KR20220092375A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal device - Google Patents

Abstract

Provided is a liquid crystal alignment agent with which a liquid crystal element having excellent liquid crystal alignment properties and a high voltage holding rate and hardly generating an afterimage can be obtained, and which can form a liquid crystal alignment membrane having high membrane strength and excellent rework properties and adhesion. A liquid crystal alignment agent contains a polymer [P] having, at a principal chain end, a partial structure (A) represented by formula (1) or formula (2). In the formula (1) or formula (2), R^1 and R^5 are a univalent organic group desorbed with at least one of heat and light. R^2 is a univalent organic group. (i) R^6 is a univalent organic group and R^7 is a bivalent alicyclic group, or (ii) R^6 and R^7 represent a ring structure constituted together with a nitrogen atom that R^6 and R^7 are bonded to.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID CRYSTAL DEVICE}

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal element.

BACKGROUND ART A liquid crystal element is applied to a wide range of applications from a relatively large display device such as a liquid crystal TV or an information display to a small display device such as a smart phone. The performance of a liquid crystal element is determined by various characteristics, such as the orientation of a liquid crystal, the magnitude|size of a pretilt angle, and voltage retention. In order to improve the performance of a liquid crystal element, improvement of the liquid crystal aligning film for aligning a liquid crystal in a fixed direction is performed conventionally other than improvement of a liquid crystal material (for example, refer patent document 1 and patent document 2).

Patent Document 1 discloses that a liquid crystal aligning film is formed using a polyimide precursor and polyimide having a structure in which an amino group bonded to a methylene group is protected by a tert-butoxycarbonyl group (Boc group) in a polymer side chain. Further, Patent Document 2 discloses that polyamic acid after polymerization is reacted with di-tert-butyl dicarbonate to introduce a Boc group into the main chain terminal of polyamic acid, and a liquid crystal aligning film is formed using this polymer.

International Publication No. 2010/050523 International Publication No. 2019/022215

In recent years, with the high definition of a liquid crystal element, the request|requirement for quality is becoming more strict. In order to satisfy such a request|requirement, it is calculated|required by a liquid crystal element to further improve liquid-crystal orientation, voltage retention, and afterimage characteristic (hardiness to produce an afterimage). In addition, in consideration of application of the rubbing method, improvement of liquid crystal alignment property and voltage retention rate, suppression of yield reduction, etc., it is required that the organic film formed using the liquid crystal aligning agent have sufficiently high strength.

In a liquid crystal display device, in order to secure a display area as large as possible, after forming a liquid crystal aligning film on the entire substrate surface, a sealing material is applied on the liquid crystal aligning film and a method of bonding the substrates together is adopted to soften the liquid crystal panel (狹額緣化) is being done. Such a structure WHEREIN: A force is easy to apply to the liquid crystal aligning film part which has arrange|positioned a sealing material, and when the adhesiveness to the board|substrate of a liquid crystal aligning film is not favorable, peeling of a liquid crystal aligning film becomes easy to generate|occur|produce in a sealing material part, and reliability of a liquid crystal element It is concerned about this decrease.

In the manufacturing process of a liquid crystal aligning film, defects, such as a pinhole and a coating-film nonuniformity, may generate|occur|produce in the liquid crystal aligning film formed on the board|substrate, peeling a liquid crystal aligning film from a board|substrate, and recycling (rework) a board|substrate is performed frequently. In the case of such rework, it is calculated|required that a coating film can be peeled easily from a board|substrate (namely, rework property is favorable).

However, it is difficult to make it satisfy|fill these some characteristics simultaneously, and there exists room for further improvement in a liquid crystal aligning agent.

This invention is made|formed in view of the said subject, While liquid-crystal orientation is favorable, voltage retention is high, and the liquid crystal element which an afterimage does not produce easily can be obtained, film strength is high, and rework property and adhesiveness are favorable liquid crystal aligning film Its main purpose is to provide a liquid crystal aligning agent capable of forming

MEANS TO SOLVE THE PROBLEM The present inventors earnestly studied in order to solve the said subject, discovered that the said subject could be solved by using the polymer which has a specific structure at the main chain terminal, and came to complete this invention. Specifically, the present invention provides the following means.

<1> 　 Liquid crystal aligning agent containing polymer [P] which has partial structure (A) represented by following formula (1) or Formula (2) in a principal chain terminal.

(In formula (1), R ¹ is a monovalent organic group that is detached by at least one of heat and light. R ² is a monovalent organic group. R ³ and R ⁴ are each independently a hydrogen atom. or a monovalent organic group, "*" represents a bond.

In formula (2), R ⁵ is a monovalent organic group which is detached by at least one of heat and light. R ⁶ and R ⁷ satisfy the following (i) or (ii).

(i) R ⁶ is a monovalent organic group. R ⁷ is a divalent alicyclic group.

(ii) R ⁶ and R ⁷ represent a ring structure constituted together with the nitrogen atom to which R ⁶ and R ⁷ are bonded.

"*" indicates that it is a bond.)

<2> 　 In the presence of a monoamine compound having a partial structure (A) represented by the formula (1) or (2), tetracarboxylic acid dianhydride, tetracarboxylic acid dianhydride and tetracarboxylic acid diester dihalide The liquid crystal aligning agent containing the polymer [P] obtained by superposing|polymerizing the monomer containing the at least 1 sort(s) of acid derivative chosen from the group which consists of, and a diamine compound, or by making it react with the said monoamine compound after superposing|polymerizing the said monomer.

<3> 　 A liquid crystal aligning film formed using the liquid crystal aligning agent of <1> or <2>.

<4> 　 A liquid crystal element provided with the liquid crystal aligning film of said <3>.

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, liquid-crystal orientation is favorable, a voltage retention is high, and the liquid crystal element which an afterimage does not produce easily can be obtained. Moreover, film strength is high and a liquid crystal aligning film with favorable rework property and adhesiveness can be formed.

(Form for implementing the invention)

《Liquid crystal aligning agent》

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

In addition, in this specification, a "hydrocarbon group" is a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain. However, saturated or unsaturated may be sufficient. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are also included. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be constituted by only the aromatic ring structure, and a chain structure or a structure of an alicyclic hydrocarbon may be included in a part thereof. An "aromatic ring" is a meaning including an aromatic hydrocarbon ring and an aromatic heterocyclic ring. An "organic group" refers to an atomic group formed by removing arbitrary hydrogen atoms from a carbon-containing compound (that is, an organic compound).

The liquid crystal aligning agent of this indication contains the polymer [P] which has in the principal chain terminal the partial structure (henceforth "partial structure (A)") represented by following formula (1) or Formula (2).

(In formula (1), R ¹ is a monovalent organic group that is detached by at least one of heat and light. R ² is a monovalent organic group. R ³ and R ⁴ are each independently a hydrogen atom. or a monovalent organic group, "*" represents a bond.

In formula (2), R ⁵ is a monovalent organic group which is detached by at least one of heat and light. R ⁶ and R ⁷ satisfy the following (i) or (ii).

(i) R ⁶ is a monovalent organic group. R ⁷ is a divalent alicyclic group.

(ii) R ⁶ and R ⁷ represent a ring structure constituted together with the nitrogen atom to which R ⁶ and R ⁷ are bonded.

"*" indicates that it is a bond.)

<Polymer [P]>

・About partial structure (A)

In the formulas (1) and (2), the monovalent organic group represented by R ¹ and R ⁵ is preferably a group (hereinafter, also referred to as a “thermal leaving group”) which is removed by heat and substituted with a hydrogen atom. When the monovalent organic group represented by R ¹ and R ⁵ is a thermal leaving group, it is preferable that the group represented by R ¹ , R ⁵ is detached by heating (post-baking) during film formation and can be replaced with a hydrogen atom. In this case, it is suitable at the point which can introduce|transduce a partial structure (A) into the main chain terminal of a polymer, aiming at the simplification of a process.

Specific examples of the thermal leaving group include, for example, a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethylpropynyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, and an allyloxy group. Carbonyl group, vinyloxycarbonyl group, cyclohexyloxycarbonyl group, methylcyclohexyloxycarbonyl group, 2-(trimethylsilyl)ethoxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloro An ethoxycarbonyl group, a phthaloyl group, p-toluenesulfonyl group, 2-nitrobenzenesulfonyl group, etc. are mentioned. Among these, from the viewpoint of detachment by heating during film formation, the thermal detachable group represented by R ¹ , R ⁵ is preferably a group desorbing at a temperature of 130 to 250°C. Specifically, a tert-butoxycarbonyl group and a 9-fluorenylmethyloxycarbonyl group are preferable, and they are excellent in heat release property, and the residual amount in the film of the detached structure can be reduced. , a tert-butoxycarbonyl group (Boc group) is particularly preferred.

The monovalent organic group represented by R ⁶ when R ⁶ and R ⁷ in the formula (2) satisfy the above (i), and the monovalent organic group represented by R ² in the formula (1), having 1 carbon atom -O-, -S-, -CO-, -COO-, -NR ^8a -, -CO-NR ^8a -, -NR ^8a between the carbon-carbon bonds of the above monovalent chain hydrocarbon group and the chain hydrocarbon group having 2 or more carbon atoms It is preferable that it is a monovalent group having -CO-O- or -NR ^8a -CO-NR ^9a - (provided that R ^8a and R ^9a are each independently a hydrogen atom or a monovalent organic group. The same applies hereinafter). The monovalent organic group of R ^8a and R ^9a is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent thermal leaving group, and more preferably an alkyl group or Boc group having 1 to 3 carbon atoms.

