KR20210126572A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same - Google Patents

Abstract

(식 (l) 중, X₁ 은 4 가의 유기기이고, Y₁ 은 2 가의 유기기이다. 식 (2) ∼ (5) 중, X₂ 는 지환식 산 2무수물 또는 지방족 산 2무수물에서 유래하는 4 가의 유기기이고, Y₂ 는 식 (m-1) 또는 (m-2) 로 나타내는 2 가의 유기기이다. R_2-5 는 수소 원자, 또는 탄소수 1 ∼ 4 의 알킬기이다. Z_21-51, Z_22-52 는 각각 독립적으로 수소 원자 등이고, * 는 결합손을 나타낸다. X₃ 은 지환식 산 2무수물 또는 지방족 산 2무수물에서 유래하는 4 가의 유기기이다. Y₃ 은 식 (l) 또는 식 (n) 으로 나타내는 부분 구조를 갖는 2 가의 유기기이다. 식 (l), (n) 중, Q¹, Q² 는 탄소수 1 ∼ 3 의 알킬기를 나타내고, Q³ 은 수소 원자 또는 탄소수 1 ∼ 3 의 알킬기를 나타낸다. X₄, X₅ 는 방향족 산 2무수물에서 유래하는 4 가의 유기기이다. Y₄ 는 식 (2) 의 Y₂ 와 동일한 의미이고, Y₅ 는 식 (3) 의 Y₃ 과 동일한 의미이다.)There is little generation|occurrence|production of the residual image and AC residual image derived from residual DC, rework is easy, and the liquid crystal aligning agent which can form the liquid crystal aligning film with high transmittance is provided.
A polymer (A) having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and the following formula (5) The liquid crystal aligning agent containing the polymer (B) which has a repeating unit represented by ).

(In formula (1), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. In formulas (2) to (5), X ₂ is derived from an alicyclic acid dianhydride or an aliphatic acid dianhydride. is a tetravalent organic group, Y ₂ is a divalent organic group represented by the formula (m-1) or (m-2) R _2-5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z _{21- 51} and Z _22-52 are each independently a hydrogen atom, etc., * represents a bond. X ₃ is a tetravalent organic group derived from an alicyclic acid dianhydride or an aliphatic acid dianhydride. Y ₃ is a formula (l) or a divalent organic group having a partial structure represented by the formula (n): In formulas (l) and (n), Q ¹ , Q ² represents an alkyl group having 1 to 3 carbon atoms, and Q ³ is a hydrogen atom or a carbon number 1 represents the alkyl group of to 3. X ₄ and X ₅ are a tetravalent organic group derived from an aromatic acid dianhydride, Y _{4 has the same meaning as Y 2} in the formula (2), and Y ₅ is Y in the formula (3). ₃ has the same meaning.)

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.

DESCRIPTION OF RELATED ART Conventionally, a liquid crystal device is widely used as a display part, such as a personal computer, a mobile phone, a smart phone, and a television receiver. Liquid crystal devices include, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling alignment of liquid crystal molecules in the liquid crystal layer, and supply to the pixel electrode It is equipped with a thin film transistor (TFT) etc. which switch the electrical signal used. As a driving method of liquid crystal molecules, a longitudinal electric field system, such as a TN system and a VA system, and a transverse electric field system, such as an IPS system and FFS (fringe field switching) system, are known (for example, patent document 1).

In general, in the transverse electric field method in which electrodes are formed only on one side of the substrate and an electric field is applied in a direction parallel to the substrate, compared to the conventional vertical electric field method in which a voltage is applied to electrodes formed on upper and lower substrates to drive liquid crystals, It has a viewing angle characteristic and is known as a liquid crystal display element in which high-quality display is possible. As a method for aligning the liquid crystal in a certain direction, there is a method of forming a polymer film such as polyimide on a substrate and rubbing the surface with a cloth, so-called rubbing treatment, which has been widely used industrially.

Although the liquid crystal aligning film which is a structural member of a liquid crystal display element is a film|membrane for arranging a liquid crystal uniformly, not only the orientation uniformity of a liquid crystal but various characteristics are needed. For example, charges are accumulated in the liquid crystal alignment film by the voltage that drives the liquid crystal, and these accumulated charges disturb the alignment of the liquid crystal, or display as an afterimage or burn-in (hereinafter referred to as residual DC-derived afterimage). Since there exists a problem of giving an influence and reducing the display quality of a liquid crystal display element remarkably, the liquid crystal aligning agent which overcomes these subjects is proposed (patent document 2).

Moreover, in an IPS system and an FFS system, stability of a liquid-crystal orientation also becomes important. When stability of orientation is small, when a liquid crystal is driven for a long time, a liquid crystal will not return to an initial state, and it will become a cause of a contrast fall and burn-in (it is hereafter called an AC afterimage). As a method of solving the said subject, in patent document 3, 1 type of polymer selected from the group which consists of polyamic acid containing specific tetracarboxylic dianhydride, specific diamine, and its imidation polymer, and the liquid crystal containing a specific compound An aligning agent is disclosed.

In addition, since the economical efficiency in the production process is very important, it is also required that the element substrate can be easily recycled and used. That is, after forming the liquid crystal aligning film from the liquid crystal aligning agent, when defects such as orientation are inspected and defects have occurred, it is required to be able to easily perform the rework process of removing the liquid crystal aligning film from the substrate and recovering the substrate, have.

Japanese Patent Laid-Open No. 2013-167782 International Publication No. WO02/33481 pamphlet International Publication No. WO2016/063834 pamphlet

It was not necessarily said that the structure of the liquid crystal aligning agent proposed conventionally can achieve all said subject. Moreover, when the liquid crystal aligning agent of patent document 2 and 3 was used, there existed a problem that the transmittance|permeability of the liquid crystal aligning film obtained became low, and there existed room for improvement. This invention is made|formed based on the above circumstances, and the objective is the liquid crystal aligning agent which there is little generation|occurrence|production of the residual image derived from residual DC and AC residual image, rework is easy, and can form the liquid crystal aligning film with high transmittance. will provide

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject was solvable by using the liquid crystal aligning agent containing a specific component, as a result of earnestly researching, 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.

(A) Component: The polymer (A) which has a repeating unit represented by following formula (1).

(B) component: has a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5), The total content of the repeating unit represented by (2) and the repeating unit represented by the following formula (3) is 60 to 99.9 mol% of the total repeating units, and the repeating unit represented by the following formula (4) and the following formula (5) Polymer (B) whose total content of the repeating unit represented by is 0.1-40 mol% of all repeating units.

[Formula 1]

(In formula (1), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group)

[Formula 2]

(X ₂ is a tetravalent organic group derived from an alicyclic acid dianhydride or an aliphatic acid dianhydride. Y ₂ is a divalent organic group represented by the following formula (m-1) or (m-2). R ₂ is a hydrogen atom or an alkyl group having 1 to 4. Z ₂₁ and Z ₂₂ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted alkenyl group having 2 to 10 carbon atoms. , an optionally substituted alkynyl group having 2 to 10 carbon atoms, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group.)

