KR20220027945A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same - Google Patents

Abstract

(단, R₂, R_4a, R_4b, R₅, R₆ 은, 각각 독립적으로, 수소 원자 또는 탄소수 1 ∼ 20 의 알킬기를 나타낸다. * 는 결합손을 나타낸다.)A liquid crystal aligning agent from which a high voltage retention can be maintained and the liquid crystal aligning film excellent in rework property is provided.
The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
(A) component: at least 1 sort(s) of polymer selected from the group which consists of a polyimide-type polymer, polyorganosiloxane, the polymer of the monomer which has a polymerizable unsaturated bond, and a cellulosic polymer.
(B) component: has either a structure or a steroid skeleton in which two or more rings are linked directly or via a linking group, and has at least one group represented by the following formulas (b-1) to (b-5), or A compound having at least two groups represented by the following formula (b-6) and having a molecular weight of 2000 or less.

(However, R ₂ , R _4a , R _4b , R ₅ , and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. * represents a bond.)

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.

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

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

In recent years, the request|requirement with respect to image quality improvement of a liquid crystal display element is increasing more and more. For example, with favorable liquid-crystal orientation, the liquid crystal display element which can maintain high voltage retention is desired, and the liquid crystal aligning agent containing a specific compound is disclosed by patent document 1 and patent document 2.

International Publication (WO) 2016/063834 Japanese Patent Laid-Open No. 2016-200798

In addition, since the economical efficiency in the production process of the liquid crystal display device is also very important, in particular, the recycling and use of the device substrate is required. That is, after forming a liquid crystal aligning film on the substrate of the device with a liquid crystal aligning agent, inspection of orientation, etc. is performed, and as a result, when a defect has occurred, the liquid crystal aligning film is removed from the substrate, and the substrate is recovered and reused , it is required to be able to easily perform a so-called rework process.

The conventionally proposed liquid crystal aligning agent cannot necessarily fully satisfy|fill the said subject, and cannot be said to be what can be achieved. This invention is made|formed based on the above circumstances, The liquid crystal aligning agent from which the liquid crystal aligning film excellent in rework property is obtained, the liquid crystal aligning film obtained from it, and the liquid crystal display element using the same, the objective maintaining high voltage retention aims to 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 some component, as a result of earnestly advancing, and came to complete this invention.

This invention has the following summary.

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

(A) component: consisting of a polyimide-based polymer (A-1), a polyorganosiloxane (A-2), a polymer of a monomer having a polymerizable unsaturated bond (A-3), and a cellulose-based polymer (A-4) At least one kind of polymer (A) selected from the group.

(B) component: has either a structure or a steroid skeleton in which two or more rings are linked directly or via a linking group, and has at least one group represented by the following formulas (b-1) to (b-5), or A compound having at least two groups represented by the formula (b-6) and having a molecular weight of 2000 or less.

[Formula 1]

(* represents a bond, R ₂ , R _4a , R _4b , R ₅ , and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, the liquid crystal aligning agent from which the liquid crystal display element which can maintain high voltage retention, and the liquid crystal aligning film excellent in rework property is obtained is obtained.

<(A) component>

The liquid crystal aligning agent of this invention has a polyimide-type polymer (A-1) which has at least 1 sort(s) of repeating unit chosen from the group which consists of a repeating unit represented by following formula (1), and a repeating unit represented by following formula (2) (A-1) contains at least one polymer (A) selected from the group consisting of polyorganosiloxane (A-2), a monomer polymer having a polymerizable unsaturated bond (A-3), and a cellulosic polymer (A-4) do.

<Polyimide-based polymer (A-1)>

As a polyimide-type polymer, the polymer which has at least 1 sort(s) of repeating unit selected from the group which consists of a repeating unit represented by following formula (1) and a repeating unit represented by following formula (2) is preferable.

[Formula 2]

However, in Formula (1) and Formula (2), X< ₁ > is a tetravalent organic group, and Y< ₁ > is a divalent organic group. R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Z ₁₁ and Z ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkyl group having 2 to 10 carbon atoms which may have a substituent an alkenyl group, an optionally substituted alkynyl group having 2 to 10 carbon atoms, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group.

Specific examples of the alkyl group having 1 to 5 carbon atoms for R ₁ in the formula (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert- A butyl group, n-pentyl group, etc. are mentioned. From the viewpoint of easiness of imidation by heating, R ₁ is preferably a hydrogen atom or a methyl group.

As a specific example of the C1-C10 alkyl group of _Z11 and _Z12 in said Formula (2), in addition to the specific example of the C1-C5 alkyl group illustrated by said R< ₁ >, a hexyl group, a heptyl group , an octyl group, a nonyl group, a decyl group, and the like. Specific examples of the alkenyl group having 2 to 10 carbon atoms for Z ₁₁ and Z ₁₂ include 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, and 2-propynyl group.

Z ₁₁ , Z ₁₂ may have a substituent, and examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, a cyano group, and an alkoxy group. there is. A point with few residual images WHEREIN: As for Z ₁₁ and Z ₁₂ , a hydrogen atom or a methyl group is preferable.

X ₁ is derived from at least one selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide (hereinafter, collectively referred to as tetracarboxylic acid derivative). and tetravalent organic groups. When specific examples are given, it is derived from aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, these tetracarboxylic acid diesters, or tetracarboxylic acid diester dihalides. A tetravalent organic group is mentioned. Y< ₁ > of Formula (1) is a divalent organic group derived from diamine.

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

X ₁ is preferably a tetravalent organic group selected from the group consisting of the following formulas (4a) to (4n), the following formulas (5a), and (6a) from the viewpoint of obtaining a high voltage retention.

[Formula 3]

However, x and y are a single bond, -O-, -CO-, -CO(=O)-, a C1-C5 alkanediyl group, 1,4-phenylene, -SO-, or -NRCO- (R represents a hydrogen atom or a methyl group.); Z ¹ to Z ⁶ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring. j and k are 0 or 1. m is an integer of 1-5. * indicates a bond.

As a preferable specific example of the said Formula (4a), the structure represented by any of the following formulas (4a-1) - (4a-4) is mentioned at the point from which a high voltage retention is obtained.

[Formula 4]

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

X ₁ in the formula (1) is selected from the group consisting of the formulas (4a) to (4h), (4j), (41), (4m), and (4n) from the viewpoint of obtaining a high voltage retention. A tetravalent organic group is preferable.

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

As Y< ₁ > of Formula (1), the divalent organic group derived from diamine is mentioned. For example, the divalent organic group derived from an aliphatic diamine, an alicyclic diamine, or an aromatic diamine is mentioned. Specific examples of the aliphatic diamine include metaxylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, and hexamethylenediamine; Examples of the alicyclic diamine include 1,4-cyclohexanediamine and 4,4'-methylenebis(cyclohexylamine).

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diamino Azobenzene, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl -1H-inden-6-amine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimizine, 3,6-diaminocarbazole, N-methyl-3,6 -diaminocarbazole, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis (4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis(4-aminophenyl)-piperazine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl) Piperidine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, the following formulas (z-1) to (z-19) Nitrogen-containing diamines such as ), carboxyl group-containing diamines such as 3,5-diaminobenzoic acid, 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, 1,3- Bis(3-aminopropyl)-tetramethyldisiloxane, the following formulas (H-1) to (H-16), (H2-1) to (H2-17), (H3-1) to (H3-4) a diamine of the following formulas (V2-1) to (V2-13), an alkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, and a steroid skeleton having 17 to 51 carbon atoms Diamine having a radical initiation function represented by the following formulas (R1) to (R5), diamine having in a side chain a group having, a structure (polycyclic structure) in which two or more rings are linked directly or via a linking group, methacrylic acid 2 -(2,4-diaminophenoxy)ethyl, a diamine having a photopolymerizable group at the terminal, such as 2,4-diamino-N,N-diallylaniline, the light described in WO2014/080865 A diamine having an orientation structure, a diamine having a carbon-carbon unsaturated bond as described in [0057], a diamine having an azobenzene skeleton as described in [0058], a diamine having photoreactivity as described in [0069] to [0072] of WO2012/086715, etc. can be heard

[Formula 5]

(n represents the integer of 2-10.)

[Formula 6]

[Formula 7]

(Boc represents a tert-butoxycarbonyl group. The same applies below.)

[Formula 8]

[Formula 9]

(R represents a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group.)

[Formula 10]

[Formula 11]

(R represents a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group. * represents a bond.)

[Formula 12]

[Formula 13]

[Formula 14]

However, in the formulas (V2-1) to (V2-13), X ^v1 to X ^v4 and X ^p1 to X ^p8 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15) ), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-, and X ^v5 represents -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-. X ^V6 , X ^V7 , and X ^s1 to X ^s4 each independently represent -O-, -COO- or -OCO-. X _a to X _f represent a single bond, -O-, -NH-, -O-(CH ₂ ) _m -O-. R ^v1 to R ^v4 and R ^1a to R ^1h each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. m represents the integer of 1-8.

