxyl group and an alkoxyl group, compounds described in [0090] to [0092] of WO 2015/008846, described in [0054] of WO 2015/072554 And compounds described in WO 2014/156314 [0126], and the like. More preferable specific examples are the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed in [181] to [185] of WO2011 / 132751, and described in [0054] of WO2015 / 072554 And compounds described in WO 2014/156314 [0126].
As a crosslinkable compound which has a polymerizable unsaturated bond, the compound as described in [0186] of WO2011 / 132751 is mentioned, for example.

In addition, the compound represented by the formula [5] described in [0188] of WO2011 / 132751 can also be used.
The above compounds are examples of crosslinkable compounds and are not limited thereto. Moreover, 1 type may be sufficient as the crosslinkable compound used for the liquid crystal aligning agent of this invention, and 2 or more types may be combined.
The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Among these, in order to allow the crosslinking reaction to proceed and to exert the desired effect, 0.1 to 100 parts by mass is preferable with respect to 100 parts by mass of all the polymer components. More preferably, it is 1 part by mass to 50 parts by mass.

The liquid crystal aligning agent of this invention can use the compound which improves the uniformity of film thickness of a liquid crystal aligning film at the time of apply | coating a liquid crystal aligning agent, and surface smoothness.
As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonion type surfactant etc. are mentioned. More specifically, for example, F-top EF301, EF303, EF352 (above, made by Tochem Products), Megafuck F171, F173, R-30 (above, made by Dainippon Ink Co., Ltd.), Florards FC430, FC431 (above, Sumitomo 3M Ltd.), Asahi Guard AG 710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.) and the like.
The proportion of these surfactants used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 parts by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal aligning agent. is there.

Furthermore, the liquid crystal aligning agent of the present invention is a compound that promotes charge transfer in the liquid crystal alignment film to promote charge loss of the device, and is disclosed on pages 69 to 73 of WO2011 / 132751 (released on October 10.2011) The nitrogen-containing heterocyclic amine compounds represented by Formula [M1] to Formula [M156] can also be added. The amine compound may be added directly to the liquid crystal aligning agent, but is preferably added after being made into a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, using a suitable solvent. The solvent is not particularly limited as long as it dissolves the specific polymer described above.
The liquid crystal aligning agent of the present invention includes, in addition to the above-mentioned poor solvents, crosslinkable compounds, compounds for improving film thickness uniformity and surface smoothness of a resin film or liquid crystal alignment film, and compounds for promoting charge loss, A dielectric or a conductive substance may be added for the purpose of changing the electrical properties such as the dielectric constant and the conductivity of the alignment film.

<Liquid crystal alignment film / Liquid crystal display element>
The liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation and the like. Moreover, in the case of the vertical alignment application etc., it can be used as a liquid crystal aligning film, without an orientation process. The substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed. In addition, in the reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can be used if it is only on one substrate, and in this case, a material that reflects light such as aluminum can also be used as an electrode.

The liquid crystal aligning agent may be applied by screen printing, offset printing, flexographic printing or inkjet method, dip method, roll coater method, slit coater method, spinner method or spray method, etc., but the production efficiency of the liquid crystal alignment film is enhanced. From the viewpoint, a method of coating by flexographic printing or an inkjet method is preferable.
30 to 300 ° C., preferably 30 to 300 ° C. depending on the solvent used for the liquid crystal aligning agent by a heating means such as a hot plate, a thermal circulation type oven or an IR (infrared) type oven after the liquid crystal aligning agent is applied on the substrate. The solvent can be evaporated at a temperature of -250 ° C. to form a liquid crystal alignment film. If the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display device, and if it is too thin, the reliability of the liquid crystal display device may be lowered. Is 10 to 100 nm.

When the display mode of the liquid crystal display element to be manufactured is a VA type, the coating film formed as described above can be used as it is as a liquid crystal alignment film, but rubbing treatment or the below-mentioned A PSA treatment may be performed. On the other hand, when the display mode of the liquid crystal display element to be manufactured is a vertical electric field system other than the VA type or a horizontal electric field system, rubbing processing, polarized ultraviolet irradiation, etc. are performed on the formed coating film Treatment to perform alignment treatment.
The liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and includes a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy ray and heat between the pair of substrates. It is preferably used also for a liquid crystal display device manufactured through a step of arranging a substance, polymerizing a polymerizable compound by at least one of irradiation of active energy rays and heating while applying a voltage between electrodes. Here, the applied voltage can be, for example, direct current or alternating current of 5 to 50 V. Moreover, as an active energy ray, an ultraviolet-ray is suitable. The ultraviolet light is ultraviolet light including light of a wavelength of 300 to 400 nm, preferably ultraviolet light including light of a wavelength of 310 to 360 nm. The irradiation dose of light is preferably 0.1 to 20 J / cm ² , more preferably 1 to 20 J / cm ² .