[Formula 3]

(* indicates a bond)

[Formula 4]

(X ₃ is a tetravalent organic group derived from an alicyclic acid dianhydride or an aliphatic acid dianhydride. Y ₃ is a divalent organic group represented by the following formula (l) or a partial structure represented by the following formula (n) It is a divalent organic group.R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z ₃₁ , Z ₃₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent an optional C2-C10 alkenyl group, an optionally substituted C2-C10 alkynyl group, tert-butoxycarbonyl group, or 9-fluorenylmethoxycarbonyl group.)

[Formula 5]

(Q ¹ , Q ² are an alkyl group having 1 to 3 carbon atoms, and Q ³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * represents a bond.)

[Formula 6]

(X ₄ , X ₅ is a tetravalent organic group derived from an aromatic acid dianhydride. Y _{4 has the same meaning as Y 2 in} Formula (2), and R ₄ has the same meaning _{as R 2 in} Formula (2) above. Z ₄₁ , Z ₄₂ have the same meaning _{as Z 21} , Z _{22 in} the formula (2), respectively _{. Y 5 has the same meaning as Y 3 in} the formula (3), and R ₅ is the formula ( It has the _{same meaning as R 3 in} 3), and Z ₅₁ and Z ₅₂ have the same meaning _{as Z 31} and Z _{32 in} Formula (3), respectively.)

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, a rework is easy and a liquid crystal aligning film with a high transmittance|permeability can be obtained. Moreover, by using the liquid crystal aligning film obtained, the residual image and AC residual image derived from residual DC are hard to generate|occur|produce, and the liquid crystal display element excellent in contrast with a high transmittance|permeability is obtained.

Below, 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 a repeating unit represented by said Formula (1). Thereby, there is little generation|occurrence|production of an AC residual image, the liquid crystal aligning film with a high transmittance|permeability can be obtained, and the liquid crystal display element by which the fall of contrast was suppressed can be obtained. In the formula (1), X ₁ and Y ₁ are as defined above. _{As X<1>} of Formula (1), the tetravalent organic group derived from tetracarboxylic dianhydride is mentioned, For example, aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic The tetravalent organic group derived from an acid dianhydride is mentioned. _{As for Y<1>} of Formula (1), the divalent organic group derived from a diamine compound is preferable.

Here, the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. The aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to 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. The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the 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.

From a viewpoint of improving the solubility of a polymer (A) _{, it is preferable that X<1>} is a tetravalent organic group selected from the group which consists of following formula (4a)-(4n), following formula (5a), and following formula (6a) .

[Formula 7]

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

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

[Formula 8]

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

There is little AC residual image and from a viewpoint of ensuring solubility, X<_1> of said Formula (1) is selected from said Formula (4a)-(4h), (4j), (4l), (4m)-(4n) It is preferable that it is a tetravalent organic group used.

It does not specifically limit as diamine which can be used for a polymer (A). Specific examples of the aliphatic diamine include metaxylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, and hexamethylenediamine. 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'-diaminodiphenyl ether, 4,4'-diaminoazobenzene, 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, 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)p Peridine, 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)]dianiline, 1,3-bis(3-aminopropyl)-tetra The diamine etc. which two amino groups couple|bonded with the divalent organic group which has methyldisiloxane and the partial structure shown by following formula (H) are mentioned.

[Formula 9]

(Q ¹¹ is -NQCO-, -COO-, -OCO-, -NQCONQ-, -CONQ-, or -(CH ₂ ) _n - (n is an integer of 1 to 20.) Provided that n is In the case of 2 to 20, any -CH ₂ - is -O-, -COO-, -OCO-, -ND-, -NQCO-, -CONQ-, -NQCONQ-, - may be substituted with NQCOO- or -OCOO-.D represents a thermal leaving group, Q represents a hydrogen atom or a monovalent organic group.Q ¹² is a single bond or a benzene ring, and any hydrogen atom on the benzene ring is 1 may be substituted with a valent organic group.*1, *2 represents a bond, and when Q ¹² is a single bond, *2 is bonded to a nitrogen atom in an amino group. When Q ¹² is a benzene ring, Q ¹¹ is a single bond It may be a combination.)

A viewpoint with few AC residual images _{WHEREIN: It is preferable that Y<1>} of said Formula (1) is a divalent organic group which has a partial structure represented by the said Formula (H). In this case, when R ⁴ in the formula (H) is a single bond, *2 is bonded to a nitrogen atom in the imide ring. _{Especially, it is preferable that Y<1>} of said Formula (1) is a divalent organic group which has a partial structure represented by any of following formula (H-1) - (H-14).

[Formula 10]

(*1, *2 represents a bond, *2 is a nitrogen atom in the imide ring)

From the viewpoint of easy synthesis, Y ₁ in the formula (1) is a divalent organic group represented by any of the formulas (H-1) to (H-14) or the following formulas (MH-1) to (MH) It is preferable that it is a divalent organic group represented by -2).

[Formula 11]

(*1 is bonded to the nitrogen atom in the imide ring. Boc represents a tert-butoxycarbonyl group.)

The polymer (A) may have a repeating unit represented by the following formula (PA-1) other than the repeating unit represented by the formula (1).

[Formula 12]

In Formula (PA-1), X ₁ and Y ₁ have the same meanings _{as X 1} and Y ₁ of Formula (1) including preferred embodiments, respectively. R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z ₁₁ , Z ₁₂ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkenyl group having 2 to 10 carbon atoms, or optionally substituted alkyl having 2 to 10 carbon atoms. a nyl group, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group.

Specific examples of the alkyl group having 1 to 5 carbon atoms for R ₁ include a methyl group, an ethyl group, a propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n- A 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.

Specific examples of the carbon number of alkyl group of from 1 to 10, wherein Z _11, Z ₁₂ example, in addition to the specific example of a carbon number of alkyl group of from 1 to 5 exemplified above R _1, hexyl group, heptyl group, octyl group, nonyl group, having and the like. Specific examples of the alkenyl group having 2 to 10 carbon atoms for Z ₁₁ and Z ₁₂ include, for example, a vinyl group, a propenyl group, and a butynyl group, 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, 2-propynyl group and the like.

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 AC afterimages _{, it is preferable that Z 11} and Z ₁₂ are each independently a hydrogen atom or a methyl group.

It is preferable that the polymer (A) contains 10-95 mol% of all the repeating units which a polymer (A) has from a viewpoint of few AC residual images, and 15-95 mol% of the repeating unit represented by the said Formula (1) It is more preferable to include Moreover, in this case, it is preferable to contain 5-90 mol% of the repeating unit represented by said Formula (PA-1), and, as for a polymer (A), it is more preferable to contain 5-85 mol%.

<Polymer (B)>

The liquid crystal aligning agent of the present invention has a repeating unit represented by the formula (2), a repeating unit represented by the formula (3), a repeating unit represented by the formula (4), and a repeating unit represented by the formula (5), The total amount of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) contains the polymer (B) which is 60 to 99.9 mol% of all repeating units. By setting it as such a structure, it is excellent in rework property and the liquid crystal aligning film by which the residual image derived from residual DC was reduced is obtained.

