KR20210137495A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same - Google Patents

Abstract

Provided is a liquid crystal display device that has a small amount of accumulated charge while maintaining a high voltage retention, and can minimize bright spots even when physical friction such as rubbing by a spacer occurs. The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
Component (A): A polymer (A) having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
(B) Component: A compound (B) having a molecular weight of 2000 or less, having a partial structure represented by the following formula (b) in the molecule, and having a basic moiety containing a nitrogen atom.
Definitions of symbols in formulas are as described in the specification.

Description

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

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

Various driving methods have been developed for liquid crystal display elements, which differ in electrode structure, physical properties of liquid crystal molecules used, manufacturing processes, etc., for example, TN (twisted nematic) type, STN (super-twisted nematic) type, Liquid crystal display elements, such as VA (vertical alignment) type, MVA (multi-domain vertical alignment) type, IPS (in-plane switching) type, FFS (fringe field switching) type, PSA (polymer-sustained alignment) type, are 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, a liquid crystal display element with little accumulation|storage charge is desired, maintaining high voltage retention, and the liquid crystal aligning agent containing a specific compound is disclosed by patent document 1.

Japanese Laid-Open Patent Publication No. 2008-052260

Moreover, as a so-called touch-panel type liquid crystal display element spreads widely, it is frequently performed that a user applies a strong pressing force to the display element with a finger|toe. At this time, the spacer which exists inside a liquid crystal display element moves in a liquid crystal display element, and rubs a liquid crystal aligning film. The liquid crystal aligning film to which the stress is applied by the spacer cannot regulate the orientation of the liquid crystal, and although the liquid crystal display element is displayed in black, for example, light leaks from the spacer periphery and is displayed as a bright spot. is becoming

It was not necessarily said that the structure of the liquid crystal aligning agent proposed conventionally can achieve all said subject. The present invention has been made on the basis of the above circumstances, and its object is to minimize the luminescent point even when physical friction such as rubbing by a spacer occurs, while maintaining a high voltage retention rate, with a small amount of accumulated charge. To provide a liquid crystal display device. Moreover, it is providing a liquid crystal aligning film suitable for such a liquid crystal display element, and its liquid crystal aligning agent.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject was solvable by using the liquid crystal aligning agent containing a specific component, as a result of earnestly researching, and came to complete this invention. Specifically, the following is a summary.

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

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

(B) Component: A compound (B) having a molecular weight of 2000 or less, having a partial structure represented by the following formula (b) in the molecule, and having a basic moiety containing a nitrogen atom.

[Formula 1]

In Formula (1), 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 They are a nyl group, a C2-C10 alkynyl group which may have a substituent, a tert- butoxycarbonyl group, or a 9-fluorenyl methoxycarbonyl group.

[Formula 2]

* represents a bond, and R<_1> represents a C1-C4 alkanediyl group. m<_1> represents the integer of 1-2.

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, there are few accumulated electric charges, maintaining high voltage retention, and also when physical friction, such as rubbing by a spacer, occurs, a liquid crystal display element which can minimize a luminescent point, and liquid crystal providing the same An alignment film is obtained.

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

<Polymer (A)>

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

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

In addition to the formula (2) Z _11, specific examples of a specific example of a carbon number of alkyl group of from 1 to 10, Z ₁₂ is a carbon number of alkyl group of from 1 to 5 exemplified in the R ₁ in the, hexyl group, heptyl group, An octyl group, a nonyl group, a decyl group, etc. are mentioned. Specific examples of the Z ₁₁ , Z ₁₂ alkenyl group having 2 to 10 carbon atoms include a vinyl group, a propenyl group 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, an iodine atom, etc.), a hydroxyl group, a cyano group, and an alkoxy group. have.

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

In the formulas (1) and (2), X ₁ and Y ₁ are as defined above. _{As X<1>} of Formula (1), at least 1 sort(s) chosen from the group which consists of tetracarboxylic dianhydride, tetracarboxylic-acid diester, and tetracarboxylic-acid diester dihalide (Hereinafter, these are collectively called, and "tetracar tetravalent organic group derived from "acid derivative"). Specific examples are derived from aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, tetracarboxylic acid diesters thereof, or tetracarboxylic acid diester dihalides and tetravalent organic groups. _Y<1> of Formula (1) is a divalent organic group derived from diamine.

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

From the viewpoint of obtaining high voltage retention and suppressing luminescent points caused by physical friction, X ₁ is a group consisting of the following formulas (4a) to (4n), the following formulas (5a) and the following formulas (6a) It is preferable that it is a tetravalent organic group selected from.

[Formula 3]

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

From the viewpoint of obtaining a high voltage retention rate and suppressing a bright spot generated by physical friction, a structure represented by the following formulas (4a-1) to (4a-4) as a preferable specific example of the formula (4a) can be heard

[Formula 4]

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

From the viewpoint of obtaining a high voltage retention rate and suppressing a luminescent point generated by physical friction, X ₁ in the formula (1) is the formula (4a) to (4h), (4j), (4l) , and may be a tetravalent organic group selected from (4m) to (4n).

From the viewpoint of obtaining a high voltage retention rate and suppressing bright spots caused by physical friction, X ₁ is selected from the group consisting of the above formulas (4a) to (4n), (5a) and (6a). A repeating unit selected from the group consisting of a repeating unit represented by the formula (1), wherein Y ₁ is a divalent organic group, and a repeating unit represented by the formula (2) (hereinafter also referred to as repeating unit (t)) ) may be 5 mol% or more, or 10 mol% or more, or 20 mol% or more with respect to the total repeating unit of the polymer (A) in total.

_{As Y<1>} of Formula (1), the divalent organic group derived from diamine is mentioned, For example, the divalent organic group derived from aliphatic diamine, alicyclic diamine, or aromatic diamine is mentioned. When a specific example is given, as an aliphatic diamine, For example, metaxylylenediamine, ethylenediamine, 1, 3- propanediamine, tetramethylenediamine, hexamethylenediamine, etc.;; Examples of the alicyclic diamine include 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), and the like;

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-indene-6-amine, a nitrogen-containing heterocyclic ring, a diamine having at least one selected from the group consisting of a diphenylamine structure and a triphenylamine structure (hereinafter also referred to as “nitrogen-containing diamine”), 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, A diamine represented by H), a diamine represented by the following formulas (H2) to (H3), a diamine represented by the following formulas (V-1) to (V-3), and a radical initiation function represented by the following formulas (R1) to (R5) Diamine having a photopolymerizable group at the terminal, such as diamine having a diamine, 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N-diallylaniline, International Publication WO2014 The diamine having a photo-alignment structure described in paragraph [0053] of /080865, the diamine having a carbon-carbon unsaturated bond described in paragraph [0057], the diamine having an azobenzene skeleton described in paragraph [0058], International Publication No. WO2012/086715 and diamines having photoreactivity as described in paragraphs [0069] to [0072].

[Formula 5]

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

[Formula 6]

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

[Formula 7]

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

[Formula 8]

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

X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -. Among these, a plurality of a1 is each independently an integer of 1 to 15, a plurality of A ₁ each independently represents an oxygen atom or -COO-, and m ₁ is 1-2. X ³ represents a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO-. X ⁴ represents -CONH-, -NHCO-, -O-, -COO- or -OCO-.

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

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

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

[Formula 9]

n represents the integer of 2-10.

Specific examples of the nitrogen-containing heterocyclic ring include pyrrole, imidazole, pyridine, pyrimidine, pyridazine, pyrazine, carbazole, benzoimidazole, piperidine, piperazine, pyrrolidine, hexamethyleneimine, and the like. and diphenylamine structures include structures such as diphenylamine, N-methyldiphenylamine, or N-tert-butoxycarbonyldiphenylamine. Specific examples of the nitrogen-containing diamine include 2,6-diaminopyridine, 3,4-diaminopyridine, 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide, 2,4-dia Minopyrimidine, 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 diamine represented by following formula (z-1) - (z-19), etc. are mentioned.

[Formula 10]

[Formula 11]

Boc represents a tert-butoxycarbonyl group.

In the formulas (H), (H2) and (H3), the hydrogen atom on the benzene ring is an alkyl group having 1 to 5 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, a fluorine atom, etc. A halogen atom, a halogenated alkyl group having 1 to 5 carbon atoms, such as a trifluoromethyl group, -NR ₁ R ₂ (R ₁ and R ₂ each represent a hydrogen atom, a methyl group or a tert-butoxycarbonyl group), a cyano group, and a hydroxyl group You may substitute with monovalent organic groups, such as these.

