JP2002338686A - Polyamic acid and polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polyamic acid and a novel polyimide useful as the liquid crystal orienting agent which can form a liquid crystal oriented film having a short period of time for erasing residual images in a liquid crystal display device. SOLUTION: The polyamic acid can be obtained from a tetracarboxylic dianhydride to be represented by formula (I) (R<1> and R<2> are each a hydrogen atom or a monovalent organic group, provided that at least one of R<1> and R<2> is a monovalent organic group; and a is an integer of 1-4) and a diamine compound to be represented by formula (II): H2 N-R<2> -NH2 (R<3> is a divalent organic group), and the polyimide is composed of a repeating unit to be represented by formula (III) R<1> , R<2> , R<3> , and a are as previously defined.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel polyamic acid and a novel polyimide useful as a liquid crystal aligning agent.

[0002]

2. Description of the Related Art At present, as a liquid crystal display device, a liquid crystal alignment film made of polyimide or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a substrate for the liquid crystal display device.
The two sheets are arranged to face each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich-structured cell, in which the major axis of the liquid crystal molecules is shifted from one substrate to the other substrate. So-called TN type (Twisted Nemati) that is continuously twisted 90 degrees toward
c) A TN type liquid crystal display device having a liquid crystal cell is known. In recent years, the ST has a higher contrast than the TN type liquid crystal display element and has less viewing angle dependence.
N (Super Twisted Nematic) type liquid crystal display devices have been developed. This STN type liquid crystal display element uses a nematic type liquid crystal blended with a chiral agent as an optically active substance as a liquid crystal, and the major axis of the liquid crystal molecule is continuously twisted over 180 degrees between substrates. This makes use of the birefringence effect generated by this. The alignment of the liquid crystal in the TN type liquid crystal display element and the STN type liquid crystal display element is usually expressed by a rubbed liquid crystal alignment film.

[0003]

However, in the conventional liquid crystal display device, the ionic charges generated when a voltage is applied are adsorbed on the liquid crystal alignment film, so that the ionic charges after the application of the voltage is released. There is a problem that an afterimage is generated on the display screen, and a sufficient contrast cannot be obtained because a difference in brightness of the liquid crystal display element between when the voltage is applied and when the voltage is released is reduced.

A first object of the present invention is to provide a novel polyamic acid which is useful as a liquid crystal aligning agent. A second object of the present invention is to provide a novel polyimide useful as a liquid crystal aligning agent.

[0005]

The polyamic acid of the present invention comprises a tetracarboxylic dianhydride comprising a compound represented by the following general formula (I) and a diamine compound represented by the following general formula (II): Characterized in that it is obtained from

[0006]

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Further, the polyimide of the present invention has the following general formula:
It has a repeating unit represented by (III).

[0008]

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According to the above-mentioned polyamic acid and / or the above-mentioned polyimide, good alignment characteristics can be exhibited, and the time from when the voltage is released to when the afterimage is erased in the liquid crystal display element ( The liquid crystal aligning agent can form a liquid crystal alignment film having a short "afterimage erasing time".

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. <Tetracarboxylic dianhydride> The polyamic acid of the present invention is a compound represented by the general formula (I) (hereinafter, referred to as a tetracarboxylic dianhydride to be subjected to the synthesis reaction).
It is referred to as “specific tetracarboxylic dianhydride”. ) Is used.

In the general formula (I) representing a specific tetracarboxylic dianhydride, R ¹ and R ² each represent a hydrogen atom or a monovalent organic group, and at least one of them is a monovalent organic group. You. When both R ¹ and R ² are hydrogen atoms, the afterimage elimination time depends on the liquid crystal aligning agent prepared using a polyamic acid and / or polyimide obtained by using these as a tetracarboxylic dianhydride. A liquid crystal alignment film having a short length cannot be formed.

Here, examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group such as a methyl group, an ethyl group and a butyl group; an aryl group such as a phenyl group and a naphthyl group; Can be.

