KR20150108742A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, compound and polymer - Google Patents

Abstract

Provided is a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a rare decease in a voltage maintenance rate for a long time and excellent reliability. The present invention relates to a liquid crystal alignment agent containing a polymer having a structure represented by Formula (1): (1) (In Formula (1), X^1 and X^2 are single bonds, oxygen atoms, sulfur atoms, carbonyl groups, or ester bonds. X^1 and X^2 are not single bonds at the same time. Y is a group obtained by removing two hydrogen atoms from a 5-ringed or 6-ringed hetero-aromatic compound including one or two hetero atoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom in a ring structure. Two coupling hands of Y directly cats from a 5-ring or 6-ring. A plurality of R^1 are a hydrogen atom or a fluorine atom. m1 and m2 are integers of 0-20, and ′*′ respectively represents coupling hands.)

Description

FIELD OF THE INVENTION [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More particularly, the present invention relates to a liquid crystal aligning agent capable of forming a liquid crystal alignment film having a small decrease in voltage holding ratio over a long period of time under severe use conditions and having high reliability, and a liquid crystal display device .

The liquid crystal display element can be classified into various modes depending on the electrode structure and physical properties of the liquid crystal molecules to be used. For example, a liquid crystal alignment film is formed on the surface of a substrate on which a transparent conductive film is formed to form a substrate for a liquid crystal display device. Two liquid crystal alignment films are disposed opposite to each other to form a nematic liquid crystal layer having positive dielectric anisotropy Called TN (Twisted Nematic) type (Patent Document 1) in which the long axis of the liquid crystal molecules is twisted by 90 degrees continuously from one substrate to the other substrate by using a cell having a sandwich structure.

STN (Super Twisted Nematic) type which can realize a higher duty ratio than a TN type liquid crystal display device (Patent Document 2);

A VA (Vertical Alignment) type in which a nematic liquid crystal layer having a negative dielectric anisotropy is injected into the pole gap and the liquid crystal is oriented substantially perpendicular to the substrate (Patent Document 3);

An IPS (In-Plane Switching) type (Patent Documents 4 and 5) in which comb electrodes are arranged in the form of comb teeth in a single substrate surface so that the driving direction of the liquid crystal upon application of an electric field is only in the in-plane direction of the substrate.

An FFS (Fringe Field Switching) type (Patent Document 6) in which the electrode structure of the IPS type is changed and the aperture ratio of the display element portion is raised to improve the brightness;

OCB (Optical Compensated Bend) type (Patent Document 7) which is excellent in high-speed response of an image screen while having little visual dependency,

Liquid crystal display devices are known.

As a material of the liquid crystal alignment film in these various liquid crystal display devices, resin materials such as polyamic acid, polyimide, polyamide, and polyester are known. In particular, a liquid crystal alignment film made of polyamic acid or polyimide has heat resistance, And is used in many liquid crystal display elements because it has excellent affinity with liquid crystals (Patent Document 8).

In such liquid crystal aligning agents, reliability (long-term stability against a severe environment) has recently been demanded more than ever before. The situation is as follows.

Liquid crystal televisions, which have been popular in recent years as compared to notebook PCs and monitor displays, which have been the main applications of conventional liquid crystal display devices, require a long replacement cycle and long life span. Here, in a liquid crystal display device for a liquid crystal projector in which the demand as a home theater is increasing in recent years, a light source having a high irradiation intensity such as a metal halide lamp is used, and therefore resistance to light and heat becomes a big problem. In addition, since a liquid crystal display element for a mobile device such as a cellular phone or a car navigation device for a vehicle is required to increase the brightness of the backlight in order to improve the visibility in sunlight containing strong ultraviolet rays, Is deteriorated. When these devices are used as a display of a television game, it is assumed that they are placed under continuous driving for a very long time under the above-described conditions.

As described above, the liquid crystal display element is exposed to a harsh environment such as high-intensity light irradiation, long-time driving, and the like, which can not be expected in the past, along with the increase in versatility.

It has been pointed out that a conventionally known liquid crystal alignment film is insufficient for such a severe environment.

Japanese Patent Application Laid-Open No. 4-153622 Japanese Patent Application Laid-Open No. 60-107020 Japanese Patent Application Laid-Open No. 11-258605 Japanese Laid-Open Patent Publication No. 56-91277 U.S. Patent No. 5,928,733 Japanese Patent Application Laid-Open No. 2002-082357 Japanese Patent Application Laid-Open No. 9-105957 Japanese Laid-Open Patent Publication No. 62-165628

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film with less deterioration of voltage holding ratio over a long period of time and having excellent reliability.

Another object of the present invention is to provide an excellent liquid crystal display element in which the display quality does not deteriorate over a long period of time.

According to the present invention, the above objects and advantages of the present invention are achieved by firstly,

A liquid crystal aligning agent characterized by comprising a polymer having a structure represented by the following formula (1): " (1) "

_{^{* -X 1 - (CR 1 2}} ) m1 -Y- (CR 1 2) m2 -X 2 - * (1)

(In the formula (1), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group or an ester bond, provided that when both of X ¹ and X ² are a single bond at the same time No,

Y is a group obtained by removing two hydrogen atoms from a five-membered or six-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom in the ring structure Group, wherein both of the two bonding hands of Y are directly emitted from the above-mentioned 5-membered ring or 6-membered ring,

A plurality of R < ¹ > are each independently a hydrogen atom or a fluorine atom,

m1 and m2 are each independently an integer of 0 to 20, and

Quot; and " * " each indicate a combined hand).

The above objects and advantages of the present invention are secondly,

And a liquid crystal alignment film formed of the above liquid crystal aligning agent.

According to the present invention, there is provided a liquid crystal aligning agent capable of forming a liquid crystal alignment film excellent in reliability with little decrease in the voltage holding ratio over a long period of time.

The liquid crystal display element of the present invention including the liquid crystal alignment film formed of the liquid crystal aligning agent does not deteriorate display quality over a long period of time.

Therefore, the technique of the present invention can be suitably applied to applications such as a liquid crystal television, a liquid crystal projector, a cellular phone, a portable game machine, an information display, and the like.

1 is a schematic view showing electrode patterns in a liquid crystal cell manufactured in Example 12 and Comparative Examples 4 and 5. FIG.

(Mode for carrying out the invention)

The liquid crystal aligning agent of the present invention contains a polymer having the structure represented by the above formula (1).

Y in the formula (1) is, for example, a group represented by each of the following formulas:

(Wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

X each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms Group;

n1 and n4 are each independently an integer of 0 to 2;

n2 is 0 or 1;

n3 are each independently an integer of 0 to 3; And

Quot; and " * " each indicate a combined hand).

The alkyl group represented by R in the above formula is preferably an alkyl group having 1 to 3 carbon atoms, and specifically, it is more preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group. Examples of the halogen atom of X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group of X include methyl, ethyl, n-propyl, isopropyl and the like;

Examples of the fluoroalkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group and the like;

Examples of the alkenyl group include a vinyl group, an allyl group and the like;

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group and the like;

Examples of the fluoroalkoxy group include a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group and the like. n1 and n4 are each independently 0 or 1, and more preferably 0.

Y in the formula (1) is particularly preferably a pyridinyl group, and among them, a 2,5-pyridinylene group, a 2,6-pyridinylene group or a 3,5-pyridinylene group is preferable.

R ¹ in the formula (1) is a hydrogen atom;

Each of m1 and m2 in the above formula (1) is preferably an integer of 0 to 2, each independently.

When X ¹ and X ² in the formula (1) are an ester bond, the bonding direction is arbitrary, but it is preferable that the carbonyl carbon of the ester bond is located inside. As X ¹ and X ² , it is preferable that one of them is an oxygen atom or an ester bond and the other is a single bond, an oxygen atom or an ester bond.

The structure represented by the formula (1) is particularly preferably a structure represented by each of the following formulas:

(&Quot; * " in the above expression represents a binding hand, respectively).