You may use the diamine represented by a following formula (H-1) - (H-17) among the diamines represented by the said Formula (H) from a viewpoint of improving the liquid-crystal orientation.

[Formula 12]

[Formula 13]

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

From a viewpoint of improving the liquid-crystal orientation, you may use the diamine represented by a following formula (H2-1) - (H2-17) among the diamines represented by the said Formula (H2).

[Formula 14]

[Formula 15]

R represents a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group. * indicates a bond. Boc represents a tert-butoxycarbonyl group.

You may use the diamine represented by a following formula (H3-1) - (H3-4) among the diamines represented by the said Formula (H3) from a viewpoint of improving the liquid-crystal orientation.

[Formula 16]

From a viewpoint of improving the liquid-crystal orientation, you may use the diamine represented by following formula (V2-1) - (V2-13) among diamine (V-1) - (V-3).

[Formula 17]

[Formula 18]

In the formula, X ^v1 to X ^v4 , X ^p1 to X ^p8 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON( CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO- represents, and X ^v5 is -O-, -CH ₂ O-, - CH ₂ OCO-, -COO-, or -OCO- is represented, and X ^V6 to X ^V7 , X ^s1 to X ^s4 each independently represent -O-, -COO- or -OCO-. X _a to X _f represent a single bond, -O-, -NH-, or -O-(CH ₂ ) _m -O-, R ^v1 to R ^v4 , R ^1a to R ^1h each independently represent a carbon number A 1-20 alkyl group, a C1-C20 alkoxy group, or a C2-C20 alkoxyalkyl group is shown. m represents the integer of 1-8.

When applying to the liquid crystal aligning agent for liquid crystal display elements of TN type, STN type, or vertical alignment type, from a viewpoint of improving liquid-crystal orientation, as for the said polymer (A), X<_1> is a tetravalent organic group, Y<_1> is said A repeating unit selected from the group consisting of a repeating unit represented by the formula (1), which is a divalent organic group derived from a diamine represented by formulas (V1) to (V3), and a repeating unit represented by the formula (2) (hereinafter, repeating unit) (a) may also be included 1 or more types. From a viewpoint of improving liquid-crystal orientation, 1 mol% or more, or 3 mol% or more, or 5 mol% or more may be sufficient as content of a repeating unit (a) in total with respect to the total repeating unit of a polymer (A).

When applying to the liquid crystal aligning agent for liquid crystal display elements of PSA type, from a viewpoint of improving liquid-crystal orientation, as for the said polymer (A), X ₁ is a tetravalent organic group, Y ₁ is the diamine which has the said radical initiation function; A repeating unit selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), which is a divalent organic group derived from a diamine selected from the group consisting of diamines having the photopolymerizable group at the terminal. (hereinafter also referred to as a repeating unit (b)) may be included. From a viewpoint of improving liquid-crystal orientation, 1 mol% or more, or 3 mol% or more, or 5 mol% or more may be sufficient as content of a repeating unit (b) in total with respect to the total repeating unit of a polymer (A). In this case, the polymer (A) may use together 1 or more types of repeating units (a). The upper limit of the content of the repeating unit (a) and the repeating unit (b) may be 99 mol% or less, or 97 mol% or less, or 95 mol% or less, respectively, based on the total repeating unit of the polymer (A). Moreover, in this case, you may include other repeating units other than the said repeating unit (a) and repeating unit (b) according to the objective.

When applying to the liquid crystal aligning agent for liquid crystal display elements of IPS type or FFS type, as for the said polymer (A), from a viewpoint of improving liquid-crystal orientation, X<_1> is a tetravalent organic group, Y<_1> is p-phenylenediamine , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminoazobenzene, 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) a divalent organic group derived from a diamine selected from the group consisting of a biphenyl, a diamine represented by the formula (H), and a diamine represented by the formulas (H2) to (H3), represented by the formula (1) One or more types of repeating units (hereinafter also referred to as repeating units (c)) selected from the group consisting of repeating units and repeating units represented by the formula (2) may be included. From a viewpoint of improving liquid-crystal orientation, 5 mol% or more or 10 mol% or more may be sufficient as content of a repeating unit (c) in total with respect to the total repeating unit of a polymer (A).

When liquid-crystal aligning ability is provided by the photo-alignment method with respect to the coating film formed with the liquid crystal aligning agent, as for the said polymer (A), X ₁ is a tetravalent organic group, Y ₁ is diamine which has the said photo-alignment structure; A repeating unit represented by the above formula (1), which is a divalent organic group derived from a diamine selected from the group consisting of a diamine having a carbon-carbon unsaturated bond, a diamine having an azobenzene skeleton, and a diamine having photoreactivity, and the formula ( 2) may contain one or more repeating units (hereinafter also referred to as repeating units (d)) selected from the group consisting of repeating units. From a viewpoint of providing liquid-crystal orientation ability, 20 mol% or more or 30 mol% or more may be sufficient as content of a repeating unit (d) in total with respect to the total repeating unit of a polymer (A). Moreover, from a viewpoint of providing liquid-crystal orientation ability by the photo-alignment method and maintaining high voltage retention, as for the said polymer (A), X<_1> is said Formula (4a)-(4c), (4f)-(4g) and Y ₁ is a divalent organic group, a repeating unit (hereinafter, also referred to as repeating unit (e)) selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) You may include more than one. 5 mol% or more or 10 mol% or more may be sufficient as content of a repeating unit (e) with respect to the total repeating unit of a polymer (A) in total.

_{The polymer (A) has a repeating unit represented by the formula (1) wherein X 1} is a tetravalent organic group and Y ₁ is a divalent organic group derived from nitrogen-containing diamine from the viewpoint of a small amount of accumulated charge, and the formula (2) ) may contain one or more repeating units (hereinafter also referred to as repeating units (n)) selected from the group consisting of repeating units represented by . The content of the repeating unit (n) may be 5 mol% or more or 10 mol% or more in total with respect to the total repeating unit of the polymer (A).

The liquid crystal aligning agent of this invention may contain one type of polymer (A), and may contain two or more types of polymers (A). Specific examples in the case of two or more polymers (A) include: any of repeating units (t) and (a) to (e) from the viewpoint of having little accumulated electric charge and suppressing bright spots caused by physical friction The aspect containing at least 1 type or more of the polymer which has one repeating unit is mentioned. Moreover, the aspect containing at least 1 type or more of a polymer which has a repeating unit (n) is mentioned from a viewpoint with few accumulated electric charges. Moreover, when a polymer (A) consists of two types, the compounding ratio of a 1st polymer and a 2nd polymer ((1st polymer)/(2nd polymer)) improves liquid-crystal orientation, there are few accumulated electric charges, and physical friction 5/95 to 95/5, or 10/90 to 90/10, or 20/80 to 80/20 by mass ratio may be sufficient from a viewpoint of being able to suppress the luminescent point which generate|occur|produces by this.

<Compound (B)>

The liquid crystal aligning agent of this invention contains the said compound (B). Since the said compound (B) has the basic site|part containing a nitrogen atom in a molecule|numerator, the imidation rate of the polymer (A) at the time of baking is raised, and the liquid crystal aligning film obtained has a high voltage retention. In addition, since a crosslinking reaction occurs between the polymer (A) and the compound (B) or between the compounds (B) because it has a methylol group in the molecule, the film strength of the obtained liquid crystal aligning film can be increased. have. Therefore, the liquid crystal display element provided with the liquid crystal aligning film of this invention can minimize a luminescent point, even when physical friction, such as rubbing by a spacer, generate|occur|produces. Moreover, since the said compound (B) is excellent in the ability to capture|acquire the impurity component derived from a board|substrate at the point which the effect of raising the crosslinking density of a liquid crystal aligning film is acquired, the liquid crystal aligning film obtained obtains the liquid crystal display element which shows high voltage retention lose Moreover, since the said compound (B) has a phenylene moiety in a molecule|numerator, the charge transfer in a liquid crystal aligning film is accelerated|stimulated, and a liquid crystal aligning film with few accumulation|storage electric charges can be obtained.

The said basic site|part means the site|part from which the pKa of a conjugated acid becomes -3 or more. It is preferable to exist in the range of -3-15, and, as for this pKa, it is more preferable to exist in the range of 0-15. In addition, this pKa means the calculated value calculated|required by ACD/ChemSketch (ACD/Labs 8.00 Release Product Version: 8.08).

The basic moiety includes, for example, a structure selected from the group consisting of a group obtained by removing one or two hydrogen atoms from a secondary amine or a tertiary amine, and a nitrogen-containing heterocyclic group. As a secondary amine or a tertiary amine, an aliphatic amine, an aromatic amine, etc. are mentioned.

