KR20210122779A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same - Google Patents

Abstract

(식 중의 기호의 정의는, 명세서에 기재된 바와 같다.)

Provided are a highly reliable liquid crystal display element, a liquid crystal aligning film suitable for the liquid crystal display element, and a liquid crystal aligning agent that has little residual image generation and can minimize bright spots even when physical friction such as rubbing by a spacer occurs.
The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
Component (A): A polymer (A) having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
(B) Component: A compound represented by the following formula (B).

(The definition of the symbol in the formula is as described in the specification.)

Description

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

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

For liquid crystal display elements, various driving methods have been developed in which electrode structures, physical properties of liquid crystal molecules to be used, manufacturing processes, and the like differ. For example, TN (twisted nematic) type, STN (super-twisted nematic) type, VA (vertical alignment) type, MVA (multi-domain vertical alignment) type, IPS (in-plane switching) type, FFS (fringe field) type A liquid crystal display element, such as a switching) type, and a PSA (polymer-sustained alignment) type, is known.

These liquid crystal display elements are equipped with the liquid crystal aligning film in order to orientate a liquid crystal molecule. As for the material of a liquid crystal aligning film, since various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable, the film which consists of polymers, such as a polyamic acid, a polyimide, and polysiloxane, is generally used.

In recent years, the request|requirement with respect to image quality improvement of a liquid crystal display element is increasing more and more. In particular, in the display or liquid crystal television of a medical device, when it is driven for a long time, the so-called "afterimage" that an image remains is a big problem, and the request|requirement with respect to reduction of an afterimage is high. From a viewpoint of the further quality improvement of a liquid crystal display element, it is desired to obtain the liquid crystal display element which an afterimage does not generate|occur|produce easily compared with the past.

In view of such a situation, the liquid crystal aligning film and liquid crystal aligning agent which provide the liquid crystal display element excellent in reduction of an afterimage are known (patent document 1, 2, 3).

Moreover, in the liquid crystal display element in the said use, the characteristic which can endure long-term use in a harsh use environment is also calculated|required, Even if it is after the liquid crystal aligning agent containing a specific compound in patent document 4 is exposed to a backlight for a long time, voltage A liquid crystal aligning film with a small fall of retention is obtained, and obtaining a reliable liquid crystal display element is indicated.

International Publication No. 2016/063834 International publication pamphlet No. 2015/060366 Japanese Laid-Open Patent Publication No. 2018-054761 International Publication Pamphlet No. 2010/074269

Moreover, as what is called a touchscreen type liquid crystal display element spreads widely, it is performed frequently for a user to apply strong pressing force with a finger to the display element. At this time, the spacer which exists inside a liquid crystal display element moves in a liquid crystal display element, and rubs a liquid crystal aligning film. The liquid crystal aligning film to which the stress is applied by the spacer cannot regulate the orientation of the liquid crystal, and even though the liquid crystal display element is displayed in black, for example, light escapes from the spacer periphery and is displayed as a bright spot. have.

It cannot be said that the liquid crystal aligning agent proposed conventionally can necessarily achieve all the said subject. The present invention has been made on the basis of the above circumstances, and the object thereof is a highly reliable liquid crystal display element that can minimize the occurrence of afterimages and minimize bright spots even when physical friction such as rubbing by a spacer occurs. It exists in providing, and it exists in providing the liquid crystal aligning film suitable for such a liquid crystal display element, and its liquid crystal aligning agent.

MEANS TO SOLVE THE PROBLEM This inventor found out that the said subject was solvable by using the liquid crystal aligning agent containing a specific component, as a result of earnestly advancing research, and came to complete this invention.

This invention makes the following a summary.

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.

Component (A): A polymer (A) having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

(B) Component: A compound (B) represented by the following formula (B).

[Formula 1]

(X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group. R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z ₁₁ , Z ₁₂ each independently represents a hydrogen atom or a substituent. optionally an alkyl group having 1 to 10 carbon atoms, an optionally substituted alkenyl group having 2 to 10 carbon atoms, an optionally substituted alkynyl group having 2 to 10 carbon atoms, tert-butoxycarbonyl group, or 9-fluorenylmethoxycarbonyl group indicate.)

[Formula 2]

(R represents an alkanediyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 1 or 2. A ¹ represents a single bond, -O-, -CO-, -OCO-, -COO-, -CONR- (R represents a hydrogen atom or a methyl group.), -NRCONR- (R represents a hydrogen atom or a methyl group.), -N=N-, -CH ₂ -, -(CH ₂ ) _n - (. _n is an integer from 2 to 18), or the - (CH _{2) n} - CH ₂ is any of, -O-, -CO-, -OCO-, -COO- , -CONR- ( R represents a hydrogen atom or a methyl group), -NRCONR- (R represents a hydrogen atom or a methyl group), and a divalent organic group (L) substituted with phenylene or biphenylene. In the organic group (L), two oxygen atoms are not adjacent to each other, and -OCO-, -COO-, -CONR- (R represents a hydrogen atom or a methyl group), and -NRCONR- (R is a hydrogen atom) or a methyl group.) The two groups selected from are not adjacent to each other, and any hydrogen atom on the phenylene or biphenylene ring may be substituted with a monovalent organic group.)

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, even when there is little generation|occurrence|production of an afterimage and physical friction, such as rubbing by a spacer, generate|occur|produces, the liquid crystal display element which can minimize a luminescent point, and the liquid crystal aligning film which provides this are obtained.

Each component contained in the liquid crystal aligning agent of this invention, and the other component mix|blended arbitrarily as needed are demonstrated.

<Polymer (A)>

The liquid crystal aligning agent of this invention contains the polymer (A) which has at least 1 type of repeating unit chosen from the group which consists of the repeating unit represented by the said Formula (1), and the repeating unit represented by the said Formula (2).

_{Specific examples of the alkyl group having 1 to 5 carbon atoms for R 1} in the formula (2) include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a s-butyl group, t-butyl group, n-pentyl group, etc. are mentioned. From a viewpoint of the easiness of imidation by heating _{, it is preferable that R<1>} is a hydrogen atom or a methyl group.

In addition to the formula (2) Z _11, specific examples of a specific example of a carbon number of alkyl group of from 1 to 10, Z ₁₂ is a carbon number of alkyl group of from 1 to 5 exemplified in the R ₁ in the, hexyl group, heptyl group, An octyl group, a nonyl group, a decyl group, etc. are mentioned. Specific examples of the Z ₁₁ , Z ₁₂ alkenyl group having 2 to 10 carbon atoms include a vinyl group, a propenyl group, a butynyl group, and the like, and these may be linear or branched. Specific examples of the alkynyl group having 2 to 10 carbon atoms for Z ₁₁ and Z ₁₂ include an ethynyl group, 1-propynyl group, and 2-propynyl group.

Z ₁₁ , Z ₁₂ may have a substituent, and examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, a cyano group, and an alkoxy group. .

From a viewpoint of few residual images _{, it is preferable that said Z 11} and Z ₁₂ are each independently a hydrogen atom or a methyl group.

In the formulas (1) and (2), X ₁ and Y ₁ are as defined above. _{As X<1>} of Formula (1), at least 1 sort(s) chosen from the group which consists of tetracarboxylic dianhydride, tetracarboxylic-acid diester, and tetracarboxylic-acid diester dihalide (Hereinafter, these are collectively named, and tetracarboxyl and tetravalent organic groups derived from acid derivatives). When a specific example is given, it is derived from aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, these tetracarboxylic acid diester, or tetracarboxylic acid diester dihalide. A tetravalent organic group is mentioned. _Y<1> of Formula (1) is a divalent organic group derived from diamine.

Here, aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including the at least 1 carboxyl group couple|bonded with an aromatic ring. Aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups couple|bonded with a chain hydrocarbon structure. However, it is not necessary to be constituted by only the chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in a part thereof. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least 1 carboxyl group couple|bonded with an alicyclic structure. However, all of these four carboxyl groups are not couple|bonded with the aromatic ring. Moreover, it is not necessary to be comprised only with an alicyclic structure, and you may have a chain hydrocarbon structure or an aromatic ring structure in a part.

There are few residual images of the liquid crystal aligning film obtained, From a viewpoint which can suppress a luminescent point WHEREIN: X<_1> is a tetravalent organic group chosen from the group which consists of following formula (4a)-(4n), Formula (5a), and Formula (6a) it is preferable

[Formula 3]

(x and y are each independently a single bond, -O-, -CO-, -COO-, an alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, sulfonyl or an amide group. Z ¹ to Z ⁶ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring. j and k are 0 or an integer of 1. m is an integer of 1 to 5. * Represents a bonding hand.)

A viewpoint with few residual images WHEREIN: As a preferable specific example of the said Formula (4a), the structure shown by any of following formula (4a-1) - (4a-4) is mentioned.

[Formula 4]

Examples of the alkanediyl group having 1 to 5 carbon atoms in the formulas (5a) and (6a) include methylene, ethylene, 1,3-propanediyl, 1,4-butanediyl, and 1,5-pentanediyl. can

From the viewpoint of less residual image and ensuring solubility, X ₁ in the formula (1) is selected from the formulas (4a) to (4h), (4j), (41), (4m) to (4n) It is preferable that it is a tetravalent organic group.

From the viewpoint of few residual images, X ₁ in the formula (1) is a tetravalent organic group selected from the formulas (4a) to (4h), (4j), (41), and (4m) to (4n). desirable.

From the viewpoint of few residual images, X ₁ is a tetravalent organic group selected from the group consisting of formulas (4a) to (4n), (5a) and (6a), and Y ₁ is a divalent organic group. The content of at least one repeating unit (hereinafter also referred to as repeating unit (t)) selected from the group consisting of the repeating unit represented by (1) and the repeating unit represented by the formula (2) is a total of all repeating units. It is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more.

