KR100487047B1 - Liquid Crystal Aligning Agent - Google Patents

Abstract

The present invention provides a polyamic acid obtained by reacting a dianhydride of tetracarboxylic acid represented by the following formula (1) with a diamine compound and / or an imidized polymer thereof, and an dianhydride of tetracarboxylic acid represented by the following formula (2); It relates to a liquid crystal aligning agent characterized by containing the polyamic acid and / or the imidation polymer thereof which can be obtained by making a diamine compound react.

[Formula 1]

[Formula 2]

In said formula, RI represents a methyl group or an ethyl group, R <2> represents a hydrogen atom, a methyl group, or an ethyl group, and a is an integer of 1-4.

Description

Liquid crystal aligning agent {Liquid Crystal Aligning Agent}

This invention relates to the liquid crystal aligning agent used for forming the liquid crystal aligning film of a liquid crystal display element, More specifically, it is related with the liquid crystal aligning agent which provides a liquid crystal aligning film with favorable liquid crystal alignability and a short residual image erasing time of a liquid crystal display element. will be.

 Conventionally, a nematic liquid crystal layer having positive dielectric anisotropy is formed between two substrates on which a liquid crystal alignment film is formed on the surface via a transparent conductive film to form a sandwich cell, and the long axis of the liquid crystal molecules is from one substrate to the other. BACKGROUND ART TN-type liquid crystal display elements having so-called twisted nematic (TN) type liquid crystal cells, which are continuously bent at 90 degrees toward the substrate, are known.

In liquid crystal display elements, such as this TN type liquid crystal display element, the orientation of a liquid crystal molecule is implement | achieved by the liquid crystal aligning film to which the orientation ability of the liquid crystal molecule was normally given by the rubbing process.

Here, as a material of the liquid crystal aligning film which comprises a liquid crystal display element, the polymer of the imide which dehydrated and closed polyamic acid and polyamic acid is known conventionally, and since these are excellent in heat resistance, affinity with a liquid crystal, mechanical strength, etc., many It is used as a liquid crystal display element.

However, in a liquid crystal display device fabricated using a liquid crystal aligning agent containing a conventionally known polyamic acid and / or imidized polymer, residuals are generated on the display screen after the applied voltage is removed, and this residual image is erased. There was a problem that you could not get enough colast because the time until it was long. Moreover, when the said liquid crystal display element is used for a long time, the white uneven display defect may generate | occur | produce, and thus the reliability as a liquid crystal display element was impaired.

This invention is made | formed in view of the above circumstances.

A first object of the present invention is to provide a liquid crystal aligning agent capable of producing a liquid crystal display element having a short time (hereinafter referred to as "afterimage erasing time") from the removal of the applied voltage until the afterimage is erased.

A second object of the present invention is to provide a liquid crystal aligning agent capable of imparting high reliability to a liquid crystal display device without causing a display defect to occur in the liquid crystal display device even when used for a long time.

The 3rd object of this invention is to provide the liquid crystal aligning agent which can form the liquid crystal aligning film excellent in liquid crystal aligning property.

The liquid crystal aligning agent of this invention is a polyamic acid (henceforth "a polyamic acid (A)" and (or) its imidation polymer which can be obtained by making the dianhydride of tetracarboxylic acid and a diamine compound represented by following General formula (1) react. (Hereinafter referred to as "imidized polymer (B)") and polyamic acid obtained by reacting a dianhydride and a diamine compound of tetracarboxylic acid represented by the following formula (2) (hereinafter referred to as "polyamic acid (C)" ) And (or) an imidized polymer thereof (hereinafter referred to as "imidized polymer (D)").

<Formula 1>

<Formula 2>

In said formula, R <1> represents a meryl group or an ethyl group,), R <-> represents a hydrogen atom, a methyl group, or an ethyl group, and a is an integer of 1-4.

<Embodiment of the invention>

Hereinafter, the present invention will be described in detail.

In the liquid crystal aligning agent of this invention, a line is made from a polyamic acid (A) and an imidation polymer (B).

At least one polymer selected from at least one polymer selected and the polyamic acid (C) and the imidized polymer (D) is contained as an essential component.

The polyamic acid (A) is a tetracarboxylic dianhydride and a diamine compound containing a dianhydride (hereinafter referred to as "specific tetracarboxylic dianhydride (i)") of the tetracarboxylic acid represented by the formula (1). It can obtain by making it react, and an imidation polymer (B) can be obtained by dehydrating and closing the said polyamic acid (A).

Polyamic acid (C) can be obtained by making tetracarboxylic dianhydride and diamine compound containing the dianhydride of the tetracarboxylic acid represented by the said Formula (2) J and the diamine compound (D) ) Can be obtained by dehydrating and closing the polyamic acid (B).