As an aromatic amine, the structure which aromatic rings, such as a benzene ring, couple|bonded with at least 1 nitrogen atom is mentioned. The hydrogen atom on the benzene ring may be unsubstituted or substituted with a monovalent organic group, and the monovalent organic group includes, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a methyl group, etc. Alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms such as methoxy group, nitro group, hydroxyl group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silanol group, sulfino group, phospho A pino group, a carboxyl group, a cyano group, a sulfo group, an acyl group, "-R ₁ -OH" group (R ₁ is a C1-C4 alkanediyl group) etc. are mentioned.

Monocyclic or polycyclic may be sufficient as a nitrogen-containing heterocyclic ring. Specific examples of the nitrogen-containing heterocyclic ring include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzoimidazole, purine, quinoline, isoquinoline, naphthylidene, quinoxaline , phthalazine, triazine, thiazole, isothiazole, benzothiazole, 5,6,7,8-tetrahydroquinoline, piperidine, piperazine, pyrrolidine, hexamethyleneimine, decahydroquinoline, imidazoline, carbazole, etc. are mentioned.

In the partial structure represented by the said formula (b), a methylene group, an ethylene group, a propanediyl group, a butanediyl group etc. are mentioned as a C1-C4 alkanediyl group of _R<1>. From a viewpoint of a high crosslinking effect, a methylene group is especially preferable. It is preferable that m<_1> is 2 from a viewpoint of a high crosslinking effect.

The compound (B) is selected from the group consisting of the following formulas (B1), (B2-1) to (B2-2), and (B3-1) to (B3-3) from the viewpoint of ease of synthesis. It is preferable that it is at least 1 type of compound.

[Formula 19]

R ₁ represents a C1-C4 alkanediyl group. L ₁ represents a divalent organic group selected from the following formulas (L1-1) to (L1-3). S _21a and S _{21b each independently represent an (m 2a} + 2) or (m _2b + 2) valent organic group represented by the following formula (2S-1) or (2S-2). S ₂₂ , S ₃₂ are each independently a single bond, -O-, -CO-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -(CH ₂ ) _n - (n represents an integer of 2 to 20), or -(CH ₂ ) _n - is not adjacent to CH ₂ , -O-, -CO-, -CH(CH ₃ )-, or -C( CH ₃ ) Represents a divalent organic group substituted with _{2 -.}

S _31a is a single bond, -O-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -(CH ₂ ) _n - (n is an integer of 2 to 18); -CO-, -C≡C-, -CH=CH-, a phenylene group, a divalent organic group selected from formulas (M-1) to (M-10), or -(CH ₂ ) _n- Any CH ₂ is -O-, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CO-, a phenylene group, or selected from formulas (M-1) to (M-11) It represents the divalent organic group substituted with the divalent organic group used.

S _31b is a divalent organic group represented by the above formula (M-11) other than the divalent organic group defined for _{S 31a , -C(R 32} ) _2-m3b (Q _3b ) _m3b - (m _3b is 1 to 2) R ₃₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

R ₂ , R ₃₁ , and R ₃₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Q _2a , Q _2b , Q _3a , and Q _3b each independently represent a monovalent organic group selected from the following formulas (Q-1) to (Q-17). However, when S ₂₂ and S ₃₂ are each a single bond, Q _2a and Q _3a are (Q-1), (Q-3), (Q-7) to (Q-13) or (Q-17) represents a monovalent organic group selected from

l ₂ and l ₃ each independently represent an integer of 1-2.

m<_1> represents the integer of 1-2, and some m<_1> may be the same or different. m _2a and m _2b each independently represent an integer of 1-2.

[Formula 20]

M represents a divalent organic group selected from the following formulas (M-1) to (M-11). R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. T ₁ and T ₂ are each independently a single bond, -O-, -NR- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -NRCONR- (R represents a hydrogen atom or a methyl group), a phenylene group, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -(CH ₂ ) _n - (n is an integer of 2 to 20) or the - (CH _{2) n} - CH ₂ is any _{of, -CH (CH 3) -,} -C (CH 3) 2 -), -O-, -NR- (R is a hydrogen atom or a methyl group represents), -CONR- (R represents a hydrogen atom or a methyl group), -NRCONR- (R represents a hydrogen atom or a methyl group), or a divalent organic group substituted with a phenylene group. Moreover, arbitrary hydrogen atoms on the phenylene group may be substituted with a monovalent organic group.

T ₃ is -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -(CH ₂ ) _n - (n is an integer of 2 to 18), a phenylene group, or the above -( CH _{2) n} - CH ₂ is any _{of, -O-, -CH (CH 3)} -, -C (CH 3) 2 -, -CONR- (R represents a hydrogen atom or a methyl group), -NRCONR- (R represents a hydrogen atom or a methyl group) and a divalent organic group substituted with a phenylene group. n1 represents the integer of 1-3. n3 represents the integer of 0-1.

[Formula 21]

R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom or a methyl group. *1 represents a bond, and *2 represents a bond bonded to a carbon atom.

[Formula 22]

*1 represents the bond bond couple|bonded with a nitrogen atom or ( _Q2b ), *2 shows the bond bond couple|bonded with a benzene ring. n represents the integer of 1-2. A _L11 , A _L12 are each independently a single bond, -O-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -(CH ₂ ) _n - (n is 2 and 20 represents an integer), -COO-, -OCO-, -CONR- ( R represents a hydrogen atom or a methyl group), or the - (CH _{2) n} - CH ₂ is any of, -O-, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -COO-, -OCO-, -CONR- (R represents a hydrogen atom or a methyl group) represents a divalent organic group substituted. When two or more A _L12 exist, several A _L12 may be same or different. A _S11 , A _S21 are each independently a single bond, -O-, -CO-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -(CH ₂ ) _n - (n is an integer of 2 to 20), a phenylene group, or a - (CH _{2) n} - CH ₂ is any _{of, -CH (CH 3) -,} -C (CH 3) 2 -, -O -, -CO-, represents a divalent organic group substituted with a phenylene group. R _L represents a hydrogen atom, a hydroxyl group, or a methyl group. p represents the integer of 1-2.

[Formula 23]

R ₁ , R ₃ , R ₇ , and R _{8 each} represent a hydrogen atom or a methyl group. R ₁₆ and R ₁₇ represent a phenyl group. *1 represents a bond, and *2 represents a bond bonded to a carbon atom.

The _{hydrogen atom on the phenylene group in L 1} is an alkyl group having 1 to 5 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, a halogen atom such as a fluorine atom, and a trifluoromethyl group You may substitute with monovalent organic groups, such as a halogenated alkyl group of 1-5, -NR ₁ R ₂ (R ₁ and R ₂ each represent a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group), a cyano group, or a hydroxyl group.

In the divalent organic group represented by the formulas (M-1) to (M-11) and the monovalent organic group represented by the formulas (Q-1) to (Q-17), any hydrogen on the benzene ring or the heterocyclic ring An atom may be substituted with a monovalent organic group, and as a specific example of such a monovalent organic group, the structure illustrated as a monovalent organic group which substitutes the hydrogen atom on the said phenylene group in _{L<1> is mentioned.}

In the above formula (B1), from the viewpoint of easy synthesis, L ₁ is, among others, the following formulas (L1-a-1) to (L1-a-12), (L1-b-1) to (L1-b) -3) or (L1-c-1) to (L1-c-3).

[Formula 24]

[Formula 25]

Said A _L11 and A _L12 are a single bond, -O-, -CH ₂ -, -(CH ₂ ) _n - (n represents an integer of 2 to 20), -COO-, -OCO-, -CONR- (R represents a hydrogen atom or a methyl group), or the - (CH _{2) n} - is any of CH _2, -O-, -CONR- (R represents a hydrogen atom or a methyl group ) and a divalent organic group substituted with ) is preferable.

From the _{viewpoint of easy synthesis, S 21a} may have the following formulas (S _21a -1-1) to (S _21a -1-5) or (S _21a -2-1), among others.

[Formula 26]

*1 represents a hand bonding to a nitrogen atom, and *2 represents a hand bonding to a benzene ring.

From the _{viewpoint of easy synthesis, S 21b} is, among others, the formulas (S _21a -1-1) to (S _21a -1-5), (S _21a -2-1), and the following formulas (S _21b -1). -1) may be used. However, in the above formulas (S _21a -1-1) to (S _21a -1-5) and (S _21a -2-1), *1 represents a bond bonded to _{(Q 2b ), *} 2 represents a bond bonded to a benzene ring.

