KR20100031078A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to form a liquid crystal alignment film enabling wide viewing angle, high definition, and good afterimage characteristic in an in-plane switching mode liquid crystal display device. CONSTITUTION: A liquid crystal alignment agent used for forming a liquid crystal alignment film of a liquid crystal display device comprises at least one kind of a polymer selected from the group consisting of polyamic acid and polyimide in which the polyamic acid is dehydrated and ring-closed. The polyamic acid is obtained by reaction of tetracarboxylic dianhydride with diamine consisting of a compound with two amino groups and a structure represented by chemical formula A.

Description

Liquid crystal aligning agent and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, the liquid crystal aligning agent which is preferably used for forming the liquid crystal aligning film of a transverse electric field type liquid crystal display element, the afterimage characteristic, the baking characteristic is excellent, and relates to the transverse electric field type liquid crystal display element which can display high quality. will be.

In a transverse electric field type liquid crystal display device in which electrodes are formed only on one side of a pair of opposed substrates, 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 it has a wide viewing angle characteristic compared with the conventional liquid crystal display element of the conventional electric field system, and is capable of high quality display. The liquid crystal display element of such a transverse electric field system is described in patent document 1, 2, and nonpatent literature 1, for example. Since the transverse electric field type liquid crystal display element responds to the electric field only in the direction parallel to the substrate, the change in the refractive index in the long axis direction of the liquid crystal molecule is not a problem, and the contrast that is visible to the observer even when the time is changed Since there is little change in the color tone of the display, high quality display is possible regardless of the time of day. In order to obtain such an advantageous effect, since it is advantageous that the incident angle dependence of incident polarization is small, the transverse electric field type liquid crystal display element is required to have a low pretilt angle in the initial orientation characteristic at the time of no electric field application.

However, in a transverse electric field type liquid crystal display element, since afterimage and burn-in may become a problem, the improvement is calculated | required. Accordingly, Patent Document 3 proposes a method of improving the afterimage characteristic and the baking characteristic by using a liquid crystal alignment film made of a polymer containing an aromatic structure in a large proportion. However, the use of the liquid crystal alignment film containing a large proportion of the aromatic structure inevitably increases the pretilt angle, thereby reducing the advantageous effects as described above in the transverse electric field display device.

The liquid crystal display element which can fully express the above advantageous effects in the transverse electric field type liquid crystal and exhibits the improved afterimage characteristic and baking characteristic is not known, and the provision of such a liquid crystal aligning agent is strongly It is requested.

[Patent Document 1] US Patent US005928733A

[Patent Document 2] Japanese Unexamined Patent Application Publication No. 56-91277

[Patent Document 3] Japanese Patent Application Laid-Open No. 2008-15497

[Patent Document 4] Japanese Unexamined Patent Publication No. 6-222366

[Patent Document 5] Japanese Unexamined Patent Publication No. 6-281937

[Patent Document 6] Japanese Patent Application Laid-Open No. 5-107544

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

This invention is made | formed in view of the above-mentioned situation, The objective is the liquid crystal which provides the liquid crystal aligning film which enables both a wide viewing angle characteristic and high quality display, favorable afterimage characteristic, and baking characteristic in a transverse electric field liquid crystal display element. It is in providing an aligning agent.

Another object of the present invention is to provide a transverse electric field type liquid crystal display device in which a wide viewing angle characteristic, high quality display, good afterimage characteristics and baking characteristics are compatible.

Still other objects and advantages of the present invention are apparent from the following description.

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

1 selected from the group consisting of a polyamic acid obtained by reaction of a tetracarboxylic dianhydride with a diamine containing a structure represented by the following formula (A) and a compound having two amino groups and a polyimide dehydrated and closed with the polyamic acid It contains at least a polymer and is achieved by a liquid crystal aligning agent used for forming a liquid crystal aligning film of a transverse electric field type liquid crystal display element.

<Formula A>

(In formula A, "*" shows a bond.)

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

It is achieved by the transverse electric field system liquid crystal display element provided with the liquid crystal aligning film formed from said liquid crystal aligning agent.

When used for the liquid crystal display element of a transverse electric field system, the liquid crystal aligning agent of this invention provides the liquid crystal aligning film which enables both the wide viewing angle characteristic and display of high quality, and favorable afterimage characteristic and baking characteristic. Therefore, the transverse electric field type liquid crystal display element of this invention provided with the liquid crystal aligning film formed from such a liquid crystal aligning agent is a thing with both wide viewing angle characteristic, high quality display, favorable afterimage characteristic, and baking characteristic, and various liquid crystal display elements, for example, a clock It can be suitably applied as a liquid crystal display element used for display apparatuses, such as a portable game, a word processor, a notebook computer, a vehicle navigation system, a camcorder, a PDA, a digital camera, a mobile telephone, various monitors, and a liquid crystal television.

The liquid crystal aligning agent of this invention is a polyamic acid obtained by reaction of tetracarboxylic dianhydride, the diamine containing the structure represented by the said Formula (A), and the compound which has two amino groups, and the polyimide which carried out the dehydration ring closure of the said polyamic acid. It contains at least one polymer selected from the group consisting of.

<Polyamic acid>

The polyamic acid in the liquid crystal aligning agent of this invention can be obtained by reaction of the tetracarboxylic dianhydride and the diamine containing the structure represented by the said Formula (A), and the compound which has two amino groups.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid in the liquid crystal aligning agent of this invention, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride are mentioned. Can be.

Specific examples of the alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutanetetracar Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic 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 dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dimu Aqueous, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro- 2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -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 -7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3, 3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 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) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1 ] Octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), the compound represented by following formula TI or T-II, etc. are mentioned.

