KR20210090158A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same - Google Patents

Abstract

(R¹, R²¹, R²² 는, 각각 독립적으로 수소 원자 또는 메틸기를 나타내고, R⁵¹, R⁵² 는, 각각 독립적으로 수소 원자 또는 메틸기를 나타낸다. S_p3, S_p4 는, 2 가의 유기기를 나타낸다. A₅ 는 단결합 또는 2 가의 유기기를 나타낸다.) The liquid crystal aligning agent from which the liquid crystal aligning film which had favorable liquid-crystal orientation and the accumulation|storage charge relaxation characteristic is provided is provided.
A diamine component containing at least one diamine selected from the group consisting of a diamine having a partial skeleton represented by the following formulas (ND-1) to (ND-4) and a diamine represented by (ND-5); What contains at least one polymer (P1) selected from the group consisting of a terminal-capped first polyimide precursor and an imidized polymer thereof, obtained by subjecting a carboxylic acid component to a polymerization reaction and reacting with an end-blocking agent The liquid crystal aligning agent characterized by the above-mentioned.

(R ¹ , R ²¹ , R ²² each independently represents a hydrogen atom or a methyl group, R ⁵¹ , R ⁵² each independently represents a hydrogen atom or a methyl group. S _p3 , S _p4 represents a divalent organic group A ₅ represents a single bond or a divalent organic group.)

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same

This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and the liquid crystal display element using the same.

Currently, a polyimide film is used for the liquid crystal aligning film used for a liquid crystal display element in many cases. The liquid crystal aligning film of this polyimide film apply|coats the solution of the polyamic acid which is a precursor of a polyimide, or the solution of a solvent-soluble polyimide to a board|substrate, The film obtained by baking is manufactured by the method of orientation processing, such as a rubbing process. Generally, this polyamic acid and a solvent-soluble polyimide are manufactured by polycondensation reaction of tetracarboxylic-acid derivatives, such as tetracarboxylic dianhydride, and a diamine compound.

In order to improve the liquid-crystal orientation in the liquid crystal aligning film obtained from a polyamic acid or a polyimide, and the characteristic which eliminates the residual image which generate|occur|produces with application of a voltage, sealing the terminal of a polyamic acid and a polyimide is proposed. .

For example, in patent document 1, in order to shorten the residual image erasing time in a liquid crystal display element, the terminal-capsulation polymer (1) selected from terminal-blocking polyamic acid etc., and the terminal-uncapsulated polymer chosen from the un-terminal polyamic acid etc. As a liquid crystal aligning agent containing (2), it is described using the liquid crystal aligning agent characterized by the ratio of the terminal sealing polymer (1) to the whole polymer in this liquid crystal aligning agent being 5 to 60 weight% .

Moreover, in patent document 2, in order not to generate|occur|produce a DC afterimage in a liquid crystal display element, it describes using the varnish for photo-alignment films containing the 1st polyamic acid type compound which has a terminal skeleton which does not contain a primary amino group. has been

Japanese Patent Publication No. 4336922 Japanese Laid-Open Patent Publication No. 2017-90781

In recent years, performance improvement of a liquid crystal display element, enlargement of a large area, power saving of a display device, etc. progress, In addition, a liquid crystal display element comes to be used in various environments, and the characteristic calculated|required of a liquid crystal aligning film has also become strict. In particular, as use of a liquid crystal display element advances, the problem that an electric charge accumulates in a liquid crystal aligning film, and the problem that it becomes difficult to ensure favorable liquid-crystal orientation are becoming remarkable.

When an electric charge accumulates in a liquid crystal aligning film, it will become easy to generate|occur|produce an afterimage also for a short drive. Moreover, when favorable liquid-crystal orientation cannot be ensured, it will become easy to generate|occur|produce light leakage and orientation defect. For this reason, although there exists a strong request|requirement with respect to favorable accumulation|storage charge relaxation characteristic and liquid-crystal orientation, the conventionally proposed technique may not fully satisfy these both requirements.

This invention was made in view of said circumstances, and aims at providing the liquid crystal aligning agent from which the liquid crystal aligning film which had favorable liquid-crystal orientation and the accumulation|storage charge relaxation characteristic is obtained.

As a result of these inventors earnestly examining, using specific diamine, the liquid crystal aligning agent containing the specific polyimide-type polymer by which the terminal was sealed discovered that said subject could be achieved.

This invention is based on such knowledge, It exists in invention containing the liquid crystal aligning agent which makes the following summary.

A diamine component containing at least one diamine selected from the group consisting of a diamine having a partial skeleton represented by any of the following formulas (ND-1) to (ND-4) and a diamine represented by (ND-5); contains at least one polymer (P1) selected from the group consisting of a terminal-capped first polyimide precursor and an imidized polymer thereof, obtained by polymerizing a tetracarboxylic acid component and reacting with a terminal blocker. Liquid crystal aligning agent characterized in that.

[Formula 1]

(R ¹ , R ²¹ , and R ²² each independently represent a hydrogen atom or a methyl group, and R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a methyl group. S _p3 , S _p4 are each independently A divalent organic group is represented. A ₅ represents a single bond or a divalent organic group.)

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, the liquid crystal aligning film which has favorable liquid-crystal orientation and a storage-charge relaxation characteristic can be obtained.

<Polymer (P1)>

The liquid crystal aligning agent of this invention is at least 1 sort(s) chosen from the group which consists of diamine which has a partial skeleton represented by any one of said Formula (ND-1) - (ND-4), and diamine represented by (ND-5) At least one selected from the group consisting of a terminal-capped first polyimide precursor obtained by polymerizing a diamine component containing diamine and a tetracarboxylic acid component and reacting with a terminal blocker, and an imidized polymer thereof. of polymer (P1).

Hereinafter, each component used as a raw material of a polymer (P1) is demonstrated.

(specific diamines)

Specific diamine is at least 1 sort(s) of diamine chosen from the group which consists of a diamine which has a partial skeleton represented by following formula (ND-1) - (ND-4), and the diamine represented by either (ND-5).

[Formula 2]

In the formula, R ¹ , R ²¹ , and R ²² each independently represent a hydrogen atom or a methyl group. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a methyl group. S _p3 and S _p4 represent a divalent organic group. A ₅ represents a single bond or a divalent organic group.

_{Preferred examples of the divalent organic group of Sp3} and _Sp4 include, for example, phenylene, pyrrolidine, piperidine, piperazine, a divalent chain hydrocarbon group having 2 to 20 carbon atoms, or a divalent _{-CH 2} - of the chain hydrocarbon group, -O-, -CO-, -CO-O-, -O-CO-, -NRCO- (R represents a hydrogen atom or a methyl group.), -NRCOO- ( R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR- (R represents a methyl group), pyrrolidine, piperidine and piper and a group substituted with a group selected from razine.

The S _p3, S 2 monovalent chain-like hydrocarbon group in the _p4, for example, ethylene group, propane-diyl, butane-diyl, pentane-diyl, hexane-diyl, heptane-diyl, octane-diyl group, no-Nadi A diary, a decandi diary, etc. are mentioned.

Preferred examples of the divalent organic group for A ₅ include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, or -CH ₂ - of the divalent chain hydrocarbon group, -O-, -CO-, -CO -O-, -O-CO-, -NRCO- (R represents a hydrogen atom or a methyl group.), -NRCOO- (R represents a hydrogen atom or a methyl group.), -CONR- (R represents a hydrogen atom or a methyl group.) is shown.) and a group substituted with .

Specific examples of the divalent chain hydrocarbon group in A ₅ include, in addition to the methylene group, the divalent chain hydrocarbon groups exemplified in _Sp3 and _{Sp4 above.}

The following formula (ND-1-1) or (ND-1-2) is mentioned as a preferable example of the diamine which has partial skeleton represented by Formula (ND-1).