[Formula 27]

*1 represents the bond bond couple|bonded with a nitrogen atom or ( _Q2b ), *2 shows the bond bond couple|bonded with a benzene ring.

From the _{viewpoint of easy synthesis, S 31a} may be a single bond or may have the following formulas (S _31a -1) to (S _31a -5).

[Formula 28]

*1 represents a bond bond to a nitrogen atom, and *2 represents a bond bond to a benzene ring. M represents a group selected from the formulas (M-1) to (M-10).

S _31b is, among others, a single bond, -O-, the above formulas (S _31a -1) to (S _31a -5), and the following formulas (S _31b -1) to (S _31b - 5) may be used. However, in the formulas (S _31a -1) to (S _31a -5), *1 _{represents a bond bonded to (Q 3b} ), and *2 represents a bond bonded to a benzene ring.

[Formula 29]

*1 _{represents a bond bonded to Q 3b,} and *2 indicates a bond bonded to a benzene ring. M represents a group selected from the formulas (M-1) to (M-10). Q _3b has the same definition as the formula (B3-2).

R ₃₃ may be a hydrogen atom, a methyl group or an ethyl group from the viewpoint of easy synthesis.

As a preferable specific example of compound (B), following formula (B1-1-1) - (B1-1-4), (B1-2-1) - (B1-2-2), (B1-3-1) ) to (B1-3-26), (B2-1-1) to (B2-1-2), (B2-2-1) to (B2-2-18), (B3-1-1) to compounds represented by (B3-1-7), (B3-2-1) to (B3-2-11), and (B3-3-1);

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

Preferable content of a compound (B) is 0.1-40 mass parts per 100 mass parts of (A) component, More preferably, it is 0.5-35 mass parts, More preferably, it is 0.5-30 mass parts.

<Method for producing polyamic acid>

The polymer (A) in the present invention includes, for example, a tetracarboxylic acid derivative having a structure of _{X 1 and a diamine having a structure of Y 1} described in International Publication WO2013/157586. It can be obtained by reacting in this way.

[Terminal modifier]

When synthesize|combining the polymer (A) in this invention, it is good also as what synthesize|combines the polymer of a terminal modification type using an appropriate terminal blocker with the above tetracarboxylic-acid derivative and diamine.

Examples of the terminal modifier include maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, the following formula (m-1 ) to (m-6), 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroiso acid monhydrides such as benzofuran-1,3-dione and 4-ethynyl phthalic anhydride;

[Formula 41]

dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinic acid chloride; Aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine monoamine compounds such as , n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; Monoisocyanate compounds, such as ethyl isocyanate, phenyl isocyanate, and naphthyl isocyanate, etc. are mentioned.

It is preferable to set it as 20 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 modifier, it is more preferable to set it as 10 mol part or less.

<Liquid crystal aligning agent>

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

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

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyro Lactone, γ-valerolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, N,N-dimethyllactoamide, 3-methoxy-N,N-dimethylpropane amide, 3-butoxy-N,N-dimethylpropanamide (these are collectively referred to as "good solvent"), and the like. From the viewpoint of good printability, among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N,N-dimethyllactoamide or γ-butyrolactone may be used. 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent from a viewpoint with favorable printability to the good solvent in the liquid crystal aligning agent of this invention, or 20-90 mass %, or 30-80 mass % may be sufficient.

Moreover, the organic solvent contained in a liquid crystal aligning agent uses the mixed solvent which used together the solvent (it is mentioned 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 above solvents It is preferable to do Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

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

Among them, from the viewpoint of good printability, the poor solvent is diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone may be used.

From the viewpoint of good printability, combinations of good solvents and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone. and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2 -Pyrrolidone, 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 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone And γ-butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, N-methyl- Combinations of 2-pyrrolidone, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, etc. are mentioned. 1-80 mass % of the whole solvent contained in a liquid crystal aligning agent, 10-80 mass %, or 20-70 mass % of these poor solvents may be sufficient. The kind and content of such a solvent are suitably selected according to the coating apparatus of a liquid crystal aligning agent, application|coating conditions, application|coating environment, etc.

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

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

[Formula 42]

In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or “*-CH ₂ —OH”, and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or “*- CH ₂ —OH”. * indicates that it is a bond.

[Formula 43]

Specific examples of the compound having an oxiranyl group include the compound described in paragraph [0037] of Japanese Patent Application Laid-Open No. 10-338880, and a compound having a triazine ring in its skeleton described in International Publication No. WO2017/170483, etc. and compounds having two or more oxiranyl groups. Among these, from the viewpoint of high crosslinking effect, 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 formula A compound containing a nitrogen atom, such as a compound represented by (r-1) to (r-3), may be used.

[Formula 44]

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

Specific examples of the compound having a protective isocyanate group include a compound having two or more protective isocyanate groups described in paragraphs [0046] to [0047] of JP 2014-224978 A, paragraphs [0119] to International Publication No. 2015/141598 The compound etc. which have 3 or more protected isocyanate groups as described in [0120] are mentioned. Among these, you may use the compound represented by following formula (bi-1) - (bi-3) from a viewpoint of a high crosslinking effect.

[Formula 45]

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

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

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

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

A methyl group, an ethyl group, and a propyl group are mentioned as a C1-C3 alkyl _{group of R<1>} , R<_2> , R<_3> of the group represented by said formula (d).

Specific examples of the compound having a group represented by the formula (d) include two or more groups represented by the formula (d) described in paragraphs [0058] of International Publication No. WO2015/072554 and Japanese Patent Application Laid-Open No. 2016-118753. The compound which has, the compound of Unexamined-Japanese-Patent No. 2016-200798, etc. are mentioned. Among these, you may use the compound represented by following formula (hd-1) - (hd-8) from a viewpoint of a high crosslinking effect.

[Formula 46]

The compound is an example of a crosslinkable compound, but is not limited thereto. For example, components other than the above disclosed in pages 53 - 55 of International Publication No. 2015/060357, etc. are mentioned. Moreover, the number of the crosslinkable compounds contained in the liquid crystal aligning agent of this invention may be one, and they may combine them two or more types.

With respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent from a viewpoint of content of the crosslinking|crosslinked compound in the liquid crystal aligning agent of this invention, a crosslinking reaction progressing, expressing the objective effect, and raising liquid-crystal orientation. , 0.5 to 20 parts by mass, or 1 to 15 parts by mass.

As the adhesion aid, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane , 3-Ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl Triethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane , 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl- 3-Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxy Silane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Silanes such as trimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane A coupling agent is mentioned. When using these silane coupling agents, it is good also as 0.1-30 mass parts or 0.1-20 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent from a viewpoint of improving liquid-crystal orientation.

<Liquid crystal alignment film, liquid crystal display element>

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

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

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

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

(1-1A)

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

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

(1-1B)

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

In either case of said (1-1A) and (1-1B), after apply|coating a liquid crystal aligning agent on a board|substrate, the coating film used as a liquid crystal aligning film or a liquid crystal aligning film is formed by removing an organic solvent. At this time, by heating further after coating-film formation, the dehydration ring-closure reaction of the polyamic acid mix|blended with the liquid crystal aligning agent which concerns on this invention, polyamic acid ester, and a polyimide is advanced, and it is good also as a more 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. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. 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 with a cloth made of fibers such as nylon, rayon, or 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, when manufacturing a VA-type liquid crystal display element, although the coating film formed in the said process (1-1) can be used as a liquid crystal aligning film as it is, you may perform an orientation ability provision process with respect to this coating film.

When providing liquid-crystal orientation ability to a coating film by a photo-alignment process, as radiation irradiated to a coating film,

For example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized or partially polarized. When the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When irradiating a non-polarized radiation, the direction of irradiation is made into an oblique direction.

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

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

Moreover, when using the ultraviolet-ray containing the light of a wavelength of 150-800 nm, although the light irradiation film obtained in the said process can be used as a liquid crystal aligning film as it is, baking the light irradiation film, washing|cleaning with water or an organic solvent, or You may implement these combinations. The firing temperature at this time is preferably 80 to 300°C, more preferably 80 to 250°C. Firing time becomes like this. Preferably it is 5 to 200 minutes, More preferably, it is 10 to 100 minutes. In addition, you may implement the frequency|count of baking by the frequency|count of 1 time or 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.