<Formula T-I>

<Formula T-II>

(In formula TI and T-II, R <^1> and R <^3> is a divalent organic group which has an aromatic ring, respectively, R <^2> and R <^4> is a hydrogen atom or an alkyl group, respectively, and ^two or more R <^2> and R <^4> are the same Or may be different)

As a specific example of the said aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride etc. are mentioned, for example.

As a specific example of the said aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride, 4,4'- nonphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3, for example , 3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride , 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4 '-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic 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'-perfluoroisopropylidenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid Anhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (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 (anhydro trimellitate) , 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2, 2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate) etc. are mentioned.

These tetracarboxylic dianhydrides can be used individually by 1 type or in combination of 2 or more types.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention is pyromellitic dianhydride and 4,4 in alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. It is preferable to include one or more types (hereinafter, referred to as "specific tetracarboxylic dianhydride") selected from the group consisting of "-non-phthalic dianhydrides."

As specific tetracarboxylic dianhydride, 1, 2-, 3, 4- cyclobutane tetracarboxylic dianhydride, 1, 3- dimethyl- 1,2,3, 4- cyclobutane tetracarboxylic dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 5- (2, 5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2, 5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5,9b Hexahydro-5- (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) -na Earth [1,2-c] furan-1,3-dione, 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, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Water, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), among the compounds represented by the above formula TI Among the compounds represented by the formulas T-1 to T-3 and the compounds represented by the formula T-II, the compounds represented by the following formula T-4, pyromellitic dianhydride and 4,4'-biphthalic dianhydride It is preferable that it is 1 or more types chosen from the group which consists of, and especially 1,2,3,4-cyclobutanetetracarboxylic 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, fatigue Melitic Acid It is preferable that it is at least 1 sort (s) chosen from the group which consists of water and 4,4'-biphthalic dianhydride.

<Formula T-1>

<Formula T-2>

<Formula T-3>

<Formula T-4>

The tetracarboxylic dianhydride used for synthesizing the polyamic acid contained in the liquid crystal aligning agent of this invention contains 60 mol% or more of said specific tetracarboxylic dianhydride with respect to the total tetracarboxylic dianhydride. It is preferable to, and it is more preferable to contain 80 mol% or more.

[Diamine]

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

<Formula A-1>

In Formula A-1, U is a methylene group, a C2-C6 alkylene group, a phenylene group, a naphthalenylene group, a cyclohexylene group, a pyrimidinylene group, or a triazinylene group, respectively, n is a 1-5 Integer, and a plurality of U's may be the same or different.)

As a specific example of U in the said General formula A-1, it is a 1, 3- propylene group, a 1, 4- cyclohexylene group, a 1, 4- phenylene group, a naphthalene-1, 5- diyl group, pyrimidine-, for example. 2, 5- diyl group, a triazine-2, 4- diyl group, etc. are mentioned.

Specific examples of the compound represented by the formula (A-1) include N, N'-bis (3-aminopropyl) piperazine, N, N'-bis (4-aminocyclohexane) piperazine, N, N'-bis (4-aminophenyl) piperazine, etc. are mentioned, Among these, N, N'-bis (4-aminophenyl) piperazine is preferable.

As a diamine used for synthesize | combining the polyamic acid in the liquid crystal aligning agent of this invention, only a compound (A) may be used independently, and a compound (A) and other diamine may be used in combination.

As other diamine which can be used for this invention, it is p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenylethane, 4,4, for example. '-Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4 '-Diaminodiphenylether, 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'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4- Bis (4-aminophenoxy) benzene, 1,3-bis (4-amino Oxy) benzene, 1,3-bis (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-4,4'-diaminobiphenyl, 2,2' -Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyl Lenisopropylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] Hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -Octafluorobiphenyl, di (4-aminophenyl) benzidine, 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, formulas D-1 and D-2, respectively Aromatic diamines such as compounds represented by;

<Formula D-1>

<Formula D-2>

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

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane , Isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (amino Aliphatic or alicyclic diamines such as methyl) cyclohexane;

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-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-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3,5-diaminophenyl)- 3-jade Diamine which has two primary amino groups and nitrogen atoms other than the said primary amino group in molecule | numerators, such as a tadecyl succinimide and a compound represented by following formula (D-I);

<Formula D-I>

(Wherein 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, and R ⁵ is a divalent organic group) R ⁶ is each an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 3, and each of a plurality of X's may be the same or different, and when a plurality of R ⁶ 's are present, they may be the same or different. Can be)

Diamino organosiloxane, such as a compound represented by following formula (D-II), etc. are mentioned.

<Formula D-II>

(In formula (D-II), R <^7> is a C1-C12 hydrocarbon group, respectively, two or more R <^7> may be same or different, respectively, p is an integer of 1-3, q is 1-20 Integer)

These diamines can be used individually or in combination of 2 or more types.

The benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). It is preferable that R <^6> in said Formula (DI) is respectively a methyl group, It is preferable that a is 0 or 1, respectively, It is more preferable that it is 0.

Preferred of these diamines are p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,7 in the aromatic diamine. -Diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropyl Liden) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) ratio Phenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 1- (4-aminophenyl) -1,3,3 -Trimethyl-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;

Among the compounds represented by the formula (D-I) to the compound represented by the formula (D-3);

1, 3-bis (-3- diaminopropyl) tetramethyl disiloxane is mentioned among the compounds represented by the said General formula (D-II).

<Formula D-3>

It is preferable that the diamine used for synthesize | combining the polyamic acid in the liquid crystal aligning agent of this invention contains a compound (A) 1 mol% or more with respect to all diamine, It is more preferable to contain 10 mol% or more, 10 It is more preferable to contain 80 mol%, and it is especially preferable to contain 15-50 mol%.

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), and is further represented by the above general formula (D-II) 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 use ratio is preferably 20 to 99 mol%, more preferably 50 to 90 mol%. And it is more preferable that it is 50-85 mol%.