The specific tetracarboxylic dianhydride is obtained by subjecting a styrene derivative represented by the following general formula (IV) to a Diels-Alder reaction with maleic anhydride, and further reacting the reaction product with maleic anhydride. Can be synthesized by

[0014]

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Here, styrene derivatives having a substituent represented by R ² at the α-position include α-methylstyrene and α-methylstyrene.
-Ethylstyrene, 3-methyl-α-methylstyrene,
4-methyl-α-methylstyrene, 3,4-dimethyl-
α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 3,4-dimethylstyrene, 4-t-butylstyrene, 4-phenylstyrene, 4-acetylstyrene, 4-naphthylstyrene, 4-t-butyl- α-methylstyrene, 4-phenyl-α-methylstyrene, 4-
Acetyl-α-methylstyrene, 4-naphthyl-α-methylstyrene and the like can be mentioned.
Α-Methylstyrene, 4-methylstyrene and 4-methyl-α-methylstyrene are preferred from the viewpoint of high reaction activity between the generated specific tetracarboxylic dianhydride and the diamine compound.

Specific examples of the specific tetracarboxylic dianhydride include compounds represented by the following chemical formulas (1) to (3). For example, the compound represented by the chemical formula (1) is a styrene derivative Is synthesized according to the following reaction formula A using α-methylstyrene.

[0017]

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[0018]

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As the tetracarboxylic dianhydride to be used in the synthesis reaction of the polyamic acid, a compound other than the specific tetracarboxylic dianhydride can be used in combination as long as the effect of the present invention is not impaired. . Here, the ratio of the specific tetracarboxylic dianhydride to the tetracarboxylic dianhydride used for the synthesis reaction is 0.1 to 1%.
00 mol%, and preferably 50 to 100 mol%.

Examples of the tetracarboxylic dianhydride that can be used in combination include, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetra Carboxylic dianhydride, 5- (2,5-
Dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-
Aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4
4'-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenylsulfonetetracarboxylic 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) ) Diphenyl sulfide dianhydride, 4,4 '
-Bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,
3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p -Phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (tri Phenylphthalic acid) -4,4'-diphenylmethane dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-
3-furanyl) -naphtho [1,2-c] -furan-1,
Examples thereof include aromatic tetracarboxylic dianhydrides such as 3-dione, and these can be used alone or in combination of two or more.

Of these, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid Dianhydride, 1,3,3
a, 4,5,9b-Hexahydro-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 ] -Oct-7-ene-2,3,5,6-
Tetracarboxylic dianhydride is preferable, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentylacetic dianhydride are particularly preferable.

<Diamine compound> Polyamic of the present invention
Represented by the above general formula (II), which is subjected to an acid synthesis reaction
As the diamine compound, p-phenylenediamine, m
-Phenylenediamine, 4,4'-diaminodiphenyl
Methane, 4,4'-diaminodiphenylethane, 4,
4'-diaminodiphenyl sulfide, 4,4'-dia
Minodiphenyl sulfone, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 4,4'-diaminobenz
Anilide, 4,4'-diaminodiphenyl ether,
1,5-diaminonaphthalene, 3,3-dimethyl-4,
4'-diaminobiphenyl, 5-amino-1- (4'-
Aminophenyl) -1,3,3-trimethylindane,
6-amino-1- (4'-aminophenyl) -1,3,3
3-trimethylindane, 3,4'-diaminodiphenyl
Luether, 3,3'-diaminobenzophenone, 3,
4'-diaminobenzophenone, 4,4'-diaminobenzo
Nzophenone, 2,2-bis [4- (4-aminopheno
Xy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] hexafluoropropa
2,2-bis (4-aminophenyl) hexafluoro
Lopropane, 2,2-bis [4- (4-aminophenoxy)
C) phenyl] sulfone, 1,4-bis (4-aminophenyl
Enoxy) benzene, 1,3-bis (4-aminopheno)
Xy) benzene, 1,3-bis (3-aminophenoxy)
B) benzene, 9,9-bis (4-aminophenyl)-
10-hydroanthracene, 2,7-diaminofluore
9,9-bis (4-aminophenyl) fluorene,
4,4'-methylene-bis (2-chloroaniline),
2,2 ', 5,5'-tetrachloro-4,4'-diami
Noviphenyl, 2,2'-dichloro-4,4'-diami
No-5,5'-dimethoxybiphenyl, 3,3'-dimethyl
Toxic-4,4'-diaminobiphenyl, 1,4,4 '
-(P-phenyleneisopropylidene) bisaniline,
4,4 '-(m-phenyleneisopropylidene) bisur
Niline, 2,2'-bis [4- (4-amino-2-tri
Fluoromethylphenoxy) phenyl] hexafluoro
Propane, 4,4'-diamino-2,2'-bis (tri
Fluoromethyl) biphenyl, 4,4'-bis [(4-
Amino-2-trifluoromethyl) phenoxy] -oct
Aromatic diamines such as tafluorobiphenyl; diamino
A hetero atom such as tetraphenylthiophene
Aromatic diamine; 1,1-meta-xylylenediamine, 1,
3-propanediamine, tetramethylenediamine, pen
Tamethylene diamine, hexamethylene diamine, hepta
Methylenediamine, octamethylenediamine, nonameti
Diamine, 4,4-diaminoheptamethylene diamine
1,4-diaminocyclohexane, isophoronedia
Min, tetrahydrodicyclopentadienylene diamide
, Hexahydro-4,7-methanoindaniline meth
Rangeamine, tricyclo [6,2,1,0 ^2.7] -C
Ndecylenedimethyldiamine, 4,4'-methylenebis
(Cyclohexylamine) and other aliphatic or cycloaliphatic di
Amine; a compound represented by the following chemical formulas (4) to (6)
These can be used alone or in combination of two or more.
Can be used together.