In the formulas (2) and (3), X ₂ , X ₃ , Y ₂ , Y ₃ , R ₂ , R ₃ , Z ₂₁ , Z ₂₂ , Z ₃₁ , and Z ₃₂ are as defined above.

As a specific example of the C1-C5 alkyl group of said R<_2> , R<_3> , the structure illustrated by _{R<1> of the said Formula (PA-1) is mentioned.} From a viewpoint of the easiness of imidation by heating _{, it is preferable that R<2>} and R<_3> are each independently a hydrogen atom or a methyl group.

Specific examples of the Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₃₂ alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and alkynyl group having 2 to 10 carbon atoms are Z in the formula (PA-1) ₁₁ and the structure illustrated by _{Z 12 are mentioned.}

Z ₂₁ , Z ₂₂ , Z ₃₁ , and Z ₃₂ may have a substituent, and examples of the substituent include the structures exemplified by _{Z 11} and Z _{12 in the formula (PA-1).}

From a viewpoint of few AC afterimages _{, it is preferable that Z 21} , Z ₂₂ , Z ₃₁ , and Z ₃₂ are each independently a hydrogen atom or a methyl group.

Examples of the tetravalent organic group derived from the alicyclic tetracarboxylic dianhydride or aliphatic tetracarboxylic dianhydride of _{X 2} and X _{3 include} the alicyclic tetracarboxylic dianhydride or aliphatic tetracarboxylic acid dianhydride exemplified in _{X 1 above.} The tetravalent organic group derived from an acid dianhydride is mentioned. In the point of view of suppressing AC image retention, X _2, X ₃ is preferably a tetravalent organic group selected from the group consisting of the formula (4a) ~ (4n).

The alkyl group of the formula (l) or (n) Q ^1, at the Q ^2, Q ³ having a carbon number of 1 to 3, there may be mentioned methyl, ethyl, propyl and the like. Increasing the transmittance of the liquid crystal alignment film, in terms of suppressing the residual image of AC residual image and the residual DC derived, Q ^1, Q ^2, Q ³ is preferably a methyl group. In addition, the arbitrary hydrogen atoms of the benzene ring in Formula (n) may be substituted by the monovalent organic group. Examples of the monovalent organic group include an alkyl group, alkenyl group, alkoxy group, fluoroalkyl group, fluoroalkenyl group or fluoroalkoxy group having 1 to 3 carbon atoms.

From a viewpoint with few AC afterimages, the structure shown by said Formula (l) by following formula (l-1) is preferable.

[Formula 13]

In the formula (n), ^{the bonding position of -NQ 3} -Ph (Ph represents a phenylene group) is preferably bonded to the 3-position of the carbazole skeleton from the viewpoint of less steric hindrance.

From the viewpoint of few residual images derived from residual DC, the divalent organic group having a partial structure represented by the formula (n) is a divalent organic group selected from the group consisting of the following formulas (n-1) to (n-3) desirable.

[Formula 14]

Expression (n-1) ~ (n -3) of the, Q ^2, Q ³ are, respectively, the same meanings, including the Q ^2, Q ³ and a preferred embodiment of the formula (n). Q ⁴ is shows the structure of a single bond or a group represented by the formula (Ar) or less, n is an integer of 1-3. * indicates a bond. In addition, the arbitrary hydrogen atoms of a benzene ring may be substituted by the monovalent organic group similarly to the case of said Formula (n).

[Formula 15]

(Q ⁵ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m 2 selected from O-, -CONQ-, and -NQCO- represents a valent organic group, k represents an integer of 1 to 5. In addition, Q represents hydrogen or a monovalent organic group, and l and m represent an integer of 1 to 5. *1 and *2 represent a bond, * ₁ is bonded to the benzene ring in formulas (n-1) to (n-3).)

A C1-C3 alkyl group is mentioned as a monovalent organic group in Q of the said Formula (Ar).

From the viewpoint of easy synthesis, the divalent organic group having a partial structure represented by the formula (n) is preferably a divalent organic group represented by any of the following formulas (cbz-1) to (cbz-7). * indicates a bond.

[Formula 16]

[Formula 17]

The said polymer (B) is a repeating unit represented by said Formula (3) from a viewpoint of few AC afterimages and residual DC-derived afterimages, and Y ₃ is a divalent organic group represented by said Formula (1); It is preferable to have a repeating unit which is a divalent organic group which has a partial structure represented by said formula (n) Y<_3>.

The said polymer (B) has a repeating unit represented by a following formula (4) from a viewpoint with few residual images derived from residual DC, and a repeating unit represented by a following formula (5).

[Formula 18]

In formulas (4) and (5), X ₄ and X ₅ are a tetravalent organic group derived from aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride exemplified by _{X 1 in the formula (1).} and tetravalent organic groups derived from In the low point of view of AC residual image after image and a residual DC origin, X _4, X ₅ is preferably a tetravalent organic group selected from the formulas (5a), (6a) according to a preferred example of the X _1.

Y _{4 has the same meaning as Y 2 in} Formula (2), including preferred embodiments. R _{4 has the same meaning as R 2} in the formula (2), including preferred embodiments. Z ₄₁ , Z _{42 have the same meaning as Z 21} , Z _{22 in} Formula (2), including preferred embodiments, respectively. Y _{5 has the same meaning as Y 3 in} Formula (3), including preferred embodiments. R _{5 has the same meaning as R 3} in the formula (3), including preferred embodiments. Z ₅₁ and Z _{52 have the same meanings as Z 31} and Z _{32 in} the formula (3), including preferred embodiments, respectively.

The total content of at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) in the polymer (B) is, from the viewpoint of obtaining a high transmittance , It is preferable that it is 60 to 99.9 mol% of all repeating units, and it is more preferable that it is 65 to 90 mol%.

The ratio of the content of the repeating unit represented by the formula (2) to the repeating unit represented by the formula (3) is preferably 10/90 to 50/50, and 15/85 to 50 in mole % ratio of the former to the latter. It is more preferable that it is /50.

The total content of at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (4) and the repeating unit represented by the formula (5) in the polymer (B) is, from the viewpoint of obtaining a high transmittance , It is preferable that it is 0.1-40 mol% of all repeating units, and it is more preferable that it is 10-35 mol%.

The ratio of the content of the repeating unit represented by the formula (4) to the repeating unit represented by the formula (5) is preferably 10/90 to 50/50, and 15/85 to 50 in mole % ratio of the former to the latter. It is more preferable that it is /50.

Polymer (B) is, in addition to the repeating unit represented by the formula (2), the repeating unit represented by the formula (3), the repeating unit represented by the formula (4), and the repeating unit represented by the formula (5), the following formula ( You may have a repeating unit represented by PA-2).

[Formula 19]

In formula (PA-2), X ₆ represents a tetravalent organic group, and Y ₆ represents a divalent organic group. However, Y ₆ is a group selected from the formulas (m-1) to (m-2), a divalent organic group represented by the formula (l), and a divalent organic group having a partial structure represented by the formula (n). do not include. R _{6 has the same meaning as R 2} in the formula (2), including preferred embodiments. Z _61, Z ₆₂ are as defined, including preferred embodiments and Z _61, Z ₆₂ in the formula (2).

