KR101565394B1 - Liquid crystal aligning agent and related compounds thereof, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

[PROBLEMS] To provide a liquid crystal aligning agent which is capable of imparting a liquid crystal alignment film excellent in film quality, excellent in electrical characteristics and heat resistance, and excellent in coating properties.
(Solution) The liquid crystal aligning agent contains at least one polymer selected from the group consisting of polyamic acid and polyimide, wherein the polymer has at least a part of the molecule thereof represented by the following formula (A ') Lt; / RTI >
R ^I - (X ^I ) _{n 1} -R ^II -O-X ^II -COO- (R ^III O) _{n 2} - ^* (A ')
(Wherein (A ') of, R ^I is a fluoroalkyl group of 1 to 30 carbon atoms or an alkyl group of 1 to 30 carbon atoms, R ^Ⅱ is a single bond, a methylene group or an alkylene group having a carbon number of 2~30, R is carbon atoms ^Ⅲ 2 to 5, and X < RTI ID = 0.0 > ^I And ^XII are each a divalent alicyclic group, a divalent heterocyclic group, an arylene group or a divalent heteroaromatic group, wherein a plurality of groups X ^I may be the same or different from each other, and n1 is an integer of 2 to 5 , N2 is an integer of 0 to 10, and " * "

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a related compound thereof, a liquid crystal alignment film and a liquid crystal display element,

The present invention relates to a liquid crystal aligning agent and its related compounds, a liquid crystal alignment film, and a liquid crystal display element. More particularly, the present invention relates to a liquid crystal aligning agent which is capable of imparting a liquid crystal alignment film having uniform film quality, excellent in electric characteristics and heat resistance, and a liquid crystal aligning agent having excellent coatability, And the deterioration of quality is suppressed.

Currently known liquid crystal display elements can be divided into the following modes from the electrode structure and the physical properties of the liquid crystal molecules used.

First, 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 element. Two liquid crystal alignment films are disposed opposite to each other to form a nematic liquid crystal layer having positive dielectric anisotropy in the gap A TN type liquid crystal display device having a so-called TN type (Twisted Nematic) liquid crystal cell in which the long axis of the liquid crystal molecules can be twisted by 90 degrees continuously from one substrate toward the other substrate as a cell having a sandwich structure (Patent Document 1 (TNN) type liquid crystal display device (Patent Document 2) capable of realizing a higher duty factor than a TN type liquid crystal display device is known. In addition, the same counter electrode arrangement as that of the TN liquid crystal display element is adopted, but a nematic liquid crystal layer having a negative dielectric anisotropy is injected into the gap between the electrodes, and VA ( Vertical Alignment type display devices are known (Patent Document 3). This VA-type display element has a high contrast and can manufacture a large-area display element.

On the other hand, an IPS (In-Plane Switching) type liquid crystal display device (Patent Document 4) in which liquid crystal is driven only in the in-plane direction of the substrate upon application of an electric field by arranging electrode pairs in a comb- (Fringe Field Switching) type liquid crystal display device (Patent Document 5) in which the aperture ratio of the display element portion is increased to improve the luminance by changing the electrode structure of the display element portion (Patent Document 5).

In addition to these, OCB (Optical Compensated Bend) type liquid crystal display device (Patent Document 6), which has a small visual dependency and is excellent in high-speed response of an image screen, has been developed.

As a material of the liquid crystal alignment film in these liquid crystal display elements, resin materials such as polyamic acid, polyimide, polyamide, polyester and the like are known. Particularly, a liquid crystal alignment film made of polyamic acid or polyimide has heat resistance, mechanical strength, And has been used in many liquid crystal display devices (Patent Documents 7 to 8).

2. Description of the Related Art In recent years, a liquid crystal display device has been developed for television applications. In addition to the development of fine display and high-speed moving picture stabilization technology, a long viewing time that can not be expected from conventional liquid crystal display devices (Normalization) has been. However, it has been pointed out that when a liquid crystal display element comprising a liquid crystal alignment film made of a conventionally known material is driven for a long time, image quality deteriorates. It is believed that this phenomenon is caused by the fact that thermal stress is applied to the liquid crystal alignment film by continuous driving for a long time and as a result, the electrical characteristics of the liquid crystal alignment film, in particular, the voltage retention ratio are significantly lowered. There is a demand for providing a liquid crystal alignment film material.

In addition, the liquid crystal television tends to have a larger screen size, and the substrate used for the liquid crystal display element tends to be larger every year from the viewpoint of reducing the manufacturing cost. Therefore, after the liquid crystal aligning agent is applied to the substrate, there is a tendency that the time (holding time) until it is baked becomes longer. It has been pointed out that if the liquid crystal aligning agent known in the art is used, the uniformity of the coating film is deteriorated or the pinhole is generated when the leaving time is long, and the display quality of the resulting liquid crystal display element is deteriorated. Even if left for a long time, And a liquid crystal aligning agent capable of providing a liquid crystal display element excellent in display quality is required.

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 Japanese Patent Application Laid-Open No. 2008-216572 Japanese Laid-Open Patent Publication No. 2009-48211 U.S. Patent No. 5,928,733 Japanese Laid-Open Patent Publication No. 62-165628

An object of the present invention is to provide a liquid crystal aligning agent capable of imparting a liquid crystal alignment film with uniform film quality and excellent electrical characteristics and heat resistance even when left standing for a long time after application.

Another object of the present invention is to provide a liquid crystal display element capable of displaying a high-quality image and further suppressing deterioration of display quality when driven for a long time.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above-

(1) at least one polymer selected from the group consisting of polyamic acid and polyimide, wherein the polymer has a group represented by the following formula (A ') in at least a part of its molecule, Orientation agent

R ^I - (X ^I ) _{n 1} -R ^II -O-X ^II -COO- (R ^III O) _{n 2} - ^* (A ')

(Wherein (A ') of, R ^I is a fluoroalkyl group of 1 to 30 carbon atoms or an alkyl group of 1 to 30 carbon atoms, R ^Ⅱ is a single bond, a methylene group or an alkylene group having a carbon number of 2~30, R is carbon atoms ^Ⅲ 2 to 5, and X < RTI ID = 0.0 > ^I And ^XII are each a divalent alicyclic group, a divalent heterocyclic group, an arylene group or a divalent heteroaromatic group, wherein a plurality of groups X ^I may be the same or different from each other, and n1 is an integer of 2 to 5 , N2 is an integer of 0 to 10, and " * "

(2) the polymer is selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a compound represented by the following formula (A) and a polyimide obtained by dehydrocondensing the polyamic acid The liquid crystal aligning agent according to the above (1), which comprises at least one kind of polymer.

(Wherein (A) of, R ^I, R ^{Ⅱ, Ⅲ} R, X ^I, X ^Ⅱ, n1 and n2 are, respectively, equal to the meaning as defined in the formula (A ').)

(3) The liquid crystal aligning agent according to (2), wherein X ^I in the formula (A) is a bivalent alicyclic group and X ^II is an arylene group,

(4) a (X ^I), _n1 is 4,4'-cyclohexylene group in the formula (A), X ^Ⅱ the liquid crystal orientation described in the above 1,4-phenylene group (3) a,

(5) The liquid crystal aligning agent according to any one of (2) to (4) above, wherein the tetracarboxylic acid dianhydride comprises 2,3,5-tricarboxycyclopentylacetic acid dianhydride,

(6) a liquid crystal alignment layer formed from the liquid crystal aligning agent,

(7) A liquid crystal display element comprising the liquid crystal alignment layer,

(8) a polyamic acid obtained by reacting tetracarboxylic acid dianhydride with a diamine containing the compound represented by the above formula (A)

(9) a polyimide obtained by dehydrocondensing a polyamic acid obtained by reacting tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A)

(10) The compound represented by the above formula (A)

Lt; / RTI >

The liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film having uniform film quality and excellent electrical characteristics and heat resistance even when left standing for a long time after application.