The polyimide-based polymer (A-1) in the present invention describes, for example, a tetracarboxylic acid derivative having a structure of X ₁ and a diamine having a structure of Y ₁ described in WO2013/157586 It can be obtained by reacting by a known method as used.

The terminal modification type polymer obtained using a terminal blocker with the above tetracarboxylic-acid derivative and diamine may be sufficient as such a polyimide-type polymer (A-1).

Examples of the terminal blocker include maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, (m-1 ) to (m-6) an acid monhydride such as a compound represented by any one of; chlorocarbonyl compounds such as di-tert-butyl bicarbonate; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid; Monoisocyanate compounds, such as ethyl isocyanate, phenyl isocyanate, and naphthyl isocyanate, etc. are mentioned.

[Formula 15]

It is preferable to set it as 40 mol part or less with respect to a total of 100 mol part of the diamine to be used, and, as for the usage ratio of a terminal blocker, it is more preferable to set it as 30 mol part or less.

<Polyorganosiloxane (A-2)>

The polyorganosiloxane polymer (A-2) can be obtained, for example, by hydrolyzing or hydrolyzing/condensing a hydrolyzable silane compound, preferably in the presence of a suitable organic solvent, water, and catalyst. The hydrolyzable silane compound used for the synthesis of the polymer (A-2) is, for example, selected from the group consisting of an oxetanyl group and an oxiranyl group in the molecule from the viewpoint of imparting a high voltage retention to a liquid crystal display device. You may have at least 1 type of functional group. Specific examples of the silane compound having an oxetanyl group or an oxiranyl group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxy Ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyl triethoxysilane etc. are mentioned.

As another silane compound used for the synthesis|combination of polymer (A-2), For example, tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, etc. of alkoxysilane; nitrogen/sulfur-containing alkoxysilanes such as 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(3-cyclohexylamino)propyltrimethoxysilane; Unsaturated bond-containing alkoxy such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and vinyltriethoxysilane silane; Trimethoxysilylpropyl succinic anhydride etc. are mentioned.

When applying to the liquid crystal aligning agent for liquid crystal display elements of TN type, STN type, or vertical alignment type, or when providing liquid-crystal aligning ability to a coating film by the photo-alignment method, to the side chain of a polymer (A-2), You may introduce|transduce specific groups, such as a liquid crystal aligning group and a photo-aligning group. Although the method of synthesizing the polymer (A-2) having these specific groups in the side chain is not particularly limited, for example, the mixture of the epoxy group-containing silane compound or the epoxy group-containing silane compound and other silane compounds is hydrolyzed and condensed. The method of synthesize|combining the polymer which has an epoxy group, and then, making the obtained epoxy-group containing polymer and the carboxylic acid which has the said specific group react, etc. are mentioned. Reaction of an epoxy-group containing polymer and carboxylic acid can be performed according to a well-known method.

As the carboxylic acid having the specific group, an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, two or more rings are Carboxylic acid which has liquid-crystal orientation groups, such as group which has a structure (polycyclic structure) connected directly or via a coupling group, carboxylic acid which has photo-alignment groups, such as a cinnamic acid structure, etc. are mentioned.

500-100,000 are preferable, as for the polymer (A-2), the weight average molecular weights (Mw) of polystyrene conversion measured by GPC have more preferable 1,000-30,000, and their 1,000-20,000 are still more preferable.

<Polymer of a monomer having a polymerizable unsaturated bond (A-3)>

The monomer used for superposition|polymerization of a polymer (A-3) will not be specifically limited, if it has a polymerizable unsaturated bond. For example, a (meth)acrylic compound, a conjugated diene compound, an aromatic vinyl compound, a maleimide compound, etc. are mentioned. From the viewpoint of imparting a high voltage retention to the liquid crystal display element, the monomer used for polymerization is, in the molecule, an oxetanyl group, an oxiranyl group, a carboxyl group, an alkoxysilane group, a cyclic carbonate group, an isocyanate group, and a group consisting of a protective isocyanate group You may have at least 1 type of functional group selected from.

As a monomer which has an oxetanyl group or an oxiranyl group, For example, Maleimide-type compounds, such as N-(4-glycidyloxyphenyl) maleimide and N-glycidyl maleimide; styrene-based compounds such as 3-(glycidyloxymethyl)styrene, 4-(glycidyloxymethyl)styrene, and 4-glycidyl-α-methylstyrene; (meth) glycidyl acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl acrylate glycidyl, (meth) acrylate 3,4-epoxybutyl, α-ethyl 3,4-epoxybutyl acrylic acid, (meth)acrylic acid 3,4-epoxycyclohexylmethyl, (meth)acrylic acid 6,7-epoxyheptyl, α-ethylacrylic acid 6,7-epoxyheptyl, acrylic acid 4-hydroxybutylgly (meth)acrylic compounds, such as cydyl ether and (meth)acrylic acid (3-ethyloxetan-3-yl)methyl, are mentioned, respectively.

As a monomer which has a carboxyl group, For example, Styrene-type compounds, such as 3-vinyl benzoic acid and 4-vinyl benzoic acid; (meth)acrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid, vinylbenzoic acid, crotonic acid, citraconic acid, mesaconic acid, itaconic acid, 3-maleimidebenzoic acid, 3-maleimidepropionic acid, maleic anhydride, and the like. there is. As the monomer having an isocyanate group or a protective isocyanate group, for example, 2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko Co., Ltd.), 2-[(3,5-dimethylpyrazolyl)carbonyl Amino] ethyl methacrylate (Carrens MOI-BP, Showa Denko Co., Ltd. make) etc. are mentioned. Examples of the monomer having an alkoxysilane group include 3-methacryloxypropyltrimethoxysilane (Silla Ace S710, manufactured by JNC Corporation), 3-methacryloxypropylmethyldimethoxysilane, and the like.

Moreover, the monomer used for superposition|polymerization of a polymer (A-3) may have a photo-alignment group, As a specific example of a photo-alignment group, the azobenzene containing group which contains azobenzene or its derivative(s) as a basic skeleton, cinnamic acid, or its derivative(s) (cinnamic acid structure) as a basic skeleton; a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton; a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton; coumarin or a derivative thereof; and a cyclobutane-containing structure including a coumarin-containing group as a basic skeleton and cyclobutane or a derivative thereof as a basic skeleton. Since the sensitivity to light is high, it is preferable that a photo-alignment group is a cinnamic-acid structure containing group especially. Specific examples include the following formulas (3-m1) to (3-m18).

[Formula 16]

The monomer used for the said polymer (A-3) may use together the monomer (henceforth another monomer.) which does not have all the said functional groups. As another monomer, For example, (meth)acrylic-type compounds, such as (meth)acrylic-acid alkyl, (meth)acrylic-acid cycloalkyl, (meth)acrylic-acid benzyl, (meth)acrylic-acid 2-ethylhexyl; styrene, methylstyrene, and divinylbenzene; 1,3-butadiene, 2-methyl-1,3-butadiene; N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, etc. are mentioned.

Use of a monomer having at least one functional group selected from the group consisting of an oxetanyl group, an oxiranyl group, a carboxyl group, an alkoxysilane group, a cyclic carbonate group, an isocyanate group and a protected isocyanate group in the synthesis of the polymer (A-3) 1 mol% or more is preferable with respect to the total amount of the monomer used for the synthesis|combination of a polymer (A-3), as for a ratio, 5 mol% or more is more preferable, and its 10 mol% or more is still more preferable. Moreover, when using together the photo-aligning group mentioned later, 90 mol% or less is preferable and, as for the usage ratio of the monomer, 80 mol% or less is preferable.

10-99 mol% is preferable with respect to the whole quantity of the monomer used for the synthesis|combination of a polymer (A-3), as for the content rate of the monomer which has a photo-alignment group, 10-95 mol% is more preferable, 20-90 mol% is more preferable.

It does not specifically limit about the manufacturing method of a polymer (A-3), The general-purpose method handled industrially can be used. Specifically, it can manufacture by cationic polymerization using the vinyl group of a monomer, radical polymerization, or anionic polymerization. Among them, radical polymerization is particularly preferable from the viewpoint of easiness of reaction control. The polymer (A-3) can be obtained by, for example, polymerizing a monomer in the presence of a polymerization initiator. Examples of the polymerization initiator to be used include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( Azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile) are preferred. It is preferable that the usage-rate of a polymerization initiator sets it as 0.01-30 mass parts with respect to 100 mass parts of all the monomers used for reaction. Examples of the organic solvent to be used include alcohol, ether, ketone, amide, ester, hydrocarbon compound, and the like.

Mw of polystyrene conversion of a polymer (A-3) measured by gel permeation chromatography (GPC) becomes like this. Preferably it is 1,000-300,000, More preferably, it is 2,000-100,000. The molecular weight distribution (Mw/Mn) represented by ratio of Mw and the number average molecular weight (Mn) of polystyrene conversion measured by GPC becomes like this. Preferably it is 10 or less, More preferably, it is 8 or less.