_{As Y<1>} of Formula (1), the divalent organic group derived from diamine is mentioned, For example, the divalent organic group derived from aliphatic diamine, alicyclic diamine, or aromatic diamine is mentioned. When a specific example is given, As an aliphatic diamine, metaxylylene diamine, ethylene diamine, 1, 3- propane diamine, tetramethylene diamine, hexamethylene diamine etc. are mentioned, for example; Examples of the alicyclic diamine include p-cyclohexanediamine and 4,4'-methylenebis(cyclohexylamine).

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diamino Azobenzene, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-inden-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl -1H-inden-6-amine, 3,5-diaminobenzoic acid, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 1,4-bis(4-aminophenyl) )-piperazine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]ether , 4,4'-bis(4-aminophenoxy)biphenyl, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4 '-propane-1,3-diylbis(piperidin-1,4-diyl)]dianiline, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, following formula (z-1) - The diamine represented by any of (z-19), the diamine represented by the following formula (H), the diamine represented by any of the following formulas (H2) to (H3), the diamine represented by any of the following formulas (V1) to (V3); Diamine having a radical initiation function represented by any of the following formulas (R1) to (R5), 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N-diallyl Diamine having a photopolymerizable group such as aniline at the terminal, diamine having a photo-alignment structure described in paragraph [0053] of International Publication No. 2014/080865 (hereinafter also referred to as WO), carbon-carbon unsaturation described in paragraph [0057] and diamines having a bond and diamines having an azobenzene skeleton described in paragraph [0058].

[Formula 5]

[Formula 6]

[Formula 7]

(R ³ represents -NRCO-, -COO-, -NRCONR-, or -(CH ₂ ) _n - (provided that n is an integer of 2 to 20.), and arbitrary -CH ₂ - is -O -, -COO-, -ND-, -NRCO-, -NRCONR-, -NRCOO- or -OCOO- may be substituted. D represents a thermal leaving group, and R represents a hydrogen atom or a monovalent organic group.) , R ⁴ is a single bond or a benzene ring, and any hydrogen atom on the benzene ring may be substituted with a monovalent organic group.)

[Formula 8]

(X ₁ is -CO-, -O-, -COO-, -L ₁ -RL ₂ - (L ₁ , L ₂ are each independently a single bond, an oxygen atom, or -COO-, R is -(CH ₂ ) _n - (n is an integer of 1 to 12), or -NRCO- (R represents a hydrogen atom or a methyl group.) X ₂ is a single bond, -NRCO- (R is represents a hydrogen atom or a methyl group.) or -COO-. n represents an integer of 1 or 2. Any hydrogen atom on the benzene ring may be substituted with a monovalent organic group.)

[Formula 9]

(two Xs each independently represent -O-, -COO-, -NHCO-, -C(=O)-, or -(CH ₂ ) _n - (n is an integer of 1 to 12); L ₁ and L ₂ are each independently a single bond, -O-, or -COO-, R is -CH ₂ -, -(CH ₂ ) _n - (n is an integer of 2 to 12); or the - (CH _{2) n} -. represents any of the groups CH _2, the oxygen atoms of any hydrogen atom on the benzene ring may be substituted with a monovalent organic).

[Formula 10]

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, - O-(CH ₂ ) _m -O-, -OC(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-, or -COO-(CH ₂ ) _m -OCO-.

X ¹ and X ² are each 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 -. Among these, a plurality of a1 is each independently an integer of 1 to 15, a plurality of A ₁ each independently represents an oxygen atom or -COO-, and m ₁ is an integer of 1 or 2. X ³ represents a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO-. X ⁴ represents -CONH-, -NHCO-, -O-, -COO- or -OCO-.

G ₁ and G ₂ are each independently selected from a divalent aromatic group having 6 to 12 carbon atoms, such as phenylene, biphenylene, and naphthalene, or a divalent alicyclic group having 3 to 8 carbon atoms, such as cyclopropylene and cyclohexylene. It represents a bivalent cyclic group to be used. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. . k represents the integer of 0 or 1, m and n are each independently the integer of 0-3, The sum total of m and n is 1-4.

R<^1> represents a C1-C20 alkyl group, a C1-C20 alkoxy group, or a C2-C20 alkoxyalkyl group. Optional hydrogens forming R ¹ may be substituted with fluorine.

R<^2> represents a C1-C20 alkyl group or a C2-C20 alkoxyalkyl group, and ^{arbitrary hydrogen which forms R<2>} may be substituted by fluorine. R ³ represents a structure having a steroid skeleton.)

[Formula 11]

(n represents the integer of 2-10.)

In the formulas (H), (H2) and (H3), the hydrogen atom on the benzene ring is an alkyl group having 1 to 5 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, a fluorine atom, etc. A halogen atom, a halogenated alkyl group having 1 to 5 carbon atoms, such as a trifluoromethyl group, -NR ₁ R ₂ (R ₁ , R ₂ each independently represents a hydrogen atom, a methyl group, or Boc.), a cyano group, a hydride You may substitute with monovalent organic groups, such as a hydroxy group. In addition, Boc represents a tert-butoxycarbonyl group, and it is the same also in the following.

As a preferable specific example of the diamine represented by the said formula (H) from a viewpoint with few residual images, the diamine represented by any of following formula (H-1) - (H-14) is mentioned.

[Formula 12]

[Formula 13]

(R represents a hydrogen atom, a methyl group, or a Boc group.)

As a preferable specific example of the diamine represented by the said Formula (H2) from a viewpoint with few residual images, the diamine represented by any of following formula (H2-1) - (H2-17) is mentioned.

[Formula 14]

[Formula 15]

(R represents a hydrogen atom, a methyl group, or a Boc group. * represents a bond.)

As a preferable specific example of the diamine represented by the said formula (H3) from a viewpoint with few residual images, the diamine represented by any of the following formulas (H3-1) - (H3-4) is mentioned.

[Formula 16]

As a more preferable specific example of the diamine represented by (V-1) - (V-3), the diamine represented by any of following formula (V2-1) - (V2-13) is mentioned.

[Formula 17]

[Formula 18]

(X ^v1 to X ^v4 , X ^p1 to X ^p8 are each 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 ^v5 is -O-, -CH ₂ O-, -CH ₂ represents OCO-, -COO-, or -OCO-. X ^v6 to X ^v7 , X ^s1 to X ^s4 each independently represent -O-, -COO- or -OCO-. X _a to X _f are , a single bond, -O-, -NH-, or -O-(CH ₂ ) _m -O- R ^v1 to R ^v4 , R ^1a to R ^1h are each independently 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 is shown, and m is an integer of 1 to 8.

When applying to the liquid crystal aligning agent for liquid crystal display elements of TN type, STN type, or vertical alignment type, as for the said polymer (A), X<_1> is a tetravalent organic group, Y<_1> is said Formula (V1) - (V3) ) a repeating unit selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), which is a divalent organic group derived from a diamine represented by any of the above (hereinafter referred to as repeating unit (a)) .) It is preferable to include one or more types. The content is preferably 1 mol% or more, more preferably 3 mol% or more, more preferably 5 mol% or more with respect to all repeating units of the polymer (A) in total.

The content of the repeating unit (a) is preferably 99 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less with respect to all the repeating units of the polymer (A).

When applying to the liquid crystal aligning agent for liquid crystal display elements of PSA type, as for the said polymer (A), X ₁ is a tetravalent organic group, Y ₁ is diamine which has the said radical initiation function, and the said photopolymerizable group at the terminal A repeating unit selected from the group consisting of a repeating unit represented by the formula (1), which is a divalent organic group derived from a diamine selected from the group consisting of diamines, and a repeating unit represented by the formula (2) (hereinafter, repeating unit (b) ) is also called.) It is preferable to include one or more types. The content is preferably 1 mol% or more, more preferably 3 mol% or more, more preferably 5 mol% or more with respect to all repeating units of the polymer (A) in total. In this case, the polymer (A) may use together 1 or more types of repeating units (a).

The content of the repeating unit (a) and the repeating unit (b) is preferably 99 mol% or less, more preferably 97 mol% or less, and more preferably 95 mol% or less, with respect to all the repeating units of the polymer (A) in total. % or less is more preferable. Moreover, in this case, you may include repeating units other than the said repeating unit (a) and repeating unit (b) according to the objective.

When applying to the liquid crystal aligning agent for liquid crystal display elements of IPS type or FFS type, as for the said polymer (A), X<_1> is a tetravalent organic group, Y<_1> is p-phenylenediamine, 4,4'-dia Minodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminoazobenzene, 1,4-bis(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4 '-diaminobiphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]ether, 4,4'-bis(4-aminophenoxy)biphenyl, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4' -Propane-1,3-diylbis(piperidin-1,4-diyl)]dianiline, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, the above formulas (z-1) to ( z-2), (z-3), selected from the group consisting of the diamine represented by any of (z-5), the diamine represented by the formula (H), and the diamine represented by any of the formulas (H2) to (H3). A repeating unit (hereinafter, also referred to as repeating unit (c)) selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), which is a divalent organic group derived from the diamine used, is 1 It is preferable to include more than one species. The content is preferably 5 mol% or more, more preferably 10 mol% or more with respect to all repeating units of the polymer (A) in total.

The content of the repeating unit (c) is preferably 99 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less, with respect to all the repeating units of the polymer (A).

When liquid-crystal aligning ability is provided by the photo-alignment method with respect to the coating film formed with the liquid crystal aligning agent, as for the said polymer (A), X ₁ is a tetravalent organic group, Y ₁ is diamine which has the said photo-alignment structure; A repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), which is a divalent organic group derived from a diamine selected from the group consisting of a diamine having a carbon-carbon unsaturated bond and a diamine having an azobenzene skeleton It is preferable to include one or more types of repeating units (hereinafter also referred to as repeating units (d)) selected from the group consisting of. The content is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 80 mol% or less with respect to all repeating units of the polymer (A) in total.

The content of the repeating unit (d) is preferably 99 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less with respect to all the repeating units of the polymer (A).