In addition, -COO-, -CO-NR ^8a -, -NR ^8a -CO-O- and -NR ^8a -CO-NR ^9a - do not specify the direction of bonding. Therefore, for example, when R ² in the formula (1) is a monovalent group having -COO- between the carbon-carbon bonds of a chain hydrocarbon group having 2 or more carbon atoms, -COO- is ) may be arranged on the nitrogen atom side, or -O- may be arranged on the nitrogen atom side in Formula (1).

As the monovalent organic group represented by R ⁶ when R ⁶ and R ⁷ in the formula (2) satisfy the above (i), and the monovalent organic group represented by R ² in the formula (1), the above formula From the viewpoint of increasing the reactivity of the nitrogen atom in (1), among them, an alkyl group having 1 to 5 carbon atoms or a monovalent group having -O- between the carbon-carbon bonds of the alkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms. , or an alkoxyalkyl group having 1 to 3 carbon atoms is more preferable.

Examples of the monovalent organic group represented by R ³ and R ⁴ in the formula (1) include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, and a monovalent aromatic group having 6 to 12 carbon atoms. Any methylene group of a hydrocarbon group or a chain hydrocarbon group having 2 or more carbon atoms is -O-, -S-, -CO-, -COO-, -NR ^8a -, -CO-NR ^8a -, -NR ^8a -CO-O- or a monovalent group formed by being substituted with -NR ^8a -CO-NR ⁹ -. Among these, it is preferable that it is a C1-C5 alkyl group or an alkoxy group, and, as for the monovalent organic group represented by R< ³ > and R< ⁴ >, it is more preferable that they are a C1-C3 alkyl group or an alkoxy group.

R ³ and R ⁴ in the formula (1) increase the reactivity of the nitrogen atom in the formula (1), and from the viewpoint of further improving the liquid crystal orientation, voltage retention, residual image characteristics, and mechanical strength of the film, hydrogen, among them It is preferably an atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

When R ⁶ and R ⁷ in the formula (2) satisfy the above (i), the divalent alicyclic group represented by R ⁷ includes, for example, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, Or a divalent group etc. which have substituents, such as a methyl group, an ethyl group, and a methoxy group, are mentioned in the ring of these groups.

When R ⁶ and R ⁷ in the formula (2) satisfy the above (ii), as a ring structure constituted together with the nitrogen atom to which R ⁶ and R ⁷ are bonded, a pyrrolidine ring, a piperidine ring, or a hexamethyleneimine ring , or groups in which two hydrogen atoms (a hydrogen atom bonded to a nitrogen atom and a hydrogen atom bonded to a carbon atom) have been removed from the ring moiety in a ring having a substituent such as a methyl group, an ethyl group, or a methoxy group in their ring; can

As a specific example of a partial structure (A), the structure etc. which are represented by each of following formula (A-1) - Formula (A-15) are mentioned, for example.

(In the formula, TMS represents a trimethylsilyl group. "*" represents a bond.)

It is preferable that partial structure (A) is a partial structure represented by said Formula (1) especially at the point with the high improvement effect of liquid-crystal orientation, voltage retention, and an afterimage characteristic, R ³ and R in said Formula (1) A partial structure in which a ^tetravalent hydrogen atom is more preferable. The number of partial structures (A) which the polymer [P] has may be one, and two or more may be sufficient as it. The number of partial structures (A) which the polymer [P] has is preferably 1 or 2 pieces.

・About polymer [P]

The main chain of the polymer [P] is not particularly limited. From the viewpoint that affinity with liquid crystal and mechanical strength is high, and a highly reliable liquid crystal aligning film can be formed, and the improvement effect of various characteristics by introduce|transducing a partial structure (A) into the main chain terminal is high, polymer [P ] is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

When the polymer [P] is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, the polymer [P] is, for example, tetracarboxylic dianhydride, tetracarboxylic dianhydride, and tetracarbon It can be obtained by a method including the process of superposing|polymerizing the monomer containing at least 1 sort(s) of acid derivative selected from the group which consists of acid diester dihalides, and a diamine compound.

(polyamic acid)

When the polymer [P] is polyamic acid, as a method for producing the polyamic acid (hereinafter also referred to as "polyamic acid [P]"), the partial structure (A) may be introduced at the end of the main chain, and there is no particular limitation. . Here, the "main chain" of a polymer refers to the part of the "stem" which consists of the chain of the longest atom in a polymer. In addition, it is permissible for the part of this "stem" to contain a ring structure. The "side chain" of a polymer means the part branched from the "stem" of a polymer.

In order to introduce the partial structure (A) into the main chain terminal of the polyamic acid, as a terminal blocker for stopping the polymerization reaction during or after the polymerization reaction, a compound having the partial structure (A) (hereinafter, "Compound [A] ') can be used. Specifically, the following methods [1] and [2] are mentioned.

[1] A method of polymerizing a monomer comprising tetracarboxylic dianhydride and a diamine compound in the presence of compound [A].

[2] A method in which a polymer obtained by polymerization is reacted with a compound [A] after polymerization of a monomer containing tetracarboxylic dianhydride and a diamine compound.

As a manufacturing method of polyamic acid [P], among these, the method of said [1] is preferable. According to the method of the above [1], the polymer terminal (more specifically, a structural unit derived from tetracarboxylic dianhydride) reacts with the compound [A] during the polymerization reaction to form the compound [A] as the polyamic acid [P]. A polymer having a structural unit derived from ] at the end of the main chain can be obtained. For this reason, the step for introducing the partial structure (A) into the end of the main chain of the polyamic acid does not need to be formed separately from the polymerization step, which is suitable in that the manufacturing process can be simplified.

(tetracarboxylic acid dianhydride)

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid [P], aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, 1,2,3,4-butanetetracarboxylic dianhydride, ethylenediamine tetraacetic acid dianhydride, etc. are used as aliphatic tetracarboxylic dianhydride; As alicyclic tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3 ,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan- 1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1 ,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride et al., 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-2 anhydride; As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-carbonyldiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, etc.; In addition to those mentioned respectively, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. As tetracarboxylic dianhydride, 1 type can be used individually or in combination of 2 or more types.

The tetracarboxylic dianhydride used for the synthesis of polyamic acid [P] is highly soluble, and a liquid crystal aligning film exhibiting good liquid crystal alignment and electrical properties can be obtained, so aliphatic tetracarboxylic dianhydride and alicyclic tetracarbon It is preferable that at least 1 sort(s) chosen from the group which consists of acid dianhydrides is included, and it is more preferable that alicyclic tetracarboxylic dianhydride is included. The proportion of alicyclic tetracarboxylic dianhydride used is preferably 20 mol% or more, more preferably 40 mol% or more, with respect to the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid [P], It is more preferable that it is 50 mol% or more.

(diamine compound)

As a diamine compound used for the synthesis|combination of polyamic acid [P], an aliphatic diamine, an alicyclic diamine, an aromatic diamine, diaminoorganosiloxane, etc. are mentioned.

Specific examples of the diamine compound include metaxylylenediamine, hexamethylenediamine, and the like as aliphatic diamine; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and the like; As aromatic diamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diamino Azobenzene, 3,5-diaminobenzoic acid, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy) Propane, 1,6-bis(4-aminophenoxy)hexane, 6,6'-(pentamethylenedioxy)bis(3-aminopyridine), N,N'-di(5-amino-2-pyridyl) )-N,N'-di(tert-butoxycarbonyl)ethylenediamine, bis[2-(4-aminophenyl)ethyl]hexane diacid, 4,4'-diaminodiphenyl ether, 4,4' -diaminodiphenylamine, 4,4'-diaminodiphenethylurea, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoro lopropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-(phenylenediisopropylidene)bisaniline, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-dia Minocarbazole, 3,6-diaminoacridine, a monomer containing a diphenylamine structure (eg, N4,N4'-bis(4-aminophenyl)-N4,N4'-dimethylbenzidine, etc.), N,N '-bis(5-aminopyridin-2-yl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, the following formula (D-1)

(In formula (D-1), R ¹¹ and R ¹² are each independently an alkanediyl group. R ¹³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a protecting group. n1 is an integer of 1 to 3 When n1 is 2 or 3, a plurality of R ¹² are the same or different from each other, and a plurality of R ¹³ are the same or different from each other.)

Main chain type diamines, such as a compound represented by;

Hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, chole Steryloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 ,5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid lanostanyl, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane , 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, *-COO-, or *-OCO- (where "*" is a bond with the diaminophenyl group side) R ^I is an alkanediyl group having 1 to 3 carbon atoms R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms R ^III is an alkyl group having 1 to 20 carbon atoms, alkoxy group, fluorine a roalkyl group or a fluoroalkoxy group, a is 0 or 1. b is an integer from 0 to 3. c is an integer from 0 to 2. d is 0 or 1, provided that 1≤a+b+c≤3 .)

side-chain diamines such as compounds represented by

Examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and the like.