The liquid crystal display element of the present invention comprising the liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention is capable of displaying a high-quality image and further suppressing deterioration of the display quality when driven for a long time. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, and can be applied to various devices such as a clock, a portable game, a word process, a notebook type personal computer, a car navigation system, a camcorder, It can be suitably used for a display device such as a telephone, various monitors, and a liquid crystal television.

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

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyimide, wherein the polymer has a group represented by the formula (A ') in at least a part of its molecule . Such a polymer is hereinafter referred to as a " specific polymer " in the present specification.

The formula (A ') as the carbon number of alkyl group of from 1 to 30 of the R ^I in, as the straight-chain alkyl group having 1 to 12 carbon atoms preferred, particularly preferred, n- propyl, n- butyl, n- pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like.

Of the R ^I group in the fluoroalkyl group of 1 to 30 carbon atoms preferable example, for example, the formula (R ^I -1) may include groups represented by the following formula (R ^I -1) due to the more linear is represented by And specific examples thereof include, for example, a trifluoromethyl group and a 4,4,5,5,5-pentafluoropentyl group.

C _i F _{2i +1} -C _j H _2j - (R ^I -1)

(Wherein i is an integer of 1 to 30 and j is an integer of 0 to 29, provided that i + j is an integer of 1 to 30.)

As R < ^II > in the formula (A '), a single bond or a methylene group is preferable, and a methylene group is particularly preferable.

As ^Ⅲ R in the formula (A '), preferably an alkylene group of carbon number 2 or 3, and as its specific examples, for example, 1,2-ethylene, 1,2-propylene group, 1,3 -Propylene group and the like. Of these, a 1,2-ethylene group or a 1,2-propylene group is more preferable. The binding direction of the 1,2-propylene group is not limited. Examples of R ^Ⅲ is particularly preferably 1,2-ethylene group.

The divalent alicyclic group represented by X ^I and X ^II in the formula (A ') may be, for example, a divalent alicyclic group having 3 to 8 carbon atoms, and specific examples thereof include 1,4 -Cyclohexylene group, 1,3-cyclohexylene group, 1,3-cyclopentylene group and the like. Each of the divalent heterocyclic groups represented by X ^I and X ^II may be, for example, a divalent heterocyclic group having 3 to 8 carbon atoms, and specific examples thereof include piperidine-1,4-diyl group , Piperazine-1,4-diyl group and the like. X ^I and the aryl group of X ^Ⅱ, respectively, for example, can be an arylene having a carbon number of 6 to 12 due date, for example, by way of example his specific 1,4-phenylene, 1,3-phenylene group, naphthalene -2 , A 6-diyl group, a naphthalene-2,7-diyl group, and a naphthalene-1,5-diyl group. X ^I and as the divalent heterocyclic aromatic group of X ^Ⅱ, respectively, for example, may be 2-valent heterocyclic aromatic date of 4 to 8 carbon atoms, as for example his sphere. For example, pyridine-2,5-diyl, pyridine-2,6-diyl, pyrazine-2,5-diyl, pyrazine-2,6-diyl, pyrimidine- An imidazole-1, 4-diyl group, a pyrazole-1,3-diyl group, and a pyrazole-1,4-diyl group. The bivalent alicyclic group having 3 to 8 carbon atoms, the divalent heterocyclic group having 3 to 8 carbon atoms, the arylene group having 6 to 12 carbon atoms, and the divalent heteroaromatic group having 4 to 8 carbon atoms represented by X ^I and X ^II have 1 Or an alkyl group having 1 to 12 carbon atoms or two or more fluorine atoms.

The X ^I in the formula (A ') is preferably a divalent alicyclic group, and n1 is preferably 2 each. The above formula ^{(A ') (X I)} n1 Examples of particularly preferred in is a 4,4'-cyclohexylene group.

As X < ^II > in the formula (A '), an arylene group is preferable, and a 1,4-phenylene group is particularly preferable.

The n2 in the formula (A ') is preferably 0 or 1.

The polyamic acid having a group represented by the formula (A ') in at least a part of the molecule may be, for example,

A tetracarboxylic acid dianhydride containing a group represented by the formula (A ') and a compound having two carbonic acid anhydride groups is reacted with a diamine,

Can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a compound represented by the formula (A ') and a compound having two amino groups,

The polyimide having at least a part of the molecule and having a group represented by the formula (A ') can be obtained, for example, by dehydration ring closure of the polyamic acid obtained as described above.

Specific examples of the polymer contained in the liquid crystal aligning agent of the present invention include a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a compound represented by the formula (A ') and a compound having two amino groups, And at least one polymer selected from the group consisting of polyimides obtained by dehydration cyclization of polyamic acid.

<Polyamic acid>

[Tetracarboxylic acid dianhydride]

Examples of the tetracarboxylic acid dianhydride used in the synthesis of the preferable polyamic acid in the liquid crystal aligning agent of the present invention include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3- 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5 -Tricarboxycyclopentyl acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- - dioxo-3-furanyl) - Dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [l, 2-c] -furan-l, 3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro- 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b-hexahydro- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ , 3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ - dione, 1,3,3a, 4, 5,9-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ Bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane- 3 '- (tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 5,8,10-tetraone, compounds represented by each of the following formulas (T-I) and (T-II), and alicyclic tetracarboxylic acid dianhydrides such as alicyclic tetracarboxylic acid dianhydrides

Wherein R ¹ and R ³ are each a divalent organic group having an aromatic ring, R ² and R ⁴ are each a hydrogen atom or an alkyl group, and a plurality of R ² and R ⁴ present are the same Or may be different);

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenylether tetracarboxylic acid dianhydride, 3,3', 4,4 '-Dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4 ' -Bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis -Dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane Bis (anhydrotrimellitate), 1,6-hexanediol-bis (trimellitic anhydride), ethylene glycol-bis (anhydrotrimellitate), propylene glycol- (Anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane- Aromatic tetracarboxylic acid dianhydrides such as compounds represented by each of T-1) to (T-4).

 The benzene ring of the aromatic tetracarboxylic dianhydride may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). These tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

Examples of the tetracarboxylic acid dianhydride used for the synthesis of the preferable polyamic acid in the present invention include the butanetetracarboxylic dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydrides, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1 , 3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -C] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3- [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro- 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, Dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 2,3', 2,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid 2 Among the compounds represented by the following formulas (T-5) to (T-7) and the compounds represented by the formula (T-II) among the compounds represented by the above formula (T- (Hereinafter referred to as &quot; specific tetracarboxylic acid dianhydride &quot;) selected from the group consisting of compounds represented by the following general formula (T-8) It is preferable that the expression of a good liquid crystal alignment liquid crystal alignment film formed perspective.

Specific tetracarboxylic acid dianhydrides are more preferably 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 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 4 , a 9-dioxa-tricyclo [5.3.1.0 ^2,6] undecane -3,5,8,10- tetrahydro-one, pyromellitic dianhydride and a compound represented by the formula (T-5) Is at least one member selected from the group eojineun, particularly preferably 2, 3, 5-tri-carboxy-cyclopentyl acetic dianhydride.