The liquid crystal display element described above controls the pretilt of liquid crystal molecules by the PSA method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, and after assembling a liquid crystal cell, ultraviolet light is applied to the photopolymerizable compound in a state where a predetermined voltage is applied to the liquid crystal layer. The pretilt of liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after removing the voltage, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. In addition, since the PSA method does not require rubbing treatment, it is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by rubbing treatment.

The liquid crystal display element of the present invention is a liquid crystal display element produced by a known method after producing a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above.
A liquid crystal cell is prepared by preparing a pair of substrates on which a liquid crystal alignment film is formed, dispersing spacers on the liquid crystal alignment film on one of the substrates so that the liquid crystal alignment film surface is on the inside, For example, there is a method in which a substrate of the above is attached and sealed by injecting a liquid crystal under reduced pressure, or a method in which a substrate is attached and sealed after liquid crystal is dropped on the liquid crystal alignment film surface to which spacers are dispersed.
The liquid crystal may be mixed with a polymerizable compound which is polymerized by ultraviolet irradiation or heat as described above. As the polymerizable compound, compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule, for example, the polymerizability as represented by the following formulas (M-1) to (M-3) Compounds are mentioned.

The amount of the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the alignment control of the liquid crystal can not be performed without polymerization of the polymerizable compound, and when the amount is more than 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display element The burn-in characteristics of the After producing the liquid crystal cell, while applying an alternating current or direct current voltage to the liquid crystal cell, heat or ultraviolet light is irradiated to polymerize the polymerizable compound. Thereby, the alignment of liquid crystal molecules can be controlled.
In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group which polymerizes between the pair of substrates by at least one of active energy ray and heat. A liquid crystal alignment film including the above may be disposed, and a liquid crystal display element manufactured through a process of applying a voltage between the electrodes, that is, the SC-PVA mode may also be used. Here, ultraviolet rays are preferable as the active energy ray. As the ultraviolet light, the ultraviolet light used in the above-mentioned PSA method can be applied including the preferred embodiment. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C., preferably 60 to 80 ° C. Also, ultraviolet light and heating may be performed simultaneously.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized from at least one of an active energy ray and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, a polymer containing a polymerizable group The method of using an ingredient is mentioned. Specific examples of the polymer containing a polymerizable group include polymers obtained by using a diamine having a function of polymerizing by the light irradiation.

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.
(Specific diamine)
W-A1: compound represented by the formula [W-A1] W-A2: compound represented by the formula [W-A2] W-A3: compound represented by the formula [W-A3]

(Other side chain type diamine compounds)
A1: a compound represented by the formula [A1]

C1: compound represented by Formula [C1], C2: compound represented by Formula [C2] C3: compound represented by Formula [C3], C4: compound represented by Formula [C4]

(Tetracarboxylic acid compound)
D1: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride D3: pyromellitic anhydride , D4: 2, 3, 5-tricarboxycyclopentylacetic acid dianhydride

<Solvent A>
NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone DMI: 1,3-dimethyl-2-imidazolidinone, GVL: γ-valerolactone GBL: γ-butyrolactone, CHP: N-cyclohexyl -2-pyrrolidone NHP: N- (n-hexyl) -2-pyrrolidone,
3 MMP: 3-methoxy-N, N-dimethylpropanamide

<Solvent B>
IAL: isoamyl lactate, nBL: n-butyl lactate, HBA: butyl glycolate EEP: ethyl 3-ethoxy propionate, DIBC: diisobutyl carbinol DIBK: diisobutyl ketone, DAA: diacetone alcohol BCA: ethylene glycol monobutyl ether acetate PB: propylene glycol monobutyl ether, PGDA: propylene glycol diacetate PC: propylene carbonate, DEME: diethylene glycol methyl ethyl ether DEDE: diethylene glycol diethyl ether DPM: dipropylene glycol monomethyl ether DME: dipropylene glycol dimethyl ether DEBM: diethylene glycol butyl methyl ether

(Molecular weight measurement)
The molecular weight of the polyimide precursor and the polyimide is as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex Co., Ltd.) It measured like.
Column temperature: 50 ° C
Eluent: N, N'-dimethylformamide (as additive, 30 mmol / L (liter) of lithium bromide-hydrate (LiBr · H ₂ O), 30 mmol of phosphoric acid / anhydrous crystal (o-phosphoric acid) / L, tetrahydrofuran (THF) 10 ml / L, flow rate: 1.0 ml / min Standard sample for preparation of calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) ) (Manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

(Measurement of imidation rate)
20 mg of polyimide powder is placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) The mixture (0.53 ml) was added and sonicated to dissolve completely. This solution was subjected to proton NMR measurement at 500 MHz with an NMR measurement device (JNW-ECA 500) (manufactured by Nippon Denshi Datum Co., Ltd.). The imidation ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid appearing around 9.5 to 10.0 ppm It calculated | required by the following formula using integration value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from the NH group of the amic acid, y is a peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidation ratio is 0%) The ratio of the number of reference protons to.

