KR101567605B1 - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal aligning agent that provides a liquid crystal alignment film capable of achieving a wide viewing angle characteristic, a high quality display, a good afterimage characteristic, and a burning characteristic in a transverse electric field type liquid crystal display device.

Wherein the liquid crystal aligning agent is a polyamic acid obtained by reaction of a tetracarboxylic dianhydride with a diamine including a structure represented by the following formula (A) and a compound having two amino groups, and polyimide obtained by dehydration cyclization of the polyamic acid And at least one polymer selected from the group consisting of

≪ Formula (A)

(In the formula (A), "*"

A liquid crystal aligning agent, a liquid crystal aligning element, a tetracarboxylic acid dianhydride, a polyamic acid

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal display element,

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More particularly, the present invention relates to a liquid crystal aligning agent which is preferably used for forming a liquid crystal alignment film of a transverse electric field type liquid crystal display element, and a transverse electric field type liquid crystal display element excellent in afterimage and baking characteristics and capable of high- will be.

In a transverse electric field type liquid crystal display element in which electrodes are formed on only one side of a pair of substrates arranged opposite to each other and an electric field is generated in a direction parallel to the substrate, electrodes are formed on both substrates to generate an electric field in a direction perpendicular to the substrate It is known that a liquid crystal display element having a wider viewing angle characteristic than that of a conventional liquid crystal display element of a conventional system allows high-quality display. Such a transverse electric field type liquid crystal display device is described in, for example, Patent Documents 1 and 2 and Non-Patent Document 1. Since the liquid crystal display element of the transverse electric field system responds to the electric field only in the direction parallel to the substrate, there is no problem in the refractive index change in the major axis direction of the liquid crystal molecule, and the contrast, Since the change in the density of the display color is small, high-quality display is possible regardless of the time. In order to obtain such an advantageous effect, it is advantageous that the incidence angle dependency of the incident polarized light is small. Therefore, in the transverse electric field type liquid crystal display device, it is required that the pretilt angle in the initial alignment characteristic of the electric field unattended state is low.

However, in the liquid crystal display element of the transverse electric field system, after-image and baking are a problem in some cases, and improvement thereof is desired. Accordingly, Patent Document 3 proposes a method of improving afterimage characteristics and baking characteristics by using a liquid crystal alignment film made of a polymer containing a large proportion of aromatic structures. However, when a liquid crystal alignment film containing a large proportion of an aromatic structure is used, the pretilt angle is inevitably increased, and the advantageous effect as described above in the transverse electric field display device is reduced.

A liquid crystal display element capable of sufficiently exhibiting the above-described advantageous effects in a liquid crystal display element of a transverse electric field system and providing a liquid crystal alignment film exhibiting improved afterimage and baking characteristics has not yet been known and the provision of such a liquid crystal aligning agent is strongly Is desired.

[Patent Document 1] US Patent No. US5928733A

[Patent Document 2] Japanese Unexamined Patent Publication (Kokai) No. 56-91277

[Patent Document 3] JP-A-2008-15497

[Patent Document 4] JP-A-6-222366

[Patent Document 5] JP-A-6-281937

[Patent Document 6] JP-A-5-107544

[Non-Patent Document 1] "Liq. Cryst.", Vol.22, p.379 (1996)

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and an object of the present invention is to provide a liquid crystal alignment film which provides a liquid crystal alignment film capable of achieving both a wide viewing angle characteristic and a high quality display, And to provide an alignment agent.

It is another object of the present invention to provide a liquid crystal display element of a transverse electric field system in which a wide viewing angle characteristic, a high quality display, a good afterimage characteristic and a baking property are compatible.

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

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

A polyamic acid obtained by reaction of a tetracarboxylic acid dianhydride with a diamine containing a structure represented by the following formula (A) and a compound having two amino groups, and a polyimide obtained by dehydration cyclization of the polyamic acid Is achieved by a liquid crystal aligning agent containing at least two kinds of polymers and used for forming a liquid crystal alignment film of a transverse electric field type liquid crystal display device.

≪ Formula (A)

(In the formula (A), "*"

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

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

The liquid crystal aligning agent of the present invention provides a liquid crystal alignment film capable of achieving both a wide viewing angle characteristic and a high quality display when used in a liquid crystal display device of a transverse electric field system, and good afterimage and baking characteristics. Therefore, the transverse electric field type liquid crystal display device of the present invention including the liquid crystal alignment film formed of such a liquid crystal aligning agent has a wide viewing angle characteristic, a high quality display, good afterimage characteristic, and a good burning property, and is suitable for various liquid crystal display devices, , A portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, various monitors, and a liquid crystal television.

The liquid crystal aligning agent of the present invention comprises a polyamic acid obtained by reaction of a tetracarboxylic acid dianhydride with a diamine containing a structure represented by the above formula (A) and a compound having two amino groups, and a polyimide obtained by dehydration cyclization of the polyamic acid And at least one polymer selected from the group consisting of

<Polyamic acid>

The polyamic acid in the liquid crystal aligning agent of the present invention can be obtained by the reaction of a tetracarboxylic acid dianhydride with a diamine including a structure represented by the above formula (A) and a compound having two amino groups.

[Tetracarboxylic acid dianhydride]

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention include alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. .

Specific examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracar 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-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 dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene- 1,2,5,6-tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: Tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-fura 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro- Furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl- 5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b-hexahydro (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] , 9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3- furanyl) -naphtho [ , 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5- dioxotetrahydrofuranyl) Hexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1 ] Octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione), a compound represented by the following formula TI or T-II.