As a specific example of X<_6> , the tetravalent organic group derived from the aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride illustrated by _X<1> of said Formula (1) can be heard Specific examples of Y _{6 include, in addition to the structure derived from the diamine exemplified by Y 1} in the formula (1), a diamine having a pyrrole structure described in International Publication No. 2017/126627 (hereinafter also referred to as WO). structure, preferably a structure derived from a diamine having a structure represented by the following formula (pr);

[Formula 20]

(In the formula (pr), R ¹ represents a hydrogen atom, hydrogen, a fluorine atom, a cyano group, a hydroxy group, or a methyl group, and R ² is each independently a single bond or a group “*1-R ³ -Ph-*2 , and R ³ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m O-, -CONH-, and -NHCO- selected from represents a divalent organic group to be used (l, m represents an integer of 1 to 5), *1 represents a site bonding to the benzene ring in the formula (pr), *2 is a site bonding to an amino group in the formula (pr) Ph represents a phenylene group. n represents 1 to 3.), a structure derived from the diamine having a pyrrole structure described in WO2018/062197, preferably a diamine having a structure represented by the following formula (pn) structure derived from

[Formula 21]

(In the formula (pn), R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ each independently represents a single bond or a group “*1-R ⁴ -Ph-*2”, and R ⁴ is a single bond , -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m represents an integer of 1 to 5), *1 represents a site for bonding to a benzene ring in formula (pn), *2 represents a site for bonding with an amino group in formula (pn), Ph represents a phenylene group n represents 1 to 3.), a structure derived from a diamine having a thiophene or furan structure described in WO2018/092759, preferably a structure derived from a diamine having a structure represented by the following formula (sf);

[Formula 22]

(In the formula (sf), Y ¹ represents a sulfur atom or an oxygen atom, R ² each independently represents a single bond or a group “*1-R ⁵ -Ph-*2”, R ⁵ represents a single bond, - O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m is represents an integer of 1 to 5), *1 represents a site for bonding to the benzene ring in formula (pn), *2 represents a site for bonding with an amino group in formula (pn). Ph represents a phenylene group. n represents 1 to 3.) and the divalent organic group described in paragraphs [0013] to [0030] of WO2018-181566.

From a viewpoint with few AC afterimages and residual images derived from residual DC WHEREIN: The content rate of the said polymer (A) and the said polymer (B) is 5/95-95/5 by weight ratio of polymer (A)/polymer (B). It is preferable to be From a viewpoint from which a liquid crystal aligning film with high reproducibility is obtained, 10/90-90/10 are more preferable, and, as for the said polymer (A)/polymer (B), 20/80-80/20 are still more preferable.

<Method for producing polyamic acid>

The polyamic acid which is a polyimide precursor used for this invention is compoundable by the method shown below.

Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at -20°C to 150°C, preferably at 0°C to 50°C, for 30 minutes to 24 hours, preferably for 1 to 12 hours. It can be synthesized by

The organic solvent used for the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of monomer and polymer solubility, and these are one or two types. You may mix and use the above. The polymer concentration is preferably from 1 to 30% by weight, more preferably from 5 to 20% by weight, from the viewpoint that polymer precipitation does not easily occur and high molecular weight is easily obtained.

The polyamic acid obtained as mentioned above can precipitate and collect|recover a polymer by inject|pouring into a poor solvent, stirring a reaction solution well. Moreover, after performing precipitation for several times and washing|cleaning with a poor solvent, the powder of the refined polyamic acid can be obtained by normal temperature or heat-drying. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

<The manufacturing method of polyamic acid ester>

The polyamic acid ester which is a polyimide precursor used for this invention is compoundable by the method of (1), (2), or (3) shown below, for example.

(1) When synthesizing from polyamic acid

Polyamic acid ester is compoundable by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine.

Specifically, the polyamic acid and the esterifying agent are synthesized by reacting them in the presence of an organic solvent at -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably for 1 to 4 hours. can

As the esterifying agent, one that can be easily removed by purification is preferable, and N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide di-t-butyl acetal, and 1-methyl-3-p- Tolyltriazine, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, etc. are mentioned. As for the usage-amount of an esterification agent, 2-6 molar equivalent is preferable with respect to 1 mol of repeating units of a polyamic acid.

The solvent used for the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of polymer solubility, and these may be used in mixture of two or more types. do. The concentration at the time of synthesis is preferably from 1 to 30% by weight, more preferably from 5 to 20% by weight, from the viewpoint that polymer precipitation is less likely to occur and a high molecular weight body is easily obtained.

(2) When synthesized by reaction of tetracarboxylic acid diester dichloride and diamine

Polyamic acid ester is compoundable from tetracarboxylic-acid diester dichloride and diamine.

Specifically, tetracarboxylic-acid diester dichloride and diamine are -20 degreeC - 150 degreeC in presence of a base and an organic solvent, Preferably it is 0 degreeC - 50 degreeC WHEREIN: 30 minutes - 24 hours, Preferably 1 - It can synthesize|combine by making it react for 4 hours.

Although pyridine, triethylamine, etc. can be used for the said base, pyridine is preferable in order for reaction to advance mildly. It is preferable that the usage-amount of a base is a quantity with which removal is easy, and it is 2-4 times mole with respect to tetracarboxylic-acid diester dichloride from a viewpoint of being easy to obtain a high molecular weight body.

As for the solvent used for said reaction, N-methyl- 2-pyrrolidone or (gamma)-butyrolactone is preferable from the solubility of a monomer and a polymer, and these may mix and use 2 or more types. The polymer concentration at the time of synthesis is preferably from 1 to 30% by weight, more preferably from 5 to 20% by weight, from the viewpoint of preventing polymer precipitation from occurring and easily obtaining a high molecular weight body. Moreover, in order to prevent hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for the synthesis|combination of polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

(3) When synthesizing polyamic acid ester from tetracarboxylic acid diester and diamine

Polyamic acid ester is compoundable by polycondensing tetracarboxylic-acid diester and diamine.

Specifically, tetracarboxylic-acid diester and diamine are 0 degreeC - 150 degreeC in presence of a condensing agent, a base, and an organic solvent, Preferably it is 0 degreeC - 100 degreeC WHEREIN: 30 minutes - 24 hours, Preferably 3 It can synthesize|combine by making it react for -15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1 Well-known compounds, such as 3,5-triazinyl methylmorpholinium, can be used.

Tertiary amines, such as pyridine, can be used for the said base.

Since high molecular weight polyamic acid ester is obtained among the manufacturing methods of said three polyamic acid ester, the manufacturing method of said (1) or said (2) is especially preferable.

<Manufacturing method of polyimide>

The polyimide used for this invention can be manufactured by imidating the said polyamic acid ester or polyamic acid. When manufacturing a polyimide from polyamic acid ester, chemical imidation which adds a basic catalyst to the polyamic acid solution obtained by dissolving the said polyamic acid ester solution or polyamic acid ester resin powder in an organic solvent is simple. Chemical imidization is preferable because the imidation reaction proceeds at a relatively low temperature, and a decrease in the molecular weight of the polymer hardly occurs during the imidization process.