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

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

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

(1-3A)

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

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

As a liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, Among them, a nematic liquid crystal is preferable, For example, Schiff base type liquid crystal, an azoxy type liquid crystal, a biphenyl type liquid crystal, a phenylcyclohexane type liquid crystal, ester Liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cuban liquid crystals, and the like can be used. Moreover, to these liquid crystals, For example, Cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate; Chiral products sold under brand names "C-15" and "CB-15" (manufactured by Merck Corporation); A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used. The liquid crystal may further include an anisotropic dye. The term "dye" may mean a material capable of intensively absorbing or transforming light within the visible light region, for example, at least a part or the entire range within the 400 nm to 700 nm wavelength range, and the term "anisotropic dye" may mean a material capable of anisotropic absorption of light in at least a part or the entire range of the visible light region. The color of the liquid crystal cell can be adjusted through the use of the dye as described above. The type of the anisotropic dye is not particularly limited, and, for example, black dye or color dye can be used. The ratio of the anisotropic dye to the liquid crystal is appropriately selected within a range that does not impair the desired physical properties, for example, the anisotropic dye may be included in a ratio of 0.01 to 5 parts by mass based on 100 parts by mass of the liquid crystal compound, but the above The ratio can be changed within an appropriate range as needed.

(1-3B)

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

[Formula 47]

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

(1-3C)

When a coating film is formed on a board|substrate using the liquid crystal aligning agent containing the compound (polymer or additive) which has a photopolymerizable group, it carries out similarly to said (1-3A), and constructs a liquid crystal cell, After that, 1 pair You may employ the method of manufacturing a liquid crystal display element by passing through the process of irradiating light to a liquid crystal cell in the state which applied voltage between the electrically conductive films which the board|substrate has. According to this method, the merit of the PSA mode can be realized with a small amount of light irradiation. As an additive which has a photopolymerizable group, the structure illustrated by said Formula (w-1) - (w-5) is mentioned, The compounding quantity is 1-30 mass with respect to solid content of the whole polymer contained in a liquid crystal aligning agent. % may be sufficient, 1-20 mass % may be sufficient, and 1-15 mass % may be sufficient. Light irradiation to a liquid crystal cell may be performed in the state which drove the liquid crystal by voltage application, or you may perform it in the state which applied the voltage low enough to not drive a liquid crystal. The voltage to be applied can be, for example, a direct current or alternating current of 0.1 to 30 V. Regarding the conditions of the light to be irradiated, the description of (1-3B) above is applicable. The light irradiation treatment here corresponds to the light irradiation treatment in a state in contact with the liquid crystal layer.

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

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

As described above, by using the liquid crystal aligning agent of the present invention, there is little generation of an afterimage and a liquid crystal aligning film capable of minimizing bright spots even when physical friction such as rubbing by a spacer occurs, and a liquid crystal display element provided with the same can be obtained Moreover, the liquid crystal display element obtained has high reliability.

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, about compound (c-2), it 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)

(tetracarboxylic dianhydride)

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

(tetracarboxylic acid diester dihalide)

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

(monocarboxylate chloride)

E-1: acryloyl chloride

(additive)

b-1 to b-9: compounds represented by the following formulas (b-1) to (b-9)

(Other additives)

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

c-2: a compound represented by the following formula (c-2)

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

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

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

M-1: 3-picolylamine

(organic solvent)

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

BCS: butyl cellosolve, DIBK: diisobutyl ketone,

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

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

DPM: dipropylene glycol monomethyl ether,

PB: propylene glycol monobutyl ether,

PGDAC: propylene glycol diacetate,

DEDE: diethylene glycol diethyl ether,

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

EEP: 3-ethoxy ethyl propionate

[Formula 48]

[Formula 49]

Boc represents a tert-butoxycarbonyl group.

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

[Formula 55]

Boc represents a tert-butoxycarbonyl group. Fmoc represents a 9-fluorenylmethyloxycarbonyl group.

[Viscosity]

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

[Molecular Weight]

The molecular weight was measured with a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated as polyethylene glycol and polyethylene oxide conversion values.

GPC apparatus: manufactured by Shodex (GPC-101), column: manufactured by Shodex (KD803, KD805 in series), column temperature: 50°C, eluent: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr) H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystals (o-phosphoric acid) are 30 mmol/L, tetrahydrofuran (THF) is 10 mL/L), flow rate: 1.0 mL/min

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

<Measurement of imidization rate>

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

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

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

[Synthesis of Compound (B)]

<Synthesis Example (b-1)>

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

[Formula 56]

To an eggplant-type flask, 2,5-pyridinedicarboxylic acid (3.00 g, 18.0 mmol), 4-aminophenol (4.11 g, 37.7 mmol) and N,N-dimethylformamide (DMF) (100 g) were added and the mixture was stirred at room temperature. Next, N-ethylmorpholine (4.34 g, 37.7 mmol) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT- MM) (10.43 g, 37.7 mmol) was added and stirred at room temperature overnight. Water (600 g) was added to the reaction solution, solid was deposited, and the obtained solid was washed with methanol. Next, the solvent was distilled off under reduced pressure to obtain 4.23 g of compound (b-1-1).

Compound (b-1-1) (2.00 g, 5.72 mmol), 24% aqueous sodium hydroxide solution (3.81 g, 22.8 mmol) and pure water (1.16 g) were added to a four-necked flask, 37 at room temperature under stirring % aqueous formaldehyde solution (4.68 g, 57.2 mmol) was added dropwise to react. After heating up and stirring the reaction solution at 35-40 degreeC, a part of reaction solution was taken out, LC/MS was measured, and the end point of reaction was confirmed from the thing which the peak of a raw material lose|disappeared. After completion of the reaction, the obtained reaction mixture was neutralized with acetic acid, followed by stirring for 2 hours, and the precipitated crystals were filtered off. The solvent was distilled off under reduced pressure to obtain 2.41 g of compound (b-1).

<Synthesis example (b-2)>

In Scheme 1, except having changed 4-aminophenol to tyramine, it synthesize|combined in the same procedure and obtained the compound (b-2).

[Formula 57]

<Synthesis Example (b-3)>

Compound (b-3) was synthesized according to the route shown below.

[Formula 58]

To an eggplant-type flask were added 4,4'-dimethoxydiphenylamine (3.00 g, 13.1 mmol), potassium carbonate (5.43 g, 39.3 mmol) and N,N-dimethylformamide (DMF) (18.6 g), The mixture was stirred at room temperature. Next, after adding iodomethane (7.43 g, 52.3 mmol), raising the temperature to 40 to 50°C and stirring, a part of the reaction solution is taken out and LC/MS is measured. The endpoint was confirmed. Tetrahydrofuran (THF) (50 g), toluene (10 g) and water (50 g) were added to the reaction solution, and the organic layer was separated. After wash|cleaning an organic layer with 10% brine, the solvent was distilled off under reduced pressure, methanol was added to the concentrate, and the compound (b-3-1) was obtained.

To an eggplant-shaped flask were added compound (b-3-1) (2.00 g, 8.22 mmol) and dichloromethane (12.7 g), and the mixture was stirred and cooled to -5°C under a nitrogen atmosphere. Next, a 17% boron tribromide solution in dichloromethane (22.69 g, 15.4 mmol) was added dropwise, and after completion of the dropwise addition, the reaction was carried out at room temperature for 2 hours. After adding ice water to the reaction solution, ethyl acetate was added, and the organic layer was extracted. The solvent was distilled off under reduced pressure to obtain a compound (b-3-2).

Compound (b-3-2) (1.68 g, 7.84 mmol), 24% aqueous sodium hydroxide solution (5.20 g, 31.4 mmol) and pure water (4.32 g) were added to a four-necked flask, and stirred at room temperature 37 % aqueous formaldehyde solution (6.35 g, 78.4 mmol) was added dropwise to react. After heating up and stirring the reaction solution at 30-40 degreeC, a part of reaction solution was taken out, LC/MS was measured, and the end point of reaction was confirmed from the thing which the peak of the raw material lose|disappeared. After completion of the reaction, the obtained reaction mixture was neutralized with acetic acid, followed by stirring for 2 hours, and the precipitated crystals were filtered off. The solvent was distilled off under reduced pressure to obtain compound (b-3).

<Synthesis example (b-4)>

Compound (b-4) was synthesized according to the route shown below.

[Formula 59]

In an eggplant-type flask, 5-(3-pyridinyl)-1,3-benzenedicarboxylic acid (CAS No. 1262962-06-0) (4.38 g, 18.0 mmol), tyramine (5.17 g, 37.7 mmol) and N,N-dimethylformamide (DMF) (100 g) was added and the mixture was stirred at room temperature. Next, N-ethylmorpholine (4.34 g, 37.7 mmol), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT- MM) (10.43 g, 37.7 mmol) was added and stirred overnight at room temperature. Water (600 g) was added to the reaction solution, solid was deposited, and the obtained solid was washed with methanol. Next, the solvent was distilled off under reduced pressure to obtain a compound (b-4-1).