&Lt; Formula T-I >

&Lt; Formula T-II >

(In the formulas TI and T-II, R ¹ and R ³ are each a divalent organic group having an aromatic ring, R ² and R ⁴ are each a hydrogen atom or an alkyl group, and a plurality of R ² and R ^4, Or may be different)

Specific examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic dianhydride and the like.

Specific examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride , 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4 '-Tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride , 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ' 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid (Triphenylphthalic acid) dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m- Diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate) Bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate) 2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate).

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

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention is preferably selected from the group consisting of alicyclic tetracarboxylic dianhydride and pyromellitic dianhydride in aromatic tetracarboxylic dianhydride, (Hereinafter referred to as "specific tetracarboxylic acid dianhydride") selected from the group consisting of dicarboxylic dianhydrides and non-phthalic dianhydrides.

Specific tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5- 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 5- 3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, cis-3,7-dibutylcycloocta-1,5-diene- 5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5,9b (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5, 9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) 2,3,4a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo- 3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride Water, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione) A compound represented by each of formulas T-1 to T-3, a compound represented by formula T-4, a pyromellitic dianhydride and a 4,4'-biphthalic dianhydride, 1, 3, 4-cyclobutane tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 - (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic dianhydride, Melitic acid dianhydride Water, and 4,4'-biphthalic acid dianhydride.

&Lt; Formula T-1 &

&Lt; Formula T-2 >

&Lt; Formula T-3 >

<Formula T-4>

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid contained in the liquid crystal aligning agent of the present invention contains at least 60 mol% of the above specific tetracarboxylic acid dianhydride with respect to the total tetracarboxylic acid dianhydride , More preferably 80 mol% or more.

[Diamine]

The diamine used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention includes the compound represented by the above formula (A) and the compound having two amino groups (hereinafter referred to as "compound (A)"). As such a compound (A), for example, a compound represented by the following formula (A-1) can be mentioned.

&Lt; Formula (A-1) >

(Wherein, in the formula (A-1), U is an alkylene group having 2 to 6 carbon atoms, a phenylene group, a naphthalenylene group, a cyclohexylene group, a pyrimidinylene group or a triazylene group, And a plurality of U's may be the same or different,

Specific examples of the U in the formula (A-1) include a 1,3-propylene group, a 1,4-cyclohexylene group, a 1,4-phenylene group, a naphthalene- A 2,5-diyl group, and a triazine-2,4-diyl group.

Specific examples of the compound represented by the above formula (A-1) include N, N'-bis (3-aminopropyl) piperazine, N, N'- (4-aminophenyl) piperazine, among which N, N'-bis (4-aminophenyl) piperazine is preferable.

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

Examples of other diamines usable in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, '-Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3 , 3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2- Bis (4-aminophenoxy) benzene, 1,3-bis (4-amino (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis 4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro- -Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '- Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] propane diisocyanate, Bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] Aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, represented by the following formulas D-1 and D-2, respectively, An aromatic diamine such as a compound represented by the formula

<Formula D-1>

<Formula D-2>

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

But are not limited to, 1,4-diaminocyclohexane, 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, , Isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 ^2,7 ] undecylenediimethyl diamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bis Methyl) cyclohexane; alicyclic or alicyclic diamines such as methylcyclohexane;

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, Aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3,5-diaminophenyl) 3-jade A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in the molecule, such as a compound represented by the following formula (D-I);

<Formula D-I>

(In the formula (DI), X is a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine and piperidine, R ⁵ is a divalent organic group , R ⁶ are each an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 3, and a plurality of Xs present may be the same or different, and when a plurality of R ^{6 s} exist, they are the same or different May be)

A diaminoorganosiloxane such as a compound represented by the following formula (D-II), and the like.

<Formula D-II>

(In the formula (D-II), R ⁷ is a hydrocarbon group of 1 to 12 carbon atoms, plural R ^{7 s} may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20 Integer)

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

The benzene ring of the aromatic diamine may be substituted with one or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). R ⁶ in the above formula (DI) is preferably a methyl group, and a is preferably 0 or 1, and more preferably 0.

Preferred among these diamines are aromatic diamines such as p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,7 Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) benzene, Phenyl, 1,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 1- -1-methyl-1H-inden-5-amine or a compound represented by the above formula (D-1) or (D-2);

1,4-cyclohexanediamine or 4,4'-methylenebis (cyclohexylamine) in the alicyclic diamine;

A compound represented by the following formula (D-3) among the compounds represented by the above formula (D-I);

And 1,3-bis (3-diaminopropyl) tetramethyldisiloxane among the compounds represented by the above formula (D-II).

<Formula D-3>

The diamine used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention preferably contains 1 mol% or more, more preferably 10 mol% or more, of the compound (A) based on the total diamine, By mole to 80% by mole, particularly preferably from 15 to 50% by mole.

The diamine used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention preferably contains an aromatic diamine in addition to the compound (A). In addition to the compound (A) and the aromatic diamine, It is more preferable to include a compound.

When the diamine used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention contains an aromatic diamine, the proportion thereof is preferably 20 to 99 mol%, more preferably 50 to 90 mol% , More preferably 50 to 85 mol%.

When the diamine used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention contains the compound represented by the above formula (D-II), the use ratio thereof is preferably 0.1 to 10 mol% , More preferably 8 mol%, still more preferably 3 mol% to 7 mol%.

