KR20220151603A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

(Y₁ 은 하기 식 (H) 로 나타내는 2 가의 유기기를 나타낸다.)

(Q₁ 은, *1-NH-C(=O)-*1 또는 *1-NH-C(=O)-NH-*1 을 갖는 탄소수 1 ∼ 18 의 2 가의 유기기를 나타낸다. * 는 결합손을 나타낸다. *1 은 탄소 원자와 결합하는 결합손을 나타낸다.)

(식 중, R₁ ∼ R₄, R, Z 는, 상기 식 (1) 과 동일한 의미이다. Y₂ 는 하기 식 (O) 로 나타내는 2 가의 유기기를 나타낸다.)

Provided is a liquid crystal aligning agent capable of obtaining a liquid crystal display element having high liquid crystal orientation, suppressing variations in brightness in plane during black display, and having improved contrast. The liquid crystal aligning agent containing the polyimide precursor which has the repeating unit (a1) of Formula (1) and the repeating unit (a2) of Formula (2), and at least 1 sort(s) of polymer (A) of its imidation polymer. The details of the symbol are the same as the specification definition.

(Y ₁ represents a divalent organic group represented by the following formula (H).)

(Q ₁ represents a divalent organic group having 1 to 18 carbon atoms having *1-NH-C(=O)-*1 or *1-NH-C(=O)-NH-*1. * is a bond Indicates a hand. *1 indicates a bond bonded to a carbon atom.)

(In the formula, R ₁ to R ₄ , R, and Z have the same meaning as in the formula (1). Y ₂ represents a divalent organic group represented by the following formula (O).)

Description

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

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

BACKGROUND ART Conventionally, liquid crystal display devices have been widely used as display units of personal computers, smart phones, mobile phones, televisions, and the like. A liquid crystal display device generally includes 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 the orientation of liquid crystal molecules in the liquid crystal layer, and electricity supplied to the pixel electrode. A thin film transistor (TFT) or the like for switching signals is provided. As a driving method for liquid crystal molecules, a vertical electric field method such as a TN method or a VA method, or a transverse electric field method such as an IPS (In Plane Switching) method or a Fringe Field Switching (FFS) method is known.

The industrially most popular liquid crystal alignment film is so-called rubbing, in which the surface of a film formed on an electrode substrate and made of polyamic acid and/or polyimide imidated therein is rubbed in one direction with a cloth such as cotton, nylon, or polyester. It is manufactured by performing a process. The rubbing treatment is an industrially useful method that is simple and has excellent productivity. However, with the increase in performance, high definition, and size of liquid crystal display elements, various problems such as scratches on the surface of the alignment film caused by rubbing treatment, dust generation, mechanical force or static electricity, and unevenness in the alignment treatment surface The problem is becoming clear. As an alignment treatment method instead of the rubbing treatment, a photo-alignment method in which liquid crystal alignment ability is provided by irradiating polarized radiation is known. As for the photo-alignment method, methods utilizing photoisomerization, photocrosslinking, and photolysis have been proposed (see Non-Patent Document 1 and Patent Documents 1 and 2).

A liquid crystal alignment film, which is a constituent member of a liquid crystal display element, is a film for aligning liquid crystals uniformly, and liquid crystal orientation is one of important characteristics. However, compared with the liquid crystal aligning film obtained by the conventional rubbing process, the liquid crystal orientation film obtained by the said photo-alignment method tends to become low, and the application range of the liquid crystal display device provided with the liquid crystal aligning film was limited.

Japanese Unexamined Patent Publication No. 9-297313 International Publication No. 2015/050135 Pamphlet

「Functional materials」 November 1997 Vol.17, No.11 pages 13 to 22

Further, in an actual liquid crystal display element, the twist angle is slightly disturbed within the surface of the liquid crystal display element due to variations in manufacturing and the like. Then, due to such an in-plane variation, the brightness at the time of black display in the liquid crystal display element is disturbed in-plane.

The present invention has been made in view of the above circumstances, and one object is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal display element having high liquid-crystal alignment, suppressing variation in brightness in plane during black display, and having improved contrast. to be

This inventor discovered that the said subject was solvable by using the liquid crystal aligning agent containing a specific component, as a result of advancing earnest research, and came to complete this invention. Specifically, the following is the gist.

At least one kind of polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit (a1) represented by the following formula (1) and a repeating unit (a2) represented by the following formula (2), and an imidized polymer thereof (A) The liquid crystal aligning agent characterized in that it contains.

[Formula 1]

(In the formula, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom containing 1 carbon atom represents a 6-membered monovalent organic group or a phenyl group, and at least one of R ¹ to R ⁴ represents a group other than a hydrogen atom in the above definition. R and Z each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ₁ represents a divalent organic group represented by the following formula (H).)

[Formula 2]

(Q ₁ represents a divalent organic group having 1 to 18 carbon atoms having *1-NH-C(=O)-*1 or *1-NH-C(=O)-NH-*1. * is a bond Indicates a hand. *1 indicates a bond bonded to a carbon atom.)

[Formula 3]

(In the formula, R ₁ to R ₄ , R, and Z have the same meaning as in the formula (1). Y ₂ represents a divalent organic group represented by the following formula (O).)

[Formula 4]

(Ar represents a benzene ring, a biphenyl structure, or a naphthalene ring each independently, and at least one of the two Ar represents a naphthalene ring. Any hydrogen atom on the ring may be substituted with a halogen atom or a monovalent organic group. Q ₂ is -(CH ₂ ) _n - (n is an integer from 2 to 18), or a part of -(CH ₂ ) _n - is -O-, -C(=O)-, or Represents a group substituted with any of -OC(=O)-. * represents a bond.)

In addition, in this specification, "integer" in the case where it is obvious that it is an "integer", such as "n is an integer of 2-18", is sometimes omitted. In addition, * represents a bonding hand in any case. Boc represents a tert-butoxycarbonyl group. Fmoc represents a 9-fluorenylmethyloxycarbonyl group.

ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal display element excellent in contrast with high liquid-crystal orientation and the dispersion|variation of in-plane brightness at the time of black display was suppressed, and the liquid crystal aligning agent which can obtain this are provided.

<Polymer (A)>

The liquid crystal aligning agent of the present invention is selected from the group consisting of a polyimide precursor having a repeating unit (a1) represented by the following formula (1) and a repeating unit (a2) represented by the following formula (2) and an imidized polymer thereof It contains at least 1 type of polymer (A). In addition, the polymer (A) may be composed of one type or two or more types. Since the polymer (A) has a hydrogen-bonded amide bond or urea bond in the molecule by containing the repeating unit (a1) or the imidized structural unit of the repeating unit (a1), the heat resistance of the obtained liquid crystal aligning film increases , the decrease in contrast due to the variation of the twist angle within the surface of the liquid crystal display element, which occurs during manufacturing, is suppressed. Moreover, since it has in a molecule|numerator the naphthalene skeleton which is excellent in heat resistance and liquid-crystal orientation by further containing the imidation structural unit of the said repeating unit (a2) or its repeating unit (a2), the heat resistance and liquid-crystal orientation of the liquid crystal aligning film obtained are It becomes high, and a liquid crystal display element excellent in contrast can be obtained. The liquid crystal display element excellent in high liquid-crystal orientation and contrast can be obtained from the liquid crystal aligning agent of this invention by the above synergistic effect.