Next, in Scheme 2, except having changed the compound (b-3-2) to the compound (b-4-1), it synthesize|combined in the same procedure, and obtained the compound (b-4).

<Synthesis Example (b-5)>

In Scheme 2, the compound (b-3-2) was synthesized in the same procedure except that the compound (b-3-2) was changed to 4,4'-(2-pyridinylmethylene)bisphenol (CAS No. 603-41-8), and the compound ( b-5) was obtained.

[Formula 60]

<Synthesis Example (b-6)>

In Scheme 2, compound (b-3-2) was replaced with 4-[[4-(2-pyridinyl)-1-piperazinyl]methyl]phenol (CAS No. 414887-31-3) Except that, it synthesize|combined in the same procedure and obtained the compound (b-6).

[Formula 61]

<Synthesis Example (b-7)>

Compound (b-7) was synthesized according to the route shown below.

[Formula 62]

2,6-bis(hydroxymethyl)-4-aminophenol was prepared according to the same procedure as described in Mameri, Samir et al., European Journal of Inorganic Chemistry (2014) 26: 4326 to 4334.

To a four-necked flask were added compound (b-7-1) (CAS No. 22100-88-5) (5.00 g, 18.9 mmol) and N,N-dimethylformamide (DMF) (45 g), and the mixture was Stirred at room temperature. Next, 2,6-bis(hydroxymethyl)-4-aminophenol (6.40 g, 37.8 mmol) was added and stirred at room temperature. Dioxane was added, solid was precipitated, the solvent was distilled off under reduced pressure from the obtained solid, and compound (b-7) was obtained.

<Synthesis Example (b-8)>

In Scheme 4, except for changing the compound (b-7-1) to 3,5-diisocyanate pyridine (CAS No. 1620557-50-7), synthesized in the same procedure to obtain the compound (b-8) got it

[Formula 63]

<Synthesis Example (b-9)>

Compound (b-9) was synthesized according to the route shown below.

[Formula 64]

In a 4-neck flask, 4-hydroxyphenylboronic acid pinacol (7.10 g, 32.3 mmol), 4,6-dibromopyrimidine (2.57 g, 10.8 mmol), potassium carbonate (4.45 g, 32.3 mmol), water ( 82 g) and 1,4-dioxane (250 ml) were added, the mixture was stirred, and the inside of the reaction system was purged with nitrogen. Next, tetrakis(triphenylphosphine)palladium (0.64 g) was added, and heating and stirring were performed at 100 degreeC overnight. After adding chloroform to the reaction solution and taking out the chloroform layer, the solvent was distilled off under reduced pressure. Methanol and water were added to the obtained concentrate to obtain a compound (b-9-1).

(b-9-1) (1.00 g, 3.78 mmol), 24% aqueous sodium hydroxide solution (2.51 g, 15.1 mmol), and pure water (2.16 g) were added to a four-neck flask, 37% under stirring at room temperature Formaldehyde aqueous solution (3.06 g, 37.8 mmol) was added dropwise to react. After heating up and stirring the reaction solution at 30-40 degreeC, a part of reaction solution was taken out, LC/MS was measured, and the end point of reaction was confirmed from the thing which the peak of the raw material lose|disappeared. After completion of the reaction, the obtained reaction mixture was neutralized with acetic acid, followed by stirring for 2 hours, and the precipitated crystals were filtered off. The solvent was distilled off under reduced pressure to obtain compound (b-9).

[Synthesis of Polymer (A)]

<Synthesis Example 1>

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

After adding NMP to this polyamic-acid solution (40g) and diluting to 6.5 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 dried under reduced pressure at 100 degreeC, and obtained polyimide powder. The imidation ratio of this polyimide was 74 %, the number average molecular weight was 12,500, and the weight average molecular weight was 38,500.

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>

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

After adding NMP to this polyamic-acid solution (40g) and diluting to 6.5 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. The imidation ratio of this polyimide was 74 %, the number average molecular weight was 13,000, and the weight average molecular weight was 39,000.

NMP is added so that solid content concentration may be 10 mass % to the obtained polyimide powder, 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 dissolves, and polyimide (PI- V-2) was obtained.

<Synthesis Example 3>

5.86 g (24.0 mmol) of DA-2, 5.46 g (16.0 mmol) of DA-10, 1.73 g (16.0 mmol) of DA-4 in a 4-neck flask equipped with a stirring device and a nitrogen inlet tube, 7.69 g (24.0 mmol) of DA-1 and 194 g of NMP were added, and it stirred, sending nitrogen, and it melt|dissolved. 17.1 g (76.4 mmol) of CA-1 is added, stirring this diamine solution, NMP is further added so that solid content concentration may be 12 mass %, it stirs at 40 degreeC for 24 hours, and polyamic-acid solution (viscosity: 549 mPa*) s) was obtained. As for the molecular weight of the polyamic acid, the number average molecular weight was 12400, and the weight average molecular weight 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. The imidation ratio of this polyimide powder was 66 %, the number average molecular weight was 11,000, and the weight average molecular weight was 28,000.

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

<Synthesis Example 4>

5.73 g (20.0 mmol) of DA-5 was weighed in the 5-L 4-necked flask with a stirring apparatus and a nitrogen introduction tube, 115 g of NMPs were added, 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, 6.01 g (40.0 mmol) of DA-3 and 6.01 g (40.0 mmol) were weighed for DA-3, 172g of NMPs were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 15.9 g (81.0 mmol) of CA-3 is added, stirring this diamine solution under water cooling, NMP is added so that solid content concentration may be 15 mass %, and s-1 is added so that it may be 1 mass % with respect to polyamic-acid solid content. And it stirred at 23 degreeC in nitrogen atmosphere for 6 hours, and obtained the solution of polyamic acid (PAA-I-4). As for the molecular weight of the polyamic acid, the number average molecular weight was 12,000, and the weight average molecular weight was 30,000.

<Synthesis Example 5>

A 500 mL four-neck flask equipped with a stirring device was used as a nitrogen atmosphere, DA-4 was 2.80 g (25.9 mmol), DA-12 was 1.54 g (6.47 mmol), NMP was 111 g, and pyridine 6.18 g as a base (78.1 mmol) was added and stirred to dissolve. Next, while stirring this diamine solution, 9.89 g (30.4 mmol) of CE-1 was added, and it was made to react at 15 degreeC overnight. 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, then, it wash|cleans 5 times with 1230 g of isopropyl alcohol (IPA), and makes it dry by making a white polya 10.2 g of mixed acid ester resin powder was obtained. The yield was 83.0%. Moreover, as for the molecular weight of this polyamic acid ester, the number average molecular weight was 20,786, and the weight average molecular weight was 40,973.

GBL was added to the obtained polyamic acid ester 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 four-neck flask equipped with a stirring device and a nitrogen inlet tube, 0.46 g (3.00 mmol) of DA-8, 3.00 g (15.0 mmol) of DA-13, 2.56 g (12.0 mmol) of DA-14, 11.0 g of NMP and 8.10 g of GBL were added, and it stirred, sending nitrogen, and it was made to melt|dissolve. 4.76 g (24.0 mmol) of CA-6 was added, stirring this diamine solution, 10.9 g of GBL was added, and it stirred at room temperature for 2 hours. Next, after adding and stirring 10.8g of GBL, 1.31g (6.01mmol) of CA-5 was added, 14.3g of GBL was added, and it stirred at room temperature for 24 hours. The viscosity in 25 degreeC of the obtained polyamic-acid solution was 2,041 mPa*s. Moreover, as for the molecular weight of a polyamic acid, the number average molecular weight was 14,200, and the weight average molecular weight was 30,110. 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 15 mass % and GBL were added to obtain a solution of polyamic acid (PAA-I-6).

<Synthesis Examples 7-11, 14-19>

Polyimides (PI-V-8) to (PI-) shown in Table 1 below by using the diamine, tetracarboxylic acid derivative, and organic solvent shown in Table 1 below, respectively, in the same procedure as in the above synthesis example. V-9), (PI-I-11) and (PI-V-19), polyamic acid (PAA-I-7), (PAA-I-10), (PAA-V-14) to (PAA- V-16) and (PAA-I-17) to (PAA-I-18) solutions were obtained. In Table 1, the numerical value in parentheses represents the compounding ratio (molar part) of each compound with respect to 100 molar parts of the total amount of the tetracarboxylic acid derivative used for the synthesis with respect to the tetracarboxylic acid component, and for the diamine component, it was used for the synthesis. The compounding ratio (molar part) of each compound with respect to 100 mol part of total amounts of diamine is shown. About the terminal modifier, the compounding ratio (molar part) with respect to 100 molar parts of the total amount of the diamine used for synthesis|combination is shown. About 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 synthesis|combination is shown.