The tetracarboxylic acid dianhydride used in the synthesis of the preferable polyamic acid in the present invention is a compound containing 10 mol% or more of the above specific tetracarboxylic acid dianhydride with respect to all the tetracarboxylic dianhydrides , More preferably 30 mol% or more, particularly preferably 40 mol% or more.

As the tetracarboxylic acid dianhydride used in the synthesis of the preferable polyamic acid in the present invention, it is most preferable to use only the above-mentioned specific tetracarboxylic dianhydride.

[Diamine]

The diamine used for the synthesis of the preferred polyamic acid in the present invention contains a compound represented by the formula (A ') and a compound having two amino groups.

The compound represented by the formula (A ') and the compound having two amino groups is preferably a compound represented by the following formula (A). The two amino groups bonded to the benzene ring in the following formula (A) are preferably 2,4-position or 3,5-position.

&Lt; Formula 1 >

(Wherein (A) of, R ^I, R ^{Ⅱ, Ⅲ} R, X ^I, X ^Ⅱ, n1 and n2 are, respectively, equal to the meaning as defined in the formula (A ').)

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

(In the formulas (A-1) to (A-4), R ^I is the same as defined in formula (A)

The compound represented by the above formula (A) can be synthesized by appropriately combining the organic compounds. For example, the compound represented by the above formula (A-1) can be synthesized, for example, according to the following reaction scheme. That is, the compound (A-b) is reacted with ethyl 4-hydroxybenzoate by reacting the compound (A-a) having a desired group R ^I with p-chlorobenzenesulfonic acid chloride to give a compound (A- (A-d) and 3,5-bis (diallylamino) phenol (compound (A-d)) are obtained by hydrolyzing, for example, (B)) to give a compound (A-1e), followed by de-allylation in the presence of N, N-dimethylbarbituric acid and tetrakis (triphenylphosphine) palladium have. The compound (B) used here can be easily obtained by reacting 1,3,5-trihydroxybenzene with 2 equivalents of diallylamine.

(In the above reaction schemes, R ^I is as defined in formula (A) above.)

The compound represented by the above formula (A-3) can be synthesized, for example, according to the following reaction scheme. That is, the intermediate (A-d) obtained in the same manner as above is reacted with 1-hydroxy-2,4-dinitrobenzene to give the compound (A-3e), and a suitable reducing system such as palladium- Can be synthesized by converting the nitro group into amino.

(In the above reaction schemes, R ^I is as defined in formula (A) above.)

As the diamine used for synthesizing the preferable polyamic acid in the present invention, only the compound represented by the formula (A) may be used alone, or the compound represented by the formula (A) and the other diamine may be used in combination It is possible.

Examples of other diamines which can be used herein include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'- Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'- 3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3 , 4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Phenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9- Aminophenyl) fluorene, bis (4-amino-2-chlorophenyl) methane, 2,2 ', 5,5'-tetrachloro- Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4 , 4 '- (p-phenylenediisopropylidene) bisaniline, 4,4' - (m-phenylenediisopropylidene) bisaniline, 2,2'-bis [4- (Trifluoromethyl) biphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) phenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'- (Trifluoro (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, The aromatic diamine such as the compound represented by each of the following formulas (D-1) to (D-5)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5);

But are not limited to, 1,1-dimethoxymethylenediamine, 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Hexahydro-4,7-methanedanediyldimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethylenediamine, 4,4'-methylenebis (Cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and alicyclic diamines;

Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- Vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 3,8-diamino-6-phenylphenanthryine, 1,4-diaminopiperazine, 3,6- diaminoacridine, N, N'-bis (4-aminophenyl) phenylamine, 3,6- Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N, N'-bis (D-I) and (D-II) represented by the following formulas (D-1) and , A diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group

(In the formula (D-I), R ⁵ is a monovalent organic group having a ring structure including a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine, X ¹ is A bivalent organic group;

In the formula (D-Ⅱ), R ⁶ is a pyridine, pyrimidine, triazine, piperidine and a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of piperazine, X ² is, Each is a divalent organic group, and plural X &lt; ² &gt; s present may be the same or different from each other);

A mono-substituted phenylenediamine such as a compound represented by the following formula (D-III)

(In the formula (D-III), R ⁷ is -O-, -COO-, -OCO-, -NHCO-, -CONH- or -CO-, and R ⁸ is a steroid skeleton, a trifluoromethylphenyl group, A monovalent organic group having a skeleton or a group selected from the group consisting of a fluoromethoxyphenyl group and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms);

And diamino organosiloxanes such as a compound represented by the following formula (D-IV).

(In the formula (D-IV), R ⁹ is a hydrocarbon group of 1 to 12 carbon atoms, and plural R ^{9 s} present may be the same or different, p is an integer of 1 to 3, q Is an integer of 1 to 20).

The aromatic diamine, the two primary amino groups in the molecule, the diamine having nitrogen atoms other than the primary amino group, and the benzene ring having mono-substituted phenylenediamine may be substituted with one or more alkyl groups having 1 to 4 carbon atoms Methyl group). The steroid skeleton in the formula (D-III) means a skeleton formed of a cyclopentano-perhydrophenanthrene nucleus, or a skeleton formed of a cyclopentano- The skeleton.

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

Examples of other diamines used for synthesizing the preferred polyamic acid in the present invention include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2'-dimethyl-4,4'- Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) benzene, Biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexyl (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diamino Pyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N- N, N'-bis (4-aminophenyl) -N, N'-bis -Dimethylbenzidine, 3,5-diaminobenzoic acid, the compound represented by the following formula (D-6) and the compound represented by the formula (D-II) in the compound represented by the formula (D- (D-7), a compound represented by the above formula (D-III), dodecaneoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecaneoxy- 2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5- Diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, the following formulas (D-8) to -15), and at least one compound selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the above formula (D-IV) Other specific diamine &quot;) is preferably used.

The diamine used in the synthesis of the polyamic acid in the present invention preferably contains the compound represented by the above formula (A) in an amount of 0.1 mol% or more, preferably 0.5 to 50 mol% , More preferably from 1 to 40 mol%.

The diamine used for the synthesis of the preferred polyamic acid in the present invention preferably contains other specific diamine as described above in addition to the compound represented by the formula (A). In this case, the use ratio of other specific diamine is preferably 30 mol% or more, more preferably 30 to 99.9 mol%, still more preferably 50 to 99.5 mol% 99% by mole.

The diamine used in the synthesis of the preferable polyamic acid in the present invention is preferably composed of only the compound represented by the above formula (A) and other specific diamines.

[Synthesis of polyamic acid]

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

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is from 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine, 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 0.1 to 24 hours, For 0.5 to 12 hours.

Examples of the organic solvent that can be used in the synthesis of polyamic acid include non-protic polar solvents, phenol and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons.

Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, , Hexamethylphosphoric triamide and the like;

Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;

Examples of the alcohol include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like;

Examples of the ketone include acetone, methyl ethyl ketone, methyl, isobutyl ketone, cyclohexanone and the like;

Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate and diethyl malonate;

Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol- Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetraethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, Hydrofuran and the like;

Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;

Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutylate, and diisopentyl ether.

Among these organic solvents, at least one selected from the group consisting of an aprotic polar solvent and a group consisting of phenol and its derivatives (first group of organic solvents), or at least one selected from organic solvents of the first group and an alcohol It is preferable to use a mixture of at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group of organic solvents, hereinafter also referred to as poor solvents). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, more preferably not more than 30% by weight.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be directly supplied to the preparation of a liquid crystal aligning agent, may be provided for preparing a liquid crystal aligning agent after the polyamic acid contained in the reaction solution is isolated, or the polyamic acid isolated may be purified May be provided for the preparation of a liquid crystal aligning agent.