[Formula 5]

(In the formula, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom containing 1 carbon atom represents a 6-membered monovalent organic group or a phenyl group, and at least one of R ₁ to R ₄ represents a group other than a hydrogen atom in the above definition. R and Z each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ₁ represents a divalent organic group represented by the following formula (H).)

[Formula 6]

(Q ₁ represents a divalent organic group having 1 to 18 carbon atoms having *1-NH-C(=O)-*1 or *1-NH-C(=O)-NH-*1. *1 is Represents the bonding hand that binds to the carbon atom.)

[Formula 7]

(In the formula, R ₁ to R ₄ , R, and Z have the same meaning as in the formula (1). Y ₂ represents a divalent organic group represented by the following formula (O).)

[Formula 8]

(Ar represents a benzene ring, a biphenyl structure, or a naphthalene ring each independently, and at least one of the two Ar represents a naphthalene ring. Any hydrogen atom on the ring may be substituted with a halogen atom or a monovalent organic group. Q ₂ is -(CH ₂ ) _n - (n is an integer from 2 to 18), or a part of -(CH ₂ ) _n - is -O-, -C(=O)- or -OC( represents a group substituted with any of =O)-.)

Specific examples of the alkyl group having 1 to 6 carbon atoms in R ₁ to R ₄ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , n-pentyl group, etc. are mentioned. Specific examples of the alkenyl group having 2 to 6 carbon atoms in R ₁ to R ₄ include, for example, a vinyl group, a propenyl group, and a butynyl group, which may be linear or branched. As a specific example of the C2-C6 alkynyl group in said R< ₁ >-R< ₄ >, an ethynyl group, 1-propynyl group, 2-propynyl group etc. are mentioned, for example. As a halogen atom in said _R1 - _R4 , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. A fluoromethyl group, a trifluoromethyl group, etc. are mentioned as a C1-C6 monovalent organic group containing a fluorine atom in said _R1 - _R4 . From the viewpoint of high photoreactivity, R ₁ to R ₄ are hydrogen atoms or methyl groups, preferably at least one of R ₁ to R ₄ is a methyl group, and more preferably at least 2 of R ₁ to R ₄ are methyl groups. . More preferably, R ₁ and R ₃ are methyl groups, and R ₂ and R ₄ are hydrogen atoms.

Moreover, from a viewpoint of obtaining the effect of this invention satisfactorily, at least one of _R1 - _R4 represents groups other than a hydrogen atom in the said definition. By setting it as the said structure, since the photoreactivity of a polyimide film becomes high and the in-plane anisotropy of the obtained liquid crystal aligning film becomes high, the fall of the contrast by the variation of the twist angle within the surface of a liquid crystal display element which arises at the time of manufacture is suppressed.

Q ₁ in the formula (H) is a divalent compound having 1 to 18 carbon atoms having *1-NH-C(=O)-*1 or *1-NH-C(=O)-NH-*1 represents an organic group, among others -NH-C(=O)-, -NH-C(=O)-NH-, or *1-NH-C(=O)-*1 or *1-NH-C( A divalent organic group having 2 to 18 carbon atoms having =O)-NH-*1 is preferable. The definition of *1 is the same as the definition in the above formula (H).

Specific examples of the divalent organic group having 2 to 18 carbon atoms having *1-NH-C(=O)-*1 or *1-NH-C(=O)-NH-*1 include 2 to 18 carbon atoms A part of -CH ₂ - of the alkylene group in the alkylene group is substituted with either *1-NH-C(=O)-*1 or *1-NH-C(=O)-NH-*1 A divalent organic group of 2 to 18 carbon atoms (a1) and a part of -CH ₂ - of the divalent organic group (a1) are -O-, -C(=O)O-, -C=C-, - and divalent organic groups (a2) having 2 to 18 carbon atoms substituted with at least one group selected from the group consisting of C≡C-, cyclohexylene groups and phenylene groups. Among these, a group in which a part of -CH ₂ - of the divalent organic group (a1) or the divalent organic group (a1) is substituted with -O- is preferable from the viewpoint of obtaining the effect of the present invention satisfactorily.

As the divalent organic group represented by the above formula (H), a divalent organic group represented by any one of the following formulas (h-1) to (h-6) is preferable from the viewpoint of obtaining the effect of the present invention favorably.

[Formula 9]

Any hydrogen atom on the ring of Ar in the formula (O) is a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, or a fluorine atom. It may be substituted with a monovalent organic group such as a monovalent organic group having 1 to 6 carbon atoms. Specific examples of these monovalent organic groups include the structures exemplified for R ₁ to R ₄ above.

As a specific example of the divalent organic group represented by the said formula (O), the divalent organic group represented by either of following formula (o-1) - (o-6) is preferable from a viewpoint of improving liquid-crystal orientation.

[Formula 10]

The polymer (A) is selected from the group consisting of a polyimide precursor having a repeating unit (a2') further represented by the following formula (2') and an imidized polymer thereof, from the viewpoint of obtaining the effect of the present invention satisfactorily. At least 1 type of polymer may be sufficient.

[Formula 11]

(X _2' represents a tetravalent organic group, and Y _2' represents a divalent organic group represented by the following formula (O2). R and Z have the same meaning as in the formula (1) above.)

[Formula 12]

(Ar _2' represents a benzene ring, and any hydrogen atom on the ring may be substituted with a halogen atom or a monovalent organic group. Q _2' is a single bond, -O-, -C(=O)-, - OC(=O)-, -(CH ₂ ) _n - (n is 2 to 18), or a part of -(CH ₂ ) _n - is -O-, -C(=O)- or -OC Represents a group substituted with any of (=O)-. m is 0 to 2. When a plurality of AR _2' and Q _2' exist, they may be the same or different.)

As X _{2 '} , in addition to the tetravalent organic group represented by the following formula (g), a tetravalent organic group represented by any of the following formulas (X-1) to (X-25), derived from aromatic tetracarboxylic dianhydride A tetravalent organic group etc. are mentioned.

[Formula 13]

(R ₁ , R ₂ , R ₃ , R ₄ have the same meaning as R ₁ , R ₂ , R ₃ , R ₄ in the formula (1) above.)

[Formula 14]

[Formula 15]

Here, aromatic tetracarboxylic dianhydride refers to an acid dianhydride obtained by intramolecular dehydration of a carboxy group bonded to an aromatic ring such as a benzene ring or a naphthalene ring. Specific examples include a tetravalent organic group represented by any of the following formulas (Xa-1) to (Xa-2) and a tetravalent organic group represented by any of the following formulas (Xr-1) to (Xr-7): have.

[Formula 16]

(x and y are each independently a single bond, ether, carbonyl, ester, alkanediyl group having 1 to 10 carbon atoms, 1,4-phenylene, sulfonyl or amide group. j and k are 0 or 1.)

[Formula 17]

The tetravalent organic group represented by the formula (Xa-1) or (Xa-2) may have a structure represented by any of the following formulas (Xa-3) to (Xa-19).

[Formula 18]

[Formula 19]

Arbitrary hydrogen atoms on the ring of Ar _2' in the formula (O2) include a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and a fluorine atom. may be substituted with a monovalent organic group such as a monovalent organic group having 1 to 6 carbon atoms. Specific examples of these monovalent organic groups include the structures exemplified for R ₁ to R ₄ above.

