KR20160010567A - Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display element using same - Google Patents

Abstract

식 중, R₁, R₂ 는 각각 독립적으로 탄소 원자수 1 ∼ 5 의 알킬렌기이다.A tetracarboxylic acid dianhydride containing at least one tetracarboxylic acid dianhydride selected from an aromatic tetracarboxylic acid dianhydride and an aliphatic tetracarboxylic dianhydride, a diamine having a tertiary nitrogen atom, A diamine component containing at least one diamine selected from the group consisting of diamines, and a polyimide obtained by imidizing the polyamic acid.

In the formulas, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment material, a liquid crystal alignment material, and a liquid crystal display device using the same. BACKGROUND OF THE INVENTION [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element using the same, which is used in a liquid crystal display element which is driven by applying an electric field parallel to a substrate.

Background Art [0002] Conventionally, a liquid crystal device has been widely used as a display portion of a personal computer, a cellular phone, a television receiver, and the like. The liquid crystal device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling orientation of liquid crystal molecules in the liquid crystal layer, A thin film transistor (TFT) for switching electric signals, and the like. As the driving method of the liquid crystal molecules, a TN system or a VA system or a transverse electric field system such as an IPS system or an FFS system is known. Generally, in the transverse electric field system in which an electrode is formed only on one side of a substrate and an electric field is applied in a direction parallel to the substrate, compared with a conventional system in which a liquid crystal is driven by applying a voltage to an electrode formed on a conventional vertical substrate, And is known as a liquid crystal display element capable of high-quality display.

Although the liquid crystal cell of the transverse electric field system has a good viewing angle characteristic, since the electrode portion formed in the substrate is small, a sufficient voltage is not applied to the liquid crystal when the voltage retention rate of the liquid crystal alignment film is low. In addition, static electricity tends to accumulate in the liquid crystal cell, and charge is accumulated in the liquid crystal cell even when application of an asymmetric voltage generated by the driving causes the accumulated electric charge to disturb the alignment of the liquid crystal, And the display quality of the liquid crystal element is remarkably lowered. In addition, control of liquid crystal molecules is not performed well at the initial stage of re-energization, and flicker (flicker) is generated. Particularly, in the transverse electric field system, since the distance between the pixel electrode and the common electrode is closer to that of the conventional system, a strong electric field acts on the alignment film and the liquid crystal layer, and such a problem is liable to be conspicuous.

On the other hand, the liquid crystal alignment film is generally formed by printing a liquid crystal aligning agent, rubbing after drying and firing, but in the transverse electric field liquid crystal cell, since the electrode structure is provided only on one side of the substrate, And an insulator such as silicon nitride is sometimes formed on the surface of the substrate. Thus, a liquid crystal aligning agent which is superior in printability as compared with the conventional alignment agent is required. Furthermore, compared with the conventional liquid crystal cell, rubbing or rubbing is liable to cause abrasion, and these peeling and scratches have a problem of deteriorating display quality. Further, in a system such as an IPS (In-Plane Switching) method in which liquid crystal molecules horizontally aligned with respect to a substrate are driven by a transverse electric field, stability of liquid crystal alignment becomes important. If the stability of alignment is low, the liquid crystal does not return to the initial state when the liquid crystal is driven for a long time, and the contrast is lowered or causes ghosting.

As a liquid crystal aligning agent having excellent printability and anti-rubbing property when used in such a transverse electric field driving liquid crystal device and having less after-image or ghosting, Patent Document 1 discloses a liquid crystal aligning agent having an amic acid unit derived from an aromatic tetracarboxylic acid And an amic acid unit derived from an alicyclic tetracarboxylic acid by copolymerization or mixing. Further, as a liquid crystal aligning agent for obtaining a liquid crystal alignment film excellent in liquid crystal aligning property, alignment regulating force, rubbing resistance, high voltage retention rate and reduced charge accumulation, Patent Document 2 discloses a liquid crystal aligning agent having a volume resistivity of 1 x A liquid crystal aligning agent containing a low resistance polyimide precursor having a specific structure of 10 ¹⁰ to 1 10 ¹⁴ ? Cm and a polyimide precursor or polyimide having a high specificity and a liquid crystal aligning agent containing the liquid crystal aligning agent A display element is disclosed.

However, with the increase in the performance of the liquid crystal display device, the characteristics required for the liquid crystal alignment film are also becoming severe, and it is difficult to satisfy all the required characteristics by the conventional technology alone.

International Publication No. WO 02/33481 pamphlet International Publication No. WO2004 / 53583 pamphlet

An object of the present invention is to obtain a liquid crystal alignment film which does not cause peeling or rubbing abrasion due to rubbing treatment while maintaining conventionally required characteristics, in particular, afterglow erasing time and stability of liquid crystal alignment.

As a result of intensive studies to solve the above problems, the present inventors have found that by using a plurality of diamine compounds having a specific structure and an aliphatic tetracarboxylic acid dianhydride having a specific structure, And found that an orientation film can be obtained, thereby completing the present invention. The present invention is based on this finding, and is based on the following points.

A tetracarboxylic acid dianhydride component containing at least one tetracarboxylic acid dianhydride selected from the group consisting of an aromatic tetracarboxylic acid dianhydride and an aliphatic tetracarboxylic acid dianhydride and a diamine having a tertiary nitrogen atom and And at least one of a polyamic acid obtained by reacting a diamine component containing at least one diamine selected from the group consisting of diamines of the following structures and a polyimide obtained by imidizing the diamine component.

[Chemical Formula 1]

In the formulas, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms.

Obtained by reacting an aromatic tetracarboxylic acid dianhydride with a diamine component containing a diamine having the following structure, and a diamine component containing a polyamic acid and an aliphatic tetracarboxylic acid dianhydride and a diamine having a tertiary nitrogen atom 1. A liquid crystal aligning agent according to 1, which contains polyamic acid.