When the diamine used for synthesizing the polyamic acid in the liquid crystal aligning agent of the present invention contains a compound represented by the above formula (D-II), the use ratio is preferably 0.1 to 10 mol%, preferably 1 to 1 It is more preferable that it is 8 mol%, and it is still more preferable that it is 3-7 mol%.

[Synthesis of Polyamic Acid]

The polyamic acid in the liquid crystal aligning agent of this invention is obtained by making tetracarboxylic dianhydride and the diamine containing a compound (A) react.

The use ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents relative to 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 in an organic solvent, preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C, preferably 1 to 72 hours, more preferably 3 to 48 Is done for hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid produced. Examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Amide compounds such as 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, dimethyl sulfoxide, γ- Aprotic compounds such as butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenolic compounds, such as m-cresol, xylenol, a phenol, and a halogenated phenol, etc. can be illustrated. As for the usage-amount of an organic solvent ((alpha): when using an organic solvent and the poor solvent mentioned later, the total amount of these), the total amount ((beta)) of tetracarboxylic dianhydride and diamine is the whole quantity ((alpha) of reaction solution. It is preferable that it is an amount which will be 0.1-30 weight% with respect to + (beta)).

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are generally known as poor solvents of polyamic acid, may be used in combination without causing precipitation of the resulting polyamic acid. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, Ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, Diethyl oxalate, diethyl malonic acid, 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, chloro Benzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamylisobutyrate, diisopentyl ether and the like.

When using together an organic solvent and the poor solvent mentioned above, the usage-amount of a poor solvent can be set suitably in the range which does not precipitate the polyamic acid produced | generated, but it is preferable that it is 30 weight% or less with respect to the whole quantity of a solvent, and it is 20 weight It is more preferable that it is% or less.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or the method of distilling a reaction solution under reduced pressure with an evaporator. Moreover, polyamic acid can be refine | purified by the method which melt | dissolves this polyamic acid again in an organic solvent, and then precipitates with a poor solvent, or performs the process of distilling off under reduced pressure with an evaporator once or several times.

<Polyimide>

The polyimide of the liquid crystal aligning agent of this invention can be obtained by dehydrating and ring-closing the above-mentioned polyamic acid and imidizing it.

The polyimide contained in the liquid crystal aligning agent of this invention may be the complete imide which dehydrated and closed all the amic acid structures which the polyamic acid which is its precursor has, and only a part of the amic acid structure is dehydrated and closed, and the amic acid structure The partial imide which the and imide ring structure coexists may be sufficient.

It is preferable that the imidation ratio is 40% or more, and, as for the polyimide contained in the liquid crystal aligning agent of this invention, it is more preferable that it is 50 to 90%. By using the polyimide whose imidation ratio is 40% or more, the liquid crystal aligning agent which can form the liquid crystal aligning film with a shorter afterimage elimination time can be obtained.

The said imidation ratio shows the ratio which the number of the number of the imide ring structures to the sum of the number of the amic acid structure of a polyimide, and the number of imide ring structures occupies as a percentage. At this time, a part of the imide ring may be an isoimide ring. The imidization ratio is obtained by dissolving polyimide in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and performing ¹ H-NMR at room temperature (for example, 25 ° C) using tetramethylsilane as a reference substance. It can obtain | require by following formula (1) from the measured result.

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

(In Formula 1, A ¹ is the peak area derived from the proton of the NH group appearing near 10 ppm of chemical shift, A ² is the peak area derived from other protons, and α is the precursor (polyamic acid) of the polyimide. Ratio of the number of other protons to one proton of the NH group of

The dehydration ring closure of the polyamic acid is preferably heated by (i) a method of heating the polyamic acid, or (ii) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to the solution, if necessary. It is done by the method.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. The reaction time is preferably 1 to 8 hours, more preferably 3 to 5 hours. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall.

On the other hand, in the method of adding the dehydrating agent and the dehydrating ring-closure catalyst in the solution of (ii) polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used. Although the usage-amount of a dehydrating agent changes with the imidation ratio made into the objective, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic-acid structure of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be made higher, so that the usage-amount of said dehydrating agent and dehydrating ring closure agent is large. As an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. 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 by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the obtained polyimide. On the other hand, in the said method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, and for the production of the liquid crystal aligning agent after isolating polyimide. It may be used, or may be used for the production of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of a polyimide can be performed by performing the same operation as mentioned above as a method of isolation and purification of a polyamic acid.

[Terminal Modified Polymer]

The polyamic acid or polyimide which the liquid crystal aligning agent of this invention may contain may be a polymer of the terminal modified form in which molecular weight was adjusted. By using the polymer of the terminal modification type, the coating characteristic of a liquid crystal aligning agent, etc. can be further improved, without impairing the effect of this invention. Such a terminal-modified polymer can be performed by adding a molecular weight modifier to the polymerization reaction system when synthesizing the polyamic acid. As a molecular weight modifier, an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. have. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Eicosylamine, etc. are mentioned. As said monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

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 of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

[Solution viscosity]

The polyamic acid or polyimide obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, more preferably 30 to 500 mPa · s when the solution has a concentration of 10% by weight. Do.

The solution viscosity (mPa · s) of the polymer is a polymer solution having a concentration of 10% by weight using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using an E-type rotational viscometer.

<Other Ingredients>

Although the vertically-aligned liquid crystal aligning film of this invention contains as an essential component 1 or more types of polymers chosen from the group which consists of the polyamic acid as mentioned above and the polyimide which dehydrated and closed this, you may contain other components as needed. . As such other components, other polymers, an adhesion improving agent, etc. are mentioned, for example.