[0023]

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Of these, p-phenylenediamine,
4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4 ′
-Diaminodiphenyl ether, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 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 and the like are particularly preferable, and p-phenylenediamine, 4,
4'-diaminodiphenylmethane and 4,4 '-(p
-Phenyleneisopropylidene) bisaniline.

<Polyamic Acid> The polyamic acid of the present invention comprises a tetracarboxylic dianhydride containing the compound represented by the above general formula (I) and a diamine compound represented by the above general formula (II). And a ring-opening polyaddition reaction.

The proportion of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid is as follows:
The ratio of the acid anhydride group of the tetracarboxylic dianhydride to 0.2 to 2 equivalents per 1 equivalent of the amino group contained in the diamine compound is preferable, and more preferably 0.3 to 1.
It is a ratio equivalent to 2 equivalents.

The synthesis reaction of the polyamic acid is carried out in an organic solvent usually at 0 to 150 ° C., preferably at 0 to 100 ° C.
Is performed under the following temperature conditions. Here, as the organic solvent,
There is no particular limitation as long as the polyamic acid to be synthesized can be dissolved. For example, N-methyl-2-pyrrolidone,
Non-protonic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; m-cresol, xylenol, phenol, halogenated phenol, etc. Can be exemplified. The amount (a) of the organic solvent used is usually such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. It is preferable that the amount is large.

The organic solvent includes alcohols, ketones, esters which are poor solvents for polyamic acid,
Ethers, halogenated hydrocarbons, hydrocarbons and the like can be used in combination as long as the generated polyamic acid does not precipitate. Specific examples of such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol,
Triethylene glycol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene Glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-
Butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.

As described above, a reaction solution obtained by dissolving the polyamic acid of the present invention is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. The polyamic acid can be purified by dissolving the polyamic acid in an organic solvent again and then performing a step of precipitating with a poor solvent once or several times.

The polyamic acid obtained as described above has a logarithmic viscosity (ηln) value of usually 0.05 to 10
dl / g, preferably 0.05 to 5 dl / g. The value of the logarithmic viscosity (ηln) in the present invention is N-methyl-
Using 2-pyrrolidone as a solvent, the concentration is 0.5 g / 1.
The viscosity is measured at 30 ° C. for a solution having a volume of 00 ml, and is determined by the following equation.

[0031]

(Equation 1)

<Polyimide> The polyimide of the present invention comprises:
(I) By heating the above-mentioned polyamic acid, or dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and an imidization catalyst to the solution, and heating as necessary, whereby the dehydration ring closure (imide Or (ii) mixing the above specific tetracarboxylic dianhydride and a diisocyanate compound and, if necessary, heating and condensing. When the polyimide obtained in this manner uses, for example, those represented by the above-mentioned chemical formulas (1) to (3) as tetracarboxylic dianhydrides, the above-mentioned formulas (III-
1) It consists of repeating units represented by (III-3).