<Cellulose polymer (A-4)>

As a specific example of a polymer (A-4), the polymer which has a structural unit represented by following formula (4-c) is mentioned.

[Formula 17]

(R ¹ to R ⁶ are each independently a hydrogen atom or a monovalent organic group. X is an oxygen atom or a sulfur atom.)

Examples of the monovalent organic group represented by R ¹ to R ⁶ include a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, these groups, -CO-, The group formed by combining at least 1 sort(s) of group selected from the group which consists of -COO-, -OCO-, and -O-, etc. are mentioned. From the viewpoint of availability, as R ¹ to R ⁶ , a contribution selected from the group consisting of the following formulas (1a) to (1m) may also be used. It is preferable that at least ¹ of R1 ^- R6 contains a carboxyl group at the point which provides high voltage retention to a liquid crystal display element. For example, they are the following formulas (1f), (1h), (1i), (1j) - (1m), etc.

[Formula 18]

[Formula 19]

However, ^X7 and ^X8 represent a benzene ring or a C1-C4 alkyl group (specifically, a methyl group, an ethyl group, n-propyl group, an isopropyl group, a butyl group, etc.). X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are a benzene ring or an alkylene group having 1 to 4 carbon atoms (specifically, a methylene group, ethylene group, n-propylene group, isopropylene group, butyl group rengi, etc.).

From the point of the solubility to a solvent and the handleability as a liquid crystal aligning agent, 100-500,000 are preferable and, as for Mn of a polymer (A-4), 100-100,000 are more preferable.

<(B) component>

Since (B) component contained in the liquid crystal aligning agent of this invention has a side chain structure in a molecule|numerator, the liquid crystal aligning film obtained will contain a flexible structure in a molecule|numerator. Thereby, since the solubility to a rework solvent can be improved, the liquid crystal aligning film of this invention expresses high rework property. Moreover, since (B) component has a hydroxyalkyl group at the molecular terminal, since a crosslinking reaction generate|occur|produces in either between (A) component and (B) component, or (B) components, bridge|crosslinking of the liquid crystal aligning film obtained density increases. As a result, since the impurity component derived from a board|substrate becomes easy to capture|acquire by a liquid crystal aligning film, the liquid crystal display element provided with this shows a high voltage retention.

When the component (B) has at least one group represented by any of the formulas (b-1) to (b-5), the above formula (b-1) You may have at least two groups represented by any one of - (b-5).

(B) As a component, the compound etc. which are represented by a following formula (3-1) or a following formula (3-2) are mentioned.

[Formula 20]

However, B ₁ represents a structure selected from the group consisting of the following formulas (b-1) to (b-6), and B ₂ represents a structure selected from the following formulas (b-1) to (b-5) . L ₁ represents the structure of the following formula (1L-1) or (1L-2). L ₂ is a single bond, the following formula (2L-1), or -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -(CH ₂ ) _n - (n is 2 to an integer of 20.) and -NR- (R represents a hydrogen atom or a methyl group.) A divalent group selected from the group consisting of (hereinafter, referred to as coupling group (2a)) is represented. In addition, any CH ₂ of -(CH ₂ ) _n - may be substituted with -O-, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CO- or -NR- . AL ₁ and AL ₂ each independently represent *-Cy ₁ -Z ₁ or *-Cy ₂ . m1 represents the integer of 1-4. m2 represents the integer of 1-2. Cy ₁ represents a structure in which two or more rings are linked directly or through a linking group. Cy ₂ represents a group having a steroid skeleton. Z ₁ represents a linear or branched hydrocarbon group having 3 or more carbon atoms.

[Formula 21]

(However, * ₁ represents the bond couple|bonded with AL1, * ₂ shows the bond bond couple|bonded with B1. n1 shows the integer of 1-2, n2 shows the integer of 1-4. A ₁₁ , A ₁₂ each independently represents a single bond, -O-, or a linking group (2a). When a plurality of A ₁₂ s exist, a plurality of A ₁₂ may be the same or different. A ₂₁ , A ₂₂ each independently represents a linking group (2a) (excluding -NR-.) A _s11 represents a single bond, -O-, -CO-, or a linking group (2a). A _s12 is, A single bond, -CO-, or a linking group (2a) (excluding -NR-) is represented.)

[Formula 22]

(However, *1 represents a bond bonded to B ₂ , and *2 indicates a bond bond to AL ₂ . A _s2 has the same meaning as A _s11 above.)

[Formula 23]

(However, * represents a bond, and R ₂ , R _4a , R _4b , R ₅ , and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

In Z ₁ , linear or branched hydrocarbon groups include at least one methylene group that is not adjacent to each other in the group by an oxygen atom, an oxygen atom-containing group such as CO or CO (=O), or a sulfur atom What was substituted, the thing in which the hydrogen atom in a methylene group was substituted by the alkoxy group, halogen, etc. may be sufficient. From the viewpoint of good rework characteristics, as Z ₁ , a linear or branched alkyl group having 3 to 20 carbon atoms, a linear or branched fluoroalkyl group having 3 to 20 carbon atoms, or a straight chain type having 3 to 20 carbon atoms. Or a branched alkoxy group, a C3-C20 linear or branched alkylester group, etc. are mentioned.

In Cy ₁ , the ring constituting the structure in which two or more rings are connected directly or through a linking group is preferably a benzene ring, a naphthalene ring, or a cyclohexane ring. The number of rings constituting the polycyclic structure should just be 2 or more, and it is preferable that it is 2-4. In addition, a plurality of rings constituting the polycyclic structure may be the same as or different from each other. When the ring is a benzene ring, it is preferable that the bonding position of the ring is para to other groups. When the ring is a naphthalene ring, it is preferable that the bonding position of the ring is the amphi position (2,6-position) with respect to the other group. When the ring is a cyclohexane ring, it is preferable that the bonding position of the ring is 1,4-position with respect to other groups. In addition, any hydrogen atom on the ring is a halogen atom, a hydroxyl group, a carboxy group, 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, or a fluorine atom containing 1 carbon atom. It may be substituted with monovalent organic groups, such as a monovalent organic group of -6 and a C1-C6 alkoxy group.

In Cy ₁ , the linking group is, for example, -O-, -CO-, -COO-, -NR ^b -, -CONR ^b - (R ^b is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or protecting group), at least one methylene group of an alkanediyl group having 1 to 10 carbon atoms or an alkanediyl group having 1 to 10 carbon atoms is -O-, -CO-, -COO-, -NR ^b - or -CONR ^b - and a divalent group substituted with . Examples of the protecting group for R ^b include a carbamate protecting group. Specific examples of the carbamate-based protecting group include a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group.

Among them, Cy ₁ preferably has a structure represented by the following formula (Rn).

[Formula 24]

In the formula (Rn), X each independently represents a single bond or a divalent group exemplified by Cy ₁ . m is 2-6. G each independently represents a benzene ring, a naphthalene ring, or a cyclohexane ring. * indicates a bond.

In Cy ₂ , the group having a steroid skeleton preferably has 17 to 51 carbon atoms, and examples thereof include a cholesteryl group, a cholestanyl group, and a lanostanyl group.

From the viewpoint of having a high voltage retention, B ₁ is preferably the formula (b-1), (b-3), (b-5), or (b-6).

The component (B) in this invention is a compound whose molecular weight is 2000 or less from the reason of improving rework property. Especially, since molecular weight improves rework property, it is preferable that it is 1800 or less, and it is more preferable that it is 1500 or less. Since the molecular weight of the compound of (B) component improves voltage retention, Preferably it is 100 or more, More preferably, it is 150 or more.

(B) As a component, it is preferable that it is a compound represented by said Formula (3-1) at the point which has a high voltage retention.

(B) As a component, it has a high voltage retention, and from the point which synthesis|combination is easy, following formula (B1-1-1) - (B1-1-43), (B1-2-1) - (B1-2) -22), (B2-1-1) to (B2-1-18), (B2-2-1) to (B2-2-34), (B2-3-1) to (B2-3-14) ) is preferred. From the viewpoint of high voltage retention, more preferably compounds of (B1-1-1) to (B1-1-43) and (B1-2-1) to (B1-2-22), and the synthesis is In terms of ease, (B1-1-1), (B1-1-3), (B1-1-4), (B1-1-6), (B1-1-8), (B1-1- 9), (B1-1-11), (B1-1-12), (B1-1-14), (B1-1-15), (B1-1-17), (B1-1-18) , (B1-1-20), (B1-1-21), (B1-1-23), (B1-1-24), or (B1-1-26) is more preferable.