(2)

In the formulas, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms.

Wherein the aliphatic tetracarboxylic acid dianhydride is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid 2-anhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and 1,2,4,5-pentanetetracarboxylic acid dianhydride. Wherein the liquid crystal aligning agent comprises at least one tetracarboxylic acid dianhydride.

The liquid crystal aligning agent according to any one of 1 to 3, wherein in the diamine containing the tertiary nitrogen atom, the tertiary nitrogen atom constitutes a heterocyclic ring.

The liquid crystal aligning agent according to any one of 1 to 4, wherein the diamine containing the tertiary nitrogen atom has the following structure.

(3)

According to the present invention, there is provided a liquid crystal alignment film which does not cause peeling or rubbing abrasion by rubbing treatment while maintaining the afterimage erasing time and stability of liquid crystal alignment, and a liquid crystal display device using the same.

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention is a composition used for forming a liquid crystal alignment film, which comprises at least one tetracarboxylic acid dianhydride selected from the group consisting of an aromatic tetracarboxylic acid dianhydride and an aliphatic tetracarboxylic acid dianhydride (Hereinafter also referred to as a first diamine) and a diamine (hereinafter also referred to as a second diamine) of a tetracarboxylic acid dianhydride component having a tertiary nitrogen atom (hereinafter, also referred to as a first diamine) And at least one of a polyamic acid obtained by reacting a diamine component containing two diamines and a polyimide obtained by imidizing the polyamic acid.

[Chemical Formula 4]

In the formulas, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms.

Further, the liquid crystal aligning agent of the present invention may be a single polyamic acid obtained by using an aromatic tetracarboxylic acid dianhydride, an aliphatic tetracarboxylic acid dianhydride, a first diamine and a second diamine, and a polyimide obtained by imidizing it However, a polyamic acid obtained by reacting an aromatic tetracarboxylic acid dianhydride with a diamine component containing a second diamine and a polyamic acid obtained by reacting an aliphatic tetracarboxylic acid dianhydride and a diamine component containing a first diamine are mixed .

≪ Aromatic tetracarboxylic acid dianhydride >

An aromatic tetracarboxylic acid dianhydride is used for the liquid crystal aligning agent of the present invention. This may be a single type or a mixture of two or more types. Examples of the tetracarboxylic acid as a raw material for obtaining the aromatic tetracarboxylic acid dianhydride include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid , 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4, Biphenyltetracarboxylic acid, 2,3,4 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) Bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2- (3,4-dicarboxyphenyl) propane, 3,3,3-hexafluoro-2,2'-bis (3,4-dicarboxyphenyl) propane, bis ), Diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine and the like. From the viewpoint of reducing the properties, it is preferable to use at least one selected from the group consisting of pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3' '- benzophenonetetracarboxylic acid, and bis (3,4-dicarboxyphenyl) ether. Particularly, pyromellitic acid and 3,3', 4,4'-biphenyltetracarboxylic acid are more preferable .

<Aliphatic tetracarboxylic acid dianhydride>

The liquid crystal aligning agent of the present invention is also used together with an aliphatic tetracarboxylic acid dianhydride. This may be a single type or a mixture of two or more types. Examples of the tetracarboxylic acid as a raw material for obtaining an aliphatic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2 , 3,4,5-tetrahydrofuran tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-pentanetetracarboxylic acid, 1,2,4,5 -Cyclohexanetetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo [ , 0] octane-2,4,6,8-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4 , 5-tetrahydrofuran tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 3,4-dicarboxy- 3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, 2,3,5- There cyclopentyl-ethyl, and the like, the liquid crystal orientation perspective 1,2,3,4-cyclobutane tetracarboxylic acid, or their derivatives. From the viewpoint of a low pretilt angle required for a liquid crystal display element for driving a transversal electric field, it is preferable to use bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, 2,3,5 -Tricarboxycyclopentylacetic acid, 1,2,3,4-butanetetracarboxylic acid and 1,2,4,5-pentanetetracarboxylic acid are preferable.

Thus, it is preferable to use a mixture of a dianhydride of 1,2,3,4-cyclobutanetetracarboxylic acid or a derivative thereof and bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, 2 , 3,5-tricarboxycyclopentyl acetic acid, butanetetracarboxylic acid, and 1,2,4,5-pentanetetracarboxylic acid are used together with the tetracarboxylic acid dianhydride, It is preferable because both good liquid crystal alignability and low pretilt angle can be achieved.

&Lt; First diamine &

The first diamine used in the synthesis of the polyamic acid used in the liquid crystal aligning agent of the present invention is a diamine having a tertiary nitrogen atom in the molecule. At this time, it is preferable that the tertiary nitrogen atom constitutes a nitrogen atom-containing heterocyclic ring. Examples of the heterocyclic structure containing a nitrogen atom include a pyrrole ring, a pyrrolidine ring, an imidazole ring, a pyridine ring, a piperidine ring and a pyrimidine ring. From the viewpoint of good electrical properties, a piperidine ring , A pyrrolidine ring, and particularly preferably a piperidine ring.

Specific examples of the second diamine include the following compounds.

[Chemical Formula 5]

&Lt; Second diamine &

The second diamine used in the synthesis of the polyamic acid used in the liquid crystal aligning agent of the present invention is represented by the following formula (1).

[Chemical Formula 6]

In the formulas, R ₁ and R ₂ each independently represent an alkylene group having 1 to 5 carbon atoms. Among them, from the viewpoint of good liquid crystal alignability, R ₁ and R ₂ are preferably an alkylene group having 1 to 3 carbon atoms, and most preferably all of R ₁ and R ₂ are alkylene groups having 2 carbon atoms .