The polymer contained in the liquid crystal aligning agent of the present invention may be suitably used without any limitations as long as it has the structure represented by the formula (1). The polymer contained in the liquid crystal aligning agent of the present invention preferably has the structure represented by the above formula (1) in the main chain of the polymer.

Here, the main chain of the polymer means a portion of the " stem " composed of a chain of the longest atoms among the polymers. To have the structure represented by the above formula (1) in the main chain means that this structure constitutes a part of the main chain. In this case, although the structure represented by the formula (1) is present in the main chain, it is prohibited that the structure is present in a part other than the main chain such as a side chain (a part branched from the "stem" It is not.

Examples of the polymer having the structure represented by the formula (1) contained in the liquid crystal aligning agent of the present invention include polyamic acid having a structure represented by the formula (1), imidized polymer of polyamic acid, polyamic acid ester, poly Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like can be given as examples of the poly (meth) acrylate. Of these, it is preferable to use at least one polymer selected from the group consisting of polyamic acid, imidized polymer of polyamic acid, polyamic acid ester and polyorganosiloxane,

It is more preferable to use at least one polymer selected from the group consisting of polyamic acid and imidized polymer thereof.

The polyamic acid may be, for example,

A method of reacting a tetracarboxylic acid dianhydride containing a tetracarboxylic acid dianhydride having a structure represented by the above formula (1) with a diamine, or

Can be preferably synthesized by a method of reacting tetracarboxylic acid dianhydride with a diamine containing a diamine having the structure represented by the formula (1).

The imidized polymer of the polyamic acid can be obtained by dehydrating and ring closure of the polyamic acid to imidize all or a part of the arid acid structure.

As the polymer contained in the liquid crystal aligning agent of the present invention,

A polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a diamine having the structure represented by the formula (1)

And an imidized polymer obtained by subjecting the polyamic acid to dehydration ring closure.

Hereinafter, a method of synthesizing a polymer particularly preferably contained in the liquid crystal aligning agent of the present invention will be described.

Examples of the tetracarboxylic acid dianhydride that can be used in the synthesis of the polyamic acid having the structure represented by the formula (1) include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, etc. . Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydro Naphtho [1,2-c] furan-1,3-dione, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, bicyclo [3.3. 0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8 , 10-tetra A;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride can be used, and tetracarboxylic acid dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

As the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid, it is preferable to include the alicyclic tetracarboxylic dianhydride,

2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, At least one member selected from the group consisting of 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride More preferably 60 mol% or more, and particularly preferably 80 mol% or more of all the tetracarboxylic acid dianhydrides selected from the group consisting of the tetracarboxylic dianhydride and the tetracarboxylic acid dianhydride. It is preferable to use at least one species selected from the group consisting of

The diamine preferably used for the synthesis of the polyamic acid having the structure represented by the formula (1) includes a diamine having the structure represented by the formula (1).

The diamine having the structure represented by the formula (1) is a compound in which the amino group is directly bonded to two bonds of the structure represented by the formula (1) via a bonding group. Examples of suitable coupling groups include a phenylene group, a naphthylene group and a biphenylene group. These aromatic rings may be substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms Or may be substituted. As the coupler, the above-mentioned optionally substituted phenylene group is preferable. Namely, as a preferred example of the diamine having the structure represented by the above formula (1), a compound represented by the following formula (MDA) can be mentioned:

^{_{H 2 N-Ph-X 1}} - (CR 1 2) m1 -Y- (CR 1 2) m2 -X 2 -Ph-NH 2 ... (MDA)

(In the formula (MDA), X ¹ , X ² , Y, R ¹ , m ¹ and m 2 have the same meanings as those in the formula (1)

And the two Ph's are each independently a phenylene group which may be substituted).

Ph in the formula (MDA) is particularly preferably a 1,4-phenylene group.

As the diamine preferably used for synthesis of the polyamic acid having the structure represented by the formula (1), only the diamine having the structure represented by the formula (1) may be used, or other diamines other than the diamine may be used in combination.

Other diamines that can be used here are classified as diamines having a pretilt angular expression group and diamines having no pretilt angular expression group.

As other diamines having a pretilt angular expression group, those which are aromatic diamines having a pretilt angular expression group are preferable, and specific examples thereof include dodecaneoxy-2,4-diaminobenzene, tetradecanoxy- 2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy- 5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy- Diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestearyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestearyloxy- 4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestearyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy ) Cholestane, 3,6-bis ( 4-aminophenoxy) cholestane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-heptylcyclohexyl) benzamide, a compound represented by the following formula (A-1), and the like can be given. have:

^Wherein X ¹ and X ² each independently represent a single bond, ^* -O-, ^* -COO- or ^* -OOC- (provided that the bond is represented by the formula * Toward the left direction of < / RTI >

R ^I is a single bond, a methylene group or an alkylene group having 2 or 3 carbon atoms;

a is 0 or 1, b is an integer of 0 to 2, provided that a and b are not 0 at the same time;

and c is an integer of 1 to 20).

Examples of the divalent group represented by X ^I -R ^I -X ^II - in the above formula (A-1) include a methylene group, an alkylene group having 2 or 3 carbon atoms, ^* -O-, ^* -COO- or ^* -O- CH ₂ CH ₂ -O- (provided that a bonding hand having "*" attached thereto is bonded to a diaminophenyl group). When c is 3 or greater in the group -C _C H _{2C +1,} it is preferable that the group is straight chain. The two amino groups in the diaminophenyl group are preferably 2,4-position or 3,5-position relative to other groups. Specific examples of the compound represented by the above formula (A-1) include (A-1-1-1), (A-1-1-2)

(In the above formula, " n- " represents a linear chain, respectively).

Examples of other diamines not having a pretilt angular expression group include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like, each having no pretilt angular expression group.

Of the other diamines not having a pretilt angular expression group, examples of the aliphatic diamine include 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of the aromatic diamine include aromatic diamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) Bis (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenoxy) Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- bis (4-aminophenoxy) benzene, 4,4'-bis (4-phenylene diisopropylidene) bisaniline, -Aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6- N, N'-bis (4-tert-butylphenyl) aminocarbazole, N-methyl-3,6-diaminocarbazole, Aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4- , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate , 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3- aminobenzylamine, 1- (2,4-diaminophenyl) piperazine- Aminophenyl-4-yl) benzene-1,3-diamine, 1,3-bis (N- -Aminoethyl) aniline, a compound represented by the following formula, and the like;

As the diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be used. In addition, diamines described in JP-A-2010-97188 can be used have.

The diamine used for synthesizing the polyamic acid having the structure represented by the formula (1) preferably contains 1 mol% or more of the diamine having the structure represented by the formula (1) By mole or more, and more preferably 5% by mole or more.

When the liquid crystal aligning agent of the present invention is applied to vertically aligned liquid crystal display devices such as VA type, it is preferable that other diamines having a pretilt angular expression group are contained in an amount of 3 mol% or more based on the total diamine, , More preferably from 5 to 90 mol%, and still more preferably from 10 to 80 mol%. On the other hand, when the liquid crystal aligning agent of the present invention is applied to a horizontal alignment type liquid crystal display device such as TN type, STN type, IPS type or FFS type, the ratio of other diamines having a pretilt angle- , Preferably 20 mol% or less, and more preferably 10 mol% or less.

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used for the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 to 2 equivalents based on 1 equivalent of the amino group contained in the diamine compound , More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably -20 to 150 占 폚, more preferably 0 to 100 占 폚, preferably 0.5 to 24 hours, 2 to 10 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized, and examples thereof include N-methyl-2-pyrrolidone, N-ethyl- N, N-dimethylimidazolinone, N, N, 2-trimethylpropionamide, dimethylsulfoxide, gamma -butyrolactone, tetramethylurea, hexamethylphosphoric triamide, Non-protonic polar solvent such as methylene chloride and Meid;

phenol-based solvents such as m-cresol, xylenol, phenol, halogenated phenol and the like. The amount (a) of the organic solvent to be used is preferably 0.1 to 50% by weight, more preferably 5 to 30% by weight, based on the total amount (a + b) of the reaction solution, of the tetracarboxylic acid dianhydride and the diamine compound %.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, .