Chemical imidation can be performed by stirring the polymer to be imidated in presence of a basic catalyst and an acid anhydride in an organic solvent. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has suitable basicity to advance the reaction. Moreover, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned as an acid anhydride, Especially, since purification after completion|finish of reaction becomes easy when acetic anhydride is used especially, it is preferable.

The temperature at the time of imidation reaction is -20 degreeC - 140 degreeC, Preferably it is 0 degreeC - 100 degreeC, and reaction time can carry out in 1 to 100 hours. The quantity of a basic catalyst is 0.5-30 mole times of an amic acid group, Preferably it is 2-20 mole times, and the quantity of an acid anhydride is 1-50 mole times of an amic acid group, Preferably it is 3-30 mole times. The imidation rate of the polymer obtained is controllable by adjusting a catalyst amount, temperature, and reaction time.

Since the catalyst etc. which added remain in the solution after imidation reaction of polyamic acid ester or polyamic acid, the obtained imidation polymer is collect|recovered by the means described below, it is made to melt|dissolve again in an organic solvent, and the liquid crystal of this invention It is preferable to set it as an aligning agent.

A polymer can be deposited by inject|pouring into a poor solvent, stirring well the solution of the polyimide obtained by making it above. Precipitation is performed several times, and after washing|cleaning with a poor solvent, the powder of the polyamic acid ester refine|purified by normal temperature or heat-drying can be obtained.

Although the said poor solvent is not specifically limited, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains a polymer (A) and a polymer (B). In addition to the polymer (A) and the polymer (B), the liquid crystal aligning agent of this invention may contain the other polymer. Examples of other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or a derivative thereof, and poly(styrene-phenylmaleimide). ) derivatives, poly(meth)acrylates, and the like.

A liquid crystal aligning agent is used in order to manufacture a liquid crystal aligning film, From a viewpoint of forming a uniform thin film, it takes the form of a coating liquid. 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 point of forming a uniform and defect-free coating film, 1 weight% or more is preferable, and from the point of storage stability of a solution, 10 weight% or less is preferable. A particularly preferable concentration of the polymer is 2 to 8% by weight.

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-buty Lolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropane amide etc. are mentioned. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or γ -Butyrolactone is preferable.

Moreover, the mixed solvent which used together the solvent which the organic solvent contained in a liquid crystal aligning agent improves the applicability|paintability at the time of apply|coating a liquid crystal aligning agent in addition to the above solvents and the surface smoothness of a coating film is preferable. 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, 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, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether (butyl cellosolve), ethylene Glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy) ethanol, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether, 3-methoxymethylpropionate, 3-ethoxy Ethyl propionate, 3-methoxyethyl propionate, 3-methoxypropyl propionate, 3-methoxybutyl propionate, lactate n-butyl ester, lactate isoamyl ester, diethylene glycol monoethyl ether, diisobutyl ketone, etc. can

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 preferable. The kind and content of a solvent are suitably selected according to the coating apparatus of a liquid crystal aligning agent, application|coating conditions, application|coating environment, etc.

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, Propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone, ethylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone, ethylene glycol monobutyl ether monoacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, ethylene glycol monobutyl ether monoacetate, and dipropylene glycol monomethyl ether. . 1-80 weight% of the whole solvent contained in a liquid crystal aligning agent is preferable, as for a poor solvent, 10-80 weight% is more preferable, and its 20-70 weight% is especially preferable. The kind and content of a solvent are suitably selected according to the apparatus of application|coating of a liquid crystal aligning agent, conditions, environment, etc.

The liquid crystal aligning agent of this invention may contain components other than a polymer component and an organic solvent further. 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 and electricity of the liquid crystal aligning film A dielectric material, an electrically-conductive material, etc. for adjusting resistance are mentioned.

As said crosslinkable compound, the group containing an oxylanyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, and an oxazoline ring structure from a viewpoint that generation|occurrence|production of an AC afterimage is small and the improvement effect of film|membrane strength is high. , a compound having at least one group selected from the group consisting of a group containing a Meldrum acid structure, a cyclocarbonate group and a group represented by the following formula (d), or a compound selected from a compound represented by the following formula (e) (hereinafter , these are collectively referred to as compound (C)) are preferred.

[Formula 23]

(Wherein, Q ₃₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ₂ -OH", and Q ₃₂ and Q ₃₃ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "* -CH ₂ -OH". * represents a bond. A represents an aromatic ring-containing (m+n) valent organic group. m represents an integer from 1 to 6, n represents an integer from 0 to 4 .)

Specific examples of the compound having an oxylanyl group include, for example, the compound described in paragraph [0037] of Japanese Unexamined Patent Publication No. 10-338880, the compound described in WO2017/170483 No. WO2017/170483, etc. and compounds having two or more oxylanyl groups. 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 any of to (r-3), is particularly preferred.

[Formula 24]

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, for example.

Specific examples of the compound having a protective isocyanate group include, for example, a compound having two or more protective isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, paragraph [0119] of WO2015/141598 and compounds having three or more protected isocyanate groups as described in [0120]. Among these, compounds represented by any of the following formulas (bi-1) to (bi-3) are preferable.

[Formula 25]

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

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, for example, Japanese Unexamined Patent Publication No. 2007-286597.

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, for example.

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

_{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 two groups represented by the formula (d) described in paragraphs [0058] of WO2015/072554 and Japanese Unexamined Patent Publication No. 2016-118753, for example. The compound which has the above, the compound of Unexamined-Japanese-Patent No. 2016-200798, etc. are mentioned. Among these, compounds represented by the following formulas (hd-1) to (hd-8) are preferable.

[Formula 26]

Examples of the (m + n) valent organic group having an aromatic ring in A in the formula (e) include a (m + n) valent aromatic hydrocarbon group having 5 to 30 carbon atoms and an aromatic hydrocarbon group having 5 to 30 carbon atoms directly or a linking group. and an (m+n) valent organic group bonded via As said aromatic hydrocarbon group, benzene, naphthalene, etc. are mentioned, for example. Examples of the aromatic heterocyclic ring include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, A benzimidazole ring, an indole ring, a quinoxaline ring, an acridine ring, etc. are mentioned. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a group in which one hydrogen atom is removed from the alkylene group, and a divalent or trivalent cyclohexane ring. In addition, arbitrary hydrogen atoms of the said alkylene group may be substituted by organic groups, such as a fluorine atom or a trifluoromethyl group. If a specific example is given, the compound etc. of WO2010/074269 are mentioned. As a preferable specific example, the following formulas (e-1) - (e-11) are mentioned.

[Formula 27]

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

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

Examples of the adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltrisilane. Ethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-Ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltri Ethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane , N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-gly Cydoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri Silane couples such as methoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane A ring agent is mentioned. When using these silane coupling agents, 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 residual images, More preferably, it is 0.1-20 weight part.

<Liquid crystal alignment film, liquid crystal display element>

A liquid crystal aligning film is a film|membrane obtained by apply|coating said liquid crystal aligning agent to a board|substrate, drying and baking. It will not specifically limit if it is a board|substrate with high transparency as a board|substrate which apply|coats a liquid crystal aligning agent, Plastic substrates, such as a glass substrate, a silicon nitride board|substrate, an acryl board|substrate, and a polycarbonate board|substrate, etc. can also be used. In that case, it is preferable from the point of simplification of a process to use the board|substrate with which the ITO electrode etc. for driving a liquid crystal were formed. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used only on one side of the substrate, and a light-reflecting material such as aluminum can also be used for the electrode in this case.

