KR101588632B1 - Liquid crystal aligning agent and related compounds thereof, and liquid crystal display device - Google Patents

Abstract

(식 (A) 중, R은 액정 배향능을 갖는 기이며, X^I는 단결합, ^#―O―, ^#―COO― 또는 ^#―OCO―(여기에서, 「#」을 붙인 결합수(手)가 R과 결합함)이며, 「×」는 결합수인 것을 나타낸다.)An object of the present invention is to provide a liquid crystal aligning agent excellent in display quality and capable of forming a liquid crystal alignment film which does not cause burn-in even when continuous driving is performed for a long period of time, and is excellent in printing property even when printing is performed with a small liquid amount.
(Solution) The liquid crystal aligning agent is 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 .
≪ Formula 1 >

(In the formula (A), R is a group having liquid crystal aligning ability, and X ^I is a single bond, ^# -O-, ^# -COO- or ^# -OCO- (here, ) Is bonded to R), and " x " indicates that the bond is a bond.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning agent and a related compound thereof,

The present invention relates to a liquid crystal aligning agent and its related compounds, and a liquid crystal display element. More particularly, the present invention relates to a liquid crystal aligning agent capable of imparting a liquid crystal alignment film excellent in burn-in resistance and having excellent printability and a liquid crystal display element obtained therefrom.

At present, as a liquid crystal display element, 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, and positive dielectric anisotropy Called twisted nematic liquid crystal cell in which a nematic liquid crystal layer having a nematic liquid crystal layer is formed as a cell having a sandwich structure and the major axis of the liquid crystal molecule is twisted by 90 ° continuously from one substrate toward the other substrate (Japanese Unexamined Patent Publication (Kokai) No. 2001-325819). In addition, a liquid crystal display device of STN (Super Twisted Nematic) type (Patent Document 2) or an IPS (In-Plane Switching) device which is less dependent on viewing angle can realize a high contrast ratio as compared with a TN type liquid crystal display device, (Patent Document 3), an optical compensating bend (OCB) type liquid crystal display device having a small visual dependency and excellent in high-speed response of an image screen (Patent Document 4), a negative liquid crystal display device having a negative dielectric anisotropy A VA (Vertical Alignment) type liquid crystal display device using a stick type liquid crystal (Patent Document 5) and the like have been developed.

Polyimides, polyamides, and polyesters are conventionally known as materials for liquid crystal alignment films in these liquid crystal display devices, and in particular, polyimide has excellent heat resistance, affinity with liquid crystal, mechanical strength, (Patent Documents 6 to 11).

In recent years, efforts have been made to improve display quality including low definition (high definition) liquid crystal display elements and low power consumption, and the use range of liquid crystal display elements has been expanded. In particular, its use as a liquid crystal television replacing a CRT television has been expanded. Along with this, there is a demand for a liquid crystal display element which is superior in electric characteristics to conventional ones, has a higher display quality, and is capable of continuous driving for a longer time.

However, conventionally known liquid crystal display devices having a liquid crystal alignment film formed of polyamic acid or polyimide have a problem in that static electricity accumulates in the liquid crystal cell when the liquid crystal display device is driven continuously for a long period of time and accordingly the alignment of liquid crystal molecules is disturbed, It is pointed out that the display quality is remarkably lowered as burn-in.

Therefore, development of a liquid crystal aligning element with good total balance, which is excellent in display quality and does not deteriorate the display quality even when it is continuously driven for a long time, and particularly excellent in toughness, is expected.

In order to effectively use the liquid crystal aligning agent, attempts have been made to reduce the liquid amount of the liquid crystal aligning agent used at the time of printing, and a liquid crystal aligning agent exhibiting excellent printability even with a small liquid amount is desired.

Japanese Patent Application Laid-Open No. 6-138457 Japanese Unexamined Patent Publication No. 5-19231 Japanese Patent Application Laid-Open No. 11-24109 Japanese Patent Application Laid-Open No. 8-327822 Japanese Patent Application Laid-Open No. 5-113561 Japanese Patent Application Laid-Open No. 4-153622 Japanese Patent Application Laid-Open No. 60-107020 Japanese Laid-Open Patent Publication No. 56-91277 U.S. Patent No. 5,928,733 Japanese Patent Application Laid-Open No. 11-258605 Japanese Laid-Open Patent Publication No. 62-165628

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to provide a liquid crystal alignment film which is excellent in display quality and which does not cause burn-in even when driven continuously for a long time, A liquid crystal aligning agent having excellent properties and a related compound thereof, and a liquid crystal display element having excellent display quality.

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

According to the present invention, the above objects and advantages of the present invention are as follows. First,

(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, ≪ / RTI >

(In the formula (A), R is a group having liquid crystal aligning ability, and X ^I is a single bond, ^# -O-, ^# -COO- or ^# -OCO- (here, ) Is bonded to R), and " * " is a combined number.)

Secondly,

(2) 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: The above objects and advantages of the present invention are achieved.

≪ Formula 1 >

(In the formula (A), R represents an alkyl group having 4 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, or a hydrocarbon having 12 to 30 carbon atoms having a bicyclohexane skeleton And X ¹ represents a single bond, ^# -O-, ^# -COO- or ^# -OCO- (in which the number of bonds having "#" attached to R) and "*" .)

Thirdly,

(3) In the above (1)

Wherein the polymer is at least one 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-1) and a polyimide obtained by dehydrating and ring- The above objects and advantages of the present invention are achieved by a liquid crystal aligning agent which is one kind of polymer.

(Wherein R and X ^I are the same as defined in the above formula (A), ^XII is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a ^# -O- , ^# -COO- or ^# -OCO- (in which the number of bonds having "#" attached thereto is combined with N) and ^XIII is independently a single bond or a group represented by the formula ( ^XIII- 1) 2-valent group.)

(In the formula ( ^XIII- 1), ^XIV represents a single bond, a methylene group, a C2-10 alkylene group, ^# -O-, ^# -COO- or ^# -OCO- combining a number of the aromatic ring of X ^ⅱ side) engages with the coupling group attached to the number of "*".)

Fourth,

(4) The liquid crystal display element comprising the liquid crystal alignment film formed of the liquid crystal aligning agent described in any one of (1) to (3) above achieves the above objects and advantages of the present invention.

Fifth,

(5) The above objects and advantages of the present invention are achieved by a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a compound represented by the following formula (A-1).

(2)

(Wherein R and X ^I are the same as defined in the above formula (A), ^XII is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a ^# -O- , ^# -COO- or ^# -OCO- (in which the number of bonds having "#" attached thereto is combined with N) and ^XIII is independently a single bond or a group represented by the formula ( ^XIII- 1) 2-valent group.)

(3)

(In the formula ( ^XIII- 1), ^XIV represents a single bond, a methylene group, a C2-10 alkylene group, ^# -O-, ^# -COO- or ^# -OCO- combining a number of the aromatic ring of X ^ⅱ side) engages with the coupling group attached to the number of "*".)

Sixth,

(6) The above objects and advantages of the present invention are achieved by a polyimide obtained by dehydrocondensing a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing a compound represented by the following formula (A-1) .

(2)

(Wherein R and X ^I are the same as defined in the above formula (A), ^XII is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a ^# -O- , ^# -COO- or ^# -OCO- (in which the number of bonds having "#" attached thereto is combined with N) and ^XIII is independently a single bond or a group represented by the formula ( ^XIII- 1) 2-valent group.)

