TWI480313B - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Description

Liquid crystal alignment agent and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal alignment agent which is excellent in film properties and which is excellent in electrical properties and heat resistance, and which is excellent in applicability, and which can exhibit high quality and can suppress display quality deterioration during long-time driving. Liquid crystal display element.

At present, a known liquid crystal display element can be distinguished according to the electrode structure and the physical properties of liquid crystal molecules used in accordance with the mode shown below.

First, a substrate for a liquid crystal display element in which a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive film is provided is formed, and two layers are arranged to face each other, and a layer of nematic liquid crystal having positive dielectric anisotropy is formed in the gap. A liquid crystal cell having a sandwich structure in which a long axis of liquid crystal molecules is continuously rotated by 90° from one substrate to another, and a so-called TN type liquid crystal display element having a TN type (twisted nematic) liquid crystal cell (Patent Document 1) and TN An STN (Super Twisted Nematic) liquid crystal display element (Patent Document 2) capable of realizing a high duty ratio is known as a liquid crystal display element. Further, the same counter electrode arrangement is performed as the TN liquid crystal display element, but a layer of nematic liquid crystal having a negative dielectric anisotropy is implanted into the electrode gap, and the liquid crystal is vertically aligned with the substrate by VA (vertical alignment) A type of display element is known (Patent Document 3). The VA type display element has high contrast and is capable of manufacturing a large-area display element.

On the other hand, by arranging the electrode pairs in a comb-tooth shape in the surface of one of the substrates, the driving direction of the liquid crystal is applied only in the IPS (in-plane switching) type liquid crystal display element in the in-plane direction of the substrate when the electric field is applied (Patent Document 4). The IPS type electrode structure and the FFS (edge electric field conversion) type liquid crystal display element (Patent Document 5) which improves the luminance of the aperture ratio of the display element portion are known, and each viewing angle characteristic is excellent.

In addition to this, an OCB (Optically Compensatory Bend) type liquid crystal display element (Patent Document 6) having a small viewing angle dependency and excellent high-speed response of an image screen is being developed.

A liquid crystal alignment film material among these liquid crystal display elements is known as a resin material such as polyacrylic acid, polyimine, polyamine or polyester, and particularly a liquid crystal alignment film composed of polyacrylic acid or polyimine. Excellent heat resistance, mechanical strength, affinity with liquid crystal, etc., can be used for various liquid crystal display elements (Patent Documents 7 to 8).

In recent years, liquid crystal display elements are being developed for television use, and in combination with display refinement and highly developed dynamic image fixing technology, long-term viewing with almost no consideration for liquid crystal display elements is being normalized. However, when a liquid crystal display element having a liquid crystal alignment film obtained from a conventionally known material is driven for a long period of time, there is a problem that image quality is deteriorated. This phenomenon is considered to be caused by thermal stress on the liquid crystal alignment film under continuous driving for a long period of time, and as a result, the electrical characteristics of the liquid crystal alignment film, particularly the voltage holding ratio, is remarkably lowered, and it is desirable to provide a liquid crystal alignment film material which does not cause such deterioration.

In addition, the liquid crystal television has a tendency to increase in size, and the substrate used in the liquid crystal display element is increasing in size from the viewpoint of reducing the manufacturing cost. Therefore, after the liquid crystal alignment agent is applied onto the substrate, the time (placement time) for baking is prolonged. When the liquid crystal alignment agent is used, when the standing time is long, it is pointed out that the uniformity of the coating film or the generation of pores and the display quality of the obtained liquid crystal display element are deteriorated, and it is desired to provide a long time. A liquid crystal alignment agent which can obtain a uniform coating film and a liquid crystal display element of excellent quality can also be obtained.

[Previous Technical Literature] [Patent Literature]

Patent Document 1 Japanese Patent Laid-Open No. Hei 04-153622

Patent Document 2, JP-A-60-107020

Patent Document 3 Japanese Patent Laid-Open No. Hei 11-258605

Patent Document 4, JP-A-56-91277

Patent Document 5 Japanese Patent Laid-Open Publication No. 2008-216572

Patent Document 6 Japanese Patent Laid-Open Publication No. 2009-48211

Patent Document 7 US Patent No. 5,928,733

Patent Document 8 JP-A-62-165628

In view of the above problems, an object of the present invention is to provide a liquid crystal alignment agent which is uniform in film quality after application for a long period of time and which can form a liquid crystal alignment film having excellent electrical properties and heat resistance.

Another object of the present invention is to provide a liquid crystal display element capable of high-quality display and capable of suppressing deterioration in display quality during long-time driving.

Further objects and advantages of the present invention will be apparent from the following description.

According to the present invention, the above object of the present invention is to provide a liquid crystal alignment agent characterized by containing at least one polymer selected from the group consisting of polylysine and polyamidiene, and intramolecularly of the above polymer. At least a portion of the group has a group represented by the following formula (A'),

R ^I -(X ^I ) _n1 -R ^II -OX ^II -COO-(R ^III O) _n2 -* (A')

(In the formula (A'), R ^I represents an alkyl group having 1 to 30 carbon atoms or a fluoroalkyl group having 1 to 30 carbon atoms, and R ^II represents a single bond, a methylene group or a carbon number of 2~ 30 alkyl, R ^III represents an alkylene group having 2 to 5 carbon atoms, and X ^I and X ^II respectively represent a divalent alicyclic group, a divalent heterocyclic group, an extended aryl group or a divalent hetero In the aromatic group, a plurality of X ^I groups may be the same or different from each other, n1 is an integer of 2 to 5, n2 is an integer of 0 to 10, and "*" represents a linkage bond).

The above object of the present invention is the second object achieved by a liquid crystal display element comprising a liquid crystal alignment film formed of the above liquid crystal alignment agent.

The liquid crystal alignment agent of the present invention has a uniform film quality when left standing for a long period of time after application, and can provide a liquid crystal alignment film excellent in electrical properties and heat resistance.

The liquid crystal display element of the present invention having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be displayed with high quality, and display quality deterioration is suppressed even under long-time driving. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices such as a clock, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, a portable information terminal, a digital camera, a mobile phone, various displays, Display devices such as LCD TVs.

The invention will be described in detail below.

The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyamidiamine, and the polymer has a group represented by the above formula (A') on at least a part of its molecule. group. Such polymers are referred to herein as "specific polymers."

In the above formula (A'), the alkyl group having 1 to 30 carbon atoms as R ^I is preferably a linear alkyl group having 1 to 12 carbon atoms, particularly preferably n-propyl group, n-butyl group or a positive group. Amyl, n-hexyl, n-heptyl, n-octyl and the like.

Preferable examples of the fluoroalkyl group having 1 to 30 carbon atoms of R ^I include a group represented by the following formula (R ^I -1).

C _i F _2i+1 -C _j H _2j - (R ^I -1)

(in the above formula, i is an integer of 1 to 30, j is an integer of 0 to 29, and i+j is an integer of 1 to 30) More preferably, it is a linear group represented by the above formula (R ^I -1). As specific examples thereof, for example, trifluoromethyl, 4,4,5,5,5-pentafluoropentyl and the like.

R ^II in the above formula (A') is preferably a single bond or a methylene group, and particularly preferably a methylene group.

R ^III in the above formula (A') is preferably an alkylene group having 2 or 3 carbon atoms, and specific examples thereof include 1,2-extended ethyl, 1,2-extended propyl, and 1 , 3-extended propyl and the like. More preferably, they are 1,2-extended ethyl or 1,2-extended propyl. The connection direction of the above 1,2-propanyl group has no relationship. R ^{III is} particularly preferably 1,2-extended ethyl.