As a compound represented by said Formula (D-1), the compound etc. which are represented by each of following formula (D-1-1) - Formula (D-1-3) are mentioned, for example. As a compound represented by said Formula (E-1), the compound etc. which are represented by each of following formula (E-1-1) - Formula (E-1-4) are mentioned, for example. In manufacture of polyamic acid [P], as a diamine compound, 1 type can be used individually or in combination of 2 or more type. In the structural formula, "Boc" represents a tert-butoxycarbonyl group (the same applies below).

(Compound [A])

Compound [A] is a compound which has a partial structure (A), For example, an acid monohydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned. Among these, it is preferable that it is preferable that it is a monoamine compound, and, as for compound [A], it is preferable that it is a compound specifically, represented by following formula (3).

(In Formula (3), A ¹ is a monovalent group having a partial structure represented by Formula (1) or Formula (2). R ⁸ is a single bond, -O-, -S-, -CO- , -COO-, -NR ¹⁰ -, -CO-NR ¹⁰ -, -NR ¹⁰ -CO-O-, -NR ¹⁰ -CO-NR ¹¹ -, divalent chain hydrocarbon group having 1 or more carbon atoms, divalent chain hydrocarbon group having 3 or more carbon atoms Any methylene group of an alicyclic hydrocarbon group or a divalent chain hydrocarbon group having 2 or more carbon atoms is -O-, -S-, -CO-, -COO-, -NR ¹⁰ -, -CO-NR ¹⁰ -, -NR ¹⁰ -CO-O- or -NR ¹⁰ -CO-NR ¹¹ - is a substituted divalent group. R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a monovalent organic group. R ⁹ is a single bond or (m+1) is a valent aromatic ring group, m is 1 or 2. However, when R ⁹ is a single bond, m is 1, and R ⁸ is a single bond or a hydrocarbon group, which is a primary in formula (3). It is bonded to an amino group. When m is 2, a plurality of R ^8s are the same or different, and a plurality of A ^1s are the same or different.)

In the formula (3), A ¹ is a monovalent group represented by the formula (1) or (2). About the specific example and preferable example of said Formula (1) and Formula (2), the above-mentioned description can be invoked. Specific examples of the monovalent group represented by A ¹ include groups represented by each of the formulas (A-1) to (A-15).

When R ⁸ is a divalent chain hydrocarbon group having 1 or more carbon atoms, the chain hydrocarbon group is preferably an alkanediyl group, more preferably a linear alkanediyl group, from the viewpoint of increasing the reactivity with a crosslinking agent described later. When R ⁸ is a divalent chain hydrocarbon group, the number of carbon atoms in the chain hydrocarbon group is excellent in film adhesion, while improving film strength (and further improving rubbing resistance), high voltage retention of liquid crystal elements, liquid crystal alignment and residual image From a viewpoint of satisfying a characteristic, 7 or less are preferable, 5 or less are more preferable, and 3 or less are still more preferable.

R ⁸ is any methylene group that the chain hydrocarbon group has -O-, -S-, -CO-, -COO-, -NR ¹⁰ -, -CO-NR ¹⁰ -, -NR ¹⁰ -CO-O- or - In the case of a divalent group substituted with NR ¹⁰ -CO-NR ¹¹ -, the above description is incorporated for specific examples and preferred examples of the chain hydrocarbon group. When R ¹⁰ and R ¹¹ are a monovalent organic group, examples of the monovalent organic group include a monovalent hydrocarbon group having 1 to 10 carbon atoms and a thermal leaving group. Among them, R ¹⁰ and R ¹¹ are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a thermal leaving group, and more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or tert-butoxycarbonyl group.

When R ⁸ is a divalent alicyclic hydrocarbon group having 3 or more carbon atoms, examples of the alicyclic hydrocarbon group include 1,4-cyclohexanediyl group, 2-methyl-1,4-cyclohexanediyl group, 2,5 -Dimethyl-1,4-cyclohexanediyl group, etc. are mentioned.

R ⁸ is, among the above, a single bond, -O-, -S-, -CO from the viewpoint of increasing the reactivity with the crosslinking agent (more specifically, compound [B]) and obtaining a liquid crystal element excellent in voltage retention and liquid crystal orientation -, -COO-, a C1-7 alkanediyl group, or an arbitrary methylene group of an alkanediyl group having 2 or more carbon atoms is preferably a divalent group having 1-7 carbon atoms in which it is substituted with -O- or -S- .

In addition, -COO-, -CO-NR ¹⁰ -, -NR ¹⁰ -CO-O- and -NR ¹⁰ -CO-NR ¹¹ - do not specify the direction of the bond. Therefore, for example, when R ⁸ in the formula (3) is -COO-, -COO- may be bonded to A 1 in the formula (3), and -CO- may be bonded to A ¹ in the formula (3), and -O- is the formula (3). ), you may couple|bond with ^A1 in.

When R ⁹ is a (m+1) valent aromatic ring group, examples of the aromatic ring group include an (m+1) valent aromatic hydrocarbon group and (m+1) valent aromatic heterocyclic group. Among these, a (m+1) valent aromatic hydrocarbon group and a (m+1) valent nitrogen-containing aromatic heterocyclic group are preferable. R ⁹ may have a substituent in the aromatic ring moiety. The substituent is preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom.

Specific examples in the case where R ⁹ is an aromatic ring group having a valence of (m+1) include an arbitrary hydrogen atom bonded to a carbon atom constituting the ring of a benzene ring, a biphenyl ring, a naphthalene ring or an anthracene ring as an aromatic hydrocarbon group having a valence of (m+1). a group formed by removing (m+1) pieces; (m+1) valent nitrogen-containing aromatic heterocyclic group, a group formed by removing (m+1) arbitrary hydrogen atoms bonded to carbon atoms constituting the pyridine ring, pyrimidine ring, pyridazine ring or pyrazine ring ring; can When R ⁹ is an aromatic ring group having a valence of (m+1), R ⁹ is preferably a group in which (m+1) hydrogen atoms have been removed from a substituted or unsubstituted benzene ring or pyridine ring.

As a compound [A], especially when A< ¹ > is group represented by said formula (1) among these, R< ⁸ > is a single bond, -O-, -S-, -CO-, -COO-, C1-C7 is a divalent group having 1 to 7 carbon atoms in which an alkanediyl group or an arbitrary methylene group of an alkanediyl group having 2 or more carbon atoms is substituted with -O- or -S-, and R ⁹ is a single bond or (m+1) When the compound which is an aromatic ring group, and A< ¹ > is group represented by said Formula (2), the compound whose R<^8> and R<^9> is a single bond can be used preferably.

Specific examples of the compound [A] include compounds represented by each of the following formulas (CA-1) to (CA-29). In addition, as a compound [A], you may use individually by 1 type, and may use it in combination of 2 or more type.

(Wherein, k, k1, and k2 are each independently an integer of 0 to 7.)

(Synthesis of polyamic acid)

The synthesis reaction of polyamic acid [P] is preferably carried out in an organic solvent. In the synthesis reaction of polyamic acid [P], the use ratio of tetracarboxylic dianhydride and diamine compound is a ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents with respect to 1 equivalent of the amino group of the diamine compound. This is preferable.

In the above synthesis reaction, the ratio of compound [A] used is the diamine compound and compound used for synthesis from the viewpoint of obtaining a polymer within a suitable molecular weight range while introducing the structural unit derived from compound [A] into the main chain terminal of the polymer. It is preferable to set it as 1 mol% or more with respect to the total amount with [A], It is more preferable to set it as 2 mol% or more, It is more preferable to set it as 5 mol% or more. Moreover, it is preferable to set it as 30 mol% or less with respect to the total amount of the diamine compound and compound [A] used for synthesis, and, as for the usage rate of compound [A], it is more preferable to set it as 20 mol% or less, and 15 mol % or less is more preferable.

Moreover, at the time of the said synthesis reaction, you may use the compound which does not have a partial structure (A) with compound [A] as a terminal blocker. Examples of the compound include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; Monoisocyanate compounds, such as phenyl isocyanate and naphthyl isocyanate, etc. are mentioned. However, the use ratio of these compounds is preferably 10 mol% or less, more preferably 5 mol% or less, and 1 mol% or less with respect to the total amount of the terminal blocker used in the synthesis reaction. It is more preferable to

In the synthesis reaction of polyamic acid [P], the reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 to 24 hours. Examples of the organic solvent used for the reaction include an aprotic polar solvent, a phenol solvent, an alcohol solvent, a ketone solvent, an ester solvent, an ether solvent, a halogenated hydrocarbon, and a hydrocarbon. Among these, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotriamide, At least one selected from the group consisting of m-cresol, xylenol, and halogenated phenol is used as the reaction solvent, or at least one of these and another organic solvent (eg, butyl cellosolve, diethylene glycol di It is preferable to use a mixture with ethyl ether, etc.). It is preferable that the usage-amount of an organic solvent sets it as the quantity used as 0.1-50 mass % with respect to the total amount of tetracarboxylic dianhydride, a diamine compound, and compound [A] with respect to the total amount of a reaction solution.