<Other diamines>

In the synthesis of the polyamic acid to be used in the liquid crystal aligning agent of the present invention, in addition to the first diamine and the second diamine, other diamine compounds may be used as long as the effect of the present invention is not impaired. Specific examples of other diamine compounds are listed below. p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-di Aminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-dia Aminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2 '-Diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diamino Phenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldi aniline, 3,3'- Bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thi Aminodiphenylamine, 3,3'-thiodi aniline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'- Diaminodiphenylamine, 2,3'-diaminodiphenylamine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4 Diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1, Diaminonaphthalene, 2,6-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4- (3-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis Aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl- (4-aminophenyl) urea, N-methyl-2- (4-aminophenyl) benzene, ) Ethylamine, 4,4 '- [1,4-phenylenebis (methylene)] dianiline, 4,4' - [ Phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, 3,4' ] Dianiline, 3,3 '- [1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone] (3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenylenebis (4-aminoben Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminophenyl) isophthalate, N, N '- (1,4-phenylphenyl) terephthalate, bis N, N '- (1,4-phenylene) bis (4-aminobenzamide), N, N' (3-aminobenzamide), N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis Aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis Bis (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4 - &lt; / RTI &gt; aminophenoxy) phenyl] hexafluoro Aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, , 1,3-bis (4-aminophenoxy) propane, 1,4-bis (3-aminophenoxy) butane, 1,5- 1-aminophenoxy) hexane, 1,7- (3-aminophenoxy) heptane, 1,8-bis 1,9-bis (3-aminophenoxy) decane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) undecane, 1,12- Hexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, But are not limited to, nobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- Decane, 1,11-diamino undecane, 1,12-diaminododecane, and the like. Of these, 4,4'-diaminodiphenylmethane, 1,3-bis (4-aminophenethyl) urea and N-methyl-2- (4-aminophenyl) ethylamine are preferable from the viewpoints of good orientation and the like Lt; / RTI &gt;

The other diamine compounds listed above may be used alone or in combination of two or more kinds depending on the properties such as volume resistivity, rubbing resistance, ion density characteristics, transmittance, liquid crystal orientation, voltage holding characteristics, It can also be mixed.

<Synthesis of polyamic acid>

When the polyamic acid used in the liquid crystal aligning agent of the present invention is obtained by the reaction of the tetracarboxylic acid dianhydride and the diamine, a method of mixing the tetracarboxylic acid dianhydride and the diamine in an organic solvent and reacting them is simple.

The organic solvent used in the reaction is not particularly limited as long as it dissolves the produced polyamic acid. For example, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethyl Sulfone, hexamethyl sulfoxide,? -Butyrolactone, and the like. These may be used alone or in combination. It is also possible to use a solvent which does not dissolve the polyamic acid in the solvent in such a range that the produced polyamic acid does not precipitate. In addition, the water content in the organic solvent inhibits the polymerization reaction and further causes the hydrolysis of the resulting polyamic acid. Therefore, it is preferable to use an organic solvent which is dehydrated and dried as much as possible.

As a method for mixing the tetracarboxylic acid dianhydride component and the diamine component in an organic solvent, a method in which a solution prepared by dispersing or dissolving a diamine component in an organic solvent is stirred and the tetracarboxylic acid dianhydride component is dispersed in the organic solvent A method in which a diamine component is added to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method in which a tetracarboxylic acid dianhydride component and a diamine component are alternately added, and the like In the present invention, any of these methods may be used. When the tetracarboxylic acid dianhydride component or the diamine component is composed of a plurality of compounds, the plural kinds of components may be reacted in advance in a mixed state, or they may be sequentially reacted individually.

The temperature at which the tetracarboxylic acid dianhydride component and the diamine component are reacted in the organic solvent is usually 0 to 150 ° C, preferably 5 to 100 ° C, more preferably 10 to 80 ° C. If the temperature is higher, the polymerization reaction is terminated quickly, but if it is too high, a polymer having a high molecular weight may not be obtained. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to perform uniform stirring. 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then an organic solvent may be added.

The molar ratio of the tetracarboxylic acid dianhydride component to the diamine component used in the polymerization reaction of the polyamic acid is preferably 1: 0.8 to 1.2. In addition, the polyamic acid obtained by excessing the diamine component may increase the coloring of the solution. Therefore, when the coloring of the solution is a concern, the above ratio may be set to 1: 0.8 to 1. As with the usual polycondensation reaction, the closer the molar ratio is to 1: 1, the larger the molecular weight of the obtained polyamic acid. If the molecular weight of the polyamic acid is too small, the strength of the coating film obtained therefrom may be insufficient. Conversely, if the molecular weight of the polyamic acid is too large, the solution viscosity becomes excessively high when the liquid crystal aligning agent is used as the coating solution. The uniformity of the coating film may be deteriorated.

The weight average molecular weight of such a polyamic acid is preferably 5,000 to 300,000, more preferably 10,000 to 200,000, and the number average molecular weight is preferably 2,500 to 150,000, more preferably 5,000 to 100,000 to be.

In the case where the solvent used for the polymerization of polyamic acid is not contained in the liquid crystal aligning agent of the present invention or the unreacted monomer component or impurity is present in the reaction solution and it is desired to remove it, Purification is carried out. The method is simple in that a polyamic acid solution is poured into a stirring solvent to precipitate and recover. Examples of the poor solvent used for the precipitation and recovery of polyamic acid are not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, . The polyamic acid precipitated by pouring into a poor solvent can be recovered by filtration and washing, and then recovered as a powder at room temperature or under reduced pressure or by heating and drying. The polyamic acid may be purified by repeating the operation of dissolving the powder in a good solvent and re-precipitating the solution two to ten times. When the impurities can not be completely removed by one settling recovery operation, this purification step is preferably carried out. When three or more poor solvents such as alcohols, ketones, and hydrocarbons are used as the poor solvent at this time, the purification efficiency is further improved, which is preferable. The above precipitate recovery and refining operations can be carried out in the same manner as in the synthesis of a polyamic acid alkyl ester or a polyimide described below.