Moreover, when providing liquid-crystal orientation ability by the photo-alignment method, from a viewpoint with few residual images, as for the said polymer (A), X<_1> is said Formula (4a)-(4c), (4f)-(4g), , Y ₁ is a divalent organic group, a repeating unit (hereinafter also referred to as repeating unit (e)) selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2); It is preferable to include the above. The content is preferably 5 mol% or more, more preferably 10 mol% or more with respect to all repeating units of the polymer (A) in total.

Although a polymer (A) may consist of 1 type, it may consist of 2 or more types. If the specific example in the case of two or more types of polymer (A) is given, there is little generation|occurrence|production of an afterimage, and from a viewpoint which can suppress a luminescent point, repeating unit (t), any repeating unit of (a)-(e) The aspect containing at least 1 type or more of the polymer which has is mentioned. Moreover, when a polymer (A) consists of two types, the blending ratio of a 1st polymer and a 2nd polymer (1st polymer / 2nd polymer) has few residual images and is 5/95 by weight ratio from a viewpoint of suppressing a luminescent point. - 95/5 are preferable, 10/90 - 90/10 are more preferable, and 20/80 - 80/20 are more preferable.

<Compound (B)>

The liquid crystal aligning agent of this invention contains the compound (B) represented by the said Formula (B). Since the compound (B) is a structure with few steric hindrances, the liquid-crystal orientation of the liquid crystal aligning film containing a polymer (A) is not inhibited remarkably, but the liquid crystal aligning film obtained has high liquid-crystal orientation. Moreover, in order to have a methylol group in a molecule|numerator, in any between a polymer (A) and a compound (B), or in any of compound (B) comrades, since a crosslinking reaction generate|occur|produces, the film|membrane intensity|strength of the liquid crystal aligning film obtained can be raised. For this reason, there is little generation|occurrence|production of an afterimage and the liquid crystal display element provided with the liquid crystal aligning film of this invention can minimize a luminescent point, even when physical friction, such as rubbing by a spacer, generate|occur|produced. Moreover, since the compound (B) is excellent in the ability to capture|acquire the impurity component derived from a board|substrate at the point which the effect of raising the crosslinking density of a liquid crystal aligning film is acquired, the liquid crystal aligning film obtained shows a high voltage retention, Therefore, a reliable liquid crystal A display element is obtained.

In said formula (B), a methylene group, an ethylene group, a propanediyl group, a butanediyl group etc. are mentioned as a C1-C4 alkanediyl group of R. From a viewpoint of a high crosslinking effect, a methylene group is especially preferable.

About the said divalent organic group (L), following formulas (L-1) - (L-25), (L2-1) - (L2-3) are given when a preferable specific example is given from a viewpoint with few residual images have.

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

(L ₁ and L ₂ are a single bond, -O-, -CO-, -OCO-, -COO-, -CONR- (R represents a hydrogen atom or a methyl group.), -NRCONR- (R is a hydrogen atom) or a methyl group.), -N=N-, -(CH ₂ ) _n - (n is an integer of 1 to 18) or the above formulas (L-1) to (L-25), and L ₃ is, -(CH ₂ ) _n - (n is an integer of 1 to 18), the formulas (L-2), (L-4), (L-7), (L-8), (L-10) to ( L-11), (L-13), (L-15), (L-17) to (L-18), (L-20) or (L-25), provided that L ₃ is ( In the case of L-2), (L-15), and (L-17), -(CH ₂ ) _{n - in L 3} bonds to -NHCO-.)

Preferred specific examples of the compound (B) include compounds represented by the following formulas (B-1) to (B-34) and (B2-1) to (B2-20).

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

Preferably content of the said compound (B) is 0.1-30 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.5-25 weight part, More preferably, it is 0.5-20 weight part. am.

<Method for producing polyamic acid>

The polymer (A) in the present invention reacts, for example, a tetracarboxylic acid derivative having a structure of _{X 1 with a diamine having a structure of Y 1} described in WO2013/157586 by a known method. can be obtained by doing

[Terminal modifier]

The polymer of a terminal modification type may be sufficient as the polymer (A) in this invention by using a terminal blocker with the above tetracarboxylic-acid derivative and diamine.

Examples of the terminal modifier include acid monoanhydride, dicarbonate diester compound, chlorocarbonyl compound, monocarboxylate compound, monoamine compound, monoisocyanate compound, and the like.

Examples of the acid monhydride include maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, the following formula (m -1) a compound represented by any one of (m-6), n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, 3-(3 -trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, etc. are mentioned.

[Formula 33]

As said dicarbonate diester compound, the compound etc. which are represented, for example by a following formula (D) are mentioned.

[Formula 34]

(R represents a monovalent organic group having 1 to 30 carbon atoms.)

As a chlorocarbonyl compound, the compound etc. which are represented, for example by a following formula (Mc) are mentioned.

[Formula 35]

(A represents a single bond, -O-, -S-, or -NR ₁ -, R and R ₁ each independently represent a monovalent organic group having 1 to 30 carbon atoms, and are bonded to each other by _{R and R 1} to form a ring structure.)

Examples of the monocarboxylic acid chloride include compounds described in paragraphs [0069] to [0082] of WO2011/115076.

As the monoamine compound, for example, 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-toluene 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-amino Benzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-aminotoluene-3-sulfonic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 3-( Trifluoromethoxy)aniline, 4-(trifluoromethoxy)aniline, triethoxysilylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethoxydiethoxysilane and the like.

As said monoisocyanate compound, ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate etc. are mentioned, for example.

Further, specific examples of the monovalent organic group having 1 to 30 carbon atoms in R in the formulas (D) and (Mc) include a methyl group, an ethyl group, a propyl group, a tert-butyl group, a cyclobutyl group, and 1-methyl An alkyl group such as a cyclobutyl group or 1-adamantyl group, an alkenyl group such as a vinyl group or an allyl group, an alkynyl group such as a 1,1-dimethylpropynyl group, 2,2,2-trichloroethyl group, or 1,1-dimethyl group A halogenoalkyl group such as a -2-chloroethyl group, a silylalkyl group such as a 2-trimethylsilylethyl group, an alkyl cyanide group such as a 1,1-dimethyl-2-cyanoethyl group, an aryl group such as a phenyl group, a naphthyl group or an anthranyl group, and benzyl group, an arylalkyl group such as 1-methyl-1-phenylethyl group or 1-methyl-1-(4-biphenylyl)ethyl group, 9-fluoronylmethyl group, a halogenated aryl group such as 2,4-dichlorobenzyl group, p -Nitrobenzyl group or nitrated aryl group such as 3,4-dimethoxy-6-nitrobenzyl group, alkoxyaryl group such as methoxyphenyl group, arylalkenyl group such as cinnamyl group, imidazole group, pyridyl group, pyrimi Heteroaryl groups such as din group, pyridazine group, pyrazine group, and quinolyl group; aliphatic heterocyclic groups such as piperidine group, N-hydroxypiperidinyl group, piperazine group, morpholine group, pyrrolidine group; and cyclic urea groups such as imide groups such as imide or succinimide, imidazolidinone groups, and combinations thereof. In addition, arbitrary -CH ₂ - of the said alkyl group may be substituted with divalent groups, such as -O-, -COO-, -NHCO-, -N(CH _{3 )CO-, -CO-, -NHCONH-.}

It is preferable to set it as 20 mol part or less with respect to a total of 100 mol part of diamine to be used, and, as for the usage ratio of a terminal modifier, it is more preferable to set it as 10 mol part or less.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention may contain the other polymer further in a polymer (A). Examples of other polymers include polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or a derivative thereof, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, etc. can be heard Moreover, as polyorganosiloxane, it is preferable to have at least any one of an oxetanyl group and an oxylanyl group from a synthetic|combination easy viewpoint.

A liquid crystal aligning agent is used in order to produce a liquid crystal aligning film, and takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is an above-described polymer component and the coating liquid containing an organic solvent. In that case, the density|concentration of the polymer in a liquid crystal aligning agent can be suitably changed according to setting of the thickness of the coating film which you want to form. From the viewpoint of forming a uniform and defect-free coating film, the concentration of the polymer is preferably 1% by weight or more, more preferably 10% by weight or less, and particularly preferably 2 to 8% by weight from the viewpoint of storage stability of the solution. .

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyro Lactone, γ-valerolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, N,N-dimethyllactoamide, 3-methoxy-N,N-dimethylpropane amide, 3-butoxy-N,N-dimethylpropanamide (these are collectively referred to as "good solvent"), 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 -It is preferable to use butyrolactone. It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 20 to 99 weight% of the whole solvent contained in a liquid crystal aligning agent, 20 to 90 weight% is more preferable, It is 30 to 80 weight% that it is especially preferable am.

Moreover, as for the organic solvent contained in a liquid crystal aligning agent, the mixed solvent which used together the solvent (it is mentioned a poor solvent) which improves the applicability|paintability at the time of apply|coating a liquid crystal aligning agent to the above solvents, and the surface smoothness of a coating film. It is preferable to use Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

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 monoiso Amyl 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 Monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether, 3-methoxymethylpropionate, 3-E Ethyl oxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2 , 6-dimethyl-4-heptanone) and the like.

Among them, diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2 -Pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone are preferably used.

Preferred combinations of the good solvent and the poor solvent 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 -Butyrolactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether and 2,6 -Dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone And propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, Combinations of propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, etc. are mentioned. 1-80 weight% of the whole solvent contained in a liquid crystal aligning agent is preferable, as for these poor solvents, 10-80 weight% is more preferable, and its 20-70 weight% 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.

The liquid crystal aligning agent of this invention may further contain components other than a polymer component, (B) component, and an organic solvent. As such additional components, an adhesion aid for increasing the adhesion between the liquid crystal aligning film and the substrate or the adhesion between the liquid crystal aligning film and the sealing material, a compound for increasing the strength of the liquid crystal aligning film (hereinafter also referred to as a crosslinking compound), the dielectric constant of the liquid crystal aligning film, A dielectric material, an electrically-conductive material, etc. for adjusting electrical resistance are mentioned.