[Synthesis of polyamic acid]

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

The ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic dianhydride is from 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine, The ratio is 0.7 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent at a temperature of preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C, preferably for 1 to 72 hours, more preferably 3 to 48 Time. Here, the organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, Amide compounds such as 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide and 3-hexyloxy- Nonpolar compounds such as butyrolactone, tetramethyl urea, and hexamethylphosphoric triamide; phenol compounds such as m-cresol, xylenol, phenol, halogenated phenol, and the like. The amount of the organic solvent (α: when the organic solvent and the following poor solvent are used in combination, the total amount thereof is referred to) is usually such that the total amount (β) of the tetracarboxylic acid dianhydride and the diamine is + &lt; RTI ID = 0.0 &gt; β). &lt; / RTI &gt;

Alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons generally known as poor solvents of polyamic acid may be added to 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 methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, But are not limited to, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, Diethyl malonate, diethyl malonate, diethyl 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, Benzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate and diisopentyl ether.

When the organic solvent and the poor solvent as described above are used in combination, the amount of the poor solvent to be used can be appropriately set within a range in which the polyamic acid to be produced does not precipitate, but is preferably 30% by weight or less based on the total amount of the solvent, % Or less.

In this way, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be used as it is for preparing a liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and used for the preparation of a liquid crystal aligning agent, or after the isolated polyamic acid is purified, . The isolation of the polyamic acid can be carried out by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or by a method of distilling off the reaction solution under reduced pressure using an evaporator. Alternatively, the polyamic acid can be purified by a method of dissolving the polyamic acid in an organic solvent, followed by precipitation with a poor solvent, or a step of distillation under reduced pressure using an evaporator once or several times.

<Polyimide>

The polyimide of the liquid crystal aligning agent of the present invention can be obtained by dehydrating and ring closure of the above-mentioned polyamic acid to imidize it.

The polyimide contained in the liquid crystal aligning agent of the present invention may be a completely imidized compound in which all of the amic acid structure possessed by the polyamic acid as a precursor thereof is dehydrated and cyclized and only a part of the amic acid structure is subjected to dehydration ring closure, And an imide ring structure in which an imidazole ring structure coexists.

The imide ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is preferably 40% or more, more preferably 50 to 90%. By using polyimide having an imidization rate of 40% or more, a liquid crystal aligning agent capable of forming a liquid crystal alignment film having a shorter afterglow erase time can be obtained.

The imidization ratio is expressed as a percentage of the ratio of the number of imide ring structures to the total number of amide structure and imide ring structure of polyimide. At this time, a part of the imide ring may be an isoimide ring. The imidization rate can be measured by dissolving the polyimide in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and measuring ¹ H-NMR at room temperature (for example, 25 ° C) using tetramethylsilane as a reference From the measured results, it can be obtained by the following formula (1).

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

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

The dehydration ring-closure of the polyamic acid is preferably carried out by heating the polyamic acid (i), 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 占 폚, more preferably 60 to 170 占 폚. The reaction time is preferably 1 to 8 hours, more preferably 3 to 5 hours. If the reaction temperature is less than 50 캜, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered.

On the other hand, in the method (ii) of adding the dehydrating agent and the dehydrating ring-closing catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic acid anhydride or trifluoro acetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the amic acid structure of the polyamic acid although it differs depending on the intended imidization ratio. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The imidization rate can be increased as the amount of the dehydrating agent and the dehydrating ring closure agent used is larger. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1 to 8 hours, more preferably 3 to 5 hours.

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

[Polymer of terminal modified type]

The polyamic acid or polyimide that may be contained in the liquid crystal aligning agent of the present invention may be a polymer of a terminal modified type having a controlled molecular weight. By using the polymer of the terminal modified type, the coating property and the like of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention. Such a terminal modified polymer can be produced by adding a molecular weight regulator to a 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 anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride and n-hexadecylsuccinic anhydride. have. 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 10 parts by weight or less, based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and diamine used in synthesizing the polyamic acid.

[Solution viscosity]

The polyamic acid or polyimide thus obtained preferably has a solution viscosity of 20 to 800 mPa 으로 when it is a 10 wt% solution, more preferably a solution viscosity of 30 to 500 mPa 바람직 Do.

The solution viscosity (mPa.s) of the polymer is preferably 10% by weight of a polymer solution prepared by using a good solvent for the polymer (for example,? -Butyrolactone, N-methyl-2-pyrrolidone or the like) Measured at 25 캜 using an E-type rotational viscometer.

<Other ingredients>

The vertical alignment type liquid crystal alignment film of the present invention contains at least one polymer selected from the group consisting of polyamic acid as described above and polyimide obtained by dehydration cyclization thereof as an essential component but may contain other components as necessary . Examples of such other components include other polymers and adhesiveness improvers.

[Other Polymers]

The other polymer may be used for improving solution properties and electrical properties. Such other polymer is a polymer other than polyimide obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing the compound (A) and a polyimide obtained by dehydration cyclization of the polyamic acid, for example, a tetracarboxylic acid dianhydride (Hereinafter referred to as "other polyamic acid"), a polyimide obtained by dehydration cyclization of the polyamic acid (hereinafter referred to as "other polyimide "), a polyamic acid obtained by reacting a diamine containing no compound Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylate, and the like can be given as examples of the poly (amic acid) ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative. Of these, other polyamic acids or other polyimides are preferred.