(viscosity)
The viscosity of the polyimide-based polymer was measured using a E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample volume of 1.1 mL, corn rotor TE-1 (1 ° 34 ', R24), and a temperature of 25 ° C. did.

<Synthesis of Specific Diamine>
W-A1 to W-A3 are novel compounds which have not been published in literatures and so forth, and were synthesized as follows.
The products described in the following Synthesis Examples 1 to 3 were identified by ¹ H-NMR analysis under the following conditions.
Equipment: Varian NMR System 400 NB (400 MHz).
Measurement solvents: CDCl _3, DMSO-d ₆ .
Reference material: tetramethylsilane (TMS) (δ 0.0 ppm for ¹ H).

Synthesis Example 1 Synthesis of W-A1

<Synthesis of Compound [1], [2]>
Into a reaction vessel, tetrahydrofuran (165.6 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (41.1 g, 135 mmol) and triethylamine (31.5 g) are added, and a nitrogen atmosphere is provided. Methanesulfonyl chloride (33.2 g) was added dropwise under ice-cold conditions and allowed to react for 1 hour to obtain compound [1]. Subsequently, p- (trans-4-heptylcyclohexyl) phenol (77.8 g) dissolved in tetrahydrofuran (246.6 g) is added, and after stirring for 1 hour at 40 ° C., water dissolved in pure water (233 g) Potassium oxide (41.0 g) was added at the same temperature and allowed to react for 21 hours. After completion of the reaction, 1.0 M aqueous hydrochloric acid solution (311 ml) and pure water (1050 g) were added to precipitate a crude product, and the crude product was recovered by filtration. The obtained crude product was dissolved by heating in tetrahydrofuran (574 g) at 50 ° C., methanol (328 g) was added to precipitate crystals, and filtration and drying gave a compound [2] (yield: 97.9 g, yield) Rate: 89%).

¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6 H), 0.96-1.05 ppm (m, 4 H), 1.19-1.39 ppm (m, 30 H), 1.80-1.85 ppm (m, 8 H), 2.33-2.40 ppm (m, 2 H), 4.77 ppm (s, 4 H), 6.66-6.70 ppm (m, 4 H), 7. 02-7.06 ppm (m, 4 H), 7.40 ppm (d, 2 H, 8.4), 8. 25 ppm (dd, 2 H, J = 2.4 Hz, J = 8.4 Hz), 8.54 ppm (d , 2H, J = 2.4 Hz).

<Composition of W-A1>
Tetrahydrofuran (1783 g), compound [2] (74.3 g, 90.9 mmol) and 3% platinum carbon (5.94 g) were added to a reaction vessel and reacted under hydrogen atmosphere at room temperature. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to a total internal weight of 145 g. Subsequently, methanol (297 g) was added to the concentrated solution, the mixture was stirred under ice cooling, filtered and dried to obtain W-A1 (yield: 59.2 g, 86%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6 H), 0.96-1.05 ppm (m, 4 H), 1.19-1.40 ppm (m, 30 H), 1.81-1.84 ppm (m, 8 H), 2.32-2.38 ppm (m, 2 H), 3.67 ppm (s, 4 H), 4.69 ppm (d, 2 H, J = 12.0 Hz), 4.74 ppm (d, 2 H, J = 11.6 Hz), 6.62 ppm (dd, 2 H, J = 2.4 Hz, J = 8.0 Hz), 6.70-6.75 ppm (m, 4 H), 6 91 ppm (d, 2 H, J = 2.4 Hz), 6.97-7.03 ppm (m, 6 H).

Synthesis Example 2 Synthesis of W-A2

<Synthesis of Compound [3]>
Tetrahydrofuran (327.2 g), 4,4'-dinitro-2,2'-diphenic acid (40.9 g, 123 mmol) and p- (trans-4-heptylcyclohexyl) phenol (72.1 g) in a reaction vessel, 4 -Dimethylaminopyridine (1.50 g) was added, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (56.6 g) was added under nitrogen atmosphere and room temperature conditions, and reacted for 3 hours. After completion of the reaction, the reaction solution was poured into pure water (1226 g) to precipitate a crude product, which was recovered by filtration. Subsequently, the crude product was slurry-washed with methanol (245 g), filtered, and the obtained crude product was dissolved by heating in tetrahydrofuran (245 g) at 60 ° C. The insoluble matter is removed by filtration, and the internal weight is reduced to 232 g by vacuum concentration, and then methanol (163 g) is added to precipitate crystals, and the mixture is stirred under ice-cold conditions, filtered and dried to obtain a compound [3] (Yield: 73.9 g, 71%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6 H), 0.98-1.06 ppm (m, 4 H), 1.18-1.43 ppm (m, 30 H), 1.83-1.86 ppm (m, 8 H), 2.41-2. 47 ppm (m, 2 H), 6. 89-6. 92 ppm (m, 4 H), 7. 17-7. 20 ppm (m, 4 H) ), 7.48 ppm (d, 2 H, 8.4), 8. 49 ppm (dd, 2 H, J = 2.4 Hz, J = 8.4 Hz), 9.11 ppm (d, 2 H, J = 2.4 Hz) .