When the polyamic acid is partially or completely imidized, the production method thereof is not particularly limited, but the polyamic acid obtained by reacting the tetracarboxylic acid dianhydride with the diamine can be imidized in the solution as it is. At this time, in order to convert part or all of the polyamic acid to polyimide, a method of dehydrating ring closure by heating or a method of ring closure chemically using a known dehydration ring closure catalyst is employed. In the heating method, any temperature of 100 占 폚 to 300 占 폚, preferably 120 占 폚 to 250 占 폚 may be selected. In the chemical ringing method, for example, pyridine, triethylamine or the like can be used in the presence of acetic anhydride or the like, and the temperature at this time can be selected arbitrarily from -20 deg. C to 200 deg.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is a liquid for forming a liquid crystal alignment film, in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing at least one of the polyamic acid described above and the polyimide obtained by imidizing the polyamic acid. At that time, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, and particularly preferably from 3% by mass to 10% by mass.

In the liquid crystal aligning agent of the present invention, all of the resin components may be polyamic acid of the present invention and polyimide obtained by imidizing the polyamic acid of the present invention, and other polymer other than the polyamic acid may be mixed. At this time, the content of the polyamic acid of the present invention in the resin component and the polymer other than the polyimide obtained by imidizing it is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

Such other polymers include, for example, polyamic acid of the present invention and polyamic acid other than polyimide obtained by imidizing it, and polyimide obtained by imidizing it.

The liquid crystal aligning agent of the present invention is obtained by reacting a polyamic acid obtained by reacting an aromatic tetracarboxylic acid dianhydride and a diamine component containing a second diamine and a diamine component containing an aliphatic tetracarboxylic acid dianhydride and a first diamine In the case where polyamic acid is mixed, the mixing ratio of the polyamic acid: aliphatic tetracarboxylic acid dianhydride and the first diamine obtained by reacting the aromatic tetracarboxylic acid dianhydride and the diamine component containing the second diamine, Is in the range of 50:50 to 10:90.

The organic solvent used in the liquid agent aligning agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the resin component. Specific examples thereof are listed below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- Dimethyl sulfoxide, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl Isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination.

The liquid crystal aligning agent of the present invention may contain components other than those described above. Examples thereof include a solvent or a compound that improves film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness or the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, 1-hexanol, n-pentane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, Propoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, And a solvent having a low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, .

These poor solvents may be one type or a mixture of plural types. When such a solvent is used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total solvent contained in the liquid crystal aligning agent.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), Prorad FC430 and FC431 (manufactured by Sumitomo 3M ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3 -Aminopropyltriethoxysilane, 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, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidyl Aminomethyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound improving the adhesion with the substrate is used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal aligning agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal aligning agent of the present invention may be a dielectric or a conductive material, and more preferably, a liquid crystal alignment film for the purpose of changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired A crosslinkable compound having the purpose of increasing the hardness or density of the film at the time of the coating may be added.

The liquid crystal aligning agent of the present invention thus obtained can be applied to a substrate after filtration if necessary and dried and fired to form a coated film. By subjecting the coated film surface to an orientation treatment such as rubbing or light irradiation, And can be used as a liquid crystal alignment film.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and it is possible to use a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like and a substrate on which an ITO electrode or the like for liquid crystal driving is formed Which is preferable from the viewpoint of process simplification. In the reflection type liquid crystal display element, it is possible to use an opaque material such as a silicon wafer if only one side substrate is used. In this case, a material that reflects light such as aluminum can also be used as the electrode in this case.

As the application method of the liquid crystal aligning agent, spin coating method, printing method, ink jet method and the like can be mentioned. In terms of productivity, the transfer printing method is industrially widely used, and the liquid crystal aligning agent of the present invention is preferably used do.

The drying step after application of the liquid crystal aligning agent is not necessarily deemed to be necessary, but it is preferable to include a drying step when the time from the application to the firing is not constant for each substrate or when the firing is not carried out immediately after application Do. This drying is not particularly limited as long as the solvent is evaporated to such an extent that the coating film shape is not deformed by transporting the substrate or the like. As a concrete example, a method of drying on a hot plate at 50 to 150 ° C, preferably 80 to 120 ° C for 0.5 to 30 minutes, preferably for 1 to 5 minutes is taken.

The firing of the liquid crystal aligning agent can be carried out at any temperature of 100 to 350 ° C, preferably 150 to 300 ° C, and more preferably 200 to 250 ° C. When the polyimide precursor is contained in the liquid crystal aligning agent, the conversion rate from the polyimide precursor to the polyimide changes depending on the baking temperature. However, the liquid crystal aligning agent of the present invention does not necessarily need to be imidized at 100%. However, it is preferable to carry out firing at a temperature higher by 10 ° C or more than the heat treatment temperature such as seal hardening required in the liquid crystal cell production process.

When the thickness of the coated film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness is excessively thin, the reliability of the liquid crystal display element may deteriorate, and therefore, it is 5 to 300 nm, preferably 10 to 100 nm.

<Liquid crystal display element>

The liquid crystal display element of the present invention is obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal aligning agent of the present invention by the above-described technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element. As an example of liquid crystal cell manufacturing, a pair of substrates on which a liquid crystal alignment film is formed is laminated with a spacer having a thickness of usually 1 to 30 μm, preferably 2 to 10 μm, and a rubbing direction of preferably 0 to 270 ° There is a general method in which the liquid crystal is sealed at an arbitrary angle, the periphery is fixed with a sealant, and a liquid crystal is injected and sealed. For the rubbing treatment on the liquid crystal alignment film, a conventional rubbing apparatus can be used. Examples of the material of the rubbing cloth at this time include cotton, rayon, nylon and the like. The method of sealing the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which liquid crystal is injected into a produced liquid crystal cell at a reduced pressure, a dropping method in which a liquid crystal is dropped, and then sealing is performed.