As the divalent organic group represented by the formula (O2), a divalent organic group represented by any one of the following formulas (o2-1) to (o2-11) is preferable from the viewpoint of less generation of AC afterimages.

[Formula 20]

The polymer (A) is selected from the group consisting of a polyimide precursor having a repeating unit (a3) further represented by the following formula (3) and an imidized polymer thereof, from the viewpoint of enhancing adhesion to the sealing compound and voltage retention characteristics. It may be at least 1 type of polymer which becomes.

[Formula 21]

(In the formula, R and Z have the same meaning as in the formula (1). X ₃ represents a tetravalent organic group, and Y ₃ represents a group “-N(D)- (D represents a carbamate-based protecting group. )” represents a divalent organic group having 6 to 30 carbon atoms in the molecule.)

Specific examples of X ₃ include the tetravalent organic groups exemplified for X _2' above. From the viewpoint of obtaining the effect of the present invention satisfactorily, X ₃ is a tetravalent organic group represented by the formula (g) or a tetravalent organic group represented by any one of the formulas (X-1) to (X-25). It is preferable, and it is more preferable that it is a tetravalent organic group represented by the said formula (g).

As a specific example of a divalent organic group having 6 to 30 carbon atoms having a group "-N(D)- (D represents a carbamate-based protecting group)" in Y ₃ in a molecule, the following formula (3- A divalent organic group having a partial structure represented by 1) or a divalent organic group represented by the following formula (3-2) is exemplified.

[Formula 22]

In the formula, Q ₅ is a single bond, -(CH ₂ ) _n - (n is 1 to 20), or any -CH ₂ - of -(CH ₂ ) _n - is -O-, -COO-, -OCO-, -NQ ₉ -, -NQ ₉ CO-, -CONQ ₉ -, -NQ ₉ -CO-NQ ₁₀ -, -NQ ₉ A group substituted with -COO- or -O-COO-, and Q ₉ and Q ₁₀ each independently represents a hydrogen atom or a monovalent organic group.

Q ₆ and Q ₇ each independently represent a group having -H, -NHD, -N(D) ₂ , and -NHD, or a group having -N(D) ₂ . Q ₈ represents a group having -NHD, -N(D) ₂ , a group having -NHD, or a group having -N(D) ₂ . D represents a carbamate-based protecting group, and examples of the carbamate-based protecting group include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group. However, at least one of Q ₅ , Q ₆ and Q ₇ has a carbamate-based protecting group in the group.

As a preferable specific example of Y ₃ , a divalent organic group represented by any one of the following formulas (Y3-1) to (Y3-5) is exemplified from the viewpoint of less AC afterimage.

[Formula 23]

The polymer (A) is a polyimide having a repeating unit (a4) represented by the following formula (4) in addition to the repeating unit (a1), the repeating unit (a2), the repeating unit (a2'), and the repeating unit (a3). It may be at least 1 type of polymer chosen from the group which consists of a precursor and its imidation polymer.

[Formula 24]

In the formula, X ₄ represents a tetravalent organic group and Y ₄ represents a divalent organic group. R and Z have the same meaning as R and Z in the above formula (1), respectively. However, Y ₄ is a divalent organic group having 6 to 30 carbon atoms having a group “-N(D)- (D represents a carbamate-based protecting group)” in the molecule or a divalent group represented by the formula (O2) When a structure other than a group is shown and X ₄ is synonymous with a tetravalent organic group represented by the formula (g), Y ₄ is a divalent organic group represented by the formula (H), 2 represented by the formula (O) A structure other than a valent organic group is shown. Specific examples of X ₄ include the structures exemplified by X ₃ .

Specific examples of X ₄ include the tetravalent organic groups exemplified for X _2' above. From the viewpoint of obtaining the effect of the present invention satisfactorily, X ₄ is preferably a tetravalent organic group represented by the formula (g) or a tetravalent organic group represented by any one of the formulas (X-1) to (X-25) And it is more preferable that it is a tetravalent organic group represented by the said formula (g).

As a specific example of the divalent organic group of Y ₄ , the divalent organic group represented by the above formula (H), the divalent organic group represented by the above formula (O), the divalent organic group represented by the above formula (O2), or A divalent organic group having 6 to 30 carbon atoms having a group "-N(D)- (D represents a carbamate-based protecting group)" in the molecule, any of the following formulas (g-1) to (g-5) In addition to the divalent organic groups represented by , divalent organic groups derived from diamine described below (divalent organic groups obtained by removing two amino groups from diamine) are exemplified.

At least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group (hereinafter, also referred to as a nitrogen atom-containing structure. However, the secondary amino group and the tertiary amino group In the amino group, the amino group does not bind to a carbamate-based protecting group.) Diamine having , 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4 -Diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid, the following formula (3b-1) to formula ( Diamine having a carboxy group such as the diamine compound represented by 3b-4), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 4,4'-diaminobenzophenone, 1- (4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene -6-amine, diamine having a photopolymerizable group such as 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N-diallylaniline at the terminal, and cholestanyl Oxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5 Diamine having a steroid skeleton, such as cholestenyl diaminobenzoate, lanostanil 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane, the following formulas (V-1) to ( Diamine represented by any of V-6), diamine having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, oxa such as the following formulas (Ox-1) to (Ox-2) A divalent organic group derived from diamine, such as diamine having a sleepy ring structure, and a group represented by any of formulas (Y-1) to (Y-167) described in International Publication No. 2018/117239.

[Formula 25]

[Formula 26]

(In the above (3b-1), A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( CH ₃ )- or -N(CH ₃ )CO-, m1 and m2 are each independently 0 to 4, and m1 + m2 are 1 to 4. In formula (3b-2), m3 and m4 are each independently 1 to 5. In formula (3b-3), A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is 1 to 5. In formula (3b-4), A ³ and A ⁴ are each independently a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O- , -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-N(CH ₃ )- or -N(CH ₃ )-CO-, and m6 is 1 to 4.),

[Formula 27]

(In the above formulas (V-1) to (V-6), X ^v1 to X ^v4 and X ^p1 to X ^p2 are each independently -(CH ₂ ) _a - (a is 1 to 15), represents -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO-, X ^v5 represents -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO- Xa is a single bond, -O-, -NH-, -O-(CH ₂ ) _m Represents -O- (m is 1 to 6), and R ^v1 to R ^v4 and R ^1a to R ^1b are each independently an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or a carbon atom group of 2 to 20 carbon atoms. 20 represents an alkoxyalkyl group.

[Formula 28]

Examples of the nitrogen atom-containing heterocycle include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzoimidazole, purine, quinoline, isoquinoline, naphthyridine, and quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, and hexamethyleneimine. Among them, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine is preferable.

The secondary amino group and tertiary amino group that the diamine having a nitrogen atom-containing structure may have are represented by the following formula (n), for example.

[Formula 29]

In the formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. "*1" represents a bond bonded to a hydrocarbon group.

Examples of the monovalent hydrocarbon group of R in the formula (n) include an alkyl group such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups, such as a cyclohexyl group; Aryl groups, such as a phenyl group and a methylphenyl group, etc. are mentioned. R is preferably a hydrogen atom or a methyl group.