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

0.1-40 mass parts is preferable per 100 mass parts of (A) component, as for content of the said (B) component, 0.5-35 mass parts is more preferable, 0.5-30 mass parts is especially preferable.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains the said (A) component and (B) component. In addition to the polymers (A-1) - (A-4) which are the said (A) component, in the liquid crystal aligning agent of this invention, you may contain the other polymer. Examples of the other polymer include polyester, polyamide, polyurea, polyacetal, polystyrene or derivatives thereof, 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, and takes the form of a coating liquid at the point which forms 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 (A) component and (B) component, and an organic solvent. In that case, content (concentration) of the polymer containing the said (A) component 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 mass % or more is preferable, From the point of storage stability of a solution, 10 mass % or less is preferable, Especially preferably, it is 2-8 mass %.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. To give specific examples, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyro Lactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, N,N-dimethyllactamide, 3-methoxy-N,N- Dimethyl propanamide and 3-butoxy-N,N-dimethyl propanamide (collectively, it is also called a good solvent) etc. are mentioned. From the viewpoint of good printability, among others, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N, Preference is given to N-dimethylpropanamide, N,N-dimethyllactamide, or γ-butyrolactone. From a point with favorable printability, 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, as for a good solvent, 20-90 mass % is more preferable, and its 30-80 mass % is especially preferable.

Moreover, the organic solvent contained in a liquid crystal aligning agent uses the solvent (it is also called a poor solvent.) which improves the applicability|paintability at the time of apply|coating a liquid crystal aligning agent, and the surface smoothness of a coating film in addition to the said solvent (it is also called a poor solvent.) it is preferable Although the specific example of a poor solvent is given below, it is not limited to these examples.

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

Among them, the poor solvent has good printability. , 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferable.

1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, as for a poor solvent, 10-80 mass % is more preferable, and its 20-70 mass % is especially 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.

As a combination of the solvent of a good solvent and a poor solvent, since printability is favorable, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, and gamma -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, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol mono Butyl ether and diisobutyl ketone, 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 and diisobutylcarbinol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and combinations of dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, and the like.

The liquid crystal aligning agent of this invention may further contain components other than that in addition to (A) component, (B) component, and an organic solvent. As an additional component, the adhesion aid for improving the adhesiveness of a liquid crystal aligning film and a board|substrate, or the adhesiveness of a liquid crystal aligning film and a sealing material, a compound for increasing the intensity|strength of a liquid crystal aligning film (hereinafter also referred to as a crosslinkable compound.), dielectric constant and electrical resistance of a liquid crystal aligning film dielectrics or conductive materials for adjusting the

As the crosslinkable compound, 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 Compounds having an oxiranyl group such as ) to (r-3), the following formulas (bi-1) to (bi-3), and compounds having a protective isocyanate group, such as the compounds described in JP-A-2016-200798, the following formulas You may use the compound chosen from the hydroxyalkylamide compound represented by (hd-1)-(hd-8), or the compound represented by following formula (e-1)-(e-8).

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

The said compound is an example of a crosslinkable compound, and is not limited to these. For example, a compound having an oxetanyl group described in [0170] to [0175] of WO2011/132751, a compound containing an oxazoline structure described in [0115] of Japanese Unexamined Patent Publication No. 2007-286597, WO2012/091088 The compound having a Meldrum acid structure described above, the compound having a cyclocarbonate group described in WO2011/155577, and components other than those disclosed in WO2015/060357 to [0116] can be mentioned. A crosslinking|crosslinked compound may use together 2 or more types.

Content of the crosslinking|crosslinked compound in the liquid crystal aligning agent of this invention expresses the effect made into the objective, and 0.5-20 mass with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent at the point which improves the liquid-crystal orientation addition is preferable, and 1-15 mass parts is more preferable.

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, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate and silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. From the point of improving liquid-crystal orientation, 0.1-30 mass parts is preferable with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent, and, as for the usage-amount of these silane coupling agents, 0.1-20 mass parts is more preferable.

<Liquid crystal alignment film, liquid crystal display element>

The liquid crystal display element which concerns on this invention is equipped with the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element is not particularly limited, and for example, TN type, STN type, vertical alignment type (VA-MVA type, VA-PVA type, etc. are included.), in-plane switching type (IPS type), FFS It can be applied to various operation modes such as type and optical compensation bend type (OCB type).

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

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

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

(1-1A)

For example, when manufacturing a TN type, STN type or VA type liquid crystal display element, first, two sheets of a substrate on which a patterned transparent conductive film is formed are set as a pair, and on each transparent conductive film formation surface, A liquid crystal aligning agent becomes like this. Preferably it is apply|coated by the offset printing method, the spin coat method, the roll coater method, or the inkjet printing method. As a board|substrate, For example, glass, such as float glass and soda glass; A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate or poly(alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (trademark of PPG Corporation) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. can be used. there is.

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

(1-1B)

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

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

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

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

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

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

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

Moreover, when using the ultraviolet-ray containing the light of a wavelength of 150-800 nm, although the light irradiation film obtained in the said process can be used as a liquid crystal aligning film as it is, baking the light irradiation film, washing|cleaning with water or an organic solvent, or You may implement these combinations. The firing temperature at this time is preferably 80 to 300°C, more preferably 80 to 250°C. Firing time becomes like this. Preferably it is 5 to 200 minutes, More preferably, it is 10 to 100 minutes. In addition, you may implement the frequency|count of baking by the frequency|count of 2 or more times. The photo-alignment process here corresponds to the process of light irradiation in the state which is not in contact with a liquid crystal layer.

Although a liquid crystal aligning film is formed on a board|substrate with a liquid crystal aligning agent as mentioned above, when a defect has generate|occur|produced in a liquid crystal aligning film, the liquid crystal aligning film formed with the liquid crystal aligning agent of this invention removes this from a board|substrate, and rework process which recycles a board|substrate excellent in

That is, although a rework process is performed by immersing the board|substrate which has a liquid crystal aligning film in a solvent at 20-100 degreeC preferably, and removing it with pure water after that, the liquid crystal aligning film formed with the liquid crystal aligning agent of this invention is a rework process has the following advantages. That is, since the liquid crystal aligning film formed of the liquid crystal aligning agent of the present invention has high solubility in the rework agent, the type of solvent that can be used increases, or the temperature or immersion time to be immersed in the solvent can be reduced. Therefore, manufacturing cost can be reduced.

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

(1-3A)

A liquid crystal cell is manufactured by preparing two board|substrates with a liquid crystal aligning film as mentioned above, and arrange|positioning a liquid crystal between the board|substrates of 2 sheets opposingly arranged. Specifically, the following two methods are mentioned.

First, the 1st method opposes arrange|positions two board|substrates through a gap|interval (cell gap) so that each liquid crystal aligning film may oppose, and bonds the periphery of two board|substrates with a sealing agent, The board|substrate surface and the sealing compound partitioned After injecting and filling the liquid crystal in the cell gap, the liquid crystal cell is manufactured by sealing the injection hole.

The second method is a method called an ODF (One Drop Fill) method. After apply|coating ultraviolet-ray-curable sealing compound to a predetermined place on one board|substrate among two board|substrates of 2 board|substrates in which the liquid crystal aligning film was formed, for example, and further dripping a liquid crystal to predetermined several points on the liquid crystal aligning film surface, a liquid crystal aligning film While bonding the other board|substrate so that this may oppose, a liquid crystal is spread out on the whole surface of a board|substrate, then, a liquid crystal cell is manufactured by irradiating an ultraviolet light to the whole surface of a board|substrate, and hardening a sealing compound. It is preferable to remove the flow orientation at the time of liquid-crystal filling by annealing to room temperature, after heating to the temperature which the liquid crystal used further takes an isotropic phase with respect to the produced liquid crystal cell also in the case by any method.

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

Examples of the liquid crystal include a nematic liquid crystal, a smectic liquid crystal, and the like, and among them, a nematic liquid crystal is preferable, for example, a thief base type, a azoxy type, a biphenyl type, a phenylcyclohexane type, an ester type, a tere type. A phenyl type, a biphenylcyclohexane type, a pyrimidine type, a dioxane type, a bicyclooctane type, a cuban type, etc. are mentioned. Moreover, to these liquid crystals, for example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate; Chiral like "C-15" and "CB-15" (merck company brand name) My ; A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added.

In addition, the liquid crystal may further include an anisotropic dye. For example, a black dye or a color dye can be used. The use ratio of the anisotropic dye to the liquid crystal is appropriately selected within a range that does not impair the target physical properties, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal compound, but may be appropriately changed as necessary.

(1-3B)

In the case of a PSA type liquid crystal display element, it is the same as that of said (1-3A) except the point injecting|pouring or dripping, for example, a photopolymerizable compound, such as following formula (w-1) - (w-5), with a liquid crystal. to build a liquid crystal cell.

[Formula 49]

The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage to be applied here can be, for example, 5 to 50 V of direct current or alternating current. Moreover, although the ultraviolet-ray or visible light containing the light of a wavelength of 150-800 nm can be used as light to irradiate, The ultraviolet-ray containing the light of a wavelength of 300-400 nm is preferable, for example. As an irradiation amount of light, Preferably it is 100-30,000 mJ/cm<2>, More preferably, it is 100-20,000 mJ/cm<2>.