[Formula 3]

In said formula, R<^1> , R<^2> represents a hydrogen atom or a methyl group. R ¹¹ and R ²² each independently represent a single bond or *1-R ³ -Ph-*2. R ³ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m O-, -CONH-, and -NHCO- divalent organic selected from group (l and m represent the integer of 1-5). In addition, *1 represents the site|part couple|bonded with the benzene ring in a formula (ND-1-1) or (ND-1-2), *2 represents a formula (ND-1-1) or (ND-1-2) The site which couple|bonds with the amino group in it is shown. Ph represents a phenylene group. n represents 1-3.

In the above formulas (ND-1-1) and (ND-1-2), from the viewpoint of easy synthesis, the substitution positions of the pyrrole ring are preferably 2-position and 5-position.

Specific examples of the diamine represented by the formulas (ND-1-1) and (ND-1-2) include diamines represented by any of the following formulas (n1-1) to (n1-14).

[Formula 4]

[Formula 5]

As an example of the diamine which has a partial skeleton represented by a formula (ND-2), the diamine represented by following formula (ND-2-1) - (ND-2-3) is mentioned.

[Formula 6]

In the formula, R ²¹ and R ^{22 have the same meaning as R 21} and R ^{22 in} the formula (ND-2), including preferred specific examples, respectively. R ²⁴ represents a single bond or the structure of the following formula (Ar), and n represents an integer of 1-3. * indicates a bond. Further, any hydrogen atom of the benzene ring may be substituted with a monovalent organic group such as an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom). do.

[Formula 7]

In the formula (Ar), R ⁵ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m O-, -CONR-, and - A divalent organic group selected from NRCO- is shown, and k is an integer of 1-5. In addition, R represents hydrogen or a monovalent organic group, and l and m represent the integer of 1-5. *1, *2 represents a bond, * ₁ couple|bonds with the benzene ring in a formula (ND-2-1) - a formula (ND-2-3).

Examples of the monovalent organic group for R in the formula (Ar) include an alkyl group having 1 to 3 carbon atoms.

As a preferable specific example of the diamine represented by said formula (ND-2-1) - (ND-2-3), the diamine represented by following formula (n2-1) - (n2-6) is mentioned.

[Formula 8]

[Formula 9]

Specific examples of the diamine having a partial skeleton represented by the formula (ND-3) or (ND-4) include a diamine represented by the following formula (ND-3-1) or (ND-4-1). .

[Formula 10]

As a preferable specific example of the diamine represented by said formula (ND-3-1), the diamine represented by following formula (n3-1) - (n3-7) is mentioned.

[Formula 11]

As a preferable specific example of the diamine represented by said formula (ND-4-1), the diamine represented by following formula (n4-1) - (n4-6) is mentioned.

[Formula 12]

As a preferable specific example of the diamine represented by said formula (ND-5), the diamine represented by following formula (n5-1) - (n5-8) is mentioned.

[Formula 13]

It is preferable that content of a specific diamine is 5 mol% or more of the whole diamine component, It is preferable that it is 10 mol% or more, It is more preferable that it is 20 mol% or more, It is especially preferable that it is 50 mol% or more.

Specific diamine is 1 type or 2 types or more depending on characteristics, such as the solubility to the solvent of a polymer (P1), applicability|paintability of a liquid crystal aligning agent, the orientation of the liquid crystal in setting it as a liquid crystal aligning film, voltage retention, accumulated electric charge, etc. Can be used.

As a diamine component for obtaining a polymer (P1), you may contain diamine (henceforth another diamine.) other than the said specific diamine. As another diamine, the diamine represented by the following general formula (2) is mentioned.

[Formula 14]

In said formula (2), A<_1> and A<_2> are respectively independently a hydrogen atom, a C1-C5 alkyl group, a C2-C5 alkenyl group, or a C2-C5 alkynyl group. From a viewpoint of liquid-crystal orientation, A ₁ and A ₂ have a preferable hydrogen atom or a methyl group. When the structure of Y<_1> is illustrated, it is as following formula (Y-1) - a formula (Y-68).

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

(Boc in the above formula represents a tert-butoxycarbonyl group. * represents a bond.)

Moreover, as another diamine, the diamine which has a thiophene or furan structure as described in International Publication WO2018/092759, The diamine preferably represented by a following formula (sf); 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc. Alicyclic diamines, such as aliphatic diamines, such as diaminoorganosiloxane and meta-xylene diamine, 4, 4- methylenebis (cyclohexylamine), etc. are mentioned. Other diamines can also use 1 type or 2 or more types together.

[Formula 19]

In the formula (sf), Y ₁ represents a sulfur atom or an oxygen atom, R ₂ each independently represents a single bond or *1-R ⁵ -Ph-*2, R ⁵ represents a single bond, - O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m is It is an integer from 1 to 5). In addition, *1 represents the site|part couple|bonded with the benzene ring in a formula (sf), and *2 shows the site|part couple|bonded with the amino group in a formula (sf). Ph represents a phenylene group. n is 1 to 3.)

(Tetracarboxylic acid component)

As a tetracarboxylic-acid component for obtaining a polymer (P1), the tetracarboxylic dianhydride represented by following formula (1), or its derivative(s) (tetracarboxylic acid, tetracarboxylic-acid dihalide, tetracarboxylic-acid dialkyl ester , or tetracarboxylic acid dialkyl ester dihalide) (these are collectively referred to as a first tetracarboxylic acid component.) can be used.

[Formula 20]

In the formula, X represents a tetravalent organic group. As the example, at least 1 sort(s) selected from the group which consists of following formula (X-1) - (X-14) is mentioned.

[Formula 21]

(x and y are each independently a single bond, methylene, ethylene, propylene, ether (-O-), carbonyl (-CO-), ester (-COO-), phenylene, sulfonyl (-SO _{2 )} -) or an amide group (-CONH-). Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a phenyl group. j and k are each independently, It is an integer of 0 or 1. m is an integer of 0 to 5. * indicates a bond.)

Preferred examples of the formula (X-1) include structures represented by the following formulas (X1-1) to (X1-4).

[Formula 22]

Preferred examples of the formula (X-13) include the following formulas (X13-1) to (X13-4).

[Formula 23]

It is preferable that content of a 1st tetracarboxylic-acid component is 5 mol% or more of the whole tetracarboxylic-acid component, It is preferable that it is 10 mol% or more, It is more preferable that it is 20 mol% or more, It is especially preferable that it is 50 mol% or more Do.

1st tetracarboxylic-acid component according to characteristics, such as the solubility with respect to the solvent of a polymer (P1), applicability|paintability of a liquid crystal aligning agent, the orientation of a liquid crystal in setting it as a liquid crystal aligning film, voltage retention, accumulated electric charge, 1 species or two or more species may be used.

Other tetracarboxylic-acid components other than a 1st tetracarboxylic-acid component can be used for the tetracarboxylic-acid component for obtaining the polymer (P1) of this invention. As another tetracarboxylic-acid component, the following tetracarboxylic dianhydride, the tetracarboxylic-acid dihalide derived from this tetracarboxylic dianhydride, tetracarboxylic-acid dialkyl ester, or tetracarboxylic-acid dialkyl ester dihalide can be heard

Specifically, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-anthracenetetracarboxylic acid 2 Anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, bis(3,4-dicarboxyphenyl)dimethyl silane dianhydride, bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride, 2,6-bis(3,4-dicarboxyphenyl)pyridine dianhydride etc. are mentioned.

Another tetracarboxylic-acid component can also be used 1 type or in mixture of 2 or more types.

(End sealant)

In this invention, a terminal blocker is a compound which reacts with the unreacted acid terminal and/or amine terminal which a polyimide precursor or its imidation polymer has, and can seal these.

Although a terminal blocker will not specifically limit if it is a compound which can block an acid terminal and/or an amine terminal, A monoamine or an acid anhydride is preferable. A monoamine can block the acid terminal of a polyimide precursor or its imidation polymer, and an acid anhydride can block the amine terminal of a polyimide precursor or its imidation polymer.