As the crosslinkable compound, from the viewpoint of less generation of residual images and a high effect of improving the film strength, a group comprising an oxylanyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, an oxazoline ring structure, A compound having at least one group selected from the group consisting of a group having a Meldrum acid structure, a cyclocarbonate group, and a group represented by the formula (d), or any of the following formulas (e-1) to (e-8) A compound selected from the compounds represented by the compound (hereinafter, these are collectively referred to as compound (C)) is preferred.

[Formula 36]

(R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or “*-CH ₂ —OH”. * represents a bond.)

[Formula 37]

Specific examples of the compound having an oxylanyl group include the compound described in paragraph [0037] of JP 10-338880 A, and a compound having a triazine ring in the skeleton described in WO2017/170483, etc. of two or more The compound which has an oxylanyl group is mentioned. Among these, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N ',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, the following formula (r-1) A compound containing a nitrogen atom, such as a compound represented by to (r-3), is particularly preferable.

[Formula 38]

Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of WO2011/132751.

Specific examples of the compound having a protective isocyanate group include compounds having two or more protective isocyanate groups described in paragraphs [0046] to [0047] of JP 2014-224978 A, paragraphs [0119] to [0120] of WO2015/141598 The compound etc. which have 3 or more protected isocyanate groups as described in are mentioned. Among these, compounds represented by the following formulas (bi-1) to (bi-3) are preferable.

[Formula 39]

As a specific example of the compound which has a protective isothiocyanate group, the compound which has the 2 or more protective isothiocyanate group described in Unexamined-Japanese-Patent No. 2016-200798 is mentioned.

Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph [0115] of JP2007-286597A.

Specific examples of the compound having a group containing a Meldrum acid structure include compounds having two or more Meldrum acid structures described in WO2012/091088.

As a specific example of the compound which has a cyclocarbonate group, the compound of WO2011/155577 is mentioned.

_{Examples of the alkyl group having 1 to 3 carbon atoms for R 1} , R ₂ , and R ₃ of the group represented by the formula (d) include the groups exemplified by the formulas (1) and (n).

Specific examples of the compound having a group represented by the formula (d) include compounds having two or more groups represented by the formula (d) described in paragraphs [0058] of WO2015/072554 and Japanese Unexamined Patent Publication No. 2016-118753, The compound of Unexamined-Japanese-Patent No. 2016-200798, etc. are mentioned. Among these, compounds represented by any of the following formulas (hd-1) to (hd-8) are preferable.

[Formula 40]

The said compound is an example of a crosslinking|crosslinked compound, It is not limited to these. For example, components other than the above disclosed in paragraphs [0105] to [0116] of WO2015/060357 are mentioned. Moreover, you may combine 2 or more types of crosslinkable compounds contained in a liquid crystal aligning agent.

As for content of the crosslinking|crosslinked compound in the liquid crystal aligning agent of this invention, 0.5-20 weight part is preferable with respect to 100 weight part of polymer components contained in a liquid crystal aligning agent, a crosslinking reaction advances, and a target effect is expressed, Moreover, from a viewpoint with few AC afterimage characteristics, More preferably, it is 1-15 weight part.

As the adhesion aid, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane , 3-Ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl Triethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane , 9-trimethoxysilyl-3,6-diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl- 3-Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxy Silane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Silane couples such as trimethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane A ring agent is mentioned. When using a silane coupling agent, it is preferable that it is 0.1-30 weight part with respect to 100 weight part of polymer components contained in a liquid crystal aligning agent from a viewpoint with few AC afterimages, More preferably, it is 0.1-20 weight part.

<Liquid crystal alignment film, liquid crystal display element>

By using the said liquid crystal aligning agent, a liquid crystal aligning film can be manufactured. Moreover, the liquid crystal display element which concerns on this invention is equipped with the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element which concerns on this invention is not specifically limited, For example, TN type, STN type, vertical alignment type (VA-MVA type, VA-PVA type etc. are included.), In-plane switching type (IPS) type), FFS type, optical compensation band type (OCB type), etc. can be applied to various operation modes.

The liquid crystal display element which concerns on this invention can be manufactured by the process which has the following processes (1-1)-(1-3), for example. In the step (1-1), the substrate used differs depending on the desired operation mode. Steps (1-2) and (1-3) are common to each operation mode.

[Step (1-1): Formation of a coating film]

First, a coating film is formed on a board|substrate by apply|coating the liquid crystal aligning agent of this invention on a board|substrate, and heating an application surface then.

(1-1A)

For example, when manufacturing a TN-type, STN-type or VA-type liquid crystal display element, first, two substrates on which a patterned transparent conductive film is formed are set as a pair, and on each transparent conductive film formation surface, Preferably the liquid crystal aligning agent prepared above is apply|coated by the offset printing method, the spin coat method, the roll coater method, or the inkjet printing method, respectively. As a board|substrate, For example, glass, such as float glass and soda glass; A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly(alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, a NESA film (trade name of PPG, USA) made of _{tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2} O ₃ -SnO ₂ ), etc. may be used. can In order to obtain the patterned transparent conductive film, for example, after forming the transparent conductive film without a pattern, the method of forming a pattern by photoetching; Method of using the mask which has a desired pattern when forming a transparent conductive film; etc. can be followed. In the application of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. You may perform pre-processing.

After apply|coating a liquid crystal aligning agent, it is the objective, such as prevention of liquid sag of the apply|coated liquid crystal aligning agent, Preferably preheating (pre-baking) is performed. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25 to 10 minutes, More preferably, it is 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and thermally imidating the amic-acid structure which exists in a polymer as needed. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5 to 200 minutes, More preferably, it is 10 to 100 minutes. The film thickness of the liquid crystal aligning film formed in this way becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(1-1B)

In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, the electrode formation surface of the substrate on which the electrode made of a transparent conductive film or metal film patterned in a comb-tooth shape is formed, and on one surface of the opposite substrate on which the electrode is not formed. A coating film is formed by apply|coating a liquid crystal aligning agent, respectively, and heating each application surface then. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after application, the patterning method of the transparent conductive film or metal film, the pretreatment of the substrate, and the preferable film thickness of the coating film to be formed are the same as in (1-1A) above. do. As the metal film, for example, a film made of a metal such as chromium can be used.

In either case of said (1-1A) and (1-1B), after apply|coating a liquid crystal aligning agent on a board|substrate, the coating film used as a liquid crystal aligning film or a liquid crystal aligning film is formed by removing an organic solvent. At this time, by heating again after coating film formation, the dehydration ring-closure reaction of the polyamic acid mix|blended with the liquid crystal aligning agent which concerns on this invention, polyamic acid ester, and a polyimide is advanced, and it is good also as a coating film imidated more.

[Step (1-2): Orientation ability imparting treatment]

When manufacturing the liquid crystal display element of TN type, STN type, IPS type, or FFS type, the process which provides liquid-crystal orientation ability to the coating film formed in the said process (1-1) is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. Examples of the alignment ability imparting treatment include a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, or cotton, and a photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. can On the other hand, when manufacturing a VA-type liquid crystal display element, although the coating film formed in the said process (1-1) can be used as a liquid crystal aligning film as it is, you may perform an orientation ability provision process with respect to this coating film.

When providing liquid-crystal orientation ability to a coating film by a photo-alignment process, as a radiation irradiated to a coating film, the ultraviolet-ray and visible light containing the light of a wavelength of 150-800 nm can be used, for example. When the radiation is polarized light, it may be linearly polarized or partially polarized. Moreover, when the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from the direction perpendicular|vertical to a board|substrate surface, may be performed from an oblique direction, or may be performed combining these. When irradiating a non-polarized radiation, the direction of irradiation is made into an oblique direction.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. Ultraviolet rays in a preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter, a diffraction grating, or the like. The radiation dose is preferably from 10 to 5,000 mJ/cm 2 , more preferably from 30 to 2,000 mJ/cm 2 .

Moreover, in order to raise the reactivity with the light irradiation with respect to a coating film, you may perform heating a coating film. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.

Moreover, when using the ultraviolet-ray containing the light of a wavelength of 150-800 nm, although the light irradiation film obtained in the said process can be used as a liquid crystal aligning film as it is, baking the light irradiation film, washing|cleaning with water or an organic solvent, or You may implement these combinations. The firing temperature at this time is preferably 80 to 300°C, more preferably 80 to 250°C. Firing time becomes like this. Preferably it is 5 to 200 minutes, More preferably, it is 10 to 100 minutes. In addition, you may implement the frequency|count of baking twice or more. The photo-alignment process here corresponds to the process of light irradiation in the state which is not in contact with a liquid crystal layer.

The organic solvent used for washing is not particularly limited, but specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, and 1-methoxy -2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, or cyclohexyl acetate.

In addition, with respect to the liquid crystal aligning film after the rubbing treatment, by irradiating an ultraviolet ray to a part of the liquid crystal aligning film, a treatment to change the pretilt angle of a part of the liquid crystal aligning film, or after forming a resist film on a part of the liquid crystal aligning film surface After performing a rubbing process in the direction different from a rubbing process, you may perform the process which removes a resist film, and you may make a liquid crystal aligning film have the liquid-crystal orientation different for every area|region. In this case, it is possible to improve the viewing characteristic of the liquid crystal display element obtained. The liquid crystal aligning film suitable for a VA-type liquid crystal display element can be used suitably also for a PSA-type liquid crystal display element.

[Step (1-3): Construction of liquid crystal cell]

(1-3A)

A liquid crystal cell is manufactured by preparing two board|substrates with a liquid crystal aligning film as mentioned above, and arrange|positioning a liquid crystal between the board|substrates of 2 sheets opposingly arranged. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a method known conventionally. First, the cell partitioned by the board|substrate surface and the sealing compound by opposingly arrange|positioning two board|substrates through the clearance gap (cell gap) so that each liquid crystal aligning film may oppose, bonding the peripheral part of two board|substrates with a sealing compound, and After injecting and filling the liquid crystal in the gap, the liquid crystal cell is manufactured by sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. After apply|coating an ultraviolet-ray-curable sealing compound to the predetermined place on one board|substrate among the board|substrates of 2 sheets which formed the liquid crystal aligning film, for example, and further dripping a liquid crystal to predetermined several points on the liquid crystal aligning film surface, a liquid crystal aligning film While bonding the other board|substrate so that this may oppose, a liquid crystal is expanded to the whole surface of a board|substrate, Then, a liquid crystal cell is manufactured by irradiating an ultraviolet light to the whole surface of a board|substrate, and hardening a sealing compound. In either case, it is preferable to remove the flow orientation at the time of liquid crystal filling by heating the liquid crystal cell produced as described above to a temperature at which the used liquid crystal takes an isotropic phase and then slowly cooling to room temperature. .