[Other polymers]

Such other polymers can be used to improve solution properties and electrical properties. These other polymers are polymers other than the polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing a compound (A) react, and the polyimide which dehydrated and closed the said polyamic acid, For example, tetracarboxylic dianhydride And a polyamic acid obtained by reacting a diamine containing no compound (A) (hereinafter referred to as "other polyamic acid"), a polyimide obtained by dehydrating and closing the polyamic acid (hereinafter referred to as "other polyimide"), Polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate and the like. Among these, other polyamic acid or other polyimide is preferable.

As tetracarboxylic dianhydride used for synthesizing another polyamic acid or another polyimide, it is mentioned as tetracarboxylic dianhydride used for synthesize | combining the polyamic acid or polyimide which is an essential component of the liquid crystal aligning agent of this invention. The same thing as what was illustrated in the example is mentioned. It is preferable to contain alicyclic tetracarboxylic dianhydride among these, and especially 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferable. It is preferable that tetracarboxylic dianhydride used for synthesize | combining another polyamic acid or another polyimide contains 30 mol% or more of alicyclic tetracarboxylic dianhydride with respect to all tetracarboxylic dianhydride, and 50 It is more preferable to contain mol% or more.

As diamine used for synthesizing another polyamic acid or another polyimide, the same thing as what was illustrated above as other diamine which can be used for synthesize | combining the polyamic acid or polyimide which is an essential component of the liquid crystal aligning agent of this invention is mentioned. have. Among them, aromatic diamines are preferable, and p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethylene and 2,2'-trifluoromethyl- It is preferable that it contains 1 or more types chosen from the group which consists of 4,4'- diaminobiphenyl and 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine. It is preferable to contain 5 mol% or more of aromatic diamine with respect to all diamine, and, as for the diamine used for synthesize | combining another polyamic acid or another polyimide, it is more preferable to contain 10 mol% or more.

The other polyamic acid and another polyimide can be synthesize | combined according to what was described above as a synthesis | combining method of the polyamic acid or polyimide which are essential components of the liquid crystal aligning agent of this invention, respectively.

The liquid crystal aligning agent of this invention consists of a polyamic acid obtained by making the said tetracarboxylic dianhydride and the diamine containing a compound (A) react when it contains another polymer, and the polyimide which dehydrated and closed the said polyamic acid. As a usage ratio of 1 or more types of polymers chosen from the group, the sum total of a polymer (polyamic acid obtained by making the tetracarboxylic dianhydride and the diamine containing a compound (A) react, and the polyimide which dehydrated and closed the said polyamic acid, etc. It is preferably 1% by weight or more, more preferably 3 to 50% by weight, and particularly preferably 5 to 45% by weight based on the total of the polymers, which is the same below).

[Adhesive Enhancer]

The said adhesive improving agent can be used for the purpose of improving the adhesiveness with respect to the board | substrate surface of the liquid crystal aligning film obtained. As such an adhesion improving agent, the compound which has one or more epoxy groups in a molecule | numerator (henceforth "epoxy compound"), a functional silane compound, etc. are mentioned, for example.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and 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 , 6-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 And 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

As a use ratio of the above epoxy compound, Preferably it is 40 weight part or less with respect to a total of 100 weight part of polymers, More preferably, it is 0.1-30 weight part.

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, 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-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-a Minopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane etc. are mentioned.

As a usage ratio of the above-mentioned functional silane compound, Preferably it is 2 weight part or less with respect to a total of 100 weight part of polymers, More preferably, it is 0.01-0.2 weight part.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is chosen from the group which consists of the polyamic acid obtained by reaction of the above-mentioned tetracarboxylic dianhydride and the diamine containing a compound (A), and the polyimide which dehydrated and closed the said polyamic acid. The at least one polymer and other additives optionally blended as required are preferably dissolved and contained in an organic solvent.

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, for example, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N -Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-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, 3-hexyloxy-N, N-dimethylpropanamide, etc. are mentioned.

Solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably it is 1 To 10% by weight. That is, the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably, the coating film used as a liquid crystal aligning film is formed by heating, However, when solid content concentration is less than 1 weight%, the film thickness of this coating film is too small. When a good liquid crystal aligning film cannot be obtained, and solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes too large and a favorable liquid crystal aligning film cannot be obtained, and the viscosity of a liquid crystal aligning agent increases and coating property falls. do.

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable by the spinner method. In the case of the printing method, it is particularly preferable that the solid content 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. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 20 degreeC-60 degreeC.

Especially the liquid crystal aligning agent of this invention obtained as mentioned above can be preferably used, in order to form the liquid crystal aligning film of the liquid crystal display element of a transverse electric field system.

<Transverse electric field liquid crystal display element>

The transverse electric field system liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention as mentioned above.

The transverse electric field liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example.

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

Here, as the substrate, a transparent conductive patterned in a comb-tooth pattern using a pair of conductive film-forming surfaces of a substrate on which a transparent conductive film patterned in a comb-tooth pattern is provided, and a substrate on which a conductive film opposite to the substrate is not formed. The liquid crystal aligning agent of this invention is apply | coated to the electrically conductive film formation surface of the board | substrate with which the film | membrane is provided, and the one surface of the board | substrate (opposing board | substrate) with which the film | membrane is not provided, respectively by roll coater method, spinner method, or inkjet printing method, respectively. Then, a coating film is formed by heating each application surface.

As a raw material which comprises a board | substrate, For example, glass, such as float glass and a soda glass; Plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly (alicyclic olefin), and the like. Examples of the transparent conductive film provided on one surface of one substrate include an NESA film (US PPG registered trademark) containing tin oxide (SnO ₂ ) and an indium tin oxide (In ₂ O ₃ -SnO ₂ ). An ITO film or the like can be used, and in order to obtain a patterned transparent conductive film, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, for example, a mask having a desired pattern when forming a transparent conductive film It can carry out by the method etc. to be used. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, and the like are previously applied to the surface on which the coating film should be formed on the substrate surface. Pretreatment can also be performed.