The tetracarboxylic acid dianhydride used for synthesizing another polyamic acid or other polyimide is preferably a tetracarboxylic acid dianhydride used for synthesizing polyamic acid or polyimide which is an essential component of the liquid crystal aligning agent of the present invention, And the like. Among them, alicyclic tetracarboxylic acid dianhydride is preferable, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride is particularly preferable. The tetracarboxylic acid dianhydride used for synthesizing another polyamic acid or other polyimide preferably contains at least 30 mol% of the alicyclic tetracarboxylic acid dianhydride with respect to the total tetracarboxylic dianhydride, Mol% or more.

Examples of the diamine used for synthesizing another polyamic acid or other polyimide are the same as those exemplified above as other diamines which can be used for synthesizing polyamic acid or polyimide which is an essential component of the liquid crystal aligning agent of the present invention have. Among them, it is preferable to contain an aromatic diamine. Particularly preferred are aromatic diamines such as p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethylene, 2,2'-trifluoromethyl- 4,4'-diaminobiphenyl, and 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine. The diamine used for synthesizing another polyamic acid or another polyimide preferably contains an aromatic diamine in an amount of 5 mol% or more, more preferably 10 mol% or more, relative to the total diamine.

Other polyamic acid and other polyimides can be synthesized in accordance with those described above as methods for synthesizing polyamic acid or polyimide, which are essential components of the liquid crystal aligning agent of the present invention.

The polyamic acid obtained by reacting the tetracarboxylic dianhydride and the diamine containing the compound (A) in the case where the liquid crystal aligning agent of the present invention contains other polymer and the polyimide obtained by dehydrating and ring closure of the polyamic acid , The total amount of the polymer (polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound (A), polyimide obtained by dehydrating and ring-closure of the polyamic acid, and others Polymer is the same as the total amount of the polymer), it is preferably at least 1% by weight, more preferably from 3 to 50% by weight, and particularly preferably from 5 to 45% by weight.

[Adhesiveness improver]

The above adhesiveness improver can be used for the purpose of improving the adhesiveness of the obtained liquid crystal alignment film to the substrate surface. Examples of such an adhesion improver include a compound having at least one epoxy group in the molecule (hereinafter referred to as an "epoxy compound"), a functional silane compound, and the like.

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-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane , 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, and the like.

The use ratio of the epoxy compound as described above is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the polymer.

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-triethoxysilylpropyl triethylenetriamine, 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-benzyl-3-aminopropyl trimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.

The amount of the functional silane compound used is preferably 2 parts by weight or less, more preferably 0.01 to 0.2 parts by weight 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 selected from the group consisting of a polyamic acid obtained by the reaction of the tetracarboxylic dianhydride and the diamine containing the compound (A) as described above and a polyimide dehydrated and cyclized with the polyamic acid One or more polymers and optionally other additives optionally blended are preferably dissolved and contained in an organic solvent.

Examples of the organic solvent usable in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxypropionate, ethylene glycol methyl ether, N-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide and 3-hexyloxy-N, N-dimethylpropanamide.

The solid concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., To 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and preferably, when heated, forms a coating film which becomes a liquid crystal alignment film. However, when the solid concentration is less than 1% by weight, On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large and a good liquid crystal alignment film can not be obtained, the viscosity of the liquid crystal aligning agent is increased and the coating property is lowered do.

Particularly preferable ranges of the solid concentration are different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 wt%. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9% by weight and the solution viscosity is in the range of 12 to 50 mPa · s. 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.

The temperature for producing the liquid crystal aligning agent of the present invention is preferably 0 to 200 캜, more preferably 20 to 60 캜.

The liquid crystal aligning agent of the present invention obtained as described above can be preferably used for forming a liquid crystal alignment layer of a liquid crystal display element of a transverse electric field system in particular.

&Lt; Transverse electric field type liquid crystal display element &

The transverse electric field type 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 transverse electric field type liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3).

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

Here, as the substrate, a conductive film formation surface of a substrate provided with a transparent conductive film patterned in a comb-like pattern and a substrate on which a conductive film not opposed thereto is used as a pair, and a transparent conductive film The liquid crystal aligning agent of the present invention is preferably applied by a roll coater method, a spinner method, or an inkjet printing method on a surface of a substrate on which a film is provided and a surface of a substrate on which a conductive film is not provided (opposed substrate) , And then each coating surface is heated to form a coating film.

Examples of the material constituting the substrate include glass such as float glass and soda glass; And plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin). Examples of the transparent conductive film provided on one surface of one substrate include a NESA film containing tin oxide (SnO ₂ ) (US PPG company registered trademark), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) An ITO film or the like can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a transparent conductive film without a pattern and then forming a pattern by photo-etching, a method of forming a mask having a desired pattern And the like. When applying the liquid crystal aligning agent, a functional silane compound, a functional titanium compound and the like are previously coated on the surface of the substrate surface on which the coating film is to be formed, in order to further improve adhesion between the substrate surface and the transparent conductive film and the coating film A pretreatment may be performed.

The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes. The film thickness of the formed coating film is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

The liquid crystal aligning agent of the present invention forms a coating film that becomes an alignment film by removing the organic solvent after coating as described above. However, when the liquid crystal aligning agent of the present invention contains a polyamic acid or a polyimide having an imide ring structure and an amic acid structure , A further dehydrated ring closure reaction may be carried out by further heating after forming a coating film to make a more imaged coating film.