As described above, the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent liquid crystal alignability and alignment regulating ability and has excellent electric characteristics. Therefore, It can be a display device. Among these liquid crystal display elements, they are particularly preferably used for a transverse electric field type liquid crystal display element in which ghosting originating from the alignment restraining force occurs well.

Example

Hereinafter, details of the production method of the present invention will be described with reference to an experimental method examining the composition and mixing ratio of raw materials, the results thereof, and examples of a typical production method. The present invention is not limited to these examples.

Explanation of the abbreviations used in this embodiment

(Tetracarboxylic acid dianhydride)

The following CA-1 to CA-7 tetracarboxylic acid dianhydrides

(7)

(Diamine)

The diamine compounds of the following DA-1 to DA-2

[Chemical Formula 8]

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(additive)

LS-3150: 3-aminopropyltriethoxysilane

Each measurement method is shown below.

&Lt; Evaluation of rub resistance &

The resultant liquid crystal aligning agent was filtered with a filter of 1.0 占 퐉 and then spin-coated on a glass substrate with a transparent electrode. The substrate was dried on a hot plate at 80 占 폚 for 5 minutes and then baked at 230 占 폚 for 20 minutes to form a film having a thickness of 100 nm Of a polyimide film was obtained. This polyimide membrane was rubbed with a rayon bath (roll diameter 120 mm, rotation speed 1000 rpm, moving speed 20 mm / sec, indentation amount 0.2 mm). The surface state of the film surface was observed using a confocal laser microscope, and the presence or absence of scratches and presence or absence of scratches were observed at a magnification of 100 times. A mark showing that no cutting residue or scratch was observed at all was evaluated as &amp; cir &amp;, and several scratches or rubbing scratches were observed as DELTA, and many scratches and rubbing scratches were observed.

&Lt; Production of liquid crystal display element &

First, a substrate with an electrode attached thereto was prepared. The substrate is a glass substrate having a size of 30 mm x 35 mm and a thickness of 0.7 mm. On the substrate, an IZO electrode having a beta-pattern constituting the counter electrode as the first layer is formed. On the first layer counter electrode, a SiN (silicon nitride) film formed by the CVD method is formed as the second layer. The thickness of the second-layer SiN film is 500 nm and functions as an interlayer insulating film. On the second-layer SiN film, pixel electrodes on the combs formed by patterning the IZO film as the third layer are disposed to form two pixels, that is, the first pixel and the second pixel. The size of each pixel is 10 mm in length and 5 mm in width. At this time, the first layer counter electrode and the third layer pixel electrode are electrically insulated by the action of the second layer SiN film.

The third-layer pixel electrode has a comb-like shape formed by arranging a plurality of elongated electrode elements bent at a central portion. The width of each electrode element in the width direction is 3 占 퐉, and the interval between the electrode elements is 6 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of elongated electrode elements bent at the center portion, the shape of each pixel is not a rectangular shape, And has a shape similar to that of FIG. Each pixel is divided into upper and lower portions with the central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.

When the first region and the second region of each pixel are compared with each other, the electrode elements of the pixel electrodes constituting the first region and the second region are different from each other. In other words, when the rubbing direction of a liquid crystal alignment film to be described later is taken as a reference, the electrode elements of the pixel electrodes are formed so as to form an angle of +10 degrees (clockwise) in the first region of the pixel, The element is formed so as to form an angle (clockwise direction) of -10 degrees. That is, in the first region and the second region of each pixel, the direction of the rotation (inflation / switching) of the liquid crystal in the substrate plane caused by the application of the voltage between the pixel electrode and the counter electrode is opposite to each other Consists of.

Next, after filtering the resultant liquid crystal aligning agent with a filter having a size of 1.0 mu m, an ITO film was formed on the back surface of the substrate on which the prepared electrode and the counter substrate were formed, and a glass substrate having a columnar spacer having a height of 4 mu m Lt; / RTI &gt; Subsequently, the substrate was dried on a hot plate at 50 占 폚 for 5 minutes, and then baked at 230 占 폚 for 30 minutes to obtain a coating film having a film thickness of 60 nm to obtain a polyimide film on each substrate. This polyimide film was subjected to ultrasonic irradiation for 1 minute in pure water after rubbing (roll diameter 120 mm, rotation speed 500 rpm, moving speed 30 mm / sec, press-in amount 0.3 mm) Followed by drying at 80 DEG C for 10 minutes.

Thereafter, using the two types of substrates having the liquid crystal alignment film formed thereon, the respective rubbing directions were combined so as to be opposite to each other, and the periphery was sealed while leaving the liquid crystal injection ports, thereby producing empty cells with a cell gap of 3.8 mu m Respectively. A liquid crystal (MLC-2041, manufactured by Merck) was injected into the open cell under vacuum at room temperature, and then the injection port was sealed to obtain an anti-parallel alignment liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the resulting liquid crystal cell was heated at 110 DEG C for 1 hour, allowed to stand overnight, and then used for evaluation.

(Residual image evaluation)

The following images were used to evaluate the afterimage.

The prepared liquid crystal cell was placed between two polarizing plates arranged so that the polarization axis thereof was orthogonal to each other. The LED backlight was turned on in a voltage-unapplied state and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of transmitted light was minimized.

Next, a V-T curve (voltage-transmittance curve) was measured while applying an AC voltage with a frequency of 30 Hz to this liquid crystal cell, and an AC voltage having a relative transmittance of 23% was calculated as a drive voltage.

In the residual image evaluation, an AC voltage of 30 Hz at which the relative transmittance was 23% was applied to drive the liquid crystal cell, and a DC voltage of 1 V was applied at the same time for 60 minutes. Thereafter, the application of the direct current voltage was stopped with the applied direct current voltage value at 0 V, and the device was further driven for 30 minutes in this state.

The evaluation of the afterimage was defined as &quot; good &quot; when the relative transmittance decreased to 25% or less after 60 minutes from the start of application of the direct current voltage. In the case where the relative transmittance was required to be lower than 25% for 60 minutes or longer, the evaluation was defined as &quot; poor &quot;.