In the above reaction (i), the reaction temperature in the method of heating the polyamic acid is usually from 60 to 25.
The temperature is set to 0 ° C, preferably 100 to 170 ° C. When the reaction temperature is lower than 60 ° C., the imidization reaction does not proceed sufficiently, and when the reaction temperature exceeds 250 ° C., the molecular weight of the obtained polyimide may decrease.

On the other hand, in the above method of adding a dehydrating agent and an imidation catalyst to the polyamic acid solution, the dehydrating agent may be an acid anhydride such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride. it can.
The amount of the dehydrating agent used is preferably 1.6 to 20 mol per 1 mol of the repeating unit of the polyamic acid. Further, as the imidation catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, but are not limited thereto. The amount of the imidization catalyst used is preferably 0.5 to 10 mol per 1 mol of the dehydrating agent used. In addition, as the organic solvent used for the dehydration ring closure reaction, the organic solvents exemplified as those used for the synthesis of polyamic acid can be exemplified. The reaction temperature of the dehydration ring-closing reaction is generally 0 to 180 ° C, preferably 60 to 150 ° C. The polyimide of the present invention can be purified by subjecting the reaction solution thus obtained to the same operation as the method for purifying a polyamic acid.

In the above reaction (ii), specific examples of the diisocyanate compound include: aliphatic diisocyanate compounds such as hexamethylene diisocyanate; cycloaliphatic diisocyanate compounds such as cyclohexane diisocyanate; diphenylmethane-4,4'-diisocyanate, diphenyl ether- 4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 1,2-diphenylethane-p, p'-diisocyanate, 2,2-diphenylpropane-p, p'-diisocyanate, 2,2-diphenyl-1,1,1,
3,3,3-hexafluoropropane-p, p'-diisocyanate, 2,2-diphenylbutane-p, p'-
Diisocyanate, diphenyl dichloromethane-4,
4'-diisocyanate, diphenylfluoromethane-
4,4′-diisocyanate, benzophenone-4,
4 'diisocyanate, N-phenylbenzoic acid amide-
Aromatic diisocyanate compounds such as 4,4'-diisocyanate can be mentioned, and these can be used alone or in combination of two or more. A catalyst is not particularly required for the reaction (ii), and the reaction temperature is usually 50 to 200 ° C, preferably 100 to 160 ° C.
° C.

The polyimide obtained by the above reactions (i) and (ii) has a logarithmic viscosity (ηln) value of usually 0.05 to 10 dl / g, preferably 0.05 to 5 d / g.
1 / g.

<Liquid Crystal Alignment Agent> The above-mentioned polyamic acid and / or polyimide are dissolved and contained in an organic solvent to obtain a liquid crystal alignment agent. Examples of the organic solvent constituting the liquid crystal aligning agent include the solvents exemplified as those used in the synthesis reaction of polyamic acid and the dehydration ring closure reaction. In addition, the poor solvents exemplified as those which can be used together in the synthesis reaction of the polyamic acid can be appropriately selected and used in combination.

The concentration of the polyamic acid and / or polyimide in the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent is applied to the surface of the substrate to form a coating film serving as a liquid crystal alignment film.
If it is less than 10% by weight, the thickness of this coating film is too small to obtain a good liquid crystal alignment film, and the concentration is 10%.
If the content is more than 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, resulting in poor coating characteristics.

The polyamic acid and the polyimide used for the liquid crystal aligning agent may be of a terminal-modified type.
By using the terminal-modified type polyamic acid and polyimide, the molecular weight is adjusted, and the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified type can be synthesized by adding an acid-anhydride or a monoamine compound to the reaction system when synthesizing the polyamic acid or the polyimide.

Here, examples of the acid-anhydride include maleic anhydride, phthalic anhydride and nadic anhydride. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine and n-butylamine. -Pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, Examples thereof include n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine.

The liquid crystal aligning agent includes polyamic acid and / or
Alternatively, from the viewpoint of improving the adhesion of the polyimide to the substrate surface, a functional silane-containing compound may be contained. Such functional silane-containing compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 1
0-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3 , 6-Diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3- Examples thereof include aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.