As described above, a polymer solution obtained by dissolving polyamic acid [P] is obtained. You may use this polymer solution for preparation of a liquid crystal aligning agent as it is, and after isolating polyamic acid [P] contained in a polymer solution, you may provide for preparation of a liquid crystal aligning agent.

・Polyamic acid ester

When the polymer [P] is a polyamic acid ester, the polyamic acid ester (hereinafter also referred to as “polyamic acid ester [P]”) is, for example, [I] a method of reacting polyamic acid [P] with an esterifying agent; [II] A method of reacting compound [A] together with a tetracarboxylic acid diester and a diamine compound or after polymerization of a tetracarboxylic acid diester and a diamine compound, [III] A tetracarboxylic acid diester dihalide and diamine It can be obtained by the method of reacting compound [A] together with a compound or after polymerization of a tetracarboxylic-acid diester dihalide and a diamine compound, etc. The polyamic acid ester [P] may have only a amic acid ester structure, or may be a partial esterified product in which the amic acid structure and the amic acid ester structure coexist. The reaction solution formed by dissolving polyamic acid ester [P] may be used for preparation of a liquid crystal aligning agent as it is, and after isolating polyamic acid ester [P] contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

・Polyimide

When the polymer [P] is a polyimide, the polyimide (hereinafter also referred to as “polyimide [P]”) can be obtained, for example, by imidizing the polyamic acid [P] synthesized as described above by dehydration and ring closure. have. The polyimide [P] may be a complete imidized product in which the entire amic acid structure of polyamic acid [P], which is its precursor, has been cyclized by dehydration, or only a part of the amic acid structure is cyclized by dehydration so that the amic acid structure and the imide ring structure coexist. Partial imide storage is fine. It is preferable that the imidation ratio is 20 to 99 %, and, as for polyimide [P], it is more preferable that it is 30 to 90 %. In addition, the imidation ratio represents the ratio which the number of imide ring structures occupies with respect to the sum total of the number of the male acid structures of a polyimide, and the number of imide ring structures, in percentage. Here, an isoimide ring may be sufficient as a part of an imide ring.

The dehydration ring closure of the polyamic acid [P] is preferably performed by dissolving the polyamic acid [P] in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary. In this method, as a dehydrating agent, acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, can be used, for example. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles with respect to 1 mole of the amic acid structure of the polyamic acid [P]. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst to be used is preferably 0.01 to 10 moles with respect to 1 mole of the dehydrating agent to be used. Examples of the organic solvent used for the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid [P]. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180°C. The reaction time is preferably 1.0 to 120 hours. Moreover, the reaction solution containing polyimide [P] may be used for preparation of a liquid crystal aligning agent as it is, and after isolating polyimide [P], you may provide for preparation of a liquid crystal aligning agent.

The solution viscosity of the polymer [P] preferably has a solution viscosity of 10-800 mPa·s, more preferably 15-500 mPa·s, when a solution having a concentration of 10% by mass is used. In addition, the solution viscosity (mPa·s) is a polymer solution having a concentration of 10% by mass prepared using a good solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer [P]. About , it is the value measured in 25 degreeC using the E-type rotational viscometer.

The weight average molecular weight (Mw) of the polymer [P] in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Moreover, the molecular weight distribution (Mw/Mn) represented by ratio of Mw and the number average molecular weight (Mn) of polystyrene conversion measured by GPC becomes like this. Preferably it is 7 or less, More preferably, it is 5 or less. In addition, at the time of preparation of a liquid crystal aligning agent, as polymer [P], you may use individually by 1 type, and may use it in combination of 2 or more type.

<Other ingredients>

A liquid crystal aligning agent may contain the component (it is also called "other components" hereafter) different from the polymer [P] as needed other than a polymer [P].

・Polymer [Q]

The liquid crystal aligning agent of this indication may further contain the polymer (henceforth "polymer [Q]") which does not have a partial structure (A) as a polymer component. The main skeleton of the polymer [Q] is not particularly limited. Examples of the polymer [Q] include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyenamine, polyurea, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxa. A sol, a cellulose derivative, polyacetal, a (meth)acrylic-type polymer, a styrene-type polymer, a maleimide-type polymer, a styrene-maleimide-type copolymer, etc. are mentioned. From the viewpoint of obtaining a highly reliable liquid crystal device, the polymer [Q] is a structural unit derived from, among these, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and a monomer having a polymerizable unsaturated carbon-carbon bond. At least one selected from the group consisting of a polymer comprising Examples of the polymer containing a structural unit derived from a monomer having a polymerizable unsaturated carbon-carbon bond include a (meth)acrylic polymer, a styrene polymer, a maleimide polymer, and a styrene-maleimide copolymer.

When making a liquid crystal aligning agent contain a polymer [Q], 1 mass % or more is preferable with respect to the total amount of a polymer [P] and a polymer [Q], and, as for the content rate of a polymer [Q], 2 mass % or more is more desirable. Moreover, 95 mass % or less is preferable with respect to the total amount of polymer [P] and polymer [Q], and, as for the content rate of polymer [Q], 90 mass % or less is more preferable. As polymer [Q], 1 type can be used individually or in combination of 2 or more type.

・Crosslinking agent

The liquid crystal aligning agent of this indication may contain the crosslinking agent further. As the crosslinking agent, a compound having a functional group capable of reacting with an amino group (hereinafter also referred to as a “crosslinking group”) can be preferably used. As a preferable specific example of the crosslinking agent contained in the liquid crystal aligning agent of this indication, as a crosslinkable group, the group which has a polymerizable carbon-carbon bond, a cyclic ether group, a cyclic thioether group, an isocyanate group, a protected isocyanate group, a methylol group, protection methylol group, cyclic carbonate group, group "-CR ²⁰ =CR ²¹ -R ²² -" (provided that R ²⁰ is a monovalent organic group that is removed by reaction with an amino group. R ²¹ is a hydrogen atom or an alkyl group; and R ²² is an electron withdrawing group.), a silanol group, and a compound having at least one group selected from the group consisting of an alkoxysilyl group (hereinafter also referred to as “compound [B]”).

Among the above crosslinkable groups, as the group having a polymerizable carbon-carbon bond, a (meth)acryloyl group, maleimide group, alkenyl group, vinylphenyl group, vinylether group, 3-methylenetetrahydrofuran-2(3H)- On-5-diary, etc. are mentioned. In the group "-CR ²⁰ =CR ²¹ -R ²² -", examples of the monovalent organic group represented by R ²⁰ include an alkoxy group having 1 to 5 carbon atoms, a pyrrolidon-1-yl group, a halogen atom (a fluorine atom , a chlorine atom, a bromine atom, an iodine atom, etc.) and the like. Examples of the electron withdrawing group for R ²² include a carbonyl group and a sulfonyl group.

The number of crosslinkable groups which compound [B] has in 1 molecule improves liquid-crystal orientation, voltage retention, and film strength with good balance, and from a viewpoint of suppressing the fall of rework property, 2-12 are preferable, and 2 - 10 is more preferable. From the viewpoint of storage stability, the molecular weight of the compound [B] is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.

Specific examples of the compound [B] are compounds having a polymerizable carbon-carbon bond, for example, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth). ) acrylate, a compound represented by each of the following formulas (b-1) to (b-6);

Examples of the compound having a cyclic (thio) ether group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and triglycidyl. Socyanurate, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N',N'- Tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4' -diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, etc.;

As a compound which has an isocyanate group or a protected isocyanate group, the compound etc. which are represented, for example by each of following formula (b-7) - formula (b-11);

As a compound which has a methylol group or a protected methylol group, For example, the compound etc. which are represented by each of following formula (b-12) - Formula (b-17);

As a compound which has a cyclic carbonate group, for example, the compound etc. which are represented by each of following formula (b-18) and Formula (b-19);

Examples of the compound having the group "-CR ²⁰ =CR ²¹ -R ²² -" include compounds represented by each of the following formulas (b-20) to (b-26);

As a compound having an alkoxysilyl group or a silanol group, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldie Toxysilane, vinyltriethoxysilane, trimethoxysilylpropyl succinic anhydride, etc. are mentioned, respectively.

(In formulas (b-7) and (b-8), R ²³ is a thermal leaving group.)

(In formula (b-16), Ac is an acetyl group.)

When the liquid crystal aligning agent of this indication contains a crosslinking agent, the polymer component contained in the liquid crystal aligning agent from a viewpoint of making the adhesiveness of a liquid crystal aligning film high, and a viewpoint of obtaining the liquid crystal element excellent in liquid crystal orientation and electrical properties. With respect to 100 mass parts of total amounts, 0.02 mass part or more is preferable. 0.5 mass part or more is more preferable with respect to 100 mass parts of whole amounts of a polymer component, and, as for content of a crosslinking agent, 1 mass part or more is still more preferable. In addition, from the viewpoint of obtaining a liquid crystal element satisfying liquid crystal orientation, electrical properties, storage stability, and reworkability, the content of the crosslinking agent is preferably 20 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer component, 15 A mass part or less is more preferable. As a crosslinking agent, you may use individually by 1 type, and may use it in combination of 2 or more type.

·solvent

The liquid crystal aligning agent of this indication is prepared as a liquid composition in which a polymer [P] and the other component used as needed preferably disperse|distribute or melt|dissolve in a suitable solvent.