<Composition of W-A2>
Tetrahydrofuran (443 g) and methanol (73.9 g), compound [3] (73.9 g, 87.4 mmol) and 5% palladium carbon (8.80 g) were added to a reaction vessel and reacted under hydrogen atmosphere at room temperature. After completion of the reaction, palladium carbon was removed by filtration and concentrated under reduced pressure to a total internal weight of 171 g. Subsequently, methanol (222 g) was added to the concentrated solution to precipitate crystals, and the mixture was stirred under ice cooling, filtered and dried to obtain W-A2 (yield: 66.6 g, yield: 97%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.90 ppm (m, 6 H), 0.96-1.05 ppm (m, 4 H), 1.17-1. 42 ppm (m, 30 H), 1.82-1.85 ppm (m, 8 H), 2.38-2.44 ppm (m, 2 H), 3. 77 ppm (s, 4 H), 6. 80-6. 87 ppm (m, 6 H), 7. 08-7.13 ppm (m, 6 H), 7.41 ppm (d, 2 H, J = 2.4 Hz).

Synthesis Example 3 Synthesis of W-A3

<Synthesis of Compound [4], [5]>
Toluene (366 g), 4- (trans-4-heptylcyclohexyl) -benzoic acid (73.1 g, 242 mmol) and N, N-dimethylformamide (0.73 g) were added to a reaction vessel, and a nitrogen atmosphere was applied at 50 ° C. Thionyl chloride (35.9 g) was added dropwise. After dropping, the mixture was reacted at the same temperature for 1 hour, and the reaction solution was concentrated under reduced pressure to obtain compound [4]. Subsequently, 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (35.0 g, 115 mmol) and triethylamine (26.8 g) are charged in tetrahydrofuran (210 g), and nitrogen atmosphere ice is used. Under cold conditions, the compound [4] dissolved in tetrahydrofuran (73. 1 g) was dropped. After completion of the dropwise addition, the reaction was allowed to proceed to room temperature for 18 hours. After completion of the reaction, the triethylamine hydrochloride was removed by filtration and then concentrated under reduced pressure to obtain an oily compound. The resulting oily compound was added to pure water (1015 g) to precipitate crystals, and the crude product was recovered by filtration. Subsequently, the obtained crude product was slurry-washed with methanol (291 g) at room temperature, slurry-washed with ethyl acetate (175 g) at room temperature, filtered and dried to obtain compound [5] (yield: 92.7 g, Rate: 92%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.89-0.91 ppm (m, 6 H), 0.99-1.09 ppm (m, 4 H), 1.20-1. 47 ppm (m, 30 H), 1.85-1.88 ppm (m, 8 H), 2.46-2.52 ppm (m, 2 H), 5.14 ppm (s, 4 H), 7.23-7.26 ppm (m, 4 H), 7. 45 ppm (d, 2 H, J = 8.4 Hz), 7.8 3-7. 86 ppm (m, 4 H), 8. 27 ppm (dd, 2 H, J = 2.4 Hz, J = 8.4 Hz), 8. 47 ppm (D, 2H, J = 2.4 Hz).

Synthesis of W-A3
Tetrahydrofuran (484 g) and methanol (161 g), compound [5] (80.5 g, 92.2 mmol) and 3% platinum carbon (6.44 g) were added to a reaction vessel and reacted under hydrogen atmosphere at room temperature. After completion of the reaction, platinum carbon was removed by filtration, and the solvent was removed by concentration under reduced pressure to a total internal weight of 96.6 g. Subsequently, methanol (322 g) was added to the concentrated solution to precipitate crystals, and the mixture was stirred under ice cooling and filtered to obtain a crude product. Subsequently, the obtained crude product was dissolved by heating at 60 ° C. with ethyl acetate (322 g), methanol (700 g) was added, crystals were precipitated under ice-cold conditions, filtered and dried to obtain W-A3. (Yield: 67.9 g, yield: 91%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.87-0.91 ppm (m, 6 H), 0.98-1.08 ppm (m, 4 H), 1.19-1.47 ppm (m, 30 H), 1.84-1.87 ppm (m, 8 H), 2.44-2.51 ppm (m, 2 H), 3.71 ppm (s, 4 H), 5.02 ppm (d, 2 H, J = 12.8 Hz), 5.09 ppm (d, 2 H, J = 12.4 Hz), 6.66 ppm (dd, 2 H, J = 2.4 Hz, J = 8.0 Hz), 6.84 ppm (d, 2 H, J = 2.4 Hz) , 7.03 ppm (d, 2 H, J = 8.0 Hz), 7.19-7.25 ppm (m, 4 H), 7.89-7.92 ppm (m, 4 H).