Specific examples of the diamine having a nitrogen atom-containing structure include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, and 3,6-diaminocarbazole. , N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarb Bazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine , 4,4'-diaminodiphenylamine, N,N-bis(4-aminophenyl)-methylamine, or a compound represented by any one of formulas (z-1) to (z-28) shown below. have.

[Formula 30]

[Formula 31]

[Formula 32]

(In the formula, Py represents a pyridine ring or a pyrimidine ring.)

From the viewpoint of obtaining the effect of the present invention satisfactorily, in the polymer (A), it is preferable that the sum of the repeating unit (a1) and the imidized structural unit of the repeating unit (a1) is 1 to 40 mol% of all repeating units, , It is more preferably 1 to 35 mol%, and more preferably 1 to 30 mol%. In addition, in the total here, the case where any of the imidation structural unit of a repeating unit (a1) and a repeating unit (a1) is 0 mol% is also included. Also in the following, when referred to as the total, the case where 1 or 2 or more of the structural unit elements is 0 mol% is also included.

From the viewpoint of obtaining the effect of the present invention satisfactorily, the polymer (A) preferably has a repeating unit (a1), a repeating unit (a2), and the total of these imidated structural units at 5 mol% or more of all repeating units, and 10 It is more preferable that it is mol% or more.

From the viewpoint of obtaining the effect of the present invention satisfactorily, in the polymer (A), the total of the repeating unit (a2) and the imidized structural unit of the repeating unit (a2) is preferably 1 to 95 mol% of all repeating units, , It is more preferable that it is 1-90 mol%, and it is still more preferable that it is 5-90 mol%.

From the viewpoint of obtaining the effect of the present invention satisfactorily, in the polymer (A), the total of the repeating unit (a3) and the imidized structural unit of the repeating unit (a3) is preferably 1 to 40 mol% of all repeating units, It is more preferably 1 to 30 mol%, and even more preferably 1 to 25 mol%.

<Polymer (B)>

The liquid crystal aligning agent of this invention may contain the polymer (B) which does not have both the said repeating unit (a1) and the said repeating unit (a2) in the same molecule other than the said polymer (A). In addition, the polymer (B) may be composed of one type or two or more types. From the viewpoint of obtaining the effect of the present invention favorably, the polymer (B) is at least one selected from the group consisting of a repeating unit (b1) represented by the following formula (5) and an imidized structural unit of the repeating unit (b1) and polymers having repeating units. Moreover, the repeating unit which comprises a polymer (B) may be comprised by 1 type or 2 or more types.

[Formula 33]

(In the formula, X ₅ is a tetravalent organic group, and Y ₅ is a divalent organic group. Z is each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent which may have Represents an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms which may have a substituent, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group R is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms indicates.)

As the tetravalent organic group in the formula X ₅ , a tetravalent organic group derived from aliphatic tetracarboxylic dianhydride, a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride, or aromatic tetracarboxylic acid 2 A tetravalent organic group derived from an anhydride is exemplified, and specific examples include the tetravalent organic group exemplified for the above X ₄ . From the viewpoint of obtaining the effect of the present invention satisfactorily, X ₅ is a tetravalent organic group represented by the formula (g), a tetravalent organic group represented by any of formulas (X-1) to (X-25), and A tetravalent organic group represented by any of formulas (Xa-1) to (Xa-2) or a tetravalent organic group represented by any of the above formulas (Xr-1) to (Xr-7) Also referred to as a device) is preferred.

From the viewpoint of obtaining the effects of the present invention favorably, the polymer (B) preferably contains at least 5 mol% of all repeating units in the polymer (B) of a repeating unit in which X ₅ is the specific tetravalent organic group described above. , It is more preferable to include 10 mol% or more.

As the divalent organic group in the formula Y ₅ , the divalent organic groups exemplified in Y ₄ are exemplified. From the viewpoint of a small residual image derived from residual DC, the polymer (B) is diamine, 2,4-diaminophenol, 3,5-diaminophenol or 3,5-diamino in which Y ₅ has the nitrogen atom-containing structure. Benzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, a divalent organic group derived from diamine having the carboxyl group, and a divalent organic group represented by the formula (H) It is preferable that it is a polymer containing the repeating unit which is a divalent organic group (These are collectively called a specific divalent organic group.).

Polymer (B) may contain 1 mol% or more of all repeating units included in polymer (B), and 5 mol of repeating units in which Y ₅ is the above-mentioned specific divalent organic group, from the viewpoint of a small residual image derived from residual DC. You may include % or more.

From the viewpoint of less residual image derived from residual DC, the content ratio of the polymer (A) and the polymer (B) may be 10/90 to 90/10 in mass ratio of [polymer (A)]/[polymer (B)]. , 20/80 to 90/10 may be sufficient, or 20/80 to 80/20 may be sufficient.

<Method for Producing Polymer (A) and Polymer (B)>

As the polyimide precursor (polyamic acid ester, polyamic acid) which is a polymer (A) and a polymer (B) used for this invention, and the polyimide which is its imidation polymer is described in international publication WO2013/157586, for example It can be synthesized by the same well-known method.

Specifically, it is synthesized by reacting (condensation polymerization) a diamine component and a tetracarboxylic acid derivative component in a solvent. Examples of the tetracarboxylic acid derivative component include tetracarboxylic dianhydride or a derivative thereof (tetracarboxylic acid dihalide, tetracarboxylic acid diester, or tetracarboxylic acid diester dihalide). When a part of polymer (A) or (B) contains an amic acid structure, a polymer (polyamic acid) having an amic acid structure is obtained by, for example, reacting a tetracarboxylic dianhydride component with a diamine component. . The solvent is not particularly limited as long as the produced polymer dissolves therein.

The diamine component and tetracarboxylic acid derivative component for obtaining the polyimide precursor of the polymer (A) are the above-mentioned formulas (1), formula (2), formula (2'), formula ( 3) Depending on the repeating unit represented by Formula (4), it is selected and used so that the structure of such a repeating unit may be obtained.

For example, when it has a repeating unit represented by Formula (1) which a polymer (A) has, as a diamine component, the structure of -N(Z)-Y ₁ -N(Z)- (Y ₁ , Z A diamine having the same definition as above) is used, and as the tetracarboxylic acid derivative component, a tetracarboxylic acid derivative having a structure of the following formula (g) (the definitions of R ₁ to R ₄ are the same as above). Carboxylic acid derivatives are used.

[Formula 34]

The polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a tetracarboxylic acid diester It can be obtained by a known method such as a method of reacting a dihalide with diamine.

As a method of obtaining polyimide, thermal imidation in which a solution containing a polyimide precursor such as polyamic acid or polyamic acid ester obtained by the above reaction is heated as it is, or catalyst imidation in which a catalyst is added to the solution can be cited. have.

<Solution viscosity/molecular weight of polymer>

The polyamic acid, polyamic acid ester, and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1000 mPa·s from the viewpoint of workability when this is used as a solution having a concentration of 10 to 15% by mass. , not particularly limited. In addition, the solution viscosity (mPa·s) of the polymer is a concentration of 10 to 15% by mass prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) It is a value measured at 25°C using an E-type rotational viscometer for the polymer solution of .