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

The polyamic acid may be isolated by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate and drying the precipitate under reduced pressure or by a method of distilling off the solvent in the reaction solution under reduced pressure . Alternatively, the polyamic acid may be dissolved again in an organic solvent and then precipitated with a poor solvent, or a solution obtained by dissolving a polyamic acid in an organic solvent may be washed, and then the solvent in the solution may be distilled off under reduced pressure The polyamic acid can be purified by a single or a plurality of steps.

<Polyimide>

The preferred polyimide in the present invention can be obtained by imidizing the polyamic acid by dehydration ring closure.

Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyimide include the same compounds as the tetracarboxylic dianhydrides used in the synthesis of the polyamic acid described above. The kind of the preferable tetracarboxylic acid dianhydride and the preferable use ratio thereof are also the same as those of the polyamic acid.

Examples of the diamine used for synthesizing the preferable polyimide in the present invention include the same diamine as the diamine used for the synthesis of the polyamic acid. That is, the diamine used in the synthesis of the polyimide contained in the liquid crystal aligning agent of the present invention contains the compound represented by the above formula (A) and only the compound represented by the above formula (A) may be used, The compound represented by the formula (A) and the above other diamine may be used in combination. The kind of other diamine and the preferred ratio of use of each diamine are also the same as in the case of polyamic acid.

The polyimide used in the present invention may be a completely imidized product obtained by dehydrating and ring closure of all of the arboric acid structures contained in the polyamic acid as a raw material and dehydrating and ring closure only a part of the arboric acid structure, It may be an imide cargo. The imide ratio of the polyimide in the present invention is preferably 30% or more, more preferably 40% or more, and particularly preferably 45% or more. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. At this time, a part of the imide ring may be an isoimide ring.

The dehydration ring-closure of the polyamic acid is preferably 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- . &Lt; / RTI &gt;

The reaction temperature in the method of heating the polyamic acid of (i) is preferably 50 to 200 캜, more preferably 60 to 170 캜. When the reaction temperature is less than 50 캜, the dehydration ring-closure reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

On the other hand, in the method of adding the dehydrating agent and dehydrating ring-closing catalyst to the polyamic acid solution of (ii), for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid, although it depends on the desired imidization rate. Examples of the dehydration ring-closing catalyst include, but are not limited to, tertiary amines such as pyridine, collidine, lutidine, and triethylamine. 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. The imidization rate can be increased as the amount of the dehydrating agent and the dehydrating ring closure agent used is larger. 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-closing reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

The polyimide obtained in the above method (i) may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided in the preparation of the liquid crystal aligning agent after the obtained polyimide is purified. On the other hand, in the method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be directly supplied 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. Alternatively, after the polyimide is isolated, May be provided in the preparation, or may be provided in the preparation of the liquid crystal aligning agent after the isolated polyimide is purified. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. Isolation and purification of polyimide can be carried out by carrying out the same operation as described above as a method for isolating and purifying polyamic acid.

- Polymers of terminal modified type -

In the present invention, each of the polyamic acid and the polyimide may be a polymer of a terminal modified type having a controlled molecular weight. By using the polymer of the terminal modified type, the coating property and the like of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention. Such a terminal modification type polymer can be carried out by adding a molecular weight regulator to the polymerization reaction system when synthesizing a polyamic acid. Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds.

Examples of the acid anhydrides include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, and n-hexadecylsuccinic anhydride;

Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, hexadecylamine, n-heptadecylamine, n-octadecylamine, n-octadecylamine, n-octadecylamine, Eicosylamine and the like;

Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

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

- solution viscosity -

The polyamic acid and the polyimide obtained as described above preferably have a solution viscosity of 20 to 800 mPa · s and a solution viscosity of 30 to 500 mPa · s, .

The solution viscosity (mPa 占 퐏) of the polymer is preferably 10% by weight or less, more preferably 10% by weight or less, in terms of a solution prepared using a good solvent (for example,? -Butyrolactone, N-methyl- Measured at 25 캜 using an E-type rotational viscometer with respect to the polymer solution.

<Other components>

The liquid crystal aligning agent of the present invention contains such a specific polymer as an essential component, but may contain other components as necessary. Such other components include, for example, other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as &quot; epoxy compound &quot;), and functional silane compounds.

[Other Polymers]

The other polymer may be used for improving solution properties and electrical properties. Such another polymer is a polymer other than a specific polymer, and examples thereof include a polyamic acid (hereinafter referred to as &quot; other polyamic acid &quot;) obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing no compound represented by the formula (A) Polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenyl (meth) acrylate), polyimide obtained by subjecting the polyamic acid to dehydration cyclization Maleimide) derivatives, and poly (meth) acrylates. Of these, other polyamic acids or other polyimides are preferable, and other polyamic acids are more preferable.

The proportion of other polymers to be used is preferably 50% by weight or less, more preferably 40% by weight or less, and more preferably 30% by weight or less based on the total amount of the polymers (the total amount of the specific polymer and the other polymers described above, By weight or less.

[Epoxy Compound]

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-dimethylanilinomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m-xylenediamine, -Tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N, Cydyl-cyclohexylamine and the like are preferably used.

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.

[Functional silane compound]

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-trimethoxysilyl-3,6-diazanonyl acetic acid Triethoxysilyl-3,6-diazanonanoic acid, 9-trimethoxysilyl-3,6-diazanonanoic acid, 9-triethoxysilyl-3,6- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltri But are not limited to, ethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

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

[Liquid crystal aligning agent]

The liquid crystal aligning agent of the present invention is preferably such that at least one kind of polymer selected from the group consisting of the polyamic acid and the polyimide and other additives optionally blended optionally are dissolved and contained in the organic solvent do.

Examples of the organic solvent usable in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N Methylene-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, N-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, di Ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutylate, 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 of the liquid crystal aligning agent other than the solvent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention forms a coating film that becomes a liquid crystal alignment film by coating on the surface of the substrate as described later, preferably by heating, but when the solid concentration is less than 1% by weight, (Excessively small), a good liquid crystal alignment film can not be obtained. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large and a good liquid crystal alignment film can not be obtained and the viscosity of the liquid crystal aligning agent is increased So that the coating property becomes poor.

A particularly preferable range of the solid concentration varies 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 solid concentration in the range of 3 to 9% by weight and the solution viscosity in the range of 12 to 50 mPa · s accordingly. In the case of the inkjet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and 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 50 캜, more preferably 20 to 30 캜.

<Liquid crystal display element>

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

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

(1) First, a liquid crystal aligning agent of the present invention is applied onto a substrate, and then a coated film is formed on the substrate by heating the coated surface.

(1-1) In the case of producing a TN type, STN type or VA type liquid crystal display device, two pairs of substrates on which patterned transparent conductive films are formed are paired, and on each of the transparent conductive film forming surfaces thereof, The liquid crystal aligning agent is preferably applied by an offset printing method, a spin coating method or an inkjet printing method, respectively, and then each coated surface is heated to form a coated film. 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, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an ITO film made of a NESA film (a registered trademark of PPG Corporation, USA), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) To obtain a patterned transparent conductive film, a method of forming a desired pattern on a substrate by, for example, forming a patterned transparent conductive film and then photoetching, a method of forming a desired pattern on a transparent conductive film, Or the like can be used. When the liquid crystal aligning agent is applied, a functional silane compound, a functional titanium compound or the like may be added to the surface of the substrate surface on which the coating film should be formed, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film The pretreatment to apply may be carried out.