The heating temperature after apply | coating a liquid crystal aligning agent becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC, Heating time becomes like this. Preferably it is 1 to 60 minutes, More preferably, it is 10 to 30 minutes. The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

Although the liquid crystal aligning agent of this invention forms the coating film used as an oriented film by removing an organic solvent after application | coating as above-mentioned, the liquid crystal aligning agent of this invention contains the polyimide which uses a polyamic acid or an imide ring structure, and an amic acid structure together. In this case, the dehydration ring-closing reaction can be advanced by further heating after the coating film is formed to form an imidized coating film.

(2) Next, the rubbing process which rubs a predetermined | prescribed direction on the coating film surface formed as mentioned above with the roll which wound the cloth which consists of fibers, such as nylon, a rayon, a cotton, for example is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.

Moreover, about the liquid crystal aligning film formed as mentioned above, for example, in patent document 4 (Unexamined-Japanese-Patent No. 6-222366) and patent document 5 (Japanese Unexamined-Japanese-Patent No. 6-281937). A process of changing the pretilt angle of a portion of the liquid crystal alignment film by irradiating a portion of the liquid crystal alignment film as described, and disclosed in Patent Document 6 (Japanese Patent Laid-Open No. 5-107544). A liquid crystal display device obtained by forming a resist film on a part of the surface of the same liquid crystal alignment film, then performing a rubbing treatment in a direction different from the above rubbing treatment, and then removing the resist film so that the liquid crystal alignment film has a different liquid crystal alignment ability for each region. It is possible to improve the field of view characteristics.

(3) A liquid crystal cell is manufactured by arrange | positioning a liquid crystal in the clearance gap of a pair of board | substrate with a liquid crystal aligning film as above-mentioned. At this time, two board | substrates are arrange | positioned so that the liquid crystal aligning film which each has may oppose, and the rubbing direction of each liquid crystal aligning film may become orthogonal or antiparallel. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a method known in the art. First, two substrates are disposed to face each other with a gap (cell spacing) so that each liquid crystal alignment film faces each other, and the two peripheral portions of the substrate are bonded together with a sealant, and the cell gap partitioned by the substrate surface and the sealant. After injecting and filling a liquid crystal in the inside, a liquid crystal cell can be manufactured by sealing an injection hole.

The second method is called a one drop fill (ODF) method. An ultraviolet-ray curable sealing material is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other board | substrate is bonded so that a liquid crystal aligning film may oppose. Then, a liquid crystal cell can be manufactured by irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing agent.

In any of the above-described first and second methods, it is preferable to remove the liquid crystal orientation by subsequently cooling the liquid crystal cell to a temperature at which the used liquid crystal takes an isotropic phase and then gradually cooling to room temperature.

Moreover, the liquid crystal display element of the transverse electric field system of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell.

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and for example, Schiff base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, and biphenyl cyclohexane liquid crystals. , Pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cuban-based liquid crystals and the like can be used. Furthermore, for these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agent sold as brand names "C-15" and "CB-15" (manufactured by Merck); Ferroelectric liquid crystals, such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate, can also be added and used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending-stretching polyvinyl alcohol, and the polarizing plate which consists of H film itself is inserted.

<Example>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

In addition, in the following synthesis example, N, N'-bis (4-aminophenyl) piperazine used the commercial item manufactured by Wakayama Seikagyo Co., Ltd. as it was.

In addition, the solution viscosity of the polymer in each synthesis example is the value measured at 25 degreeC using the E-type viscosity meter.

Synthesis of Polyimide

Synthesis Example 1

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic 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-diyl) bis (propylamine) and A solution containing polyamic acid was dissolved by dissolving 100.5 g (0.375 mol) of N, N'-bis (4-aminophenyl) piperazine in 2,440 g of N-methyl-2-pyrrolidone and reacting at room temperature for 6 hours. Got it. A small amount of the obtained polyamic acid solution was aliquoted, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 75 mPa · s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent substituted with fresh N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the imidation reaction by this operation were removed out of the system, which is the same below), and then concentrated by , 2,500 g of a solution containing 15% by weight of polyimide (A-1) having an imidation ratio of about 51% was obtained. A small amount of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone was 25 mPa · s.

Synthesis Example 2

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic 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'-trifluoromethyl-4,4'-diaminobiphenyl and N, 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. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 60 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone, and then concentrated to give a solution 2500 containing 15% by weight of polyimide (A-2) having an imidization ratio of about 51%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 22 mPa * s.

Synthesis Example 3

2,3,5-tricarboxycyclopentylacetic dianhydride 224 g (1.0 mol) as tetracarboxylic dianhydride, p-phenylenediamine 35 g (0.33 mol) as diamine, 1- (4-aminophenyl)- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 23 g (0.1 mol) of 4,4'-diaminodiphenylmethane, 3,3 '-(tetramethyldisiloxane 1 12.4 g (0.050 mol) of, 3-diyl) bis (propylamine) and 87.1 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine were added to 2,460 g of N-methyl-2-pyrrolidone. It dissolved and reacted at room temperature for 6 hours, and obtained the solution containing polyamic acid. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 70 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After dehydration ring closure, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone, and then concentrated to give a solution 2500 containing 15% by weight of polyimide (A-3) having an imidization ratio of about 50%. g was obtained. The solution viscosity was fractionated, the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 24 mPa * s.

Synthesis Example 4

2,3,5-tricarboxycyclopentylacetic dianhydride 224 g (1.0 mol) as tetracarboxylic dianhydride, p-phenylenediamine 35 g (0.33 mol) as diamine, 1- (4-aminophenyl)- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 23 g (0.1 mol) of 4,4'-diaminodiphenylmethane, 2,2'-trifluoromethyl-4 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-2-pyrrolidone The solution containing polyamic acid was obtained by making it react for 6 hours at room temperature. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 58 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,600 containing 15% by weight of polyimide (A-4) having an imidization rate of about 53%. g was obtained. A small amount of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone was 21 mPa · s.