The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000 . The molecular weight distribution (Mw/Mn) expressed by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. By existing in such a molecular weight range, favorable orientation and stability of a liquid crystal display element are securable.

<liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains a polymer (A) and a polymer (B) as needed. In addition to the polymer (A) and the polymer (B), the liquid crystal aligning agent of the present invention may contain other polymers. Examples of other polymers include polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or derivative thereof, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, etc. can be heard

A liquid crystal aligning agent is used in order to manufacture 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 a coating liquid containing said polymer component and an organic solvent. In that case, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. 1 mass % or more is preferable from the point of forming a uniform and defect-free coating film, and 10 mass % or less is preferable from the point of storage stability of a solution. A particularly preferred concentration of the polymer is 2 to 8% by mass.

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, dimethyl sulfoxide, and γ-butyro Lactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethyl and propanamide (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 -Butyrolactone is preferred. It is preferable that it is 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent, as for content of a good solvent, it is more preferable that it is 20-90 mass %, and it is especially preferable that it is 30-80 mass %.

In addition, the organic solvent contained in the liquid crystal aligning agent is used in combination with a solvent (also referred to as a poor solvent) that improves the coating property at the time of applying the liquid crystal aligning agent and the surface smoothness of the coating film in addition to the above solvent. desirable. Although the specific example of the poor solvent used together is given below, it is not limited to these.

For example, diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1 ,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3- Ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl Ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, 3-methoxymethylpropionate, 3-ethoxy Ethyl propionate, 3-methoxyethylpropionate, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 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, or diisobutyl ketone is preferred.

1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, as for content of a poor solvent, 10-80 mass % is more preferable, and 20-70 mass % is especially preferable. The kind and content of a poor solvent are suitably selected according to the coating device of a liquid crystal aligning agent, coating conditions, coating environment, etc.

Preferable combinations of solvents of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 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, propylene glycol monobutyl ether and diisobutyl Ketones, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol monobutyl ether and diisobutylcarbinol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether etc. can be mentioned.

The liquid crystal aligning agent of this invention may further contain components (henceforth an additive component) other than a polymer component and an organic solvent. As such an additive component, an adhesion adjuvant for improving the adhesion between the liquid crystal aligning film and the substrate or the adhesion between the liquid crystal aligning film and the sealing agent, a compound for increasing the strength of the liquid crystal aligning film (hereinafter, also referred to as a crosslinkable compound), and promoting imidation. Dielectrics, electrically conductive substances, etc. for adjusting the dielectric constant and electric resistance of the compound for doing, the liquid crystal aligning film, etc. are mentioned.

As the crosslinkable compound, from the viewpoint of exhibiting good resistance to AC afterimage and improving film strength, it contains an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, and an oxazoline ring structure. A group consisting of 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 following formula (d), and a compound represented by the following formula (e) It may be at least one compound selected from (Hereinafter, these are collectively referred to as compound (C).).

[Formula 35]

(In formula (d), R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ₂ -OH". * indicates a bond. In formula (e), A represents a (m+n) valent organic group having an aromatic ring, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m is 1 to 6, and n is 0 to 4. The aromatic ring of A is It may be substituted with a monovalent group, and specific examples of the monovalent group include the monovalent group represented by the substituent for AR _2' in the formula (O2).)

Specific examples of the compound having an oxiranyl group include the compound described in paragraph [0037] of Japanese Patent Laid-Open No. 10-338880 and the compound having a triazine ring in its skeleton described in International Publication WO2017/170483. The compound which has the above oxiranyl 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) to ( It may be a compound containing a nitrogen atom, such as a compound represented by any of r-3).

[Formula 36]

Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751.

As specific examples of the compound having a protected isocyanate group, the compound having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of JP-A 2014-224978, paragraph [0119] to International Publication No. 2015/141598 compounds having three or more protected isocyanate groups described in [0120], and the like, and may be compounds represented by any of the following formulas (bi-1) to (bi-3).

[Formula 37]

As a specific example of the compound which has a protected isothiocyanate group, the compound which has 2 or more protected isothiocyanate groups of 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 ring structures described in paragraph [0115] of Unexamined-Japanese-Patent No. 2007-286597.

Specific examples of the compound having a group containing a Meldrum acid structure include a compound having two or more Meldrum acid structures described in International Publication No. WO2012/091088.

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

A methyl group, an ethyl group, a propyl group, and an isopropyl group are mentioned as a C1 _- C3 alkyl group of _R2 and R3 of the group represented by said formula (d).

As a specific example of the compound having a group represented by the formula (d), two or more groups represented by the formula (d) described in International Publication WO2015/072554 or paragraph [0058] of JP-A-2016-118753 The compound having, the compound of Unexamined-Japanese-Patent No. 2016-200798, etc. are mentioned, The compound represented by any of following formula (hd-1) - (hd-8) may be sufficient.

[Formula 38]

As the (m + n) valent organic group having an aromatic ring in A in the above formula (e), a (m + n) valent aromatic hydrocarbon group having 6 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, directly or as a linking group (m+n) valent organic groups bonded via , and (m+n) valent groups having an aromatic heterocyclic ring. As said aromatic hydrocarbon group, benzene, naphthalene, etc. are mentioned, for example. Examples of the aromatic heterocycle include structures exemplified in the above nitrogen atom-containing heterocycle. As the linking group, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), an alkylene group having 1 to 10 carbon atoms, or a group obtained by removing one hydrogen atom from the alkylene group, divalent or trivalent. A valent cyclohexane ring etc. are mentioned. Arbitrary hydrogen atoms of the alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group. As the alkyl group having 1 to 5 carbon atoms in R in the formula (e), specific examples of the alkyl groups exemplified for R ₁ to R ₄ in the formula (1) can be given.

If the specific example of the said formula (e) is given, the compound of international publication WO2010/074269 and the compound represented by either of following formula (e-1) - (e-10) are mentioned.

[Formula 39]

The above compound is an example of a crosslinkable compound, but is not limited thereto. For example, the components other than the above which are disclosed on page 53 [0105] - page 55 [0116] of International Publication No. 2015/060357, etc. are mentioned. Moreover, you may combine two or more types of crosslinkable compounds.

It is preferable that it is 0.5-20 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent, and, as for content of the crosslinkable compound in the liquid crystal aligning agent of this invention, a crosslinking reaction advances, and AC residual image From the viewpoint of expressing good tolerance, it is more preferably 1 to 15 parts by mass.

Examples of the adhesion adjuvant include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltri 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-glycemic Sidoxypropylmethyldimethoxysilane, 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, 3-isocyanatepropyltriethoxysilane, etc. A ring agent can be mentioned. When using a silane coupling agent, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent, and it is more 0.1-20 mass parts from a viewpoint of expressing favorable tolerance with respect to AC afterimage. desirable.

As the compound for promoting the imidation, a basic site (e.g., a primary amino group, an aliphatic heterocycle (e.g., pyrrolidine skeleton), an aromatic heterocycle (e.g., an imidazole ring, an indole ring), or guanine A compound having a dino group or the like (however, the above crosslinkable compound and the adhesion auxiliary agent are excluded), or a compound that generates the above basic site during firing is preferred. More preferably, it is a compound in which the basic site is generated upon firing, and a preferred specific example is an amino acid in which part or all of the basic site of an amino acid is protected. Specific examples of the amino acid include glycine, alanine, cysteine, methionine, asparagine, glutamine, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine, and ornithine. More preferable specific examples of the compound for accelerating imidation include N-α-(9-fluorenylmethoxycarbonyl)-N-τ-(tert-butoxycarbonyl)-L-histidine. .