When the polyamic acid is subjected to dehydration ring closure to form an imide, the reaction solution may be directly supplied to the dehydration ring-closing reaction. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then subjected to a dehydration ring- The crude acid may be purified and then subjected to a dehydration ring-closing reaction.

The polyamic acid can be isolated and purified by a known method.

The imide of the polyamic acid having the structure represented by the above formula (1) can be obtained by imidizing the polyamic acid synthesized as described above by dehydration ring closure. At this time, the whole of the arctic structure may be completely imidized by dehydration ring closure, or only a part of the arid acid structure may be subjected to dehydration ring closure to form a partial imide, in which an acid structure and an imide structure coexist. The imidization rate of the imide of the polyamic acid is preferably 10% or more, more preferably 30 to 95%.

The dehydration ring-closure of the polyamic acid can be carried out by a method of (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring- . Of these, the method (ii) is preferred.

On the other hand, in the method (ii), examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structural unit. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, the present invention is not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

In this way, a reaction solution containing an imide of polyamic acid can be obtained. This reaction solution may be supplied directly to the preparation of the liquid crystal aligning agent or may be provided to the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. After the imide is separated and purified, May be provided to the preparation of Removal of the dehydrating agent and the dehydration cyclization catalyst and isolation and purification of the imide can be carried out by a known method.

The liquid crystal aligning agent of the present invention contains a polymer having the structure represented by the above formula (1) as an essential component, and preferably these are constituted as a solution composition dissolved in a solvent to be described later. However, Or may be further contained. Examples of the other components include other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as " epoxy compound "), and functional silane compounds.

The other polymer is a polymer having no structure represented by the formula (1) and can be used for improving the solution characteristics (coating properties) and electric characteristics of the liquid crystal aligning agent of the present invention.

Examples of the other polymer include polyamic acid having no structure represented by the formula (1), imidized polymer of the polyamic acid, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly Styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.

The use ratio of the other polymer is preferably 90% by weight or less based on 100% by weight of the sum of the polymers (meaning the sum of the polymer having the structure represented by the formula (1) and the other polymer; By weight, more preferably not more than 50% by weight, and particularly preferably no other polymer.

The epoxy compound and the functional silane compound may be contained in the liquid crystal aligning agent of the present invention in order to further improve the adhesion between the obtained liquid crystal alignment film and the substrate.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl N, N, N ', N'-bis (N, N-diglycidylaminomethyl) cyclohexane, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N, Glycidyl-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, based on 100 parts by weight of the total amount of the polymers.

Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazononanoate, Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl- N-phenyl-3-aminopropyltriethoxysilane, and the like.

The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, and more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total amount of the polymers.

The liquid crystal aligning agent of the present invention is constituted by dissolving and containing a polymer having the structure represented by the formula (1) and optionally other optional components as required, in a solvent.

As the solvent usable in the liquid crystal aligning agent of the present invention, it is preferable to use an organic solvent, and examples thereof include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxypropyl acetate, ethyl lactate, N-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethyleneglycol-ethyl 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, diethyl Ethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The solid concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and preferably, it is heated to form a coating film which becomes a liquid crystal alignment film. When the solid concentration is less than 1% by weight, On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent increases, The characteristic becomes poor.

A particularly preferable range of the solid concentration is different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 wt%. In the case of the printing method, it is particularly preferable to set the solids concentration in the range of 3 to 9 wt% and the solution viscosity in the range of 12 to 50 mPa · s accordingly. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and thus the solution viscosity is in the range of 3 to 15 mPa · s.

The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 45 占 폚, more preferably 20 to 30 占 폚.

A liquid crystal alignment film can be formed using the liquid crystal aligning agent of the present invention. That is, a liquid crystal alignment film can be formed by applying a liquid crystal aligning agent of the present invention on a substrate to form a coating film, and preferably, rubbing or irradiating the coating film.

The liquid crystal aligning agent of the present invention can be applied to the production of liquid crystal display devices having suitable liquid crystal cells such as TN type, STN type, IPS type, FFS type, VA type, MVA type and the like. However, it is preferable to apply it to a liquid crystal display element having a so-called horizontally aligned liquid crystal cell, such as a TN type, an STN type, an IPS type, and an FFS type, because the advantageous effect of the present invention is maximized.

When a liquid crystal alignment film formed of the liquid crystal alignment film of the present invention is applied to a TN type or STN type liquid crystal display device, two substrates on which a patterned transparent conductive film is formed are used in pairs, The alignment agent is applied on the surface on which the transparent conductive film of each substrate is formed. On the other hand, when the liquid crystal alignment film is applied to an IPS or FFS type liquid crystal display device, the substrate may be a substrate having a transparent conductive film or a metal film patterned in a comb shape on one side, And the liquid crystal aligning agent is applied to the formation surface of the comb-like electrode and one surface of the counter substrate.

In any of the above cases, examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or polycarbonate can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ , a NESA (registered trademark) film made of SnO ₂ , or the like can be used. As the metal film, for example, a film made of a metal such as chromium can be used. The patterning of the transparent conductive film and the metal film includes, for example, a method of forming a pattern by a photo-etching method or a sputtering method after forming a pattern-free transparent conductive film, a method of using a mask having a desired pattern in forming a transparent conductive film And so on.

In order to improve the adhesion between the substrate and the transparent conductive film or the metal film and the coating film at the time of applying the liquid crystal aligning agent for optical alignment onto the substrate, A functional silane compound, a titanate compound and the like may be applied.

The application of the liquid crystal aligning agent for photo alignment onto the substrate can be preferably carried out by an appropriate application method such as offset printing, spin coating, roll coatering, inkjet printing, etc., Baking) and post-baking (post baking). The prebaking condition is preferably 0.1 to 5 minutes at 40 to 120 캜. The post-baking condition is preferably 120 to 300 占 폚, more preferably 150 to 250 占 폚, preferably 5 to 200 minutes, and more preferably 10 to 100 minutes.

Subsequently, the coating film formed as described above is subjected to a rubbing treatment or a light irradiation treatment to give a coating film with a liquid crystal aligning ability to form a liquid crystal alignment film. When at least one of X ¹ and X ² in the formula (1) is an ester bond, it is preferable to carry out light irradiation treatment.

The rubbing treatment can be carried out by rubbing the surface of the coating film formed on the substrate in a predetermined direction with a roll of cloth made of, for example, nylon, rayon, cotton or the like.

As the light to be irradiated in the light irradiation treatment, for example, ultraviolet light or visible light including light having a wavelength of 150 to 800 nm can be used. It is preferable to use ultraviolet rays containing light having a wavelength of 200 to 400 nm as irradiation light. As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an Hg-Xe lamp and an excimer laser can be used. The ultraviolet ray of the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with a filter, a diffraction grating, or the like. The irradiation light may be polarized light or unpolarized light, but polarized light is preferable. The irradiation direction is preferably in a direction perpendicular to the substrate surface.

The irradiation amount of light is preferably 100 J / m 2 or more, more preferably 400 to 20,000 J / m 2, and further preferably 1,000 to 10,000 J / m 2.

By using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film can be formed on the substrate as described above. A liquid crystal display element can be manufactured as follows using a substrate having this liquid crystal alignment film.

A pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a configuration in which liquid crystal is sandwiched between the pair of substrates is manufactured. For example, the following two methods can be used to manufacture the liquid crystal cell.