As a sealing agent, the epoxy resin etc. containing the aluminum oxide sphere as a hardening|curing agent and a spacer can be used, for example.

As a liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. are mentioned. Among them, nematic liquid crystals are preferable, for example, thief base, azoxy, biphenyl, phenylcyclohexane, ester, terphenyl, biphenylcyclohexane, pyrimidine, dioxane, and biphenyl. A cyclooctane-based liquid crystal or a Cuban-based liquid crystal is used.

Moreover, to these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate; You may add a ferroelectric liquid crystal, such as a chiral agent sold as C-15 and CB-15 (merck company brand name), p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate, etc. The liquid crystal may further include an anisotropic dye. "Dye" means a material capable of intensively absorbing or transforming light in the visible light region, for example, at least a part or the entire range within a wavelength range of 400 nm to 700 nm. "Anisotropic dye" refers to a material capable of anisotropic absorption of light in at least a part or the entire range of the visible light region. The color of the liquid crystal cell can be controlled through the use of the dye. The type of the anisotropic dye is not particularly limited, and, for example, a black dye or a color dye may be used. The ratio of the anisotropic dye to the liquid crystal is appropriately selected, for example, the anisotropic dye can be preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the liquid crystal compound.

(1-3B)

When manufacturing a PSA type liquid crystal display element, except for injecting|pouring or dripping a photopolymerizable compound, such as following formula (w-1) - (w-5), with a liquid crystal, for example, (1-3A) and In the same manner, a liquid crystal cell is constructed.

[Formula 41]

Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage to be applied here can be, for example, 5 to 50 V of direct current or alternating current. Moreover, although the ultraviolet-ray and visible light containing the light of a wavelength of 150-800 nm can be used as light to irradiate, The ultraviolet-ray containing the light of a wavelength of 300-400 nm is preferable, for example. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. In addition, the ultraviolet rays in the above preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter diffraction grating or the like. The amount of light irradiated is preferably 100 mJ/cm 2 or more and less than 30,000 mJ/cm 2 , more preferably 100 to 20,000 mJ/cm 2 .

(1-3C)

When a coating film is formed on a board|substrate using the liquid crystal aligning agent containing the compound (polymer or additive) which has a photopolymerizable group, it carries out similarly to said (1-3A), and constructs a liquid crystal cell, After that, 1 pair You may employ|adopt the method of manufacturing a liquid crystal display element by passing through the process of irradiating light to a liquid crystal cell in the state which applied voltage between the conductive film which has on the board|substrate of. According to this method, the advantages of the PSA mode can be realized with a small amount of light irradiation. Light irradiation to a liquid crystal cell may be performed in the state which drove the liquid crystal by voltage application, or you may perform it in the state which applied the voltage low enough to not drive a liquid crystal. The voltage to be applied can be, for example, a direct current or alternating current of 0.1 to 30 V. Regarding the conditions of the light to be irradiated, the description of (1-3B) above is applicable. The light irradiation treatment here corresponds to the light irradiation treatment in a state in contact with the liquid crystal layer.

And the liquid crystal display element which concerns on this invention can be obtained by bonding a polarizing plate together on the outer surface of a liquid crystal cell. As a polarizing plate bonded to the outer surface of the liquid crystal cell, a polarizing plate consisting of a polarizing film called "H film" in which iodine is absorbed while stretching or aligning polyvinyl alcohol is sandwiched by a cellulose acetate protective film, or a polarizing plate composed of H film itself. can be heard

The liquid crystal display element according to the present invention can be effectively applied to various devices, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, It can be used for various display devices, such as a smart phone, various monitors, a liquid crystal television, and an information display.

By using the liquid crystal aligning agent of this invention as mentioned above, there is little generation|occurrence|production of an afterimage, and even when physical friction, such as rubbing by a spacer, occurs, a liquid crystal aligning film which can minimize a luminescent point, and reliable liquid crystal provided with this A display element can be obtained.

Example

The present invention will be more specifically described below with reference to 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.

(diamine)

DA-1 to DA-22: compounds each represented by the following formulas (DA-1) to (DA-22)

(tetracarboxylic dianhydride)

CA-1 to CA-8: compounds each represented by the following formulas (CA-1) to (CA-8)

(tetracarboxylic acid diester dihalide)

CE-1: a compound represented by the following formula (CE-1)

(monocarboxylate chloride)

E-1: acryloyl chloride

(Compound B)

B-1 to B-10: compounds each represented by the following formulas (B-1) to (B-10)

(additive)

c-1 to c-3: compounds each represented by the following formulas (c-1) to (c-3)

F-1: N-α-(9-fluorenylmethyloxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine (compound represented by the following formula (F-1))

s-1: 3-glycidoxypropyltriethoxysilane (compound represented by the following formula (s-1))

s-2: 3-glycidoxypropylmethyldiethoxysilane (compound represented by the following formula (s-2))

M-1: 3-picolylamine

(organic solvent)

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

BCS: butyl cellosolve, DIBK: diisobutyl ketone,

NEP: N-ethyl-2-pyrrolidone, DAA: diacetone alcohol

PC: propylene carbonate, DME: dipropylene glycol dimethyl ether,

DPM: dipropylene glycol monomethyl ether,

PB: propylene glycol monobutyl ether,

PGDAC: propylene glycol diacetate,

DEDE: diethylene glycol diethyl ether,

GVL: γ-valerolactone, DML: N,N-dimethyllactoamide

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

(Fmoc represents a 9-fluorenylmethyloxycarbonyl group.)

[Viscosity]

The E-type viscometer TVE-22H (manufactured by Toki Industries, Ltd.) was used, the sample amount was 1.1 ml, and the cone rotor TE-1 (1°34', R24) was measured at 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 polyethyleneglycol and polyethyleneoxide conversion values.

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) is 30 mmol/L, phosphoric acid/anhydrous crystals (o-phosphoric acid) are 30 mmol/L, tetrahydrofuran (THF) is 10 mL/L), flow rate: 1.0 mL/min

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.

<Measurement of imidization rate>

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53 ml) was added, and ultrasonic wave was applied to completely dissolve it. Proton NMR of 500 MHz was measured for this solution with the NMR measuring instrument (JNW-ECA500) (made by Nippon Electronics Datum). The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and the integrated peak of this proton and the integrated value of the proton peak derived from the NH group of the amic acid appearing around 9.5 ppm to 10.0 ppm. It was used and calculated|required by the following formula|equation.

Imidization rate (%) = (1 - α·x/y) × 100

In the above formula, X is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated peak of the reference proton, and α is the NH of the amic acid in the case of polyamic acid (imidization rate is 0%) It is the ratio of the number of reference protons to one group proton.

[Synthesis of Polymer (A)]

<Synthesis Example 1>

To a four-neck flask equipped with a stirrer and a nitrogen inlet tube, CA-2 (2.25 g, 8.99 mmol), DA-6 (2.97 g, 8.99 mmol), and DA-7 (3.43 g, 9.01 mmol) and NMP (34.6 g) were added and dissolved, and it was made to react at 60 degreeC for 4 hours. Then, CA-3 (1.75 g, 8.92 mmol) and NMP (6.99 g) were added, and it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (40g) and diluting to 6.5 weight%, acetic anhydride (7.06g) and pyridine (2.19g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4 hours. This reaction solution was thrown into methanol (463 g), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder. The imidation ratio of this polyimide was 74 %, Mn was 12500, and Mw was 38500.

NMP (18.0g) is added to the obtained polyimide powder (2.0g), M-1 is added so that it may become 1 weight% with respect to polyimide solid content, it stirs at 70 degreeC for 12 hours, and it melt|dissolves, and solid content concentration is 10% A solution of phosphorus polyimide (PI-V-1) was obtained.

<Synthesis Example 2>

In a 4-neck flask equipped with a stirrer and a nitrogen inlet tube, CA-2 (1.20 g, 4.80 mmol), DA-8 (1.46 g, 9.59 mmol), DA-9 (1.74 g, 7.18 mmol), and DA-7 (2.74 g, 7.20 mmol) and NMP (28.58 g) were added and dissolved, followed by reaction at 60°C for 2 hours. Then, CA-5 (1.05 g, 4.81 mmol) and NMP (4.19 g) were added, followed by reaction at room temperature for 4 hours, and further CA-3 (2.78 g, 14.18 mmol) and NMP (11.1 g) were added. And it was made to react at room temperature for 4 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (40g) and diluting to 6.5 weight%, acetic anhydride (8.90g) and pyridine (2.76g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4 hours. This reaction solution was thrown into methanol (472 g), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder. The imidation ratio of this polyimide was 74 %, Mn was 13000, and Mw was 39000.

NMP is added to the obtained polyimide powder so that solid content concentration may be 10 weight%, M-1 is added so that it may become 1 weight% with respect to polyimide solid content, stirred at 70 degreeC for 12 hours to dissolve, and polyimide (PI- V-2) was obtained.

<Synthesis Example 3>

5.86 g (24.0 mmol) of DA-2, 5.46 g (16.0 mmol) of DA-10, 1.73 g (16.0 mmol) of DA-4 in a 4-neck flask equipped with a stirring device and a nitrogen inlet tube, 7.69 g (24.0 mmol) of DA-1 and 194 g of NMP were added, and it stirred, sending nitrogen, and it melt|dissolved. 17.1 g (76.4 mmol) of CA-1 is added, stirring this diamine solution, NMP is further added so that solid content concentration may be 12 weight%, it stirs at 40 degreeC for 24 hours, and polyamic-acid solution (viscosity: 549 mPa*) s) was obtained. As for the polyamic acid, Mn was 12400, and Mw was 33000.