Preferred examples of monoamines include aniline, 2-aminophenol, 3-aminophenol, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-o-cresol , 4-amino-m-cresol, 5-amino-o-cresol, 6-amino-m-cresol, 4-amino-2,3-xylenol, 4-amino-3,5-xylenol, 6 -Amino-2,4-xylenol, 2-amino-4-ethylphenol, 3-amino-4-ethylphenol, 2-amino-4-tert-butylphenol, 2-amino-4-phenylphenol, 4 -Amino-2,6-diphenylphenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-amino-m-toluic acid, 3-Amino-o-toluic acid, 3-amino-p-toluic acid, 4-amino-m-toluic acid, 6-amino-o-toluic acid, 6-amino-m-toluic acid, 3-aminobenzenesulfonic acid , 4-aminobenzenesulfonic acid, 4-aminotoluene-3-sulfonic acid, and the like. You may use these 2 or more types.

The acid anhydride is preferably an acid anhydride having a cyclic structure or an acid anhydride having a crosslinkable group. Examples of the acid anhydride include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimetic anhydride, the following formulas (m-1) to (m-6) and compounds represented by . You may use these 2 or more types.

[Formula 24]

<Polymer (P2)>

The liquid crystal aligning agent of this invention is at least 1 sort(s) of polymer chosen from the group which consists of a 2nd polyimide precursor obtained by making a diamine component and a tetracarboxylic-acid component react with a polymer (P1), and its imidation polymer ( P2) may be further contained. In this case, for example, the polymer (P1) has a function excellent in the accumulated charge relaxation characteristic, and the polymer (P2) is preferable at the point which can be set as the aspect which has the function excellent in the liquid-crystal orientation.

As for the polyimide precursor of a polymer (P2), or its imidation polymer, the terminal may be sealed, In that case, the diamine component of a polymer (P2) contains diamines other than the said specific diamine. For specific examples, in addition to the other diamines exemplified in the polymer (P1), in order to orient the liquid crystal vertically, the diamine described in International Publication No. WO2018-159733 and the specific diamine described in International Publication No. WO2016-104365 (1) ), etc., in order to increase the response speed of liquid crystals, specific diamines (4) described in International Publication No. WO2016-104365 or diamines having a polymerization initiation function described in Japanese Patent Application Laid-Open No. 2018-081225 may be used. .

When the terminal of the polymer (P2) is not sealed, as a diamine component for obtaining the polymer (P2), other than the diamine exemplified above, a diamine component for obtaining the polymer (P1) can be used.

The diamine component for obtaining a polymer (P2) can contain the at least 1 sort(s) of diamine chosen from following formula (3), Formula (4), and Formula (5) from a viewpoint of improving the liquid-crystal orientation.

[Formula 25]

In the formula, A ₁ , A ₄ each independently represents a single bond or a divalent organic group, A ₂ is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, a phosphoric acid group, or a carbon number of 1 A monovalent organic group of to 20 _{is shown, and A 3} shows a divalent organic group. a is an integer of 1 to 4, and when a is 2 or more, _{the structures of A 2} may be the same or different. b and c are each independently an integer of 1 or 2. d is an integer of 0 or 1.

Examples _{of the divalent organic group for A 1} and A ₄ include a divalent chain hydrocarbon group having 2 to 20 carbon atoms, or -CH ₂ - valency of the divalent chain hydrocarbon group, -O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group.), -NRCOO- (R represents a hydrogen atom or a methyl group.), -CONR- (R represents a hydrogen atom or a methyl group.) , -COS-, -NR ₁ -CO-NR ₂ - (R ₁ , R ₂ each independently represents a hydrogen atom or a methyl group.), -NR- (R represents a methyl group), pyrrolidine, p group (h1) substituted with a group selected from peridine and piperazine; Further, some or all of the hydrogen atoms of the chain hydrocarbon group and the group (h1) may be substituted with an alkyl group having 1 to 3 carbon atoms such as a methyl group, or a halogen atom such as a fluorine atom or a chlorine atom.

The _{divalent organic group for A 3} is a divalent chain hydrocarbon group having 1 to 20 carbon atoms, or -CH ₂ - valency of the divalent chain hydrocarbon group, -O-, -CO-, -CO- O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS -, -NR ₁ -CO-NR ₂ - (R ₁ , R ₂ each independently represents a hydrogen atom or a methyl group), -NR- (R represents a methyl group), pyrrolidine, piperidine, and a group (h2) substituted with a group selected from piperazine. In addition, it may be substituted with halogen atoms, such as the A ₃ chain-like hydrocarbon group and a group (h2) has a part or all the methyl groups of 1 to 3 carbon atoms such as an alkyl group, a fluorine atom, a chlorine atom of a hydrogen atom.

Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include methanediyl group, ethanediyl group, n-propanediyl group, i-propanediyl group, n-butanediyl group, i-butanediyl group, sec - alkanediyl groups, such as a butanediyl group and t-butanediyl group;

Alkenediyl groups, such as an etenediyl group, a propenediyl group, and a butenediyl group; Alkynediyl groups, such as an ethyndiyl group, a propyndiyl group, and a butyndiyl group, etc. are mentioned.

As the monovalent organic group having 1 to 20 carbon atoms in _{A 2 , for example, the divalent chain hydrocarbon group having 1 to 20 carbon atoms of A 3} , group (h2), or its divalent chain having 1 to 20 carbon atoms One hydrogen atom is exemplified as a group in which some or all of the hydrogen atoms of the hydrocarbon group and group (h2) are substituted with an alkyl group having 1 to 3 carbon atoms such as a methyl group, or a halogen atom such as a fluorine atom or a chlorine atom plus groups and the like.

As a preferable specific example of the at least 1 sort(s) of diamine selected from said formula (3), following formula (4), and following formula (5), following formula (DA-3-1), (DA-4-1) - ( DA-4-23) and at least 1 sort(s) of diamine chosen from the group which consists of (DA-5-1)-(DA-5-3) is mentioned.

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

From a viewpoint of improving liquid-crystal orientation, the total amount of at least 1 type of diamine chosen from said Formula (3), Formula (4), and Formula (5) is 10 mol% or more of the whole diamine component for obtaining a polymer (P2) it is preferable

From the viewpoint of enhancing functional separation between the polymer (P1) and the polymer (P2), the diamine component for obtaining the polymer (P1) and/or the polymer (P2) preferably contains a diamine represented by the following formula (6). .

[Formula 30]

In the formula, Y ₆ represents a divalent organic group having a structure represented by the following formula (7). A ₆ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. From a viewpoint of liquid-crystal orientation, A ₆ has a preferable hydrogen atom or a methyl group.

[Formula 31]

(D is a t-butoxycarbonyl group.)

As an example of the divalent organic group containing the structure represented by the said Formula (7), group represented by a following formula (J-1) or a formula (J-2) is mentioned.

[Formula 32]

In the above formula, R ₅ is a single bond, -(CH ₂ ) _n - (n is an integer from 1 to 20), or any -CH _{2 - of -(CH 2} ) _n - are not adjacent to each other. represents a group substituted with -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR-, -NRCONR-, -NRCOO-, -OCOO-. R represents a hydrogen atom or a monovalent organic group. R ₆ and R ₇ each independently represent a group having -H, -NHD, or a group having -N(D) ₂ . R ₈ represents a group having -N(D) ₂ , -NHD , or a group having -N(D) ₂ . D represents a t-butoxycarbonyl group. However, _{at least one of R 5} , R ₆ and R ₇ has a t-butoxycarbonyl group in the group.

More preferable specific examples of the divalent organic group represented by the formula (J-1) or (J-2) are the following formulas (J-1-a) to (J-1-d), (J- It is a divalent organic group represented by 2-1). In addition, Boc represents a t-butoxycarbonyl group.

[Formula 33]

As a tetracarboxylic-acid component for obtaining a polymer (P2), the tetracarboxylic-acid component for obtaining a polymer (P1) can be used. Specifically, the said 1st tetracarboxylic-acid component can be used from a viewpoint of improving the liquid-crystal orientation. More preferably, it is preferable to use 10 mol% or more of the whole tetracarboxylic-acid component used for a polymer (P2) as said 1st tetracarboxylic-acid component.