(3)

(In the formula ( ^XIII- 1), ^XIV represents a single bond, a methylene group, a C2-10 alkylene group, ^# -O-, ^# -COO- or ^# -OCO- combining a number of the aromatic ring of X ^ⅱ side) engages with the coupling group attached to the number of "*".)

In the seventh,

(7) The above objects and advantages of the present invention are achieved by the compound represented by the following formula (A-1).

 (2)

(Wherein R and X ^I are the same as defined in the above formula (A), ^XII is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a ^# -O- , ^# -COO- or ^# -OCO- (in which the number of bonds having "#" attached thereto is combined with N) and ^XIII is independently a single bond or a group represented by the formula ( ^XIII- 1) 2-valent group.)

(3)

(In the formula ( ^XIII- 1), ^XIV represents a single bond, a methylene group, a C2-10 alkylene group, ^# -O-, ^# -COO- or ^# -OCO- combining a number of the aromatic ring of X ^ⅱ side) engages with the coupling group attached to the number of "*".)

The liquid crystal aligning agent of the present invention can form a coating film excellent in uniformity of film quality even when printing is performed in a small liquid amount and further can form a liquid crystal alignment film excellent in anti-toughness.

The liquid crystal display element of the present invention having the liquid crystal alignment layer formed of the liquid crystal alignment agent of the present invention can display a high quality and does not cause burning even by driving for a long period of time, . Accordingly, the liquid crystal display of the present invention can be suitably applied to various apparatuses, and can be applied to various devices such as a clock, a portable game, a word processor, a notebook personal computer, a car navigation system, a camcorder, Telephone, various monitors, liquid crystal television, and the like.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

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

Examples of R in the formula (A) include an alkyl group having 4 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a hydrocarbon group having a steroid skeleton having 17 to 51 carbon atoms, a carbon number having a bicyclohexane skeleton And hydrocarbon groups of 12 to 30 carbon atoms. Here, the steroid skeleton refers to a skeleton composed of a cyclopentano-perhydrophenanthrene nucleus or a skeleton in which one or two or more carbon-carbon bonds thereof are doubly bonded. The alkyl group is preferably an alkyl group having from 6 to 18 carbon atoms.

The R in the formula (A) is more preferably an alkyl group having 8 to 13 carbon atoms or a group represented by any one of the following formulas (R-1) to (R-6). The alkyl group is preferably a linear chain. R is particularly preferably an n-octyl group, an n-dodecyl group, or an n-tridecyl group or a group represented by any one of the following formulas (R-1-1) to (R-6-1).

(Wherein R ^I is, independently of each other, a group represented by any one of the following formulas, and " * "

(In the above formula, " + "

(In the above formula, " * "

As X ^I in the above formula (A), it is preferable that ^# -OCO- (here, the number of bonds having "#" attached to R bonds).

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

Reacting a tetracarboxylic acid dianhydride containing a group represented by the above formula (A) and a compound having two carbonic acid anhydride groups with a diamine, or

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

The polyimide having a group represented by the formula (A) in at least a part of the molecule can be obtained, for example, by dehydrating and ring-closing 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 group represented by the formula (A) and a compound having two amino groups, And at least one kind of polymer selected from the group consisting of polyimides obtained by dehydrating and ring closure.

≪ 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-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3- 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5- Tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy norbornan-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tert Furanyl) -naphtho [l, 2-c] -furan-l, 3-dione, 1,3,3a, 4,5,9b-hexahydro- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] 3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ Dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro- ) - 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro- Furan-1, 3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl- Cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy- ^2- carboxynorbornane-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2 , 6} ] undecane-3,5,8,10-tetraone, compounds represented by each of the following formulas (T-I) and (T-II), and alicyclic tetracarboxylic acid dianhydrides such as alicyclic tetracarboxylic acid 2 anhydride

(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 the plural 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) dianhydride, (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, Ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol- Bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane- ) To (T-4). The aromatic tetracarboxylic acid dianhydride may be, for example, These may be used singly or in combination of two or more.

Examples of the tetracarboxylic acid dianhydride used for synthesizing the preferred polyamic acid in the liquid crystal aligning agent of the present invention include the butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid Dioxo-3-furanyl) -naphtho [1,2-c] furan-1, 2, 3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ ] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) 1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, (Tetrahydrofuran-2 ', 5 ' -dione), 5- (2,5-dioxotetrahydro 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-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'-benzophenone tetracarbon Acid dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 2,2'3,3'-biphenyltetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetra 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 formula (T- (Hereinafter referred to as " specific tetracarboxylic acid ") selected from the group consisting of compounds represented by the formula (T-8) Is preferable in view of being able to exhibit good liquid crystal alignability.

Specific examples of the tetracarboxylic acid include 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 [ 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3- Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane- -Dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the above formula (T-5) And particularly preferably is 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

The tetracarboxylic acid dianhydride used for synthesizing the preferred polyamic acid in the liquid crystal aligning agent of the present invention is a tetracarboxylic acid dianhydride having a specific tetracarboxylic acid content of at least 20 mol% , More preferably 50 mol% or more, and particularly preferably 80 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 specific tetracarboxylic dianhydride as described above.

<Diamine>

The diamine used for synthesizing the preferred polyamic acid in the liquid crystal aligning agent of the present invention is a diamine represented by the formula (A) and a compound having two amino groups (hereinafter referred to as &quot; compound (A) &quot;) .

As such a compound (A), an aromatic diamine having a group represented by the formula (A) is preferable, and for example, a compound represented by the following formula (A-1) can be mentioned.

(2)

(Wherein R and X ^I are the same as defined in the above formula (A), ^XII is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a ^# -O- , ^# -COO- or ^# -OCO- (in which the number of bonds having "#" attached thereto is combined with N) and ^XIII is independently a single bond or a group represented by the formula ( ^XIII- 1) 2-valent group.)

(3)

(In the formula ( ^XIII- 1), ^XIV represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, ^# -O-, ^# -COO- or ^# -OCO- combining the number and binds the aromatic ring of X ^ⅱ side) engages with the coupling group attached to the number of "*".)

In the formula (A-1), group -X ^Ⅲ -NH ₂ is preferably in the 2,4-position or 3,5-position relative to the piperidin dinhwan from a benzene ring (還上).

Examples of ^Ⅱ X in the above formula (A-1), preferably a single bond, as X ^Ⅲ, from a single bond, or X is ^{Ⅳ #} -O- (where in the formula (X ^Ⅲ -1), " divalent group of the number of combined attach the # "binds the aromatic ring of X ^ⅱ thereof) are preferred.

As such a compound (A), it is particularly preferable to use at least one compound selected from the group consisting of the compounds represented by the following formulas (A-1-1) to (A-1-36)

The alkyl group bonded to the group -COO- or -O- in the formulas (A-1-25) to (A-1-36) is preferably a straight chain.

Such a compound (A) can be synthesized by appropriately combining the methods of organic chemistry.

(A-1-1), (A-1-2), (A-1-5) (A-1-12), (A-1-21), (A-1-22) Can be prepared by adding isonipecotic acid to dinitrofluorobenzene in the presence of a suitable base such as cesium fluoride and then adding N, N-dimethylaminopyridine and di The cholesterol, cholesterol, lanosterol, ergosterol or lumisterol are added in the presence of cyclohexylcarbodiimide to effect an ester forming reaction, and then the nitro group is reduced using an appropriate reducing agent such as palladium carbon and hydrazine monohydrate to obtain an amino group .