As the solvent, an organic solvent is preferably used. Specific examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, Phenol, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, 1- Hexanol, 2-hexanol, propane-1,2-diol, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, methyl lactate, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, aceto Methyl acetate, ethyl acetoacetate, ethyl propionate, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, Ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutylate, diisopentyl ether, ethylene carbonate, propylene carbonate, propylene glycol monomethyl Ether (PGME), diethylene glycol diethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol diacetate, cyclopentanone, cyclohexanone, etc. are mentioned. As a solvent, 1 type can be used individually or in mixture of 2 or more types.

As another component contained in a liquid crystal aligning agent, antioxidant, a metal chelate compound, a hardening accelerator, surfactant, a filler, a dispersing agent, a photosensitizer, etc. are mentioned other than the above, for example. The blending ratio of other components can be appropriately selected according to each compound within a range that does not impair the effects of the present disclosure.

Although the solid content concentration (ratio which the total mass of components other than the solvent of a liquid crystal aligning agent occupies to the total mass of a liquid crystal aligning agent) in a liquid crystal aligning agent considers a viscosity, volatility, etc. and is selected suitably, Preferably it is 1- It is the range of 10 mass %. The film thickness of a coating film can fully be ensured that solid content concentration is 1 mass % or more, and it is suitable at the point which can obtain the liquid crystal aligning film which shows more favorable liquid-crystal orientation. On the other hand, if solid content concentration is 10 mass % or less, a coating film can be made into suitable thickness, and the liquid crystal aligning film which shows favorable liquid-crystal orientation is easy to be obtained, Furthermore, the viscosity of a liquid crystal aligning agent becomes appropriate, and applicability|paintability can be made favorable tends to

«Liquid crystal alignment film and liquid crystal element»

The liquid crystal aligning film of this indication is manufactured with the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal element of this indication is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The driving method of the liquid crystal in the liquid crystal element is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type ( It can be applied to various modes such as Optically Compensated Bend) type and PSA (Polymer Sustained Alignment) type. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate used differs depending on the desired operation mode. Steps 2 and 3 are common to each operation mode.

<Step 1: Formation of a coating film>

First, a liquid crystal aligning agent is apply|coated on a board|substrate, Preferably a coating film is formed on a board|substrate by heating an application surface. 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. In the case of manufacturing the TN type, STN type, VA type or PSA type liquid crystal element, two substrates on which the patterned transparent conductive film is formed are used. On the other hand, when manufacturing an IPS type or FFS type liquid crystal element, the board|substrate on which the electrode patterned in comb-tooth shape is formed, and the counter board|substrate on which the electrode is not formed are used. As the transparent conductive film, an NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Corporation in the United States), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), or the like can be used.

The coating method of the liquid crystal aligning agent to a board|substrate is not specifically limited. Application of the liquid crystal aligning agent to a substrate is, for example, a spin coating method, a printing method (eg, an offset printing method, a flexographic printing method, etc.), an inkjet method, a slit coating method, a bar coater method, and extrusion. It can be carried out by a die method, a direct gravure coater method, a chamber doctor coater method, an offset gravure coater method, an impregnation coater method, an MB coater method, or the like.

After apply|coating a liquid crystal aligning agent, for purposes, such as liquid flow prevention of the apply|coated liquid crystal aligning agent, Preferably, preliminary heating (pre-baking) is performed. Pre-baking temperature becomes like this. Preferably it is 30-200 degreeC, and pre-baking time becomes like this. Preferably it is 0.25 to 10 minutes. After that, the solvent is completely removed and, if necessary, a calcination (post-baking) step is performed for the purpose of thermal imidization of the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-280 degreeC, More preferably, it is 80-250 degreeC. Post-baking time becomes like this. Preferably it is 5 to 200 minutes. The film thickness of the film to be formed is preferably 0.001 to 1 µm.

<Step 2: Orientation treatment>

When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, the process (orientation process) which provides liquid-crystal orientation ability is performed with respect to the coating film formed in the said process 1. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. It is preferable to use the rubbing process which rubs the surface of the coating film formed on the board|substrate with cotton, nylon, etc. as an orientation treatment, or the photo-alignment process which irradiates light to a coating film and provides liquid-crystal orientation ability. When manufacturing the liquid crystal element of a vertical alignment type, you may use the coating film formed in the said process 1 as it is as a liquid crystal aligning film, and in order to further improve liquid-crystal orientation ability, you may orientation-process with respect to the said coating film. The liquid crystal aligning film suitable for the liquid crystal element of a vertical alignment type can be used suitably also for a PSA type liquid crystal element.

Light irradiation for photo-alignment is a method of irradiating the coating film after the post-baking process, a method of irradiating the coating film after the pre-baking process and before the post-baking process, heating the coating film in at least any of the pre-baking process and the post-baking process It can carry out by the method of irradiating with respect to a coating film, etc. in the middle. As radiation irradiated to the coating film, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used. Preferably, it is an ultraviolet-ray containing light of a wavelength of 200-400 nm. When the radiation is polarized light, linearly polarized light or partially polarized light may be sufficient. 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. The irradiation direction in the case of non-polarized radiation 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. are mentioned, for example. The radiation dose is preferably 200 to 30,000 J/m 2 , more preferably 500 to 10,000 J/m 2 . After light irradiation for imparting orientation ability, the substrate surface is washed with, for example, water, an organic solvent (eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) ) or a mixture thereof may be used for cleaning or heating the substrate.

<Step 3: Construction of liquid crystal cell>

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, for example, two board|substrates are opposingly arrange|positioned through a gap so that a liquid crystal aligning film may oppose, the periphery of two board|substrates is joined with a sealing compound, The cell gap surrounded by the board|substrate surface and a sealing compound. A method of sealing an injection hole by injecting and filling a liquid crystal inside, a method using an ODF method, etc. are mentioned. 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 these, a nematic liquid crystal is preferable.

In the PSA mode, a polymerizable compound (for example, a polyfunctional (meth)acrylate compound, etc.) is filled in the cell gap together with the liquid crystal, and after the liquid crystal cell is constructed, the voltage between the conductive films of the pair of substrates is A process of irradiating light to the liquid crystal cell in a state in which is applied is performed. In the case of manufacture of a PSA type liquid crystal element, the usage-rate of a polymeric compound is 0.01-3 mass parts with respect to a total of 100 mass parts of a liquid crystal, Preferably it is 0.05-1 mass part.

When manufacturing a liquid crystal display device, a polarizing plate is joined to the outer surface of a liquid crystal cell successively. As a polarizing plate, the polarizing plate which sandwiched the polarizing film called "H film" which absorbed iodine while extending|stretching orienting polyvinyl alcohol, with a cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

The liquid crystal element of this indication can be effectively applied to various uses. Specifically, for example, various display devices such as watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, various monitors, liquid crystal TVs, information displays, and the like; , a dimming device, retardation film, and the like.

(Example)

EXAMPLES Hereinafter, although embodiment is described in more detail based on an Example, this invention is not interpreted limitedly by a following Example.

In the following examples, the imidation ratio of the polyimide in the polymer solution and the weight average molecular weight (Mw) and number average molecular weight (Mn) of the styrene-maleimide-based copolymer were measured by the following methods. The required amounts of the raw material compound and the polymer used in the following examples were ensured by repeating the synthesis on the synthesis scale shown in the following synthesis examples as needed.

[Imidation rate of polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR measurement was performed at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the following formula (1).

Imidization ratio [%] = (1-(A ¹ /(A ² ×α))) × 100 … (One)

(In formula (1), A ¹ is the peak area derived from protons of the NH group appearing in the vicinity of 10 ppm of the chemical shift, A ² is the peak area derived from other protons, and α is the polymer precursor (polyamic acid) It is the ratio of the number of other protons to one proton of the NH group.)

[Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)]

Mw and Mn are polystyrene conversion values measured by GPC in the following conditions.

Column: TSKgelGRCXLⅡ, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40℃

Pressure: 68kgf/cm2

The abbreviation of a compound is as follows. In addition, below, the compound represented by Formula (X) may be simply represented by "compound (X)".

(tetracarboxylic acid dianhydride)

(diamine compound)

(end-encapsulating amines)

(Siloxane Monomers and Reactive Compounds)

(Styrene-maleimide-based copolymer polymerization monomer)

(crosslinking agent)

(In formula (AD-5), R is a tert-butoxycarbonyl group or a group derived from methylethylketoxime (*-ON=C(CH ₃ )(C ₂ H ₅ )).)

<Synthesis of polymer>

1. Synthesis of polyamic acid

[Synthesis Example 1]

70 mole parts of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 30 mole parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and As a diamine compound, 60 mol parts of 1,2-bis(4-aminophenoxy)ethane and 40 mol parts of compound (DB-13) were dissolved in N-methyl-2-pyrrolidone (NMP), and reacted at room temperature for 6 hours. was performed to obtain a solution containing 15% by mass of polyamic acid (this is referred to as polymer (PA-1)).

[Synthesis Examples 2, 4 to 13]

Except for changing the type and amount of the tetracarboxylic dianhydride and diamine compound to be used as shown in Tables 1 and 2, the same operation as in Synthesis Example 1 was performed, and polyamic acid (polymer (PA-2), (PA -4), (PA-5), and (PA-16) to (PA-23)) were obtained. In addition, in the synthesis examples 4 and 5, the terminal-blocking amine was melt|dissolved in NMP with tetracarboxylic dianhydride and a diamine compound, and it reacted.