As a first method, a pair of substrates are disposed to face each other with a space (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, and peripheral portions of the pair of substrates are bonded to each other using a sealant, A liquid crystal is injected and filled in a cell gap defined by the liquid crystal cell, and then the liquid crystal cell is manufactured by sealing the injection port.

As a second method, for example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which a liquid crystal alignment film is formed, and further liquid crystal is dropped to a predetermined number of places on the liquid crystal alignment film surface A liquid crystal cell is manufactured by joining the other substrate so that the liquid crystal alignment film is opposed to the liquid crystal alignment film and spreading the liquid crystal on the entire surface of the substrate and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant ODF (One Drop Fill) method).

In any of the above-described methods, it is preferable that the liquid crystal using the liquid crystal cell is heated to a temperature at which the liquid crystal takes an isotropic phase, and then gradually cooled to room temperature to remove the flow orientation at the time of filling the liquid crystal. Then, the liquid crystal display element of the present invention can be obtained by bonding the polarizing plate to the outer surface of the liquid crystal cell in a predetermined direction.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal or the like can be used.

In the case of producing a horizontally oriented liquid crystal display element, nematic liquid crystals having positive dielectric anisotropy are preferable, and examples thereof include biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, Hexane-based liquid crystals, pyrimidine-based liquid crystals, fluorinated benzene-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, quaternary type liquid crystals and the like. A cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal, or the like may be added to these liquid crystals and used. On the other hand, when a vertically aligned liquid crystal display device is manufactured, a nematic liquid crystal having negative dielectric anisotropy is preferable. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a cypher base liquid crystal, Biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, and the like.

Examples of the polarizing plate used for the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called an " H film " in which oxyne is absorbed while polyvinyl alcohol is oriented in a stretched state, a polarizing plate comprising the H film itself, have.

(Example)

≪ Synthesis of diamine having the structure represented by the above formula (1) >

Synthesis Example MDA-1

(Compound (MDA-1)) represented by the formula (MDA-1) was synthesized according to the following Reaction Scheme 1:

(In Scheme 1, Boc is a t-butoxycarbonyl group).

(0.050 mol) of 3,5-dibromopyridine, 609 mg (2.0 mmol) of tri-o-tolylphosphine and 112 mg (0.5 mmol) of palladium acetate as a catalyst were mixed in a reaction vessel, 152 mL of N, N-dimethylformamide, 16.7 mL (0.120 mol) of triethylamine and 17.5 mL (0.120 mol) of tert-butyl acrylate were added and the reaction was carried out at 120 ° C for 3 hours with stirring. After completion of the reaction, air was blown into the reaction mixture to deactivate palladium acetate. After the catalyst remnants were removed by Celite filtration, 500 mL of ethyl acetate was added to the filtrate, and the obtained organic layer was extracted and washed with 500 mL of distilled water four times. Subsequently, the solvent was removed from the organic layer under reduced pressure to obtain a solid. Recrystallization was performed using 150 mL of ethanol to obtain 13.6 g (0.041 mol, yield: 82%) of a yellow compound (mda-1-1).

13.6 g (0.041 mol) of the compound (mda-1-1) obtained above and 1.36 g of 5 wt% palladium carbon (50 wt% aqueous solution) were mixed in a reaction vessel equipped with a stirrer, 80 ml of hydrofuran and 80 ml of ethanol were added, and a balloon filled with hydrogen was placed in the cock, the vessel was put under a hydrogen atmosphere, and the reaction was carried out under the atmosphere at 50 캜 for 5 hours with stirring. After completion of the reaction, the palladium carbon was removed from the reaction mixture by Celite filtration, and the solvent was removed from the obtained filtrate under reduced pressure to obtain 13.1 g (0.038 mol, yield 95%) of a pale brown compound (mda- .

In the reaction vessel, 13.1 g (0.039 mol) of the compound (mda-1-2) obtained above, 80 mL of dichloromethane and 40 mL of trifluoroacetic acid were mixed, and the reaction was carried out at 20 캜 for 3 hours with stirring. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure, and the obtained solid was recrystallized from 120 mL of ethanol to obtain 7.14 g (0.032 mol, yield: 82%) of a pale brown compound (mda-1-3).

Then, 7.14 g (0.032 mol) of the compound (mda-1-3) obtained above, 13.4 g (0.064 mol) of 4- (tert-butoxycarbonylamino) phenol and 128 mL of dichloromethane were mixed in a reaction vessel. The vessel was cooled in an ice bath and 14.7 g (0.077 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1.56 g (0.077 mol) of N, (0.013 mol) was added thereto, and the reaction was carried out at 20 DEG C for 2 hours with stirring. After completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was extracted and washed three times with 300 mL of distilled water. The solvent was removed from the organic layer after the washing under reduced pressure to obtain a solid. Recrystallization was performed using 100 mL of ethanol to obtain 15.7 g (0.026 mol, yield 81%) of a pale brown compound (mda-1-4).

Further, 15.7 g (0.026 mol) of the compound (mda-1-4) obtained above, 52 mL of dichloromethane and 26 mL of trifluoroacetic acid were mixed in a reaction vessel, and the reaction was carried out at 20 ° C for 3 hours with stirring. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure, and the obtained solid was recrystallized from 100 mL of ethanol to obtain 8.86 g (0.022 mol, yield: 84%) of a violet compound (MDA-1).

Synthesis Example MDA-2

(Compound (MDA-2)) represented by the formula (MDA-2) was synthesized according to the following Reaction Scheme 2:

(In Scheme 2, Boc is a t-butoxycarbonyl group).

(0.060 mole) of 3,5-lutidine, 60 ml of acetonitrile, 48.1 g (0.360 mole) of N-chlorosuccinimide and 2.46 g of 2,2'-azobis (isobutyronitrile) 0.015 mol) were mixed, and the reaction was carried out with stirring at 80 占 폚 for 8 hours. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure, and the resulting solid was purified by column chromatography (filler: silica gel, developing solvent: hexane / ethyl acetate = 3/1 (volume ratio)) to obtain a pale brown compound (0.038 mol, 63% yield) of the title compound (mda-2-1).

Subsequently, 6.65 g (0.038 mol) of the compound (mda-2-1) obtained above, 15.9 g (0.076 mol) of 4- (tert-butoxycarbonylamino) phenol, (0.091 mol) of potassium carbonate were mixed, and the reaction was carried out at 90 DEG C for 5 hours with stirring. After completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was extracted and washed with 300 mL of distilled water four times. The solvent was removed from the organic layer after the washing under reduced pressure to obtain a solid, and recrystallization was performed using 100 mL of ethanol to obtain 16.6 g (0.032 mole, yield 84%) of a pale brown compound (mda-2-2).

Further, 16.6 g (0.032 mol) of the compound (mda-2-2) obtained above was mixed with 64 mL of dichloromethane and 32 mL of trifluoroacetic acid, and the reaction was carried out at 20 ° C for 3 hours with stirring. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure, and the resulting solid was recrystallized from 100 mL of ethanol to obtain 9.26 g (0.029 mole, yield 90%) of a violet compound (MDA-2).

Synthesis Example MDA-3

(Compound (MDA-3)) represented by the formula (MDA-3) was synthesized according to the following Reaction Scheme 3.

(0.164 mol) of 4-aminophenol, 80 mL of dimethylsulfoxide, 8.0 mL of toluene, and 9.88 g (0.176 mol) of potassium hydroxide were mixed in a flask equipped with a Dean-Stark tube, and the mixture was stirred at 135 캜 for 4 hours, (0.080 mol) of 2,6-dichloropyridine was added, the temperature was raised to 135 ° C again, and the reaction was carried out with stirring for 4 hours. After completion of the reaction, the reaction mixture was poured into 500 mL of distilled water, and the resultant precipitate was collected. The recovered precipitate was recrystallized using 100 mL of ethanol to obtain 15.9 g (0.054 mol, yield 68%) of a purple compound (MDA-3).