<Specific tetracarboxylic dianhydride (i)>

Specific examples of the specific tetracarboxylic dianhydride (i) used to obtain the polyamic acid (A) include 1,3,3a, 4,5,9b-hexahydro-7-methyl 5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (Tetrahydro2,5 dioxo-3 furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -8-methyl-5- (tetrahydro-2,5-dioxo-3 furanyl) naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-8-ethyl-5- (tetrahydro 2,5-dioxo-3-furanyl) -naphtho [l, 2-c] furan-1,3-dione and 1 , 3,3a, 4,5,9b-hexahydro 5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] -furan- 1,3-dione etc. can be mentioned, These can be used individually or in combination of 2 or more types. Among them, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1.3-dione is particularly preferred.

<Specific tetracarboxylic dianhydride (ii)>

Specific tetracarboxylic dianhydride (ii) used to obtain polyamic acid (C) is 2,3,5 tricarboxycyclopentyl dianhydride.

<Available tetracarboxylic dianhydride>

Tetracarboxylic dianhydride for obtaining polyamic acid (A) and polyamic acid (C)

As a specific tetracarboxylic dianhydride in the range which does not impair the effect of this invention,

Tatracarboxylic dianhydrides other than (i) and specific tetracarboxylic dianhydride (ii) can be used together.

As tetracarboxylic dianhydride which can be used together, for example, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3, 4 cyclobutanetetracarboxylic dianhydride, 1,3 dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 dichloro-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydrides, 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 acid 3,5,6-tricarboxy norbornane-2-acetic acid2,3, 4,5 tetrahydrofurantetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydrol 2,5-dioxo-3-furanyl) -naphtho [ l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl 5- ( Trahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-cJ-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, 5- (2,5-dioxotetrahydrofural) -3-methyl- 3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -octo-7-ene-2,3,5,6 tetracarboxylic dianhydride, the following formulas 3 to Aliphatic tetracarboxylic dianhydrides such as compounds represented by 4 and alicyclic tetracarboxylic dianhydrides;

Pyromellitic acid 3,3 ', 4,4'-benzophenonetetracarboxylic acid 3,3', 4,4'-biphenylsulfontetracarboxylic acid 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4,4 'dimethyldiphenyl Silanetatracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetatracarboxylic dianhydride, 1,2,3,4-furanthracarboxylic dianhydride, 4,4' Bis (3,4-dicarboxyphenoxy) diphenylsulphide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfon dianhydride, 4,4'-bis (3, 4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4 ι perfluoroisopropyllydandiphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride Water, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) Dianhydrides, m-phenylene-bis (triphenylphthalic acid) dianhydrides bis (triphenylphthalic acid) -4,4'-diphenylether dianhydrides, bis (triphenylphthalic acid) -4,4 'diphenylmethane dianhydrides , Ethyl nglycol call-bis (Anthrowtrimellitate), propyl langlycol call-bis (Anthrowtrimellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1 , 6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane bis (anhydro Trimellitate) and aromatic tetracarboxylic dianhydrides such as compounds represented by the following formulas (5) to (8). These may be used alone or in combination of two or more thereof.

[Formula 3]

[Formula 4]

In the above formula, R3 and R5 represent a divalent organic group having an aromatic ring, and R4 and R6 represent a hydrogen atom or an alkyl group. Two or more R4 and R6 may be same or different, respectively.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

Of these, butanetetracarboxylic dianhydride, 1,2,3,4 cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl 1,2,3,4-cyclobutanetetracharic dianhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4, S, 9b-hexahydro-S- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-cJ furan-1,3-dione , Bicyclo [2,2,2J-octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone Tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsumfontetracharic dianhydride, 1,4, S, 8-naphthalenetetracarboxylic dianhydride, among the compounds represented by the formula (3) To the compound represented by the formula (9) to 11 and the compound represented by the formula (4) It is preferable from a viewpoint that the compound to which a compound can express can express favorable liquid-crystal orientation, and it is a preferable thing and is 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1, 3- dimethyl- 1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 , -c] furan-1,3-dione, pyromellitic dianhydride, and the compound represented by following formula (12) are mentioned.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

The ratio of use of specific tetracarboxylic dianhydride (i) to tetracarboxylic dianhydride for obtaining polyamic acid (A) and specific tetracarboxyl to tetracarboxylic dianhydride for obtaining polyamic acid (C). The use ratio of acid dianhydride (ii) is usually 30 mol% or more, preferably 50 mol% or more, and more preferably 70 mol% or more.