(2) Then, the coating film surface formed as described above is subjected to rubbing treatment in which the cloth is rubbed in a predetermined direction, for example, a roll of cloth made of fibers such as nylon, rayon or cotton. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

The liquid crystal alignment film formed as described above is also disclosed in, for example, Patent Document 4 (Japanese Patent Application Laid-Open No. 6-222366) and Patent Document 5 (Japanese Patent Application Laid-Open No. 6-281937) A process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film as described above with ultraviolet rays and a process of changing the pretilt angle of a part of the liquid crystal alignment film as disclosed in Japanese Patent Application Laid-open No. 5-107544 A process of forming a resist film on a part of the surface of the same liquid crystal alignment film and then rubbing treatment in a direction different from the rubbing treatment performed previously is performed to remove the resist film so that the liquid crystal alignment film has a liquid crystal aligning ability different for each region, It is possible to improve the field of view characteristics.

(3) A liquid crystal cell is manufactured by arranging liquid crystals in a gap between a pair of substrates on which a liquid crystal alignment film is formed as described above. At this time, the liquid crystal alignment layers of the two substrates face each other, and the rubbing directions of the respective liquid crystal alignment layers are arranged orthogonally or inversely. In order to produce a liquid crystal cell, for example, the following two methods can be mentioned.

The first method is a conventionally known method. First, two substrates are opposed to each other with a gap (cell interval) 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, and the cell gap The liquid crystal cell can be manufactured by sealing the injection hole after filling and filling the liquid crystal in the liquid crystal cell.

The second method is a method called ODF (One Drop Fill) method. An ultraviolet 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 the liquid crystal is dropped on the liquid crystal alignment film surface and then the other substrate is bonded so that the liquid crystal alignment film is opposed And then irradiating ultraviolet light to the entire surface of the substrate to cure the sealing agent, thereby manufacturing a liquid crystal cell.

In any of the above-described first and second methods, it is preferable that the liquid crystal cell is subsequently heated to a temperature at which the liquid crystal used is isotropic, and then gradually cooled to room temperature to remove the liquid crystal alignment.

Further, by bonding the polarizing plate to the outer surface of the liquid crystal cell, the liquid crystal display device of the transverse electric field system of the present invention can be obtained.

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

Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, a nematic liquid crystal is preferable. Examples thereof include Schiff salt mechanical liquid crystal, agar watch liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, 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. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck); and a ferroelectric liquid crystal such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate.

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 polyvinyl alcohol is sandwiched between cellulose acetate protective films or a polarizing plate made of H film itself can be given.

<Examples>

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

In the following Synthesis Examples, N, N'-bis (4-aminophenyl) piperazine was commercially available from Wakayama Seika Kogyo Co., Ltd.

In addition, the solution viscosities of the polymers in the respective synthesis examples were values measured at 25 캜 using an E-type viscometer.

<Synthesis of polyimide>

Synthesis Example 1

(1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 40.5 g (0.38 mol) of p-phenylenediamine as diamine, 1- (4-aminophenyl) 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 12.4 g (0.050 mol) of 3,3 '- (tetramethyldisiloxane 1,3- 100.5 g (0.375 mol) of N, N'-bis (4-aminophenyl) piperazine was dissolved in 2,440 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to give a solution containing polyamic acid . A small amount of the obtained polyamic acid solution was diluted by addition of N-methyl-2-pyrrolidone, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10% by weight, and the viscosity of the solution was 75 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 (pyridine and acetic anhydride used in the imidization reaction were removed from the system by this operation, the same applies hereinafter) To obtain 2,500 g of a solution containing 15% by weight of polyimide (A-1) having an imidization rate of about 51%. A small amount of this solution was collected and the solution viscosity was measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone, and the solution viscosity was 25 mPa..

Synthesis Example 2

(1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 40.5 g (0.38 mol) of p-phenylenediamine as diamine, 1- (4-aminophenyl) 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 16.0 g (0.050 mol) of 2,2'- 100.5 g (0.375 mol) of N'-bis (4-aminophenyl) piperazine was dissolved in 2,460 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by addition of N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 60 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution 2500 containing 15% by weight of polyimide (A-2) g. A small amount of this solution was collected and the solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding N-methyl-2-pyrrolidone to obtain 22 mPa 占 퐏.

Synthesis Example 3

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 35 g (0.33 mole) of p-phenylenediamine as diamine, 1- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 23 g (0.1 mol) of 4,4'-diaminodiphenylmethane, (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine were added to 2,460 g of N-methyl-2-pyrrolidone And the mixture was reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10% by weight, and the viscosity of the solution was 70 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution 2500 containing 15% by weight of polyimide (A-3) having an imidization rate of about 50% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone to obtain 24 mPa..

Synthesis Example 4

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 35 g (0.33 mole) of p-phenylenediamine as diamine, 1- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 23 g (0.1 mol) of 4,4'- diaminodiphenylmethane and 2,2'- , 16.0 g (0.050 mol) of 4'-diaminobiphenyl and 87.1 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine were dissolved in 2,460 g of N-methyl- , And reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 58 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a 2,600 solution containing 15% by weight of polyimide (A-4) having an imidization rate of about 53% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0% by weight by adding a small amount of this solution and adding N-methyl-2-pyrrolidone was 21 mPa.s.