(A-1-13), (A-1-7), (A-1-11) Each of the compounds represented by the formula (I) and (II) is obtained by adding 4-bromopiperidine to dinitrofluorobenzene in the presence of a suitable base such as cesium fluoride, and then adding cholesterol, cholesterol, Adding a potassium salt of sterol or lumisterol to perform an ether forming reaction, and then reducing the nitro group using a suitable reducing agent such as palladium carbon and hydrazine monohydrate to obtain an amino group.

(A-1-14), (A-1-8), (A-1-12) Each of the compounds represented by the formulas is obtained by adding nifecoctanoic acid to dinitrofluorobenzene in the presence of a suitable base such as cesium fluoride and then adding N, N-dimethylaminopyridine and dicyclohexyl A cholesterol, cholesterol, lanosterol, ergosterol, or lumisterol is added in the presence of silca-bodiimide to effect an ester formation reaction, and then the nitro group is reduced using an appropriate reducing agent such as palladium carbon and hydrazine monohydrate to obtain an amino group Can be synthesized.

(A-1-25), (A-1-26), (A-1-29) to (A- 1-30), (A- 1-33) Each of the compounds represented by the above formulas is obtained by adding isonipecotic acid to dinitrofluorobenzene in the presence of a suitable base such as cesium fluoride and then adding N, N-dimethylaminopyridine and dicyclo An alcohol having a desired alkyl group is added in the presence of hexylcarbodiimide to effect an ester forming reaction and then the nitro group is reduced using an appropriate reducing agent such as palladium carbon and hydrazine monohydrate to obtain an amino group.

The compound represented by each of the above formulas (A-1-27), (A-1-31) and (A-1-35) can be obtained by subjecting a compound represented by the formula 4-bromopiperidine is added to nitrofluorobenzene, followed by the addition of a potassium salt of an alcohol having a desired alkyl group to an ether forming reaction, followed by reduction of the nitro group using a suitable reducing agent such as palladium carbon and hydrazine monohydrate To give an amino group.

Further, the compounds represented by each of the above formulas (A-1-28), (A-1-32) and (A-1-36) can be obtained by, for example, Nifecoate acid was added to dinitrofluorobenzene, and an alcohol having a desired alkyl group was then added to the reaction product in the presence of N, N-dimethylaminopyridine and dicyclohexylcarbodiimide to effect an ester forming reaction. Then, palladium Can be synthesized by reducing the nitro group using an appropriate reducing agent such as carbon and hydrazine monohydrate to obtain an amino group.

As the diamine used for synthesizing the preferred polyamic acid in the liquid crystal aligning agent of the present invention, only the compound (A) may be used as described above, or the compound (A) and other diamines may be used in combination.

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, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 , 4'-diaminobiphenyl, 3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1- (4 ' Aminophenyl) -1,3,3-trimethyl indane, 3,4'-diaminodiphenyl ether, 3,3-trimethyl indane, 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) ] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, Benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9- (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'- Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4 '- (p- Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluorophosphate, bis 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] Aromatic diamines such as phenylphenyl;

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 Alicyclic diamines such as cyclohexylamine (cyclohexylamine) 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, 6,9-diamino-2-ethoxy acridactate, 3,8-diamino-6-phenylphenanthridine, 3,6-diamino arc Aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl (D-I), wherein the compound (A) is not a compound represented by the formula (I), and the compound represented by the formula ), A compound represented by the following formula (D-II), or the like, having two primary amino groups 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 pyridine, pyrimidine, triazine, piperidine and piperazine, X ¹ represents a divalent organic group It is a device.)

(Wherein (D-Ⅱ), R ⁶ is a pyridine, pyrimidine, triazine, piperidine and a divalent organic group having a ring structure containing a nitrogen atom is selected from piperazine, X ^2, respectively, A plurality of X ² present may be the same or different;

Mono-substituted phenylenediamine represented by the following formula (D-III) (wherein the compound corresponds to the compound (A)),

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

A diamino organosiloxane such as a compound represented by the following formula (D-IV)

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

And compounds represented by each of the following formulas (D-1) to (D-5).

(Wherein 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)

Examples of other diamines used for synthesizing the preferred polyamic acid in the liquid crystal aligning agent of the present invention include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) (4-aminophenyl) hexafluoropropane, 4,4 '- (p-phenylphenyl) hexafluoropropane, 2,2- (M-phenylene diisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4- Bis (4-aminophenoxy) benzene, 4,4'-bis (4-amyl Naphthoxy) biphenyl, compounds represented by each of the above formulas (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4- Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl- (D-6) among the compounds represented by the above formula (D-I), the compound represented by the formula (D-6) Among the compounds represented by the formula (D-II), the dodecanoxy-2,4-diaminobenzene, the pentadecanoxy- 2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecanoxy- 5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy (Hereinafter referred to as "other specific diamine") selected from the group consisting of compounds represented by the following formulas (D-8) to (D-16) .

The diamine used for the synthesis of the polyamic acid in the liquid crystal aligning agent of the present invention preferably contains 1 mol% or more of the compound (A) based on the total diamine, and preferably 1 to 80 mol% , More preferably from 5 to 50 mol%, even more preferably from 5 to 30 mol%.

The diamine used for synthesizing the polyamic acid which may be contained in the liquid crystal aligning agent of the present invention preferably further contains 20 to 99 mol% of other specific diamine in the total diamine as described above, , More preferably from 70 to 95 mol%.

The diamine used in the synthesis of the polyamic acid in the present invention is preferably composed only of the compound (A) and specific diamine.

<Synthesis of polyamic acid>

A preferred polyamic acid in the liquid crystal aligning agent of the present invention can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing the compound (A).

The ratio of the tetracarboxylic 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 0.2 to 2 equivalents based on 1 equivalent of the amino group contained in the diamine , More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably -20 to 150 占 폚, more preferably 0 to 100 占 폚. The reaction time is preferably 1 to 24 hours, more preferably 2 to 12 hours.

The organic solvent used herein is not particularly limited as long as it can dissolve the polyamic acid to be synthesized, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, Amide, dimethylsulfoxide,? -Butyrolactone, tetramethylurea, hexamethylphosphoric triamide and the like; phenol solvents such as m-cresol, xylenol, phenol, halogenated phenol and the like. The amount of the organic solvent (a: when the single organic solvent and the below-mentioned poor solvent are used in combination, they are the total amount thereof) is determined by the total amount (b) of the tetracarboxylic acid dianhydride and the diamine, a + b) is preferably in the range of 0.1 to 30% by weight.

Ketones, esters, ethers, halogen hydrocarbons, hydrocarbons, etc., which are commonly regarded as poor solvents for polyamic acid, can be used in combination with the organic solvent in such a range that the resulting polyamic acid is not precipitated. Specific examples of such a poor solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, Butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, di Ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, Benzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutylate and diisopentyl ether.

When the organic solvent and the poor solvent as described above are used in the synthesis of the polyamic acid, the ratio of the poor solvent is preferably 50% by weight or less based on the total amount of the organic solvent and the poor solvent, Is not more than 10% 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 using a separator . The polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent, followed by precipitation with a poor solvent, or a step of distillation under reduced pressure using a separator, once or several times.