After adding NMP to this polyamic-acid solution (225g) and diluting to 9.0 weight%, acetic anhydride (17.1g) and pyridine (3.54g) were added as an imidation catalyst, and it was made to react at 55 degreeC for 3 hours. This reaction liquid was thrown into methanol (1111 g), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried at 60 degreeC for 12 hours, and obtained polyimide powder. The imidation ratio of this polyimide powder was 66 %, Mn was 11000, and Mw was 28000.

NMP was added to the obtained polyimide powder so that solid content concentration might be 15 weight%, and it stirred and melt|dissolved at 70 degreeC for 24 hours, and obtained the solution of polyimide (PI-I-3).

<Synthesis Example 4>

5.73 g (20.0 mmol) of DA-5 was weighed in a 5 L four-necked flask equipped with a stirring device and a nitrogen introduction tube, NMP was added so that the solid content concentration was 7%, and it was dissolved by stirring while sending nitrogen. . While stirring this diamine solution under water cooling, CA-3 was added 2.94g (15.0 mmol), NMP was added so that solid content concentration might be 6%, and it stirred at 23 degreeC in nitrogen atmosphere for 1 hour. Then, 11.9 g (40.0 mmol) of DA-3 and 6.01 g (40.0 mmol) of DA-11 were weighed, and it stirred, sending nitrogen, and it was made to melt|dissolve. 15.9 g (81.0 mmol) of CA-3 is added, stirring this diamine solution under water cooling, NMP is added so that solid content concentration may be 15 weight%, and s-1 is added so that it may become 1 weight% with respect to polyamic acid solid content. And it stirred at 23 degreeC in nitrogen atmosphere for 6 hours, and obtained the solution of polyamic acid (PAA-I-4). As for the polyamic acid, Mn was 12000 and Mw was 30000.

<Synthesis Example 5>

A 500 mL four-neck flask equipped with a stirring device was used as a nitrogen atmosphere, DA-4 was 2.80 g (25.9 mmol), DA-2 was 1.58 g (6.47 mmol), NMP was 111 g, and pyridine was 6.18 g as a base. (78.1 mmol) was added and stirred to dissolve. Next, while stirring this diamine solution, 9.89 g (30.4 mmol) of CE-1 was added, and it was made to react at 15 degreeC overnight. After stirring overnight, 0.38 g (4.21 mmol) of E-1 was added, and the mixture was reacted at 15°C for 4 hours. White polyamic acid ester resin powder 10.2 by injecting|throwing-in stirring the solution of the obtained polyamic acid ester to 1230 g of water, filtration collecting the precipitated white precipitate, then, washing|cleaning 5 times with 1230 g of IPA, and drying g was obtained. The yield was 83.0%. Moreover, as for this polyamic acid ester, Mn was 20,786, and Mw was 40,973.

GBL was added to the obtained polyamic acid ester so that solid content concentration might be 10 weight%, it stirred and melt|dissolved at room temperature for 24 hours, and the solution of polyamic acid ester (PAE-I-5) was obtained.

<Synthesis Example 6>

In a four-neck flask equipped with a stirring device and a nitrogen inlet tube, 0.46 g (3.00 mmol) of DA-8, 3.00 g (15.0 mmol) of DA-13, 2.56 g (12.0 mmol) of DA-14, 11.0 g of NMP and 8.10 g of GBL were added, and stirred and dissolved while sending nitrogen. 4.76 g (24.0 mmol) of CA-6 was added, stirring this diamine solution, 10.9 g of GBL was added, and it stirred at room temperature for 2 hours. Next, after adding and stirring 10.8g of GBL, 1.31g (6.01mmol) of CA-5 was added, 14.3g of GBL was added, and it stirred at room temperature for 24 hours. The viscosity in 25 degreeC of the obtained polyamic-acid solution was 2,041 mPa*s. Moreover, as for the polyamic acid, 14,200 and Mw were 30,110 of Mn. Then, s-2 is added so that it may become 1 weight% with respect to polyamic-acid solid content, and the mixing ratio of NMP and GBL becomes NMP:GBL=20:80 by weight ratio, NMP so that solid content concentration may be 15 weight%. And GBL was added, and the solution of polyamic acid (PAA-I-6) was obtained.

<Synthesis Examples 7 to 11>

Polyimides (PAA-I-7, (PI-V) shown in Table 1 below by using the diamine, tetracarboxylic acid derivative, and organic solvent shown in Table 1 below, respectively, in the same procedure as in the above synthesis example. -8), (PI-V-9), (PAA-I-10), and (PI-I-11) each solution was obtained.These are combined with the synthesis examples 1 to 6, and are shown in Table 1.

In Table 1, the numerical value in parentheses represents the compounding ratio (molar part) of each compound with respect to 100 molar parts of the total amount of the tetracarboxylic acid derivative used for the synthesis with respect to the tetracarboxylic acid component, and for the diamic acid component, The compounding ratio (molar part) of each compound with respect to 100 molar parts of the total amount of the used diamine is shown. About the terminal modifier, the compounding ratio (molar part) with respect to 100 molar parts of the total amount of the diamine used for synthesis|combination is shown. About the organic solvent, the compounding ratio (weight part) of each organic solvent with respect to 100 weight part of total amounts of the organic solvent used for synthesis|combination is shown.

[Table 1]

[Synthesis of other polymers]

<Synthesis Example 12>

According to the method described in paragraph [0091] of Japanese Patent Laid-Open No. 2018-54761, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS) was used to obtain a reactive polyorganosiloxane polymer. Next, according to the method described in paragraph [0093] of Japanese Patent Application Laid-Open No. 2018-54761, a polymer of polyorganosiloxane represented by the following formula (P-S1) was obtained. In addition, the numerical value in Formula (P-S1) shows the use ratio of each compound with respect to the total of each silane compound used for synthesis|combination.

[Formula 48]

<Synthesis Example 13>

According to the method described in paragraph [0091] of Japanese Patent Laid-Open No. 2018-54761, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS) was used to obtain a reactive polyorganosiloxane polymer. Next, according to the method described in paragraph [0093] of Japanese Patent Application Laid-Open No. 2018-54761, a polymer of polyorganosiloxane represented by the following formula (P-S2) was obtained. In addition, the numerical value in Formula (P-S2) shows the usage ratio of each compound with respect to the sum total of each silane compound used for the synthesis|combination.

[Formula 49]

<Example 1>

[Preparation of liquid crystal aligning agent]

Using the solution of the polyimide (PI-V-1) obtained in Synthesis Example 1 and the solution of the polyimide (PI-V-2) obtained in Synthesis Example 2, diluted with NMP and BCS, and further compound (B -3) was added so as to be 5 parts by weight based on 100 parts by weight of all polymers, followed by stirring at room temperature. Next, the obtained solution was filtered with a filter having a pore size of 0.5 µm, so that the polymer component ratio was (PI-V-1): (PI-V-2) = 30: 70 (solid content conversion weight ratio), and the solvent composition ratio was NMP: BCS=60:40 (weight ratio), 4.5% of polymer solid content concentration, and the compounding ratio of compound (B-3) obtained the liquid crystal aligning agent (V1) used as 5 weight part (following Table 2-1 - Table 2-3) Reference). 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 2 to 47, Comparative Examples 1 to 4)

Liquid crystal aligning agents (V2) - (V11), (I12-P) - (I29-P) by carrying out similarly to Example 1 except having used the polymer and additive shown in following Table 2-1 - Table 2-3 ), (I30-U) to (I37-U), (V38) to (V43), (I44-P) to (I47-P), (R-V1) to (R-V2), (R-I3 -P) to (R-I4-P) were obtained.

In Tables 2-1 to 2-3, the numerical values in parentheses indicate the blending ratio (parts by weight) of each polymer component or additive with respect to a total of 100 parts by weight of the polymer component used for preparation of liquid crystal exclusion, respectively, for the polymer and the additive. indicates. About an organic solvent, the compounding ratio (weight part) of each organic solvent with respect to 100 weight part of total amounts of the organic solvent used for preparation of a liquid crystal aligning agent is shown.

[Table 2-1]

[Table 2-2]

[Table 2-3]

[Production and evaluation of liquid crystal display elements]

1-1. Fabrication of PSA type liquid crystal display element

An ITO electrode substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) on which an ITO electrode pattern having a pixel size of 200 µm × 600 µm and a line/space of 3 µm is formed, and a photo having a height of 3.2 µm A glass substrate (length: 35 mm, width: 30 mm, thickness: 0.7 mm) with an ITO electrode in which the spacer was patterned was prepared and washed with pure water and isopropyl alcohol. Next, spin-coat the liquid crystal aligning agents (V1)-(V11), (V38)-(V43) and (R-V1)-(R-V2) which filtered with the filter with a hole diameter of 1.0 micrometer on each ITO surface, respectively And it heat-processed at 70 degreeC for 90 second on a hotplate at 230 degreeC for 30 minute(s) in a heat circulation type clean oven, and obtained the ITO board|substrate with a liquid crystal aligning film with a film thickness of 100 nm.

In addition, the ITO electrode board|substrate on which this ITO electrode pattern is formed is divided|segmented into 4 in a cross checker (checkered pattern) shape, and it becomes possible to drive separately in every 4 area.

Next, the periphery was apply|coated with the sealing compound (XN-1500T by Mitsui Chemicals). Then, after turning the surface of the side by which the liquid crystal aligning film of the other board|substrate was formed inside and sticking with the board|substrate in front, the sealing material was hardened and the empty cell was produced. Liquid crystal MLC-3023 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, and the liquid crystal cell was produced.