Synthesis Example 5

2,3,5-tricarboxycyclopentylacetic dianhydride 224 g (1.0 mol) as tetracarboxylic dianhydride, p-phenylenediamine 35 g (0.33 mol) as diamine, 1- (4-aminophenyl)- 53.2 g (0.20 mol) of 1,3,3-trimethyl-1H-inden-5-amine, 20 g (0.1 mol) of 4,4'-diaminodiphenylether, 3,3 '-(tetramethyldisiloxane 1 12.4 g (0.050 mol) of, 3-diyl) bis (propylamine) and 87.1 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine were added to 2,450 g of N-methyl-2-pyrrolidone. It dissolved and reacted at room temperature for 6 hours, and obtained the solution containing polyamic acid. A small amount of the obtained polyamic acid solution was aliquoted, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 73 mPa · s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution 2,600 containing 15% by weight of polyimide (A-5) having an imidization rate of about 54%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 26 mPa * s.

Synthesis Example 6

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride, 35 g of p-phenylenediamine as diamine (0.33) Mole), 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine 53.2 g (0.20 mole), 23 g (0.1 mole) 4,4'-diaminodiphenylmethane 16.0 g (0.050 mol) of 2,2'-trifluoromethyl-4,4'-diaminobiphenyl and 87.1 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine A solution containing polyamic acid was obtained by dissolving in 2,450 g of methyl-2-pyrrolidone and reacting at room temperature for 6 hours. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 59 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,600 containing 15 wt% of polyimide (A-6) having an imidation ratio of about 51%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 22 mPa * s.

Synthesis Example 7

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride, 35 g of p-phenylenediamine as diamine (0.33) Mole), 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'-diaminodiphenylether 16.0 g (0.050 mol) of 2,2'-trifluoromethyl-4,4'-diaminobiphenyl and 87.1 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine A solution containing polyamic acid was obtained by dissolving in 2,450 g of methyl-2-pyrrolidone and reacting at room temperature for 6 hours. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 60 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,600 containing 15% by weight of polyimide (A-7) having an imidation ratio of about 51%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 24 mPa * s.

Synthesis Example 8

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra as tetracarboxylic dianhydride 32.0 g (0.10 mol) of hydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 35 g (0.33 mol) of p-phenylenediamine as diamine , 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine 53.2 g (0.20 mol), 4,4'-diaminodiphenylmethane 23 g (0.1 mol), 2 16.0 g (0.050 mol) of 2'-trifluoromethyl-4,4'-diaminobiphenyl and 87.1 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine were added to N-methyl- A solution containing polyamic acid was obtained by dissolving in 2530 g of 2-pyrrolidone and reacting at room temperature for 6 hours. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 58 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,600 containing 15 wt% of polyimide (A-8) having an imidation ratio of about 51%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 23 mPa * s.

Synthesis Example 9

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra as tetracarboxylic dianhydride 32.0 g (0.10 mol) of hydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 35 g (0.33 mol) of p-phenylenediamine as diamine , 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine 53.2 g (0.20 mol), 4,4'-diaminodiphenyl ether 20 g (0.1 mol), 2 16.0 g (0.050 mol) of 2'-trifluoromethyl-4,4'-diaminobiphenyl and 87.1 g (0.325 mol) of N, N'-bis (4-aminophenyl) piperazine were added to N-methyl- A solution containing polyamic acid was obtained by dissolving in 2530 g of 2-pyrrolidone and reacting at room temperature for 6 hours. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 56 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,600 containing 15 wt% of polyimide (A-8) having an imidation ratio of about 51%. g was obtained. A small amount of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone was 21 mPa · s.

<Synthesis of other polyamic acid>

Synthesis Example 10

196 g (0.90 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 19.6 g (0.10 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, p-phenylenediamine 22 as diamine 15 weights of polyamic acid (B-1) was dissolved by dissolving g (0.20 mol) and 180 g (0.80 mol) of 4,4'-diaminodiphenyl ether in 2,400 g of NMP, and reacting at 60 DEG C for 4 hours. About 2,700 g of solutions containing% were obtained. The solution viscosity of this polyamic acid solution was 200 mPa · s.

<Synthesis of other polyimide>

Synthesis Example 11

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 81 g (0.75 mol) of p-phenylenediamine as diamine, 1- (4-aminophenyl)- 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-diyl) bis (propylamine) A solution containing polyamic acid was obtained by dissolving in 2,440 g of N-methyl-2-pyrrolidone and reacting at room temperature for 6 hours. The obtained polyamic acid solution was fractionated, diluted with N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 73 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution containing 15% by weight of polyimide (A-10) having an imidation ratio of about 51% 2,500 g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 23 mPa * s.

Synthesis Example 12

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 81 g (0.75 mol) of p-phenylenediamine as diamine, 1- (4-aminophenyl)- 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'-diaminobiphenyl A solution containing polyamic acid was obtained by dissolving in 2460 g of methyl-2-pyrrolidone and reacting at room temperature for 6 hours. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 60 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution containing 15% by weight of polyimide (A-11) having an imidation ratio of about 51% 2,500 g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 22 mPa * s.

Synthesis Example 13

2,3,5-tricarboxycyclopentylacetic dianhydride 224 g (1.0 mol) as tetracarboxylic dianhydride, p-phenylenediamine 35 g (0.33 mol) as diamine, 1- (4-aminophenyl)- 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 A solution containing polyamic acid was obtained by dissolving 12.4 g (0.050 mol) of, 3-diyl) bis (propylamine) in 2,460 g of N-methyl-2-pyrrolidone and reacting at room temperature for 6 hours. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 70 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,500 containing 15% by weight of polyimide (A-12) having an imidization rate of about 50%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 24 mPa * s.