(1-3C)

When a coating film is formed on a board|substrate using the liquid crystal aligning agent containing the compound which has a photopolymerizable group, it carries out similarly to said (1-3A), and constructs a liquid crystal cell, After that, the electrical conduction which a pair of board|substrate has You may employ|adopt the method of manufacturing a liquid crystal display element by passing through the process of irradiating light to a liquid crystal cell in the state which applied the voltage between films|membrane. As an additive which has a photopolymerizable group, the structure illustrated by said Formula (w-1) - (w-5) is mentioned. 1-30 mass % is preferable with respect to solid content contained in a liquid crystal aligning agent, as for the compounding quantity, 1-20 mass % is more preferable, 1-15 mass % is especially preferable.

Light irradiation to a liquid crystal cell may be performed in the state which drove the liquid crystal by voltage application, or you may perform it in the state which applied the voltage low enough to not drive a liquid crystal. The voltage to be applied can be, for example, a direct current or alternating current of 0.1 to 30 V. Regarding the conditions of the light to be irradiated, the explanation of the above (1-3B) is applicable. The light irradiation treatment here corresponds to the light irradiation treatment in a state in contact with the liquid crystal layer.

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

Example

The present invention will be more specifically described below 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. In addition, compound (c-1) was synthesize|combined according to the method described in the synthesis example 3 of Unexamined-Japanese-Patent No. 2008-052260.

(diamine)

DA-1 to DA-27: compounds represented by the following formulas (DA-1) to (DA-27), respectively

(tetracarboxylic dianhydride)

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

(tetracarboxylic acid diester dihalide)

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

(monocarboxylic acid chloride)

E-1: acryloyl chloride

(Component B)

b-1 to b-8: compounds represented by the following formulas (b-1) to (b-8), respectively

(Other additives)

c-1 to c-4: compounds represented by the following formulas (c-1) to (c-4), respectively

F-1: N-α-(9-fluorenylmethyloxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine (compound of formula (F-1))

s-1: 3-glycidoxypropyltriethoxysilane (compound of formula (s-1))

s-2: 3-glycidoxypropylmethyldiethoxysilane (compound of formula (s-2))

M-1: 3-picolylamine

(organic solvent)

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

BCS: butyl cellosolve, DIBK: diisobutyl ketone,

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

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

DPM: dipropylene glycol monomethyl ether,

PB: propylene glycol monobutyl ether,

PGDAC: propylene glycol diacetate,

DEDE: diethylene glycol diethyl ether,

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

EEP: 3-Ethoxypropionate Ethyl

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

[Formula 55]

[Formula 56]

(Fmoc represents a 9-fluorenylmethyloxycarbonyl group. In formula (c-4), R represents either a methylol group or a -CH ₂ -OC ₈ H ₁₇ group.)

[Viscosity]

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

[Molecular Weight]

It measured with the normal temperature GPC (gel permeation chromatography) apparatus, and computed Mn and Mw as polyethyleneglycol and polyethyleneoxide conversion values.

GPC apparatus: manufactured by Shodex (GPC-101), column: manufactured by Shodex (GPC KD-803, GPC KD-805 in series), column temperature: 50°C, eluent: N,N-dimethylformamide (as an additive, Lithium bromide monohydrate (LiBr H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystals (o-phosphate) are 30 mmol/L, tetrahydrofuran (THF) is 10 mL/L), flow rate: 1.0 ml/min

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

<Imidation rate>

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), 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 ratio is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and the integrated peak value of this proton and the proton peak derived from the NH group of the amic acid appearing around 9.5 ppm to 10.0 ppm. It calculated|required by the following formula using a 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 value of the reference proton, and α is the polyamic acid (imidization rate is 0%) of the amic acid in the case of It is the ratio of the number of reference protons to one NH group proton.

[Synthesis of (B) component]

<Synthesis Example (b-1)>

Compound (b-1) was synthesized according to the route shown below.

[Formula 57]

In an eggplant-type flask, compound (b-1-1) (5.00 g, 16.5 mmol), toluene (19.64 g), thionyl chloride (5.90 g, 49.5 mmol) and N,N-dimethylformamide (DMF) was added dropwise with a Pasteur pipette, stirred at room temperature, heated to 70° C., and reacted under a nitrogen atmosphere for 6 hours. Compound (b-1-2) was obtained by concentrating the reaction solution under reduced pressure.

Then, diethanolamine (3.47 g, 33.0 mmol), triethylamine (2.51 g, 24.8 mmol) and 30 ml of dichloromethane were added to another eggplant-type flask, and it stirred on ice-cooling conditions. Next, a solution obtained by dissolving the compound (b-1-1) obtained above in 8 ml of dichloromethane was added, followed by stirring overnight. After completion of the reaction, saturated brine was added to the reaction solution, the organic layer was taken out, and the organic layer was further washed with saturated brine. The obtained organic layer was dried over sodium sulfate, and the obtained solution was concentrated under reduced pressure. The precipitated solid was washed with heptane to obtain 5.29 g of compound (b-1).

<Synthesis example (b-2)>

Compound (b-2) was synthesized according to the route shown below.

[Formula 58]

To an eggplant-type flask, 5-aminoisophthalic acid (11.97 g, 66.1 mmol) and N,N-dimethylacetamide (DMAc) (111.97 g) were added and stirred. Next, the solution in which the compound (b-1-2) (21.21 g, 66.1 mmol) was dissolved in toluene (28.00 g) was dripped at this eggplant-type flask, and it heated up to 60 degreeC. After making the reaction overnight in a nitrogen atmosphere, the reaction solution was poured into a mixed solution of ethanol (80 ml) and water (400 ml) to precipitate a solid. After collect|recovering the obtained solid, it dried and obtained 31.07g of compound (b-2-1).

Then, in an eggplant-type flask, compound (b-2-1) (5.00 g, 10.7 mmol), diethanolamine (2.37 g, 22.5 mmol), THF (27.27 g), and 4-(4,6- Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) (6.23 g, 22.5 mmol) was added, and it was made to react at room temperature for 5 hours. Saturated brine was added to the reaction solution, and the organic layer was taken out. The organic layer was dried over sodium sulfate, and acetonitrile was added to the obtained solution to precipitate a solid. After collect|recovering the obtained solid, it dried and obtained 3.57g of compound (b-2).

<Synthesis Example (b-3)>

Compound (b-3) was obtained according to the same procedure as in Synthesis Example (b-2) except that ethanolamine was used instead of diethanolamine.

[Formula 59]

<Synthesis example (b-4)>

Compound (b-4) was synthesized according to the following route. In addition, compound (b-4-4) was synthesize|combined in the same procedure as Example 3 of Unexamined-Japanese-Patent No. 2010-285367.

[Formula 60]

[Formula 61]

To an eggplant-type flask, compound (b-4-1) (5.00 g, 21.4 mmol) and THF (70 g) were added, and compound (b-4-1) was dissolved. In this regard, next, diethanolamine (4.72 g, 44.9 mmol) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride ( DMT-MM) (6.23 g, 22.5 mmol) was added and stirred at room temperature. Saturated brine was added to the obtained solution, and the organic layer was taken out. The organic layer was dried over sodium sulfate, and the resulting solution was concentrated under reduced pressure to obtain 5.90 g of compound (b-4-2).

Next, the compound (b-4-2) (5.00 g, 12.3 mmol) and 160 ml of 4N hydrochloric acid/ethyl acetate were added to an eggplant-type flask, and it stirred at room temperature for 4 hours. Next, the solvent was distilled off under reduced pressure from the stirred liquid to obtain 3.50 g of compound (b-4-3).

Then, in an eggplant-type flask, compound (b-4-3) (3.00 g, 9.76 mmol), compound (b-4-4) (4.77 g, 9.76 mmol), 4-(4,6-dimethoxy -1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) (2.77 g, 10.0 mmol) and THF (50 g) were added and reacted at room temperature for 5 hours . Saturated brine was added to the reaction solution, and the organic layer was taken out. The organic layer was dried over sodium sulfate, and the resulting solution was concentrated under reduced pressure to obtain 5.00 g of compound (b-4).

<Synthesis Example (b-5)>

Compound (b-5) was obtained according to the same procedure as in Synthesis Example (b-4) except that diethanolamine was used instead of compound (b-4-3).

[Formula 62]

<Synthesis example (b-6)>

Except for using trishydroxymethylaminomethane instead of compound (b-4-3) and trans, trans-4'-amylbicyclohexyl-4-carboxylic acid instead of compound (b-4-4) , according to the same procedure as in Synthesis Example (b-4), to obtain a compound (b-6).

[Formula 63]

<Synthesis Example (b-7)>

Compound (b-7) was synthesized according to the following route. In addition, compound (b-7-1) was synthesized in the same procedure as in Synthesis Example 4 of WO2018/159733. In addition, compound (b-7-2) was synthesize|combined in the same procedure as synthesis example (b-2) except having used compound (b-7-1) instead of compound (b-1-2). Subsequently, the compound (b-7) is a synthesis example except that (b-7-2) is used instead of the compound (b-2-1) and trishydroxymethylaminomethane is used instead of the diethanolamine. It was synthesized in the same order as (b-2).