The divalent alicyclic group of X ^I and X ^II in the above formula (A') may be, for example, a divalent alicyclic group having 3 to 8 carbon atoms, and specific examples thereof are, for example, 1,4- Cyclohexylene, 1,3-cyclohexylene, 1,3-cyclopentyl and the like. The divalent heterocyclic group of X ^I and X ^II may be, for example, a divalent heteroalicyclic group having 3 to 8 carbon atoms, and specific examples thereof include, for example, piperidine-1,4- Dibasic -1,4-diyl and the like. The aryl group of X ^I and X ^II may be, for example, an extended aryl group having 6 to 12 carbon atoms, and specific examples thereof include, for example, 1,4-phenylene, 1,3-phenylene, naphthalene- 2,6-diyl, naphthalene-2,7-diyl, naphthalene-1,5-diyl and the like. The divalent heteroaromatic group of X ^I and X ^II is, for example, a divalent heteroaromatic group having 4 to 8 carbon atoms, and specific examples thereof include, for example, pyridine-2,5-diyl and pyridine. -2,6-diyl, pyridyl -2,5-diyl, pyridyl -2,6-diyl, pyrimidine-2,5-diyl, pyrrole-2,5-diyl, imidazolium-1,4-diyl, pyrazole-1,3-diyl, pyrazole-1, 4-diyl and the like. The above-mentioned X ^I and X ^{II have} a divalent alicyclic group having 3 to 8 carbon atoms, a divalent heterocyclic group having 3 to 8 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, and carbon. The divalent heteroaromatic group having 4 to 8 atoms may be substituted by one or two or more fluorine atoms or an alkyl group having 1 to 12 carbon atoms.

In the above formula (A'), X ^{1 is} preferably a divalent alicyclic group, and n 1 is preferably 2. (X ^I ) _n1 in the above formula (A') is particularly preferably a 4,4'-linked cyclohexyl group.

As X ^II in the above formula (A'), an aryl group is preferred, and a 1,4-phenyl group is particularly preferred.

In the above formula (A'), n2 is preferably 0 or 1.

The polyproline which has a group represented by the above formula (A') in at least a part of the molecule can be, for example, a tetracarboxylic acid which comprises a compound having a group represented by the above formula (A') and two carboxylic anhydride groups. The anhydride is reacted with a diamine, or a tetracarboxylic dianhydride is reacted with a diamine comprising a compound represented by the above formula (A') and a compound of two amine groups, and at least a part of the molecule has the above formula (A) The polyimine of the group represented by ') can be obtained, for example, by subjecting the polyamic acid obtained as described above to dehydration ring closure.

The specific polymer contained in the liquid crystal alignment agent of the present invention is preferably at least one polymer selected from the group consisting of polylysine and polyamidene obtained by dehydration ring closure of the polylysine, the polyamine The acid is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound having the structure represented by the above formula (A') and two amine groups.

<polylysine>

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid in the liquid crystal alignment agent of the present invention include butane tetracarboxylic dianhydride and 1,2,3,4-cyclobutane IV. Carboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane IV Carboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4 '-Dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5 , 9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3, 3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1] ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-di-oxyl- 3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(four -2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 8-Methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a ,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene And [1,2-c]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxa Bicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-di-oxo-4 Hydrogen-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnordecane-2:3,5 :6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, the following formula (TI) and (T-II)

(wherein R ¹ and R ³ each represent a divalent organic group having an aromatic ring, R ² and R ⁴ each represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 present} may be the same or different from each other) An aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride such as a compound; pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3, 3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-four Phenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4 , 4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4 ' -bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3 ',4,4'-Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3' biphenyl Tetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenyl o-) Phthalic anhydride Bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol- Bis(anhydrotriphenyl hexaformate), propylene glycol-bis(anhydrotriphenyl hexaformate), 1,4-butanediol-bis(anhydrotriphenyl hexaformate), 1,6-hexanediol-double ( Dehydrated triphenyl hexacarboxylate), 1,8-octanediol-bis(anhydrotriphenyl hexaformate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotriphenyl hexaformate), The following formula (T-1)~(T-4)

An aromatic tetracarboxylic dianhydride such as a compound represented by each. The benzene ring of the aromatic tetracarboxylic dianhydride may be substituted with one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms.

These tetracarboxylic dianhydrides may be used singly or in combination of two or more.

The tetracarboxylic dianhydride which is preferably used in the synthesis of polyamic acid in the present invention includes, in the above, a butane tetracarboxylic dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride. , 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-three Carboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2 -c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furan -Naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro- 2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3 ,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-di Ketone), 5-(2,5-di-oxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxyl -2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10- Tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic acid Anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the following formula in the compound represented by the above formula (TI) (T- 5)~(T-7).

The compound represented by the above formula and the compound represented by the above formula (T-II) have the following formula (T-8)

At least one selected from the group consisting of the compounds (hereinafter referred to as "specific tetracarboxylic dianhydride") is preferred from the viewpoint that the formed liquid crystal alignment film exhibits good liquid crystal alignment.

More preferably, the specific tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3, 3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1, 3-diketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-( 2,5-di-side oxytetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl Decalin-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, benzene tetra At least one selected from the group consisting of acid dianhydride and the compound represented by the above formula (T-5) is particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

The tetracarboxylic dianhydride used in the synthesis of the polyamic acid which is preferred in the present invention preferably contains 10 mol% or more, more preferably 30 mol%, and particularly preferably 40 mol% based on the total tetracarboxylic dianhydride. Ears above the specific tetracarboxylic dianhydride as described above.

Most preferably, the tetracarboxylic dianhydride used in the synthesis of the polyamic acid in the present invention uses only the specific tetracarboxylic dianhydride as described above.

[diamine]

The diamine used in the synthesis of the polylysine which is preferred in the present invention includes a compound having a group represented by the above formula (A') and two amine groups.

The compound represented by the above formula (A') and the compound of two amine groups are preferably the following formula (A).

(In the formula (A), R ^I , R ^II , R ^III , X ^I , X ^II , n1 and n2 are each a compound represented by the above formula (A')). The two amine groups bonded to the benzene ring in the above formula (A) are preferably at the 2,4-position or the 3,5-position.

More specific examples of the compound represented by the above formula (A) include, for example, the following formulas (A-1) to (A-4).

(In the formulae (A-1) to (A-4), R ^I is a compound respectively represented by the above formula (A)).

The compound represented by the above formula (A) is synthesized by a suitable combination of conventional methods for synthesizing an organic compound. For example, the compound represented by the above formula (A-1) can be illustrated by, for example, the following

(In the above illustration, R ^I is synonymous with the above formula (A)). A compound (A) having a desired group R ^I and a p-chlorobenzenesulfonate chloride are reacted to prepare a compound (Ab), and after reacting the compound (Ab) with ethyl 4-hydroxybenzoate to obtain a compound (Ac), for example, Hydrolysis to give the intermediate (Ad) in the presence of a suitable base, and reacting the intermediate (Ad) with 3,5-bis(diallylamino)phenol (Compound B) to form the compound (A-Ie) It is preferably synthesized by de-allyl in the presence of N,N-dimethylbarbituric acid and tetrakis(triphenylphosphine)palladium. The compound (B) used herein can be easily obtained by reacting I,3,5-trihydroxybenzene and 2 equivalents of diallylamine.

Further, the compound represented by the above formula (A-3) can be illustrated by, for example, the following

(In the above illustration, R ^{1 is} synonymous with the above formula (A)) is synthesized. That is, the intermediate (Ad) obtained in the same manner as above and 1-hydroxy-2,4-dinitrobenzene are reacted to prepare a compound (A-3e), and then an appropriate reduction system such as palladium carbon or hydrogen is used. The nitro group is converted to an amine group for synthesis.

The diamine used in the synthesis of the polyamic acid which is preferable in the present invention may be a compound represented by the above formula (A), or a combination of the compound represented by the above formula (A) and another diamine.