<Polyimide>

The preferred polyimide in the present invention can be obtained by imidizing the above preferable 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 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. Namely, the diamine used for the synthesis of the preferable polyimide in the present invention contains the compound (A) as described above, and only the compound (A) may be used, or the diamine Or may be used in combination. The kind of the other diamine and the preferable ratio of use of each diamine are also the same as those of the polyamic acid.

The polyimide in the present invention may be a completely imidized product obtained by dehydrating and ring closure of all of the arboric acid structure of the polyamic acid which is a precursor of the polyimide. Alternatively, only a part of the arboric acid structure may be dehydrated and cyclized, It may be a partial imide cargo. The imide ratio of the polyimide in the present invention is preferably 20% or more, more preferably 40 to 80%. 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 isomeric ring. The imidation rate can be calculated from the results of ¹ H-NMR measurement at room temperature using tetramethylsilane as a reference material and polyimide dissolved in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) ). &Lt; / RTI &gt;

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

(In the formula (1), A ¹ is the peak area originating from the proton of the NH group near 10 ppm of the chemical shift, A ² is the peak area derived from the other proton, and α is the peak area of the polyimide precursor The ratio of the number of other protons to the number of protons of the NH group.

The dehydration ring closure of the polyamic acid is preferably carried out by (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, . &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 ° C, the dehydration ring-closure reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimide may be lowered. The reaction time is preferably 1 to 24 hours, more preferably 2 to 8 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. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, but are not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The imidization rate can be increased as the use ratio of the dehydrating agent and dehydrating ring closure agent is increased. Examples of the organic solvent used in the dehydration ring closure reaction include the organic solvents exemplified above, which are used for 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 to 24 hours, more preferably 2 to 8 hours.

The polyimide obtained in the above method (i) can be directly supplied to the preparation of the liquid crystal aligning agent, or the polyimide obtained may be provided in the preparation of the liquid crystal aligning agent after the purification. 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 performing the same operation as described above as a method for isolating and purifying polyamic acid.

- Polymers of terminal modified type -

The preferred polyamic acid and polyimide in the present invention may each be a polymer of the end-modified type having a controlled molecular weight. By using a polymer of a terminal modified type, the application properties of the liquid crystal aligning agent and the like can be further improved without impairing the effect of the present invention. Such a terminal modified polymer can be produced 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 modifier is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and 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, respectively, .

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 Polymers>

The liquid crystal aligning agent of the present invention contains the above specific polymer as an essential component. However, in order to improve the solution properties of the obtained liquid crystal aligning agent and the electric characteristics of the liquid crystal alignment layer to be formed, other polymers may be used together with the specific polymer have.

Such other polymer may be a polymer other than a specific polymer, for example, 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 (A) Polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (styrene-phenylmaleimide) derivative, Poly (meth) acrylate, and the like. Of these, other polyamic acids or other polyimides are preferable, and other polyamic acids are particularly preferable. The proportion of the other polymer to be used is preferably 50% by weight or more and less than 100% by weight, more preferably 60 to 90% by weight, based on the sum of the polymers (the total amount of the specific polymer and the other polymer, By weight, more preferably 65 to 85% by weight.

As the polymer contained in the liquid crystal aligning agent of the present invention, a polyimide having a group represented by the formula (A) may be used, or a polyimide having a group represented by the formula (A) It is particularly preferable to use them in combination.

<Other components>

The liquid crystal aligning agent of the present invention contains the above-mentioned specific polymer as an essential component, optionally containing other polymer, and may further contain other components as required. Such other components include, for example, a compound having at least one epoxy group in the molecule (hereinafter referred to as an &quot; epoxy compound &quot;), and a functional silane 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, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- -Aminomethylcyclohexane, and the like can be preferably used. The compounding ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 parts by weight or less, and most preferably 0.1 parts by weight or less, based on 100 parts by weight of the total amount of the polymers (the total amount of the specific polymer and other polymers contained in the liquid crystal aligning agent, To 30 parts by weight.

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

The mixing ratio of these functional silane compounds is preferably 40 parts by weight or less based on 100 parts by weight of the total amount of the polymer.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is constituted by dissolving and containing the above-mentioned polymer and optionally other components optionally mixed in an organic solvent.

Examples of the organic solvent usable in the liquid crystal aligning agent of the present invention include the solvents exemplified for use in the synthesis reaction of polyamic acid. Further, the poor solvents exemplified as those which can be used in combination in the synthesis reaction of the polyamic acid can also be suitably selected and used in combination. Preferable examples of such an organic solvent 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, ethylene glycol ethyl ether, ethylene glycol Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, 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 the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent removed from the organic solvent) is appropriately selected in consideration of viscosity, volatility, etc., To 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate and the organic solvent is removed to form a coating film as the liquid crystal alignment film. When the solid concentration is less than 1% by weight, the film thickness of the coating film becomes excessively small It is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large to make it difficult to obtain a good liquid crystal alignment film in some cases. So that the coating properties may be deteriorated.

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 range of 1.5 to 4.5 wt% is particularly preferable. 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 ink-jet 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 accordingly.

<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 is preferably a VA type liquid crystal display element and can be produced by the following method, for example.

(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate on which a patterned transparent conductive film is formed by, for example, a roll coater method, a spinner method, a printing method, an inkjet method, A coating film is formed by heating. 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, or alicyclic polyolefin can be used. As the transparent conductive film to be formed on one surface of the substrate, an NESA film (a registered trademark of PPG Corporation, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) . The patterned transparent conductive film can be obtained, for example, by forming a pattern-free transparent conductive film on a substrate and then forming a desired pattern by photoetching, a method of forming a transparent conductive film by patterning using a mask having a desired pattern A method of directly forming a transparent conductive film, or the like can be used. For application of the liquid crystal aligning agent, for example, a functional silane compound, a functional titanium compound and the like may be previously coated in order to further improve the adhesion between the substrate surface and the coating film. Preheating (prebaking) is preferably performed for the purpose of preventing the liquid flow of the alignment agent applied after application of the liquid crystal aligning agent, and 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 0.1 to 10 minutes, more preferably 0.5 to 3 minutes. Thereafter, a firing (post-baking) step is performed for the purpose of completely removing the solvent and the like. The post-baking temperature is preferably 80 to 300 占 폚, more preferably 120 to 250 占 폚. The post baking time is preferably 1 to 180 minutes, more preferably 10 to 120 minutes.

The liquid crystal aligning agent of the present invention forms a coating film as a liquid crystal alignment film by removing the organic solvent after application. When the liquid crystal aligning agent of the present invention contains a polyimide having both a polyamic acid or imide ring structure and an acidic structure, The coating film may be further heated to form a coating film (liquid crystal alignment film) which is imidized by progressing the dehydration ring-closure reaction in the unit of the acid.

The film thickness of the liquid crystal alignment film formed here is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

(2) Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is arranged between the two substrates to manufacture a liquid crystal cell. For example, the following two methods can be used for disposing the liquid crystal between two substrates.

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 the peripheral portions of the two substrates are bonded together using a sealant to form a cell A liquid crystal cell can be manufactured by injecting and filling a liquid crystal in a gap and then sealing an injection hole (injection hole).