<Method for Producing Polymer (P1)>

Polymer (P1) is selected from the group which consists of the 1st polyimide precursor in which the terminal was sealed, and its imidation polymer, The diamine component containing at least 1 sort(s) of diamine chosen from specific diamine, and a tetracarboxylic-acid component It is obtained by subjecting it to (condensation) polymerization reaction, and also making it react with a terminal blocker.

Here, a polyimide precursor means a polyamic acid or polyamic-acid alkylester. The liquid crystal aligning agent of this invention WHEREIN: It is preferable that the polymer (P1) is the polyimide precursor by which the terminal was sealed, and especially the polyamic acid by which the terminal was sealed is more preferable.

In the embodiment of the present invention, the polymer (P1) is obtained by polymerization-reacting a diamine component containing at least one diamine selected from specific diamines and a tetracarboxylic acid component to obtain a polyimide precursor or an imidized polymer thereof, Moreover, it is preferable to obtain by making this polyimide precursor or its imidation polymer react with a terminal blocker.

The said polymer (P1) can also be obtained by superposing|polymerizing the diamine component containing at least 1 sort(s) of diamine chosen from specific diamine, and a tetracarboxylic-acid component, or supplying a terminal blocker during superposition|polymerization.

Reaction of a diamine component and a tetracarboxylic-acid component is normally performed in a solvent. It will not specifically limit, if the produced|generated polyimide precursor melt|dissolves as a solvent used in that case. Although the specific example of the solvent used for reaction is given below, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy -N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, dimethylsulfoxide, or 1,3-dimethyl-imidazolidinone. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, etc. can be used.

These solvents may be used independently and may be mixed and used. Moreover, even if it is a solvent in which a polyimide precursor is not dissolved, you may use it in the range in which the produced|generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since the water|moisture content in a solvent inhibits a polymerization reaction and becomes a cause of hydrolyzing the produced|generated polyimide precursor by extension, it is preferable to use the solvent which carried out dehydration and drying.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, the solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as it is or by dispersing or dissolving it in the solvent, conversely, tetracarboxylic acid component is added. A method of adding a diamine component to a solution in which a carboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component to the reaction system, etc. may be used, any of these methods may be used. do. In addition, when making a diamine component or a tetracarboxylic-acid component use and react using multiple types, respectively, you may make it react in the state previously mixed, you may make it react individually and sequentially, and also mix and react the individually reacted low molecular weight substance. It is good also as a polymer.

Although the temperature which polycondenses a diamine component and a tetracarboxylic-acid component can select the arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC. The reaction can be carried out at any concentration, but when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, the density|concentration of a polymer becomes like this. Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. The reaction initial stage can be performed at high concentration, and a solvent can be added after that.

In the polymerization reaction which obtains a polyimide precursor, it is preferable that ratio of the total number of moles of a tetracarboxylic-acid component with respect to the total number of moles of a diamine component is 0.8-1.2. As in a typical polycondensation reaction, the closer this molar ratio to 1.0, the greater the molecular weight of the polyimide precursor produced.

The imidized polymer is a polyimide obtained by ring-closing a polyimide precursor, and in this polyimide, the ring-closure rate (also referred to as imidation rate) of the amic acid group (amic acid group) is not necessarily 100%, It can be arbitrarily adjusted according to the use or purpose.

As a method of imidating a polyimide precursor, the thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

The temperature in the case of thermal imidation of the polyimide precursor in solution is preferably 100 to 400°C, more preferably 120 to 250°C, and the method is carried out while removing water generated by the imidization reaction to the outside of the system. desirable. Catalyst imidation of a polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the solution of a polyimide precursor, and stirring at -20-250 degreeC Preferably it is 0-180 degreeC.

Preferably the quantity of a basic catalyst is 0.5-30 mole times of an amic acid group, More preferably, it is 2-20 mole times, The quantity of an acid anhydride becomes like this. Preferably 1-50 mole times of an amic acid group, More preferably, it is 3-30 mole times. to be.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a suitable basicity for advancing the reaction.

As an acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned. In particular, use of acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidation can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

In the case of recovering the polyimide precursor produced from the reaction solution or the imidized polymer thereof, the reaction solution may be poured into a solvent for precipitation. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer charged and precipitated in the solvent may be collected by filtration, then dried under normal pressure or reduced pressure at room temperature or by heating. Moreover, when the recovered polymer is re-dissolved in a solvent and the operation of reprecipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. As a solvent at this time, alcohol, ketones, hydrocarbon etc. are mentioned, for example. When three or more types of solvents selected from these are used, since the efficiency of refinement|purification further improves, it is preferable.

In the present invention, when the polyimide precursor is a polyamic acid alkyl ester, specific methods for producing it include, for example, the methods described in paragraphs [0054] to [0062] of International Publication No. WO2011-115077. .

Next, in order to seal the acid terminal or the amine terminal of the polyimide precursor or its imidized polymer, the polyimide precursor or its imidized polymer may be reacted by adding a terminal blocker either during or after production.

Although the usage-amount of a terminal blocker is not specifically limited, 0.001-0.8 equivalent is preferable with respect to 1 equivalent of the amino group in the diamine component involved in the polymerization reaction of a polyimide precursor or its imidation polymer, 0.01-0.2 equivalent is more preferable. Do.

Moreover, 0.001-0.8 equivalent is preferable with respect to 1 equivalent of the carboxyl group (or its derivative structure) in the tetracarboxylic-acid component involved in the polymerization reaction of a polyimide precursor or its imidation polymer, 0.01-0.2 equivalent is preferable.

-50-150 degreeC is preferable and, as for the reaction temperature at the time of sealing the terminal, -30-100 degreeC is more preferable. Moreover, reaction time is 0.1 to 100 hours normally.

<Method for Producing Polymer (P2)>

A polymer (P2) is selected from the group which consists of a 2nd polyimide precursor and its imidation polymer, It is obtained by making a diamine component and a tetracarboxylic-acid component react. About reaction of a diamine component and a tetracarboxylic-acid component, it is the same as that of description in the manufacturing method of said polymer (P1).

When the polymer (P2) is selected from the group consisting of a terminal-sealed polyimide precursor and an imidized polymer thereof, the polyimide precursor or an imidized polymer thereof is prepared in either or both during or after production, the following formula What is necessary is just to react the terminal blocker chosen from (R-1)-(R-2).

[Formula 34]

(R ₂ and R ₂ 'represents a monovalent organic group. N is an integer of 1-2.)

Specific examples of R ₂ and R ₂ ′ include a methyl group, 9-fluoronylmethyl group, 2,2,2-trichloroethyl group, 2-trimethylsilylethyl group, 1,1-dimethylpropynyl group, 1-methyl-1- phenylethyl group, 1-methyl-1-(4-biphenylyl)ethyl group, 1,1-dimethyl-2-haloethyl group, 1,1-dimethyl-2-cyanoethyl group, tert-butyl group, cyclobutyl group, 1-methylcyclobutyl group, 1-adamantyl group, vinyl group, allyl group, cinnamyl group, 8-quinolyl group, N-hydroxypiperidinyl group, benzyl group, p-nitrobenzyl group, 3,4-dimethyl group and a oxy-6-nitrobenzyl group and a 2,4-dichlorobenzyl group. Especially, in relation to the firing temperature in the liquid crystal display element manufacturing process, tert-butyl group, 2,2,2-trichloroethyl group, 2-trimethylsilylethyl group, 1,1-dimethylpropynyl group, 1-methyl group -1-(4-biphenylyl)ethyl group, 1,1-dimethyl-2-haloethyl group, 1,1-dimethyl-2-cyanoethyl group, t-butyl group, cyclobutyl group, 1-methylcyclobutyl group , vinyl group, allyl group, cinnamyl group and N-hydroxypiperidinyl group are more preferable, and 1,1-dimethyl-2-haloethyl group, 1,1-dimethyl-2-cyanoethyl group and tert-butyl group are particularly desirable.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains a polymer (P1) and a polymer (P2) as needed. 2-10 mass % is preferable in a liquid crystal aligning agent, and, as for content of the polymer (P1) in a liquid crystal aligning agent, 3-8 mass % is more preferable.