[Synthesis Example 3]

Polymerization was carried out in the same manner as in Synthesis Example 1 except that the types and amounts of tetracarboxylic dianhydride and diamine compounds used were changed as shown in Table 1 to obtain a polymer solution containing polyamic acid. Next, the solution containing a polymer (PA-3) was obtained by adding terminal blocking amine (MA-3) to the obtained polymer solution, and also performing reaction at room temperature for 3 hours.

2. Synthesis of polyimide

[Synthesis Example 14]

It superposed|polymerized similarly to the said synthesis example 1, and obtained the solution containing 15 mass % of polymers (PA-1). Next, NMP was added to the obtained polymer solution, it was set as the solution with a polyamic acid concentration of 10 mass %, pyridine and acetic anhydride were added, and dehydration ring closure reaction was performed at 60 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 15% by mass of a polyimide having an imidization rate of about 80% (this is referred to as a polymer (PI-1)).

[Synthesis Examples 15 to 21, 23 to 26]

The same operation as in Synthesis Example 14 was performed except that the types and amounts of the tetracarboxylic dianhydride and diamine compounds used were changed as shown in Tables 3 and 4, and polyimides (polymers (PI-2) to (PI -8), (PI-10), and (PI-11)) were obtained. In addition, in the synthesis examples 15, 17-21, 24, 25, the terminal-blocking amine was melt|dissolved in NMP with tetracarboxylic dianhydride and a diamine compound, and it reacted.

[Synthesis Example 22]

Polymerization was carried out in the same manner as in Synthesis Example 1 except that the types and amounts of tetracarboxylic dianhydride and diamine compounds used were changed as shown in Table 3 to obtain a polymer solution containing polyamic acid. Next, the terminal blocking amine (MA-1) was added to the obtained polymer solution, and also it reacted at room temperature for 3 hours. Thereafter, polyamic acid was imidized in the same manner as in Synthesis Example 14 to obtain a solution containing a polymer (PI-9) as a polyimide.

3. Synthesis of polyorganosiloxane

[Synthesis Example 27]

In a 1000 mL three-necked flask, 100.0 g of 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (compound represented by the above formula (s-1)), 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine and mixed at room temperature. Next, 100 g of deionized water was dripped from the dropping funnel over 30 minutes, and then, the reaction was performed at 80°C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass aqueous ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. Methyl isobutyl ketone was added in an appropriate amount, and the 50 mass % solution of the polymer (ESSQ-1) which is polyorganosiloxane which has an epoxy group was obtained.

In a 500 mL three-neck flask, 3.10 g of compound (c-1) (20 mol% with respect to the amount of epoxy groups in the polymer (ESSQ-1)), 3.24 g of compound (c-2) (epoxy groups in the polymer (ESSQ-1)) 10 mol% with respect to quantity), tetrabutylammonium bromide 1.00g, polymer (ESSQ-1) containing solution 20.0g, and methylisobutylketone 290.0g were added, and it stirred at 90 degreeC for 18 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. After that, the organic layer is recovered, and the concentration and NMP dilution are repeated twice with a rotary evaporator, and then adjusted so that the solid content concentration is 10% by mass using NMP, and polyorganosiloxane (a polymer (PSQ- An NMP solution of 1) was obtained.

4. Synthesis of styrene-maleimide-based copolymer

[Synthesis Example 28]

In a 100 mL two-neck flask under nitrogen, as a polymerization monomer, 10 mole parts of compound (M-1), 10 mole parts of compound (M-2), 30 mole parts of compound (M-3), 10 mole parts of compound (M-4), compound 20 mol parts of (M-5), 20 mol parts of compound (M-6), 2 mol parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, and 50 mL of tetrahydrofuran as a solvent In addition, it superposed|polymerized at 70 degreeC for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum dried at room temperature for 8 hours to obtain a styrene-maleimide-based copolymer (hereinafter referred to as polymer (MI-1)). About the polymer (MI-1), the weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 92700, and molecular weight distribution (Mw/Mn) was 4.78.

<Preparation and evaluation of liquid crystal aligning agent>

[Example 1: Rubbing FFS type liquid crystal display device]

1. Preparation of liquid crystal aligning agent

To the solution of the polymer (PI-4) obtained in Synthesis Example 17, 5 parts by mass of the compound (AD-1) as a crosslinking agent was added with respect to 100 parts by mass of the polymer (solid content), and diluted with NMP and butylcellosolve (BC). Thus, the solvent composition was NMP/BC = 80/20 (mass ratio) and the solid content concentration was a solution of 3.5% by mass. A liquid crystal aligning agent (AL-1) was prepared by filtering this solution with the filter with a hole diameter of 0.2 micrometer.

2. Preparation of FFS-type liquid crystal cell using rubbing method

A glass substrate having a flat electrode (bottom electrode), an insulating layer and a comb-toothed electrode (top electrode) laminated on one side in this order (referred to as a first substrate), and a glass substrate without an electrode (referred to as a second substrate) ) was prepared. Next, the liquid crystal aligning agent (AL-1) was apply|coated with the spinner to each of the single side|surface of the electrode formation surface of a 1st board|substrate and a 2nd board|substrate, and it heated (pre-baked) for 3 minutes on a 110 degreeC hotplate. Then, drying (post-baking) was performed for 30 minutes in 230 degreeC oven which replaced the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.08 micrometer was formed. Next, the coating film surface was rubbed with a rubbing machine having a roll wound with rayon cloth at a roll rotation speed of 1000 rpm, a stage movement speed of 3 cm/sec, and a bushy foot press-in length of 0.3 mm. Then, a pair of board|substrates which have a liquid crystal aligning film were obtained by performing ultrasonic cleaning for 1 minute in ultrapure water, and drying for 10 minutes in 100 degreeC clean oven then.

Then, with respect to a pair of board|substrates which have a liquid crystal aligning film, the epoxy resin adhesive which left the liquid crystal injection hole in the edge of the surface on which the liquid crystal aligning film was formed, and put the aluminum oxide sphere of diameter 3.5 micrometers was screen-printed and apply|coated. Then, the board|substrates were superimposed on each other and pressed, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Next, in the liquid crystal injection port, after filling the gap between a pair of board|substrates with negative liquid crystal (Merck company make, MLC-6608), the liquid crystal injection port was sealed with the epoxy adhesive. Moreover, in order to remove the flow orientation at the time of liquid crystal injection, after heating this at 120 degreeC, it cooled slowly to room temperature, and the liquid crystal cell was manufactured. In addition, when a pair of board|substrates were overlapped with each other, it was made so that the rubbing method of each board|substrate became antiparallel.

3. Evaluation of liquid crystal orientation

The liquid crystal cell manufactured in said 2. was left still on the high-brightness backlight of 27,000 cd/m<2> for 500 hours, and liquid-crystal orientation was evaluated by the retardation change rate in before and behind irradiation of a backlight. First, about the liquid crystal cell manufactured in said 2., retardation was measured by the Optoscience company Axoscan, and the change rate alpha of retardation before and behind backlight irradiation was computed by following Numerical formula (z-1). It can be said that the liquid-crystal orientation is favorable, so that change rate (alpha) is small. The case where the rate of change α was less than 1% was called “good (○)”, the case where it was 1% or more and less than 2% was “possible (Δ)”, and the case where it was 2% or more was called “poor (x)”.

α=Δθ/θ1… (z-1)

(In formula (z-1), Δθ represents the retardation difference before and after irradiation, and θ1 represents the retardation value before irradiation.)

As a result, evaluation of the liquid-crystal orientation of this Example was evaluation of "good|favorableness (circle)".

4. Evaluation of AC Afterimage Characteristics

For the liquid crystal cell manufactured in 2. above, after driving at an alternating voltage of 10 V for 72 hours, using a device in which a polarizer and an analyzer are disposed between the light source and the light quantity detector, the minimum relative transmittance expressed by the following Equation (2) ( %) was measured.

Minimum relative transmittance (%) = (β-B0)/(B100-B0) × 100　　... (2)

(In formula (2), B0 is the amount of light transmitted from the blank to the cross nicol. B100 is the amount of light transmitted from the blank to the para-nicol. β is the liquid crystal cell between the polarizer and the analyzer under the cross nicol. It is the minimum amount of light transmitted through the

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal cell, and in the FFS type liquid crystal cell, the smaller the black level in the dark state, the better the contrast. Those having a minimum relative transmittance of less than 0.3% are “good (◎)”; It was said to be "defective (x)". As a result, in this Example, it was evaluation of "excellence (double-circle)".

5. Assessment of Initial VHR

After leaving still the liquid crystal cell manufactured by said 2. in 60 degreeC oven, the voltage retention ratio (VHR) was measured on the conditions of 1V and 1670 msec using the Toyo Technica company VHR measuring apparatus "VHR-1". As evaluation criteria, when VHR is higher than 80%, it was set as "good (○)", when 80% or less and 60% or more, "possible (Δ)", and when less than 60%, "bad (x)" was set. As a result, evaluation of the initial stage VHR of this Example was "good (circle)".