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 sealant by irradiating ultraviolet light to the entire surface of the substrate. The liquid crystal aligning agent of the present invention has an advantage that a liquid crystal display element free from ODF unevenness can be obtained even when a VA type liquid crystal display element is manufactured by the ODF method because a liquid crystal alignment film having excellent vertical orientation can be formed.

In either case, it is preferable to heat the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cool to room temperature to remove the flow alignment at the time of filling the liquid crystal.

By attaching a polarizing plate to the outer surface of the liquid crystal cell, the liquid crystal display device of the present invention can be manufactured.

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

Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, a nematic liquid crystal is preferable, and examples thereof include a liquid crystal such as a schiff base liquid crystal, an agar liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal , A pyrimidine-based liquid crystal, a dioxane-based liquid crystal, a bicyclooctane-based liquid crystal, a quartz-based liquid crystal, and 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 may be added and used.

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 "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched between cellulose acetate protective films or a polarizing plate composed of H film itself have.

(Example)

&Lt; Synthesis of Compound (A) >

Synthesis Example 1 [Synthesis of Compound Represented by the Formula (A-1-2)

The compound represented by the above formula (A-1-2) (hereinafter referred to as "compound (A-1-2)") was synthesized according to the following reaction scheme (Scheme 1).

<Reaction Scheme 1>

(1) Synthesis of Compound (A-1a)

186 g of 2,4-dinitrofluorobenzene, 194 g of isonipecotic acid and 1,000 mL of dimethylsulfoxide were placed in a 3,000 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, and dissolved uniformly. Subsequently, 167 g of cesium fluoride was added thereto, and the reaction was carried out at room temperature for 4 hours. After completion of the reaction, 3,000 mL of ethyl acetate was added to the reaction mixture to obtain an organic layer. The organic layer was washed three times with water, dried with magnesium sulfate and then the solvent was removed to obtain 290 g of the compound (A-1a).

(2) Synthesis of compound (A-1-2a)

148 g of the compound (A-1a) obtained above, 194 g of cholestanol, 12.2 g of N, N-dimethylaminopyridine and 2,000 mL of tetrahydrofuran were placed in a 3,000 mL three-necked flask equipped with a thermometer, And cooled in an ice bath (ice bath). Subsequently, 124 g of dicyclohexylcarbodiimide (DCC) was added thereto, and the reaction was carried out in an ice bath for 30 minutes with stirring, followed by further reaction at room temperature for 5 hours. After completion of the reaction, the precipitate was removed by filtration, and 2,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed with water three times, dried with magnesium sulfate, and then the solvent was removed. The crude product thus obtained was recrystallized (recrystallized) from a mixed solvent consisting of 2,000 mL of ethyl acetate and 330 mL of tetrahydrofuran, (A-1-2a).

(3) Synthesis of Compound (A-1-2)

133 g of the compound (A-1-2a) obtained above, 1,480 mL of ethanol, 740 mL of tetrahydrofuran and 6.6 g of 5% by weight palladium carbon were placed in a 5,000 mL three-necked flask equipped with a reflux condenser, Further, 48.5 mL of hydrazine monohydrate was added slowly, and the reaction was carried out with stirring at room temperature for 1 hour, followed by further reaction at 66 DEG C for 1 hour under reflux. After completion of the reaction, palladium carbon was removed by filtration, and 5,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed three times with water and then the solvent was removed to obtain 99 g of a powder of the compound (A-1-2).

Synthesis Example 2 [Synthesis of the compound represented by the above formula (A-1-18)] [

The compound represented by the above formula (A-1-18) (hereinafter referred to as "compound (A-1-18)") was synthesized according to the following reaction scheme 2.

<Reaction Scheme 2>

(1) Synthesis of Compound (A-1-18a)

139 g of the compound (A-1a) obtained in the above (1) of Synthesis Example 1, 119 g of 4'-pentyl-bicyclohexyl-4-ol, 12 g of N-dimethylaminopyridine and 2,500 mL of tetrahydrofuran were placed, followed by cooling in an ice bath. Subsequently, 116 g of dicyclohexylcarbodiimide (DCC) was added thereto, and the reaction was carried out in an ice bath for 30 minutes with stirring, followed by further reaction at room temperature for 5 hours. After completion of the reaction, the precipitate was removed by filtration, and 3,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed with water three times, dried over magnesium sulfate, and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 5: 1 (volume ratio) To obtain 200 g of the compound (A-1-18a).

(2) Synthesis of Compound (A-1-18)

180 g of the compound (A-1-18a) obtained above, 2,000 mL of ethanol, 1,000 mL of tetrahydrofuran, and 8.6 g of 5 wt% palladium carbon were added to a 5,000 mL three-necked flask equipped with a reflux condenser, 86 mL of hydrazine monohydrate was slowly added thereto, and the reaction was carried out at room temperature for 1 hour with stirring. The reaction was further carried out for one hour under reflux. After completion of the reaction, palladium carbon was removed by filtration, and then 10,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed three times with water and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 10: 3 (volume ratio) 18) powder was obtained.

Synthesis Example 3 [Synthesis of a compound represented by the following formula (A-1-26)

(Hereinafter referred to as "compound (A-1-26)") represented by the following formula (A-1-26) was synthesized according to the following reaction scheme 3.

<Reaction Scheme 3>

(1) Synthesis of Compound (A-1-26a)

139 g of the compound (A-1a) obtained in the same manner as in (1) of Synthesis Example 1, 88 g of 1-dodecanol and 12 g of N, N-dimethylaminopyridine were placed in a 5,000 ml three-necked flask equipped with a thermometer, And 2,500 mL of tetrahydrofuran, and the mixture was cooled in an ice bath. Subsequently, 116 g of dicyclohexylcarbodiimide (DCC) was added thereto, and the reaction was carried out in an ice bath for 30 minutes with stirring, followed by further reaction at room temperature for 5 hours. After completion of the reaction, the precipitate was removed by filtration, and 3,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed with water three times, dried over magnesium sulfate, and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 5: 1 (volume ratio) To obtain 175 g of the compound (A-1-26a).

(2) Synthesis of compound (A-1-26)

158 g of the compound (A-1-26a) obtained above, 2,000 mL of ethanol, 1,000 mL of tetrahydrofuran, and 8.6 g of 5 wt% palladium carbon were added to a 5,000 mL three-necked flask equipped with a stirrer, 86 mL of hydrazine monohydrate was slowly added thereto, and the reaction was carried out at room temperature for 1 hour with stirring. The reaction was further carried out for one hour under reflux. After completion of the reaction, palladium carbon was removed by filtration, and then 10,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed three times with water and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 10: 3 (volume ratio) 26) was obtained.

Synthesis Example 4 [Synthesis of compound represented by the following formula (A-1-30)] [

(Hereinafter referred to as "compound (A-1-30)") represented by the following formula (A-1-30) was synthesized according to the following reaction scheme 4.

<Reaction Scheme 4>

(1) Synthesis of compound (A-1-30a)

139 g of the compound (A-1a) obtained in the same manner as in (1) of Synthesis Example 1, 61 g of 1-tridecanol, 1 g of N, N-dimethylamino 12 g of pyridine and 2,500 mL of tetrahydrofuran, and the mixture was cooled in an ice bath. Subsequently, 116 g of dicyclohexylcarbodiimide (DCC) was added thereto, and the reaction was carried out in an ice bath for 30 minutes with stirring, followed by further reaction at room temperature for 5 hours. After completion of the reaction, the precipitate was removed by filtration, and 3,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed with water three times, dried over magnesium sulfate, and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 5: 1 (volume ratio) , Thereby obtaining 180 g of the compound (A-1-30a).