<Synthesis of specified polymer>
Synthesis Example 1
D2 (2.50 g, 10.0 mmol), W-A1 (3.03 g, 4.00 mmol), and C1 (1.73 g, 16.0 mmol) in NMP (18.1 g) and NEP (18.1 g) After dissolving in mixed solvent and reacting at 60 ° C for 3 hours, D1 (1.78 g, 9.10 mmol) is added and allowed to react at 40 ° C for 3 hours to obtain a 20 mass% resin solid content concentration of polyamic acid solution (viscosity : 840 mPa · s) was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5 mass%, acetic anhydride (4.43 g) and pyridine (1.37 g) are added as an imidation catalyst, and the reaction is carried out at 80 ° C. It was allowed to react for 3 hours. The reaction solution was poured into methanol (382 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (PI-1). The imidation ratio of this polyimide was 76.4%, Mn was 16,165, and Mw was 49, 988.

Synthesis Example 2
D2 (2.50 g, 10.0 mmol), W-A2 (3.14 g, 4.00 mmol), and C1 (1.84 g, 16.0 mmol) in NMP (11.1 g) and PC (25.8 g) After dissolving in a mixed solvent and reacting at 60 ° C. for 3 hours, D1 (1.84 g, 9.38 mmol) is added and allowed to react at 40 ° C. for 3 hours, and a polyamic acid solution (resin viscosity 20% by mass solid content) : 658 mPa · s) was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5 mass%, acetic anhydride (4.38 g) and pyridine (1.36 g) are added as an imidation catalyst, and the reaction is carried out at 80.degree. It was allowed to react for 3 hours. The reaction solution was poured into methanol (382 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (PI-2). The imidation ratio of this polyimide was 75.8%, Mn was 15,430, and Mw was 45,756.

Synthesis Example 3
D2 (2.50 g, 10.0 mmol), W-A3 (3.25 g, 4.00 mmol), and C1 (1.73 g, 16.0 mmol) are mixed in GBL (37.3 g), at 60 ° C. After reacting for 3 hours, D1 (1.84 g, 9.38 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution (viscosity: 656 mPa · s) having a resin solid concentration of 20% by mass.
GBL was added to the obtained polyamic acid solution (20.0 g) and diluted to 6.5 mass%, then acetic anhydride (4.32 g) and pyridine (1.34 g) were added as an imidization catalyst, and the mixture was heated to 80 ° C. It was allowed to react for 3 hours. The reaction solution was poured into methanol (382 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (PI-3). The imidation ratio of this polyimide was 74.7%, Mn was 13,340, and Mw was 41,948.

[Comparative Example 1]
A1 (0.63 g, 1.2 mmol), C4 (2.36 g, 21.8 mmol) and NMP were added to dissolve the diamine, then D4 (4.12 g, 22.4 mmol) and NMP were added to set the concentration 20 It was mass%. After reacting at 60 ° C. for 3 hours, a polyamic acid solution (viscosity: 250 mPa · s) having a resin solid concentration of 20% by mass was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5 mass%, acetic anhydride (4.64 g) and pyridine (1.44 g) are added as an imidation catalyst, and the reaction is carried out at 80 ° C. It was allowed to react for 3 hours. The reaction solution was poured into methanol (382 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (PI-R1). The imidation ratio of this polyimide was 75%, Mn was 13,100, and Mw was 33,200.

[Comparison Example 2]
A polyimide powder (PI-R2) was obtained in the same manner as in the polymer comparative synthesis example 1 except that the type and composition of the diamine used were changed as described in Table 1 below. The imidation ratio of this polyimide was 55%, Mn was 10,500, and Mw was 20,900.

Example 1
NMP was added to the polyimide (PI-1) obtained in the above Polymer Synthesis Example 1 until the amount of the polyimide was 12% by mass, and then stirred at 70 ° C. for 24 hours for dissolution. Next, the mixture was diluted with a mixed solution of NMP and PB to obtain a liquid crystal aligning agent (S-1) having a solid content concentration of 3% by mass and a solvent composition of NMP: PB = 50: 50 (mass ratio). This was subjected to the following evaluation of filterability, printability and liquid crystal alignment.

<Evaluation of filterability>
The yield after filtering 100 ml of a liquid crystal aligning agent with a syringe filter (manufactured by Whatman) with a pore diameter of 0.2 μm and a diameter of 13 mm was measured, and the filterability was judged according to the following criteria.
(Evaluation criteria)
Excellent: The yield of the liquid crystal aligning agent is at least 40 ml: the yield of the liquid crystal aligning agent is at least 5 ml and less than 40 ml, the yield of the liquid crystal aligning agent is less than 5 ml

<Evaluation of printability>
The liquid crystal aligning agent obtained by the above evaluation of filterability was applied on an ITO surface of a 40 mm × 30 mm ITO electrode-attached glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) as an inkjet coater HIS-200 ( The coating film was produced using Hitachi plant technology company make). The coating conditions at this time were a coating area of 70 mm × 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, and a coating speed of 40 mm / sec. After standing for 60 seconds after application, the filterability was judged according to the following criteria.
(Evaluation criteria)
Excellent: neither pinhole nor reed can be seen.
Good: either a pinhole or a reed can be seen.
Impossible: Both pinhole and reed can be seen.