<Liquid crystal display element> A liquid crystal display element obtained by using a liquid crystal aligning agent can be manufactured, for example, by the following method.

(1) A liquid crystal aligning agent is applied to one surface of a substrate on which a patterned transparent conductive film is provided, for example, by a roll coater method, a spinner method, a printing method, and the like, and then the coated surface is heated. This forms a coating film. Here, as the substrate, for example, a transparent substrate made of glass such as float glass or soda glass; or a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or polycarbonate can be used. As the transparent conductive film provided on one surface of a substrate, NESA film (US PPG registered trademark) made of tin oxide (SnO _2), indium oxide - such as an ITO film made of tin oxide (In ₂ O ₃ -SnO ₂₎ the For the patterning of these transparent conductive films, a photo-etching method or a method using a mask in advance is used. In applying the liquid crystal aligning agent, a functional silane-containing compound, a functional titanium-containing compound, etc. are applied in advance to the substrate surface and the surface of the substrate in order to further improve the adhesion between the transparent conductive film and the coating film. You can also. The heating temperature is from 80 to 250 ° C, preferably from 120 to 200 ° C. The thickness of the formed coating film is usually 0.001 to 1 μm, preferably 0.01 μm.
05 to 0.5 μm. In addition, the liquid crystal alignment agent containing polyamic acid forms a coating film to be an alignment film by removing the organic solvent after coating, but further proceeds with dehydration ring closure by further heating, and the imidized coating film. You can also.

(2) A rubbing treatment is performed in which the formed coating film surface is rubbed in a predetermined direction with a roll around which a cloth made of fibers such as nylon, rayon, cotton or the like is wound. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

The liquid crystal alignment film formed by the liquid crystal alignment agent is partially irradiated with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. A process in which a pretilt angle is changed or a resist film is partially formed on the surface of a liquid crystal alignment film which has been subjected to a rubbing process as disclosed in JP-A-5-107544, which is different from the rubbing process. By performing a process of changing the alignment ability of the liquid crystal alignment film by removing the resist film after performing the rubbing process in the direction, the visibility characteristics of the liquid crystal display element can be improved.

(3) Two substrates on which a liquid crystal alignment film is formed as described above are prepared, and the two substrates are separated by a gap so that the rubbing directions of the respective liquid crystal alignment films are orthogonal or antiparallel. (Cell gap)
The peripheral portions of the two substrates are bonded to each other using a sealant, and liquid crystal is injected and filled into the substrate surface and a cell gap defined by the sealant, and the injection hole is sealed to form a liquid crystal cell. Then, a polarizing plate is provided on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, and the polarization direction thereof coincides with or is orthogonal to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. Thus, a liquid crystal display element is obtained.

Here, as the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable. For example, a Schiff base liquid crystal, an azoxy liquid crystal,
Biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cubane-based liquid crystal, and the like can be used. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate, and chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck & Co.) It can also be used by adding it. Further, p-decyloxybenzylidene-p
Ferroelectric liquid crystals such as -amino-2-methylbutylcinnamate can also be used. Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate or an H film in which a polarizing film called an H film absorbing iodine is sandwiched by a cellulose acetate protective film while stretching and aligning polyvinyl alcohol. A polarizing plate composed of itself can be mentioned.

[0048]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the methods for evaluating the afterimage elimination time and the orientation of the liquid crystal in the liquid crystal display device are as follows.

[Afterimage erasing time] After a DC voltage of 10 V was applied to the liquid crystal cell for one hour, the application of the voltage was released, the display screen was visually observed, and after the application of the voltage was released, the display on the screen was stopped. The time until the afterimage was eliminated was measured.

[Orientation of Liquid Crystal] The presence or absence of abnormal domains when the voltage was turned on / off (applied / released) was observed with a polarizing microscope, and the case where there were no abnormal domains was judged as “good”.

Synthesis Example 1 30.66 g (97.5 g) of the specific tetracarboxylic dianhydride represented by the above chemical formula (1)
6 mmol) and 4,4'-diaminodiphenylmethane 1
9.34 g (97.56 mmol) and N-methyl-
It was dissolved in 450 g of 2-pyrrolidone and reacted at 60 ° C. for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate a reaction product. Thereafter, the resin is washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid of the present invention having a logarithmic viscosity of 1.00 dl / g [this is referred to as “polyamic acid (a)”. 38.44 g was obtained.

