JP2003107486A - Liquid crystal aligning agent for transverse electric field system liquid crystal display element and transverse electric field system liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent which makes it possible to give a liquid crystal display element having liquid crystal aligning layers and which is surely imparted with the alignment ability of liquid crystal molecules by a rubbing treatment, has excellent liquid crystal alignment characteristics and excellent after-image characteristics, a liquid crystal aligning agent for a transverse electric field system liquid crystal display element having high film strength and a transverse electric field system liquid crystal display element. SOLUTION: The liquid crystal aligning agent for the transverse electric field system liquid crystal display element characterized in forming a resin film containing at least one kind selected from a polyamic acid and polyimide, having a water contact angle of >=65 deg. and pencil hardness of HB or above, is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystal aligning agent for a horizontal electric field type liquid crystal display device. More specifically, it relates to a liquid crystal aligning agent for a horizontal electric field type liquid crystal display device having a low surface adsorptivity and a high film strength.

[0002]

2. Description of the Related Art At present, as a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide or the like is formed on the surface of a substrate provided with a transparent conductive film to form a liquid crystal display element substrate, and two of them are opposed to each other. A layer of a nematic liquid crystal having a positive dielectric anisotropy is formed in the gap to form a cell having a sandwich structure, and the long axis of the liquid crystal molecules is continuously moved from one substrate to the other substrate. The so-called TN type (Twisted Nemati)
c) A TN type liquid crystal display device having a liquid crystal cell is known. In addition, the contrast is higher than that of the TN type liquid crystal display element, and the STN (Super
Twisted Nematic) type liquid crystal display device,
Vertical alignment 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 which is an optically active substance as liquid crystal,
It utilizes the birefringence effect generated by the state in which the major axis of liquid crystal molecules is continuously twisted between the substrates over 180 degrees or more.

On the other hand, the horizontal electric field type liquid crystal display element is
Two electrodes for driving the liquid crystal are arranged on one side of the substrate in a comb shape, and an electric field parallel to the substrate surface is generated to control the liquid crystal molecules. This device is characterized in that it can obtain a wide viewing angle comparable to that of a cathode ray tube without gradation reversal or color tone change without using an optical compensation film.
The alignment of the liquid crystal in these liquid crystal display elements is usually expressed by a liquid crystal alignment film that has been subjected to a rubbing treatment.

[0004]

However, a liquid crystal aligning agent containing a conventionally known polyamic acid or an imide polymer having a structure obtained by dehydration and ring closure of the polyamic acid is used to produce a lateral electric field type liquid crystal display device or the like. In the case of manufacturing, since impurities such as a cleaning agent that may be used in the cleaning step after the rubbing process remain and are adsorbed on the surface of the liquid crystal alignment film, display unevenness occurs on the liquid crystal display element due to long-term use. In addition, there is a problem that the afterimage characteristic is deteriorated.

The present invention has been made in view of the above circumstances, and a first object of the present invention is to surely impart the aligning ability of liquid crystal molecules by rubbing treatment and to obtain excellent liquid crystal aligning property. Another object of the present invention is to provide a liquid crystal aligning agent capable of providing a liquid crystal display device having a liquid crystal aligning film having
A second object of the present invention is to provide a liquid crystal aligning agent that provides a liquid crystal aligning film for a liquid crystal display device having excellent afterimage characteristics. A third object of the present invention is that the adsorbability of impurities is low,
It is to provide a liquid crystal aligning agent having high film strength. Other objects and advantages of the present invention will be apparent from the following description.

[0006]

According to the present invention, the above-mentioned problems include, firstly, containing at least one selected from polyamic acid and polyimide, having a water contact angle of 65 ° or more and a pencil hardness. This is achieved by a liquid crystal aligning agent for a horizontal electric field type liquid crystal display device, which is characterized by forming a resin film having a HB or more.