<Manufacture of liquid crystal cell>
After coating is performed under the conditions described in the evaluation of the printability, heat treatment is performed at 70 ° C. for 90 seconds on a hot plate at 230 ° C. for 30 minutes in a heat circulating clean oven, and the film thickness is 80 nm The ITO substrate with a liquid crystal alignment film of Two ITO substrates with a liquid crystal alignment film thus obtained were prepared, and a bead spacer (with Jiro Catalyst Chemicals Co., Ltd., spherical sphere, SW-D1) having a diameter of 4 μm was coated on the liquid crystal alignment film surface of one of the substrates.
Next, the periphery was coated with a sealing agent (Mitsui Chemical Co., Ltd., XN-1500T). Next, with the surface on the side on which the liquid crystal alignment film of the other substrate was formed facing inside, and pasted to the previous substrate, the sealing material was cured to produce an empty cell. A negative liquid crystal MLC-3023 (trade name of Merck & Co., Inc.) was injected into this empty cell by a pressure reduction injection method to prepare a liquid crystal cell.
Then, in the resulting state of applying a DC voltage of 15V to the liquid crystal cell, using an ultraviolet irradiation apparatus using a high pressure mercury lamp as a light source, ultraviolet rays through a band-pass filter having a wavelength of 365 nm 15 J / cm ² was irradiated A vertical alignment type liquid crystal display device was obtained. In addition, the UV-35 light receiver was connected to UV-M03A manufactured by ORC and used for measurement of the ultraviolet irradiation amount.

<Evaluation of liquid crystal alignment>
The liquid crystal alignment of the liquid crystal display element was observed with a polarization microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to check whether the liquid crystal was vertically aligned. Specifically, those in which no bright spots due to defects due to the liquid crystal flow or alignment defects were found were considered to be good.
[Examples 2 to 30 and Comparative Examples 1 to 4]
Liquid crystal aligning agents (S-2) to (S-30), in the same manner as in Example 1, except that the type and composition of the polymer and solvent used were changed as described in Table 2 below. (RS-1) to (RS-4) were prepared respectively. Moreover, the filterability was evaluated about each liquid crystal aligning agent. Among these, liquid crystal aligning agents (S-2) to (S-3), (S-6) to (S-7), (S-9) to (S-19), (S-23) to (S-23) In the same manner as in Example 1, S-30) was applied to a glass substrate with an ITO electrode, and the printability and the liquid crystal alignment were evaluated. With regard to the liquid crystal aligning agents (S-4), (S-5), (S-8), and (S-20) to (S-22), alignment film printing machines (“ONG Stromer” manufactured by Nissha Printing Co., Ltd.) The printability and the liquid crystal alignment were evaluated in the same manner as in Example 1 except that the coating of the liquid crystal alignment agent was performed using the above. The results are shown in Table 2 below.

In Table 2, the numerical value of the polymer indicates the blending ratio (mass ratio) of each polymer to the total amount of the polymer used for the preparation of the liquid crystal aligning agent. The numerical value of the solvent composition indicates the blending ratio (mass ratio) of each compound to the total amount of the solvent used for the preparation of the liquid crystal aligning agent.
As can be seen from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the example has a liquid crystal alignment film that is superior in liquid crystal alignment to the liquid crystal alignment film obtained from the liquid crystal alignment agent of the comparative example Can. Moreover, the liquid crystal aligning agent of an Example can obtain the liquid crystal aligning agent which is excellent in filterability and printability compared with the liquid crystal aligning agent of a comparative example.

The liquid crystal aligning agent of the present invention is excellent in filterability and printability, and can obtain a liquid crystal alignment film excellent in liquid crystal alignment. In addition, a liquid crystal display device having this liquid crystal alignment film enables high quality image display, and can be suitably used for a large screen and high definition liquid crystal television, etc., and in particular, TN elements, STN elements, TFT liquid crystal elements, etc. It is useful for a vertical alignment type liquid crystal display device.

The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2017-223900 filed on Nov. 21, 2017 are hereby incorporated by reference as the disclosure of the specification of the present invention. , Is to introduce.

Claims (17)

1. At least one polymer selected from the group consisting of a polyamic acid or a polyamic acid ester having a structure of the following formula [1], and a polyimide which is an imidized product thereof;
   At least one solvent A selected from the group consisting of the following formulas (d-1) to (d-5) and the following formula (e), and the group consisting of the following formulas (B-1) to (B-4) A solvent containing at least one solvent B to be selected;
   Liquid crystal aligning agent characterized by containing.
   