<Method for Manufacturing Liquid Crystal Alignment Film>

The manufacturing method of the liquid crystal aligning film using the liquid crystal aligning agent of this invention is the process (process (1)) of apply|coating said liquid crystal aligning agent, the process (process (2)) of heating the applied liquid crystal aligning agent, and obtaining a film|membrane, process The step of irradiating the film obtained in step (2) with polarized ultraviolet rays (step (3)) and the step of baking the film obtained in step (3) at a temperature of 100° C. or higher and higher than that of step (2) (step (4) )) is characterized in that sequentially performed.

<Process (1)>

The substrate to which the liquid crystal aligning agent used in the present invention is coated is not particularly limited as long as it is a substrate having high transparency, and plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates and polycarbonate substrates can also be used. In that case, it is preferable to use a substrate having an ITO electrode or the like for driving the liquid crystal in view of simplifying the process. In addition, in the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is only a substrate on one side, and a material that reflects light such as aluminum can also be used for the electrode in this case.

Although the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, an inkjet method, etc. is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.

<Process (2)>

A process (2) is a process of heating the liquid crystal aligning agent apply|coated on the board|substrate, and forming a film|membrane. Specifically, the solvent is evaporated from the liquid crystal aligning agent applied on the substrate in step (1) by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared ray) type oven, or an amic acid in a polymer Alternatively, thermal imidization of amic acid ester can be performed or carried out. The heating process of the liquid crystal aligning agent apply|coated on the board|substrate in process (1) can select arbitrary temperature and time, and you may perform it multiple times. As a temperature to heat, it can implement at 40-180 degreeC, for example, and from a viewpoint of shortening a process, it is preferable to implement at 40-150 degreeC, and it is more preferable to implement at 40-120 degreeC. Although it does not specifically limit as heating time, 1 to 10 minutes, or 1 to 5 minutes are mentioned. When performing thermal imidation of the amic acid or amic acid ester in a polymer, the process heated in the temperature range of 190-250 degreeC or 200-240 degreeC after the said heating process can be performed, for example. Although it does not specifically limit as heating time, A heating time of 5 to 40 minutes or 5 to 30 minutes is mentioned.

<Process (3)>

Step (3) is a step of irradiating the film obtained in step (2) with polarized ultraviolet rays. As a wavelength of ultraviolet-ray, 200-400 nm is preferable, and especially, the ultraviolet-ray which preferably has a wavelength of 200-300 nm is more preferable. In order to improve liquid-crystal orientation, you may irradiate an ultraviolet-ray, heating the board|substrate on which the liquid crystal aligning film was coated at 50-250 degreeC. Moreover, 1-10,000 mJ/cm< ² > is preferable, and, as for the irradiation amount of the said ultraviolet-ray, ^100-5,000 mJ/cm2 is more preferable. The liquid crystal aligning film manufactured in this way can stably orientate liquid crystal molecules in a fixed direction.

The higher the extinction ratio of the polarized ultraviolet rays is, the higher the anisotropy can be imparted, which is preferable. Specifically, the extinction ratio of linearly polarized ultraviolet rays is preferably 10:1 or higher, and more preferably 20:1 or higher.

<Process (4)>

Step (4) is a step of firing the film obtained in step (3) at a temperature of 100°C or higher and higher than that of step (2). The firing temperature is not particularly limited as long as it is 100°C or higher and higher than the firing temperature in step (2), but is preferably from 150 to 300°C, more preferably from 150 to 250°C, and still more preferably from 200 to 250°C. desirable. The firing time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, still more preferably 5 to 30 minutes.

Since the reliability of a liquid crystal display element may fall when the thickness of the liquid crystal aligning film after baking is too thin, 5-300 nm is preferable and 10-200 nm is more preferable.

Moreover, after performing any of the said process (3) or (4) process, the obtained liquid crystal aligning film can also be contact-treated using water or a solvent.

As a solvent used for the said contact treatment, it will not be specifically limited if it is a solvent which melt|dissolves the degradation product produced|generated from the liquid crystal aligning film by irradiation of an ultraviolet-ray. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate , diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, or cyclohexyl acetate. Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferable, and water, 1-methoxy-2-propanol, or ethyl lactate is more preferable, from the viewpoint of versatility and safety of the solvent. . One type of solvent may be used, or two or more types may be combined.

As said contact treatment, ie, the process of water or a solvent to the liquid crystal aligning film which irradiated the polarized ultraviolet-ray, immersion process or spray process (it is also mentioned spray process) is mentioned. As for the processing time in these processes, 10 second - 1 hour are preferable at the point which melt|dissolves the degradation product produced|generated from the liquid crystal aligning film efficiently by an ultraviolet-ray. Especially, it is preferable to perform immersion treatment for 1 to 30 minutes. Further, the solvent at the time of the contact treatment may be heated even at normal temperature, but is preferably 10 to 80°C, more preferably 20 to 50°C. In view of the solubility of the degraded product, ultrasonic treatment or the like may be performed, if necessary.

It is preferable to perform rinsing (it is also mentioned rinse) by low boiling point solvents, such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone, and baking of a liquid crystal aligning film after the said contact process. At that time, either one of rinsing and baking may be performed, or both may be performed. The firing temperature is preferably 150 to 300°C, more preferably 180 to 250°C, and still more preferably 200 to 230°C. Moreover, 10 second - 30 minutes are preferable and, as for the time of baking, 1 to 10 minutes are more preferable especially.

<Liquid Crystal Alignment Layer>

The liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent.

The liquid crystal aligning film of the present invention is suitable as a liquid crystal aligning film of a liquid crystal display element of a horizontal electric field system such as an IPS system or a FFS system, and is particularly useful as a liquid crystal alignment film of a liquid crystal display element of an FFS system.

<liquid crystal display element>

The liquid crystal display element of this invention is equipped with the said liquid crystal aligning film.

After a liquid crystal display element obtains the board|substrate with a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention, it manufactures a liquid crystal cell by a known method, and is obtained using this liquid crystal cell.

As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Alternatively, it may be a liquid crystal display element having an active matrix structure in which switching elements such as TFT (Thin Film Transistor) are formed in each pixel portion constituting the image display.

Specifically, a transparent glass substrate is prepared, and a common electrode is formed on one substrate and a segment electrode is formed on the other substrate. These electrodes can be, for example, ITO electrodes, and are patterned so that 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 alignment film is formed on each substrate, the other substrate is overlaid on one substrate so that the liquid crystal alignment film surfaces are opposed to each other, and the periphery is bonded with a sealant. In order to control the gap between the substrates, the sealant is usually mixed with a spacer, and it is preferable to spread the spacer for controlling the gap between the substrates also in the in-plane portion where the sealant is not formed. An opening portion capable of being filled with liquid crystal from the outside is formed in a part of the sealant. Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through an opening formed in the sealant, and then the opening is sealed with an adhesive. For injection, a vacuum injection method may be used, or a method using capillarity in the air may be used. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material may be used. Next, the polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surface of the two substrates on the opposite side to the liquid crystal layer.