<Diamine Compound>

Especially as a diamine compound for obtaining a polyamic acid (A) and a polyamic acid (C),

Without limitation, for example p-phenylenediamine, m-phenylenediamine. 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane 4.4'-diaminodiphenylsulfide 4.4'-diaminodiphenylsulfone, 3,3'-dimethyl 4,4'- Diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5 amino-1- (4-11 aminophenyl) -1,3,3-trimethylindane, 6-amino-1-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3, 4'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2 bis [4- (4-amino Phenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4aminophenoxy) phenyl] sulfone, 1,4-bis (4 aminophenoxy) benzene 1.3-bis (4 aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene , 9,9- rain S (4-aminophenyl) -10-hydroanthracene, 2,7 diaminofluorene, 9,9-bis (4-aminophenal) fluorene, 4,4'-methylene-bis (2-chloroaniline ), 2,2 ', 5,5'-ter 1 trachloro 4,4'-diaminobiphenyl, 2,2'dichloro-4,4'diamino-5,5'-dimethoxybiphenyl, 3 , 3'-dimethoxy-4,4'-diaminobiphenyl 144 '-(p-, "per1 nyleneisopropyllimene) bisaniline, 4,4'-em phenyleneisopropyllinene) bisaniline , 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino 2,2'-bis (trifluoromethyl) Aromatic diamines such as biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy) octafluorobiphenyl;

1,1 methaxylenediamine, 1,3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, laptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminolaptamethylenediamine, 1, 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo'J- [6,2,1,0-0 ' Aliphatic and alicyclic diamines such as] -undecylenedimethyldiamine and 4,4'-methylenebis (cyclohexylamine);

2,3-diaminopyridine, 2,6 diaminopyridine, 3,4 diaminopyridine, 2,4-diaminopy12limidine, 5,6-diamino-2,3-dicyanopyrazine, 5 , 6-diamino-2,4-dihydroxypyrimidine, 2,4-diomino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3 aminopropyl) piperazine , 2,4-diamino 6-isopropoxy-1,3,5 triazine, 2,4-diomino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6methyl-s-triazine, 2,4-diamino-1,3,5 triazine, 4,6-diamino- 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-phenylphenanthrylated tI 14,, diaminopiperazine, 3,6-diaminoacridine, bis (4 ← aminophenal) phenylamine and the following Compounds having two primary amino groups such as compounds represented by the formulas (13) to (14) and nitrogen atoms other than the nitrogen atoms constituting the primary amino group in the molecule;

Mono-substituted phenylenediamines represented by the following formula (15); Diamino organosiloxane represented by following formula (16);

The compound etc. which are represented by following formula (17-21) are mentioned. Dia of these

A min compound can be used individually or in combination of 2 or more types.

[Formula 13]

In the above formula, R7 represents a divalent organic group, and R8 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine.

[Formula 14]

In the above formula, R ⁹ represents a divalent organic group, and a plurality of R ^{9 's} may be the same or different. R ¹⁰ is a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine The divalent organic group which has is shown.

[Formula 15]

In the formula, R ^ll represents a divalent organic group selected from -0-, -COO-, -OCO-, -NHCO-, -CONH-, and -co, R ¹² represents a steroidoid skeleton, a trifluoromethyl group and Monovalent organic group or alkyl group having 6 to 30 carbon atoms having at least one group selected from fluoro groups.

[Formula 16]

In said formula, R <^13> represents a C1-C12 hydrocarbon group and two or more R <13> may be same or different, respectively. p is an integer from 1 to 3, q is an integer from 1 to 20

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

In said formula, Y is an integer of 2-12, Z is an integer of 1-5.

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '→ diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,7-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 dan) bisaniline, 4, 4 '← (m phenylenediisopropylidane) bisaniline, 2,2-bis [4- (4 aminophenoxy) phenyl] sulfone, 1,4 bis (4-aminophenoxy) benzene, 1,4-cyclo Hexanediamine, 4,4'-methylenebis (cyclonuxylamine), 4,4'-diaminobenzanilide, 1,4-bis (4-aminophenoxy) benzene 4,4'bis (4-aminophenoxy ) Biphenyl, the compound represented by Formula 17 to 21, 2,6 diaminopyridine, 3,4-dia Nopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, among the compounds represented by Formula 13, the compound represented by the following Formula 22, and the compound represented by the following Formula 14, Among the compounds represented by the following formulas and the compounds represented by the following formula (15), the compounds represented by the following formulas (24 to 29) are preferable.