Synthesis Example 5

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 35 g (0.33 mole) of p-phenylenediamine as diamine, 1- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 20 g (0.1 mol) of 4,4'- diaminodiphenyl ether, 3,3 '- (tetramethyldisiloxane 1 (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine were added to 2,450 g of N-methyl-2-pyrrolidone And the mixture was reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 73 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution containing 2,600 (weight%) of a polyimide (A- g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone was 26 mPa 占 퐏.

Synthesis Example 6

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride as tetracarboxylic dianhydrides and 35 g (0.33 mol) of p-phenylenediamine 53.2 g (0.20 mol) of 4,4'-diaminodiphenylmethane and 23 g (0.1 mol) of 4,4'-diaminodiphenylmethane were added thereto, (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine and 16.0 g (0.050 mol) of 2,2'-trifluoromethyl-4,4'- Methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity was 59 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a 2,600 solution containing 15% by weight of polyimide (A-6) having an imidization rate of about 51% g. A small amount of this solution was collected and the solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding N-methyl-2-pyrrolidone to obtain 22 mPa 占 퐏.

Synthesis Example 7

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride as tetracarboxylic dianhydrides and 35 g (0.33 mol) of p-phenylenediamine 53.2 g (0.20 mole) of 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 20 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine and 16.0 g (0.050 mol) of 2,2'-trifluoromethyl-4,4'- Methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by addition of N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 60 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution containing 15% by weight of a polyimide (A-7) having an imidization rate of about 51% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone to obtain 24 mPa..

Synthesis Example 8

(0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 1,3-dihydroxy-8-methyl-5- (tetra 32.0 g (0.10 mol) of p-phenylenediamine, 35 g (0.33 mol) of p-phenylenediamine as diamine, , 53.2 g (0.20 mol) of l- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 23 g (0.1 mol) of 4,4'- diaminodiphenylmethane, (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine and 16.0 g (0.050 mol) of 2'-trifluoromethyl-4,4'- Dissolved in 2,530 g of 2-pyrrolidone, and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 58 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution containing 2,600 g of a polyimide (A-8) having an imidization rate of about 51% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone to obtain 23 mPa..

Synthesis Example 9

(0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 1,3-dihydroxy-8-methyl-5- (tetra 32.0 g (0.10 mol) of p-phenylenediamine, 35 g (0.33 mol) of p-phenylenediamine as diamine, , 53.2 g (0.20 mol) of 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 20 g (0.1 mol) of 4,4'- (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine and 16.0 g (0.050 mol) of 2'-trifluoromethyl-4,4'- Dissolved in 2,530 g of 2-pyrrolidone, and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and diluted by addition of N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 56 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution containing 2,600 g of a polyimide (A-8) having an imidization rate of about 51% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0% by weight by adding a small amount of this solution and adding N-methyl-2-pyrrolidone was 21 mPa.s.

&Lt; Synthesis of other polyamic acid >

Synthesis Example 10

As the tetracarboxylic acid dianhydride, 196 g (0.90 mol) of pyromellitic dianhydride and 19.6 g (0.10 mol) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride were added, and p-phenylenediamine 22 180 g (0.80 mol) of 4,4'-diaminodiphenyl ether were dissolved in 2,400 g of NMP and the reaction was carried out at 60 DEG C for 4 hours to obtain polyamic acid (B-1) % &Lt; / RTI &gt; The solution viscosity of this polyamic acid solution was 200 mPa..

&Lt; Synthesis of other polyimide >

Synthesis Example 11

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 81 g (0.75 mole) of p-phenylenediamine as diamine, 1- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine and 12.4 g (0.050 mol) of 3,3 '- (tetramethyldisiloxane 1,3- Dissolved in 2,440 g of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and diluted with N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 73 mPa 占 퐏.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution 2,500 g of 15% by weight of a polyimide (A-10) having an imidization rate of about 51% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone to obtain 23 mPa..

Synthesis Example 12

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, 81 g (0.75 mole) of p-phenylenediamine as diamine, 1- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine and 16.0 g (0.050 mol) of 2,2'-trifluoromethyl-4,4'- Methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by addition of N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 60 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution 2,500 g of a solution containing 15% by weight of polyimide (A-11) g. A small amount of this solution was collected and the solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding N-methyl-2-pyrrolidone to obtain 22 mPa 占 퐏.

Synthesis Example 13

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 35 g (0.33 mole) of p-phenylenediamine as diamine, 1- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 96 g (0.425 mol) of 4,4'- diaminodiphenylmethane, and 3,3'- (tetramethyldisiloxane 1 , 3-diyl) bis (propylamine) was dissolved in 2,460 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10% by weight, and the viscosity of the solution was 70 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution 2,500 g of 15% by weight of polyimide (A-12) g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone to obtain 24 mPa..

Synthesis Example 14

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 35 g (0.33 mole) of p-phenylenediamine as diamine, 1- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 96 g (0.425 mol) of 4,4'- diaminodiphenylmethane and 2,2'- (0.050 mol) of 4'-diaminobiphenyl were dissolved in 2,460 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 58 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution containing 15% by weight of a polyimide (A-13) having an imidization rate of about 53% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0% by weight by adding a small amount of this solution and adding N-methyl-2-pyrrolidone was 21 mPa.s.

Synthesis Example 15

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 35 g (0.33 mole) of p-phenylenediamine as diamine, 1- (4-aminophenyl) 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 85 g (0.425 mol) of 4,4'- diaminodiphenyl ether and 3,3'- (tetramethyldisiloxane 12.4 g (0.050 mol) of 1,3-diyl) bis (propylamine) was dissolved in 2,450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 71 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution containing 2,600 of polyimide (A-14) having an imidization rate of about 54% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone to obtain 24 mPa..