Thereafter, a DC voltage of 15 V was applied to the obtained liquid crystal cell, and in a state in which all the pixel areas were driven, an ultraviolet irradiation device using a high-pressure mercury lamp as a light source was used, and ultraviolet rays through a band-pass filter having a wavelength of 365 nm were emitted. It irradiated at 10 J/cm<2>, and obtained the vertically-aligned liquid crystal display element. For the measurement of the amount of ultraviolet irradiation, a UV-35 light receiver was connected to UV-M03A manufactured by ORC, and used.

1-2. Evaluation of liquid crystal display elements

(i) Evaluation of afterimage by long-term AC drive

Using the liquid crystal display element produced in said 1-1, 60 Hz, the alternating voltage of 20 Vp-p was applied to two diagonal areas among four pixel areas, and it was made to drive under the temperature of 23 degreeC for 168 hours. Thereafter, all of the four pixel areas were driven with an alternating voltage of 5 Vp-p, and the luminance difference of the pixels was visually observed. The state in which the luminance difference was hardly confirmed was made favorable, and the case where the luminance difference was confirmed was made into bad. An evaluation result is shown to Table 3-1 - Table 3-3.

(ii) Voltage retention evaluation

Two 40 mm × 30 mm glass substrates with ITO electrodes (length: 40 mm, width: 30 mm, thickness: 1.1 mm) were prepared, and the film thickness was The liquid crystal aligning film of 100 nm was produced. To the liquid crystal aligning film surface of one board|substrate, the 4 micrometers diameter bead spacer (The Nikki Catalyst Chemical Company make, Jinsa ball, SW-D1) was apply|coated.

Next, the periphery was apply|coated with the sealing compound (XN-1500T by Mitsui Chemicals). Then, after turning the surface of the side by which the liquid crystal aligning film of the other board|substrate was formed inside and sticking with the board|substrate in front, the sealing material was hardened and the empty cell was produced. Liquid crystal MLC-3023 (merck company brand name) was inject|poured into this empty cell by the reduced pressure injection method, and the liquid crystal cell was produced.

Then, in a state in which a DC voltage of 15 V was applied to the obtained liquid crystal cell, using an ultraviolet irradiation device using a high-pressure mercury lamp as a light source, 15 J/cm 2 of ultraviolet rays through a band-pass filter having a wavelength of 365 nm were irradiated, A vertical alignment type liquid crystal display element was obtained. In addition, the UV-35 light receiver was used for UV-M03A by ORC for the measurement of the ultraviolet irradiation amount. Next, after leaving this liquid crystal display element still in 80 degreeC oven under LED lamp irradiation for 200 hours, it left still in room temperature, and it cooled naturally to room temperature. Then, in 60 degreeC, after applying the voltage of 1V with the application time of 60 microseconds, and the span of 1667 milliseconds, the voltage retention after 1000 milliseconds from application release was measured. As a measuring apparatus, the Toyo Technica make was used.

(iii) evaluation of scratch resistance

On a pair of glass substrates (length: 40 mm, width: 30 mm, thickness: 1.1 mm), the liquid crystal aligning film was produced in the same procedure as said 1-1. About each liquid crystal aligning film surface, the scratch test was implemented using UMT-2 (made by Bruker AXS Corporation).

FVL was selected for the sensor of UMT-2, and a 1.6 mm sapphire ball was attached to the tip of the scratch part.

In the state in which the front-end|tip of a scratch part was made to contact the liquid crystal aligning film surface with a load of 40 mN, the range of width 0.5mm and length 2.0mm was scratched. At this time, the moving direction of the front-end|tip of a scratch part was set as reciprocating with respect to the horizontal direction, and the moving speed was implemented at 5.0 mm/sec. The movement with respect to the vertical direction of a scratch area was performed by moving the board|substrate with a liquid crystal aligning film at 20 micrometers/sec in a vertical direction.

After the scratch test, liquid crystal (MLC-3019) was dripped onto the surface of the liquid crystal aligning film of the clutch test agent. What spread|dispersed the spacer with a diameter of 4 micrometers on the board|substrate with another 1 sheet of liquid crystal aligning film there overlapped so that mutual liquid crystal aligning film surfaces might face each other, and the dripped liquid crystal was sandwiched.

In a state where the polarization axes of the upper and lower polarizing plates of a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) were set to be 90° (Cross Nichol), the point where the scratch test was applied was observed, and whether light was transmitted was observed. About the point where the scratch test was performed, the state in which a bright spot or light leakage was not seen at all was made good, and the state in which the whole scratched point became light leakage is set as bad, and it is shown in Table 6.

2-1. Fabrication of FFS-type liquid crystal display device by photo-alignment

First, a substrate to which an electrode is attached was prepared. The substrate is a glass substrate having a size of 30 mm in length x 50 mm in width 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, a SiN (silicon nitride) film formed as a second layer by the CVD method is formed. The film thickness of the SiN film of the second layer is 500 nm, and functions as an interlayer insulating film. On the SiN film of the 2nd layer, the comb-tooth-shaped pixel electrode formed by patterning the ITO film|membrane as 3rd layer is arrange|positioned, and two pixels of a 1st pixel and a 2nd 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 the comb-tooth-shaped shape comprised by arranging a plurality of "<"-shaped electrode elements in which the central part was bent at 160 degrees inside. The width in the width direction of each electrode element is 3 mu m, and the interval between the electrode elements is 6 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of curved U-shaped electrode elements in the central portion, the shape of each pixel is not a rectangle, but a bold letter that is bent in the central portion like the electrode element. It has a shape similar to the “” character of 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 the bending|flexion part, and the 2nd area|region below.

Next, liquid crystal aligning agent (I12-P) - (I29-P), (I44-P) - (I47-P), (R-I3-P) - (R-I4-P) of 1.0 micrometer of hole diameter After filtration with a filter, spin coating was applied to a glass substrate having a columnar spacer having a height of 4 µm on which an ITO film was formed on the substrate and the substrate with the electrode.

About the coating film obtained from liquid crystal aligning agent (I12-P) - (I29-P), (R-I3-P) - (R-I4-P), after drying 5 minutes on an 80 degreeC hotplate, 230 degreeC It baked for 20 minutes in the hot-air circulation type oven, and obtained the polyimide film with a film thickness of 100 nm. Thereafter, 500 mJ/cm 2 of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 were irradiated to the coating film surface through a polarizing plate, followed by baking in a hot air circulation type oven at 230°C for 30 minutes, and a film thickness of 100 The board|substrate with a nm liquid crystal aligning film was obtained.

About the coating film obtained from liquid crystal aligning agent (I44-P) - (I47-P), after drying for 5 minutes on an 80 degreeC hotplate, wavelength 254nm which carried out linearly polarized light of extinction ratio 26:1 through a polarizing plate on the coating-film surface. 500 mJ/cm<2> of ultraviolet ray was irradiated, then, it baked in 230 degreeC hot-air circulation type oven for 30 minutes, and obtained the board|substrate with a liquid crystal aligning film with a film thickness of 100 nm.

Next, the sealing compound was printed on one of the said 1 set of glass substrates with a liquid crystal aligning film, the other board|substrate was bonded together so that a liquid crystal aligning film surface might face, the sealing compound was hardened, and the empty cell was produced. 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 display element was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand overnight, the residual image characteristic was evaluated.

2-2. Evaluation of liquid crystal display elements

(i) Evaluation of afterimage by long-term AC drive

Using the liquid crystal cell produced in said 2-1, the alternating voltage of +/-5V was applied by 60 Hz in a 60 degreeC constant temperature environment 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 installed 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.

When this angle Δ was less than 0.3°, it was considered good, and when Δ was 0.3° or more, it was considered bad. An evaluation result is shown to Table 3-1 - Table 3-3.

(ii) Voltage retention evaluation

Two 40 mm × 30 mm glass substrates with ITO electrodes (length: 40 mm, width: 30 mm, thickness: 1.1 mm) were prepared, and the film thickness was The liquid crystal aligning film of 100 nm was produced. To the liquid crystal aligning film surface of one board|substrate, the 4 micrometers diameter bead spacer (The Nikki Catalyst Chemical Company make, Jinsa ball, SW-D1) was apply|coated.

Next, the periphery was apply|coated with the sealing compound (XN-1500T by Mitsui Chemicals). Then, after turning the surface of the side by which the liquid crystal aligning film of the other board|substrate was formed inside and sticking with the board|substrate in front, the sealing material was hardened and the empty cell was produced. Liquid crystal MLC-3019 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, and the liquid crystal display element was produced. Next, after leaving this liquid crystal display element still in 80 degreeC oven under LED lamp irradiation for 200 hours, it left still in room temperature, and it cooled naturally to room temperature. Then, evaluation was performed in the same procedure as (ii) of 1-2.

(iii) evaluation of scratch resistance

Using the liquid crystal aligning film similar to said 2-1, except having made the liquid crystal MLC-3019, it implemented by the procedure similar to (iii) of said 1-2.

3-1. Fabrication of FFS-type liquid crystal display device by rubbing alignment

First, the liquid crystal aligning agent (I30-U) - (I37-U) which filtered with the filter with a hole diameter of 1.0 micrometer on each surface of a pair of glass substrate same as said 2-1 is inkjet coating apparatus (HIS-200, Hitachi) Plant Technology Co., Ltd.) was used for application|coating. Application|coating was performed under the conditions of 70 x 70 mm of application area, 0.423 mm of nozzle pitch, 0.5 mm of scan pitch, and application|coating speed of 40 mm/sec, and preserving from application|coating to drying for 60 seconds. Next, after drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the polyimide film with a film thickness of 100 nm was obtained. Rubbing this polyimide film with a rayon cloth (roller diameter: 120 mm, number of roller rotations: 500 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm, rubbing direction: 10° inclined with respect to the 3rd layer IZO comb electrode direction), washing was performed by ultrasonic irradiation for 1 minute in pure water to remove water droplets. Then, it dried at 80 degreeC for 15 minutes, and obtained the board|substrate with a liquid crystal aligning film. Using these two substrates with a liquid crystal aligning film as one set, the sealing agent is printed in the form that the liquid crystal injection hole is left on the substrate, and the other substrate is set so that the liquid crystal aligning film faces are facing and the rubbing direction is antiparallel and attached. Then, the sealing compound was hardened and the cell gap produced the empty cell whose cell gap is 4 micrometers. Liquid crystal MLC-7026-100 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal display element of the FFS system was obtained. Then, after heating the obtained liquid crystal display element at 120 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for evaluation of afterimage evaluation.