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

<Polyamic acid>

In the synthesis reaction of the polyamic acid [polyamic acid (A) and polyamic acid (C)] which comprises the liquid crystal aligning agent of this invention, the use ratio of tetracarboxylic dianhydride and a diamine compound is 1 equivalent of the amino group contained in a diamine compound. The ratio of the acid anhydride group of the tetracarboxylic dianhydride to 0.2 to 2 equivalents is preferable, and more preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid constituting the liquid crystal aligning agent of the present invention is carried out in an organic solvent.

Is usually carried out at a reaction temperature of from 0 to 150 캜, preferably from 0 to 100 캜 over 1 to 48 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid (A) produced in the reaction. Specifically, for example, N-methyl 2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, y-butyrolactone, tetramethylurea, hexamethylphosphor Phenolic solvents such as aprotic polar solvents such as triamide, m-cresol, xylenol, phenol, halogenated phenol, etc. The amount of the organic solvent is usually the total amount of the tetracarboxylic dianhydride and the diamine compound. The amount which becomes 0.1-30 weight% with respect to the total amount of this reaction solution is preferable.

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of the polyamic acid, can be used in combination without causing precipitation of the polyamic acid. As an example of such a poor solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, acetic acid Methyl ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monophenyl ether, ethylene glycol methyl phenyl ether, ethylene glycol ethyl phenyl ether, 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, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether Acetate, 4-hydroxy-4-meth 2 pentanone, 2,4-pentanedione, 2,5-hexanedione, 2 ← ethyl hydroxypropionate, 2-hydroxy-2 ethylpropionate, 2-hydroxyethyl 2-methylpropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, 3-methoxypropy

Methyl oncetate, 3-methoxy ethylpropionate, 3-ethoxypropionate ethyl, 3-ethoxypropionate methyl, pyruvate, ethyl pyruvate, hydroxymethyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl methoxybutanol, ethyl meth Methoxybutanol, methylethoxybutanol, ethylethoxybutanol, tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydro-3-furanmethanol, 201,3-dioxolane, 1,3-dioxane, 4-methyl- 1,3-dioxolane, dichloromethane, 1,2 dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-c1 chlorobenzene, hexane, hamtan, octane, benzene, toluene, xylene, etc. These can be used individually or in combination of 2 or more types.

The reaction solution which melt | dissolves a polyamic acid by the above synthesis reaction can be obtained. Then, the reaction solution is placed in a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. The polyamic acid is further dissolved in an organic solvent, followed by precipitation in a poor solvent. The polyamic acid can be refine | purified by performing it several times or several times.

<Imidized polymer>

The imidized polymer [imidized polymer (B) and imidized polymer (D)] which comprises the liquid crystal aligning agent of this invention removes the said polyamic acid [a polyamic acid (A) and a polyamic acid (C)]. It can prepare by stepping down. Dehydration ring closure of the polyamic acid is carried out by (a) heating the polyamic acid or (b) dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. .

The reaction temperature in the method of heating the said polyamic acid (a) is 50-200 degreeC normally, Preferably it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of said polyamic acid (b), acid anhydrides, such as acetic anhydride, a propionic anhydride, and trifluoroacetic anhydride, can be used as a dehydrating agent, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, coridine, lutidine, triethylamine and the like can be used, but the present invention is not limited thereto. The amount of the dehydrating ring-closure catalyst is preferably 0.01 to 10 moles per 1 mole of the dehydrating ring. The organic solvents used for the synthesis of the polyamic acid may be exemplified as the organic solvent used for the dehydrating ring-closure reaction. The reaction temperature of the dehydration ring closure reaction is usually O to 180 ° C, preferably 10 to 150 ° C. Moreover, the imidation polymer can be refine | purified by performing the same operation as the purification method of a polyamic acid about the reaction solution obtained in this way.

<Polymer of Terminal Modified Type>

The polymer [polyamic acid (A) imidation polymer (B), polyamic acid (C), and imidation polymer (D)] which comprise the liquid crystal aligning agent of this invention may be terminal modified form in which molecular weight was adjusted. By using the terminal-modified polymer, the effect of the present invention can be improved without impairing the effect of the present invention. Such terminal-modified type is an acid anhydride, a monoamine compound, a monoisocyanate compound when the polyamic acid is synthesized. It can synthesize | combine by adding etc. to a reaction system. Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride and the like. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine n pentylamine, nhexylamine, n-hamtylamine, n-octylamine, n-nonylamine, n-decylamine n-undecyl Amine, n-dodecylamine, n- tridecylamine, n- tetradecylamine, n- pentadecylamine, n-hexadecylamine, n-hamtadecylamine, n-octadecylamine, n-ecosylamine, etc. Can be mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

Logarithmic viscosity of the polymer

The value of the logarithmic viscosity ((eta) In) of the polymer which comprises the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0.05-10 dl / g, More preferably, it is 0.05-5 dl / g. Here, the value of the logarithmic viscosity (η In) is measured using a N-methyl-2-pyrrolidone as a solvent and the viscosity at 30 ° C. for a solution having a polymer concentration of 0.5 g / IOO mR, Was obtained by.