   

   In formula [1], X is a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-, -NHCO-, -COO-,-(CH ₂ ) _m -,- _{SO 2 -, - O- (CH} 2) m -O -, - O-C (CH 3) 2 -, - CO- (CH 2) m -, - NH- (CH 2) m -, - SO 2 _{- (CH 2) m -,} - CONH- (CH 2) m -, - CONH- (CH 2) m -NHCO- and -COO- _{(CH 2)} m ₂ divalent organic radical from the group consisting of -OCO- And m represents an integer of 1 to 8. Two Y independently represent a side chain structure derived from the following formulas [S1] to [S3] or tocopherol.
   

   

   However, X ¹ and X ² are independently a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -COO-, -OCO-, or ((CH ₂ ) _a1 -A ₁ ) _m1- (a1 represents an integer of 1 to 15, and A ₁ represents an oxygen atom, -COO or OCO is shown, and m ₁ is 1 to 2). G ¹ and G ^{2 each} independently represent a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms, The optional hydrogen atom above is an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms or a fluorine atom And may be substituted. m and n are independently an integer of 0 to 3, and the sum thereof is 1 to 4. R ¹ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxyalkyl having 2 to 20 carbons, and any hydrogen in these groups may be substituted by a fluorine atom.
   X ³ represents a single bond, -CONH-, -NHCO-, -CON (CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or OCO-, and R ² represents carbon The alkyl is an alkyl of 1 to 20 or an alkoxyalkyl of 2 to 20 carbons, and any hydrogen in these groups may be substituted by a fluorine atom.
   X ⁴ represents —CONH—, —NHCO—, —O—, —COO— or OCO—, and R ³ represents a structure having a steroid skeleton.
   

   

   However, R _1a represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a monovalent group having —O— between carbon-carbon bonds in the hydrocarbon group. R _2a and R _2b independently represent an alkyl group having 1 to 6 carbon atoms. R _3a represents a methyl group or an ethyl group, R _5a represents an alkyl group having 1 to 6 carbon atoms, and R _5b and R _5c independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms Or a monovalent group having —O— between carbon-carbon bonds of the hydrocarbon group. r _1a and r _1b independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 2 to 6, and n is an integer of 1 or 2.
   

   