The residual image evaluation according to the above-described method was performed under a temperature condition in which the temperature of the liquid crystal cell was 23 占 폚. The evaluation results are shown in Table 3.

&Lt; Evaluation of afterimage by long-term driving >

Using this liquid crystal cell, an AC voltage of 10 VPP was applied for 100 hours at a frequency of 30 Hz under a constant temperature environment of 60 占 폚. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left to stand at room temperature for one day.

After leaving the liquid crystal cell, the liquid crystal cell was placed between two polarizing plates arranged so that the polarization axis thereof was orthogonal to each other, and the backlight was turned on in a voltage unapplied state, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light was minimized. The rotation angle when the liquid crystal cell was rotated from the angle where the second area of the first pixel darkest to the angle where the first area becomes darkest was calculated as the angle?. Similarly, in the second pixel, the second region and the first region were compared and the same angle? Was calculated. Then, the average value of the angles? Of the first and second pixels was calculated as the angle? Of the liquid crystal cell. When the value of the angle? Of the liquid crystal cell exceeds 0.2 degrees, it is defined as &quot; defective &quot;. When the value of the angle? Of the liquid crystal cell does not exceed 0.2 degrees, it is defined as &quot; good &quot;

&Lt; Synthesis of Polymer &

&Lt; Synthesis Example 1 &

7.64 g (26.5 mmol) of DA-1, 10.4 g (26.5 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen- And dissolved with stirring while nitrogen was being transferred. 5.78 g (26.5 mmol) of CA-1 and 3.98 g (15.9 mmol) of CA-3 were added while stirring the diamine solution, and the mixture was stirred at 50 ° C for 3 hours. Thereafter, the temperature of the reaction solution was lowered to 23 占 폚 and 1.66 g (8.48 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so that the solid content concentration became 15 mass% A solution of polyamic acid (abbreviated as P1) was obtained. The viscosity of this polyamic acid (P1) solution at 25 캜 was confirmed to be 481 mPa s by an E-type viscometer (manufactured by Toki Industry Co., Ltd.).

87.4 g of N-methyl-2-pyrrolidone, 0.075 g of LS-3150 and 50 g of butyl cellosolve were added to 100 g of this polyamic acid (P1) solution to obtain liquid crystal alignment with a concentration of P1 of 5.97 mass% (Q1) was obtained.

&Lt; Synthesis Example 2 &

7.79 g (27.0 mmol) of DA-1, 10.6 g (27.0 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen- And dissolved with stirring while nitrogen was being transferred. While stirring the diamine solution, 5.89 g (27.0 mmol) of CA-1 and 3.21 g (16.2 mmol) of CA-4 were added and stirred at 50 ° C for 3 hours. Thereafter, the temperature of the reaction solution was lowered to 23 ° C to add 1.70 g (8.64 mmol) of CA-2 and N-methyl-2-pyrrolidone so that the solids concentration became 15 mass%, and the mixture was stirred at 23 ° C for 20 hours A solution of polyamic acid (abbreviated as P2) was obtained. The viscosity of this polyamic acid (P2) solution at 25 占 폚 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 512 mPa 占 퐏.

87.4 g of N-methyl-2-pyrrolidone, 0.075 g of LS-3150 and 50 g of butyl cellosolve were added to 100 g of this polyamic acid (P2) solution to obtain liquid crystal alignment with a concentration of P2 of 5.86% by mass (Q2) was obtained.

&Lt; Synthesis Example 3 &

7.79 g (27.0 mmol) of DA-1, 10.6 g (27.0 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen- And dissolved with stirring while nitrogen was being transferred. 5.89 g (27.0 mmol) of CA-1 and 3.44 g (16.2 mmol) of CA-4 were added while stirring the diamine solution, and the mixture was stirred at 50 캜 for 3 hours. Thereafter, the temperature of the reaction solution was lowered to 23 ° C to add 1.70 g (8.64 mmol) of CA-2 and N-methyl-2-pyrrolidone so that the solids concentration became 15 mass%, and the mixture was stirred at 23 ° C for 20 hours A solution of polyamic acid (abbreviated as P3) was obtained. The viscosity of this polyamic acid (P3) solution at 25 캜 was confirmed to be 492 mPa s by an E-type viscometer (manufactured by Toki Industry Co., Ltd.).

87.4 g of N-methyl-2-pyrrolidone, 0.075 g of LS-3150 and 50 g of butyl cellosolve were added to 100 g of this polyamic acid (P3) solution to obtain a liquid crystal alignment with a P3 concentration of 5.96% (Q3) was obtained.

&Lt; Synthesis Example 4 &

7.79 g (27.0 mmol) of DA-1, 10.6 g (27.0 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen- And dissolved with stirring while nitrogen was being transferred. 5.89 g (27.0 mmol) of CA-1 and 3.63 g (16.2 mmol) of CA-6 were added while stirring the diamine solution, and the mixture was stirred at 50 占 폚 for 3 hours. Thereafter, the temperature of the reaction solution was lowered to 23 ° C to add 1.70 g (8.64 mmol) of CA-2 and N-methyl-2-pyrrolidone so that the solids concentration became 15 mass%, and the mixture was stirred at 23 ° C for 20 hours A solution of polyamic acid (abbreviated as P4) was obtained. The viscosity of this polyamic acid (P4) solution at 25 캜 was confirmed to be 479 mPa s by an E-type viscometer (manufactured by Toki Industry Co., Ltd.).

87.4 g of N-methyl-2-pyrrolidone, 0.075 g of LS-3150 and 50 g of butyl cellosolve were added to 100 g of the polyamic acid (P4) solution to obtain a liquid crystal alignment with a P4 concentration of 5.99% (Q4) was obtained.