By using the manufacturing method of the present invention, afterimages due to long-term alternating-current drive occurring in liquid crystal display elements of an IPS drive system or an FFS drive system can be suppressed. Moreover, in a process (2), after heating in a temperature range of 40-150 degreeC, a liquid crystal aligning film can be obtained with fewer process numbers than before by performing a process (3). After the liquid crystal aligning agent of this invention removes the organic solvent in the temperature range of 40-150 degreeC in the process (2), it is especially preferable in the manufacturing method of the liquid crystal aligning film which includes the process of implementing a process (3) can be used

Example

The present invention will be described more specifically by way of examples below, but the present invention is not limited thereto. The symbol of the compound and the measurement method of each characteristic in the following are as follows.

(menstruum)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve,

(diamine)

DA-1 to DA-12: Compounds represented by the following formula (DA-1) to formula (DA-12);

(tetracarboxylic dianhydride)

CA-1 to CA-2: Compounds represented by the following formula (CA-1) to formula (CA-2);

(additive)

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

S-1: A compound represented by the following formula (S-1);

F-1: A compound represented by the following formula (F-1)

[Formula 40]

[Formula 41]

[Formula 42]

<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 completely dissolved by the application of ultrasonic waves. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum Co., Ltd.). For the imidation rate, a proton derived from a structure that does not change before and after imidation is determined as a standard proton, and the peak integration value of this proton and the proton peak integration derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm The values were used and determined by the following formula.

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

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

[Synthesis Example of Polymer]

<Synthesis Example 1>

9.34 g (38.3 mmol) of DA-1 and 1.60 g (6.75 mmol) of DA-3 were weighed into a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and NMP at a concentration of 12% by mass was added. It was added as much as possible and dissolved by stirring while sending nitrogen. 9.28g (41.4 mmol) of CA-1 was added stirring this diamine solution, NMP was added so that density|concentration might be set to 12 mass %, and it stirred at 40 degreeC for 24 hours, and obtained the solution of a polyamic acid.

35 g (9.3 mmol) of the resulting polyamic acid solution was placed in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 11.7 g of NMP was added, and the mixture was stirred for 30 minutes. To the obtained solution, 2.86 g of acetic anhydride (3 equivalence relative to the mole of polyamic acid) and 0.74 g of pyridine (equivalent quantity relative to the mole of polyamic acid) were added, followed by heating at 55°C for 3 hours to perform chemical imidation. The obtained reaction liquid was injected into 150 mL of methanol with stirring, the precipitated precipitate was collected by filtration, and the resin powder was washed by performing the same operation twice, and then dried under reduced pressure at 60 ° C. for 12 hours to obtain a polyimide resin powder. got it The imidation rate of this polyimide resin powder was 71%. 3.60 g of the obtained polyimide resin powder was taken in a 100 mL Erlenmeyer flask, NMP was added so that the solid content concentration would be 12%, it was stirred and dissolved at 70 degreeC for 24 hours, and the polyimide solution (PI-1) was obtained.

<Synthesis Examples 2 to 11>

Polyimide solutions (PI-2) to (PI-12) were obtained in the same manner as in Synthesis Example 1 except that the type and amount of the monomers used were changed as shown in Table 1 below. In Table 1, the numerical values in parentheses represent the compounding ratio (molar parts) of each compound with respect to the total amount of 100 molar parts of the tetracarboxylic acid derivatives used in the synthesis for the tetracarboxylic acid component, and for the diamine component, The compounding ratio (molar parts) of each compound with respect to 100 molar parts of the total amount of diamine used is shown. Regarding the organic solvent, the blending ratio (parts by mass) of each organic solvent relative to 100 parts by mass of the total amount of organic solvents used for preparation of the polyimide solution is shown.

<Synthesis Example 13>

2.69 g (9.0 mmol) of DA-6 and 7.17 g (36.0 mmol) of DA-11 were weighed into a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and NMP at a concentration of 12% by mass was added. It was added as much as possible and dissolved by stirring while sending nitrogen. 12.2g (41.4 mmol) of CA-2 was added stirring this diamine solution, NMP was added so that density|concentration might be set to 12 mass %, and it stirred at 70 degreeC for 24 hours, and obtained the solution (PAA-1) of a polyamic acid.

[Preparation of liquid crystal aligning agent]

<Comparative Example 1>

In a sample tube containing a stirrer, the polyimide solution (PI-1) obtained in Synthesis Example 1 and the polyamic acid solution (PAA-1) obtained in Synthesis Example 13 were mixed so that the solid content ratio of the polymer was 50:50 in mass ratio, NMP and BCS were added and diluted, and S-1, C-1, and F-1 were added at 1 part by mass, 10 parts by mass, and 15 parts by mass, respectively, based on 100 parts by mass of the total polymer solid content, and stirred for 30 minutes. . After stirring, the mass ratio of the polymer solid content of the polyimide (PI-1) and the polyamic acid (PAA-1) is 50:50, the polymer solid content concentration is 6 mass%, and the solvent composition is NMP:BCS = 80:20 in mass ratio liquid crystal An alignment agent (R1) was obtained.

<Comparative Examples 2 to 5, Examples 1 to 14>

Except that the polymer component to be used was changed as described in Table 2 below, it was carried out in the same manner as in Comparative Example 1 above, and liquid crystal aligning agents (R2) to (R5) and liquid crystal aligning agents (1) to (14), respectively. got In Table 2, the numerical value in parentheses shows the compounding ratio (mass part) of each polymer component or additive with respect to 100 mass parts of total polymer components used for preparation of a liquid crystal aligning agent, respectively about a polymer and an additive. About the organic solvent, the compounding ratio (mass part) of each organic solvent with respect to 100 mass parts of total amounts of the organic solvent contained in a liquid crystal aligning agent is shown.

Using the liquid crystal aligning agent obtained by making it above, the FFS drive liquid crystal cell was manufactured in the procedure shown below, and the characteristic evaluation was performed.

[Configuration of FFS driven liquid crystal cell]

A liquid crystal cell for Fringe Field Switching (FFS) mode is a first glass substrate having a FOP (Finger on Plate) electrode layer formed on the surface of a planar common electrode-insulating layer-comb-shaped pixel electrode. and a second glass substrate having a columnar spacer with a height of 3.5 μm on the front surface and an ITO film for preventing static electricity on the back surface. The above pixel electrode has a comb shape in which a plurality of electrode elements having a width of 3 μm and a central portion bent at an internal angle of 160 ° are arranged in parallel at intervals of 6 μm, and one pixel has a plurality of electrode elements It has a first area and a second area with a line connecting the bent part as a boundary.

In addition, when the liquid crystal alignment film formed on the 1st glass substrate carries out orientation processing so that the orientation direction of the liquid crystal may orthogonally cross the direction which divides the inside angle of a pixel bent part, and the liquid crystal alignment film formed on the 2nd glass substrate manufactures a liquid crystal cell, Alignment treatment is performed so that the orientation direction of the liquid crystal on the first substrate and the orientation direction of the liquid crystal on the second substrate coincide.