6. Evaluation of film strength (rubbing resistance)

The liquid crystal aligning agent (AL-1) prepared in said 1. was apply|coated using the spinner on a glass substrate, and it heated (pre-baked) for 3 minutes on a 110 degreeC hotplate. Thereafter, drying (post-baking) was performed for 30 minutes in an oven at 230° C. in which the inside of the furnace was purged with nitrogen to form a coating film having an average film thickness of 0.08 μm, and the haze value of the coating film was measured using a hazemeter. . Next, with respect to this coating film, the rubbing process was performed 5 times with a roll rotation speed of 1000 rpm, a stage moving speed of 3 cm/sec, and a bushy foot press-in length of 0.3 mm with the rubbing machine which has a roll wound with cotton cloth. Then, the haze value of the liquid crystal aligning film was measured using the haze meter, and the difference (haze change value) with the haze value before a rubbing process was calculated. When the haze value of the film before the rubbing treatment is Hz1 (%) and the haze value of the film after the rubbing treatment is Hz2 (%), the haze change value is expressed by the following formula (z-2).

Haze change value (%) = Hz2-Hz1　　… (z-2)

The case where the haze change value in the liquid crystal aligning film is less than 0.5 is "good (◎)", the case of 0.5 or more and less than 0.8 is "good (○)", the case of 0.8 or more and less than 1.0 is "possible (Δ)", the case of 1.0 or more It evaluated as "defect (x)". When the haze change value is less than 1.0, it can be said that the film strength is sufficiently high and the rubbing resistance is high, that is, the mechanical properties of the film are good. As a result, in this Example, it was evaluation of the film|membrane strength "excellent (double-circle)".

7. Evaluation of film adhesion

The liquid crystal aligning agent (AL-1) prepared in 1. was applied on a glass substrate using a spinner, and pre-baked on a hot plate at 80° C. for 1 minute, followed by nitrogen substitution in the oven at 230° C. A coating film having an average film thickness of 0.1 µm was formed by heating (post-baking) for 1 hour. By repeating operation similar to this, two glass substrates with a coating film were produced. On the coating film of one glass substrate on which the coating film was formed, ODF sealing compound (S-WB42 by Sekisui Chemical Co., Ltd.) was apply|coated so that a diameter might be set to 4.8-5.2 mm, and the coating film of another glass substrate and ODF seal|sticker I glued them to contact. Then, after irradiating the light of 30,000 J/m<2> (365 nm conversion) using a metal halide lamp, it heated in 120 degreeC oven for 1 hour. Then, the adhesiveness of the film|membrane was evaluated by measuring the adhesive force using the tensile compression tester (model number: SDWS-0201-100SL) of Imada Seisakusho.

In the evaluation, the adhesion is "good (○)" when the adhesion is 300 gf/mm2 or more, the adhesion is "good (○)" when it is 200 gf/mm2 or more and less than 300 gf/mm2, and the adhesion is "possible" when it is 100 gf/mm2 or more and less than 200 gf/mm2. ((triangle|delta))" and the case where it was less than 100 gf/mm<2> was made into adhesiveness "defect (x)." As a result, in this Example, it was evaluation of adhesiveness "excellence (double-circle)".

8. Evaluation of reworkability

On a transparent conductive film made of an ITO film formed on one surface of a glass substrate having a thickness of 1 mm, the liquid crystal aligning agent (AL-1) prepared above is applied with a spinner, and pre-baked on a hot plate at 100° C. for 90 seconds. Thus, a coating film having a film thickness of about 0.08 µm was formed. This operation was repeated, and two board|substrates with a coating film were created. Next, the obtained two board|substrates were stored in the dark room of 25 degreeC under nitrogen atmosphere. After 12 hours and 48 hours from the start of storage, one substrate is taken out, respectively, immersed in a beaker containing NMP heated to 40° C. for 2 minutes, washed with ultrapure water several times, and the surface is air blown water droplets were removed. About this board|substrate, the peelability (rework property) from the board|substrate of a liquid crystal aligning film was evaluated by observing with the optical microscope and investigating the presence or absence of the residue of a coating film.

In the evaluation, even if the substrate was taken out after 48 hours from the start of storage, the rework property was "good (○)" when no residue of the coating film was observed after NMP immersion, and the residue of the coating film was observed on the substrate after 48 hours, but after 12 hours The case where it was not observed in the board|substrate was called rework property "possible ((triangle|delta))", and the case where the residue of a coating film was observed in the board|substrate after 12 hours was called rework property "poor (x)". As a result, in this Example, the rework property was "good (circle)".

[Examples 2 to 20 and Comparative Examples 1 to 4]

Except having changed the composition of the liquid crystal aligning agent like Table 5, it carried out similarly to Example 1, and prepared the liquid crystal aligning agent. Moreover, using the obtained liquid crystal aligning agent, it carried out similarly to Example 1, the FFS-type liquid crystal cell was manufactured by the rubbing method, and various evaluation was performed. Their results are shown in Table 5. In addition, in Examples 3-5, 7, 8, 12, 14, 19, and 20, 2 types or 3 types of polymers were used as a polymer component. In Table 5, the numerical value of an aligning agent composition shows the compounding ratio (mass part) of each compound with respect to 100 mass parts of whole amounts of the polymer component used for preparation of a liquid crystal aligning agent (it is the same also about Table 6 and Table 7).

In Table 5, the abbreviation of a crosslinking agent is as follows.

AD-6: Product name "TRIXENE7982", manufactured by Baxenden

As shown in Table 5, Examples 1-20 using the liquid crystal aligning agent containing a polymer [P] compared with Comparative Examples 1-4 using the liquid crystal aligning agent which does not contain a polymer [P], liquid-crystal orientation, The afterimage characteristic, initial stage VHR, film|membrane strength (rubbing resistance), the adhesiveness of a film|membrane, and rework property were balanced, and it was a favorable result.

[Example 21: Optical FFS type liquid crystal display element]

1. Preparation of liquid crystal aligning agent

To the solution containing the polymer (PI-6) obtained in Synthesis Example 19, 3 parts by mass of the compound (AD-3) as a crosslinking agent is added with respect to 100 parts by mass of the polymer (solid content), diluted with NMP and BC, and the solvent composition This NMP/BC=80/20 (mass ratio) and solid content concentration set it as the solution of 3.5 mass %. A liquid crystal aligning agent (AL-21) was prepared by filtering this solution with the filter with a hole diameter of 0.2 micrometer.

2. Manufacture of FFS-type liquid crystal display device using photo-alignment method

The 1st board|substrate and 2nd board|substrate similar to Example 1 were prepared. Next, a liquid crystal aligning agent (AL-21) is apply|coated with a spinner to each of the electrode formation surface of a 1st board|substrate, and one board|substrate surface of a 2nd board|substrate, and it heats on an 80 degreeC hotplate for 1 minute (pre-baking) did. Then, drying (post-baking) was performed for 30 minutes in the 230 degreeC oven which substituted the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.1 micrometer was formed. The obtained coating film was subjected to photo-alignment treatment by irradiating 1,000 J/m 2 of ultraviolet rays containing a linearly polarized 254 nm bright line from the normal line direction to the substrate using an Hg-Xe lamp. In addition, this irradiation amount is the value measured using the photometer measured with wavelength 254nm reference|standard. Next, the coating film to which the photo-alignment process was given was heat-processed by heating in 230 degreeC clean oven for 30 minutes, and the liquid crystal aligning film was formed.

Next, about one board|substrate among a pair of board|substrates in which the liquid crystal aligning film was formed, the epoxy resin adhesive which put the aluminum oxide sphere of diameter 3.5 micrometers in the outer edge of the surface which has a liquid crystal aligning film was apply|coated by screen printing. Then, the board|substrates were superimposed and pressed together so that the projection direction of the polarization axis|shaft to the board|substrate surface at the time of light irradiation might be antiparallel, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Next, after filling a negative liquid crystal (Merck Corporation make, MLC-6608) between a pair of board|substrates in the liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive, and the liquid crystal cell was obtained. Moreover, in order to remove the flow orientation at the time of liquid crystal injection, after heating this at 120 degreeC, it cooled slowly to room temperature. In addition, three or more liquid crystal cells with different ultraviolet irradiation amounts are manufactured by carrying out a series of said operation by respectively changing the ultraviolet irradiation amount after post-baking in the range of 100-10,000 J/m<2>, and the exposure amount which showed the most favorable orientation characteristic It evaluated using the liquid crystal cell of (optimum exposure amount).

3. Evaluation

Using the liquid crystal aligning agent prepared by said 1., and the liquid crystal cell manufactured by said 2., it carried out similarly to Example 1, and various evaluation was performed. Table 6 shows the evaluation results.

[Examples 22 to 24 and Comparative Examples 5 to 7]

Except having changed the composition of the liquid crystal aligning agent like Table 6, it carried out similarly to Example 21, and prepared the liquid crystal aligning agent. Moreover, using the obtained liquid crystal aligning agent, it carried out similarly to Example 21, the FFS-type liquid crystal cell was manufactured by the photo-alignment method, and various evaluation was performed. Their results are shown in Table 6.