Although the application|coating method in the board|substrate of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, an offset printing, a flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc., You may use these according to the objective.

After apply|coating a liquid crystal aligning agent on a board|substrate, a solvent can be evaporated by heating means, such as a hot plate, heat circulation type oven, or IR (infrared) type|mold oven, and it can be set as a liquid crystal aligning film. Drying after apply|coating a liquid crystal aligning agent, and a baking process can select arbitrary temperature and time. Usually, in order to fully remove the solvent to contain, it bakes at 50-120 degreeC for 1 to 10 minutes, and then the conditions to bake at 150-300 degreeC for 5 to 120 minutes are mentioned. When the thickness of the liquid crystal aligning film after baking is too thin, since the reliability of a liquid crystal display element may fall, 5-300 nm is preferable and 10-200 nm is more preferable.

Although the rubbing treatment method may be sufficient as the method of orientating the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention, a photo-alignment processing method may be used.

In the alignment treatment by rubbing treatment or photo-alignment treatment, in order to improve the liquid crystal alignment property, in some cases, preferably after heat treatment at a temperature of 150 to 250 ° C., the alignment treatment may be performed, and the liquid crystal alignment film is coated You may orientation-process a board|substrate heating at 50-250 degreeC.

Moreover, in the said method, the impurity adhering to the liquid crystal aligning film by performing a contact process to the liquid crystal aligning film which orientation-processed using water or a solvent can also be removed.

The solvent used for the contact treatment 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.

The liquid crystal aligning film of this invention is preferable as a liquid crystal aligning film of the liquid crystal display element of transverse electric field systems, such as an IPS system and an FFS system, Especially useful as a liquid crystal aligning film of the liquid crystal display element of an FFS system. After obtaining the board|substrate with a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention, a liquid crystal display element manufactures a liquid crystal cell by a known method, and is obtained using the liquid crystal cell.

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

Specifically, a transparent glass substrate is prepared, a common electrode is formed on one substrate, and a segment electrode is formed on the other substrate. These electrodes can be set as, for example, an ITO electrode, and are patterned so that a desired image display can be performed. Next, an insulating film is formed on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a SiO ₂ -TiO ₂ film formed by a sol-gel method.

Next, a liquid crystal aligning film is formed on each board|substrate, the other board|substrate is superimposed on one board|substrate so that a mutual liquid crystal aligning film surface may oppose, and the periphery is adhere|attached with a sealing compound. In order to control a board|substrate clearance gap in a sealing compound, it is preferable to mix the spacer normally, and to disperse|distribute the spacer for board|substrate clearance gap control also also to the in-plane part which does not form a sealing compound. In a part of a sealing compound, the opening part which can be filled with a liquid crystal from the outside is provided. Next, a liquid crystal material is inject|poured into the space surrounded by the board|substrate of 2 sheets and sealing agent through the opening part formed in the sealing compound, and this opening part is sealed with an adhesive agent after that. A vacuum injection method may be used for injection|pouring, and the method which utilized capillary phenomenon in air|atmosphere may be used. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material may be used, but a negative liquid crystal material is preferable. Next, a polarizing plate is installed. A pair of polarizing plates are affixed to the surface on the opposite side to the liquid-crystal layer of two board|substrates specifically,.

By using the liquid crystal aligning agent of this invention as mentioned above, there is little generation|occurrence|production of the residual image and AC residual image derived from residual DC, and a rework is easy and a liquid crystal aligning film with a high transmittance|permeability can be obtained.

Example

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

(diamine)

l-1, n-1, DA-1 to DA-7: compounds represented by the following formulas (l-1), (n-1), (DA-1) to (DA-7), respectively

(tetracarboxylic dianhydride)

CA-1 to CA-5: compounds each represented by the following formulas (CA-1) to (CA-5)

(Compound C)

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

(Compound D)

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

(Compound E)

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

(organic solvent)

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

BCS: Butyl Cellosolve, BCA: Butyl Cellosolve Acetate

[Formula 28]

[Formula 29]

[Formula 30]

[Viscosity]

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

<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)), 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 value of the peak of this proton and the proton peak derived from the NH group of the amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It calculated|required with the following formula using the integrated value.

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]

<Synthesis Example 1>

46.35 g (189.8 mmol) of DA-2, 28.81 g (51.75 mmol) of DA-4, and 41.25 g (103.5 mmol) of DA-3 were weighed in a 1 L 4-neck flask equipped with a stirring device and a nitrogen inlet tube. was added, NMP was added so that solid content concentration might be set to 15 %, and it stirred and melt|dissolved, conveying nitrogen. 50.27 g (224.3 mmol) of CA-1 was added, stirring this diamine solution under water cooling, NMP was further added so that solid content concentration might be 18%, and it stirred at 40 degreeC in nitrogen atmosphere for 1 hour. Then, 14.21g (72.5 mmol) addition of CA-3 was carried out, stirring under water cooling, NMP was added so that solid content concentration might be 18%, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours, and obtained the polyamic-acid solution. .

1000.0 g of the polyamic acid solution obtained above is fractionated to the 3 L Erlenmeyer flask with a stirrer, 105.99 g of NMP 500.0g, acetic anhydride 27.37g, and after adding 27.37g of pyridines, and stirring at room temperature for 30 minutes, at 50 degreeC The reaction was carried out for 2 hours. This reaction solution was thrown into 6500 g of methanol, and the obtained deposit was separated by filtration. After wash|cleaning this deposit with methanol, it dried under reduced pressure at the temperature of 80 degreeC, and the powder of polyimide was obtained. The imidation ratio of the powder of this polyimide was 75 %.

In a 1000 ml Erlenmeyer flask with a stirrer, 100.00 g of the powder of this polyimide is aliquoted, 400.0 g of NMP is added, stirred at 70°C for 24 hours to dissolve, and a polyimide (PI-A-) having a solid content concentration of 20% (PI-A- A solution of 1) was obtained.

<Synthesis Example 2>

The polyamic acid of the composition shown in following Table 1 was obtained by performing in the same procedure as Synthesis Example 1, respectively, using the diamine, tetracarboxylic acid derivative, and organic solvent shown in following Table 1. Thus, after fractionating 1000.0 g of the obtained polyamic-acid solution, 45.32 g (207.63 mmol) of compound E-1 addition and stirring for 12 hours, it is similar to Synthesis Example 1, and NMP, acetic anhydride, and pyridine are used Thus, a solution of polyimide (PI-A-2) was obtained. 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 diamine used for synthesis|combination with respect to a tetracarboxylic-acid component, About a diamine component, the total amount of diamine used for synthesis 100 The compounding ratio (molar part) of each compound with respect to a molar part 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.