[Production of liquid crystal cell]

The liquid crystal aligning agent filtered by the 1.0 micrometer filter was apply|coated to the surface of each of the said 1 set of glass substrates by spin coat application|coating, and it was made to dry for 2 minutes on an 80 degreeC hot plate. Thereafter, the coating film surface was irradiated with 150 to 350 mJ/cm ² of ultraviolet rays having a wavelength of 254 nm and linearly polarized at an extinction ratio of 26: 1 through a polarizing plate, and then fired in a hot air circulation oven at 230 ° C. for 30 minutes, Two substrates with a liquid crystal aligning film having a film thickness of 100 nm were obtained.

Next, a sealing compound was printed on one side of the above-mentioned one set of substrates with a liquid crystal alignment film, and the other substrate was bonded so that the liquid crystal alignment film surfaces faced each other, and the sealing compound was cured to prepare an empty cell. . A liquid crystal (MLC-3019, manufactured by Merck & Co., Ltd.) was vacuum-injected into this empty cell by a vacuum injection method at normal temperature, the injection port was sealed, and an FFS drive liquid crystal cell was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand overnight, it used for each evaluation.

<Evaluation of liquid crystal orientation>

Using the liquid crystal cell before the ISO process, evaluation was performed by defining "poor" and those without initial flow orientation as "good" for those having an initial flow orientation.

<Evaluation of in-plane uniformity of contrast>

The twist angle of the liquid crystal display element was evaluated using OPTIPRO-micro by Syntec Corporation. The prepared liquid crystal cell was installed on a measurement stage, and the inside of the first pixel plane was measured at 20 points in a state where no voltage was applied, and the standard deviation was calculated. Evaluation was defined as "defect" when the twist angle standard deviation was 0.5 or more, and evaluated as "good" when it was less than 0.5.

<Evaluation result>

An evaluation result is shown in Table 3 about the liquid crystal display element obtained using the liquid crystal aligning agent (1)-(14) obtained by said Examples 1-14 and Comparative Examples 1-5 and (R1) - (R5).

The liquid crystal aligning agent of this invention is widely used for the liquid crystal display element of vertical electric field systems, such as a TN system and a VA system, especially, the horizontal electric field system, such as an IPS system and a FFS system.

In addition, the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2020-039386 filed on March 6, 2020 and Japanese Patent Application No. 2020-123011 filed on July 17, 2020 are hereby incorporated by reference. and is to be taken as the disclosure of the specification of the present invention.

Claims (15)

At least one kind of polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit (a1) represented by the following formula (1) and a repeating unit (a2) represented by the following formula (2), and an imidized polymer thereof (A) The liquid crystal aligning agent characterized in that it contains.

(In the formula, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom containing 1 carbon atom represents a 6-membered monovalent organic group or a phenyl group, and at least one of R ₁ to R ₄ represents a group other than a hydrogen atom in the above definition. R and Z each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ₁ represents a divalent organic group represented by the following formula (H).)

(Q ₁ represents a divalent organic group having 1 to 18 carbon atoms having *1-NH-C(=O)-*1 or *1-NH-C(=O)-NH-*1. * is a bond Indicates a hand. *1 indicates a bond bonded to a carbon atom.)

(In the formula, R ₁ to R ₄ , R, and Z have the same meaning as in the formula (1). Y ₂ represents a divalent organic group represented by the following formula (O).)

(Ar represents a benzene ring, a biphenyl structure, or a naphthalene ring each independently, and at least one of the two Ar represents a naphthalene ring. Any hydrogen atom on the ring may be substituted with a halogen atom or a monovalent organic group. Q ₂ is -(CH ₂ ) _n - (n is an integer from 2 to 18), or a part of -(CH ₂ ) _n - is -O-, -C(=O)- or -OC( =O)- represents a group substituted with any of them. * represents a bond.) According to claim 1,
A liquid crystal aligning agent in which the divalent organic group represented by the formula (H) is a divalent organic group represented by either of the following formulas (h-1) to (h-6).

According to claim 1 or 2,
A liquid crystal aligning agent in which the divalent organic group represented by the formula (O) is a divalent organic group represented by either of the following formulas (o-1) to (o-6).

According to any one of claims 1 to 3,
The liquid crystal aligning agent which is at least 1 sort(s) of polymer chosen from the group which the said polymer (A) becomes from the polyimide precursor which has a repeating unit (a2') further represented by following formula (2'), and its imidation polymer.

(X _2' represents a tetravalent organic group, and Y _2' represents a divalent organic group represented by the following formula (O2). R and Z have the same meaning as in the formula (1) above.)

(Ar _2' represents a benzene ring, and any hydrogen atom on the ring may be substituted with a halogen atom or a monovalent organic group. Q _2' is a single bond, -O-, -C(=O)-, - OC(=O)-, -(CH ₂ ) _n - (n is an integer from 2 to 18), or a part of -(CH ₂ ) _n - is -O-, -C(=O)-, or Represents a group substituted with any of -OC(=O)-. m represents an integer from 0 to 2. * represents a bond. When a plurality of Ar _2' and Q _2' exist, they may be the same or different. You can do it.) According to claim 4,
A liquid crystal aligning agent in which the divalent organic group represented by the formula (O2) is a divalent organic group represented by any of the following formulas (o2-1) to (o2-11).

According to any one of claims 1 to 5,
The liquid crystal aligning agent which is at least 1 sort(s) of polymer chosen from the group which the said polymer (A) becomes from the polyimide precursor which has a repeating unit (a3) further represented by following formula (3), and its imidation polymer.

(In the formula, R and Z have the same meaning as in the formula (1). X ₃ represents a tetravalent organic group, and Y ₃ represents a group “-N(D)- (D represents a carbamate-based protecting group. )” represents a divalent organic group having 6 to 30 carbon atoms in the molecule. R and Z have the same meaning as in the formula (1) above.) According to claim 6,
The liquid crystal aligning agent which is a structure where said Y< ₃ > is represented by any of following formula (Y3-1) - (Y3-5).

(In each formula, Boc represents a tert-butoxycarbonyl group, and * represents a bond.) According to any one of claims 1 to 7,
The liquid crystal aligning agent whose sum total of the imidation structural unit of the said repeating unit (a1) and its repeating unit (a1) is 1-40 mol% of all repeating units. According to any one of claims 1 to 8,
The liquid crystal aligning agent in which the sum total of the said repeating unit (a1), repeating unit (a2), and those imidation structural units is 5 mol% or more of all repeating units. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-9. A liquid crystal display element provided with the liquid crystal aligning film of Claim 10. The manufacturing method of the liquid crystal aligning film including the following process (1)-(3).
Process (1): The process of apply|coating the liquid crystal aligning agent in any one of Claims 1-9 on a board|substrate.
Process (2): Process of heating the liquid crystal aligning agent apply|coated at process (1), and obtaining a film|membrane.
Step (3): A step of irradiating the film obtained in step (2) with polarized ultraviolet rays. According to claim 12,
The manufacturing method of the liquid crystal aligning film which further includes the following process (4).
Process (4): The process of baking the film obtained in process (3) at 100 degreeC or more, and also higher temperature than process (2). According to claim 12 or 13,
The manufacturing method of the liquid crystal aligning film which is a process in which the said process (2) heats in a temperature range of 40-180 degreeC, and obtains a film|membrane. The liquid crystal display element provided with the liquid crystal aligning film obtained by the manufacturing method of the liquid crystal aligning film in any one of Claims 12-14.