When a liquid crystal aligning agent contains a polymer (P2), 30 mass parts or more are preferable, and, as for content of a polymer (P1), 50 mass parts or more are preferable with respect to 100 mass parts of total amounts of a polymer (P1) and a polymer (P2). more preferably, more preferably 60 parts by mass or more, and most preferably 70 parts by mass or more.

The liquid crystal aligning agent of this invention may contain other polymers other than a polymer (P1) and a polymer (P2). Examples of other polymers include cellulose polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamide, polysiloxane, and the like. 0.5-15 mass parts is preferable with respect to a total of 100 mass parts of a polymer (P1) and a polymer (P2), and, as for content of other polymers other than that, 1-10 mass parts is more preferable.

Moreover, although a liquid crystal aligning agent contains an organic solvent normally, it is preferable that content of an organic solvent is 70-99.9 mass % with respect to a liquid crystal aligning agent. This content can be suitably changed according to the coating method of a liquid crystal aligning agent, and the film thickness of the liquid crystal aligning film made into the objective.

The solvent (it is also mentioned a good solvent) in which the organic solvent used for a liquid crystal aligning agent melt|dissolves a polymer (P1) and a polymer (P2) is preferable. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide; 3-butoxy-N,N-dimethylpropanamide and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or γ -Butyrolactone is preferable.

It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent, 20-90 mass % is more preferable, It is 30-80 mass % especially preferable .

The liquid crystal aligning agent of this invention can use the solvent (it is also mentioned a poor solvent) which improves the coating-film property of a liquid crystal aligning film at the time of apply|coating a liquid crystal aligning agent, and surface smoothness. The specific example is given below.

For example, diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1 ,2-Butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3- Ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl Ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether, 3-methoxymethylpropionate, 3-ethoxy Ethyl propionate, 3-methoxyethyl propionate, 3-methoxypropyl propionate, 3-methoxybutyl propionate, lactate n-butyl ester, lactate isoamyl ester, diethylene glycol monoethyl ether, diisobutyl ketone (2, 6-dimethyl-4-heptanone) and the like.

Among them, preferred combinations of solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N- Methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyro Lactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and 2,6-dimethyl- 4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone with propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone with γ-butyrolactone and propylene glycol Monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, gamma -butyrolactone, dipropylene glycol dimethyl ether, etc. are mentioned. 1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, as for these poor solvents, 10-80 mass % is more preferable, and its 20-70 mass % is especially preferable. The kind and content of such a solvent are suitably selected according to the coating apparatus of a liquid crystal aligning agent, application|coating conditions, application|coating environment, etc.

To the liquid crystal aligning agent of this invention, the dielectric constant for the purpose of changing electrical characteristics, such as dielectric constant and electroconductivity of a liquid crystal aligning film, the silane coupling agent for the objective of improving the adhesiveness of a liquid crystal aligning film and a board|substrate, hardness and density of the film|membrane when it is set as a liquid crystal aligning film You may contain the crosslinking|crosslinked compound for the purpose of raising a degree, and the imidation promoter etc. for the objective of advancing the imidation by heating of a polyimide precursor efficiently when baking a coating film by extension.

As a compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, a functional silane containing compound and an epoxy group containing compound are mentioned, For example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethyl Toxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis (oxyethylene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N, N-diglycidylaminomethyl) cyclohexane, or N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. are mentioned.

Moreover, in order to raise the mechanical strength of a liquid crystal aligning film, you may contain the following additives (CL-1) - (CL-15) in the liquid crystal aligning agent of this invention.

[Formula 35]

It is preferable that said additive is 0.1-30 mass parts with respect to 100 mass parts of the polymer component contained in a liquid crystal aligning agent. More preferably, it is 0.5-20 mass parts.

<Method for Producing Liquid Crystal Alignment Film>

A liquid crystal aligning film forms a film by application|coating etc. on a board|substrate of the said liquid crystal aligning agent, Preferably it dries, and it bakes and is obtained. As the substrate, a substrate having high transparency is preferable, and as the material, ceramics such as glass and silicon nitride, plastics such as an acrylic resin or polycarbonate, etc. can be used. It is preferable from the point of process simplification to use the board|substrate with which the ITO (Indium Tin Oxide) electrode etc. for driving a liquid crystal were formed as a board|substrate. Moreover, in a reflective liquid crystal display element, opaque things, such as a silicon wafer, can be used for a board|substrate on one side, and a material which reflects light, such as aluminum, can also be used for the electrode.

Screen printing, offset printing, flexographic printing, inkjet method, etc. can be used for the method of forming a film on a board|substrate from a liquid crystal aligning agent, Moreover, the dip method, the roll coater method, the slit coater method, the spinner method, the spray method etc. are also available It can be used according to the purpose.

After forming the film of a liquid crystal aligning agent on a board|substrate, as for a film, by heating means, such as a hotplate, heat circulation type oven, IR (infrared) type|mold oven, Preferably it is 30-120 degreeC, More preferably, it is 50 It is preferable to evaporate a solvent by drying at -120 degreeC, Preferably it is 1 minute - 10 minutes, More preferably, it is 1 minute - 5 minutes.

When performing thermal imidation of the imide precursor in a polymer, the film obtained from a liquid crystal aligning agent then is by the heating means similar to said drying process, Preferably it is 120-250 degreeC, More preferably, 150- It is calcined at 230°C. Although the time of a calcination process changes also with calcination temperature, Preferably they are 5 minutes - 1 hour, More preferably, they are 5 minutes - 40 minutes.

The thickness of the film after the baking treatment is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may decrease, and if it is too thick, the electrical resistance of the liquid crystal aligning film obtained increases, so 5-300 nm is preferable, 10-200 nm is more preferable.

After the above firing treatment, the obtained film is subjected to an orientation treatment. As a method of orientation-processing, a rubbing process method, the photo-alignment process method, etc. are mentioned.

As a specific example of the photo-alignment treatment, the surface of the film is irradiated with radiation deflected in a certain direction. As the radiation, ultraviolet or visible light having a wavelength of 100 to 800 nm can be used. Especially, the ultraviolet-ray which has a wavelength of 100-400 nm is preferable, More preferably, it is an ultraviolet-ray which has a wavelength of 200-400 nm. In order to improve liquid-crystal orientation, you may irradiate an ultraviolet-ray, heating the board|substrate with which the liquid crystal aligning film was coated at 50-250 degreeC. Moreover, as for the irradiation amount of the said radiation, 1-10,000 mJ/cm<2> is preferable. Especially, 100-5,000 mJ/cm<2> is preferable. The liquid crystal aligning film manufactured in this way can orientate a liquid crystal molecule stably in a fixed direction.

Since higher anisotropy can be provided, it is so preferable that the extinction ratio of the polarized ultraviolet-ray is high. Specifically, 10:1 or more is preferable and, as for the extinction ratio of the ultraviolet-ray polarized linearly, 20:1 or more is more preferable.

You may give at least 1 process chosen from the group which consists of a heat process and the contact process by a solvent further to the film which performed the said orientation process.

Heat treatment after orientation treatment can be performed by the same heating means as said drying process and baking process, Preferably it is 180-250 degreeC, More preferably, it is 180-230 degreeC. When the temperature of heat processing is implemented in said range, the contrast of the liquid crystal display element obtained with the liquid crystal aligning film obtained can be raised. Although the time of heat processing changes also with heating temperature, Preferably it is 5 minutes - 1 hour, More preferably, it is 5-40 minutes.

It will not specifically limit, if it is a solvent which melt|dissolves the impurity etc. which had adhered to the liquid crystal aligning film as a solvent used for the contact process by the said solvent.

Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate. , diacetone alcohol, 3-methoxy methyl propionate, 3-ethoxy ethyl propionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. are mentioned. Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferable from the viewpoint of versatility and solvent safety. More preferred are water, 1-methoxy-2-propanol or ethyl lactate. The number of these solvents may be one, or 2 or more types may be sufficient as them.

As said contact process, an immersion process and a spray process (it is also mentioned a spray process) are mentioned. As for the processing time in these processes, 10 second - 1 hour are preferable, and the aspect which performs an immersion process especially for 1 to 30 minutes is mentioned. Moreover, although normal temperature or heating may be sufficient as the temperature at the time of a contact process, Preferably it is 10-80 degreeC, and 20-50 degreeC is mentioned. In the case of contact processing, you may further perform ultrasonic processing etc. as needed.

After the contact treatment, rinsing (also referred to as rinsing) or drying with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone may be performed. In that case, either one of rinsing and drying may be performed, and both may be performed. As for drying temperature, 50-150 degreeC is preferable and 80-120 degreeC is mentioned. Moreover, 10 second - 30 minutes are preferable, and, as for drying time, 1 to 10 minutes are preferable.

After performing the contact process by the said solvent, you may perform the heat processing after the said orientation process. By setting it as such an aspect, the liquid crystal aligning film excellent in liquid-crystal orientation is obtained.

<Liquid crystal display element>

Although the liquid crystal aligning film of this invention can be applied to various drive modes, such as a TN system, STN system, IPS system, FFS system, VA system, MVA system, PSA system, Transverse electric field systems, such as an IPS system and FFS system, It is suitable as a liquid crystal aligning film of a liquid crystal display element, and is useful especially for the liquid crystal display element of an FFS system. After obtaining the board|substrate with a liquid crystal aligning film obtained from the said liquid crystal aligning agent, the liquid crystal display element of this invention manufactures a liquid crystal cell by a known method, and sets it as an element using the liquid crystal cell.

As an example of the manufacturing method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is taken as an example and demonstrated. Moreover, the liquid crystal display element of the active matrix structure in which switching elements, such as TFT, were formed in each pixel part which comprises an image display may be sufficient.

Specifically, a transparent glass substrate is prepared, a common electrode is formed on one substrate, and a segment electrode is formed on the other substrate. These electrodes can be, for example, ITO electrodes, and are patterned so that a desired image display can be performed. Next, an insulating film is formed on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film made of _{SiO 2} -TiO _{2 formed by a sol-gel method.} Next, a liquid crystal aligning film is formed on each board|substrate under the same conditions as the above, and the other board|substrate is superposed on one board|substrate so that the liquid crystal aligning film surface of each other may oppose, and the periphery is adhere|attached with a sealing compound. In order to control a board|substrate clearance gap in a sealing compound, it is preferable to mix a spacer normally. Moreover, it is preferable to spread|disperse the spacer for board|substrate gap|interval control also to the in-plane part which does not form a sealing compound. It is preferable to provide the opening part which can fill a liquid crystal from the outside in a part of sealing compound.

Then, liquid-crystal material is inject|poured in the space surrounded by the board|substrate of 2 sheets and sealing agent through the opening part provided in the sealing compound. Next, this opening is sealed with an adhesive. For the injection, a vacuum injection method or a method using capillary action in the atmosphere is exemplified, and an ODF (One Drop Fill) method may be used. As a liquid crystal material, either positive or negative dielectric anisotropy may be used. In this invention, although the direction of the liquid crystal which has negative dielectric anisotropy is preferable from a viewpoint of liquid-crystal orientation, it can use properly according to a use.

After the liquid crystal material is injected into the liquid crystal cell, a polarizing plate is installed. Specifically, it is preferable to affix a pair of polarizing plates to the surface on the opposite side to the liquid-crystal layer of 2 sheets of board|substrates.

Example

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited thereto. The abbreviation of the compound in the following and the measuring method of each characteristic are as follows.

NMP: N-methyl-2-pyrrolidone, GBL: γ-butyrolactone

BCS : Butyl Cellosolve

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Viscosity]

Using an E-type viscometer TVE-22H (manufactured by Toki Industries, Ltd.), it measured at a sample amount of 1.1 ml, cone rotor TE-1 (1°34', R24), and a temperature of 25°C.

[Molecular Weight]

It measured with the GPC (normal temperature gel permeation chromatography) apparatus, and computed the number average molecular weight (Mn) and the weight average molecular weight (Mw) as polyethylene oxide conversion value.

GPC apparatus: manufactured by Shodex (GPC-101), column: manufactured by Shodex (KD803, KD805 in series), column temperature: 50°C, eluent: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr) ·H ₂ O) contains 30 mmol/L, phosphoric acid/anhydrous crystals (o-phosphoric acid) contain 30 mmol/L, and tetrahydrofuran (THF) contains 10 ml/L), flow rate: 1.0 ml/ minute

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories (peak top molecular weight (Mp) about 12,000, 4,000, 1,000). In the measurement, in order to avoid overlapping peaks, two samples of a sample in which four kinds of 900,000, 100,000, 12,000, and 1,000 were mixed, and a sample in which three kinds of 150,000, 30,000, and 4,000 were mixed were separately measured.

[Production of liquid crystal cell]

A liquid crystal cell having a structure of a fringe field switching (FFS) mode liquid crystal display element is manufactured.

First, a substrate to which an electrode is attached was prepared. The substrate is a glass substrate having a size of 30 mm x 50 mm and a thickness of 0.7 mm. On the board|substrate, the ITO electrode provided with the beta phase pattern which comprises a counter electrode as a 1st layer is formed. On the counter electrode of the first layer, as the second layer, a SiN (silicon nitride) film formed by the CVD method is formed. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-tooth-shaped pixel electrode formed by patterning the ITO film as the third layer is disposed, and two pixels of the first pixel and the second pixel are formed. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the 3rd layer has a comb-tooth-shaped shape comprised by arranging a plurality of "<"-shaped electrode elements in which the central part is bent at an inner angle of 160 degrees. The width in the transverse direction of each electrode element is 3 µm, and the distance between the electrode elements is 6 µm. Since the pixel electrode forming each pixel is constituted by arranging a plurality of "<-"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangular shape, but is bent in the central part similarly to the electrode element, It has a shape resembling the bold letter 'K'. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has the 1st area|region above and the 2nd area|region below the bending|flexion part.

Next, after filtering the liquid crystal aligning agent with a filter having a pore diameter of 1.0 µm, spin coating on a glass substrate having a columnar spacer having a height of 4 µm in which an ITO film is formed on the prepared substrate and the back surface with the electrode, applied by law. After drying for 2 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 30 minutes, and the coating film with a film thickness of 100 nm was formed. The ultraviolet-ray of wavelength 254nm which carried out linearly polarized more than 10:1 extinction ratio through the polarizing plate was irradiated to this coating-film surface. This board|substrate was baked for further 30 minutes in 230 degreeC hot-air circulation type oven, and the board|substrate with a liquid crystal aligning film was obtained. In addition, the liquid crystal aligning film formed on the substrate with the electrode is oriented so that the direction dividing the inner angle of the pixel bent portion into equal parts and the alignment direction of the liquid crystal are orthogonal to each other, and the liquid crystal aligning film formed on the second glass substrate is used to manufacture a liquid crystal cell When it did, it orientation-processed so that the orientation direction of the liquid crystal on a 1st board|substrate and the orientation direction of the liquid crystal on a 2nd board|substrate may correspond. The two substrates are set as one set, the sealing compound is printed on the substrate, and the other substrate is bonded so that the liquid crystal aligning film face is facing and the alignment direction is 0 °, and then the sealing compound is cured, An empty cell was prepared. Liquid crystal MLC-3019 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, after heating the obtained liquid crystal cell at 110 degreeC for 1 hour and leaving it to stand overnight, it was used for each evaluation.

[Evaluation of afterimage by long-term AC drive]

The liquid crystal cell of the structure similar to the liquid crystal cell used for said afterimage evaluation was prepared.