<Synthesis Example 3>

In a 1 liter four-necked flask equipped with a stirring device and a nitrogen inlet tube, DA-2 was 24.12 g (98.8 mmol), DA-1 was 22.74 g (98.8 mmol), and 1-1 was 42.12 g (197.5 mmol) It was weighed, and 464.9 g of NMP and 185.7 g of GBL were added so that solid content concentration might be 12 %, and it stirred and melt|dissolved, conveying nitrogen. 50.0 g (255.0 mmol) of CA-3 which is an aliphatic acid dianhydride is added, stirring this diamine solution under water cooling, with 237.7 g of GBL, it adds so that solid content concentration may be 13.5 %, it is added, and it is 2 hours under water cooling under nitrogen atmosphere. stirred. Furthermore, 25.84 g (118.5 mmol) of CA-5 which is an aromatic acid dianhydride is added, and GBL is added so that solid content concentration may be 15%, and it stirs at 50 degreeC in nitrogen atmosphere for 15 hours, and is 15% of solid content and NMP. The solution of the polyamic acid (PAA-B-1) used as /GBL=50/50 was obtained.

<Synthesis Examples 4 to 10>

Polyamic acids (PAA-B-2) - (PAA-) shown in Table 1 below by carrying out in the same procedure as in Synthesis Example 3, respectively, using the diamine, tetracarboxylic acid derivative, and organic solvent shown in Table 1 below. B-8) was obtained. In Table 1, the numerical value in parentheses represents the orientation ratio (molar part) of each compound when the total amount of the diamine used for synthesis|combination is 100 mol part about a tetracarboxylic-acid component, About a diamine component, the diamine used for synthesis|combination The compounding ratio (mol part) of each compound with respect to the total amount of 100 mol part 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.

<Example 1>

[Preparation of liquid crystal aligning agent]

Using the solution of the polyimide (PI-A-1) obtained in Synthesis Example 1 and the solution of the polyamic acid (PAA-B-1) obtained in Synthesis Example 3, diluted with NMP, GBL and BCS, and further compound ( 1 part by weight of compound (D-1) was added with respect to 100 parts by weight of all polymers so that C-1) was 3 parts by weight based on 100 parts by weight of all polymers, and the mixture was stirred at room temperature. Then, the obtained solution was filtered with a filter having a pore size of 0.5 µm, so that the polymer component ratio was (PI-A-1): (PAA-B-1) = 20: 80 (solid content conversion weight ratio), and the solvent composition ratio was solid content: NMP:GBL:BCS=4.5:30:45.5:20 (weight ratio), the liquid crystal aligning agent ( 1) was obtained (Table 2 below). 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 2-11, Comparative Examples 1-4>

Liquid crystal aligning agents (2)-(15) were obtained by implementing similarly to Example 1 except having used the polymer of following Table 2, a compound (C), and a compound (D). In Table 2, the numerical value in parentheses is each polymer component or compound (C) with respect to a total of 100 weight part of the polymer component used for preparation of a liquid crystal aligning agent, respectively about a polymer and a compound (C) and a compound (D), or a compound (C), a compound ( The mixing ratio (parts by weight) of D) is shown. 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.

[Manufacturing of liquid crystal display element]

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

First, a substrate to which an electrode is attached was prepared. The substrate is a glass substrate having a size of 30 mm x 50 mm and a thickness of 0.7 mm. On the board|substrate, the ITO electrode provided with the beta phase pattern which comprises a counter electrode as a 1st layer is formed. On the counter electrode of the first layer, 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 two or more "<"-shaped electrode elements in which the center part was bent. 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 "<"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangular shape, but is bent at the central part similarly to the electrode element. It has a shape resembling the “ど” character. 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.

Comparing the 1st area|region and 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, based on the rubbing direction of the liquid crystal alignment layer to be described later, the electrode element of the pixel electrode is formed to form an angle of +10° (clockwise) in the first region of the pixel, and the electrode of the pixel electrode in the second region of the pixel The elements are formed to form an angle of -10° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotational operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the substrate plane are opposite to each other. Consists of.

Next, after filtering the liquid crystal aligning agent with a filter having a pore diameter of 1.0 μm, the prepared substrate with the electrode and a glass substrate having a columnar spacer with a height of 4 μm on which an ITO film is formed on the back surface are coated by spin coating. did. 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 60 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 direction with respect to the 3rd layer IZO comb electrode ), washing was performed by ultrasonic irradiation for 1 minute in pure water, and water droplets were removed by air blowing. 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 face and the rubbing direction is antiparallel and pasted it Then, the sealing compound was hardened and the cell gap produced the empty cell whose cell gap is 4 micrometers. 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 liquid crystal cell of the FFS system was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for evaluation of liquid-crystal orientation.

[evaluation]

1. Afterimage evaluation by long-term AC drive

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

In the state which put this liquid crystal cell on the high-intensity backlight, the alternating voltage of +/-5V was applied at the frequency of 60 Hz for 168 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 standing, the liquid crystal cell was installed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, 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 when the liquid crystal cell was rotated 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 (DELTA) is less than 0.15 degree, it was set as the favorable liquid-crystal orientation. Table 3 shows the evaluation results.

2. Measurement of the relaxation rate of the accumulated charge

A liquid crystal cell manufactured in the same manner as above (manufacture of liquid crystal cell) is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the pixel electrode and the counter electrode are short-circuited to the same potential under the two polarizing plates. The angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light of the LED backlight measured on the two polarizing plates was minimized. Next, V-T curve (voltage-transmittance curve) was measured, applying the alternating voltage of frequency 60 Hz to this liquid crystal cell, and relative transmittance computed the alternating voltage used as 23 % as a drive voltage.

In residual image evaluation, a 1V DC voltage was simultaneously applied, and it was made to drive for 120 minutes, applying the alternating voltage of the frequency 60Hz used as 23 % and driving a liquid crystal cell in relative transmittance. After that, only the application of the DC voltage was stopped, and the drive was made only with the AC voltage for an additional 15 minutes.

From the time when DC voltage application is stopped, until 10 minutes have elapsed, when the relative transmittance is relaxed to 25% or less, it is set to "good", and 10 minutes or more is required until the relative transmittance is reduced to 26% or less. , it was evaluated as "defective".

And the residual image evaluation by the method mentioned above was performed on the temperature condition of the state whose temperature of a liquid crystal cell is 40 degreeC.

3. Black level evaluation

The liquid crystal cell prepared in the same manner as above (manufacture of liquid crystal cell) is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, the backlight is turned on in a state where no voltage is applied, and the luminance of the transmitted light is the smallest. The placement angle of the was adjusted. The liquid crystal cell was observed using a digital CCD camera "C8800-21C" manufactured by Hamamatsu Photonics, and the luminance was quantified using the company's analysis software "ExDcam Image capture Software" for the captured image. If the luminance value of this liquid crystal cell was 580 or less, "good|favorableness" and more were made into "poor".

4. Evaluation of reworkability

The liquid crystal aligning agent of this invention was apply|coated to the ITO board|substrate by spin coat application|coating. After drying for 1 minute 30 second on a 60 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. Then, after immersing the manufactured board|substrate in the rework material (KR-31) heated to 35 degreeC for 600 second and developing, it washed with running water for 30 second with ultrapure water. Thereafter, it was dried by air blow and the amount of the remaining film was observed. At this time, when there is no residual film, it was set as "good", and when there was a residual film, it was set as "poor".