Synthesis Example 16

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride as tetracarboxylic dianhydrides and 35 g (0.33 mol) of p- 53.2 g (0.20 mol) of 4,4'-diaminodiphenylmethane, 96 g (0.425 mol) of 4,4'-diaminodiphenylmethane, And 16.0 g (0.050 mol) of 2,2'-trifluoromethyl-4,4'-diaminobiphenyl were dissolved in 2,450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours, A solution containing a mixed acid was obtained. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10% by weight, and the viscosity of the solution was 57 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution containing 15% by weight of a polyimide (A-15) having an imidization rate of about 51% g. A small amount of this solution was collected, and the solution viscosity was measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone to obtain a solution viscosity of 20 mPa.s.

Synthesis Example 17

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride as tetracarboxylic dianhydrides and 35 g (0.33 mol) of p-phenylenediamine 53.2 g (0.20 mol) of 4,4'-diaminodiphenyl ether, 85 g (0.425 mol) of 4,4'-diaminodiphenyl ether, And 16.0 g (0.050 mol) of 2,2'-trifluoromethyl-4,4'-diaminobiphenyl were dissolved in 2,450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours, To obtain a solution containing a mixed acid. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 58 mPa..

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution having a imidization rate of about 50% and a polyimide (A-16) g. A small amount of this solution was collected and the solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding N-methyl-2-pyrrolidone to obtain 22 mPa 占 퐏.

Synthesis Example 18

(0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 1,3-dihydroxy-8-methyl-5- (tetra 32.0 g (0.10 mol) of p-phenylenediamine, 35 g (0.33 mol) of p-phenylenediamine as diamine, 53.2 g (0.20 mol) of 4,4'-diaminodiphenylmethane, 96 g (0.425 mol) of 4,4'-diaminodiphenylmethane and 2 g 16.0 g (0.050 mol) of 2'-trifluoromethyl-4,4'-diaminobiphenyl was dissolved in 2,530 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain polyamic acid Was obtained. A small amount of the obtained polyamic acid solution was collected and diluted by addition of N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 56 mPa.s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a solution having a imidization rate of about 51% and a polyimide (A-17) g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0% by weight by adding a small amount of this solution and adding N-methyl-2-pyrrolidone was 21 mPa.s.

Synthesis Example 19

(0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 1,3-dihydroxy-8-methyl-5- (tetra 32.0 g (0.10 mol) of p-phenylenediamine, 35 g (0.33 mol) of p-phenylenediamine as diamine, 53.2 g (0.20 mol) of 4,4'-diaminodiphenyl ether, 85 g (0.425 mol) of 4,4'-diaminodiphenyl ether and 2 g 16.0 g (0.050 mol) of 2'-trifluoromethyl-4,4'-diaminobiphenyl was dissolved in 2,530 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain polyamic acid Was obtained. A small amount of the obtained polyamic acid solution was diluted by adding N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polyamic acid concentration of 10 wt% was 54 mPa s.

Next, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 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 and then concentrated to obtain a 2,600 solution containing 15% by weight of polyimide (A-18) having an imidization rate of about 51% g. The solution viscosity was measured as a solution having a polyimide concentration of 6.0 wt% by adding a small amount of this solution and adding N-methyl-2-pyrrolidone was 19 mPa..

Example 1

&Lt; Preparation of liquid crystal aligning agent &

A solution containing polyimide (A-1) obtained in Synthesis Example 1 in an amount corresponding to 20 parts by weight in terms of polyimide (A-1) and the polyamic acid (B-1) obtained in Synthesis Example 10 (B-1) were mixed in an amount corresponding to 80 parts by weight, and? -Butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve were mixed with? -Butyrolactone N, N ', N ' -tetra as an adhesive property enhancer was added so that the ratio of lactone: N-methyl-2-pyrrolidone: butyl cellosolve was 40:40:20 by weight. 2 parts by weight of glycidyl-4,4'-diaminodiphenylmethane was added to prepare a solution having a solid content concentration of 3.5 wt. This solution was sufficiently stirred, and then filtered using a filter having an opening diameter of 1 탆 to prepare a liquid crystal aligning agent.

&Lt; Production and Evaluation of Liquid Crystal Display Device >

Using the liquid crystal aligning agent prepared above, a liquid crystal display device was produced and evaluated as follows. Further, the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film of a transverse electric field type liquid crystal display device, but liquid crystal alignability and pretilt angle are replaced by producing and evaluating a liquid crystal display device having an anti-parallel alignment.

(1) Production of Liquid Crystal Alignment Property and Liquid Crystal Display Device for Evaluation of Pretilt Angle (Antiparallel Liquid Crystal Display Device)

The liquid crystal aligning agent prepared above was applied on a transparent conductive film containing an ITO film provided on one side of a glass substrate having a thickness of 1 mm under the conditions of a rotation number of 2,000 rpm and a rotation time of 20 seconds by using a spinner, To remove the solvent, thereby forming a coating film having a thickness of 0.08 mu m. The coating film was rubbed with a rubbing machine having a roll of rayon cloth rolled under the conditions of a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair embroidering length of 0.4 mm Thereby giving a liquid crystal aligning ability to the coating film, thereby forming a liquid crystal alignment film. The substrate having this liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes.