Examples of other diamines used herein include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, and 4 , 4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4' -diaminophenyl benzophenone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3 , 3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-Diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4- Aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3- Aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminoguanidine, 9,9-dimethyl-2,7- Aminoguanidine, 9,9-bis(4-aminophenyl)anthracene, bis(4-amino-2-chlorophenyl)methane, 2,2',5,5'-tetrachloro-4,4 '-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 4,4'-(p-phenylenediisopropyl)diphenylamine, 4,4'-(m-phenyleneisopropylidene)diphenylamine, 2,2'-bis[4 -(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-bis(trifluoromethyl)biphenyl, 4, 4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluoro Benzene, 3,5-diamino benzoic acid, 2,4-diaminobenzoic acid, the following formula (D-1)~(D-5)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5), such as an aromatic diamine such as a compound; 1,1-meta-xylene Diamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, jiapaya Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene bridge indane dimethylene Amine, tricyclo[6.2.1.0 ^2,7 ]-undecene dimethylene diamine, 4,4'-methylene bis(cyclohexylamine), 1,3-bis(aminomethyl) An aliphatic diamine such as cyclohexane or 1,4-bis(aminomethyl)cyclohexane; and an alicyclic diamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridine ,5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-three 1,4-bis(3-aminopropyl)per 2,4-Diamino-6-isopropoxy-1,3,5-three 2,4-diamino-6-methoxy-1,3,5-three 2,4-diamino-6-phenyl-1,3,5-three 2,4-diamino-6-methyl-s-three 2,4-diamino-1,3,5-three 4,6-Diamino-2-vinyl-s-three , 2,4-Diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino- 1,2,4-triazole, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminophene , 3,6-diamino acridine, N,N'-bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diamine Ketrazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-linked Aniline, N,N'bis(4-aminophenyl)-N,N'-dimethyl-benzidine, and the following formulas (DI) and (D-II)

(In the formula (DI), R ⁵ is derived from pyridine, pyrimidine, and tri Piperidine and piperazine a monovalent organic group of a ring structure containing a nitrogen atom selected from the group consisting of X ¹ being a divalent organic group; and in the formula (D-II), R ⁶ is having a pyridine, pyrimidine, or the like Piperidine and piperazine a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of X ² may be a divalent organic group, and a plurality of compounds each having a different X ² may be the same or different) a diamine having two primary amine groups in the molecule and a nitrogen atom other than the tertiary amine group; the following formula (D-III)

(In the formula (D-III), R ⁷ is -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and R ⁸ has a steroid skeleton, trifluoromethylphenyl group a monosubstituted benzene extending such as a monovalent organic group of a skeleton or a group selected from the group consisting of a trifluoromethoxyphenyl group and a fluorophenyl group or an alkyl group having a carbon number of 6 to 30) a diamine organooxane such as a compound represented by the following formula (D-IV);

(In the formula (D-IV), R ⁹ each represents a hydrocarbon group having 1 to 12 carbon atoms, and when a plurality of R ⁹ are present, they may be the same or different, p represents an integer of 1 to 3, and q represents 1 to 20, respectively. Integer).

The aromatic diamine, a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group, and a benzene ring having a monosubstituted phenyldiamine may be one or more carbons. An alkyl group (preferably a methyl group) having 1 to 4 atoms is substituted. Further, the steroid skeleton in the above formula (D-III) means a skeleton composed of a cyclopentane fully hydrogenated phenanthrene nucleus or a skeleton in which one or two or more carbon-carbon bonds are double bonds.

These diamines may be used alone or in combination of two or more.

The other diamines which are preferably used in the synthesis of poly-proline are preferably selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodi Phenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis ( Trifluoromethyl)biphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-amine Phenylphenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropyl)diphenylamine, 4,4'-(m-phenyleneisopropylidene)diphenylamine, 1,4-bis(4- Aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) , 1,3-bis(aminomethyl)cyclohexane, a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diamine Pyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-B 3-,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis (4- Phenylphenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 3,5-diaminobenzoic acid, represented by the above formula (DI) The following formula (D-6)

The compound represented by the above formula (D-7) in the compound represented by the above formula (D-II)

The compound represented by the above formula, the lauryloxy-2,4-diaminobenzene, the pentadecyloxy-2,4-diaminobenzene, the hexadecyloxy group in the compound represented by the above formula (D-III) 2,4-Diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-di Aminobenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (D-8)~(D-15)

At least one selected from the group consisting of a compound represented by the above formula and 1,3-bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D-IV) (hereinafter referred to as "Other specific diamines").

The preferred diamine for the synthesis of poly-proline is more preferably 0.1 mol% or more of the compound represented by the above formula (A), more preferably 0.5 to 50 mol% based on the entire diamine. The compound represented by the formula (A) is particularly preferably from 1 to 40 mol%.

The diamine which is preferably used for the synthesis of polylysine in the present invention preferably contains the above-mentioned other specific diamine in addition to the compound represented by the above formula (A). In this case, the ratio of use of the other specific diamine is preferably 30 mol% or more, more preferably 30 to 99.9 mol%, still more preferably 50 to 99.5 mol%, and particularly preferably 60, based on the entire diamine. ~99 mole%.

The preferred diamine for the synthesis of polylysine in the present invention is preferably composed only of the compound represented by the above formula (A) and other specific diamines.

[Synthesis of polyglycine]

The polypolyglycolic acid which is preferred in the present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A).

The ratio of the tetracarboxylic dianhydride and the diamine used for providing the synthesis reaction of polylysine is 1 to 2 equivalents to the amine group of the diamine, and the ratio of the acid anhydride group of the tetracarboxylic dianhydride is preferably 0.2 to 2. The equivalent weight is more preferably 0.3 to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from -20 ° C to 150 ° C, more preferably from 0 to 100 ° C, preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours. .

The organic solvent which can be used in the synthesis of polyamic acid is, for example, an aprotic polar solvent, phenol and a derivative thereof, an alkanol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like.

Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylammonium, and γ-. Butyrolactone, tetramethyl urea, hexamethylphosphine tridecylamine, etc.; as the above phenol derivative, for example, m-cresol, xylenol, halogenated phenol, etc.; as the above-mentioned alcohol, for example, methanol, ethanol, and isopropyl Alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.; as the above ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ring Hexanone; as the above ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate An ester, diethyl malonate or the like; as the above ether, for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl Ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; as the above halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; as the above hydrocarbon, for example, hexane, heptane, octane, benzene, toluene, Xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like.

Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and a derivative thereof (the first group of organic solvents), or one or more selected from the first group of organic solvents, and the like are preferably used. One or more mixtures selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (second group of organic solvents). In the latter case, the use ratio of the second group of organic solvents is preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably the total of the first group of the organic solvent and the second group of the organic solvent. 30% by weight or less.

As described above, a reaction solution obtained by dissolving polyamic acid was obtained.

The reaction solution may be supplied to the preparation of the liquid crystal alignment agent as it is, or may be supplied to the preparation of the liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or after refining the separated polyamic acid. It is supplied to the preparation of the liquid crystal alignment agent.

When the polycyclic imide is obtained by dehydrating the closed polyamine, the reaction solution may be supplied to the dehydration ring-closure reaction as it is, or may be supplied to the dehydration ring-closure reaction after separation of the polylysine contained in the reaction solution, or may be purified and separated. The polylysine is then supplied to the dehydration ring closure reaction.

The separation of the polyamic acid is carried out by injecting the above reaction solution into a large amount of a poor solvent, obtaining a precipitate, drying the precipitate under reduced pressure, or distilling off the solvent in the reaction solution by an evaporator under reduced pressure. Further, the polylysine is redissolved in an organic solvent, followed by precipitation by a poor solvent, or a solution obtained by redissolving the polylysine into an organic solvent, and then the solution is distilled off under reduced pressure using an evaporator. The step of the solvent is carried out one or more times to refine the poly-proline.

<polyimine]

The preferred polyimine of the present invention can be obtained by dehydrating the poly-proline by dehydration as described above.

The tetracarboxylic dianhydride used for the synthesis of the above polyimine can be exemplified by the same compound as the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid. The type of the preferred tetracarboxylic dianhydride and its preferred use ratio are also the same as in the case of polyglycolic acid.