[Equation 1]

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is at least 1 sort (s) of polymer chosen from a polyamic acid (A) and an imidation polymer (B), and at least 1 sort (s) of polymer chosen from a polyamic acid (C) and an imidization polymer (D). It consists of the solution (polymer solution) contained in the organic solvent. Although the compounding ratio of each polymer in the liquid crystal aligning agent of this invention can be suitably selected, at least 1 sort (s) of polymer chosen from a polyamic acid (A) and an imidation polymer (B) with respect to polymer whole quantity becomes like this. Preferably it is 10-90 weight It is preferable that at least 1 sort (s) of polymer chosen from%, a polyamic acid (C), and an imidation polymer (D) mix | blend preferably 10 to 90 weight%. The liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate by a printing method, a spin coat method, etc., for example, and a thin film which is an oriented film material is formed by drying a coating film and removing a solvent.

Although the content rate of the polymer in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is 0.1-20 weight% of a liquid crystal aligning agent, More preferably, it is the range of 1-10 weight%. If the polymer content is less than 0.1% by weight, the film thickness of the formed thin film may be too small to obtain a good liquid crystal alignment film. If the content is more than 20% by weight, the film thickness of the thin film is too large to obtain a good liquid crystal alignment film. It is difficult, and the viscosity of a liquid crystal aligning agent may increase and inferior a coating characteristic.

The organic solvent for dissolving the polymer is not particularly limited as long as it can dissolve the polyamic acid and the imidized polymer, and examples thereof include solvents exemplified as those used in the synthesis reaction and the dehydration ring closure reaction of the polyamic acid. Moreover, the poor solvent illustrated as what can be used together in the synthesis reaction of polyamic acid can also be selected suitably, and can be used together.

The functional silane containing compound and the epoxy group containing compound may be mix | blended with the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness of the thin film (polymer) with respect to a board | substrate surface. As such a functional silane containing compound, 3 aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-urei E propyltrimethoxysilane, 3-ureidepropyltriethoxysilane , N-ethoxycarbonyl-3 aminopropyltrimethoxysilane, N-ethoxycarbonyl 3 aminopropyltriethoxysilane, N-triethoxysilylpropyltriethyl ethylenetriamine, N-trimethoxysilylpropyl Triylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triadecane, 9-trimethoxysilyl-3, 6-diazonyl acetate, 9-triethoxysilyl-3,6 diazanonyl acetate, N benzyl-3-aminopropyl Limethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl 3-aminopropyltriethoxysilane, N-bis (oxyethylene)- 3-aminopropyltrimethoxysilane, N bis (oxyethylene) -3-aminopropyl triethoxysilane, etc. are mentioned. As the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , Yeah

Opentylglycol 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 (NN diglycidylaminomethyl) cyclohexane, N, N , N ', N' tetraglycidyl 4,4'- diaminodiphenylmethane etc. are mentioned as a preferable thing. The compounding ratio of these functional silane containing compounds and epoxy group containing compounds is 40 weight part or less normally with respect to 100 weight part of polymers, Preferably it is 0.1-30 weight part.

<Liquid crystal display element>

The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example by the following method.

(1) The liquid crystal aligning agent of this invention is apply | coated to the transparent conductive film side of the board | substrate with which the patterned transparent conductive film was installed, for example by the method of a roll coater method, a spinner method, the printing method, etc., and then a thin film is formed by heating a coating surface. . As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass, plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used. As the transparent conductive film provided on one surface of the substrate, an NESA film made of SnO2, an ITO film made of In20rSnO, and the like can be used. For the patterning of these transparent conductive films, a photo-etching method, a method of using a mask in advance, and the like can be used.

In application of a liquid crystal aligning agent, in order to further improve the adhesiveness of a board | substrate, a transparent conductive film, and a thin film, a functional silane containing compound, a titanate, etc. may be apply | coated previously on a board | substrate and a transparent conductive film. Moreover, as for heating temperature, 80-250 degreeC is preferable, More preferably, it is 120-200 degreeC. The film thickness of the formed thin film is usually 0.001 to 1 m, preferably 0.005 to 0.5 m.