After the application of the liquid crystal aligning agent, preheating (prebaking) is preferably carried out for the purpose of preventing the flow of the applied aligning agent or the like. The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the polyamic acid. The firing (post-baking) temperature is preferably 80 to 300 占 폚, more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the film thickness of the film to be formed is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

(1-2) On the other hand, in the case of manufacturing an IPS type liquid crystal display device, on one surface of a conductive film-formed surface of a substrate on which a transparent conductive film patterned in a comb shape is formed and on an opposite substrate on which a conductive film is not formed, Is preferably applied by an offset printing method, a spin coating method, or an inkjet printing method, respectively, and then each coating surface is heated to form a coating film.

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

The preferable film thickness of the formed coating film is the same as that of the above (1-1).

(2) When the liquid crystal display element manufactured by the method of the present invention is a liquid crystal display element of VA type, the coating film formed as described above can be used as it is as a liquid crystal alignment film as it is. It may be provided for use after it is done.

On the other hand, in the case of manufacturing a liquid crystal display device other than VA type, a coating film formed as described above is subjected to rubbing treatment to form a liquid crystal alignment film.

The rubbing treatment can be performed by rubbing the coating film surface formed as described above in a predetermined direction with a roll formed of a fiber such as nylon, rayon, or cotton, for example. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

Further, the liquid crystal alignment film formed as described above can be applied to liquid crystal alignment films as shown in, for example, Patent Document 13 (Japanese Unexamined Patent Application Publication No. Hei 6-222366) and Japanese Patent Application Laid-Open No. 6-281937 A process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the alignment film with ultraviolet rays and a process of changing the pretilt angle of a part of the surface of the liquid crystal alignment film as shown in Patent Document 15 (Japanese Patent Application Laid-open No. 5-107544) After performing a rubbing treatment in a direction different from that of the rubbing treatment after the resist film is formed, and then removing the resist film, so that the liquid crystal alignment film has a liquid crystal aligning ability different for each region, It is possible to improve.

(3) A liquid crystal cell is prepared by preparing two substrates on which the liquid crystal alignment film is formed as described above, and arranging the liquid crystal between two substrates opposed to each other. Here, when the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other such that the rubbing directions of the coating films are at a predetermined angle, for example, orthogonal or anti-parallel to each other.

For example, the following two methods can be used for manufacturing the liquid crystal cell.

The first method is a conventionally known method. First, two substrates are opposed to each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and peripheral portions of the two substrates are bonded together using a sealant, The liquid crystal is injected and filled in the gap, and then the injection hole is sealed, whereby the liquid crystal cell can be manufactured.

The second method is a so-called ODF (One Drop Fill) method. For example, an ultraviolet light-curable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is further dropped on the liquid crystal alignment film side, and then the liquid crystal alignment film is opposed to the other side A liquid crystal cell can be manufactured by laminating a substrate and then curing the sealing agent by irradiating ultraviolet light to the entire surface of the substrate.

Regardless of the method, the liquid crystal cell manufactured as described above is then heated to a temperature at which the liquid crystal used has an isotropic phase, and then slowly cooled to room temperature to obtain a liquid crystal cell having a flow orientation Is preferably removed.

The liquid crystal display element of the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.

Here, as the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer may be used.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal and the like can be used, and among them, a nematic liquid crystal is preferable. In the VA type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable, and examples thereof include a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a hept base liquid crystal, an agar liquid crystal, a biphenyl liquid crystal, Based liquid crystal or the like is used. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable, and examples thereof include biphenyl type liquid crystal, phenyl cyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, A cyclohexane-based liquid crystal, a pyrimidine-based liquid crystal, a dioxane-based liquid crystal, a bicyclooctane-based liquid crystal, a quadruple liquid crystal, or the like. Examples of the liquid crystal include cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, and the like.

As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched by a cellulose acetate protective film or a polarizing plate comprising H film itself have.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

The ¹ H-NMR, the solution viscosity of the polymer and the imidization rate of the polyimide of the synthesized compound in the following Synthesis Examples were respectively measured by the following methods.

[ ¹ H-NMR]

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

Measuring apparatus: ECX 400P (manufactured by Nihon Denshi Kogyo Co., Ltd.)

Magnetic field intensity: 400MHz

Solvent: Dimethylsulfoxide-d ₆

Standard substance: tetramethylsilane

Measuring temperature: 25 ° C

[Solution viscosity of polymer]

The solution viscosity (mPa s) of the polymer was measured at 25 캜 using an E-type rotational viscometer for a polymer solution adjusted to a polymer concentration of 10% by weight using the solvent described in each Synthesis Example.

[Imidization Rate of Polyimide]

A small amount of the polyimide-containing solution obtained in each synthesis example was taken in pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and tetramethylsilane was dissolved in a standard substance (1) from the ¹ H-NMR spectrum measured at room temperature.

Imidization ratio (%) = (1-A ¹ / A ² × α) × 100 (1)

(1), A ¹ is the peak area derived from the proton of the NH group in the vicinity of the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and? Is the peak area derived from the proton of the polyimide precursor (polyamic acid) And the ratio of the number of other protons to one proton of the NH group.)

&Lt; Synthesis Example of Compound Represented by the Formula (A)

The synthesis of the following compounds (including intermediates) was repeated as necessary according to the scales described below to ensure the required amount in the synthesis of the following compounds and polymers.

Synthesis Example A-1

Compound (A-1-1) was synthesized according to Scheme 1 below.

266.5 g of the compound (A-1-1a), 253.3 g of p-chlorobenzenesulfonyl chloride and 1,000 mL of dichloromethane were placed in a 5,000 mL three-necked flask under a nitrogen atmosphere, and the mixture was stirred at 0 캜. A solution prepared by dissolving 180 mL of triethylamine in 200 mL of dichloromethane was added dropwise over 30 minutes, and the reaction was carried out at room temperature (25 DEG C) for 3 hours with stirring. Then, 1,000 mL of dichloromethane was added to the reaction mixture obtained, and the obtained organic layer was washed with distilled water. The organic layer after washing was dried with magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. To this colorless viscous liquid was added 3,000 mL of ethanol and sufficiently stirred, and the precipitated white solid was recovered by filtration to obtain 335.6 g of the compound (A-1-1b).

Next, 220.5 g of the above compound (A-1-1b), 166.2 g of ethyl 4-hydroxybenzoate, 172.8 g of potassium carbonate and 2,000 mL of N, N-dimethylformamide were placed in a 5,000 mL three- And the reaction was carried out with stirring for 8 hours. After completion of the reaction, 4,000 mL of toluene was added to the obtained reaction mixture, and the organic layer was washed with distilled water. The organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. To the obtained colorless viscous liquid, 3,000 mL of ethanol was added and sufficiently stirred, and the precipitated white solid was filtered off to obtain 184.1 g of the compound (A-1-1c).

165.8 g of the above compound (A-1-1c), 40.0 g of sodium hydroxide, 1,500 mL of tetrahydrofuran, 500 mL of distilled water and 500 mL of ethanol were placed in a 5,000 mL three-necked flask, and the reaction was carried out at 90 ° C for 6 hours with stirring. After completion of the reaction, 1500 ml of 1N hydrochloric acid was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. Then, 2,500 mL of toluene was added to the reaction mixture, and the organic layer was washed with distilled water.

Subsequently, the solvent was removed from the organic layer using a rotary evaporator to obtain 154.2 g of a compound (A-1-1d) as a glossy white powder.