Synthesis Example MDA-4

(Compound (MDA-4)) represented by the formula (MDA-4) was synthesized according to the following Reaction Scheme 4:

(In Scheme 4, Boc is a t-butoxycarbonyl group).

20.3 g (0.097 mol) of 4- (tert-butoxycarbonylamino) phenol, 300 mL of tetrahydrofuran and 27.0 mL (0.194 mol) of triethylamine were mixed in a reaction vessel. A solution in which 19.4 g (0.088 mmol) of 5-bromonicotinoyl chloride was dissolved in 50 mL of tetrahydrofuran while cooling the vessel in an ice bath was added dropwise. After completion of dropwise addition, the temperature was raised to 20 占 폚 and the reaction was carried out at the same temperature for 4 hours with stirring. After completion of the reaction, 750 ml of ethyl acetate was added to the reaction mixture, and the obtained organic layer was extracted and washed with 750 ml of distilled water four times. The solvent was removed from the organic layer after the washing under reduced pressure, and the resulting solid was recrystallized from 150 mL of ethanol to obtain 29.4 g (0.075 mol, yield 85%) of a pale brown compound (mda-4-1).

Then, 29.4 g (0.075 mol) of the compound (mda-4-1) obtained in the above-mentioned reaction vessel and 0.2 g of N- [4- (4,4,5,5,5-N-tetramethyl- (1,1'-bis (diphenylphosphino) ferrocene] dichloroacetate as a catalyst, 15.9 g (0.150 mol) of sodium carbonate and 23.9 g (0.075 mol) of tert- butyldicarbonyl- 2.74 g (3.75 mmol) of palladium were mixed and purged with nitrogen. Then, 40 mL of toluene, 40 mL of ethanol and 40 mL of distilled water were added, and the reaction was carried out at 60 ° C for 16 hours with stirring. After completion of the reaction, air was blown into the reaction mixture to inactivate the palladium catalyst, and the catalyst remnants were removed by filtration through Celite. 500 mL of ethyl acetate was added to the filtrate, and the obtained organic layer was extracted and washed with 500 mL of distilled water four times. The solvent was removed from the organic layer after the washing under reduced pressure to obtain 22.8 g (0.045 mol, yield 60%) of a pale brown compound (mda-4-2) by recrystallization using 200 mL of ethanol.

In the reaction vessel, 22.8 g (0.045 mol) of the compound (mda-4-2) obtained above, 90 mL of dichloromethane and 45 mL of trifluoroacetic acid were mixed, and the reaction was carried out at 20 ° C for 3 hours with stirring. After completion of the reaction, the solvent was removed under reduced pressure, and the resulting solid was recrystallized from ethyl acetate (30 mL) and hexane (120 mL) to obtain 11.0 g (0.036 mol, yield 80%) of a brown compound (MDA-4).

Synthesis Example MDA-5

(Compound (MDA-5)) represented by the formula (MDA-5) was synthesized according to the following Reaction Scheme 5:

(In Scheme 5, Boc is a t-butoxycarbonyl group).

In the reaction vessel, 42.6 g (0.150 mol) of 5-bromo-2-iodopyridine, N- [4- (4,4,5,5-N-tetramethyl-1,3,2-dioxabor 47.5 g (0.450 mol) of sodium carbonate and 8.67 g (7.50 mmol) of tetrakis (triphenylphosphine) palladium as a catalyst were mixed to obtain a mixture of nitrogen After substitution, 500 mL of tetrahydrofuran and 250 mL of distilled water were added, and the reaction was carried out at 60 캜 for 20 hours with stirring. After the completion of the reaction, air was blown into the reaction mixture to inactivate the palladium catalyst, and the catalyst remnants were removed by filtration through Celite. To the filtrate was added 1,000 mL of ethyl acetate, and the obtained organic layer was extracted and washed four times with 800 mL of distilled water. The solvent was removed from the organic layer after the washing under reduced pressure, and the obtained solid was recrystallized from 300 mL of ethanol to obtain 29.3 g (0.084 mol, yield: 56%) of a pale brown compound (mda-5-1).

Subsequently, 29.3 g (0.084 mol) of the compound (mda-5-1) obtained above, 1.02 g (3.4 mmol) of tri-o-tolylphosphine and 189 mg (0.84 mmol) of palladium acetate as a catalyst After the mixture was purged with nitrogen, 255 mL of N, N-dimethylformamide, 14.0 mL (0.100 mol) of triethylamine and 14.6 mL (0.100 mol) of tert-butyl acrylate were added and the reaction was carried out at 120 ° C for 4 hours with stirring . After completion of the reaction, air was blown into the reaction mixture to inactivate the palladium catalyst, and the catalyst remnants were removed by filtration through celite. 700 mL of ethyl acetate was added to the filtrate, and the obtained organic layer was extracted and washed with 700 mL of distilled water four times. The solvent was removed from the organic layer after the washing under reduced pressure to obtain 26.2 g (0.066 mol, yield: 79%) of a pale brown compound (mda-5-2) using 250 mL of ethanol.

26.2 g (0.066 mol) of the compound (mda-5-2) obtained above and 2.62 g of 5 wt% palladium carbon (50 wt% aqueous solution) were mixed in a reaction vessel equipped with a stirrer, , 132 mL of tetrahydrofuran and 132 mL of ethanol were added. A balloon filled with hydrogen was placed in a cock of the reaction vessel, and the inside of the vessel was put under a hydrogen atmosphere, and the reaction was carried out at 50 占 폚 under stirring for 5 hours. After completion of the reaction, palladium carbon was removed from the reaction mixture by Celite filtration, and the solvent was removed from the resulting filtrate under reduced pressure to obtain 24.3 g (0.061 mole, yield: 93%) of a pale brown compound (mda- 5-3) .

In the reaction vessel, 24.3 g (0.061 mol) of the compound (mda-5-3) obtained above, 120 mL of dichloromethane and 60 mL of trifluoroacetic acid were mixed and reacted for 3 hours at 20 캜 with stirring. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure to obtain a solid. Recrystallization was performed using 150 mL of ethanol to obtain 18.5 g (0.054 mol) of a pale brown compound (mda-5-4) in a yield of 89%.

18.5 g (0.054 mol) of the compound (mda-5-4) obtained above, 11.3 g (0.054 mol) of 4- (tert-butoxycarbonylamino) phenol and 108 mL of dichloromethane were mixed in a reaction vessel, (0.065 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1.32 g (0.011 mol) of N, N-dimethyl-4-aminopyridine were added thereto while cooling to 5 캜 in an ice bath. ) Was added. Thereafter, the temperature was raised to 20 占 폚, and the reaction was carried out at the same temperature for 3 hours under stirring. After completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed three times with 500 mL of distilled water. The solvent was removed from the organic layer after the washing under reduced pressure to obtain a solid. Recrystallization was performed using 150 mL of ethanol to obtain 25.6 g (0.048 mol, yield 89%) of a pale brown compound (mda-5-5).

Further, 25.6 g (0.048 mol) of the compound (mda-5-5) obtained above, 96 mL of dichloromethane and 48 mL of trifluoroacetic acid were mixed in a reaction vessel, and reaction was carried out at 20 ° C for 3 hours with stirring. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure, and the obtained solid was recrystallized from 150 mL of ethanol to obtain 12.7 g (0.038 mol, yield 80%) of a purple compound (MDA-5).

Synthesis Example MDA-6

(Compound (MDA-6)) represented by the formula (MDA-6) was synthesized according to the following Reaction Scheme 6:

(In Scheme 6, Boc is a t-butoxycarbonyl group).

A 500 mL three-necked flask equipped with a dropping funnel and a nitrogen inlet tube was charged with 7.1 g of 4-aminophenol and 350 mL of tetrahydrofuran. A solution obtained by dissolving 14.6 g of t-butyl-p-t-butyl in 60 mL of tetrahydrofuran was added dropwise from a dropping funnel while keeping the inner temperature of the flask at 6 캜 or lower, and the reaction was carried out at room temperature for 24 hours. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure, and the obtained solid was dissolved in 500 mL of ethyl acetate and the solution was washed with 500 mL of distilled water. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure to obtain 12.6 g of white crystals of intermediate 1.