Using this liquid crystal cell, the alternating voltage of +/-5V was applied in a 60 degreeC constant temperature environment at the frequency of 60 Hz for 120 hours. Then, it was set as the state made short between the pixel electrode of a liquid crystal cell, and a counter electrode, and it was left to stand at room temperature as it is for one day.

After leaving, the liquid crystal cell was placed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, and the backlight was turned on in a state where no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light was the smallest. And the rotation angle at the time of rotating a liquid crystal cell from the angle at which the 2nd area|region of a 1st pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as angle (DELTA). Similarly, in the second pixel, the same angle Δ was calculated by comparing the second region and the first region.

<Synthesis Example 1> (Polyamic acid whose terminal is not sealed)

In a 3 L 4-neck flask equipped with a stirring device and a nitrogen introduction tube, 17.30 g (159.98 mmol) of diamine DA-1, 58.63 g (240.0 mmol) of diamine DA-2, and 76.89 g of diamine DA-3 ( 240.0 mmol) and 54.63 g (159.99 mmol) of diamine DA-4 were weighed and contained, 2458.13 g of NMP was added, and stirred while sending nitrogen to dissolve. 171.27 g (764.02 mmol) of tetracarboxylic dianhydride TA-1 is added, stirring this diamine solution, NMP is further added so that solid content concentration may be 12 mass %, and it stirs at 40 degreeC for 20 hours, , a polyamic acid solution (PAA-1) was obtained.

The viscosity of this polyamic-acid solution was 426 mPa*s. Moreover, the molecular weight of this polyamic acid was Mn=12,380 and Mw=33,250.

<Synthesis Example 2> (Polyamic acid whose terminal is not sealed)

5.29 g (26.98 mmol) of tetracarboxylic dianhydride TA-2 was weighed and contained in a 100 ml four-necked flask equipped with a stirring device and a nitrogen inlet tube, and 80.13 g of NMP was added, followed by stirring while sending nitrogen. dissolved. Stirring this carboxylic acid dianhydride solution, for 2.96 g (14.86 mmol) of diamine DA-5, 2.28 g (5.41 mmol) of diamine DA-6, and 1.61 g (5.43 mmol) of diamine DA-7 Furthermore, NMP was added so that solid content concentration might be set to 12 mass %, and it stirred at 40 degreeC for 20 hours, and obtained the polyamic-acid solution (PAA-2).

The viscosity of this polyamic-acid solution was 437 mPa*s. Moreover, the molecular weight of this polyamic acid was Mn=16,331, Mw=35,853.

<Synthesis Example 3> (Polyamic acid whose terminal is not sealed)

In a 100 ml four-neck flask equipped with a stirring device and a nitrogen inlet tube, 2.98 g (14.96 mmol) of diamine DA-5, 2.11 g (5.00 mmol) of diamine DA-6, and 1.49 g of diamine DA-7 (4.99 mmol) was weighed, 74.16g of NMP was added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 4.64 g (23.66 mmol) of tetracarboxylic dianhydride TA-2 is added, stirring this diamine solution, NMP is further added so that solid content concentration may be 12 mass %, and it stirs at 40 degreeC for 20 hours, , a polyamic acid solution (PAA-3) was obtained.

The viscosity of this polyamic-acid solution was 443 mPa*s. Moreover, the molecular weight of this polyamic acid was Mn=12,155 and Mw=35,725.

<Synthesis Example 4> (Polyamic acid in which the end is sealed)

In a 50 ml Erlenmeyer flask, 20.0 g of polyamic acid (PAA-2) was weighed and contained, and 0.035 g (0.38 mmol, 0.04 equivalents with respect to 1 equivalent of the amino group in the diamine involved in the polymerization reaction) of MA-1 was added. And it stirred at 40 degreeC for 20 hours, and obtained the polyamic-acid solution (PAA-4). As for the polyamic acid solution (PAA-4), the acid terminal was sealed.

<Synthesis Examples 5 to 8> (Polyamic acid sealed at the end)

The polyamic acid solution (PAA-5) - (PAA-8) shown in following Table 2 were obtained by performing similarly to the synthesis example 4, respectively, using the polyamic-acid solution and terminal blocker shown in following Table 2. As for the polyamic-acid solution (PAA-5), the acid terminal was sealed, and, as for the polyamic-acid solution (PAA-6) - (PAA-8), the amine terminal was sealed.

(Component 1: Liquid crystal aligning agent whose blend ratio (mass ratio) of component 2 is 5:5)

<Example 1>

12 mass % polyamic acid solution (PAA-4) (component 1) 2.29 g and 12 mass % polyamic acid solution (PAA-1) (component 2) 2.29 g are taken in a 50 ml Erlenmeyer flask, NMP 2.41g, BCS 3.00 g was added, it mixed at 25 degreeC for 2 hours, and the liquid crystal aligning agent (A1) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid crystal aligning agent, but it was confirmed that it is a uniform solution.

<Examples 4, 7, 10, 13>

Instead of polyamic acid solution (PAA-4), except having used polyamic acid solution (PAA-5) - (PAA-8), by carrying out similarly to Example 1, liquid crystal aligning agent (A4), (A7), (A10) and (A13) were obtained.

<Comparative Examples 1 and 4>

Instead of polyamic acid solution (PAA-4), except having used polyamic acid solution (PAA-2) - (PAA-3), by implementing similarly to Example 1, liquid crystal aligning agent (B1) and (B4) got it

(Component 1: Liquid crystal aligning agent whose blend ratio (mass ratio) of component 2 is 6:4)

<Example 2>

12 mass % polyamic acid solution (PAA-4) (component 1) 2.75 g and 12 mass % polyamic acid solution (PAA-1) (component 2) 1.83 g are taken in a 50 ml Erlenmeyer flask, NMP 2.41g, BCS 3.00 g was added, it mixed at 25 degreeC for 2 hours, and the liquid crystal aligning agent (A2) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid crystal aligning agent, but it was confirmed that it is a uniform solution.

<Examples 5, 8, 11, 14>

Instead of polyamic acid solution (PAA-4), except having used polyamic acid solution (PAA-5) - (PAA-8), by implementing similarly to Example 2, liquid crystal aligning agent (A5), (A8), (A11) and (A14) were obtained.

<Comparative Examples 2 and 5>

Instead of polyamic acid solution (PAA-4), except having used polyamic acid solution (PAA-2) - (PAA-3), by implementing similarly to Example 2, liquid crystal aligning agent (B2) and (B5) got it

(Component 1: Liquid crystal aligning agent whose blend ratio (mass ratio) of component 2 is 7:3)

<Example 3>

12 mass % polyamic acid solution (PAA-4) (component 1) 3.21 g and 12 mass % polyamic acid solution (PAA-1) (component 2) 1.38 g are taken in a 50 ml Erlenmeyer flask, NMP 2.41g, BCS 3.00 g was added, it mixed at 25 degreeC for 2 hours, and the liquid crystal aligning agent (A3) was obtained. Abnormalities, such as turbidity and precipitation, were not seen by this liquid crystal aligning agent, but it was confirmed that it is a uniform solution.

<Examples 6, 9, 12, 15>

Instead of polyamic acid solution (PAA-4), except having used polyamic acid solution (PAA-5) - (PAA-8), by carrying out similarly to Example 3, liquid crystal aligning agent (A6), (A9), (A12) and (A15) were obtained.

<Comparative Examples 3 and 6>

Instead of polyamic acid solution (PAA-4), except having used polyamic acid solution (PAA-2) - (PAA-3), by implementing similarly to Example 3, liquid crystal aligning agent (B3) and (B6) got it

(Result of afterimage evaluation by long-term AC drive)

<Example 16>

After filtering the liquid crystal aligning agent (A1) obtained in Example 1 with a filter having a pore size of 1.0 µm, the prepared substrate with the electrode and an ITO film on the back surface of the prepared glass substrate having a columnar spacer having a height of 4 µm, It was applied by spin coat application. After drying for 2 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 30 minutes, and the coating film with a film thickness of 100 nm was formed. 0.3 J/cm 2 of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 were irradiated to this coating film surface through a polarizing plate. This board|substrate was baked for 30 minutes in 230 degreeC hot-air circulation type oven, and the board|substrate with a liquid crystal aligning film was obtained.