[Formula 64]

<Synthesis Example (b-8)>

Compound (b-8) was obtained according to the same procedure as in Synthesis Example (b-4) except that trishydroxymethylaminomethane was used instead of compound (b-4-3).

[Formula 65]

<Synthesis example (c-3)>

Compound (c-3) was obtained according to the same procedure as in Synthesis Example (b-4) except that monoethanolamine was used instead of compound (b-4-3).

<Synthesis example (c-4)>

Compound (c-4) was synthesized in the same procedure as in Example 4 of Japanese Patent Application Laid-Open No. 2011-70161.

[Synthesis of Polymer (A)]

<Synthesis Example 1>

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

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

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

<Synthesis Example 2>

CA-2 (1.20 g, 4.80 mmol), DA-8 (1.46 g, 9.59 mmol), DA-9 (1.74 g, 7.18 mmol) in a 4-neck flask equipped with a stirrer and nitrogen inlet tube , DA-7 (2.74 g, 7.20 mmol), and NMP (28.58 g) were added and dissolved, and it was made to react at 60 degreeC for 2 hours. After that, CA-5 (1.05 g, 4.81 mmol) and NMP (4.19 g) were added and reacted at room temperature for 4 hours, and further CA-3 (2.78 g, 14.18 mmol) and NMP (11.1 g) was added and reacted at room temperature for 4 hours to obtain a polyamic acid solution.

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

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

<Synthesis Example 3>

In a 4-neck flask with a stirring device and a nitrogen introduction tube, 5.86 g (24.0 mmol) of DA-2, 5.46 g (16.0 mmol) of DA-10, and 1.73 g (16.0 mmol) of DA-4 , 7.69 g (24.0 mmol) of DA-1, and 194 g of NMP were added, and stirred to dissolve while transferring nitrogen. 17.1 g (76.4 mmol) of CA-1 is added, stirring this diamine solution, NMP is further added so that solid content concentration may be 12 mass %, it stirs at 40 degreeC for 24 hours, and polyamic-acid solution (viscosity: 549m) Pa·s and Mn of the polyamic acid were 12400 and Mw was 33000).

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

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

<Synthesis Example 4>

5.73 g (20.0 mmol) of DA-5 and 115 g of NMP were added to the 5 L 4-necked flask with a stirring apparatus and a nitrogen introduction tube, and it stirred, sending nitrogen, and it was made to melt|dissolve. While stirring this diamine solution under water cooling, CA-3 was added 2.94g (15.0 mmol), 19.1g of NMPs were added, and it stirred at 23 degreeC in nitrogen atmosphere for 1 hour. Then, 11.9 g (40.0 mmol) of DA-3 and 6.01 g (40.0 mmol) of DA-11 were weighed and put, 72 g of NMP was added, and it stirred while conveying nitrogen to melt|dissolve. 15.9 g (81.0 mmol) of CA-3 is added, stirring this diamine solution under water cooling, so that NMP may be added so that solid content concentration may be 15 mass %, so that s-1 may be 1 mass % with respect to polyamic-acid solid content It added and stirred at 23 degreeC in nitrogen atmosphere for 6 hours, and obtained the solution of polyamic acid (PAA-I-4, Mn:12000, Mw:30000).

<Synthesis Example 5>

A 500 mL four-necked flask with a stirring device was made into a nitrogen atmosphere, DA-4 is 2.80 g (25.9 mmol), DA-2 is 1.58 g (6.47 mmol), NMP is 111 g, and pyridine as a base 6.18 g (78.1 mmol) was added and stirred to dissolve. Next, 9.89 g (30.4 mmol) of CE-1 was added, stirring this diamine solution, and it was made to react at 15 degreeC overnight. 0.38 g (4.21 mmol) of E-1 was added after stirring overnight, and it was made to react at 15 degreeC for 4 hours. The solution of the obtained polyamic acid ester is thrown into 1230 g of water, stirring, and the precipitated white precipitate is collected by filtration, and the white polya is then washed 5 times with 1230 g of isopropyl alcohol (IPA) and dried. 10.2 g (yield: 83.0%) of mixed acid ester powder (Mn:20786, Mw:40973) was obtained.

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

<Synthesis Example 6>

In a 4-neck flask equipped with a stirring device and a nitrogen introduction tube, 0.46 g (3.00 mmol) of DA-8, 3.00 g (15.0 mmol) of DA-13, and 2.56 g (12.0 mmol) of DA-14 , 11.0 g of NMP, and 8.10 g of GBL were added, and dissolved by stirring while transferring nitrogen. 4.76 g (24.0 mmol) of CA-6 was added, stirring this diamine solution, 10.9 g of GBL was added, and it stirred at room temperature for 2 hours. Next, after adding and stirring 10.8g of GBL, 1.31g (6.01 mmol) of CA-5 was added, 14.3g of GBL was added, and it stirred at room temperature for 24 hours. The viscosity of the solution of the obtained polyamic acid (Mn:14200, Mw:30110) was 2,041 mPa*s.

Then, s-2 is added so that it may become 1 mass % with respect to polyamic-acid solid content, the mixing ratio of NMP and GBL becomes NMP:GBL=20:80 by mass ratio, NMP so that solid content concentration may be set to 15 mass % and GBL were added to obtain a solution of polyamic acid (PAA-I-6).

<Synthesis Examples 7-11, 14-20>

Polyimides (PI-VV-8), (PI-V-) shown in Table 1 below by using the diamine, tetracarboxylic acid derivative, and organic solvent shown in Table 1 below and carrying out in the same procedure as in the above synthesis example, respectively. 9), (PI-I-11), (PI-V-19) and (PI-V-20), polyamic acid (PAA-I-7), (PAA-I-10), (PAA-V- 14) to (PAA-V-16), (PAA-I-17) and (PAA-I-18) solutions were obtained.

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

[Table 1]

[Synthesis of other polymers]

<Synthesis Example 12>

According to the method described in Japanese Patent Application Laid-Open No. 2018-54761, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS) was used to obtain a reactive polyorganosiloxane polymer. Next, according to the method described in Japanese Patent Application Laid-Open No. 2018-54761, a polymer of polyorganosiloxane represented by the following formula (P-S1) was obtained. In addition, the numerical values (70, 20, 10) in Formula (P-S1) show the usage ratio (molar part) of each compound with respect to the total of each silane compound used for the synthesis|combination.

[Formula 66]

<Synthesis Example 13>

According to the method described in Japanese Patent Application Laid-Open No. 2018-54761, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS) was used to obtain a reactive polyorganosiloxane polymer. Next, according to the method described in Japanese Patent Application Laid-Open No. 2018-54761, a polymer of polyorganosiloxane represented by the following formula (P-S2) was obtained. In addition, the numerical values (70, 30) in Formula (P-S2) show the usage ratio (molar part) of each compound with respect to the total of each silane compound used for the synthesis|combination.

[Formula 67]

<Example 1>

[Preparation of liquid crystal aligning agent]

Using the solution of the polyimide (PI-V-1) obtained in Synthesis Example 1 and the solution of the polyimide (PI-V-2) obtained in Synthesis Example 2, diluted with NMP and BCS, and further compound (b -1) and (b-2) were added so that 1 part by mass and 5 parts by mass, respectively, with respect to 100 parts by mass of all polymers, and stirred at room temperature. Next, by filtering the obtained solution with a filter having a pore size of 0.5 µm, the component ratio (mass ratio in terms of solid content) of the polymer is (PI-V-1): (PI-V-2) = 30: 70, solvent composition ratio (mass ratio) Liquid crystal aligning agent (V1) from which 1 mass part and 5 mass parts of compounding ratios of a compound (b-2) of a NMP:BCS=60:40, polymer solid content concentration of 4.5 %, and a compound (b-1) become 5 mass parts was obtained (see Table 2-1 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 2-50, Comparative Examples 1-6>

Liquid crystal aligning agents (V2) - (V11), (I12-P) - (I29-P) by carrying out similarly to Example 1 except having used the polymer and additive of following Table 2-1 - Table 2-4 , (I30-U) to (I37-U), (V38) to (V43), (I44-P) to (I47-P), (V48-P) to (V49-P), (I50-U) , (R-V1) to (R-V2), (R-I3-P), (R-I4-U), (R-V5) to (R-V6) were obtained. In Tables 2-1 to 2-4, the numerical value in parentheses is the compounding ratio (mass part) of each polymer component or additive with respect to a total of 100 mass parts of the polymer component used for preparation of a liquid crystal aligning agent, respectively about a polymer and an additive. indicates About an organic solvent, the compounding ratio (mass part) of each organic solvent with respect to 100 mass parts of total amounts of the organic solvent used for preparation of a liquid crystal aligning agent is shown.