Synthesis Example 14

2,3,5-tricarboxycyclopentylacetic dianhydride 224 g (1.0 mol) as tetracarboxylic dianhydride, p-phenylenediamine 35 g (0.33 mol) as diamine, 1- (4-aminophenyl)- 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'-trifluoromethyl-4 16.0 g (0.050 mol) of 4'-diaminobiphenyl was dissolved in 2460 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 58 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution containing 15% by weight of polyimide (A-13) having an imidization rate of about 53% 2,600 g was obtained. A small amount of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone was 21 mPa · s.

Synthesis Example 15

224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 35 g (0.33 mol) 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'-diaminodiphenylether 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 aliquoted, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 71 mPa · s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution 2,600 containing 15% by weight of polyimide (A-14) having an imidization rate of about 54%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 24 mPa * s.

Synthesis Example 16

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride, 35 g of p-phenylenediamine as diamine (0.33) Mole), 53.2 g (0.20 mole) of 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 96 g (0.425 mole) of 4,4'-diaminodiphenylmethane And 16.0 g (0.050 mole) of 2,2'-trifluoromethyl-4,4'-diaminobiphenyl are dissolved in 2,450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. A solution containing mic acid was obtained. A small amount of the obtained polyamic acid solution was aliquoted, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 57 mPa · s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,600 containing 15% by weight of polyimide (A-15) having an imidation ratio of about 51%. g was obtained. A small fraction of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone was 20 mPa · s.

Synthesis Example 17

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride, 35 g of p-phenylenediamine as diamine (0.33) Mole), 53.2 g (0.20 mole) of 1- (4-aminophenyl) -1,3,3-trimethyl-1H-inden-5-amine, 85 g (0.425 mole) of 4,4'-diaminodiphenylether And 16.0 g (0.050 mole) of 2,2'-trifluoromethyl-4,4'-diaminobiphenyl are dissolved in 2,450 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. A solution containing mic acid was obtained. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 58 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone, and then concentrated to concentrate 2,600 solutions containing 15% by weight of polyimide (A-16) having an imidization ratio of about 50%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 22 mPa * s.

Synthesis Example 18

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra as tetracarboxylic dianhydride 32.0 g (0.10 mol) of hydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 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, 96 g (0.425 mol) and 4,4'-diaminodiphenylmethane 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. The solution containing was obtained. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 56 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone, and then concentrated to give a solution containing 15% by weight of polyimide (A-17) having an imidation rate of about 51% 2,600 g was obtained. A small amount of this solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone was 21 mPa · s.

Synthesis Example 19

202 g (0.90 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra as tetracarboxylic dianhydride 32.0 g (0.10 mol) of hydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione, 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, 85 g (0.425 mol) and 4,4'-diaminodiphenylether 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. The solution containing was obtained. The obtained polyamic acid solution was aliquoted in small amounts, N-methyl-2-pyrrolidone was added and diluted, and the solution viscosity measured as a solution of 10 weight% of polyamic acid concentration was 54 mPa * s.

Subsequently, 2,500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80.2 g of pyridine and 103 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone and then concentrated to give a solution of 2,600 containing 15 wt% of polyimide (A-18) having an imidation ratio of about 51%. g was obtained. This solution was aliquoted in small amounts, and the solution viscosity measured as a solution of 6.0 weight% of polyimide concentration by adding N-methyl- 2-pyrrolidone was 19 mPa * s.

Example 1

<Production of Liquid Crystal Alignment Agent>

Converting the solution containing the polyimide (A-1) obtained in Synthesis Example 1 to polyimide (A-1), the amount equivalent to 20 parts by weight and the polyamic acid (B-1) obtained in Synthesis Example 10 The solution containing was converted into polyamic acid (B-1) and mixed in an amount equivalent to 80 parts by weight, and γ-butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve were converted into γ-buty. The ratio of lactone: N-methyl-2-pyrrolidone: butyl cellosolve is 40:40:20 by weight ratio, and further, N, N, N ', N'-tetra which is an epoxy compound as an adhesion improving agent. 2 parts by weight of glycidyl-4,4'-diaminodiphenylmethane was added to prepare a solution having a solid content of 3.5 weight parts. After fully stirring this solution, the liquid crystal aligning agent was manufactured by filtering using the filter of 1 micrometer of pore diameters.

<Production and Evaluation of Liquid Crystal Display Elements>

Using the liquid crystal aligning agent manufactured above, the liquid crystal display element was manufactured and evaluated as follows. In addition, although the liquid crystal aligning agent of this invention is used for formation of the liquid crystal aligning film of a transverse electric field system liquid crystal display element, it replaced by manufacturing and evaluating the liquid crystal aligning property and the pretilt angle of the liquid crystal display element of antiparallel orientation.

(1) Manufacturing of liquid crystal display element (antiparallel alignment liquid crystal display element) for liquid crystal orientation and pretilt angle evaluation

The liquid crystal aligning agent prepared above was apply | coated on the transparent conductive film containing the ITO film | membrane provided in the one surface of the glass substrate of thickness 1mm using the spinner on condition of rotation speed 2,000rpm and rotation time 20 second, and it is 200 hours at 200 degreeC. Heating to remove the solvent to form a coating film with a film thickness of 0.08 mu m. About this coating film, the rubbing process is performed by the rubbing machine which has the roll which wound the cloth made from rayon on condition of roll rotation speed 400rpm, the moving speed of 3 cm / sec of a stage, and 0.4 mm of bristle indentation lengths. By providing a liquid crystal aligning ability to a coating film, it was set as the liquid crystal aligning film. The board | substrate which has this liquid crystal aligning film was ultrasonically cleaned in ultrapure water for 1 minute, and then dried in 100 degreeC clean oven for 10 minutes.