(2) The formed thin film is subjected to a rubbing treatment by rubbing in a fixed direction with a roll wound around a cloth made of synthetic fibers such as nylon to impart an alignment ability of liquid crystal molecules to the thin film to form a liquid crystal alignment film. Moreover, a liquid crystal aligning film can also be oriented by the method of irradiating a polarization ultraviolet-ray to a thin film outer surface, and providing an orientation capability other than the method by a living process, and the method of obtaining a thin film by the uniaxial stretching method, the Langmuir project method, etc. Moreover, in order to remove the fine powder (foreign substance) which arises at the time of a rubbing process, and to make the surface wash, it is preferable to wash the formed liquid crystal aligning film with isopropyl alcohol etc. Moreover, the furry which changes a pretilt angle by partially irradiating an ultraviolet-ray to the liquid crystal aligning film formed by the liquid crystal aligning agent of this invention, for example as Unexamined-Japanese-Patent No. 6-222366 and 6-281937 is carried out. Alternatively, as shown in Japanese Patent Application Laid-Open No. 5-107544, a resist film is partially formed on the rubbed liquid crystal alignment film and subjected to a rubbing treatment in a direction different from that of the teacher rubbing treatment, and then the resist film is removed to It is possible to improve the clock characteristic of a liquid crystal display element by performing the process which changes an orientation ability.

 (3) Two board | substrates in which the liquid crystal aligning film was formatted as mentioned above are produced, and two board | substrates are opposed through the gap (cell gap) so that the rubbing direction in each liquid crystal aligning film may be orthogonal or antiparallel, The periphery of the long substrate is bonded with a sealant, the liquid crystal is filled in the cell gap partitioned by the substrate surface and the sealant, and the filling hole is sealed to form a liquid crystal sal. And a liquid crystal display element can be obtained by bonding the polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface side of each substrate constituting the liquid crystal cell, so that its polarization direction is coincident with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. have.

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

Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, an azokee clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, Ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cuban liquid crystal and the like can be used. Moreover, these liquid crystals are commercially available as cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate, and trade names "C-15J" and "CB-15" (manufactured by Merck). Or a chiral agent, or the like. A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino 2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate etc. which made the polarizing film called H film | membrane which absorbed iodine while extending | stretching polyvinyl alcohol through the cellulose acetate protective film, or the polarizing plate which consists of H film itself etc. are mentioned. .

<Example>

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

In addition, the measurement about the liquid crystal display element produced by the following example and the comparative example

The method and evaluation method are as follows.

[Orientation of liquid crystal]

The presence or absence of the abnormal domain in the liquid crystal cell at the time of turning on and off the voltage to a liquid crystal display element was observed with the polarization microscope, and it judged that the case where there was no abnormal domain was "good".

[Afterimage erasing time]

After applying a DC voltage of 7 V to the liquid crystal cell for 5 hours, the application of the voltage was canceled.

The display screen was visually observed, and the time from the release of the voltage to the afterimage on the screen was measured.

Reliability Test of Liquid Crystal Display Devices (Presence or Absence of Display Defects)

Under the high temperature and high humidity environment (temperature 70 degreeC, relative humidity 80%), the liquid crystal display element was driven with the square wave of 5V and 60Hz, and after 1500 hours, the presence or absence of the white defect display defect was observed with the polarization microscope.

Synthesis Example 1

1,3,3, a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan 314.30 g (1.00 mole) of -1,3-dione, 86.51 g (0.80 mole) of p-phenylenediamine, and 84.48 g (0.20 mole) of the diamine compound of formula 28 are dissolved in 1500 g of N-methyl-2-pyrrolidone. The solution was reacted at 40 ° C. for 6 hours. The reaction solution obtained was then placed in a large excess of pure water to precipitate the reaction product. Thereafter, the solid was separated, washed with pure water, and dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining a polyamic acid (A) having a logarithm viscosity (η 1n) of 1.12 dl / g [this is referred to as “polymer (A-1)”] 451.3 g was obtained.

Synthesis Example 2

30.0 g of the polymer (A-I) obtained in Synthesis Example 1 was dissolved in 570 g of y-butyrolactone, and 33.3 g of pyridine and 25.8 g of acetic anhydride were added and dehydrated and closed for 3 hours at 50 ° C. Subsequently, the reaction product is precipitated, separated, washed, and dried in the same manner as in Synthesis example l to give an imidized polymer (B) having a logarithmic viscosity (Shaped In) of 1.14 dl / g [this is referred to as "polymer (B-2)". 28.3 g were obtained.