[Table 2-1]

[Table 2-2]

[Table 2-3]

[Table 2-4]

[Evaluation of reworkability of liquid crystal aligning agent]

The liquid crystal aligning agent obtained above 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 NMP heated to 35 degreeC or 50 degreeC for 5 minutes, it washed with running water for 20 second with ultrapure water. Those that were immersed in NMP at 35°C for 5 minutes and had no coating film left were considered “good”, those that had been immersed in NMP at 35°C for 5 minutes and had no coating film left were considered “good”, and those that had been immersed in NMP at 50°C for 5 minutes were considered “good”. was set as "defective".

[Manufacturing and evaluation of liquid crystal display elements]

1-1. Manufacturing of vertical alignment type liquid crystal display device

Two glass substrates with an ITO electrode (length: 40 mm, width: 30 mm, thickness: 1.1 mm) were prepared and washed with pure water and isopropyl alcohol. Next, liquid crystal aligning agents (V1)-(V11), (V38)-(V43) and (R-V1)-(R-V2), (R- V5) to (R-V6) were spin-coated, respectively, and heat-treated on a hot plate at 70° C. for 90 seconds and at 230° C. for 30 minutes in a heat circulation type clean oven to form an ITO substrate with a film thickness of 100 nm. got

Next, the periphery was apply|coated with the sealing compound (XN-1500T by Mitsui Chemicals). Next, after turning the surface of the side by which the liquid crystal aligning film of the other board|substrate was formed inside and bonding together with the board|substrate previously, the sealing material was hardened and the empty cell was manufactured. In the empty cell using liquid crystal aligning agent (V1) - (V2), (V5) - (V11), (V38) - (V43), and (R-V1) liquid crystal MLC-3023 (merck company make brand name) to the reduced pressure injection method By injecting, the liquid crystal cell was manufactured.

Then, in the state in which a DC voltage of 15V was applied to the obtained liquid crystal cell and all the pixel areas were driven, the ultraviolet-ray which passed the band-pass filter of wavelength 365nm using the ultraviolet irradiation apparatus which used the high-pressure mercury-vapor lamp as a light source. 10 J/cm<2> was irradiated, and the liquid crystal display element for evaluation was obtained. For the measurement of the amount of ultraviolet irradiation, a UV-35 light receiver was connected to UV-M03A manufactured by ORC, and used.

Liquid crystal MLC-6608 (merck company make brand name) is inject|poured into the empty cell using liquid crystal aligning agent (V3) - (V4) and (R-V2), (R-V5) - (R-V6) by a reduced pressure injection method, The liquid crystal display element for evaluation was obtained. As a result of observing the obtained liquid crystal display element with a polarizing microscope, it was confirmed that all liquid crystals are orientating uniformly.

1-2. Evaluation of liquid crystal display elements

[Voltage retention rate evaluation]

After leaving the liquid crystal display element manufactured in said 1-1 in 80 degreeC oven under LED lamp irradiation for 200 hours, it left still in room temperature, and was naturally cooled to room temperature. Then, in 60 degreeC, after applying the voltage of 1V with the application time of 60 microseconds, and the span of 1667 milliseconds, the voltage retention rate 1,000 milliseconds after application cancellation|release was measured. As a measuring apparatus, the Toyo Technica make was used. Table 3 shows the evaluation results.

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

First, a glass substrate with electrodes (length: 30 mm, width: 50 mm, thickness: 0.7 mm) was prepared. On the board|substrate, the ITO electrode provided with the solid-shaped pattern which comprises a counter electrode as a 1st layer is formed. On the counter electrode of the first layer, as the second layer, a SiN (silicon nitride) film formed by the CVD method is formed. The 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 a comb-tooth-like shape comprised by arranging a plurality of "<"-shaped electrode elements in which the central part was bent at an inner angle of 160 degrees. The width in the width direction of each electrode element is 3 µm, and the interval between the electrode elements is 6 µm. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has a 1st area|region above a bending part, and a 2nd area|region below.

Next, after filtering liquid crystal aligning agents (I12-P) - (I29-P), (I44-P) - (I47-P) and (R-I3-P) with a filter with a pore diameter of 1.0 micrometer, the said electrode The formed substrate and a glass substrate having a columnar spacer having a height of 4 µm on which an ITO film was formed on the back surface were applied by spin coating.

About the coating film obtained from liquid crystal aligning agent (I12-P) - (I29-P) and (R-I3-P), after drying on an 80 degreeC hotplate for 5 minutes, it is 230 degreeC hot-air circulation type oven for 20 minutes It baked and obtained the polyimide film with a film thickness of 100 nm. Thereafter, 500 mJ/cm 2 of ultraviolet rays having a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 were irradiated to the coating film surface through a polarizing plate, followed by baking in a hot air circulation type oven at 230° C. for 30 minutes, and a film thickness of 100 The board|substrate with a nm liquid crystal aligning film was obtained. In addition, the liquid crystal aligning film formed on the substrate on which the electrode is formed is oriented so that the direction dividing the inner angle of the pixel bent portion into equal parts and the alignment direction of the liquid crystal are orthogonal to each other, and the liquid crystal aligning film formed on the substrate having a columnar spacer is a liquid crystal cell When preparing , the alignment treatment was performed so that the alignment direction of the liquid crystal on the substrate on which the electrode was formed and the alignment direction of the liquid crystal on the substrate having the columnar spacer coincide.

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

Next, the sealing compound was printed on one of the glass substrates with a liquid crystal aligning film of the said 1 set, and the other board|substrate was bonded together so that a liquid crystal aligning film surface might face, the sealing compound was hardened, and the empty cell was manufactured. Liquid crystal MLC-3019 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the FFS drive liquid crystal display element was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand overnight, when this liquid crystal display element was observed with the polarizing microscope, it was confirmed that all liquid crystals are orientating uniformly.

2-2. Evaluation of liquid crystal display elements

[Voltage retention rate evaluation]

Prepare two glass substrates (length: 40 mm, width: 30 mm, thickness: 1.1 mm) with an ITO electrode, and manufacture a liquid crystal aligning film with a film thickness of 100 nm on the ITO surface in the same order as said 2-1 did. To the liquid crystal aligning film surface of one board|substrate, the 4 micrometers diameter bead spacer (The Nikki Catalyst Chemical Company make, Jinsagu, SW-D1) was apply|coated.

Next, the periphery was apply|coated with the sealing compound (The Mitsui Chemicals make, XN-1500T). Next, after turning the surface of the side by which the liquid crystal aligning film of the other board|substrate was formed inside and bonding together with the board|substrate of the first, the sealing material was hardened and the empty cell was manufactured. Liquid crystal MLC-3019 (trade name manufactured by Merck Corporation) was injected into this empty cell by the reduced pressure injection method, and the liquid crystal display element was manufactured. Next, after leaving this liquid crystal display element still in 80 degreeC oven under LED lamp irradiation for 200 hours, it left still in room temperature, and was naturally cooled to room temperature. Thereafter, evaluation was performed in the same procedure as in 1-2 above. Table 3 shows the evaluation results.

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

First, liquid crystal aligning agents (I30-U) - (I37-U), (I50-U), (R- I4-U) was applied using an inkjet coating device (HIS-200, manufactured by Hitachi Plant Technology). Application was performed under the conditions of an application area of 70 × 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, an application rate of 40 mm/sec, and storage for 60 seconds from application to drying. Next, after drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the polyimide film with a film thickness of 100 nm was obtained. Rubbing this polyimide film with a rayon cloth (roller diameter: 120 mm, number of roller rotations: 500 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm, rubbing direction: 10° inclined with respect to the 3rd layer IZO comb electrode direction), washing was performed by ultrasonic irradiation for 1 minute in pure water to remove water droplets. Then, it dried at 80 degreeC for 15 minutes, and obtained the board|substrate with a liquid crystal aligning film. A set of the substrates on which these two liquid crystal aligning films are formed, the sealing agent is printed in the form that the liquid crystal injection hole is left on the substrate, and the other one substrate is made such that the liquid crystal aligning film faces are opposite to each other, and the rubbing direction is antiparallel was pasted. Then, the sealing compound was hardened and the cell gap manufactured the 4 micrometers empty cell. Liquid crystal MLC-7026-100 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal display element of the FFS system was obtained. Then, after heating the obtained liquid crystal display element at 120 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for evaluation of afterimage evaluation. As a result of observing the obtained liquid crystal display element with a polarizing microscope, it was confirmed that all liquid crystals are orientating uniformly.

3-2. Evaluation of liquid crystal display elements

[Voltage retention rate evaluation]

The same procedure as said 2-2 evaluated using the liquid crystal aligning film similar to said 3-1 except having made liquid crystal MLC-7026-100. Table 3 shows the evaluation results.