&Lt; Synthesis Example 5 &

7.35 g (25.5 mmol) of DA-1, 10.01 g (25.5 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen- And dissolved with stirring while nitrogen was being transferred. While stirring the diamine solution, 7.50 g (25.5 mmol) of CA-7 and 3.83 g (15.3 mmol) of CA-3 were added, and the mixture was stirred at 50 ° C for 3 hours. Thereafter, the temperature of the reaction solution was lowered to 23 占 폚, and 1.60 g (8.16 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so that the solid content concentration became 15 mass% A solution of polyamic acid (abbreviated as P5) was obtained. The viscosity of this polyamic acid (P5) solution at 25 캜 was confirmed to be 465 mPa s by an E-type viscometer (manufactured by Toki Industry Co., Ltd.).

87.4 g of N-methyl-2-pyrrolidone, 0.075 g of LS-3150 and 50 g of butyl cellosolve were added to 100 g of the polyamic acid (P5) solution to obtain a liquid crystal alignment with a P5 concentration of 5.88% (Q5) was obtained.

&Lt; Synthesis Example 6 &

13.55 g (47.0 mmol) of DA-1 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being transferred. 9.74 g (44.7 mmol) of CA-1 and N-methyl-2-pyrrolidone were added thereto so that the solid content concentration became 12 mass% while stirring the diamine solution, and the mixture was stirred at 50 캜 for 24 hours. Thereafter, the temperature of the reaction solution was lowered to 23 DEG C to obtain a solution of polyamic acid (abbreviated as P6). The viscosity of this polyamic acid (P6) solution at 25 占 폚 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.), and found to be 318 mPa 占 퐏.

60 g of N-methyl-2-pyrrolidone and 40 g of LS-3150 and butyl cellosolve were added to 100 g of this polyamic acid (P6) solution to obtain a liquid crystal aligning agent (Q6 ).

&Lt; Synthesis Example 7 &

13.35 g (34.0 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being transferred. 2.33 g (11.9 mmol) of CA-2 was added thereto while stirring the diamine solution, and the mixture was stirred at 23 占 폚 for 5 hours. Then, 3.37 g (17.0 mmol) of CA-4 was added, and the mixture was further stirred at 23 캜 for 5 hours. Thereafter, 0.85 g (4.34 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so that the solids concentration became 10 mass%, and the mixture was further stirred at 23 캜 for 3 hours to obtain a solution of polyamic acid P7) was obtained. The viscosity of this polyamic acid (P7) solution at 25 占 폚 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 1045 mPa 占 퐏.

33.55 g of N-methyl-2-pyrrolidone, 0.1 g of LS-3150 and 33.02 g of butyl cellosolve were added to 100 g of this polyamic acid (P7) solution to obtain a liquid crystal alignment (Q7) was obtained.

&Lt; Synthesis Example 8 &

20.0 g of liquid crystal aligning agent (Q6) and 80 g of liquid crystal aligning agent (Q7) were mixed and stirred at 23 占 폚 for 20 hours to obtain liquid crystal aligning agent (Q8).

&Lt; Synthesis Example 9 &

12.56 g (32.0 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200-ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being transferred. 2.20 g (11.2 mmol) of CA-2 was added while stirring the diamine solution, and the mixture was stirred at 23 占 폚 for 5 hours. Then, 4.00 g (16.0 mmol) of CA-4 was added, and the mixture was further stirred at 23 ° C for 5 hours. Thereafter, 0.89 g (4.56 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so as to have a solid content concentration of 10% by mass and stirred at 23 캜 for further 3 hours to obtain a solution of polyamic acid Quot; P8 &quot;). The viscosity of this polyamic acid (P8) solution at 25 占 폚 was confirmed by an E-type viscometer (Toki Industries Co., Ltd.) and found to be 981 mPa 占 퐏.

33.55 g of N-methyl-2-pyrrolidone, 0.1 g of LS-3150 and 33.02 g of butyl cellosolve were added to 100 g of this polyamic acid (P8) solution to obtain liquid crystal alignment (Q9) was obtained.

&Lt; Synthesis Example 10 &

20.0 g of liquid crystal aligning agent (Q6) and 80 g of liquid crystal aligning agent (Q9) were mixed and stirred at 23 占 폚 for 20 hours to obtain liquid crystal aligning agent (Q10).

&Lt; Synthesis Example 11 &

12.56 g (32.0 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200-ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being transferred. 2.33 g (11.9 mmol) of CA-2 was added thereto while stirring the diamine solution, and the mixture was stirred at 23 占 폚 for 5 hours. Then, 3.61 g (17.0 mmol) of CA-5 was added, and the mixture was further stirred at 23 캜 for 5 hours. Thereafter, 0.96 g (4.90 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so as to have a solid content concentration of 10% by mass and stirred at 23 캜 for further 3 hours to obtain a solution of polyamic acid P9) was obtained. The viscosity of this polyamic acid (P9) solution at 25 캜 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.), and found to be 1005 mPa s.

To 100 g of this polyamic acid (P9) solution was added 33.55 g of N-methyl-2-pyrrolidone, 0.1 g of LS-3150 and 33.02 g of butyl cellosolve to obtain a liquid crystal alignment with a concentration of P9 of 5.97% (Q11) was obtained.

&Lt; Synthesis Example 12 &

20.0 g of liquid crystal aligning agent (Q6) and 80 g of liquid crystal aligning agent (Q11) were mixed and stirred at 23 占 폚 for 20 hours to obtain liquid crystal aligning agent (Q12).

&Lt; Synthesis Example 13 &

12.96 g (34.0 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being transferred. 2.27 g (11.9 mmol) of CA-2 was added while stirring the diamine solution, and the mixture was stirred at 23 占 폚 for 5 hours. Thereafter, 3.70 g (17.0 mmol) of CA-6 was added, and the mixture was further stirred at 23 캜 for 5 hours. Thereafter, 0.92 g (4.85 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so as to have a solid content concentration of 10% by mass and further stirred at 23 캜 for 3 hours to obtain a solution of polyamic acid Quot; P10 &quot;). The viscosity of this polyamic acid (P10) solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 977 mPa 占 퐏.