[Synthesis of other polymers]

<Synthesis Example 12>

According to the method described in paragraph [0091] of Japanese Patent Application Laid-Open No. 2018-054761, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS) was used to obtain a reactive polyorganosiloxane polymer. Next, according to the method described in paragraph [0093] of Japanese Patent Application Laid-Open No. 2018-054761, a polymer of polyorganosiloxane represented by the following formula (P-S1) was obtained. In addition, the numerical value shows the ratio of each compound used with respect to the sum total of each silane compound used for the synthesis|combination.

[Formula 65]

<Synthesis Example 13>

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

[Formula 66]

<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) was added so that it might become 10 mass parts with respect to 100 mass parts of all polymers, and it stirred at room temperature. Next, the obtained solution was filtered with a filter having a pore size of 0.5 µm, so that the polymer component ratio was (PI-V-1): (PI-V-2) = 30: 70 (solid content conversion mass ratio), and the solvent composition ratio was NMP: BCS=60:40 (mass ratio), 4.5% of polymer solid content concentration, obtained the liquid crystal aligning agent (V1) from which the compounding ratio of a compound (b-1) becomes 10 mass parts with respect to a total of 100 mass parts of a polymer component (below Table 2). 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 1-5>

Liquid crystal aligning agents (V2) - (V11), (I12-P) - (I29-P), (I30-U) by carrying out similarly to Example 1 except having used the polymer and additive of following Tables 2-6 ) 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) and (R-V5) were obtained. In Table 2, the numerical value in parentheses shows 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 about a polymer and an additive, respectively. 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.

[Production and evaluation of liquid crystal display elements]

1-1. Fabrication of a vertically aligned liquid crystal display device

Two 40 mm x 30 mm glass substrates (length: 40 mm, width: 30 mm, thickness: 1.1 mm) with an ITO electrode were prepared, and were wash|cleaned with pure water and isopropyl alcohol. Next, liquid crystal aligning agents (V1)-(V11), (V38)-(V43) and (R-V1)-(R-V2), (R- V5) was spin-coated, respectively, and heat treatment was performed on a hot plate at 70° C. for 90 seconds and at 230° C. for 30 minutes in a thermal cycle clean oven to obtain an ITO substrate with a film having a thickness of 100 nm.

Next, the periphery was apply|coated with the sealing compound (XN-1500T by Mitsui Chemicals). Then, after turning inside the surface of the side by which the liquid crystal aligning film of the other board|substrate was formed and affixing with the previous board|substrate, the sealing material was hardened and the empty cell was produced. In the empty cell using liquid crystal aligning agent (V1) - (V2), (V5) - (V11), (V38) - (V43), and (R-V1) liquid crystal MLC-3023 (made by Merck Corporation) to the reduced pressure injection method By injecting, the liquid crystal cell was produced.

Thereafter, a DC voltage of 15 V was applied to the obtained liquid crystal cell, and in a state in which all pixel areas were driven, an ultraviolet irradiation device using a high-pressure mercury lamp as a light source was used to emit ultraviolet rays through a band pass filter having a wavelength of 365 nm. 10 J/cm<2> irradiation was carried out, 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 (made by Merck Corporation) is inject|poured into the empty cell using liquid crystal aligning agent (V3) - (V4), (R-V2), and (R-V5) by the reduced pressure injection method, and the liquid crystal display element for evaluation got 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

(i) evaluation of accumulated charge

_{A square wave of 30 Hz, 7.8 V pp} superimposed on DC 2 V was applied to the liquid crystal display device fabricated in 1-1 above at 23° C. for 72 hours, and the voltage remaining in the liquid crystal cell 1 hour after disconnecting the DC voltage (residual DC voltage) was obtained by the flicker cancellation method. When this value was less than 50 mV, it was judged as “good”, when it was greater than 50 mV and less than 150 mV was “good”, and when it was greater than 150 mV, it was judged as “bad”. The evaluation results are shown in Tables 7 to 9.

(ii) Voltage retention evaluation

1-1 above. After leaving the liquid crystal display device fabricated in an oven at 80° C. under irradiation with an LED lamp for 200 hours, it was left still at room temperature and 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 after 1000 milliseconds from application release was measured. As a measuring apparatus, the Toyo Technica make was used.

(iii) evaluation of scratch resistance

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

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

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

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

In a state where the polarization axes of the upper and lower polarizing plates of a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) were set to be 90° (Cross Nichol), the point where the scratch test was applied was observed, and whether light was transmitted was observed. For the points subjected to the scratch test, a state in which no bright spot or light leakage was observed was set to “good”, and a state in which the entire scratched spot exhibited light leakage was referred to as “bad”, and are shown in Tables 7 to 9.

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

First, a substrate to which an electrode is attached was prepared. The substrate is a glass substrate having a size of 30 mm x 50 mm and a thickness of 0.7 mm. 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, a SiN (silicon nitride) film formed as a second layer by the CVD method is formed. The film thickness of the SiN film of the second layer is 500 nm, and functions as an interlayer insulating film. On the SiN film of the 2nd layer, the comb-tooth-shaped pixel electrode formed by patterning the ITO film 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 third layer has a comb-tooth-shaped shape constituted by arranging a plurality of V-shaped electrode elements in which the central portion is bent at an inner angle of 160°. The width in the width direction of each electrode element is 3 mu m, and the interval between the electrode elements is 6 mu m. Since the pixel electrode forming each pixel is constituted by arranging a plurality of "<"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangle, but is bent in the central part like the electrode element, It has a shape similar to the “” character in bold. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has the 1st area|region above the bending|flexion part, and the 2nd area|region below.

Next, 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 It apply|coated to this board|substrate and the glass substrate which has a columnar spacer with a height of 4 micrometers in which the ITO film|membrane is formed into a film on the back surface by spin coating application|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.

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

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

2-2. Evaluation of liquid crystal display elements

(i) evaluation of accumulated charge

Using the liquid crystal cell prepared in 2-1 above, it is installed between two polarizing plates arranged so that the polarization axes are perpendicular to each other, and the pixel electrode and the counter electrode are short-circuited to have the same potential, and the LED backlight is irradiated from under the two polarizing plates. The angle of the liquid crystal cell was adjusted so that the brightness|luminance of the LED backlight transmitted light measured on two polarizing plates might become the minimum. Next, the V-T characteristic (voltage-transmittance characteristic) under 23 degreeC temperature was measured, applying the square wave of frequency 30Hz to this liquid crystal cell, and the relative transmittance computed the alternating voltage used as 23 %. Next, in the temperature of 23 degreeC, after applying the square wave of 30 Hz with the alternating voltage used as 23 % of the relative transmittance|permeability for 5 minutes, the DC voltage of +1.0V was superimposed, and it was made to drive for 30 minutes. Then, the DC voltage was cut off, and only the square wave with a frequency of 30 Hz was further applied with the alternating voltage from which a relative transmittance will be 23 % again for 30 minutes. When the relative transmittance decreased to less than 27% after 30 minutes of superimposition of DC voltage, it was defined as “good”, when it decreased from 27% to less than 29%, “good”, and when the relative transmittance was 29% or more, it was defined as “poor”. Thus, evaluation was performed.

(ii) Voltage retention evaluation

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

Next, the periphery was apply|coated with the sealing compound (XN-1500T by Mitsui Chemicals). Next, after turning the surface of the side by which the liquid crystal aligning film of the other board|substrate was formed inside and sticking with the board|substrate in front, the sealing material was hardened and the empty cell was manufactured. Liquid crystal MLC-3019 (trade name by Merck Corporation) was inject|poured 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. Then, evaluation was performed in the same procedure as (ii) of 1-2.