4-1. Manufacture of VA-type liquid crystal display device by photo-alignment

Prepare two glass substrates same as said 1-1, spin-coat liquid crystal aligning agent (V48-P) or (V49-P) on each board|substrate, and on a hotplate at 80 degreeC for 90 second, heat circulation type It heat-processed for 40 minutes at 200 degreeC in clean oven, and obtained the ITO board|substrate with a liquid crystal aligning film with a film thickness of 100 nm.

Next, the substrate is exposed to linearly polarized UV light at an incident angle of 40° with respect to the normal to the surface of the substrate. The applied exposure amount was 20 mJ/cm 2 . After exposure, a cell having two substrates was assembled so that the exposed alignment layer faced the inside of the cell, and the substrate was adjusted so that the alignment directions were parallel to each other. Next, liquid crystal MLC-7067 (manufactured by Merck Corporation) was injected. Then, after annealing at about 90 degreeC for 10 minutes and cooling to room temperature, it used for evaluation of afterimage evaluation. As a result of observing the obtained liquid crystal display element with a polarizing microscope, it was confirmed that all liquid crystals are orientating uniformly.

4-2. Evaluation of liquid crystal display elements

[Voltage retention rate evaluation]

After leaving the liquid crystal display element manufactured in said 4-1 in 80 degreeC oven under LED lamp irradiation for 200 hours, it left still at room temperature, and was naturally cooled to room temperature. Evaluation was performed in the same procedure as in 1-2 above. Table 3 shows the evaluation results. In addition, in Table 3, Examples 1-50 are evaluation results of the liquid crystal aligning agent of the Example of this invention, and Examples 51-56 are evaluation results of the liquid crystal aligning agent of a comparative example.

[Table 3]

Industrial Applicability

The liquid crystal aligning agent of this invention is useful for formation of the liquid crystal aligning film in various liquid crystal display elements, such as a vertical alignment type and an FFS drive system. The liquid crystal display element provided with the liquid crystal aligning agent of this invention can be effectively applied to various devices, For example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, PDA, a digital camera, It can be used for various display apparatuses, such as a mobile phone, a smartphone, various monitors, a liquid crystal television, and an information display. Moreover, it is not limited to the above, The liquid crystal aligning film for retardation films, the liquid crystal aligning film for scanning antennas or liquid crystal array antennas, or the liquid crystal aligning film for transmission and scattering type liquid crystal dimming elements, or uses other than these, for example, a color filter It can also be used as a protective film, a gate insulating film of a flexible display, and a substrate material.

In addition, the specification of Japanese Patent Application No. 2019-127053 for which it applied on July 8, 2019, a claim, drawing, and the abstract are cited here, and it takes in as an indication of the specification of this invention.

Claims (16)

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
(A) component: at least 1 sort(s) of polymer selected from the group which consists of a polyimide-type polymer, polyorganosiloxane, the polymer of the monomer which has a polymerizable unsaturated bond, and a cellulosic polymer.
(B) component: has either a structure or a steroid skeleton in which two or more rings are linked directly or via a linking group, and has at least one group represented by the following formulas (b-1) to (b-5), or A compound having at least two groups represented by the following formula (b-6) and having a molecular weight of 2000 or less.

(However, R ₂ , R _4a , R _4b , R ₅ , and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. * represents a bond.) The method of claim 1,
Liquid crystal aligning agent whose said polyimide-type polymer is a polymer (A-1) which has at least 1 sort(s) of repeating unit chosen from the group which consists of a repeating unit represented by following formula (1), and a repeating unit represented by following formula (2) .

(However, X ₁ represents a tetravalent organic group. Y ₁ represents a divalent organic group. R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z ₁₁ , Z ₁₂ are each independently a hydrogen atom , an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkenyl group having 2 to 10 carbon atoms, an optionally substituted alkynyl group having 2 to 10 carbon atoms, tert-butoxycarbonyl group, or 9-fluorene It represents a nyl methoxycarbonyl group.) 3. The method of claim 2,
The liquid crystal aligning agent whose said X< ₁ > is a tetravalent organic group chosen from the group which consists of following formula (4a) - (4n), following formula (5a), and following formula (6a).

(However, x and y are a single bond, -O-, -CO-, -COO-, an alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, -SO-, or -NRCO- (R is represents a hydrogen atom or a methyl 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 and k are 0 or an integer of 1. .m is an integer from 1 to 5. * indicates a bond.) 4. The method of claim 3,
Repetition represented by the formula (1) wherein X ₁ is a tetravalent organic group selected from the group consisting of formulas (4a) to (4n), (5a) and formula (6a), and Y ₁ is a divalent organic group The liquid crystal aligning agent whose content of 1 or more types of the repeating unit chosen from the group which consists of a unit and the repeating unit represented by said Formula (2) is 5 mol% or more with respect to all repeating units in total. 5. The method according to any one of claims 1 to 4,
The liquid crystal aligning agent whose said (B) component is a compound represented by following formula (3-1) or following formula (3-2).

(However, B ₁ represents a structure selected from formulas (b-1) to (b-6), and B ₂ represents a structure selected from formulas (b-1) to (b-5). L ₁ represents the following formula (1L-1) or (1L-2): L ₂ is a single bond, the following formula (2L-1), or -CH ₂ -, -CH(CH ₃ )-, -C( A divalent group selected from the group consisting of CH ₃ ) ₂ -, -(CH ₂ ) _n - (n represents an integer of 2 to 20) and -NR- (R represents a hydrogen atom or a methyl group) (hereinafter , referred to as a linking group (2a).) In addition, any CH ₂ of -(CH ₂ ) _n - is -O-, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -; It may be substituted with -CO- or -NR- AL ₁ , AL ₂ are each independently *-Cy ₁ -Z ₁ or *-Cy ₂ indicates m1 represents the integer of 1-4. m2 represents the integer of 1-2. Cy ₁ represents a structure in which two or more rings are linked directly or via a linking group. Cy ₂ represents a group having a steroid skeleton. Z ₁ represents a linear or branched hydrocarbon group having 3 or more carbon atoms.)

(However, * ₁ represents the bond couple|bonded with AL1, * ₂ shows the bond bond couple|bonded with B1. n1 shows the integer of 1-2, n2 shows the integer of 1-4. A ₁₁ , A ₁₂ each independently represents a single bond, -O-, or a linking group (2a). When a plurality of A ₁₂ s exist, a plurality of A ₁₂ may be the same or different. A ₂₁ , A ₂₂ Each independently represents a linking group (2a) (excluding -NR-.) A _s11 represents a single bond, -O-, -CO-, or a linking group (2a). A _s12 is provided that A bond, -CO-, or a linking group (2a) (excluding -NR-) is represented.)

(However, *1 represents a bond bonded to B ₂ , and *2 indicates a bond bond to AL ₂ . A _s2 has the same meaning as A _s11 .) 6. The method of claim 5,
The liquid crystal aligning agent whose said (B) component is a compound represented by said Formula (3-1). 7. The method according to claim 5 or 6,
Z ₁ is a linear or branched alkyl group having 3 to 20 carbon atoms, a linear or branched fluoroalkyl group having 3 to 20 carbon atoms, a linear or branched alkoxy group having 3 to 20 carbon atoms, Or the liquid crystal aligning agent which is a C3-C20 linear or branched alkylester group. 8. The method according to any one of claims 5 to 7,
The liquid crystal aligning agent in which said Cy< ₁ > is represented by a following formula (Rn).

In formula (Rn), each X is independently a single bond, -O-, -CO-, -COO-, -NR ^b -, -CONR ^b - (R ^b is a hydrogen atom and has 1 to 6 carbon atoms) an alkyl group or ^a protecting group of A divalent group substituted with CONR ^b - is represented. m is 2-6. G each independently represents a benzene ring, a naphthalene ring, or a cyclohexane ring. * indicates a bond. 9. The method according to any one of claims 1 to 8,
The liquid crystal aligning agent whose said (B) component is a compound represented by any one of following formula (b-1) - formula (b-8).

10. The method according to any one of claims 1 to 9,
Liquid crystal aligning agent in which the said (A) component contains at least 1 sort(s) of polymer selected from the group which consists of a polyorganosiloxane, the polymer of the monomer which has a polymerizable unsaturated bond, and a cellulosic polymer together with a polyimide-type polymer . 10. The method according to any one of claims 1 to 9,
The liquid crystal aligning agent in which the said (A) component contains polyorganosiloxane with a polyimide-type polymer. 12. The method according to any one of claims 1 to 11,
The liquid crystal aligning agent whose content of the said (B) component is 0.1-40 mass parts per 100 mass parts of said (A) components. 13. The method according to any one of claims 1 to 12,
The liquid crystal aligning agent contains an organic solvent, and as the organic solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, N,N-dimethyllactamide, 3 A liquid crystal aligning agent comprising at least one good solvent selected from the group consisting of -methoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide. 14. The method of claim 13,
The liquid crystal aligning agent further comprises diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy- A liquid crystal aligning agent comprising at least one poor solvent selected from the group consisting of 4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-14. A liquid crystal display element provided with the liquid crystal aligning film of Claim 15.