The diamine which is preferably used in the synthesis of polyimine in the present invention can be exemplified by a diamine similar to the diamine used in the synthesis of the above polyamic acid. In other words, the diamine used in the synthesis of the polyimine contained in the liquid crystal alignment agent of the present invention includes the compound represented by the above formula (A), and only the compound represented by the above formula (A) may be used. The combination of the compound represented by the formula (A) and the above other diamine. It is preferred that the other diamine species and the preferred use ratio of each diamine are also the same as in the case of polyglycolic acid.

The preferred polyimine of the present invention may be a fully hydrazinated product in which the proline structure of the raw material polyamic acid is dehydrated and closed, or a part of the structure of the proline may be dehydrated and closed. A partial oxime imidization product in which a proline structure and a quinone ring structure coexist is obtained. The polyimine of the present invention preferably has a ruthenium iodide ratio of 30% or more, more preferably 40% or more, and particularly preferably 45% or more. The ruthenium imidation ratio is a percentage of the number of ruthenium ring structures in relation to the number of guanidine structures of the polyimine and the number of quinone ring structures. At this time, the moiety of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, heating as needed The way to proceed.

The reaction temperature in the above (i) method of heating the polyamic acid is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction is insufficient, and when the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimine is lowered. The reaction time is preferably from 1.0 to 24 hours, more preferably from 1.0 to 12 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the poly-proline in the above (ii), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is adjusted depending on the desired oxime imidization ratio, but is preferably 0.01 to 20 mols relative to the proline structure of 1 mol of polylysine. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. But not limited to these. The amount of the dehydration ring-closure catalyst used is preferably 0.01 to 10 moles per 1 mol of the dehydrating agent. The more the amount of the above-mentioned dehydrating agent and dehydration ring-closing reactant is used, the higher the sulfhydrylation rate. The organic solvent used in the dehydration ring closure reaction may, for example, be an organic solvent used in the synthesis of polylysine. The reaction temperature of the dehydration ring closure is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

The polyimine obtained in the above method (i) can be supplied to the preparation of the liquid crystal alignment agent as it is, or the obtained polyimine can be purified and supplied to the preparation of the liquid crystal alignment agent. On the other hand, in the above method (ii), a reaction solution containing polyienimine is obtained. The reaction solution may be supplied to the preparation of the liquid crystal alignment agent as it is, or may be supplied to the preparation of the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, or may be separated from the polyimine and then supplied to the liquid crystal alignment agent. In the preparation, or the separation of the separated polyimine, it is supplied to the preparation of the liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closure catalyst can be removed from the reaction solution by, for example, solvent replacement. The separation and purification of the polyimine can be carried out in the same manner as the separation and purification method of the polyamic acid.

- terminal modified polymer -

The above polylysine and polyimine in the present invention may each be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating properties and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be carried out by adding a molecular weight modifier to a polymerization reaction system in synthesizing polyamic acid. The molecular weight modifier may, for example, be a monoanhydride, a monoamine compound, a monoisocyanate compound or the like.

Examples of the monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-lauryl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and the like; Examples of the above monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and n-xylylene. An amine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-dodecylamine or the like; as the above monoisocyanate compound, for example, benzene can be exemplified Isocyanate, naphthyl isocyanate, and the like.

The ratio of use of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyamic acid.

- solution viscosity -

The polylysine or polyimine obtained as above preferably has a solution viscosity of 20 to 800 mPa ‧ when it is made into a solution having a concentration of 10% by weight, more preferably a solution viscosity of 30 to 500 mPa ‧ s.

The solution viscosity (mPa ‧ s) of the above polymer is a polymer solution prepared by using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer to prepare a polymer solution having a concentration of 10% by weight. The value measured by an E-type rotational viscometer at 25 °C.

<Other ingredients>

The liquid crystal alignment film of the present invention contains the above specific polymer as an essential component, and may contain other components as needed. Examples of the other component include other polymers, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, and the like.

[Other polymers]

The other polymers described above can be used to improve solution properties and electrical properties. The other polymer is a polymer other than the specific polymer, and examples thereof include polyamines obtained by reacting a dicarboxylic acid dianhydride with a diamine not including the compound represented by the above formula (A) (hereinafter referred to as "other poly "Proline"), a polyamidene (hereinafter referred to as "other polyimine") obtained by dehydration of the polyglycine, a polyphthalate, a polyester, a polyamine, a polyoxyalkylene , cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. Among them, other polyamines or other polyimines are preferred, and other polylysines are more preferred.

The ratio of use of the other polymer is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight based on the total of the polymer (the total of the specific polymer and the other polymer described above). %the following.

[epoxy compound]

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopenta Glycol diglycidyl ether, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Alkane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl Amino-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, and the like.

The mixing ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the total amount of the polymer.

[functional decane compound]

As the above functional decane compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltri Ethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-Aminopropyltriethoxydecane, N-triethoxycarbamidopropyltriethylenetriamine, N-trimethoxymethylidenepropyltriethylenetriamine, 10-trimethoxyformane 1,-,4,7-triazane, 10-triethoxycarbamimidyl-1,4,7-triazinane, 9-trimethoxyformamidin-3,6-diazaindole Acetate, 9-trimethoxycarbamido-3,6-diazadecyl acetate, 9-triethoxycarbamido-3,6-diazadecyl acetate, 9- Methyl trimethoxycarbamido-3,6-diazepine, methyl 9-triethoxycarbamido-3,6-diazonium hydride, N-benzyl-3-aminopropyl Trimethoxydecane, N-benzyl-3- Aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyl Trimethoxydecane, glycidoxymethyltriethoxydecane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-ring Oxypropoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like.

The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, per 100 parts by weight of the total of the polymer.

The liquid crystal alignment agent of the present invention is composed of at least one polymer selected from the group consisting of polylysine and polyimine as described above, and other additives optionally mixed as needed, preferably dissolved in an organic solvent.

The organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide or N. , N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl Ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), B 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 isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, etc. . They may be used singly or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the liquid crystal alignment agent other than the solvent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 10% by weight. The scope. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, and the liquid crystal alignment film is preferably formed into a coating film by heating. However, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small to be obtained. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, a good liquid crystal alignment film is not obtained, and if the viscosity of the liquid crystal alignment agent is increased, the coating property is deteriorated. .

The range of the particularly preferable solid content concentration differs depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. The solid content concentration in the printing method is in the range of 3 to 9% by weight, whereby the solution viscosity is particularly preferably in the range of 12 to 50 mPa·s. In the inkjet method, the solid content concentration is controlled in the range of 1 to 5% by weight, and the solution viscosity is preferably controlled in the range of 3 to 15 mPa·s.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C, more preferably from 20 ° C to 30 ° C.

<Liquid crystal display element>

The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above.

The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). The step (1) is different depending on the substrate used in the desired operation mode. Steps (2) and (3) are the same for each action mode.

(1) First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate.

(1-1) When manufacturing a TN type, STN type or VA type liquid crystal display element, two substrates each having a patterned transparent conductive film are provided as a pair, and it is preferable to pass the transparent conductive film forming surface thereof. The liquid crystal alignment agent of the present invention is applied by an offset printing method, a spin coating method or an inkjet printing method, respectively, and then a coating film is formed by heating each coated surface. Here, as the substrate, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin) can be used. A transparent substrate made of plastic. As the transparent conductive film provided on one surface of the substrate, an NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. In the patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film having no pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, or the like can be used. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film or the coating film, a surface on which the coating film is formed on the surface of the substrate may be preliminarily coated with a functional decane compound or a functional titanium compound. .