(iii) evaluation of scratch resistance

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

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

First, liquid crystal aligning agents (I30-U) - (I37-U), (I50-U), (R-) filtered by a filter with a hole diameter of 1.0 µm on each surface of a pair of glass substrates identical to those of 2-1 above I4-U) was applied using an inkjet coating apparatus (HIS-200, manufactured by Hitachi Plant Technology). Application|coating was performed under the conditions of 70 x 70 mm of application area, 0.423 mm of nozzle pitch, 0.5 mm of scan pitch, and application|coating speed of 40 mm/sec, and preserving from application|coating to drying for 60 seconds. Next, after drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the polyimide film with a film thickness of 100 nm was obtained. Rubbing this polyimide film with a rayon cloth (roller diameter: 120 mm, number of roller rotations: 500 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm, rubbing direction: 10° inclined with respect to the 3rd layer IZO comb electrode direction), washing was performed by ultrasonic irradiation for 1 minute in pure water to remove water droplets. Then, it dried at 80 degreeC for 15 minutes, and obtained the board|substrate with a liquid crystal aligning film. Using these two substrates with a liquid crystal aligning film as one set, the sealing agent is printed in the form that the liquid crystal injection hole is left on the substrate, and the other substrate is set so that the liquid crystal aligning film faces are facing and the rubbing direction is antiparallel and attached. Then, the sealing compound was hardened and the cell gap produced the empty cell whose cell gap is 4 micrometers. Liquid crystal MLC-7026-100 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal display element of the FFS system was obtained. Then, after heating the obtained liquid crystal display element at 120 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for evaluation of afterimage evaluation. 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

(i) evaluation of accumulated charge

Using the liquid crystal display element produced in said 3-1, except having made liquid crystal MLC-7026-100, it evaluated by the procedure similar to (i) of said 2-2.

(ii) Voltage retention evaluation

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

(iii) evaluation of scratch resistance

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

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

Two glass substrates identical to those in 1-1 are prepared, a liquid crystal aligning agent (V48-P) or (V49-P) is spin-coated on each substrate, and on a hot plate at 80°C for 90 seconds, heat circulation type It heat-processed for 40 minutes at 200 degreeC in clean oven, and a film thickness obtained the ITO board|substrate with a liquid crystal aligning film of 100 nm.

Next, the substrate is exposed to linearly polarized UV light at an angle of incidence of 40° with respect to the normal to the substrate surface. 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

(i) evaluation of accumulated charge

Using the liquid crystal display element produced in said 4-1, the procedure similar to said 1-2 (i) evaluated. The evaluation results are shown in Tables 7 to 9.

(ii) Voltage retention evaluation

Using the liquid crystal aligning film similar to said 4-1, except having made liquid crystal MLC-7067, it evaluated by the procedure similar to (ii) of said 1-2. The evaluation results are shown in Tables 7 to 9.

(iii) evaluation of scratch resistance

Using the liquid crystal aligning film similar to said 4-1, except having made liquid crystal MLC-7067, it evaluated by the procedure similar to (iii) of said 1-2. The evaluation results are shown in Tables 7 to 9.

Industrial Applicability

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

In addition, the specification of Japanese Patent Application No. 2019-044856 for which it applied on March 12, 2019, a claim, and the abstract are cited here, and it takes in as an indication of the specification of this invention.

Claims (13)

The following (A) component and (B) component are contained, The liquid crystal aligning agent characterized by the above-mentioned.
Component (A): A polymer (A) having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
(B) Component: A compound (B) having a molecular weight of 2000 or less, having a partial structure represented by the following formula (b) in the molecule, and having a basic moiety containing a nitrogen atom.

In Formula (1), 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 They are a nyl group, a C2-C10 alkynyl group which may have a substituent, a tert- butoxycarbonyl group, or a 9-fluorenyl methoxycarbonyl group.

* represents a bond, and R<_1> represents a C1-C4 alkanediyl group. m<_1> represents the integer of 1-2. The method of claim 1,
The liquid crystal aligning agent whose said X<_1> is a tetravalent organic group chosen from the group which consists of following formula (4a) - (4n), following formula (5a), and following formula (6a).

x and y are single bond, ether, carbonyl, ester, alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, sulfonyl or amide group. Z ¹ to Z ⁶ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring. j and k are 0 or 1. m is an integer of 1-5. * indicates a bond. 3. The method of claim 2,
In the polymer (A), the X ₁ is a tetravalent organic group selected from the group consisting of the formulas (4a) to (4n), (5a) and the formula (6a), and Y ₁ is a divalent organic group. At least one repeating unit (repeating unit (t)) selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) is included, and the content of the repeating unit (t) is the total The liquid crystal aligning agent which is 5 mol% or more with respect to the total repetition unit of a polymer (A). 4. The method according to any one of claims 1 to 3,
In the polymer (A), X ₁ is a tetravalent organic group and Y ₁ is a divalent diamine derived from a diamine having at least one selected from the group consisting of a nitrogen-containing heterocyclic ring, a diphenylamine structure and a triphenylamine structure. contains at least one repeating unit selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), which is an organic group, wherein the content of the one or more repeating units is a polymer (A) The liquid crystal aligning agent which is 5 mol% or more with respect to the total repetition unit. 5. The method according to any one of claims 1 to 4,
The polymer (A) is, X ₁ is a tetravalent organic group, and, Y ₁ repeats represented by the divalent organic group the formula (1) derived from a diamine represented by the following formula (V1) ~ (V3), the unit and the formula (2) contains at least one repeating unit (repeating unit (a)) selected from the group consisting of repeating units represented by It is 1 mol% or more with respect to the liquid crystal aligning agent.

X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, -O -(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m -OCO- is represented.
X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -. Among these, a plurality of a1 is each independently an integer of 1 to 15, a plurality of A ₁ each independently represents an oxygen atom or -COO-, and m ₁ is 1-2. X ³ represents a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO-, or -OCO-. X ⁴ represents -CONH-, -NHCO-, -O-, -COO- or -OCO-.
G ₁ and G ₂ each independently represent a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. do. k represents 0 or 1, m and n are each independently an integer of 0-3, and the sum total of m and n is 1-4.
R<^1> represents a C1-C20 alkyl group, a C1-C20 alkoxy group, or a C2-C20 alkoxyalkyl group. Optional hydrogens forming R ¹ may be substituted with fluorine.
R<^2> represents a C1-C20 alkyl group or a C2-C20 alkoxyalkyl group, and ^{arbitrary hydrogen which forms R<2>} may be substituted by fluorine. R ³ represents a structure having a steroid skeleton. 6. The method according to any one of claims 1 to 5,
In the polymer (A), X ₁ is a tetravalent organic group, Y ₁ is p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4 '-diaminoazobenzene, 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, diamine represented by the following formula (H) and the following formulas (H2) to (H3) A repeating unit selected from the group consisting of a repeating unit represented by the formula (1), which is a divalent organic group derived from a diamine selected from the group consisting of diamines represented by ) is included, and content of a repeating unit (c) is 5 mol% or more with respect to the total repeating unit of a polymer (A) in total, The liquid crystal aligning agent.

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

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

In the formula, two X's are each independently -O-, -COO-, -NHCO-, -C(=O)-, or -(CH ₂ ) _n - (n is an integer of 1 to 12) represents, L ₁ and L ₂ are each independently a single bond, -O-, or -COO-, R is -CH ₂ -, or -(CH ₂ ) _n - (n is an integer of 2 to 12) ), or the - (CH _{2) n} - any of the CH ₂ represents an oxygen atoms. Any hydrogen atom on the benzene ring may be substituted with a monovalent organic group. 7. The method according to any one of claims 1 to 6,
The above formula, wherein the polymer (A) is a divalent organic group derived from a diamine selected from the group consisting of a diamine having a radical initiation function and a diamine having a photopolymerizable group at the terminal _{, in which X 1} is a tetravalent organic group and Y _{1 is a divalent organic group} At least one repeating unit (repeating unit (b)) selected from the group consisting of the repeating unit represented by (1) and the repeating unit represented by the formula (2) is included, and the content of the repeating unit (b) is the total , The liquid crystal aligning agent which is 1 mol% or more with respect to the total repetition unit of a polymer (A). 8. The method according to claim 5 or 7,
The polymer (A) contains the repeating unit (a) defined in claim 5 and the repeating unit (b) defined in claim 7, and the upper limit of the content of the repeating unit (a) and the repeating unit (b) is The liquid crystal aligning agent which is 99 mol% or less with respect to the total repetition unit of a polymer (A), respectively. 9. The method according to any one of claims 1 to 8,
The said liquid crystal aligning agent contains polyorganosiloxane further, The said polyorganosiloxane has at least any one of an oxetanyl group and an oxiranyl group, The liquid crystal aligning agent. 10. The method according to any one of claims 1 to 9,
The liquid crystal aligning agent in which the said (A) component consists of two or more types of polymers (A). 11. The method according to any one of claims 1 to 10,
The liquid crystal aligning agent whose content of the said compound (B) is 0.1-40 mass parts per 100 mass parts of (A) component. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-11. A liquid crystal display element provided with the liquid crystal aligning film of Claim 12.