(2) Synthesis of Compound (A-1-30)

162 g of the compound (A-1-30a) obtained above, 2,000 mL of ethanol, 1,000 mL of tetrahydrofuran, and 8.6 g of 5% by weight palladium carbon were added to a 5,000 mL three-necked flask equipped with a stirrer, 86 mL of hydrazine monohydrate was slowly added thereto, and the reaction was carried out at room temperature for 1 hour with stirring. The reaction was further carried out for one hour under reflux. After completion of the reaction, palladium carbon was removed by filtration, and then 10,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed three times with water and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 10: 3 (volume ratio) 30) powder was obtained.

Synthesis Example 5 [Synthesis of compound represented by the following formula (A-1-34)] [

(Hereinafter referred to as "compound (A-1-34)") represented by the above formula (A-1-34) was synthesized according to the following reaction scheme 5.

<Reaction Scheme 5>

(1) Synthesis of Compound (A-1-34a)

139 g of the compound (A-1a) obtained in the same manner as in (1) of Synthesis Example 1, 94 g of 1-octanol and 50 g of N, N-dimethylaminopyridine And 2,500 mL of tetrahydrofuran, and the mixture was cooled in an ice bath. Subsequently, 116 g of dicyclohexylcarbodiimide (DCC) was added thereto, and the reaction was carried out in an ice bath for 30 minutes with stirring, followed by further reaction at room temperature for 5 hours. After completion of the reaction, the precipitate was removed by filtration, and 3,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed with water three times, dried over magnesium sulfate, and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 5: 1 (volume ratio) , 151 g of the compound (A-1-34a) was obtained.

(2) Synthesis of compound (A-1-34)

138 g of the compound (A-1-34a) obtained above, 2,000 mL of ethanol, 1,000 mL of tetrahydrofuran, and 8.6 g of 5% by weight palladium carbon were added to a 5,000 mL three-necked flask equipped with a reflux condenser, 86 mL of hydrazine monohydrate was slowly added thereto, and the reaction was carried out at room temperature for 1 hour with stirring. The reaction was further carried out for one hour under reflux. After completion of the reaction, palladium carbon was removed by filtration, and then 10,000 mL of ethyl acetate was added to the filtrate to obtain an organic layer. The organic layer was washed three times with water and then the solvent was removed. The resulting crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 10: 3 (volume ratio) 34) powder was obtained.

&Lt; Synthesis of Specific Polymer &

[Synthesis of polyimide having a group represented by the above formula (A)] [

Synthesis Example F-1

36.2 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 19.7 g of a compound (A-1-2) as a diamine (the same as in Synthesis Example 1, (Corresponding to 0.2 moles with respect to 1 mole of TCA) and 14.1 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 4 hours, % Solution. For this solution, the viscosity of the solution measured at 25 캜 was 1,385 mPa..

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 12.8 g of pyridine and 16.5 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (by removing the pyridine and anhydrous acetic acid used in the dehydration ring-closure reaction out of the system by this solvent substitution operation, To obtain a solution containing 20% by weight of polyimide (F-1) having an imidization ratio of 49%.

Synthesis Example F-2

41.0 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 11.1 g of a compound (A-1-2) as a diamine (corresponding to 0.1 mol of 1 mol of TCA) And p-phenylenediamine (17.9 g) were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing 20 wt% of polyamic acid. For this solution, the solution viscosity measured at 25 캜 was 1,517 mPa s.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14.5 g of pyridine and 18.7 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-2) having an imidization rate of 52%.

Synthesis Example F-3

36.2 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as tetracarboxylic dianhydride and 19.7 g of the compound (A-1-2) as a diamine (corresponding to 0.2 mol of 1 mol of TCA) And 14.1 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing 20 wt% of polyamic acid. For this solution, the solution viscosity measured at 25 占 폚 was 1,325 mPa 占 퐏.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 25.6 g of pyridine and 33.0 g of acetic anhydride were added, followed by dehydration ring closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-3) having an imidization ratio of 82%.

Synthesis Example F-4

41.0 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 11.1 g of a compound (A-1-2) as a diamine (corresponding to 0.1 mol of 1 mol of TCA) And p-phenylenediamine (17.9 g) were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing 20 wt% of polyamic acid. For this solution, the solution viscosity measured at 25 캜 was 1,490 mPa..

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 28.9 g of pyridine and 37.3 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-4) having an imidization rate of 80%.

Synthesis Example F-5

16.5 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 9.0 g of a compound (A-1-2) as a diamine (corresponding to 0.2 mol of 1 mol of TCA) , 3.9 g of the compound represented by the above formula (D-10) (corresponding to 0.1 mole with respect to 1 mole of TCA) and 5.6 g of p-phenylenediamine were dissolved in 140 g of N-methyl-2-pyrrolidone, C for 4 hours to obtain a solution containing 20 wt% of polyamic acid. For this solution, the solution viscosity measured at 25 캜 was 1,071 mPa..

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 5.8 g of pyridine and 7.5 g of acetic anhydride were added, followed by dehydration ring closure reaction 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 20% by weight of polyimide (F-5) having an imidization rate of 51%.

Synthesis Example F-6

38.7 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as the tetracarboxylic acid dianhydride and 16.3 g of the compound (A-1-18) as the diamine (the same as in Synthesis Example 2, (Corresponding to 0.2 moles with respect to 1 mole of TCA) and 15.0 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a polyamic acid solution % Solution. For this solution, the solution viscosity measured at 25 캜 was 1,871 mPa..

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 13.7 g of pyridine and 17.6 g of acetic anhydride were added, followed by dehydration ring closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-6) having an imidization rate of 51%.

Synthesis Example F-7

42.5 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as the tetracarboxylic acid dianhydride and 9.0 g of the compound (A-1-18) as the diamine (corresponding to 0.1 mol per 1 mol of the TCA) And 18.5 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing 20% by weight of polyamic acid. For this solution, the solution viscosity measured at 25 占 폚 was 2,109 mPa 占 퐏.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 15.0 g of pyridine and 19.4 g of acetic anhydride were added, followed by dehydration ring closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-7) having an imidization rate of 50%.

Synthesis Example F-8

38.7 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 16.3 g of a compound (A-1-18) as diamine (corresponding to 0.2 mol of 1 mol of TCA) And 15.0 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing 20% by weight of polyamic acid. For this solution, the solution viscosity measured at 25 캜 was 1,880 mPa..

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, 27.3 g of pyridine and 35.2 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-8) having an imidization rate of 80%.

Synthesis Example F-9

43.8 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 9.2 g of a compound (A-1-18) as a diamine (corresponding to 0.1 mol of 1 mol of TCA) And 17.0 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing 20% by weight of polyamic acid. For this solution, the solution viscosity measured at 25 占 폚 was 2,018 mPa 占 퐏.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 30.9 g of pyridine and 39.9 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-9) having an imidization rate of 78%.