33.55 g of N-methyl-2-pyrrolidone, 0.1 g of LS-3150 and 33.02 g of butyl cellosolve were added to 100 g of this polyamic acid (P10) solution to obtain a liquid crystal alignment of 5.95% (Q13) was obtained.

&Lt; Synthesis Example 14 &

20.0 g of liquid crystal aligning agent (Q6) and 80 g of liquid crystal aligning agent (Q13) were mixed and stirred at 23 占 폚 for 20 hours to obtain liquid crystal aligning agent (Q14).

<Comparative Synthesis Example 1>

17.58 g (61.0 mmol) of DA-1 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being transferred. 6.65 g (30.5 mmol) of CA-1, 5.38 g (27.5 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so that the solids concentration became 15 mass% Lt; 0 &gt; C for 5 hours to obtain a solution of polyamic acid (abbreviated as P11). The viscosity of this polyamic acid (P11) solution at 25 占 폚 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 1028 mPa 占 퐏.

100 g of N-methyl-2-pyrrolidone and 50 g of LS-3150 and butyl cellosolve were added to 100 g of this polyamic acid (P11) solution to obtain a liquid crystal aligning agent having a concentration of P11 of 5.91 mass% (Q15 ).

&Lt; Comparative Synthesis Example 2 &

6.20 g (21.5 mmol) of DA-1, 8.44 g (21.5 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen- And dissolved with stirring while nitrogen was being transferred. 8.91 g (40.9 mmol) of CA-1 and N-methyl-2-pyrrolidone were added thereto so that the solid content concentration became 12 mass% while stirring the diamine solution, and the mixture was stirred at 50 캜 for 24 hours. Thereafter, the temperature of the reaction solution was lowered to 23 占 폚 to obtain a solution of polyamic acid (abbreviated as P12). The viscosity of this polyamic acid (P12) solution at 25 占 폚 was determined by an E-type viscometer (manufactured by Toki Industries Co., Ltd.) and found to be 351 mPa 占 퐏.

60 g of N-methyl-2-pyrrolidone and 40 g of LS-3150 and butyl cellosolve were added to 100 g of this polyamic acid (P12) solution to obtain a liquid crystal aligning agent having a concentration of P12 of 5.9% by mass ).

&Lt; Comparative Synthesis Example 3 >

20.02 g (40.8 mmol) of DA-2 and 100 g of N-methyl-2-pyrrolidone were added to a 200 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, and dissolved with stirring while nitrogen was being transferred. 2.22 g (10.2 mmol) of CA-1, 7.68 g (39.2 mmol) of CA-2 and N-methyl-2-pyrrolidone were added thereto so that the solids concentration became 15 mass% C for 5 hours to obtain a solution of polyamic acid (abbreviated as P13). The viscosity of this polyamic acid (P13) solution at 25 占 폚 was confirmed by an E-type viscometer (manufactured by Toki Industries Co., Ltd.), and found to be 825 mPa 占 퐏.

100 g of N-methyl-2-pyrrolidone and 50 g of LS-3150 and butyl cellosolve were added to 100 g of this polyamic acid (P13) solution to obtain a liquid crystal aligning agent having a concentration of P13 of 5.85% by mass (Q17 ).

&Lt; Examples 1 to 9 >

Rubbing resistance evaluation, afterimage evaluation and residual image evaluation by long-term driving were carried out using the liquid crystal aligning agents obtained in Synthesis Examples 1 to 5, 8, 10, 12 and 14. The results are shown in Table 1.

&Lt; Comparative Examples 1 to 3 >

Rubbing resistance evaluation, afterimage evaluation and residual image evaluation by long-term driving were performed using the liquid crystal aligning agent obtained in Comparative Synthesis Examples 1 to 3. The results are shown in Table 1.

As described above, the liquid crystal aligning agent of the present invention exhibited satisfactory results in any of the rubbing resistance evaluation, the afterimage evaluation, and the after-image evaluation by long-term driving. However, the liquid crystal aligning agent produced in Comparative Examples 1 to 3, &Lt; / RTI &gt;

Claims (7)

A tetracarboxylic acid dianhydride component containing at least one tetracarboxylic acid dianhydride selected from the group consisting of an aromatic tetracarboxylic acid dianhydride and an aliphatic tetracarboxylic acid dianhydride and a diamine having a tertiary nitrogen atom and A liquid crystal aligning agent containing at least one of a polyamic acid obtained by reacting a diamine component containing at least one diamine selected from the group consisting of diamines of the following structures and a polyimide obtained by imidizing the diamine component:
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms. The method according to claim 1,
Obtained by reacting an aromatic tetracarboxylic acid dianhydride with a diamine component containing a diamine having the following structure, and a diamine component containing a polyamic acid and an aliphatic tetracarboxylic acid dianhydride and a diamine having a tertiary nitrogen atom Liquid crystal aligning agent containing polyamic acid:
(2)

Wherein R ₁ and R ₂ are each independently an alkylene group having 1 to 5 carbon atoms. 3. The method according to claim 1 or 2,
Wherein the aliphatic tetracarboxylic acid dianhydride is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid 2-anhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and 1,2,4,5-pentanetetracarboxylic acid dianhydride. Wherein the liquid crystal aligning agent contains at least one tetracarboxylic acid dianhydride. 4. The method according to any one of claims 1 to 3,
And the tertiary nitrogen atom constitutes a heterocyclic ring in the diamine containing the tertiary nitrogen atom. 5. The method according to any one of claims 1 to 4,
A liquid crystal aligning agent characterized in that the diamine containing the tertiary nitrogen atom has the following structure:
(3)

. A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of claims 1 to 5. A liquid crystal display element comprising the liquid crystal alignment film of claim 6.