The obtained said two board|substrates are made into one set, a sealing compound is printed on a board|substrate, and after bonding the other board|substrate so that a liquid crystal aligning film surface may face and an orientation direction may be 0 degree, a sealing compound is hardened to prepare empty cells. Liquid crystal MLC-3019 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 110 degreeC for 1 hour, it was left to stand overnight, and the residual image evaluation by a long-term alternating current drive was performed. The value of the angle (DELTA) of this liquid crystal cell after a long-term alternating current drive was 0.26 degree|times.

<Examples 17 to 21, Comparative Examples 7 to 9>

Instead of liquid crystal aligning agent (A1), except having used liquid crystal aligning agent A2 - A5, B1-B3 shown in Table 3 respectively, respectively, it is the method exactly similar to Example 16, manufactures FFS drive liquid crystal cell, Long-term alternating current drive The residual image evaluation was performed by Table 4 shows the value of the angle Δ of this liquid crystal cell after the long-term alternating current drive in each.

<Examples 22-30, Comparative Examples 10-12>

Instead of the liquid crystal aligning agent (A1), except having used the liquid crystal aligning agents A7-A15 and B4-B6 shown in Table 4 respectively, respectively, by the method exactly similar to Example 16, an FFS drive liquid crystal cell is manufactured, and long-term alternating current drive The residual image evaluation was performed by Table 5 shows the value of the angle Δ of this liquid crystal cell after the long-term alternating current drive in each.

In Table 4, when comparing Comparative Example 7 and Examples 16 and 19, Comparative Example 8 and Examples 17 and 20, Comparative Example 9 and Examples 18 and 21, the polyamic acid in which the acid terminal is modified with a monoamine is blended When it does, it turns out that there exists a tendency for the afterimage by alternating current drive to reduce.

In addition, in Table 5, when Comparative Example 10 and Examples 22, 25, 28, Comparative Example 11 and Examples 23, 26, 29, Comparative Example 12 and Examples 24, 26, 30 are compared, respectively, the amine terminus is When the polyamic acid modified with carboxylic acid anhydride was blended, it was confirmed that there exists a tendency for the residual image by a long-term alternating current drive to reduce.

For Comparative Examples and Examples with the same blend ratio, when the difference of the Δ values is taken, the higher the blend ratio of component 1, the greater the difference between the Δ value of the comparative example and the Δ value of the Example. From this, this method is especially useful when it intends to raise the ratio of component 1.

Industrial Applicability

The liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention has a high yield in liquid crystal panel manufacture, and can reduce the residual image by the alternating current drive which generate|occur|produces in the liquid crystal display element of an IPS drive system or an FFS drive system, Afterimage The liquid crystal display element of the IPS drive method or FFS drive method excellent in a characteristic is obtained. Therefore, it is used especially in the liquid crystal display element by which high display quality is calculated|required.

In addition, the specification of Japanese Patent Application No. 2018-214005 for which it applied on November 14, 2018, a claim, drawings, and all the content of an abstract are referred here, and it takes in as an indication of the specification of this invention.

Claims (13)

A diamine component containing at least one diamine selected from the group consisting of a diamine having a partial skeleton represented by any of the following formulas (ND-1) to (ND-4) and a diamine represented by (ND-5); , at least one polymer selected from the group consisting of a terminal-sealed first polyimide precursor obtained by polymerization-reacting a tetracarboxylic acid component and reacting with an end-blocking agent, and an imidized polymer thereof. (P1) is contained, The liquid crystal aligning agent characterized by the above-mentioned.

(R ¹ , R ²¹ , and R ²² each independently represent a hydrogen atom or a methyl group, and R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a methyl group. S _p3 , S _p4 are each independently A divalent organic group is represented. A ₅ represents a single bond or a divalent organic group.) The method of claim 1,
The liquid crystal aligning agent in which the said tetracarboxylic-acid component contains the tetracarboxylic dianhydride represented by following formula (1).

(X represents a tetravalent organic group selected from the following formulas (X-1) to (X-14).)

(x and y each independently represent a single bond, methylene, ethylene, propylene, ether, carbonyl, ester, phenylene, sulfonyl or amide group. Z ¹ to Z ⁴ are each independently a hydrogen atom; represents a methyl group, an ethyl group, a propyl group, a chlorine atom or a phenyl group. j and k are integers of 0 or 1. m is an integer of 0-5. * denotes a bond.) 3. The method of claim 2,
The liquid crystal aligning agent whose content of tetracarboxylic dianhydride represented by said Formula (1) is 5 mol% or more of the whole tetracarboxylic-acid component. 4. The method according to any one of claims 1 to 3,
Content of at least 1 sort(s) of diamine selected from the group which consists of the diamine containing the partial skeleton represented by said Formula (ND-1) - (ND-4), and the diamine represented by (ND-5) is 5 of the whole diamine component The liquid crystal aligning agent which is mol% or more. 5. The method according to any one of claims 1 to 4,
Liquid crystal in which the said diamine component contains at least 2 types of diamines selected from the group which consists of the diamine represented by the diamine represented by the said formula (ND-1)-(ND-4), and the diamine represented by (ND-5) containing a partial skeleton, Orienting agent. 6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent whose diamine containing the partial skeleton represented by said (ND-1) is a diamine represented by a following formula (ND-1-1) or (ND-1-2).

(R ¹ , R ² each independently represents a hydrogen atom or a methyl group, R ¹¹ , R ²² each independently represents a single bond or *1-R ³ -Ph-*2, R ³ represents a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m Represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m represents an integer of 1 to 5.) *1 represents a site bonded to a benzene ring in formula (ND-1-1) or (ND-1-2), *2 represents formula (ND-1-1) or (ND-1-2) represents a site bonding with an amino group. Ph represents a phenylene group. n is an integer of 1 to 3.) 7. The method according to any one of claims 1 to 6,
The liquid crystal aligning agent which further contains the at least 1 sort(s) of polymer (P2) chosen from the group which consists of a 2nd polyimide precursor obtained by making a diamine component and a tetracarboxylic-acid component react, and its imidation polymer. 8. The method of claim 7,
The liquid crystal aligning agent in which the diamine component which is a raw material of the said polymer (P2) contains the at least 1 sort(s) of diamine chosen from the group which consists of following formula (3), following formula (4), and following formula (5).

(A ₁ , A ₄ each independently represents a single bond or a divalent organic group, and A ₂ represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, a phosphoric acid group, or a C1-C20 group. represents a monovalent organic group, and A ₃ represents a divalent organic group. a is an integer of 1 to 4, and when a is 2 or more, _{the structures of A 2} may be the same or different. b and c are each independent is an integer of 1 to 2. d is an integer of 0 or 1.) 9. The method according to claim 7 or 8,
The diamine component which is a raw material of the said polymer (P2) is following formula (DA-3-1), (DA-4-1) - (DA-4-23), and (DA-5-1) - (DA- The liquid crystal aligning agent containing the at least 1 sort(s) of diamine chosen from the group which consists of 5-3).

10. The method according to any one of claims 1 to 9,
The liquid crystal aligning agent whose said terminal blocker is an acid anhydride or a monoamine. 11. The method according to any one of claims 7 to 10,
The liquid crystal aligning agent whose content of the said polymer (P1) is 30 mass parts or more with respect to 100 mass parts of total amounts of the said polymer (P1) and the said polymer (P2). The liquid crystal aligning film obtained by apply|coating the liquid crystal aligning agent in any one of Claims 1-11, and irradiating the ultraviolet-ray which polarized to the film|membrane obtained by baking. A liquid crystal display element provided with the liquid crystal aligning film of Claim 12.