(Synthesis Example 2) 25.00 g of the polyamic acid (a) obtained in Synthesis Example 1 was dissolved in 450 g of N-methyl-2-pyrrolidone, and 7.72 g of pyridine was added to this solution.
And 9.96 g of acetic anhydride were added, and heated at 115 ° C. for 4 hours to cause a dehydration ring closure reaction. Next, the reaction product solution is precipitated and dried in the same manner as in Synthesis Example 1 to obtain a polyimide of the present invention having a logarithmic viscosity of 1.00 dl / g [this is referred to as “polyimide (a)”. 14.91 g
I got

(Synthesis Example 3) The amount of the specific tetracarboxylic dianhydride was changed to 37.20 g (118.36 mmol), and 12.80 g of p-phenylenediamine was substituted for 4,4'-diaminodiphenylmethane ( 118.36 mmol) in the same manner as in Synthesis Example 1 except that
The polyamic acid of the present invention having a logarithmic viscosity of 1.10 dl / g [this is referred to as “polyamic acid (b)”. ] 3
2.60 g were obtained.

Synthesis Example 4 26.16 g (83.2 g) of the specific tetracarboxylic dianhydride represented by the above chemical formula (1)
4 mmol), 4.08 g (20.80 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5.06 g (46.80 mmol) of p-phenylenediamine and 4,4′-diaminodiphenylmethane 9.28 g
(46.80 mmol) and 5.42 g (10.36 mmol) of the diamine compound represented by the above chemical formula (4) were dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. Except that, in the same manner as in Synthesis Example 1, the polyamic acid of the present invention having an logarithmic viscosity of 0.90 dl / g [this is referred to as “polyamic acid (c)”. 40.06 g was obtained. Then, the logarithmic viscosity was 0.90 dl / in the same manner as in Synthesis Example 2 except that polyamic acid (c) was used instead of polyamic acid (a).
g of the polyimide of the present invention [this is referred to as “polyimide (b)”. 17.98 g was obtained.

(Synthesis Example 5) A specific tetracarboxylic dianhydride represented by the above chemical formula (2) in place of the specific tetracarboxylic dianhydride represented by the above chemical formula (1)
A polyamic acid of the present invention having a logarithmic viscosity of 0.92 dl / g [this is referred to as “polyamic acid (d)” in the same manner as in Synthesis Example 1 except that 65 g (97.56 mmol) was used. 36.62 g was obtained. Next, the logarithmic viscosity was 0.1 in the same manner as in Synthesis Example 2 except that polyamic acid (d) was used instead of polyamic acid (a).
92 dl / g of the polyimide of the present invention [this is referred to as “polyimide (c)”. 16.04 g was obtained.

(Comparative Synthesis Example 1) Instead of the specific tetracarboxylic dianhydride, 24.86 g (126.76 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was used, and 4,4 Except that the amount of '-diaminodiphenylmethane used was changed to 25.14 g (126.76 mmol), the logarithmic viscosity was 1.
20 dl / g of a comparative polyamic acid [this is referred to as “polyamic acid (x)”. 44.42 g was obtained.

(Comparative Synthesis Example 2) Instead of the specific tetracarboxylic dianhydride, 32.22 g (164.28 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was used, and 4,4 17.78 g of p-phenylenediamine instead of '-diaminodiphenylmethane (164.
A polyamic acid for comparison having a logarithmic viscosity of 1.26 dl / g [this is referred to as "polyamic acid (y)" in the same manner as in Synthesis Example 1 except that 28 mmol) was used. 41.90 g was obtained.

(Comparative Synthesis Example 3) Instead of the specific tetracarboxylic dianhydride represented by the above chemical formula (1), 1,3,3
a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2
-C] -furan-1,3-dione 29.30 g (97.
A polyamic acid for comparison having a logarithmic viscosity of 0.90 dl / g [this is referred to as “polyamic acid (z)” in the same manner as in Synthesis Example 1 except that 56 mmol) was used. 38.96 g was obtained. Then, the logarithmic viscosity was 0.90 dl / in the same manner as in Synthesis Example 2 except that polyamic acid (z) was used instead of polyamic acid (a).
g for comparison polyimide [this is referred to as “polyimide (z)”. 17.44 g was obtained.