Synthesis Example F-10

17.5 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 7.4 g of a compound (A-1-18) as a diamine (corresponding to 0.2 mol of 1 mol of TCA) , 4.1 g of the compound represented by the above formula (D-10) (corresponding to 0.1 mole with respect to 1 mole of TCA) and 6.0 g of p-phenylenediamine were dissolved in 140 g of N-methyl-2-pyrrolidone, C for 4 hours to obtain a solution containing 20 wt% of polyamic acid. The solution viscosity measured at 25 캜 for this solution was 1,390 mPa..

Subsequently, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 6.2 g of pyridine and 8.0 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-10) having an imidization rate of 48%.

Synthesis Example F-11

32.4 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 20.5 g of a compound (A-1-18) as diamine (corresponding to 0.3 mol of 1 mol of TCA) And 3.90 g of 1,4-bis- (4-amino-phenyl) -piperazine (corresponding to 0.1 mol of TCA per mole of TCA) and 13.3 g of 3,5-diaminobenzoic acid Equivalent) was dissolved in 280 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 60 DEG C for 4 hours to obtain a solution containing 20 wt% of polyamic acid. For this solution, the solution viscosity measured at 25 占 폚 was 812 mPa 占 퐏.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 17.1 g of pyridine and 22.1 g of acetic anhydride were added, followed by dehydration ring closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-11) having an imidization rate of 64%.

Synthesis Example F-12

31.9 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 10.1 g of a compound (A-1-18) as a diamine (corresponding to 0.15 mol based on 1 mol of TCA) And 13.2 g of 3,5-diaminobenzoic acid (corresponding to 0.6 moles with respect to 1 mole of TCA) and 11.2 g (corresponding to 0.15 moles with respect to 1 mole of TCA) of the compound represented by the above formula (D-10) (Corresponding to 0.1 mol of 1 mol of TCA) were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours To obtain a solution containing 20 wt% of polyamic acid. For this solution, the solution viscosity measured at 25 占 폚 was 1,112 mPa 占 퐏.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 16.9 g of pyridine and 21.8 g of acetic anhydride were added and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-12) having an imidization rate of 65%.

Synthesis Example F-13

32.1 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 10.2 g of a compound (A-1-18) as a diamine (corresponding to 0.15 mol based on 1 mol of TCA) , 10.7 g (corresponding to 0.15 mol based on 1 mol of TCA) of the compound represented by the above formula (D-8), 13.2 g of 3,5-diaminobenzoic acid (corresponding to 0.6 mol based on 1 mol of TCA) 3.9 g (corresponding to 0.1 mol of 1 mol of TCA) of 4-bis- (4-amino-phenyl) -piperazine was dissolved in 280 g of N-methyl-2-pyrrolidone, To obtain a solution containing 20 wt% of polyamic acid. For this solution, the solution viscosity measured at 25 캜 was 1,114 mPa s.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 17.0 g of pyridine and 22.0 g of acetic anhydride were added and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-13) having an imidization rate of 64%.

Synthesis Example F-14

40.0 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 14.5 g of a compound (A-1-26) as a diamine (the same as in Synthesis Example 3, (Corresponding to 0.2 moles with respect to 1 mole of TCA) and 15.5 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a polyamic acid % Solution. For this solution, the viscosity of the solution measured at 25 占 폚 was 1,901 mPa 占 퐏.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 28.2 g of pyridine and 36.4 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-14) having an imidization rate of 80%.

Synthesis Example F-15

32.6 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as tetracarboxylic acid dianhydride and 29.5 g of the compound (A-1-26) as diamine (corresponding to 0.5 mol of 1 mol of TCA) And 7.9 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing 20% by weight of polyamic acid. For this solution, the solution viscosity measured at 25 占 폚 was 1,856 mPa 占 퐏.

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 11.5 g of pyridine and 14.85 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-15) having an imidization rate of 49%.

Synthesis Example F-16

39.7 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 14.9 g of a compound (A-1-30) (obtained in the above Synthesis Example 4) as a diamine (TCA 1 0.2 mol), and 15.4 g of p-phenylenediamine were dissolved in 280 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a polyamic acid solution containing 20 wt% Solution. For this solution, the solution viscosity measured at 25 캜 was 1,890 mPa..

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14.0 g of pyridine and 18.1 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 by solvent to obtain a solution containing 20% by weight of polyimide (F-16) having an imidization rate of 49%.

Synthesis Example F-17

34.6 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic acid dianhydride and 27.0 g of a compound (A-1-34) (obtained in the above Synthesis Example 5) as a diamine (TCA 1 And 8.4 g of p-phenylenediamine were dissolved in 280 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 containing 20% by weight of polyamic acid Solution. For this solution, the solution viscosity measured at 25 캜 was 1,861 mPa..

Subsequently, 650 g of N-methyl-2-pyrrolidone was added to the resulting polyamic acid solution, 24.4 g of pyridine and 31.5 g of acetic anhydride were added, and the dehydration ring-closure reaction 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 20% by weight of polyimide (F-17) having an imidization rate of 79%.

&Lt; Synthesis of other polymer >

[Synthesis of other polyamic acids]

Synthesis Example G-1

109 g (0.50 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride, 98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 4,4-diaminodiphenyl ether as diamine Pyrrolidone was dissolved in 2,290 g of N-methyl-2-pyrrolidone and reacted at 40 DEG C for 3 hours. Then, 1,350 g of N-methyl-2-pyrrolidone was added to obtain another polyamic acid ( G-1) was obtained in an amount of about 3,990 g.

The solution viscosity of this other polyamic acid solution was 180 mPa · s.

Synthesis Example G-2

98 g (0.50 mol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 109 g (0.50 mol) of pyromellitic dianhydride as tetracarboxylic dianhydrides, and 4,4'-diaminodiphenyl 198 g (1.0 mol) of methane was dissolved in 2,290 g of N-methyl-2-pyrrolidone, and the reaction was carried out at 40 DEG C for 3 hours. Then, 1,350 g of N-methyl- About 4,000 g of a solution containing 10% by weight of (G-2).

The solution viscosity of this other polyamic acid solution was 113 mPa · s.

Synthesis Example G-3

196 g (1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mole) of 4,4'-diaminodiphenyl ether as a diamine were dissolved in N-methyl-2 -Pyrrolidone and reacted at 40 占 폚 for 4 hours. Then, 1,321 g of N-methyl-2-pyrrolidone was added to this solution to obtain a solution containing 10% by weight of other polyamic acid (G-3) About 3,900 g was obtained.

The solution viscosity of this other polyamic acid solution was 189 mPa s.

Synthesis Example G-4

(1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride as a tetracarboxylic dianhydride and 212 g (1.0 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl as a diamine, Was dissolved in 3,670 g of N-methyl-2-pyrrolidone and reacted at 40 DEG C for 3 hours to obtain about 4,020 g of a solution containing 10% by weight of other polyamic acid (G-4).

The solution viscosity of this other polyamic acid solution was 144 mPa · s.

Synthesis Example G-5

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride and 200 g (1.0 mole) of 4,4'-diaminodiphenyl ether as diamine were dissolved in N-methyl- And 412 g of N-methyl-2-pyrrolidone was added to obtain a solution containing about 4,200 g of a solution containing 10% by weight of other polyamic acid (G-5) &Lt; / RTI &gt;

The solution viscosity of this other polyamic acid solution was 162 mPa · s.