Table 3 shows the results of the experiments 1 to 4 above.

Industrial Applicability

The liquid crystal aligning agent of this invention is useful for formation of the liquid crystal aligning film in wide liquid crystal display elements, such as an IPS drive system and an FFS drive system.

In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2019-023807 filed on February 13, 2019 and Japanese Patent Application No. 2019-082233 filed on April 23, 2019 It is incorporated herein by reference and is taken in as a disclosure of the specification of the present invention.

Claims (13)

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
(A) Component: The polymer (A) which has a repeating unit represented by following formula (1).
(B) component: has a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5), The total content of the repeating unit represented by (2) and the repeating unit represented by the following formula (3) is 60 to 99.9 mol% of the total repeating units, and the repeating unit represented by the following formula (4) and the following formula (5) Polymer (B) whose total content of the repeating unit represented by is 0.1-40 mol% of all repeating units.

(X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group)

(X ₂ is a tetravalent organic group derived from an alicyclic acid dianhydride or an aliphatic acid dianhydride. Y ₂ is a divalent organic group represented by the following formula (m-1) or (m-2). R ₂ is a hydrogen atom or an alkyl group having 1 to 4. Z ₂₁ and Z ₂₂ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted alkenyl group having 2 to 10 carbon atoms. , an optionally substituted alkynyl group having 2 to 10 carbon atoms, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group.)

(* indicates a bond)

(X ₃ is a tetravalent organic group derived from an alicyclic acid dianhydride or an aliphatic acid dianhydride. Y ₃ is a divalent organic group represented by the following formula (l) or a partial structure represented by the following formula (n) It is a divalent organic group.R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z ₃₁ , Z ₃₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent an optional C2-C10 alkenyl group, an optionally substituted C2-C10 alkynyl group, tert-butoxycarbonyl group, or 9-fluorenylmethoxycarbonyl group.)

(Q ¹ , Q ² are an alkyl group having 1 to 3 carbon atoms, and Q ³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * represents a bond.)

(X ₄ , X ₅ is a tetravalent organic group derived from an aromatic acid dianhydride. Y _{4 has the same meaning as Y 2 in} Formula (2), and R ₄ has the same meaning _{as R 2 in} Formula (2) above. Z ₄₁ , Z ₄₂ have the same meaning _{as Z 21} , Z _{22 in} the formula (2), respectively _{. Y 5 has the same meaning as Y 3 in} the formula (3), and R ₅ is the formula ( It has the _{same meaning as R 3 in} 3), and Z ₅₁ and Z ₅₂ have the same meaning _{as Z 31} and Z _{32 in} Formula (3), respectively.) The method of claim 1,
2 wherein the polymer (B) is a repeating unit represented by the formula (3), a repeating unit in which Y ₃ is a divalent organic group represented by the formula (l), and _{a partial structure in which Y 3} is represented by the formula (n) The liquid crystal aligning agent which has a repeating unit which is a valent organic group. 3. The method according to claim 1 or 2,
The liquid crystal aligning agent whose divalent organic group which has a partial structure represented by the said Formula (n) is a divalent organic group represented by any one of following formula (n-1) - (n-3).

(Q ² , Q ³ has the same meaning ^{as Q 2} and Q ³ of the formula (n), respectively ^{. Q 4} represents a single bond or a structure of the following formula (Ar). n is an integer of 1 to 3 .* denotes a bonding hand.)

(Q ⁵ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m 2 selected from O-, -CONQ-, and -NQCO- is a valent organic group, and k is an integer of 1 to 5. In addition, Q represents hydrogen or a monovalent organic group, and l and m are integers of 1 to 5. *1 and *2 represent a bond, * ₁ is bonded to the benzene ring in formulas (n-1) to (n-3).) 4. The method according to any one of claims 1 to 3,
_{The liquid crystal aligning agent whose Y<1>} of said Formula (1) is a bivalent organic group which has a partial structure represented by following formula (H).

(Q ¹¹ is -NQCO-, -COO-, -OCO-, -NQCONQ-, -CONQ-, or -(CH ₂ ) _n - (n is an integer of 1 to 20.) Provided that n is In the case of 2 to 20, any -CH ₂ - is -O-, -COO-, -OCO-, -ND-, -NQCO-, -CONQ-, -NQCONQ-, - may be substituted with NQCOO- or -OCOO-.D represents a thermal leaving group, Q represents a hydrogen atom or a monovalent organic group.Q ¹² is a single bond or a benzene ring, and any hydrogen atom on the benzene ring is 1 may be substituted with a valent organic group.*1, *2 represents a bond, and when Q ¹² is a single bond, *2 is bonded to a nitrogen atom in an amino group. When Q ¹² is a benzene ring, Q ¹¹ is a single bond It may be a combination.) 5. The method according to any one of claims 1 to 4,
_{The liquid crystal aligning agent whose Y<1>} of said Formula (1) is a divalent organic group which has a partial structure represented by any one of following formula (H-1) - (H-14).

(*1, *2 represents a bond, *2 is a nitrogen atom in the imide ring) 6. The method according to any one of claims 1 to 5,
Y ₁ in the formula (1) is a divalent organic group represented by any of the formulas (H-1) to (H-14), or a divalent organic group represented by any of the following formulas (MH-1) to (MH-2) The liquid crystal aligning agent which is a bivalent organic group.

(*1 is bonded to the nitrogen atom in the imide ring. Boc represents a tert-butoxycarbonyl group.) 7. The method according to any one of claims 1 to 6,
_{The liquid crystal aligning agent whose X<1>} of said Formula (1) is at least 1 sort(s) chosen from the group which consists of following formula (4a) - (4l), following formula (5a), and following formula (6a).

(x and y are each independently a single bond, carbonyl, ester, phenylene, sulfonyl or amide group. Z ¹ to Z ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a chlorine group. represents an atom or a benzene ring. j is an integer of 0 or 1. m is an integer of 0 to 5. * represents a bond.) 8. The method according to any one of claims 1 to 7,
The liquid crystal aligning agent whose content rate of the said polymer (A) and the said polymer (B) is 5/95-95/5 by weight ratio of polymer (A)/polymer (B). 9. The method according to any one of claims 1 to 8,
In addition, an oxylanyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum acid structure, a cyclocarbonate group, and the following formula (d) The liquid crystal aligning agent containing the compound (C) which has at least 1 sort(s) of group chosen from the group which consists of group which consists of group and the partial structure represented by following formula (e).

(Q ₃₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ₂ -OH", Q ₃₂ and Q ₃₃ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ₂ -OH". * represents a bond. A represents an (m+n) valent organic group having an aromatic ring. m represents an integer from 1 to 6, n represents an integer from 0 to 4.) 10. The method of claim 9,
The liquid crystal aligning agent whose content of the said compound (C) is 0.5-20 weight part with respect to 100 weight part of polymer components contained in a liquid crystal aligning agent. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-10. A liquid crystal display element provided with the liquid crystal aligning film of Claim 11. 13. The method of claim 12,
A liquid crystal display device with a transverse electric field driving method.