In a 3,000 mL three-necked flask, 116.0 g of the above compound (A-1-1d), 62.0 g of p-toluenesulfonyl chloride, 23 mL of N, N-dimethylformamide and 600 mL of pyridine were placed, Stirring time. A solution prepared by dissolving 92.4 g of 3,5-bis (diallylamino) phenol (compound (B)) in 150 mL of pyridine was added dropwise over 15 minutes, and the reaction was carried out at 100 ° C for 6 hours with stirring. After completion of the reaction, 2,000 mL of distilled water was added to the reaction mixture, and the mixture was extracted with chloroform (2,500 mL) to obtain an organic layer. The obtained organic layer was washed with distilled water, further dried with magnesium sulfate, and then the solvent was removed by a rotary evaporator to obtain a crude product. The resulting crude product was applied to a column chromatograph (filler: silica gel, developing solvent: hexane / ethyl acetate = 20/1 (weight ratio)) and the solvent was removed under reduced pressure from the resulting oil (distillate) 103.8 g of the compound (A-1-1e) was obtained.

In a 5,000 ml three-necked flask, 97.9 g of the above compound (A-1-1e), 70.3 g of N, N-dimethylbarbituric acid, 3.5 g of tetrakis (triphenylphosphino) palladium (0) 2,000 mL of methane was added, and the reaction was carried out at 35 캜 for 8 hours with stirring. After completion of the reaction, the reaction mixture was concentrated to remove about 1 L of dichloromethane, and the precipitated powder was recovered by filtration. The obtained glossy yellowish powder was dissolved in 5,000 mL of tetrahydrofuran, 60 g of activated carbon was added to the obtained solution, and the mixture was stirred at room temperature for 15 minutes. The activated carbon was removed from the resulting mixture by Celite filtration, and then the solvent was removed under reduced pressure to obtain 55.2 g of Compound (A-1-1) as a white powder.

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

Synthesis Example A-2

Compound (A-2-1) was synthesized according to Scheme 2 below.

(B)), 220.2 g of ethylene carbonate, 16.1 g of tetrabutylammonium bromide, and 10 g of N, N-dimethylformamide 1,000 mL, and the reaction was carried out at 150 ° C for 6 hours with stirring. To the reaction mixture obtained, 2,000 mL of ethyl acetate and 500 mL of methanol were added, and the obtained organic layer was washed successively with 1 N aqueous solution of sodium hydroxide and distilled water, dried with magnesium sulfate, and then the solvent was removed using a rotary evaporator A crude product was obtained. The obtained crude product was applied to a column chromatograph (filler: silica gel, developing solvent: hexane / ethyl acetate = 4/1 (weight ratio)) and the solvent was removed from the resulting oil by decompression to obtain a pale- A-2-1a).

Then, 154.6 g of the compound (A-1-1d) synthesized in the same manner as in Synthesis Example A-1, 76.3 g of p-toluenesulfonyl chloride, 76.3 g of N, N -Dimethylformamide and 800 mL of pyridine were placed, and the mixture was stirred at 100 占 폚 for 1 hour. Then, a solution prepared by dissolving 131.4 g of the compound (A-2-1a) obtained above in 200 mL of pyridine was added dropwise over 15 minutes, and the resulting mixture was reacted at 100 deg. C for 12 hours with stirring. After completion of the reaction, 2,000 mL of distilled water was added to the reaction mixture, and the mixture was extracted with chloroform (2,500 mL) to obtain an organic layer. The obtained organic layer was washed with distilled water, dried with magnesium sulfate, and then the solvent was removed by a rotary evaporator to obtain a crude product. The obtained crude product was applied to a column chromatograph (filler: silica gel, developing solvent: hexane / ethyl acetate = 10/1 (weight ratio)) and the solvent was removed from the resulting oil by reduced pressure to obtain a pale yellow viscous liquid compound -2-1b).

174.3 g of the above compound (A-2-1b), 117.1 g of 1,3-dimethylbarbituric acid, 5.8 g of tetrakis (triphenylphosphino) palladium (0) and 2,000 mL of dichloromethane was added, and the reaction was carried out at 35 캜 for 8 hours with stirring. After completion of the reaction, 2,000 mL of chloroform was added to the reaction mixture, and the resulting organic layer was washed with 1N sodium carbonate aqueous solution to remove unreacted 1,3-dimethylbarbituric acid, and further washed with distilled water. The solvent was removed from the organic layer by reduced pressure, and the resulting powder was thoroughly washed with ethanol. 100 g of activated carbon was added to a solution obtained by dissolving the washed powder (pale yellow) in 2,000 ml of tetrahydrofuran, and the mixture was stirred at room temperature for 15 minutes. The activated carbon was removed from the resulting mixture by Celite filtration, and then the solvent was removed under reduced pressure to obtain 88.6 g of Compound (A-2-1) as a white powder.

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

Synthesis Example A-3

APPLICATION According to Scheme 3, compound (A-2-2) was synthesized.

238.2 g of the compound (A-2-2a), 253.3 g of p-chlorobenzenesulfonyl chloride and 1,000 mL of dichloromethane were placed in a 5,000 mL three-neck flask under a nitrogen atmosphere, and the mixture was stirred at 0 占 폚. A solution prepared by dissolving 180 mL of triethylamine in 200 mL of dichloromethane was added dropwise over 30 minutes, and then the reaction was carried out at room temperature for 3 hours with stirring. After completion of the reaction, 1,000 ml of dichloromethane was added to the reaction mixture obtained, and the obtained organic layer was washed with distilled water, further dried with magnesium sulfate, and then the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. To the resulting colorless viscous liquid was added 3,000 mL of ethanol and sufficiently stirred, and the precipitated white solid was recovered by filtration to obtain 318.2 g of the compound (A-2-2b).

Subsequently, 206.1 g of the compound (A-2-2b), 166.2 g of ethyl 4-hydroxybenzoate, 172.8 g of potassium carbonate and 2,000 mL of N, N-dimethylformamide were placed in a 5,000 mL three-necked flask, The reaction was carried out with stirring for 8 hours. After completion of the reaction, 4,000 mL of toluene was added to the obtained reaction mixture, and the resulting organic layer was washed with distilled water, further dried with magnesium sulfate, and then the solvent was removed by a rotary evaporator to obtain a colorless viscous liquid. To the resulting colorless viscous liquid was added 3,000 mL of ethanol and sufficiently stirred, and the precipitated white solid was recovered by filtration to obtain 174.6 g of a compound (A-2-2c).

154.5 g of the above compound (A-2-2c), 40.0 g of sodium hydroxide, 1,500 mL of tetrahydrofuran, 500 mL of distilled water and 500 mL of ethanol were placed in a 5,000 mL three-necked flask, and the reaction was carried out at 90 deg. C for 6 hours with stirring. After completion of the reaction, 1,500 mL of 1N hydrochloric acid was added to the obtained reaction mixture, and the mixture was stirred at room temperature for 1 hour. Then, 2,500 mL of toluene was added to the resulting mixture, and the resulting organic layer was washed with distilled water. The solvent was removed by a rotary evaporator to obtain 142.9 g of a glossy white powder (Compound A-2-2d).

Toluene sulfonyl chloride, 23 mL of N, N-dimethylformamide and 600 mL of pyridine were placed in a 3,000 mL three-necked flask under nitrogen atmosphere, and a solution of 1 Stirring time. Then, a solution prepared by dissolving 106.7 g of the compound (A-2-1a) synthesized in the same manner as in Synthesis Example A-2, in 150 mL of pyridine was added dropwise over 15 minutes, The reaction was carried out with stirring. After completion of the reaction, 2,000 mL of distilled water was added to the obtained reaction mixture, and the mixture was further extracted with chloroform (2,500 mL) to obtain an organic layer. The obtained organic layer was washed with distilled water, dried with magnesium sulfate, and then the solvent was removed by a rotary evaporator to obtain a crude product. The obtained crude product was applied to a column chromatograph (filler: silica gel, developing solvent: hexane / ethyl acetate = 20/1 (weight ratio)) to remove the solvent from the resulting oil under reduced pressure to obtain a pale yellow viscous liquid compound (A- 2-2e).