Synthesis Example 3

75.70 g (O.70 mole) of p phenylenediamine, 39.65 g (0.20 mole) of 4,4'-diaminodiphenylmethane, and 42.24 g (O.10 mole) of the diamine compound of Formula 28 as diamine compounds A polyamic acid (A) having a logarithmic viscosity (η In) of 1.01 dl / g was obtained in the same manner as in Synthesis example 1, except that 439.1 g of "a polymer (A-3) j" was obtained. Subsequently, the same procedure as in Synthesis Example 2 was carried out except for using 30.0 g of polymer (A-3) instead of polymer (A-I) to give an imidized polymer (B) having a logarithmic viscosity (Shaped In) of 1.05 dl / g. Polymer (B-4) "] to 27.9 g.

Synthesis Example 4

The algebraic viscosity (η) was obtained in the same manner as in Synthesis Example 1 except that 86.51 g (O.80 mol) of p-phenylenediamine and 104.16 g (O.20 mol) of 3,5-diaminobenzoic acid cholesterol were used as the diamine compound. In) 469.6 g of a polyamic acid (A) of 0.87 dl / g was obtained, which is referred to as "polymer (A-5) j". Thereafter, an imidized polymer (B) having a logarithmic viscosity (T) In) of 0.90 dl / g was used in the same manner as in Synthesis Example 2, except that 30.0 g of the polymer (A-5) was used for the polymer (A-I) election. Let it be "polymer (B-6)"] 28.4 g was obtained.

Synthesis Example 5

The logarithmic viscosity (η In) was 0.99 dl / in the same manner as in Synthesis Example 1, except that 86.51 g (O.80 mol) of p-phenylenediamine and 74.48 g (O.20 mol) of the diamine compound represented by Chemical Formula 29 were used as the diamine compound. 442.0 g of polyamic acids (A) [where this is referred to as "polymer (A-7)"] were obtained. Thereafter, an imidized polymer (B) having a logarithmic viscosity (η In) of 0.99 dl / g was used in the same manner as in Synthesis Example 2, except that 30.0 g of the polymer (A-7) was used instead of the polymer (A-1). Polymer (B-8) '] to 28.3 g.

Synthesis Example 6

As tetracarboxylic 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 251.44 g (O.80 mol) and 1,3dimethyl-1,2,3,4 cyclobutanetetracarboxylic dianhydride 44.83 g (O.20 mol) In the same manner as in Synthesis Example l, 434.3 g of a polyamic acid (A) having a logarithmic viscosity (Shaped In) of 0.92 dl / g was obtained as "polymer (A-9)" and then obtained polymer (A-1). An imidized polymer (B) having a logarithmic viscosity (η In) of 0.96 dl / g [this is referred to as "polymer (B-10)" except that 30.0 g of polymer (A-9) was used instead of 28.1 g were obtained.

Synthesis Example 7

Synthesis except that 224.17 g (1.00 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride was used as tetracarboxylic dianhydride and 108.14 gO.OO mol) of p-phenylenediamine was used as a diamine compound. In the same manner as in Example 1, 309.0 g of a polyamic acid (C) having a logarithmic viscosity (η In) of 1.68 dl / g was referred to as "polymer (C-11)". Thereafter, an imidized polymer (D) having a logarithmic viscosity (η In) of 1.73 dl / g was obtained in the same manner as in Synthesis Example 2, except that 30.0 g of polymer (C-11) was used instead of polymer (A-1). Polymer (D-l2) "] to 28.5 g

Synthesis Example 8

Polya having a logarithmic viscosity (η In) of 1.58 d ν g in the same manner as in Synthesis Example 7 except that 432.50 g (1.00 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone was used as the diamine compound. 610.7 g of mixed acids (C) [this is referred to as "polymer (C-13) j") were obtained.

Synthesis Example 9

Synthesis Example 7 except that 179.34 g (O.80 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 43.62 g (O.20 mol) of pyromellitic dianhydride were used as tetracarboxylic dianhydride. In the same manner as described above, 307.8 g of a polyamic acid (C) having a logarithmic viscosity (η In) of 1.75 d v g [this is referred to as “polymer (C-14) j”) was obtained.

<Example 1>

2.0 g of the polymer (AI) obtained in Synthesis Example 1 and 8.0 g of the polymer (C-11) obtained in Synthesis Example 7 were dissolved in N-Meryl 2-pyrrolidone to give a solution having a solid content of 4% by weight, and the solution was changed to pore size. It filtered by the filter of 1 micrometer, and prepared the liquid crystal aligning agent of this invention.

This liquid crystal aligning agent was applied to the transparent electrode side of the glass substrate provided with the transparent electrode which consists of an ITO film | membrane using the aligning agent application printing machine, and dried for 20 minutes on a 180 degreeC hotplate, Formed.