10.14 g of the intermediate 1 obtained above, 4.05 g of 2,5-dicarboxylic acid pyridine and 150 mL of methylene chloride were placed in a 300-mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube. 12.08 g of hydrochloric acid salt of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 2.37 g of N, N-dimethylaminopyridine were added thereto while maintaining the same temperature, and the reaction was carried out for 6 hours under stirring . Stirring was then continued at room temperature for an additional 6 hours. After stirring for a total of 12 hours, 300 mL of ethyl acetate, 300 mL of tetrahydrofuran, and 300 mL of distilled water were added to the reaction mixture, followed by liquid separation and washing, and the organic layer was recovered. The obtained organic layer was concentrated to about 200 mL, and then 100 mL of ethanol was added to perform solvent substitution. After concentration again, the precipitated white solid (Intermediate 2) was filtered out. The yield of intermediate 2 was 10.0 g.

8.4 g of Intermediate 2 obtained above was suspended in 150 mL of methylene chloride, and 30 mL of trifluoroacetic acid was added to the 300 mL eggplant flask equipped with a nitrogen inlet tube, and the reaction was carried out for 24 hours under stirring. After completion of the reaction, a saturated aqueous solution of sodium carbonate was added to the reaction mixture until the pH reached 7 or more, and then ethyl acetate (200 mL) and tetrahydrofuran (200 mL) were added to separate the organic layer. The organic layer was washed with 300 mL of distilled water three times, and then concentrated. During the concentration, the liquid turned black. The precipitated solid was collected by filtration and washed with a mixed solvent of ethanol and pure water (ethanol: water = 4: 1 (volume ratio)) to obtain 4.2 g of a yellow compound (MDA-6).

≪ Synthesis of Polymer Having Structure Represented by Formula (1)

Synthesis Examples PI-1 to PI-11

Tetracarboxylic acid dianhydride and diamine were mixed so as to have the ratios (molar ratios) shown in Table 1, and N-methyl-2-pyrrolidone (NMP) By weight. This solution was subjected to a reaction under stirring at 40 DEG C for 4 hours to obtain a solution containing 20 wt% of polyamic acid. In Synthesis Example PI-7, in addition to the tetracarboxylic acid dianhydride and the diamine, the monoamines shown in Table 1 were further used at the ratios (molar ratios) shown in the tables.

Next, NMP was added to the polyamic acid solution obtained above to dilute the polyamic acid concentration to 10 wt%, and then pyridine and acetic anhydride were added to the polyamic acid solution so that the relative amounts to the amount (mol number) And the mixture was stirred at 110 캜 for 4 hours to carry out a dehydration ring-closure reaction. After completion of the reaction, the reaction mixture was subjected to solvent substitution with NMP to obtain a solution containing 15% by weight of each of the imidized polymers (PI-1) to (PI-11). The imidization ratios of the imidized polymers obtained as measured by ¹ H-NMR are shown in Table 1. < tb >< TABLE >

Synthesis Example PA-1

(PA-1) was obtained in the same manner as in Synthesis Example PI-1 except that the tetracarboxylic acid dianhydride and the diamine used in Table 1 were used so that the ratios (molar ratios) ) Was obtained in an amount of 20% by weight.

In this synthesis example, the obtained polyamic acid solution was directly supplied to the preparation of the liquid crystal aligning agent without performing the dehydration ring-closure reaction.

≪ Synthesis of other polymer >

Synthesis Examples rpi-1 to rpi-3

Tetracarboxylic acid dianhydride and diamine were used so as to have the ratios (molar ratios) shown in Table 1,

(Rpi-1) to (rpi-3) were each subjected to the same procedure as in Synthesis Example PI-1 except that the amounts of pyridine and acetic anhydride used were adjusted to the ratios shown in Table 1, % Solution. The imidization ratios of the imidized polymers obtained as measured by ¹ H-NMR are shown in Table 1. < tb >< TABLE >

Synthesis Examples rpa-1 to rpa-4

Except that the tetracarboxylic acid dianhydride and the diamine were used so as to have the ratios (molar ratios) shown in Table 1, respectively, in the same manner as in Synthesis Example PI-1 to obtain polyamic acid (rpa -1) to (rpa-4), respectively.

In these synthesis examples, the obtained polyamic acid solution was directly supplied to the preparation of the liquid crystal aligning agent without performing the dehydration ring-closure reaction.

The abbreviations in the monomer chambers in Table 1 have the following meanings respectively.

≪ Tetracarboxylic acid dianhydride >

TCA: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

BODA: 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride

CB: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride

MTDA: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ -1,3-dione

PMDA: pyromellitic acid dianhydride

TA-1: Compound represented by the following formula (TA-1)

<Diamine>

[Diamine having the structure represented by the formula (1) above]

MDA-1: Compound (MDA-1) synthesized in Synthesis Example MDA-1

MDA-2: Compound (MDA-2) synthesized in Synthesis Example MDA-2

MDA-3: Compound (MDA-3) synthesized in Synthesis Example MDA-3,

MDA-4: Compound (MDA-4) synthesized in Synthesis Example MDA-4,

MDA-5: Compound (MDA-5) synthesized in Synthesis Example MDA-5

MDA-6: Compound (MDA-6) synthesized in Synthesis Example MDA-6 above

[Other diamines]

PDA: p-phenylenediamine

HCDA: 3,5-diaminobenzoic acid cholestanyl

35DAB: 3,5-diaminobenzoic acid

HCODA: cholestanyloxy-2,4-diaminobenzene

LDA: 4- {4- [2- (4'-Pentyl-1,1'-bicyclohexyl) ethyl] phenoxy} benzene-1,3-diamine

D-1: 1,3-Diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

D-2: 1,3-bis (3-aminopropyl) -tetramethyldisiloxane

D-3: 3,6-bis (4-aminobenzoyloxy) cholestane

D-5: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl

D-6: 4,4'-diaminodiphenylmethane

D-7: 2,2'-Dimethyl-4,4'-diaminobiphenyl

D-8: 4,4'-diaminodiphenyl ether

DA-2: A compound represented by the following formula (DA-2)

DA-3: Compound represented by the following formula (DA-3)

mda-1: Compound represented by the following formula (mda-1)

mda-2: Compound represented by the following formula (mda-2)

[Monoamine]

D-4: Aniline

Synthesis Example rps-1

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, And mixed at room temperature. Subsequently, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the reaction was carried out at 80 DEG C for 6 hours while stirring under reflux. After the completion of the reaction, the organic layer was taken out and washed with an aqueous 0.2 wt% ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group To give a crude transparent liquid. As a result of ¹ H-NMR analysis of the polyorganosiloxane, it was confirmed that a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm as the theoretical intensity, and no side reaction of the epoxy group occurred during the reaction . The polyorganosiloxane having an epoxy group thus obtained had a weight average molecular weight Mw of 3,500 and an epoxy equivalent of 180 g / mol.

Then, 10.0 g of the polyorganosiloxane having the epoxy group obtained above, 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as a carbonic acid, and UCAT 18X (trade name, Manufactured by SANA PRO Co., Ltd.), and the reaction was carried out at 100 ° C for 48 hours with stirring. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the organic layer was washed with water three times, dried over magnesium sulfate and then the solvent was distilled off to obtain 9.0 g of polyorganosiloxane (rps-1). The weight average molecular weight Mw of the obtained polyorganosiloxane (rps-1) was 9,900.