In a 5,000 mL three-necked flask under nitrogen atmosphere, 100.3 g of the compound (A-2-2e), 70.3 g of 1,3-dimethylbarbituric acid, 3.5 g of tetrakis (triphenylphosphino) palladium 2,000 mL of dichloromethane was added, and the reaction was carried out at 35 캜 for 8 hours with stirring. After completion of the reaction, the reaction mixture was concentrated to remove about 1,000 mL of dichloromethane, and the precipitated powder was recovered by filtration. The obtained pale yellow powder was dissolved in 5,000 mL of tetrahydrofuran, 60 g of activated carbon was added to the obtained solution, and the mixture was stirred at room temperature for 15 minutes. The activated carbon was removed from the resulting mixture by Celite filtration, and then the solvent was removed under reduced pressure to obtain 63.0 g of Compound (A-2-2) as a white powder.

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

<Synthesis Example of Polyimide>

Synthesis Example PI-1

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 43 g (0.40 mole) of p-phenylenediamine as a diamine and 43 g (0.40 mole) of the compound obtained in Synthesis Example A- -1-1) (490 g) was dissolved in 798 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. A small amount of the resulting polyamic acid solution was collected and N-methyl-2-pyrrolidone was added thereto to give a solution viscosity of 62 mPa 으로서 as a solution having a polyamic acid concentration of 10 wt%.

Then, 2,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone (pyridine and anhydrous acetic acid used in the dehydration ring-closure reaction in this operation were removed out of the system) To obtain a solution containing about 15% by weight of 50% polyimide (B-1). A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 49 mPa · s.

Synthesis Example PI-2

66 g (0.30 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 1 g of 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- (0.20 mole) of p-phenylenediamine as diamine, 38 g (0.35 mole) of p-phenylenediamine as diamine and 60 g 81 g (0.15 mol) of the compound (A-2-1) obtained in Reference Example 2 were dissolved in 980 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was taken out and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 58 mPa · s.

Then, 2,280 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added and subjected to dehydration cyclization at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-2) having an imidization rate of about 50%. A small amount of the obtained polyimide solution was fractionated and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 48 mPa · s.

Synthesis Example PI-3

88 g (0.40 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 20 g (0.10 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 0.1 g of p- 26 g (0.05 mol) of the compound (A-2-2) obtained in Synthesis Example A-3 and 48 g (0.45 mol) of phenylenediamine were dissolved in 728 g of N-methyl-2-pyrrolidone, The reaction was carried out to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was taken and N-methyl-2-pyrrolidone was added thereto to measure the solution viscosity as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 65 mPa · s.

Next, 1,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added, followed by dehydration ring closure at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-3) having an imidization rate of about 50%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 50 mPa · s.

Synthesis Example PI-4

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride and 43 g (0.40 mol) of p-phenylenediamine as diamine and the compound (A- 1-1) (490 g, 0.10 mol) was dissolved in 798 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was taken and N-methyl-2-pyrrolidone was added thereto to measure the solution viscosity as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 45 mPa · s.

Next, 2,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80 g of pyridine and 102 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-4) having an imidization rate of about 80%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10% by weight, and the solution viscosity was 49 mPa · s.

Synthesis Example PI-5

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 32 g (0.30 mole) of p-phenylenediamine as a diamine, 10 g of 4,4'-diaminodiphenylmethane (0.15 mol) of the compound (A-2-1) obtained in Synthesis Example A-2 was dissolved in 932 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain polyamic acid Was obtained. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 47 mPa · s.

Then 2,160 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80 g of pyridine and 102 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-5) having an imidization rate of about 80%. A small amount of the obtained polyimide solution was fractionated and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 48 mPa · s.

Synthesis Example PI-6

(0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 38 g (0.35 mol) of p-phenylenediamine as diamine, and 20 g (0.35 mol) of 4,4'-diaminodiphenylmethane (0.05 mol) of the compound (A-2-2) obtained in Synthesis Example A-3 were dissolved in 780 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain polyamic acid Was obtained. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 43 mPa · s.

Then, 1,800 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, and 80 g of pyridine and 102 g of acetic anhydride were added, followed by dehydration cyclization at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (B-6) having an imidization rate of about 80%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 50 mPa · s.

&Lt; Comparative Synthesis Example of Polyimide >

Comparative Synthesis Example pi-1

(0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 43 g (0.40 mol) of p-phenylenediamine as diamine and 3- (3,5-diaminobenzoyloxy) 52 g (0.10 mol) of cholestane was dissolved in 830 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was taken out and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity was 60 mPa · s.

Next, 1,900 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-1) having an imidization rate of about 50%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 47 mPa · s.

Comparative Synthesis Example pi-2

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 43 g (0.40 mole) of p-phenylenediamine as diamine and 3 g of 3 (3,5-diaminobenzoyloxy) 52 g (0.10 mol) of stannane was dissolved in 830 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 4 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 44 mPa · s.

Next, 1,900 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80 g of pyridine and 102 g of acetic anhydride were added, and dehydration cyclization was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-2) having an imidization rate of about 80%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 47 mPa · s.

Comparative Synthesis Example pi-3

66 g (0.30 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 1 g of 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- 60 g (0.20 mol) of p-phenylenediamine as diamine and 38 g (0.35 mol) of 3-aminopyrimidine as diamine (Diaminobenzoyloxy) cholestane were dissolved in 970 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was taken out and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity was 60 mPa · s.

Then, 2,240 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-3) having an imidization rate of about 50%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 47 mPa · s.

Comparative Synthesis Example pi-4

(0.50 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 32 g (0.30 mole) of p-phenylenediamine as a diamine, 10 g of 4,4'-diaminodiphenylmethane (0.15 mol) of 3 (3,5-diaminobenzoyloxy) cholestane were dissolved in 920 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 4 hours to obtain a polyamic acid- Solution. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 44 mPa · s.

Then, 2,140 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, 80 g of pyridine and 102 g of acetic anhydride were added and the dehydration ring closure was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (b-4) having an imidization rate of about 80%. A small amount of the obtained polyimide solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyimide concentration of 10 wt%, and the solution viscosity was 47 mPa · s.

&Lt; Preparation and evaluation of liquid crystal aligning agent >

Example 1

(I) Preparation of liquid crystal aligning agent

N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to a solution containing the polyimide (B-1) obtained in Synthesis Example PI-1 and N And N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl methane in an amount of 10 parts by weight based on 100 parts by weight of polyimide and sufficiently stirred to obtain a solvent composition of NMP: BC = 50:50 (Weight ratio), and a solid content concentration of 7.0% by weight. This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent.

(II) Evaluation of liquid crystal aligning agent

The liquid crystal aligning agent prepared above was evaluated by the following method. The evaluation results are shown in Table 1.

(1) Evaluation of application property (influence of time left after application)

The liquid crystal aligning agent prepared above was applied to each transparent electrode surface of five glass substrates with transparent electrodes made of ITO film by using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengaten Co., Ltd.) The time until the start of the reaction was allowed to stand for 30 seconds, 60 seconds, 80 seconds, 100 seconds, and 120 seconds, and left to stand for one minute on a hot plate at 80 DEG C to remove the solvent. (Post-baking) for 10 minutes on a hot plate at 230 deg. C to form coating films each having an average film thickness of 600 ANGSTROM and a different retention time. This coating film was examined for unevenness in printing and existence of pinholes by a microscope having a magnification of 20 times, and the longest leaving time without printing unevenness and pinholes was examined. If this value is 60 seconds or more, it can be said that the coating property is good.