After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed in order to prevent the liquid of the applied alignment agent from flowing down. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 100 ° C. The prebaking time is preferably from 0.25 to 10 minutes, preferably from 0.5 to 5 minutes. The solvent is then completely removed, and a calcination (post-baking) step is carried out in order to thermally iridize the polyamic acid as needed. The calcination (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C, and the post-baking time is preferably from 5 to 200 minutes, more preferably from 10 to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

(1-2) On the other hand, when manufacturing an IPS type liquid crystal display element, it is preferable to use a conductive film formation surface of a substrate provided with a comb-shaped pattern of a transparent conductive film and a surface of a counter substrate on which a conductive film is not provided. The liquid crystal alignment agent of the present invention is applied by an offset printing method, a spin coating method or an inkjet printing method, respectively, and then a coating film is formed by heating each coated surface.

The material of the substrate and the transparent conductive film used at this time, the patterning method of the transparent conductive film, the pretreatment of the substrate, and the heating method after applying the liquid crystal alignment agent are the same as those of the above (1-1).

The film thickness to be formed is preferably the same as that of the above (1-1).

(2) When the liquid crystal display element produced by the method of the present invention is a VA type liquid crystal display element, the coating film formed as described above is used as the liquid crystal alignment film as it is, but it can also be used after the following rubbing treatment as desired.

On the other hand, when a liquid crystal display element other than the VA type is produced, a liquid crystal alignment film is formed by performing a rubbing treatment on the coating film formed as described above.

The rubbing treatment is a coating film surface formed as described above, and can be rubbed in a predetermined direction by, for example, a roll of a cloth in which fibers such as nylon, rayon, or cotton are wound. Thereby, a liquid crystal alignment film which imparts an alignment energy to liquid crystal molecules on the coating film is prepared.

Furthermore, the liquid crystal alignment film formed as described above is irradiated with ultraviolet rays on a portion of the liquid crystal alignment film shown in the patent document 13 (Japanese Laid-Open Patent Publication No. Hei 6-222366) or the patent document 14 (JP-A No. 6-281937). The process of changing the pretilt angle of the partial region of the liquid crystal alignment film, or forming a resist film on the portion of the surface of the liquid crystal alignment film as shown in the patent document 15 (JP-A-5-107544), which is different from the previous rubbing treatment. After the rubbing treatment is performed in the direction, the treatment for removing the resist film is performed, and the liquid crystal alignment elements can be improved in various regions of the liquid crystal alignment film to improve the visual characteristics of the obtained liquid crystal display element.

(3) A liquid crystal cell is produced by preparing two substrates on which the liquid crystal alignment film is formed, and disposing liquid crystal between the two substrates disposed opposite each other. Here, when the rubbing treatment is performed on the coating film, the two substrates are disposed at an angle to each other in the rubbing direction of each of the coating films, for example, vertically or anti-parallel.

Examples of the production of the liquid crystal element include the following two methods.

The first method is a conventionally known method. First, the two liquid crystal alignment films are arranged to face each other with a certain gap (cell gap) therebetween, and the peripheral portions of the two substrates are bonded together with a sealant, and the liquid crystal is filled in the cell gap separated by the substrate surface and the sealant, and then passed through. The liquid crystal element is fabricated by sealing the injection hole.

The second method is a method called the ODF (One Drop Fill) method. Applying, for example, a UV curable sealing material to a certain area on one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, and then bonding the liquid crystal alignment film to each other in a relative manner The substrate is then irradiated with ultraviolet light to the entire surface of the substrate to cure the sealant to produce a liquid crystal cell.

When any of the methods is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used is equiaxed, and then slowly cooled to room temperature to desirably remove the flow alignment at the time of liquid crystal injection.

Next, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell.

Here, as the sealant, for example, a curing agent and an epoxy resin containing an alumina ball as a spacer or the like can be used.

As the liquid crystal, for example, a nematic liquid crystal, a disk type liquid crystal, or the like can be used, and among them, a nematic liquid crystal is preferable. In the case of a VA type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable, and for example, a dicyanobenzene liquid crystal or a ruthenium can be used. Liquid crystal, Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and the like. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having a positive dielectric anisotropy is preferable, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, or a terphenyl group can be used. Liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, two An alkane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal or the like. Further, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl phthalate or cholesteryl carbonate may be added to these liquid crystals; a chiral agent sold under the trade names C-15 and CB-15 (manufactured by Merck); A ferroelectric liquid crystal such as a nonoxybenzylidene-p-amino-2-methylbutylcinnamate.

The polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called an "H film" which absorbs iodine is sandwiched by a cellulose acetate protective film, or a polyvinyl chloride protective film may be used. A polarizing plate composed of an H film.

[Examples]

The invention will be more specifically described below based on the examples, but the invention is not limited to the examples.

The ¹ H-NMR of the compound synthesized in the following Synthesis Example, the solution viscosity of the polymer, and the ruthenium iodide ratio of the polyimine were each measured by the following method.

[ ¹ H-NMR]

The ¹ H-NMR of the compound represented by the above formula (A) was measured according to the following conditions.

Measuring device: ECX 400P (manufactured by JEOL Ltd.)

Magnetic field strength: 400MHz

Solvent: dimethyl azine-d ₆

Reference material: tetramethyl decane

Measuring temperature: 25 ° C

[Solution viscosity of polymer]

The solution viscosity (mPa ‧ s) of the polymer was measured by adjusting the polymer concentration to 10% by weight to the solvent used in each synthesis example, and measuring it at 25 ° C using an E-type rotational viscometer.

[醯Iminization rate of polyimine]

A small amount of the polyimine-containing solution obtained in each of the synthesis examples is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in dihydrogenated dimethyl hydrazine to tetramethyl decane. ¹ H-NMR spectrum measured as a reference substance at room temperature by the following formula (1)

Yttrium imidation rate (%) = (1-A ¹ /A ² ×α)×100 (1)

(In the formula (1), A ¹ is a peak area of a proton derived from an NH group in the vicinity of a chemical shift of 10 ppm, A ² is a peak area from other protons, and α is a polyimine precursor (polyglycine) The ratio of the number of other protons of one proton in the NH group is calculated and calculated.

<Synthesis Example of Compound represented by the above formula (A)>

The synthesis of the following compounds (including intermediates) is repeated as required by the procedure described below to ensure the necessary amount in the synthesis of the following compound and polymer.

Synthesis Example A-1

The compound (A-1-1) was synthesized according to the following Scheme 1.

Under a nitrogen atmosphere, 266.5 g of the compound (A-1-1a), 253.3 g of p-chlorobenzenesulfonium chloride, and 1000 mL of dichloromethane were placed in a 5000 mL three-necked flask, and the mixture was stirred at 0 °C. Here, a solution in which 180 mL of triethylamine was dissolved in 200 mL of dichloromethane was added dropwise for 30 minutes, and the mixture was stirred at room temperature (25 ° C) for 3 hours to carry out a reaction. Next, 1000 mL of dichloromethane was added to the obtained reaction mixture, and the obtained organic layer was washed with distilled water. After the washed organic layer was dried over magnesium sulfate, the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. After adding 3000 mL of ethanol to the colorless viscous liquid and stirring well, the precipitated white solid was filtered and recovered to obtain 335.6 g of a compound (A-1-1b).

Next, in a 5000 mL three-necked flask, 220.5 g of the above compound (A-1-1b), 166.2 g of ethyl 4-hydroxybenzoate, 172.8 g of potassium carbonate and 2000 mL of N,N-dimethylformamide were added. The reaction was carried out by stirring at 80 ° C for 8 hours. After the reaction was terminated, 4000 mL of toluene was added to the obtained reaction mixture, and the organic layer was washed with distilled water. After the organic layer was dried over magnesium sulfate, the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. To the obtained colorless viscous liquid, 3000 mL of ethanol was added, and after sufficiently stirring, the precipitated white solid was filtered to obtain 184.1 g of the compound (A-1-1c).

165.8 g of the above compound (A-1-1c), 40.0 g of sodium hydroxide, 1500 mL of tetrahydrofuran, 500 mL of distilled water and 500 mL of ethanol were placed in a 5000 mL three-necked flask, and the mixture was stirred at 90 ° C for 6 hours to carry out a reaction. After the reaction was terminated, 1500 mL of 1 standard diluted hydrochloric acid was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. Next, 2500 mL of toluene was added to the reaction mixture, and the organic layer was washed with distilled water.