By repeating these series of operations, two substrates (one pair) having liquid crystal alignment films were produced.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the respective outer edge portions of the substrate having the liquid crystal alignment film of the pair of liquid crystal alignment films, and then the liquid crystal alignment film surfaces were superimposed on each other so as to face each other, And cured. Subsequently, a nematic liquid crystal (MLC-2019, manufactured by Merck & Co., Inc.) showing positive values of anisotropy of dielectric constant was charged between the substrates from the liquid crystal injection port, the liquid crystal injection hole was sealed with an acrylic light curing adhesive, To prepare a liquid crystal display element having an anti-parallel alignment.

(2) Evaluation of liquid crystal alignment property

When the liquid crystal display device manufactured as described above was observed with an optical microscope, it was evaluated that the liquid crystal aligning property "good" and the liquid crystal aligning property "poor" were observed in which the light leakage was not observed. The liquid crystal alignment property was "good ".

(3) Evaluation of Pretilt Angle

The pretilt angle at room temperature of the liquid crystal display device manufactured as described above was measured by the Senarmont method. When the value was less than 1.5, the pretilt angle was evaluated as "good" and when it was 1.5 or more, the pretilt angle was evaluated as "defective ", and the value of the pretilt angle of the liquid crystal display element was evaluated as" good ".

(4) Manufacture of a liquid crystal display element (transverse electric field type liquid crystal display element) for evaluation of residual image characteristics

In the production of the antiparallel alignment liquid crystal display element, a glass substrate having two lines of a comb-shaped transparent conductive film pattern including chrome and a glass substrate having no transparent conductive film are used as a pair, and a transparent conductive film having a comb- A transverse electric field type liquid crystal display device was produced in the same manner as in the production of the antiparallel alignment liquid crystal display device except that the liquid crystal aligning agent was applied on the transparent conductive film of the substrate and one side of the other substrate.

FIG. 1 is a schematic view showing a structure of a transparent electrode pattern on the glass substrate.

The two types of transparent conductive film patterns of the transverse electric field type liquid crystal display device manufactured as described above are hereinafter referred to as "electrode (A)" and "electrode (B)", respectively.

(5) Evaluation of afterimage characteristic

A voltage of 3.5 V for an AC voltage and a voltage of 5 V for a DC voltage was applied to the electrode (A) for 2 hours without applying a voltage to the electrode (B) under the environment of 25 캜 and 1 atm. Respectively. Immediately thereafter, a voltage of 4 V of alternating current was applied to both the electrode (A) and the electrode (B). The time from when the application of the voltage of 4 V of alternating current to both the electrodes was started until the difference in light transmittance between the electrodes A and B was eliminated was measured. When the time was 500 seconds or less, the afterimage characteristic was evaluated as "good ", and the afterimage characteristic of the transverse electric field type liquid crystal display element was evaluated as" good ".

Examples 2 to 18 and Comparative Examples 1 to 18

The same procedure as in Example 1 was carried out except that the solution containing the polymer of the type shown in Table 1 was used as the solution containing the polymer and only the amount corresponding to the amount described in Table 1 was used in terms of the polymer contained therein A liquid crystal aligning agent was prepared, and a liquid crystal display element was produced and evaluated. The results are shown in Table 1.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the configuration of two transparent conductive film patterns of a transverse electric field type liquid crystal display device manufactured for evaluation of afterimage characteristics in Examples and Comparative Examples; FIG.

Claims (8)

A polyamic acid obtained by reaction of a tetracarboxylic acid dianhydride with a diamine containing a structure represented by the following formula (A) and a compound having two amino groups, and a polyimide obtained by dehydration cyclization of the polyamic acid A first polymer having a number of species or more, and A polyamic acid obtained by reaction of a tetracarboxylic acid dianhydride with a diamine not containing a compound represented by the formula (A) and a compound having two amino groups, and polyimide dehydrated and cyclized with the polyamic acid At least one second polymer And is used for forming a liquid crystal alignment film of a liquid crystal display element. &Lt; Formula (A)

(In the formula (A), "*" The liquid crystal aligning agent according to claim 1, wherein the compound represented by the formula (A) and the compound having two amino groups is a compound represented by the following formula (A-1). &Lt; Formula (A-1) >

(Wherein, in the formula (A-1), U is an alkylene group having 2 to 6 carbon atoms, a phenylene group, a naphthalenylene group, a cyclohexylene group, a pyrimidinylene group or a triazylene group, And a plurality of U's may be the same or different, The method according to any one of claims 1 to 3, wherein the diamine used for synthesizing the first polymer further comprises at least one selected from aromatic diamines in addition to the compound having a structure represented by the above formula (A) and two amino groups And a liquid crystal alignment agent. 4. The liquid crystal aligning agent according to claim 3, wherein the diamine used for synthesizing the first polymer further comprises a compound represented by the following formula (D-II). <Formula D-II>

(In the formula (D-II), R ⁷ is a hydrocarbon group of 1 to 12 carbon atoms, plural R ^{7 s} may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20 Integer) 3. The method according to claim 1 or 2, wherein the tetracarboxylic dianhydride used for synthesizing the first polymer is 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3,3a, (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 2, , 3,5-tricarboxycyclopentylacetic acid dianhydride, pyromellitic acid dianhydride, and 4,4'-biphthalic dianhydride. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent according to any one of claims 1 to 3. The liquid crystal alignment agent according to claim 1, wherein the liquid crystal display element is a transverse electric field system. delete

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