Example 1 (1) Preparation of Liquid Crystal Alignment Agent: The polyimide (a) obtained in Synthesis Example 2 was dissolved in γ-butyrolactone to obtain a solution having a solid content concentration of 4% by weight, and this solution was subjected to pore size analysis. The mixture was filtered through a 1 μm filter to prepare a liquid crystal aligning agent.

(2) Production of liquid crystal display element: ITO provided on one surface of a glass substrate having a thickness of 1 mm
The liquid crystal aligning agent prepared as described above was applied on a transparent conductive film composed of a film by using a spinner, and dried at 180 ° C. for 1 hour to form a coated film having a dry film thickness of 800 °.

A rubbing treatment was performed on the surface of the formed coating film using a rubbing machine having a roll around which a nylon cloth was wound, thereby producing a liquid crystal alignment film. Here, the rubbing treatment conditions are as follows:
The rotation speed of the stage was 1 cm / sec at 0 rpm.

Two substrates on which a liquid crystal alignment film is formed as described above are prepared, and an epoxy resin-based adhesive containing aluminum oxide spheres having a diameter of 17 μm is applied to the outer edge of each substrate by a screen printing method. After that, the two substrates were arranged to face each other with a gap therebetween so that the rubbing directions of the respective liquid crystal alignment films were antiparallel, and the outer edges were brought into contact with each other and pressed to cure the adhesive.

A nematic liquid crystal “MLC-2001” (manufactured by Merck) is injected and filled into the cell gap defined by the adhesive on the surface of the substrate and the outer edge, and then the injection hole is sealed with an epoxy adhesive. The liquid crystal cell was constituted by stopping the operation. Thereafter, a polarizing plate was attached to the outer surface of the liquid crystal cell so that the polarization direction coincided with the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate, thereby producing a liquid crystal display device.

In the liquid crystal display device manufactured as described above, no abnormal domain was observed when the voltage was applied to and released from the liquid crystal cell, and the liquid crystal orientation was good. The afterimage erasing time of the liquid crystal display element was 0.36.
Seconds were extremely short.

Example 2 Instead of polyimide (a),
A liquid crystal aligning agent was prepared and a liquid crystal display device was prepared in the same manner as in Example 1 except that the polyamic acid (b) obtained in Synthesis Example 3 was used. In the manufactured liquid crystal display element, no abnormal domain was observed when the voltage was applied to and released from the liquid crystal cell, and the liquid crystal orientation was good. The afterimage erasing time of the liquid crystal display element was as short as 0.22 seconds.

Example 3 A liquid crystal aligning agent was prepared and a liquid crystal display device was produced in the same manner as in Example 2 except that the drying temperature after applying the liquid crystal aligning agent was 250 ° C. By setting the drying temperature to 250 ° C., the imidization of the coating film proceeded simultaneously with the removal of the solvent, and a liquid crystal alignment film mainly composed of polyimide was formed. In the manufactured liquid crystal display element, no abnormal domain was observed when the voltage was applied to and released from the liquid crystal cell, and the liquid crystal orientation was good. The afterimage erasing time of the liquid crystal display element was as short as 0.25 seconds.

Example 4 Instead of polyimide (a),
A liquid crystal alignment agent was prepared and a liquid crystal display device was produced in the same manner as in Example 1 except that the polyimide (b) obtained in Synthesis Example 4 was used. In the manufactured liquid crystal display element, no abnormal domain was observed when the voltage was applied to and released from the liquid crystal cell, and the liquid crystal orientation was good. Also,
The afterimage erasing time of the liquid crystal display element was as short as 0.33 seconds.

Example 5 Instead of polyimide (a),
A liquid crystal alignment agent was prepared and a liquid crystal display device was prepared in the same manner as in Example 1 except that the polyimide (c) obtained in Synthesis Example 5 was used. In the manufactured liquid crystal display element, no abnormal domain was observed when the voltage was applied to and released from the liquid crystal cell, and the liquid crystal orientation was good. Also,
The afterimage erasing time of the liquid crystal display element was as short as 0.20 seconds.