Example 1

1. Preparation of liquid crystal aligning agent

NMP and butyl cellosolve (BC) were added to a solution containing the imidized polymer (PI-1) obtained in the above Synthesis Example PI-1 and sufficiently stirred to prepare a solution having a solvent composition of NMP: BC = 60:40 , And a solid content concentration of 2.5% by weight. This solution was filtered using a filter having a pore diameter of 1 탆 to prepare a liquid crystal aligning agent.

2. Evaluation of liquid crystal aligning agent

The printability of the liquid crystal aligning agent prepared above and the reliability of the liquid crystal display element prepared using the liquid crystal aligning agent were evaluated by the following methods.

The evaluation results are shown in Table 2.

Examples 2 to 8, 10 and 11 and Comparative Examples 1 to 3

1. Preparation of liquid crystal aligning agent

As the solution containing the polymer, a solution containing the polymer shown in Table 2 was used. A liquid crystal aligning agent was prepared in the same manner as in &quot; Preparation of liquid crystal aligning agent &quot;.

In Examples 7 and 8, two kinds of polymers were mixed in the proportions shown in Table 2, respectively.

2. Evaluation of liquid crystal aligning agent

Each of the liquid crystal aligning agents prepared above was evaluated in the same manner as in Example 1 above.

The evaluation results are shown in Table 2.

Example 9

1. Preparation of liquid crystal aligning agent

The polyorganosiloxane (rps-1) obtained in Synthesis Example rps-1 was added to a solution containing the imidized polymer (PI-9) obtained in Synthesis Example PI-9 and further NMP and butyl cellosolve Solvent (BC) was added and sufficiently stirred to obtain a solution having a solvent composition of NMP: BC = 60: 40 (weight ratio) and a solid content concentration of 2.5% by weight. Here, the imidized polymer (PI-9) and the polyorganosiloxane (rps-1) were used in such a ratio that the weight ratio of PI-9: rps-1 was 95: 5.

This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent.

2. Evaluation of liquid crystal aligning agent

The liquid crystal aligning agent prepared above was evaluated in the same manner as in Example 1 above.

The evaluation results are shown in Table 2.

&Lt; Evaluation method of liquid crystal aligning agent (1) >

The liquid crystal aligning agents prepared in Examples 1 to 11 and Comparative Examples 1 to 3 were evaluated by the following methods, respectively.

1. Evaluation of printability

The printing properties (continuous printing property) of the liquid crystal aligning agent prepared in each of the examples and the comparative examples when the printing on the substrate was performed continuously were evaluated.

First, the dropping amount of the liquid crystal aligning agent in anisoxrolox was measured under the conditions of reciprocating 20 drops (about 0.2 g) using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Shingen Co., Ltd., product name "Ong Stromer S40L-532" , Each liquid crystal aligning agent was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film. Application to the substrate was carried out 20 times while using a new substrate at intervals of one minute.

Subsequently, a liquid crystal aligning agent was dispensed (one way) on an anilox roll at intervals of one minute, and an operation (empty operation) of bringing the anilox roll and the printing plate into contact each other was performed 10 times in total. In the meantime, printing on a glass substrate is not performed. This coarse operation is an operation performed to intentionally perform printing of the liquid crystal aligning agent under a severe condition.

After 10 times of ball driving, the printing was continued using a glass substrate. In this printing, five substrates were placed at intervals of 30 seconds after the ball operation, each substrate after applying the liquid crystal aligning agent was heated (prebaked) at 80 DEG C for 1 minute to remove the solvent, (Post baking) for a minute to form a coating film having a film thickness of about 80 nm. This coating film was observed under a microscope with a magnification of 20 times to evaluate the printability.

The evaluation was made based on the following criteria.

When no precipitation of polymer was observed in the coating film from the first printing of the main printing after the ball operation: A (good)

In the first printing after the blank printing, precipitation of the polymer was observed in the coating film, but no precipitation of the polymer was observed during the fifth printing of this printing: B (good)

When the precipitation of the polymer was observed in the coating film even after repeating this printing five times: C (poor)

With respect to the liquid crystal aligning agent obtained in the evaluation in the above-mentioned evaluation, the same number of times of the open operation was changed 25 times and the same evaluation was performed again. As a result, when the precipitation of the polymer was not observed in the coating film from the first printing after the 25th printing operation, it was evaluated as &quot; AA (particularly excellent). &Quot;

2. Evaluation of Liquid Crystal Cell

(1) Production of liquid crystal cell

Each of the liquid crystal aligning agents prepared in the above Examples and Comparative Examples was coated on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Shingen Co., Ltd.) (Prebaked) on a hot plate for 1 minute to remove the solvent and then heated on a hot plate at 210 占 폚 for 30 minutes (post baking) to form a coating film having an average film thickness of 80 nm.

The coating film was subjected to a rubbing treatment with a rubbing machine having a roll covered with a rayon cloth at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair embroidering length of 0.4 mm to give a liquid crystal aligning ability . Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, and then the substrate was dried in a 100 占 폚 clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 占 퐉 was applied to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, leaving a liquid crystal injection port. Then, And the adhesive layers were superimposed on each other so as to be opposed to each other to cure the adhesive. Subsequently, a nematic liquid crystal (product name: "MLC-6221", manufactured by Merck & Co., Inc.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to manufacture a liquid crystal cell.

(2) Evaluation of reliability

The reliability of the liquid crystal cell manufactured as described above was evaluated.

First, a voltage of 5 V was applied to the liquid crystal cell at an application time of 60 microseconds and a span of 167 milliseconds, and a voltage maintenance ratio (VHR1) after 167 milliseconds from the application of the release was measured. Subsequently, the liquid crystal cell was allowed to stand in an oven at 80 캜 for 200 hours under irradiation with an LED lamp, allowed to stand at room temperature, and naturally cooled to room temperature. A voltage of 5 V was applied to the liquid crystal cell after cooling at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio (VHR2) after 167 milliseconds from the application of the release was measured.

The rate of change (? VHR) of the voltage holding ratio at this time was calculated by the following equation (1), and the reliability was evaluated according to the following value of? VHR.

? VHR [%] = {(VHR1-VHR2) / (VHR1)} 100 (1)

When? VHR was less than 1%: A (good)

When? VHR was 1% or more and less than 2%: B (Good)

△ When VHR was more than 2%: C (poor)

Example 12

1. Preparation of liquid crystal aligning agent

NMP and butyl cellosolve (BC) were added to the solution containing the polyamic acid (PA-1) obtained in Synthesis Example PA-1 and sufficiently stirred to obtain a solvent composition of NMP: BC = 60:40 (weight ratio) And a solid content concentration of 2.5% by weight.

This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent.

2. Evaluation of liquid crystal aligning agent

The printability of the liquid crystal aligning agent prepared above and the reliability of the liquid crystal cell produced using the liquid crystal aligning agent were evaluated by the following methods.

The evaluation results are shown in Table 3.

Comparative Examples 4 and 5

1. Preparation of liquid crystal aligning agent

As a solution containing the polymer, a solution containing the polymer shown in Table 3 was used. A liquid crystal aligning agent was prepared in the same manner as in &quot; Preparation of liquid crystal aligning agent &quot;.

2. Evaluation of liquid crystal aligning agent

Each of the liquid crystal aligning agents prepared above was evaluated in the same manner as in Example 12.

The evaluation results are shown in Table 3.

&Lt; Evaluation method of liquid crystal aligning agent (2) >

The liquid crystal aligning agents prepared in Example 12 and Comparative Examples 4 and 5 were evaluated by the following methods, respectively.

1. Evaluation of printability

With respect to each of the liquid crystal aligning agents prepared in the above Examples and Comparative Examples, the continuous printing property on the substrate was evaluated by the same method as in Examples 1 to 11 and Comparative Examples 1 to 3, And showed better results than Comparative Examples 4 and 5.