As shown in Table 6, Examples 21-24 using the liquid crystal aligning agent containing a polymer [P] compared with Comparative Examples 5-7 using the liquid crystal aligning agent which does not contain a polymer [P], liquid-crystal orientation, A residual image characteristic, initial stage VHR, film strength, the adhesiveness of a film|membrane, and rework property were balanced, and it was the same as the case where the liquid crystal aligning film was manufactured by the rubbing method, and it was a favorable result.

[Example 25: PSA type liquid crystal display device]

1. Preparation of liquid crystal aligning agent

A solution containing 5 parts by mass of the polymer (PSQ-1) obtained in Synthesis Example 27 and a solution containing 95 parts by mass of the polymer (PI-12) obtained in Synthesis Example 25 are mixed, diluted with NMP and BC, and solvent composition This NMP/BC=50/50 (mass ratio) and solid content concentration set it as the solution of 3.5 mass %. A liquid crystal aligning agent (AL-25) was prepared by filtering this solution with the filter with a hole diameter of 0.2 micrometer.

2. Preparation of liquid crystal composition

With respect to 10 g of nematic liquid crystal (the Merck company make, MLC-6608), 0.3 mass of the photopolymerizable compound represented by 5 mass % of a liquid crystalline compound represented by a following formula (L1-1) and a following formula (L2-1) with respect to 10 g % was added and mixed to obtain liquid crystal composition LC1.

3. Preparation of PSA type liquid crystal cell

After applying the liquid crystal aligning agent (AL-25) prepared above using a spinner on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film|membrane, pre-baking in 80 degreeC hotplate for 1 minute, nitrogen By heating at 200°C for 1 hour in an oven substituted with , and removing the solvent, a coating film (liquid crystal aligning film) having a film thickness of 0.08 µm was formed. This coating film was rubbed with a rubbing machine having a roll wound with rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm/sec, and a bushy foot press-in length of 0.1 mm. Then, the board|substrate which has a liquid crystal aligning film was obtained by performing ultrasonic cleaning for 1 minute in ultrapure water, and drying for 10 minutes in 100 degreeC clean oven then. This operation was repeated and a pair (two sheets) of board|substrates which have a liquid crystal aligning film were obtained. In addition, this rubbing process is a weak rubbing process performed for the purpose of controlling collapse of a liquid crystal and performing orientation division|segmentation by a simple method.

An epoxy resin adhesive having an aluminum oxide sphere having a diameter of 3.5 µm is applied to the outer periphery of the surface having a liquid crystal aligning film in the substrate by screen printing, and then the liquid crystal aligning film surfaces of a pair of substrates are opposed to each other and overlapped The adhesive was thermally cured by pressing and heating at 150°C for 1 hour. Next, after filling the gap of the substrate with the liquid crystal composition LC1 in the liquid crystal injection port, the liquid crystal injection port is sealed with an epoxy adhesive, and in order to further remove the flow orientation during liquid crystal injection, it is heated at 150° C. for 10 minutes and then at room temperature annealed until

Next, with respect to the obtained liquid crystal cell, an alternating current of 10 V with a frequency of 60 Hz is applied between the electrodes, and in a state in which the liquid crystal is driven, an ultraviolet irradiation device using a metal halide lamp as a light source is used, and the ultraviolet ray is irradiated with an irradiation amount of 50,000 J/m2 investigated with In addition, this irradiation amount is the value measured using the photometer measured with wavelength 365nm reference|standard. Thereby, the PSA type liquid crystal cell was manufactured.

4. Evaluation

About the liquid crystal cell manufactured by said 3., the method similar to Example 1 evaluated the liquid-crystal orientation, initial stage VHR, adhesiveness of a film|membrane, and rework property. Table 7 shows the evaluation results.

[Examples 26 and 27 and Comparative Examples 8 and 9]

Except having changed the composition of the liquid crystal aligning agent like Table 7, it carried out similarly to Example 25, and prepared the liquid crystal aligning agent. Moreover, using the obtained liquid crystal aligning agent, it carried out similarly to Example 25, the PSA type liquid crystal cell was manufactured, and various evaluation was performed. Table 7 shows the evaluation results.

As shown in Table 7, Examples 25-27 using the liquid crystal aligning agent containing a polymer [P] compared with Comparative Examples 8 and 9 using the liquid crystal aligning agent which does not contain a polymer [P], liquid-crystal orientation, The initial VHR, the adhesiveness of a film|membrane, and the rework property were balanced, and it was the same as the FFS type liquid crystal display element, and it was a favorable result. In particular, the improvement effect by using the polymer [P] was high in the adhesive evaluation of a film|membrane. It is thought that this is because the mechanical strength of a film|membrane improved by using polymer [P].

From the above results, according to the liquid crystal aligning agent containing a polymer [P], a voltage retention rate is high, the liquid crystal element which an afterimage does not produce easily can be obtained, Furthermore, film strength is high, and rework property and adhesiveness are favorable liquid crystal aligning film It became clear that it is possible to form

Claims (9)

The liquid crystal aligning agent containing the polymer [P] which has the partial structure (A) represented by following formula (1) or Formula (2) in the principal chain terminal.

(In formula (1), R ¹ is a monovalent organic group that is detached by at least one of heat and light; R ² is a monovalent organic group; R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group: "*" represents a bond;
In formula (2), R ⁵ is a monovalent organic group which is detached by at least one of heat and light; R ⁶ and R ⁷ satisfy the following (i) or (ii);
(i) R ⁶ is a monovalent organic group; R ⁷ is a divalent alicyclic group;
(ii) R ⁶ and R ⁷ represent a ring structure constituted together with the nitrogen atom to which R ⁶ and R ⁷ are bonded;
"*" indicates that it is a bond) According to claim 1,
The said polymer [P] has a structural unit derived from the compound represented by following formula (3) in the principal chain terminal, The liquid crystal aligning agent.

(In Formula (3), A ¹ is a monovalent group having a partial structure represented by Formula (1) or Formula (2); R ⁸ is a single bond, -O-, -S-, -CO- , -COO-, -NR ¹⁰ -, -CO-NR ¹⁰ -, -NR ¹⁰ -CO-O-, -NR ¹⁰ -CO-NR ¹¹ -, divalent chain hydrocarbon group having 1 or more carbon atoms, divalent chain hydrocarbon group having 3 or more carbon atoms Any methylene group of an alicyclic hydrocarbon group or a divalent chain hydrocarbon group having 2 or more carbon atoms is -O-, -S-, -CO-, -COO-, -NR ¹⁰ -, -CO-NR ¹⁰ -, -NR ¹⁰ -CO-O- or -NR ¹⁰ -CO-NR ¹¹ - is a divalent group substituted with -; R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a monovalent organic group; R ⁹ is a single bond or (m+1) is an aromatic ring group; m is 1 or 2; provided that, when R ⁹ is a single bond, m is 1, and R ⁸ is a single bond or a hydrocarbon group, a primary amino group in Formula (3) is bonded to; when m is 2, a plurality of R ⁸ are the same or different, and a plurality of A ¹ are the same or different) According to claim 1,
The said polymer [P] is at least 1 sort(s) chosen from the group which consists of polyamic acid, polyamic acid ester, and a polyimide, Liquid crystal aligning agent. 4. The method of claim 3,
The said polymer [P] has a structural unit derived from alicyclic tetracarboxylic dianhydride, The liquid crystal aligning agent. According to claim 1,
A group having a polymerizable carbon-carbon bond, a cyclic ether group, a cyclic thioether group, an isocyanate group, a protected isocyanate group, a methylol group, a protected methylol group, a cyclic carbonate group, a group “-CR ²⁰ =CR ²¹ -R ²² -" (provided that R ²⁰ is a monovalent organic group that leaves by reaction with an amino group; R ²¹ is a hydrogen atom or an alkyl group, and R ²² is an electron withdrawing group), a silanol group, and an alkoxysilyl group. The liquid crystal aligning agent which further contains the compound which has at least 1 sort(s) of group chosen. According to claim 1,
The liquid crystal aligning agent which further contains the polymer which does not have the said partial structure (A) in the principal chain terminal. In the presence of a monoamine compound having a partial structure (A) represented by the following formula (1) or formula (2), from the group consisting of tetracarboxylic dianhydride, tetracarboxylic dianhydride and tetracarboxylic acid diester dihalides The liquid crystal aligning agent containing the polymer [P] obtained by superposing|polymerizing the monomer containing the at least 1 sort(s) of chosen acid derivative, and a diamine compound, or by making it react with the said monoamine compound after superposing|polymerizing the said monomer.

(In formula (1), R ¹ is a monovalent organic group that is detached by at least one of heat and light; R ² is a monovalent organic group; R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group: "*" represents a bond;
In formula (2), R ⁵ is a monovalent organic group which is detached by at least one of heat and light; R ⁶ and R ⁷ satisfy the following (i) or (ii);
(i) R ⁶ is a monovalent organic group; R ⁷ is a divalent alicyclic group;
(ii) R ⁶ and R ⁷ represent a ring structure constituted together with the nitrogen atom to which R ⁶ and R ⁷ are bonded;
"*" indicates that it is a bond) The liquid crystal aligning film formed with the liquid crystal aligning agent in any one of Claims 1-7. A liquid crystal element provided with the liquid crystal aligning film of Claim 8.