The solvent was then removed from the organic layer by a rotary evaporator to obtain 154.2 g of a white powdery compound (A-1-1d).

Under a nitrogen atmosphere, 116.0 g of the above compound (A-1-1d), 62.0 g of p-toluenesulfonium chloride, 23 mL of N,N-dimethylformamide and 600 mL of pyridine were added in a 3000 mL three-necked flask at 100 ° C. Stir for 1 hour. Here, a solution of 92.4 g of 3,5-bis(diallylamino)phenol (compound (B)) dissolved in 150 mL of pyridine was added dropwise thereto over 15 minutes, and the mixture was stirred at 100 ° C for 6 hours to carry out a reaction. After the reaction was terminated, 2000 mL of distilled water was added to the reaction mixture, and extracted with 2500 mL of chloroform to obtain an organic layer. The obtained organic layer was washed with distilled water and dried over magnesium sulfate, and then the solvent was removed by a rotary evaporator to obtain a crude product. The obtained crude product was applied to column chromatography (filler: silicone, developing solvent: hexane / ethyl acetate = 20/1 (weight ratio)), and the solvent was removed from the obtained fraction under reduced pressure to obtain a pale yellow color. The viscous liquid compound (A-1-1e) was 103.8 g.

Further, 97.9 g of the above compound (A-1-1e), 70.3 g of 1,3-dimethylbarbituric acid, and 3.5 g of tetrakis(triphenylphosphino) were added to a 5000 mL three-necked flask under a nitrogen atmosphere. Palladium (0) and 2000 mL of dichloromethane were stirred at 35 ° C for 8 hours to carry out a reaction. After the reaction was terminated, the reaction mixture was concentrated to remove about 1 L of dichloromethane, and the precipitated powder was collected by filtration. The obtained glossy pale yellow powder was dissolved in 5000 mL of tetrahydrofuran, and 60 g of activated carbon was added to the obtained solution, and the mixture was stirred at room temperature for 15 minutes. The obtained mixture was filtered through celite to remove activated carbon, and the solvent was evaporated under reduced pressure to give 55.2 g of white powder compound (A-1-1).

The ¹ H-NMR spectrum of the obtained compound (A-1-1) is shown in Fig. 1.

Synthesis Example A-2

The compound (A-2-1) was synthesized according to the following Scheme 2.

In a 5000 mL three-necked flask, 142.2 g of 3,5-bis(diallylamino)phenol (compound (B)), 220.2 g of ethylene carbonate, 16.1 g of tetrabutylammonium bromide, and 16.1 g of tetrabutylammonium bromide were added under a nitrogen atmosphere. 1000 mL of N,N-dimethylformamide was stirred at 150 ° C for 6 hours to carry out a reaction. 2000 mL of ethyl acetate and 500 mL of methanol were added to the obtained reaction mixture, and the obtained organic layer was washed successively with a 1 N aqueous solution of sodium hydroxide and distilled water, dried over magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a crude product. The obtained composition was applied to column chromatography (filler: silicone, developing solvent: hexane/ethyl acetate = 4/1 (weight ratio)), and the obtained fraction was removed under reduced pressure to obtain a pale orange viscosity. The liquid compound (A-2-1a) was 138.6 g.

Next, 154.6 g of the compound (A-1-1d) synthesized in the same manner as the above Synthesis Example A-1, 76.3 g of p-toluenesulfonium chloride, and 32 mL of N, N-di were placed in a 3000 mL three-necked flask under a nitrogen atmosphere. Methylformamide and 800 mL of pyridine were stirred at 100 ° C for 1 hour. Here, a solution of 131.4 g of the compound (A-2-1a) obtained above was dissolved in 200 mL of pyridine dropwise over 15 minutes, and the obtained mixture was stirred at 100 ° C for 12 hours to carry out a reaction. After the reaction was terminated, 2000 mL of distilled water was added to the reaction mixture, and extracted with 2500 mL of chloroform to obtain an organic layer. The obtained organic layer was washed with distilled water, dried over magnesium sulfate, and then evaporated. The obtained crude product was applied to column chromatography (filler: silicone, developing solvent: hexane/ethyl acetate = 10/1 (weight ratio)), and the obtained fraction was removed under reduced pressure to obtain a pale yellow viscosity. The liquid compound (A-2-1b) was 178.4 g.

Further, 174.3 g of the above compound (A-2-1b), 117.1 g of 1,3-dimethylbarbituric acid, and 5.8 g of tetrakis(triphenylphosphino) were placed in a 5000 mL three-necked flask under a nitrogen atmosphere. Palladium (0) and 2000 mL of dichloromethane were stirred at 35 ° C for 8 hours to carry out a reaction. After the reaction was terminated, 2000 mL of chloroform was added to the reaction mixture, and the obtained organic layer was washed with a 1 N aqueous solution of sodium carbonate to remove unreacted 1,3-dimethylbarbituric acid, and then washed with distilled water. The solvent was removed from the organic layer under reduced pressure, and the obtained powder was washed thoroughly with ethanol. To the solution obtained by dissolving the washed powder (light yellow) in 2000 mL of tetrahydrofuran, 100 g of activated carbon was added, and the mixture was stirred at room temperature for 15 minutes. After removing the activated carbon from the obtained mixture by Celite filtration, the solvent was removed under reduced pressure to give a white powdery compound (A-2-1) (88.6 g).

The ¹ H-NMR spectrum of the obtained compound (A-2-1) is shown in Fig. 2.

Synthesis Example A-3

The compound (A-2-2) was synthesized according to the following Scheme 3.

Under a nitrogen atmosphere, 238.2 g of the compound (A-2-2a), 253.3 g of p-chlorobenzenesulfonium chloride and 1000 mL of dichloromethane were placed in a 5,000 mL three-necked flask, and stirred at 0 °C. Here, a solution in which 180 mL of triethylamine was dissolved in 200 mL of dichloromethane was added dropwise thereto over 30 minutes, and the mixture was stirred at room temperature for 3 hours to carry out a reaction. After the reaction was terminated, 1000 mL of dichloromethane was added to the obtained reaction mixture, and the obtained organic layer was washed with distilled water and dried over magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. 3000 mL of ethanol was added to the obtained colorless viscous liquid, and after stirring well, the precipitated white solid was collected by filtration, and the compound (A-2-2b) 318.2g was obtained.

Next, in a 5000 mL three-necked flask, 206.1 g of the above compound (A-2-2b), 166.2 g of ethyl 4-hydroxybenzoate, 172.8 g of potassium carbonate and 2000 mL of N,N-dimethylformamide were added. The reaction was carried out by stirring at 80 ° C for 8 hours. After the reaction was terminated, 4000 mL of toluene was added to the obtained reaction mixture, and the obtained organic layer was washed with distilled water and dried over magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. 3000 mL of ethanol was added to the obtained colorless viscous liquid, and after stirring well, the precipitated white solid was collected by filtration, and the compound (A-2-2c) 174.6 g was obtained.

154.5 g of the above compound (A-2-2c), 40.0 g of sodium hydroxide, 1500 mL of tetrahydrofuran, 500 mL of distilled water and 500 mL of ethanol were placed in a 5000 mL three-necked flask, and the mixture was stirred at 90 ° C for 6 hours to carry out a reaction. After the reaction was terminated, 1500 mL of a 1 equivalent concentration of dilute hydrochloric acid was added to the obtained reaction mixture, and the mixture was stirred at room temperature for 1 hour. Next, 2500 mL of toluene was added to the obtained mixture, and the obtained organic layer was washed with distilled water, and the solvent was removed by a rotary evaporator to obtain 142.9 g of a white powdery compound (A-2-2d).