(2) Evaluation of Film Thickness Uniformity of Coating Film

With respect to the coating film formed at the longest leaving time in which neither printing unevenness nor pinholes were observed, the film thickness at the center of the substrate and the film thickness at the center of the substrate were measured with a contact type film thickness meter (manufactured by KLA Tencor Corporation) The film thickness at a position shifted from the outer edge of the film by 15 mm to the center was measured, and the film thickness difference between both films was examined. If the film thickness difference is 20 angstroms or less, it can be said that the film thickness uniformity is good.

(3) Production of liquid crystal cell

The liquid crystal aligning agent prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode formed of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengattsu Co., Ltd.), left for 1 minute, (Pre-baked) on a hot plate for 1 minute to remove the solvent, and further heated on a hot plate at 230 캜 for 10 minutes (post baking) to form a coating film (liquid crystal alignment film) having an average film thickness of 600 Å. This operation was repeated to obtain a pair of substrates (two pieces) having a liquid crystal alignment film on the ITO film.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the outer edges of each of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces were superimposed on each other so as to be opposed to each other To thereby cure the adhesive. Subsequently, a nematic liquid crystal (Merck, MLC-6608) 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 produce a liquid crystal cell.

(4) Evaluation of voltage holding ratio

The voltage holding ratio (VHR ₀ ) after 167 milliseconds from the application of the liquid crystal display cell manufactured above was measured by applying a voltage of 5 V at 60 캜 for an application time of 60 microseconds and a span of 167 milliseconds, Quot; VHR-1 &quot; manufactured by TOYO TECHNICAL CO., LTD.

(5) Evaluation of heat resistance stability

A rectangular wave of 30 Hz and 3.0 V, in which an alternating current of 6.0 V (peak-peak) was superimposed, was applied to the liquid crystal cell prepared above at 500 ° C. for 500 hours at an environmental temperature of 70 ° C. The voltage holding ratio (VHR ₅₀₀ ) of the cell after 500 hours has elapsed is measured in the same manner as in the above (4), and this value is compared with the initial value (voltage holding ratio measured in (4) above, VHR ₀ ) ? VHR) was investigated by the following formula (2). When the value was less than 10%, the heat-resistant stability was evaluated as &quot; good &quot; and when the value was 10% or more, the heat-resistant stability was evaluated as &quot; poor &quot;.

VHR (%) = VHR _{0 -} VHR ₅₀₀ (2)

Examples 2 to 12 and Comparative Examples 1 to 4

The procedure of Example 1 was repeated except that the solution containing the polymer shown in Table 1 was used instead of the solution containing the polyimide (B-1), and the amount of the epoxy compound used was changed as shown in Table 1 A liquid crystal aligning agent was prepared in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 1.

In addition, in Comparative Examples 2 and 4, since polyimide precipitation was observed when N-methyl-2-pyrrolidone and butyl cellosolve were added to a solution containing polyimide, the liquid crystal aligning agent was evaluated I could not.

Comparative Examples 5 and 6

In Comparative Examples 2 and 4, in the same manner as in Comparative Examples 2 and 4 except that both solvents were added so that the ratio of N-methyl-2-pyrrolidone to butyl cellosolve was 70:30 (weight ratio) To prepare a liquid crystal aligning agent.

The evaluation results are shown in Table 1.

Claims (10)

Wherein the polymer has at least one group selected from the group consisting of polyamic acid and polyimide, wherein the polymer has at least a group represented by the following formula (A ') in its molecule.
R ^I - (X ^I ) _{n 1} -R ^II -O-X ^II -COO- (R ^III O) _{n 2} - ^* (A ')
(Wherein (A ') of, R ^I is a fluoroalkyl group of 1 to 30 carbon atoms or an alkyl group of 1 to 30 carbon atoms, R ^Ⅱ is a single bond, a methylene group or an alkylene group having a carbon number of 2~30, R is carbon atoms ^Ⅲ 2 to 5, and X &lt; RTI ID = 0.0 &gt; ^I And ^XII are each a divalent alicyclic group, a divalent heterocyclic group, an arylene group or a divalent heteroaromatic group, wherein a plurality of groups X ^I may be the same or different from each other, and n1 is an integer of 2 to 5 , N2 is an integer of 0 to 10, and &quot; * &quot; The method according to claim 1,
Wherein the polymer is at least one member selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a compound represented by the following formula (A) and a polyimide obtained by dehydrating and ring- Of a polymer.
&Lt; Formula 1 >

(Wherein (A) of, R ^I, R ^{Ⅱ, Ⅲ} R, X ^I, X ^Ⅱ, n1 and n2 are, respectively, equal to the meaning as defined in the formula (A ').) 3. The method of claim 2,
Wherein X ^I in the formula (A) is a bivalent alicyclic group and X ^II is an arylene group. The method of claim 3,
In the formula (A) ^(I X) _n1 is 4,4'-cyclohexane and xylene group, X ^Ⅱ the first liquid crystal 1,4-phenylene group. 3. The method of claim 2,
Wherein the tetracarboxylic acid dianhydride comprises 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal alignment film formed from 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 according to claim 6. A polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a compound represented by the following formula (A).
&Lt; Formula 1 >

(Wherein (A) of, R ^I is a fluoroalkyl group of 1 to 30 carbon atoms or an alkyl group of 1 to 30 carbon atoms, R ^Ⅱ is a single bond, a methylene group or an alkylene group having a carbon number of 2~30, R is ^C2-Ⅲ To 5, and X &lt; RTI ID = 0.0 &gt; ^I And ^XII are each a divalent alicyclic group, a divalent heterocyclic group, an arylene group or a divalent heteroaromatic group, wherein a plurality of groups X ^I may be the same or different from each other, and n1 is an integer of 2 to 5 And n2 is an integer of 0 to 10.) A polyimide obtained by dehydration ring closure of a polyamic acid obtained by reacting tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A).
&Lt; Formula 1 >

(Wherein (A) of, R ^I is a fluoroalkyl group of 1 to 30 carbon atoms or an alkyl group of 1 to 30 carbon atoms, R ^Ⅱ is a single bond, a methylene group or an alkylene group having a carbon number of 2~30, R is ^C2-Ⅲ To 5, and X &lt; RTI ID = 0.0 &gt; ^I And ^XII are each a divalent alicyclic group, a divalent heterocyclic group, an arylene group or a divalent heteroaromatic group, wherein a plurality of groups X ^I may be the same or different from each other, and n1 is an integer of 2 to 5 And n2 is an integer of 0 to 10.) A compound represented by the following formula (A).
&Lt; Formula 1 >

(Wherein (A) of, R ^I is a fluoroalkyl group of 1 to 30 carbon atoms or an alkyl group of 1 to 30 carbon atoms, R ^Ⅱ is a single bond, a methylene group or an alkylene group having a carbon number of 2~30, R is ^C2-Ⅲ To 5, and X &lt; RTI ID = 0.0 &gt; ^I And ^XII are each a divalent alicyclic group, a divalent heterocyclic group, an arylene group or a divalent heteroaromatic group, wherein a plurality of groups X ^I may be the same or different from each other, and n1 is an integer of 2 to 5 And n2 is an integer of 0 to 10.)

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