[Comparative Example 1] Instead of polyimide (a),
A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the polyamic acid (x) obtained in Comparative Synthesis Example 1 was used, and a liquid crystal display device was produced. In the manufactured liquid crystal display element, abnormal domains were not observed when voltage was applied to and released from the liquid crystal cell, and the orientation of the liquid crystal was good. However, the afterimage erasing time of the liquid crystal display element was 12 seconds.
It took a long time before the afterimage was erased.

[Comparative Example 2] Instead of polyimide (a),
A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the polyamic acid (y) obtained in Comparative Synthesis Example 2 was used, and a liquid crystal display device was produced. In the manufactured liquid crystal display element, abnormal domains were not observed when voltage was applied to and released from the liquid crystal cell, and the orientation of the liquid crystal was good. However, the afterimage erasing time of the liquid crystal display element was 10 seconds.
It took a long time before the afterimage was erased.

[Comparative Example 3] Instead of polyimide (a),
A liquid crystal aligning agent was prepared and a liquid crystal display device was produced in the same manner as in Example 1 except that the polyimide (z) obtained in Comparative Synthesis Example 3 was used. In the manufactured liquid crystal display element, abnormal domains were not observed when voltage was applied to and released from the liquid crystal cell, and the orientation of the liquid crystal was good.
The afterimage erasing time of the liquid crystal display element was 6 seconds, and it took a long time until the afterimage was erased.

[0072]

According to the present invention, a novel polyamic acid and / or a novel polyimide useful as a liquid crystal aligning agent can be provided. According to these polyamic acids or polyimides, good alignment characteristics can be obtained. It is possible to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film having a short afterimage erasing time in a liquid crystal display element.

The liquid crystal alignment film formed by the liquid crystal alignment agent is suitable for forming various liquid crystal display elements such as a TN type liquid crystal display element, an STN type liquid crystal display element and an SH (Super Homeotropic) type liquid crystal display element. Can be used. Further, the liquid crystal display device provided with the liquid crystal alignment film has excellent liquid crystal alignment and reliability, and can be effectively used for various devices. For example, a desk calculator, a wristwatch, a clock, a counting display, a word processor It can be suitably used as a display device such as a personal computer and a liquid crystal television.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuo Matsuki 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd. (72) Inventor Akio Hiraharu 2-11-24 Tsukiji, Chuo-ku, Tokyo No. Japan synthetic rubber F term (reference) 2H090 HB09 HB10 HC06 HC15 MA01 MA02 4J043 PA02 PA04 PA19 QB15 QB26 QB31 QB58 RA35 RA39 SA02 SA06 SA15 SA42 SA43 SA44 SA46 SA47 SA52 SA54 SA63 SA72 SB01 SB02 TA22 TA66 TA67 TA71 TB01 TB02 UA022 UA031 UA032 UA041 UA042 UA051 UA061 UA062 UA082 UA121 UA122 UA131 UA132 UA141 UA142 UA151 UA152 UA221 UA231 UA232 UA241 UA251 UA261 UA262 UA622 UA632 UA662 UA672 UA711 UA761 UA762 UA771 UB011 UB021 UB022 UB061 UB062 UB121 UB122 UB131 UB132 UB151 UB152 UB171 UB221 UB281 UB282 UB301 UB302 UB322 UB382 UB401 UB402 VA011 VA021 VA022 VA031 VA032 VA041 VA051 VA061 VA062 VA071 VA072 VA081 YA06 YA08 ZB23

Claims (4)

[Claims] 1. A polyamic acid obtained from a tetracarboxylic dianhydride comprising a compound represented by the following general formula (I) and a diamine compound represented by the following general formula (II). Embedded image 2. The polyamic acid according to claim 1, wherein the tetracarboxylic dianhydride is a compound represented by any one of the following chemical formulas (1) to (3). Embedded image 3. A polyimide comprising a repeating unit represented by the following general formula (III). Embedded image 4. A polyimide comprising a repeating unit represented by any of the following formulas (III-1) to (III-3). Embedded image