3-2. Evaluation of liquid crystal display elements

(i) Evaluation of afterimage by long-term AC drive

Using the liquid crystal aligning film similar to said 3-1, except having made liquid crystal MLC-7026-100, it evaluated by the procedure similar to (i) of said 2-2. In addition, evaluation made favorable when the obtained angle (DELTA) was less than 0.2 degree, and made the time when (DELTA) was 0.2 degrees or more as bad.

(ii) Voltage retention evaluation

Using the liquid crystal aligning film similar to said 3-1, except having made liquid crystal MLC-7026-100, it evaluated by the procedure similar to (ii) of said 2-2.

(iii) evaluation of scratch resistance

Using the liquid crystal aligning film similar to said 3-1, except having made liquid crystal MLC-7026-100, it evaluated by the procedure similar to (iii) of said 2-2.

[Table 3-1]

[Table 3-2]

[Table 3-3]

Industrial Applicability

The liquid crystal aligning agent of this invention is useful for formation of the liquid crystal aligning film in various liquid crystal display elements, such as a vertical alignment type and an FFS drive system.

In addition, the specification of Japanese Patent Application No. 2019-018889 for which it applied on February 5, 2019, a claim, drawing, and the abstract are cited here, and it takes in as an indication of the specification of this invention.

Claims (13)

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
Component (A): A polymer (A) having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
(B) Component: A compound (B) represented by the following formula (B).

(X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group. R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z ₁₁ , Z ₁₂ are each independently a hydrogen atom, a substituent An alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, tert-butoxycarbonyl group, or 9-fluorenylmethoxy represents a carbonyl group.)

(R represents an alkanediyl group having 1 to 4 carbon atoms. m and n are each independently an integer of 1 or 2. A ¹ is a single bond, -O-, -CO-, -OCO-, - COO-, -CONR- (R represents a hydrogen atom or a methyl group), -NRCONR- (R represents a hydrogen atom or a methyl group), -N=N-, -CH ₂ -, -(CH ₂ ) _n - (. n is an integer from 2 to 18), or the - (CH _{2) n} - is any CH _2, -O-, -CO-, -OCO-, -COO- , -CONR- (R a represents a hydrogen atom or a methyl group), -NRCONR- (R represents a hydrogen atom or a methyl group), and a divalent organic group (L) substituted with phenylene or biphenylene. In the device (L), two oxygen atoms are not adjacent to each other, and -OCO-, -COO-, -CONR- (R represents a hydrogen atom or a methyl group), and -NRCONR- (R is a hydrogen atom or represents a methyl group). The method of claim 1,
The liquid crystal aligning agent whose said X<_1> is a tetravalent organic group chosen from the group which consists of following formula (4a) - (4n), a formula (5a), and a formula (6a).

(x and y each independently represent a single bond, -O-, -CO-, -COO-, an alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, sulfonyl or amide group. Z ¹ to Z ⁶ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring. j and k are 0 or an integer of 1. m is an integer of 1 to 5. * Represents a bonding hand.) 3. The method according to claim 1 or 2,
The liquid crystal aligning agent whose said divalent organic group (L) is group chosen from the group which consists of following formula (L-1) - (L-25), (L2-1) - (L2-3).

(L ₁ and L ₂ are a single bond, -O-, -CO-, -OCO-, -COO-, -CONR- (R represents a hydrogen atom or a methyl group.), -NRCONR- (R is a hydrogen atom) or a methyl group.), -N=N-, -(CH ₂ ) _n - (n is an integer of 1 to 18) or the above formulas (L-1) to (L-25). L ₃ is -(CH ₂ ) _n - (n is an integer of 1 to 18), the above formulas (L-2), (L-4), (L-7), (L-8), (L- 10) to (L-11), (L-13), (L-15), (L-17) to (L-18), (L-20) or (L-25) are represented. _{When 3} is (L-2), (L-15), (L-17), -(CH ₂ ) _{n - in L 3} bonds to -NHCO-.) 4. The method according to claim 2 or 3,
In the polymer (A), X ₁ is a tetravalent organic group selected from the group consisting of formulas (4a) to (4n), (5a) and (6a), and Y ₁ is a divalent organic group. Liquid crystal alignment, wherein the content of at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is 5 mol% or more in total with respect to all repeating units My. 4. The method according to any one of claims 1 to 3,
In the said polymer (A), X<_1> is a tetravalent organic group, and Y<_1> is a divalent organic group derived from the diamine represented by any of the following formulas (V1) - (V3) Repetition represented by the said formula (1) unit and at least one repeating unit (repeating unit (a)) selected from the group consisting of repeating units represented by the formula (2), the content of which in total is 1 mol% or more with respect to all repeating units , liquid crystal aligning agent.

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, - O-(CH ₂ ) _m -O-, -OC(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-, or -COO-(CH ₂ ) _m -OCO-, X ¹ and X ² are each independently, provided that 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 -. Among these, a plurality of a1 are each independently an integer of 1 to 15, and a plurality of A ₁ are each independently an oxygen atom or -COO- represents, and m ₁ is an integer of 1 or 2. X ³ is a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, - represents COO- or -OCO-. X ⁴ represents -CONH-, -NHCO-, -O-, -COO- or -OCO-. G ₁ and G ₂ each independently represent 6 to 12 carbon atoms; A divalent cyclic group which is a divalent aromatic group or a divalent alicyclic group having 3 to 8 carbon atoms is represented. It may be substituted with a fluorine-containing alkyl group of 3, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom, k is 0 or an integer of 1, m and n are each independently an integer of 0 to 3, m and the sum of n is 1 ~ 4. R ¹ denotes an alkoxy group having 1 to 20 carbon atoms an alkyl group, having 1 to 20 carbon atoms or an alkoxy group having from 2 to 20 carbon atoms in a. a R ¹ Optional hydrogen to be formed may be substituted with fluorine. R<^2> represents a C1-C20 alkyl group or a C2-C20 alkoxyalkyl group, and ^{arbitrary hydrogen which forms R<2>} may be substituted by fluorine. R ³ represents a structure having a steroid skeleton.) 4. The method according to any one of claims 1 to 3,
In the polymer (A), X ₁ is a tetravalent organic group, and Y ₁ is p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4 ,4'-diaminoazobenzene, 1,4-bis(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,3-bis(4-aminophenoxy) C) benzene, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] ether, 4,4'-bis (4-aminophenoxy) biphenyl, 4 -(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4) -diyl)]dianiline, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, in the following formulas (z-1), (z-2), (z-3), (z-5) Repetition represented by the formula (1), which is a divalent organic group derived from a diamine selected from the group consisting of a diamine represented by any one, a diamine represented by the following formula (H), and a diamine represented by any of the following formulas (H2) to (H3) unit and at least one repeating unit (repeating unit (c)) selected from the group consisting of repeating units represented by the formula (2), the content of which in total is 5 mol% or more with respect to all repeating units , liquid crystal aligning agent.

(R ³ represents -NRCO-, -COO-, -NRCONR-, or -(CH ₂ ) _n - (provided that n is an integer of 2 to 20), and optional -CH ₂ - is -O-, may be substituted by -COO-, -ND-, -NRCO-, -NRCONR-, -NRCOO-, or -OCOO-. D represents the thermal desorption group, R represents a hydrogen atom or a monovalent organic. R ⁴ is a single bond or a benzene ring, and any hydrogen atom on the benzene ring may be substituted with a monovalent organic group.)

(X ₁ is -CO-, -O-, -COO- or -L ₁ -RL ₂ - (L ₁ , L ₂ each independently represents a single bond, an oxygen atom, or -COO-, R represents -(CH ₂ ) _n - (n is an integer of 1 to 12) or -NRCO- (R is a hydrogen atom or a methyl group.) X ₂ is a single bond, -NRCO- (R is a hydrogen atom) or a methyl group.) or -COO-. n is an integer of 1 or 2. Any hydrogen atom on the benzene ring may be substituted with a monovalent organic group.)

(two Xs are each independently -O-, -COO-, -NHCO-, or -C(=O)-, -(CH ₂ ) _n - (n is an integer of 1 to 12.) L ₁ and L ₂ each independently represent a single bond, -O-, or -COO-. R is -CH ₂ -, -(CH ₂ ) _n - (n is an integer of 2 to 12) ), or the - (CH _{2) n} -. any CH ₂ a represents an oxygen atom substituted for any hydrogen atom on the benzene ring is optionally substituted with a monovalent organic). 4. The method according to any one of claims 1 to 3,
In the polymer (A), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group derived from a diamine selected from the group consisting of a diamine having a radical initiation function and a diamine having a photopolymerizable group at the terminal. At least one repeating unit (repeating unit (b)) selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) is included, and the content thereof is in total, The liquid crystal aligning agent which is 1 mol% or more with respect to a unit. 8. The method of claim 7,
Liquid crystal in which the polymer (A) contains repeating units (a) and (b), and the content of the repeating unit (a) and the repeating unit (b) is 99 mol% or less in total with respect to all repeating units Orienting agent. 9. The method according to any one of claims 1 to 8,
The liquid crystal aligning agent in which the said liquid crystal aligning agent contains polyorganosiloxane further, and the said polyorganosiloxane has at least any one of an oxetanyl group and an oxylanyl group. 10. The method according to any one of claims 1 to 9,
The liquid crystal aligning agent which consists of two or more types of the said polymer (A). 11. The method according to any one of claims 1 to 10,
The liquid crystal aligning agent in which 0.1-30 weight part of said (B) components are contained with respect to 100 weight part of said (A) components. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-11. A liquid crystal display element provided with the liquid crystal aligning film of Claim 12.