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

Example 1

[Preparation of liquid crystal aligning agent for evaluation of printability]

A solution containing the polyimide (F-1) obtained in the above Synthesis Example F-1 was taken in an amount corresponding to 100 parts by weight in terms of the polyimide (F-1) contained therein, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to 20 parts by weight of N, N, N ', N'-tetraglycidyl- (NMP: BC = 60: 40, weight ratio) and a solid concentration of 7% by weight. This solution was filtered using a filter having a pore diameter of 1 탆 to prepare a liquid crystal aligning agent (P-1) for printability evaluation.

[Evaluation of printability]

Using a liquid crystal alignment film printing machine (Nippon Sha Shingen Co., Ltd., type "Ong Stromer S40L-532"), the liquid crystal aligning agent (P-1) prepared above was subjected to liquid crystal alignment The dropping amount was applied on the surface of the transparent electrode of the glass substrate with transparent electrode made of ITO film under the condition of 20 droplets (about 0.2 g) reciprocating. Here, the drop amount of the liquid crystal aligning agent is a stricter printing condition because the liquid amount is smaller as compared with a dropping amount (30 drops reciprocating (about 0.3 g)) which is usually employed for a printing machine of the same type.

The substrate after the application of the liquid crystal aligning agent was heated (prebaked) at 80 占 폚 for 1 minute to remove the solvent, and then heated at 180 占 폚 for 10 minutes (post baking) to form a coating film having a thickness of 80 nm.

The coating film was visually observed to examine whether pinholes and unevenness of printing were observed. As a result, neither pinholes nor printing irregularities were observed, and the printability of the liquid crystal aligning agent (P-1) was good.

[Preparation of liquid crystal aligning agent for liquid crystal cell production]

A liquid crystal aligning agent (S-1) for producing a liquid crystal cell was prepared in the same manner as described above except that the solid content concentration of the solution before filtration was changed to 4% by weight in the preparation of the liquid crystal aligning agent for printability evaluation.

[Production of liquid crystal cell]

The liquid crystal aligning agent (S-1) prepared above was applied onto a transparent conductive film made of an ITO film formed on the entire surface of a glass substrate having a thickness of 1 mm by means of a spinner, Minute, and then baked in a clean oven at 200 DEG C for 30 minutes to form a coating film (liquid crystal alignment film) having a thickness of 0.08 mu m. This operation was repeated to prepare a pair of substrates (two substrates) having a liquid crystal alignment film on the transparent conductive film.

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 the adhesive was superimposed on each other so as to face the liquid crystal alignment film faces to cure the adhesive . Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curable adhesive to prepare a vertically aligned liquid crystal cell.

[Evaluation of liquid crystal cell]

(1) Evaluation of voltage holding ratio

A voltage of 5 V was applied to the liquid crystal cell prepared above at 60 캜 with a span of 16.7 microseconds for an application time of 60 microseconds and then the voltage maintenance rate after 16.7 milliseconds .

Almost the results are shown in Table 2.

(2) Evaluation of Inner Toughness

The residual DC voltage after applying a voltage of 5 V at 60 캜 for 20 hours to the liquid crystal cell manufactured in the same manner as above was measured. When this value was 0 to 500 mV, the triboelectric &quot; good &quot; mV or less, the toughness was evaluated as &quot; good &quot;.

The evaluation results are shown in Table 2.

Examples 2 to 21 and 55

N, N ', N', N ', N'-tetramethylethylenediamine) was used in place of the solution containing the polyimide (F-1) (P-2) to (P-21) and (P-2) for printability evaluation were prepared in the same manner as in Example 1, except that the amount of tetraglycidyl-m- (P-55) and liquid crystal aligning agents (S-2) to (S-21) and (S-55) for liquid crystal cell production were respectively prepared. Evaluation of printability and production and evaluation of liquid crystal cell were carried out.

The evaluation results thereof are shown in Tables 1 and 2.

Example 22

[Preparation of liquid crystal aligning agent for evaluation of printability and evaluation of printing property]

20 parts by weight of the solution containing the polyimide (F-1) obtained in Synthesis Example F-1 in terms of polyimide (F-1) and the amount corresponding to 20 parts by weight of the polyamic acid (G -1) in an amount corresponding to 80 parts by weight in terms of polyamic acid (G-1) of a solution containing N, N, N ', N'-tetraglycidyl- (NMP: BC = 60:40 (weight ratio), a solid concentration of 7% by weight, and a solvent concentration of 20% by weight) . This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent for printing evaluation (P-22).

Printing performance was evaluated in the same manner as in Example 1 except that the liquid crystal aligning agent for printing evaluation (P-22) prepared above was used.

The evaluation results thereof are shown in Table 1.

[Preparation and evaluation of liquid crystal aligning agent for liquid crystal cell preparation]

A liquid crystal aligning agent (S-22) for liquid crystal cell preparation was prepared in the same manner as described above except that the solid content concentration of the solution before filtration was changed to 4% by weight in the above [preparation of liquid crystal aligning agent for printability evaluation].

Production and evaluation of a liquid crystal cell were carried out in the same manner as in Example 1 except that the liquid crystal aligning agent (S-22) for liquid crystal cell preparation prepared above was used.

The evaluation results are shown in Table 2.

Examples 23 to 54 and 56 to 58

In Example 22, the solution containing the polyimide and the polyamic acid of the kind and amount shown in Table 1 was used, and the epoxy compound N, N, N ', N'-tetraglycidyl-m- (P-23) to (P-54) and (P-56) to (P) were prepared in the same manner as in Example 22 except that the amount of xylenediamine used was changed as shown in Table 1, -58) and liquid crystal aligning agents (S-23) to (S-54) and (S-56) to (S-58) for liquid crystal cell preparation were prepared respectively and evaluated for printability, .

The evaluation results thereof are shown in Tables 1 and 2.

Claims (7)

delete delete Wherein the polymer contains at least one polymer selected from the group consisting of polyamic acid and polyimide, wherein the polymer is a reaction product of a tetracarboxylic acid dianhydride and a diamine containing a compound represented by the following formula (A-1) A liquid crystal aligning agent which is at least one kind of polymer selected from the group consisting of a polyamic acid obtained by dehydration condensation of a polyamic acid and a polyimide obtained by dehydrocondensing the polyamic acid:
(2)

(In the formula (A-1), R represents an alkyl group having 4 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, or a hydrocarbon group having 12 to 30 carbon atoms having a bicyclohexane skeleton a hydrocarbon group, X ^I is a single bond, -O- ^{#, # #} -COO- or -OCO-, and (wherein, also the number of combined attach the '#' combined with R), ^ⅱ X is a single bond, methylene , ^# -O-, ^# -COO-, or ^# -OCO- (wherein the number of bonds to which "#" is bonded is combined with N) and ^XIII are each independently an alkylene group having 2 to 10 carbon atoms, A single bond or a bivalent group represented by the following formula ( ^XIII- 1));
(3)

(In the formula ( ^XIII- 1), ^XIV represents a single bond, a methylene group, a C2-10 alkylene group, ^# -O-, ^# -COO- or ^# -OCO- combining a number of the aromatic ring of X ^ⅱ side), must not bond attached to "*" in combination with an amino group). A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent according to claim 3. A polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing the compound represented by the formula (A-1) described in claim 3. A polyimide obtained by dehydration ring closure of a polyamic acid obtained by reacting tetracarboxylic acid dianhydride with a diamine containing the compound represented by the formula (A-1) described in claim 3. delete