The rubbing process was performed using the rubbing machine which has the roll which wound the cloth of the rayon agent to the surface of the thin film formed in this way, and the orientation ability of liquid crystal molecules was provided to the said thin film, and the liquid crystal aligning film was formed. The rubbing process conditions were made into the rotation speed of 500 rpm of a roll, the moving speed of a stage of 1 em / sec, and the length of the pushed hair of 0.4 mrn.

Two board | substrates with a liquid crystal aligning film were produced as mentioned above, the epoxy resin containing the aluminum oxide sphere of diameter of 17 micrometers was apply | coated by the screen printing method in the outer edge part of each board | substrate, and in each liquid crystal aligning film, The two substrates were disposed to face each other so that the rubbing direction of the substrate was antiparallel, and the outer edge portions were abutted and pressed to cure the adhesive. Subsequently, nematic liquid crystal rZLI-4792J (manufactured by Merck Co., Ltd.) was filled into the cell cap partitioned by the adhesive on the surface of the substrate and the outer edge portion, and then the injection hole was sealed with an epoxy adhesive to constitute a liquid crystal cell. Next, the liquid crystal display element was produced by bonding a polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface of each board | substrate which comprises a liquid crystal cell, so that a polarization direction may correspond with the rubbing direction of the liquid crystal aligning film formed in one surface of the said board | substrate.

When the liquid crystal aligning property was investigated about the liquid crystal display element produced as mentioned above, when the voltage was turned on and off, the abnormal domain was not confirmed in the liquid crystal cell, and it was confirmed that it had the outstanding orientation. In addition, the afterimage erasing time was very short for 0.7 second. Moreover, even if it used for a long time under solid solution high humidity, the display defect of white unevenness was high reliability which was not recognized. The above result was shown in Table 1.

<Examples 2 to 11>

Polyamic acid (A) or imidized polymer (B) and according to the prescription shown in Table 1

The liquid crystal aligning agent of the present invention was prepared in the same manner as in Example 1 except that the polyamic acid (C) or the imidized polymer (D) was dissolved in N-methyl-2-pyrrolidone to prepare a solid content of 4% by weight. It prepared, the thin film and the liquid crystal aligning film were formed, and the liquid crystal display element was produced. In this way, about the produced liquid crystal display element, the orientation of liquid crystal was evaluated, the afterimage erasing time was measured, and the reliability test was done. The results are shown in Table 1.

<Comparative Examples 1 and 2>

Example 1 except that each of the polymer (B-2) and the polymer (C-11) was dissolved in N-methyl-2-pyrrolidone according to the prescription shown in Table 1 to prepare a solid content concentration of 4% by weight. A liquid crystal aligning agent for comparison was prepared in the same manner as above, and a thin film and a liquid crystal aligning film were formed to prepare a liquid crystal display element. Thus, the orientation of liquid crystal was evaluated about the produced liquid crystal display element, the afterimage erase time was measured, and the reliability test was done. The results are shown in Table 1.

TABLE 1

According to the liquid crystal aligning agent of this invention, the liquid crystal display element with a short residual image erasing time can be manufactured.

Moreover, according to the liquid crystal aligning agent of this invention, even if it uses for a long time, it lists in a liquid crystal display element.

A defect does not generate | occur | produce at the time, and high fastness can be given to the said liquid crystal display element.

Moreover, according to the liquid crystal aligning agent of this invention, the liquid crystal aligning film excellent in the liquid-crystal orientation is

Can be formed.

It is provided with the liquid crystal aligning film formed with the liquid crystal aligning agent of this invention.

The liquid crystal display element is not only a TN type liquid crystal display element but also a STN (Super Twisted NematiC> type liquid crystal display element, SH (Super HomeotropiC) type liquid crystal display element, IPS (In-Plane-

Switching) It can be used suitably as various liquid crystal display elements, such as a liquid crystal display element, a ferroelectric liquid crystal display element, and an antiferroelectric liquid crystal display element. The liquid crystal display element can be effectively used in various devices, and can be suitably used as a display device such as a table calculator, a wrist watch, a table clock, a counting plate, a word processor, a personal computer, a liquid crystal television, or the like.

Claims (1)

At least one polymer selected from polyamic acid and imidized polymer thereof obtained by reacting a dianhydride of tetracarboxylic acid represented by the following general formula (1) with a diamine compound, and an dianhydride of tetracarboxylic acid represented by the following general formula (2) And a polyamic acid obtained by reacting a diamine compound with at least one polymer selected from imidized polymers thereof. <Formula 1>

<Formula 2>

In said formula, R <^1> represents a methyl group or an ethyl group, R <^2> represents a hydrogen atom, a methyl group, or an ethyl group, and a is an integer of 1-4.