107.5 g of the above compound (A-2-2d), 62.0 g of p-toluenesulfonium chloride, 23 mL of N,N-dimethylformamide and 600 mL of pyridine were added to a 3000 mL three-necked flask under nitrogen atmosphere at 100 ° C. Stir under 1 hour. Here, 106.7 g of a solution of the compound (A-2-1a) synthesized in the same manner as in the above Synthesis Example A-2 was dissolved in 150 mL of pyridine, and the mixture was stirred at 100 ° C for 6 hours to carry out a reaction. After the reaction was terminated, 2000 mL of distilled water was added to the obtained reaction mixture, followed by extraction with 2500 mL of chloroform to obtain an organic layer. The obtained organic layer was washed with distilled water, dried over magnesium sulfate, and then evaporated. The obtained crude product was applied to a column chromatography (filler: silicone, developing solvent: hexane / ethyl acetate = 20/1 (weight ratio)), and the solvent was removed from the obtained fraction under reduced pressure to obtain a pale yellow color. The viscous liquid compound (A-2-2e) was 111.6 g.

Further, 100.3 g of the above compound (A-2-2e), 70.3 g of 1,3-dimethylbarbituric acid, and 3.5 g of tetrakis(triphenylphosphino) were added to a 5000 mL three-necked flask under a nitrogen atmosphere. Palladium (0) and 2000 mL of dichloromethane were stirred at 35 ° C for 8 hours to carry out a reaction. After the reaction was terminated, the reaction mixture was concentrated to remove about 1000 mL of dichloromethane, and the precipitated powder was collected by filtration. After the obtained glossy pale yellow powder was dissolved in 5000 mL of tetrahydrofuran, 60 g of activated carbon was added to the obtained solution, and the mixture was stirred at room temperature for 15 minutes. After removing activated carbon from the obtained mixture by celite filtration, the solvent was removed under reduced pressure to give 63.0 g of white powdery compound (A-2-2).

The ¹ H-NMR spectrum of the obtained compound (A-2-2) is shown in Fig. 3.

<Synthesis Example of Polyimine]

Synthesis example PI-1

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 43 g (0.40 mol) as diamine were dissolved in 798 g of N-methyl-2-pyrrolidone. P-phenylenediamine and 49 g (0.10 mol) of the compound (A-1-1) obtained in the above Synthesis Example A-1 were reacted at 60 ° C for 6 hours to obtain a solution containing polylysine. A solution of a small amount of the obtained polyaminic acid solution, N-methyl-2-pyrrolidone, and a solution having a polyglycine concentration of 10% by weight was found to have a solution viscosity of 62 mPa·s.

Next, 2000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent (the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed from the system in the present operation, the same below), and about 15 is obtained. A solution of polyethylenimine (B-1) having a weight percent of oxime imidization of about 50%. A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 49 mPa·s.

Synthesis Example PI-2

66 g (0.30 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 60 g (0.20 mol) 1,3 as tetracarboxylic dianhydride were dissolved in 980 g of N-methyl-2-pyrrolidone. 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione 38 g (0.35 mol) of p-phenylenediamine as a diamine and 81 g (0.15 mol) of the compound (A-2-1) obtained in the above Synthesis Example A-2 were reacted at 60 ° C for 6 hours to obtain a content. A solution of polylysine. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 58 mPa·s.

Next, 2280 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a polyimine (B-2) containing about 15% by weight of a ruthenium iodide ratio of about 50%. The solution. A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 48 mPa·s.

Synthesis Example PI-3

88 g (0.40 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 20 g (0.10 mol) 1,2 as tetracarboxylic dianhydride were dissolved in 728 g of N-methyl-2-pyrrolidone. 3,4-cyclobutanetetracarboxylic dianhydride, 48 g (0.45 mol) of p-phenylenediamine as a diamine, and 26 g (0.05 mol) of the compound obtained in the above Synthesis Example A-3 (A-2-2) The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 65 mPa·s.

Next, 1700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of polyimine (B-3) having an oxime imidization ratio of about 50%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 50 mPa·s.

Synthesis Example PI-4

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 43 g (0.40 mol) as diamine were dissolved in 798 g of N-methyl-2-pyrrolidone. P-phenylenediamine and 49 g (0.10 mol) of the compound (A-1-1) obtained in the above Synthesis Example A-1 were reacted at 60 ° C for 4 hours to obtain a solution containing polylysine. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 45 mPa·s.

Next, 2000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80 g of pyridine and 102 g of acetic anhydride were added, and the mixture was subjected to dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of polyimine (B-4) having an oxime imidization ratio of about 80%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 49 mPa·s.

Synthesis Example PI-5

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 32 g (0.30 mol) as a diamine were dissolved in 932 g of N-methyl-2-pyrrolidone. P-phenylenediamine, 10 g (0.05 mol) of 4,4'-diaminodiphenylmethane, 81 g (0.15 mol) of the compound (A-2-1) obtained in the above Synthesis Example A-2, at 60 The reaction was carried out at ° C for 4 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 47 mPa·s.

Next, 2160 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80 g of pyridine and 102 g of acetic anhydride were added, and the mixture was subjected to a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of polyimine (B-5) having an oxime imidization ratio of about 80%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 48 mPa·s.

Synthesis Example PI-6

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 38 g (0.35 mol) as a diamine were dissolved in 780 g of N-methyl-2-pyrrolidone. P-phenylenediamine, 20 g (0.10 mol) of 4,4'-diaminodiphenylmethane, 26 g (0.05 mol) of the compound (A-2-2) obtained in the above Synthesis Example A-3, at 60 The reaction was carried out at ° C for 4 hours to obtain a solution containing polyamic acid. A solution of a small amount of the obtained polyamic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 43 mPa·s.

Next, 1800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80 g of pyridine and 102 g of acetic anhydride were added, and the mixture was subjected to dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of polyimine (B-6) having an oxime imidization ratio of about 80%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 50 mPa·s.

<Comparative Synthesis Example of Polyimine]

Comparative synthesis example pi-1

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 43 g (0.40 mol) as diamine were dissolved in 830 g of N-methyl-2-pyrrolidone. Phenylenediamine and 52 g (0.10 mol) of 3(3,5-diaminobenzimidyloxy)cholestane were reacted at 60 ° C for 6 hours to obtain a solution containing polylysine. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 60 mPa·s.

Next, 1900 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the mixture was subjected to dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of a polyamidimide (b-1) having a ruthenium iodide ratio of about 50%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 47 mPa·s.

Comparative synthesis example pi-2

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 43 g (0.40 mol) as diamine were dissolved in 830 g of N-methyl-2-pyrrolidone. P-phenylenediamine, 52 g (0.10 mol) of 3(3,5-diaminobenzimidyloxy)cholestane, was reacted at 60 ° C for 4 hours to obtain a solution containing polylysine. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 44 mPa·s.

Next, 1900 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80 g of pyridine and 102 g of acetic anhydride were added, and the mixture was subjected to dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of polyimine (b-2) having an oxime imidization ratio of about 80%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 47 mPa·s.

Comparative synthesis example pi-3

66 g (0.30 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 60 g (0.20 mol) 1,3 as tetracarboxylic dianhydride were dissolved in 970 g of N-methyl-2-pyrrolidone. 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione 38 g (0.35 mol) of p-phenylenediamine as a diamine and 78 g (0.15 mol) of 3(3,5-diaminobenzimidyloxy)cholestane were reacted at 60 ° C for 6 hours. A solution containing polylysine is obtained. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 60 mPa·s.

Next, 2240 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the mixture was subjected to a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of a polyamidimide (b-3) having a ruthenium iodide ratio of about 50%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 47 mPa·s.

Comparative synthesis example pi-4

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 32 g (0.30 mol) as a diamine were dissolved in 920 g of N-methyl-2-pyrrolidone. P-phenylenediamine, 10 g (0.05 mol) of 4,4'-diaminodiphenylmethane and 78 g (0.15 mol) of 3(3,5-diaminobenzimidyloxy)cholestane, The reaction was carried out at 60 ° C for 4 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a polyglycine concentration of 10% by weight was 44 mPa·s.