By repeating these series of operations, the board | substrate which has a liquid crystal aligning film was produced (two pairs).

Subsequently, after apply | coating the 5.5-micrometer diameter aluminum oxide sphere containing epoxy resin adhesive agent on each outer edge part which has a liquid crystal aligning film of the board | substrate which has this pair of liquid crystal aligning films, it overlaps and compresses so that a liquid crystal aligning film surface may face, and an adhesive agent is Cured. Subsequently, after filling the nematic liquid crystal (MLC-2019 by Merck Co., Ltd.) which shows a positive value of dielectric anisotropy between a liquid crystal injection hole and a board | substrate, the liquid crystal injection hole is sealed with acrylic photocuring adhesive, and both surfaces of the outer side of a board | substrate are The liquid crystal display element of the antiparallel orientation was manufactured by bonding a polarizing plate to this.

(2) Evaluation of liquid crystal alignment

When the liquid crystal display element manufactured above was observed with the optical microscope, when the liquid crystal aligning "good" and the light leakage were observed that the light leakage was not observed were evaluated as liquid crystal aligning "bad", Liquid crystal orientation was "good."

(3) Evaluation of the pretilt angle

About the liquid crystal display element manufactured above, the pretilt angle at room temperature was measured by the Senarmont method. When this value was less than 1.5 degree, when it evaluated as a pretilt angle "good", and when it was 1.5 degree or more, the pretilt angle "bad", the value of the pretilt angle of the said liquid crystal display element was "good".

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

In the production of the anti-parallel alignment liquid crystal display device, a glass substrate having two lines of a comb-patterned transparent conductive film pattern containing chromium and a glass substrate not having a transparent conductive film are used as a pair to have a comb-like transparent conductive film. Except having apply | coated the said liquid crystal aligning agent on the transparent conductive film of a board | substrate and one surface of the other board | substrate, respectively, it carried out similarly to manufacture of the said antiparallel alignment liquid crystal display element, and manufactured the transverse electric field system liquid crystal display element.

The schematic diagram which showed the structure of the transparent electrode pattern on the said glass substrate is shown in FIG.

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

(5) Evaluation of Afterimage Characteristics

The above-described transverse electric field type liquid crystal display device was subjected to a combined voltage of an AC voltage of 3.5 V and a DC voltage of 5 V for 2 hours without applying a voltage to the electrode B under an environment of 25 ° C. and 1 atmosphere. Authorized. Immediately thereafter, an alternating voltage of 4 V was applied to both the electrode (A) and the electrode (B). The time from the time when the voltage of alternating current 4V was applied to both electrodes until the difference in the light transmittance between the electrodes A and B was measured. When this time was 500 seconds or less, it evaluated as the afterimage characteristic "good." The afterimage characteristic of the said transverse electric field system liquid crystal display element was "good."

Examples 2-18 and Comparative Examples 1-18

As a solution containing a polymer, it carried out similarly to Example 1 except having used only the quantity equivalent to the quantity of Table 1 which converted the solution containing the polymer of the kind shown in Table 1 to the polymer contained in this, respectively. The liquid crystal aligning agent was produced, respectively, and the liquid crystal display element was manufactured and evaluated. The results are shown in Table 1.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the structure of the 2 types of transparent conductive film pattern which the transverse electric field system liquid crystal display element manufactured for evaluation of an afterimage characteristic in an Example and a comparative example has.

Claims (8)

1 selected from the group consisting of a polyamic acid obtained by reaction of a tetracarboxylic dianhydride with a diamine containing a structure represented by the following formula (A) and a compound having two amino groups and a polyimide dehydrated and closed with the polyamic acid It contains at least a polymer and is used in order to form the liquid crystal aligning film of a liquid crystal display element, The liquid crystal aligning agent characterized by the above-mentioned. <Formula A>

(In formula A, "*" shows a bond.) The liquid crystal aligning agent according to claim 1, wherein the compound represented by the formula (A) and the compound having two amino groups are compounds represented by the following formula (A-1). <Formula A-1>

In Formula A-1, U is a methylene group, a C2-C6 alkylene group, a phenylene group, a naphthalenylene group, a cyclohexylene group, a pyrimidinylene group, or a triazinylene group, respectively, n is a 1-5 Integer, and a plurality of U's may be the same or different.) The liquid crystal aligning agent according to claim 1 or 2, wherein the diamine further comprises at least one member selected from aromatic diamines, in addition to the compound represented by the formula (A) and a compound having two amino groups. The liquid crystal aligning agent of Claim 3 in which the said diamine further contains the compound represented by following formula (D-II). <Formula D-II>

(In formula (D-II), R <^7> is a C1-C12 hydrocarbon group, respectively, two or more R <^7> may be same or different, respectively, p is an integer of 1-3, q is 1-20 Integer) The tetracarboxylic dianhydride according to claim 1 or 2, wherein the tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic 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-tricarboxycyclopentyl Liquid crystal aligning agent which is 1 or more types chosen from the group which consists of an acetic dianhydride, a pyromellitic dianhydride, and a 4,4'- nonphthalic dianhydride. The polyamic acid and the polyamic acid according to claim 1 or 2, further obtained by the reaction of tetracarboxylic dianhydride with a diamine which does not contain a compound represented by the above formula (A) and a compound having two amino groups. The liquid crystal aligning agent containing 1 or more types of polymers chosen from the group which consists of polyimide which dehydrated the ring. The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 1 or 2 is provided. The liquid crystal display element characterized by the above-mentioned. The liquid crystal aligning agent of Claim 1 whose said liquid crystal display element is a transverse electric field system.

Images