2. Evaluation of Liquid Crystal Cell

(1) Preparation of Liquid Crystal Cell for Liquid Crystal Alignment Property, Voltage Conservation Rate and Contrast Evaluation

Each of the liquid crystal aligning agents prepared in the above Examples and Comparative Examples was coated on each transparent electrode surface of two glass substrates with a transparent electrode made of ITO film using a spinner and heated at 80 DEG C for 1 minute (Pre-baked) to form coating films, respectively. On the surface of these coated films, ultraviolet rays of polarized light including a 254-nm bright line were irradiated with an irradiation dose of 10,000 J / m 2 from the normal direction of the substrate using a Hg-Xe lamp, and then heated in a clean oven at 230 캜 for 1 hour Baking) to form liquid crystal alignment films on two (one pair) substrates.

Next, with respect to one of the pair of substrates subjected to the light irradiation treatment, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied by screen printing while leaving a liquid crystal injection port on the outer periphery of the surface on which the liquid crystal alignment film was formed , A pair of substrates were superimposed on each other so as to be in contact with each other so that the liquid crystal alignment film formation surface was opposed and the projection direction of the polarization plane of the light irradiation onto the substrate surface coincided with each other and heated at 150 占 폚 for 1 hour to thermally cure the adhesive.

Subsequently, a nematic liquid crystal (product name: "MLC-7028", manufactured by Merck & Co., Inc.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 캜 and then gradually cooled to room temperature to produce a liquid crystal cell.

(2) Evaluation of liquid crystal alignment property

The presence or absence of an abnormal domain when an AC voltage of 5 V was turned on / off (applied / released) to the liquid crystal cell prepared above was observed with a polarizing microscope.

A (good) "when the abnormal domain was not observed in the display area, and" C "(poor) in the liquid crystal alignment when the abnormal domain was observed in the display area.

(3) Evaluation of Voltage Conservation Rate

A voltage of 5 V was applied to the liquid crystal cell manufactured in the above manner at 60 microseconds and 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the voltage was measured.

VHR-1 &quot; manufactured by Toyo Technica Co., Ltd. was used as a device for measuring the voltage holding ratio.

Evaluation was made according to the following criteria.

When the voltage holding ratio was 98% or more: The voltage holding ratio "A (good)"

When the voltage holding ratio was less than 98%: The voltage holding ratio "C (bad)"

(4) Production of liquid crystal cell for evaluation of residual image characteristic

(1) liquid crystal cell for evaluation of afterimage characteristics (FFS) was prepared in the same manner as in the above "(1) Production of liquid crystal cell for alignment, voltage holding ratio and contrast evaluation" Type liquid crystal cell), and a polarizing plate was bonded to both outer sides of the substrate to obtain a liquid crystal display element.

Here, as the electrode substrate, a glass substrate on which electrodes of two systems (electrode A 101 and electrode B 102) made of chromium having a comb-shaped pattern shown in Fig. 1 are formed;

As the counter substrate, a glass substrate on which no electrode was formed was used. The application of the liquid crystal aligning agent was carried out on the electrode formation surface of the electrode substrate and one surface of the counter substrate.

(5) Evaluation of afterimage characteristics (burn-in)

The liquid crystal display device prepared above was placed under an environment of 25 占 폚 and 1 atmospheric pressure, and a voltage was applied to the electrode A and a synthesized voltage of an AC voltage of 3.5 V and a DC voltage of 5 V was applied to the electrode A for 2 hours. After a lapse of 2 hours, an AC voltage of 4 V was immediately applied to both the electrode A and the electrode B. The time from when the voltage of 4 V of AC was started to be applied to the positive electrode until the difference in the light transmittance between the positive and negative electrodes could not be visually confirmed was measured.

Evaluation was made according to the following criteria.

When the time measured in the above was less than 100 seconds: the afterimage characteristic &quot; A (good) &quot;

100 seconds to less than 150 seconds: The afterimage characteristic is &quot; B (possible) &quot;

When exceeding 150 seconds: afterimage characteristic "C (bad)"

(6) Evaluation of reliability

The reliability of the liquid crystal display device manufactured as described above was evaluated in the same manner as in Examples 1 to 11 and Comparative Examples 1 to 3. As a result, it was found that Example 12 had better reliability than Comparative Examples 4 and 5 Results are shown.

Claims (9)

A liquid crystal aligning agent characterized by containing a polymer having a structure represented by the following formula (1)
_{^{* -X 1 - (CR 1 2}} ) m1 -Y- (CR 1 2) m2 -X 2 - * (1)
(In the formula (1), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group or an ester bond, provided that when both of X ¹ and X ² are a single bond at the same time No,
Y is a group obtained by removing two hydrogen atoms from a five-membered or six-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom in the ring structure Group, wherein both of the two bonding hands of Y are directly emitted from the above-mentioned 5-membered ring or 6-membered ring,
A plurality of R &lt; ¹ &gt; are each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 20, and
Quot; and &quot; * &quot; each indicate a combined hand). The method according to claim 1,
A liquid crystal aligning agent wherein Y in the formula (1) is a pyridinylene group. The method according to claim 1,
Wherein the polymer comprises
Tetracarboxylic acid dianhydride,
A liquid crystal aligning agent which is a polymer synthesized through a process of reacting a diamine containing a compound represented by the following formula (MDA)
^{_{H 2 N-Ph-X 1}} - (CR 1 2) m1 -Y- (CR 1 2) m2 -X 2 -Ph-NH 2 ... (MDA)
(In the formula (MDA), X ¹ , X ² , Y, R ¹ , m ¹ and m 2 have the same meanings as those in the formula (1)
And the two Ph's are each independently a phenylene group which may be substituted). The method of claim 3,
Wherein the tetracarboxylic acid dianhydride is at least one selected from the group consisting of
2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, At least one member selected from the group consisting of 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt; A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 4. A liquid crystal display element comprising the liquid crystal alignment film according to claim 5. A compound represented by the formula (MDA):
^{_{H 2 N-Ph-X 1}} - (CR 1 2) m1 -Y- (CR 1 2) m2 -X 2 -Ph-NH 2 ... (MDA)
(In the formula (MDA), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group or an ester bond, provided that when both X ¹ and X ² are a single bond at the same time No,
Y is a group obtained by removing two hydrogen atoms from a five-membered or six-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom in the ring structure Group, wherein both of the two bonding hands of Y are directly emitted from the above-mentioned 5-membered ring or 6-membered ring,
A plurality of R &lt; ¹ &gt; are each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 20,
And the two Ph's are each independently a phenylene group which may be substituted). A polymer having a structure represented by the following formula (1):
_{^{* -X 1 - (CR 1 2}} ) m1 -Y- (CR 1 2) m2 -X 2 - * (1)
(In the formula (1), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group or an ester bond, provided that when both of X ¹ and X ² are a single bond at the same time No,
Y is a group obtained by removing two hydrogen atoms from a five-membered or six-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom in the ring structure Group, wherein both of the two bonding hands of Y are directly emitted from the above-mentioned 5-membered ring or 6-membered ring,
A plurality of R &lt; ¹ &gt; are each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 20, and
Quot; and &quot; * &quot; each indicate a combined hand). Tetracarboxylic acid dianhydride,
A polymer synthesized through a process of reacting a diamine comprising a compound represented by the following formula (MDA):
^{_{H 2 N-Ph-X 1}} - (CR 1 2) m1 -Y- (CR 1 2) m2 -X 2 -Ph-NH 2 ... (MDA)
(In the formula (MDA), X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom, a carbonyl group or an ester bond, provided that when both X ¹ and X ² are a single bond at the same time No,
Y is a group obtained by removing two hydrogen atoms from a five-membered or six-membered heteroaromatic compound containing one or two heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom in the ring structure Group, wherein both of the two bonding hands of Y are directly emitted from the above-mentioned 5-membered ring or 6-membered ring,
A plurality of R &lt; ¹ &gt; are each independently a hydrogen atom or a fluorine atom,
m1 and m2 are each independently an integer of 0 to 2,
And the two Ph's are each independently a phenylene group which may be substituted).

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