Next, 2140 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80 g of pyridine and 102 g of acetic anhydride were added, and the mixture was subjected to a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent to obtain a solution containing about 15% by weight of polyimine (b-4) having an oxime imidization ratio of about 80%. . A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added thereto, and the solution viscosity of the solution having a concentration of 10% by weight of polyimine was 47 mPa·s.

<Preparation and evaluation of liquid crystal alignment agent>

Example 1

(I) Preparation of liquid crystal alignment agent

In a solution containing the polyimine (B-1) obtained in the above Synthesis Example PI-1, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) are added, and further, relative to 100 parts by weight. Polyimine is added with 10 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane as an epoxy compound, and stirred well to prepare a solvent composition of NMP. : BC = 50:50 (weight ratio), and a solution having a solid concentration of 7.0% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent.

(II) Evaluation of liquid crystal alignment agent

The liquid crystal alignment agent prepared above was evaluated according to the method described below. The evaluation results are shown in Table 1.

(1) Evaluation of coatability (effect of placement time after coating)

The liquid crystal alignment agent prepared above was applied to each of the transparent electrode faces of the glass substrate having the transparent electrode made of the ITO film by using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.), from the end of the coating. The time until the start of prebaking (placement time) is controlled to 30 seconds, 60 seconds, 80 seconds, 100 seconds, and 120 seconds. After being placed, it is heated on a hot plate at 80 ° C for 1 minute (prebaking) to remove After the solvent, it was heated on a hot plate at 230 ° C for 10 minutes (post-baking) to form an average film thickness of 600, respectively. Coating film with different time. The coating film was observed by a microscope having a magnification of 20 times for unevenness in printing and pores, and the longest standing time of both printing unevenness and pores was not observed.

When the value is 60 seconds or more, the coating property is considered to be good.

(2) Evaluation of film thickness uniformity of coating film

In the coating film formed as described above, the film thickness formed in the center of the substrate was measured using a stylus type film thickness meter (manufactured by KLA TENCOR Co., Ltd.) for the coating film formed at the longest standing time in which neither printing unevenness nor pores were observed. The film thickness difference between the two sides from the outer end of the substrate to the center of the distance of 15 mm was calculated. The film thickness difference is as long as 20 Hereinafter, the film thickness uniformity is good.

(3) Fabrication of liquid crystal cells

The liquid crystal alignment agent prepared above was applied onto a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.), and left for 1 minute, at 80 The plate was heated on a hot plate at °C for 1 minute (prebaking), the solvent was removed, and further heated on a hot plate at 230 ° C for 10 minutes (post-baking) to form an average film thickness of 600. Coating film (liquid crystal alignment film). By repeating this operation, a pair of substrates (two pieces) having a liquid crystal alignment film on the ITO film were obtained.

Next, an epoxy resin adhesive having an alumina ball having a diameter of 3.5 μm is applied onto the outer edge of the liquid crystal alignment film of the pair of substrates, and then the surface of the liquid crystal alignment film is superposed and pressure-bonded to cure the adhesive. . Next, a nematic liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was filled between a pair of substrates close to the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell.

(4) Evaluation of voltage retention rate

For the liquid crystal display device manufactured above, a voltage of 5 V was applied at 60 ° C for 60 μsec, and after a 167-millisecond interval was applied, the voltage holding ratio (VHR0) after the application was released to 167 msec was used as a measuring device. The company's "VHR-1" was measured.

(5) Evaluation of heat stability

The liquid crystal cell produced as described above was applied at a temperature of 70 ° C for 500 hours, and a rectangular wave of 30 Hz and 3.0 V having an alternating current of 6.0 V (peak-peak) was superposed. The voltage holding ratio (VHR ₅₀₀ ) of the cartridge after 500 hours has been measured in the same manner as in the above (4), and the value is compared with the initial value (the voltage holding ratio measured in the above (4), VHR ₀ ), and the difference therebetween (Δ) VHR) is adjusted according to the following formula (2). When the value is less than 10%, the heat resistance stability is considered to be "good", and when it is 10% or more, the heat resistance stability is considered to be "not good".

△VHR(%)=VHR ₀ -VHR ₅₀₀ (2)

Examples 2 to 12 and Comparative Examples 1 to 4

In the first embodiment, a solution containing the polymer described in Table 1 was used instead of the solution containing the polyimine (B-1), and the amount of the epoxy compound used was as shown in Table 1, and Example 1 was used. The liquid crystal alignment agent was prepared in the same manner and evaluated. The evaluation results are shown in Table 1.

Further, in Comparative Examples 2 and 4, when N-methyl-2-pyrrolidone and butyl cellosolve were added to the solution containing polyimine, the evaluation of the liquid crystal alignment agent could not be performed because the precipitation of the polyimine was observed. .

Comparative Examples 5 and 6

In Comparative Examples 2 and 4, a liquid crystal alignment agent was prepared in the same manner as in Comparative Examples 2 and 4 except that two solvents such as N-methyl-2-pyrrolidone: butyl cellosolve = 70:30 (weight ratio) were added. Evaluation.

The evaluation results are shown in Table 1.

Fig. ^{1 is a 1} H-NMR chart of the compound (A-1-1) obtained in Synthesis Example A-1.

Fig. 2 is a ¹ H-NMR chart of the compound (A-2-1) obtained in Synthesis Example A-2.

Fig. 3 is a ¹ H-NMR chart of the compound (A-2-2) obtained in Synthesis Example A-3.

Claims (10)

A liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine and polyamidiamine, at least a part of a molecule of the polymer having a formula (A') a group, R ^I -(X ^I )n ₁ -R ^II -OX ^II -COO-(R ^III O)n ₂ -* (A') In the formula (A'), R ^I represents a carbon number of 3~ An alkyl group, a trifluoromethyl group or a 4,4,5,5,5-pentafluoropentyl group, R ^II represents a single bond or a methylene group, and R ^III represents an alkylene group having 2 to 5 carbon atoms. X ^I and X ^II each represent a divalent alicyclic group, a divalent heterocyclic group, an extended aryl group or a divalent heteroaromatic group, and a plurality of X ^I groups may be the same or different from each other, and n1 is 2 to 5 The integer, n2 is an integer from 0 to 10, and "*" indicates a connection key. The liquid crystal alignment agent of claim 1, wherein the polymer is a polymer selected from the group consisting of at least one polyimine prepared by dehydrating a polyphthalic acid and the polyglycolic acid. The polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A). In the formula (A), R ^I , R ^II , R ^III , X ^I , X ^II , n1 and n2 are respectively the same as defined in the above formula (A'). The liquid crystal alignment agent of claim 2, wherein X ^I in the above formula (A) is a divalent alicyclic group, and X ^II represents an exoaryl group. The liquid crystal alignment agent of claim 3, wherein (X ^I ) _n1 in the above formula (A) represents a 4,4′-linked cyclohexyl group, and X ^II represents a 1,4-phenylene group. The liquid crystal alignment agent according to any one of claims 2 to 4, wherein the tetracarboxylic dianhydride contains 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 5. A liquid crystal display element obtained by laminating a polarizing plate on an outer surface of a liquid crystal cell, wherein the liquid crystal cell is prepared by preparing two substrates having a liquid crystal alignment film as in claim 6 of the patent application, and The liquid crystal is disposed between the two substrates disposed. A poly-proline acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the formula (A) in the liquid crystal alignment agent of any one of claims 2 to 5; The carboxylic acid dianhydride is composed of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b- Hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4, 5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione , 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5- Bilateral oxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane- 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, pyromellitic dianhydride and At least one selected from the group consisting of compounds represented by the following formula (T-5); The tetracarboxylic dianhydride and the diamine are used in an amine group based on 1 equivalent of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. A polyimine which is obtained by dehydration ring closure of polylysine according to item 8 of the patent application. A compound represented by the formula (A) in the liquid crystal alignment agent according to any one of claims 2 to 5.