   However, _Ap1 and _Ap2 independently represent a C1-C6 alkyl group, _Ap5 represents a hydrogen atom or a C1-C6 alkyl group, and _Aq1 represents -O- or -COO- A _q2 represents a single bond or a carbonyl group, A _q3 represents -O-, and A _k1 , A _k2 and A _k6 independently represent an alkanediyl group having 2 to 4 carbon atoms, n1 is 1 Indicates ~ 3. A _p3 and A _p4 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A _x is -C (OH) R _a- , -CHR _b- (R _a , R _b is independently represents a hydrogen, a methyl group or an ethyl group), -. CO-, or -COO -. * (* is showing the binding position of the _{a k4) indicates,} a _{k4, a k5} carbon atoms independently 1 And an alkyl group of -4 is shown. m is an integer of 0 or 1, and n4 is an integer of 1 to 3. However, the case where n 4 is 1, A _{k 6} is an alkanediyl group having 2 carbon atoms, and A _{p 5} is an alkyl group having 4 carbon atoms is excluded.
2. The X in the formula [1] is a single bond, -O-, -NH-, or -O- (CH ₂ ) _m -O- (m represents an integer of 1 to 8). The liquid crystal aligning agent as described in.
3. Solvent A is N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N- (n-hexyl) -2- Pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, 3-butoxy-N, N-dimethylpropanamide, The liquid crystal aligning agent according to claim 1 or 2, which is at least one solvent selected from the group consisting of 3-methoxy-N, N-dimethylpropanamide, ethylene carbonate, and propylene carbonate.
4. _{A k1} in Formula (B-1) is an ethylene group, a 1,3-propanediyl group, or a 1,4-butanediyl group, the liquid crystal alignment agent according to any one of claims 1 to 3.
5. The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the content ratio of the solvent A in the solvent is 5 to 99% by mass, and the content ratio of the solvent B in the solvent is 1 to 95% by mass. .
6. Solvent group B includes: diisobutyl ketone, diisobutyl carbinol, 4,6-dimethyl-2-heptanone, diacetone alcohol, n-butyl lactate, isoamyl lactate, butyl glycolate, ethyl 3-ethoxypropionate, propylene glycol monomethyl Ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl propyl ether, diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate and propylene glycol It consists of diacetate At least one solvent selected from the liquid crystal alignment agent according to any one of claims 1 to 5.
7. The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the solvent contains one combination selected from the group consisting of ms1 to ms12 below.
   Ms1: N-methyl-2-pyrrolidone and propylene glycol monobutyl ether ms2: N-methyl-2-pyrrolidone and dipropylene glycol monomethyl ether ms3: N-methyl-2-pyrrolidone and dipropylene glycol dimethyl ether ms4: N -Methyl-2-pyrrolidone and propylene glycol monomethyl ether-ms5: N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether-ms6: N-ethyl-2-pyrrolidone and dipropylene glycol monomethyl ether-ms 7: N-ethyl-2 -Pyrrolidone and dipropylene glycol dimethyl ether · ms 8: N-ethyl 2-pyrrolidone and propylene glycol monomethyl ether · ms 9: N-methyl 2-pyrrolidone and isoamyl lactate s10: N-methyl-2-pyrrolidone and diacetone alcohol · ms11: .gamma.-butyrolactone and ethyl-3-ethoxypropionate · MS 12: N-ethyl-2-pyrrolidone and diisobutyl ketone
8. The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the solvent contains three or more kinds consisting of one or more kinds of solvent A and one or more kinds of solvent B.
9. The liquid crystal aligning agent according to claim 8, wherein the solvent comprises one combination selected from the group consisting of MS1 to MS23 below.
   ・ MS1: N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether ・ MS2: N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol monomethyl ether ・ MS3: N-methyl-2-pyrrolidone γ-butyrolactone and dipropylene glycol dimethyl ether · MS4: N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether · MS5: N-ethyl 2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether · MS 6: N -Ethyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol monomethyl ether · MS 7: N-ethyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether Tell MS8: N-ethyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monomethyl ether MS9: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and propylene glycol monobutyl ether MS10: N-ethyl- 2-Pyrrolidone, N-Methyl-2-Pyrrolidone, Dipropylene Glycol Monomethyl Ether, MS 11: N-Ethyl-2-Pyrrolidone, N-Methyl-2-Pyrrolidone, Dipropylene Glycol Dimethyl Ether, MS 12: N-Ethyl-2-Pyrrolidone And N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monomethyl ether · MS13: N-methyl 2-pyrrolidone and diacetone alcohol and diethylene glycol diethyl ether · MS 14: N-methyl- -Pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether MS15: N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone and diisobutylcarbinol MS16: N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether And diisobutyl ketone MS17: N-ethyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate and dipropylene glycol monomethyl ether MS18: N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and diacetone alcohol MS19: γ-butyrolactone and 1,3-dimethyl-2-imidazolidinone and ethyl-3-ethoxypropionate MS20: N-methyl-2-pyrrolidone and 3-methoxy-N, N Dimethylpropanamide and diacetone alcohol MS21: N-methyl-2-pyrrolidone and propylene carbonate and diacetone alcohol MS22: N-methyl-2-pyrrolidone and butyl glycolate and dipropylene glycol dimethyl ether MS23: N-ethyl- 2-Pyrrolidone, diacetone alcohol, propylene glycol monobutyl ether, MS 24: N-ethyl 2-pyrrolidone, diacetone alcohol, ethyl 3-ethoxy propionate, MS 25: γ-valerolactone, γ-butyrolactone, ethyl-3 -Ethoxypropionate MS26: N-methyl-2-pyrrolidone, diethylene glycol diethyl ether and dipropylene glycol monomethyl ether MS27: N-methyl-2-pyrrolidone B propylene glycol monobutyl ether and diethylene glycol butyl methyl ether · MS28: N-ethyl-2-pyrrolidone and diethylene glycol ethyl methyl ether and diisobutyl ketone · MS29: N- methyl-2-pyrrolidone and diacetone alcohol and propylene glycol diacetate
10. The polyamic acid or polyamic acid ester is a tetracarboxylic acid compound, a diamine containing a diamine represented by the following formula [2], or a diamine compound containing a diamine represented by the following formula [2] and another diamine: The liquid crystal aligning agent according to any one of claims 1 to 9, which is obtained by reacting.
    

    

    However, X and Y are synonymous with X and Y in said Formula [1].
11. The liquid crystal aligning agent of Claim 10 whose said other diamine is a diamine which has a function which generate | occur | produces superposition | polymerization or a radical by light irradiation.
12. The liquid crystal aligning agent of Claim 10 or 11 in which the said tetracarboxylic acid compound contains the tetracarboxylic dianhydride of the structure shown by following formula [4], or its derivative (s).
    

    

    Here, Z represents a structure selected from the following [4a] to [4k].
    

    

    However, * 1 is a bonding position bonded to one acid anhydride group, and * 2 is a bonding position bonded to the other acid anhydride group. In the formula [4a], Z ¹ to Z ⁴ independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring.
13. The tetracarboxylic acid compound according to claim 12, wherein the tetracarboxylic acid compound contains 5 mol% or more of tetracarboxylic acid dianhydride having a structure represented by the following formula [4] or a derivative thereof in 100 mol% of the tetracarboxylic acid compound. Liquid crystal aligning agent.
14. A method for producing a liquid crystal alignment film, which comprises applying the liquid crystal aligning agent according to any one of claims 1 to 13 on the surface of a substrate by flexographic printing or an ink jet method, and baking it.
15. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 13.
16. A liquid crystal composition comprising a liquid crystal layer is provided between a pair of substrates provided with an electrode, and a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates. The liquid crystal alignment film according to claim 15, which is used for a liquid crystal display device manufactured through the step of polymerizing the polymerizable compound while applying a voltage between them.
17. The liquid crystal display element which comprises the liquid crystal aligning film of Claim 15.