Further, according to the present invention, secondly, the above-mentioned problem is characterized by containing a polyamic acid and / or a polyimide which satisfies at least one of the following (1) and (2). , A liquid crystal aligning agent for a horizontal electric field type liquid crystal display device. (1) At least one group represented by the following formula (1-1) and the following formula (1-2) (hereinafter, “(1-
1)) "also referred to as" (1-2) group ").

[0008]

[Chemical 2]

(In the formula, R ^a , R ^b , R ^c and R ^d each independently represent a halogen atom or a monovalent organic group,
m and n each independently represent an integer of 0 to 3, and p and q each independently represent an integer of 0 to 4. )

(2) It contains a fluorine atom.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polyamic acid used in the liquid crystal aligning agent for a horizontal electric field type liquid crystal display device of the present invention (hereinafter, also simply referred to as “the liquid crystal aligning agent of the present invention”) is a tetracarboxylic dianhydride and a diamine compound in an organic solvent. Obtained by reacting.
Further, the polyimide used in the liquid crystal aligning agent of the present invention,
The polyamic acid can be obtained by dehydration ring closure.
The liquid crystal aligning agent of the present invention forms a resin film having a water contact angle of 65 ° or more and a pencil hardness of HB or more, preferably H or more. When the water contact angle of the obtained resin film is less than 65 °, the obtained liquid crystal alignment film easily adsorbs impurities, and tends to adversely affect long-term reliability and afterimage characteristics. If the pencil hardness of the obtained resin film is softer than HB,
The rubbing treatment tends to damage the surface of the liquid crystal alignment film, which tends to adversely affect display characteristics and long-term reliability. The polyamic acid and polyimide used in the present invention are not particularly limited as long as the resin film obtained satisfies the above conditions. Preferable examples include polyamic acid and / or polyimide which satisfy the above condition (1) or (2).

The polyamic acid and polyimide satisfying the above condition (1) have a group (1-1) and / or a group (1-2) as a tetracarboxylic dianhydride and / or a diamine compound. It is obtained by using. Preferably, a tetracarboxylic dianhydride having a group (1-1) and / or a diamine compound having a group (1-2) is used. The polyamic acid and polyimide satisfying the above condition (2) can be obtained by using a tetracarboxylic dianhydride and / or a diamine compound containing a fluorine atom.

The polyamic acid used in the present invention
And polyimide are required to meet both conditions (1) and (2) above.
It may satisfy the following. Such a polyamic
Acids and polyimides are tetracarboxylic dianhydrides and
And / or a diamine compound as the group (1-1)
And / or (1-2), R in the formula^a , R
^b , R^c And R^d At least one of them is a fluorine atom
Or with a fluorine-containing organic group such as a trifluoromethyl group
Using a group of (1-1) and / or
Is a tetracarboxylic dianhydride having a group of (1-2)
And / or diamine compound and fluorine atom
Tetracarboxylic acid dianhydride and / or diamine compound
To obtain polyamic acid or polyimide
Or a polyamic that satisfies the above condition (1)
Satisfies the above condition (2) with acid and / or polyimide
Mix with polyamic acid and / or polyimide
It can be obtained by using it.

The polyamic acid and polyimide used in the present invention can be used as a mixture with other polyamic acid and polyimide which do not satisfy the above condition (1) or (2). Further, as the tetracarboxylic dianhydride and the diamine compound, the group (1-1), (1-
By copolymerizing a tetracarboxylic acid dianhydride and a diamine compound having neither a group of 2) nor a fluorine atom (hereinafter, also referred to as "another tetracarboxylic acid dianhydride" and "another diamine compound", respectively). It can also be used. In the present invention, the group (1-1) and the group (1-
The total proportion of the tetracarboxylic dianhydride and the diamine compound having at least one selected from the group 2) is
It is preferably 5% by weight or more based on the total amount of all tetracarboxylic dianhydrides and all diamine compounds used in the liquid crystal aligning agent of the present invention. Further, the total proportion of the tetracarboxylic dianhydride and the diamine compound containing a fluorine atom is 5% by weight with respect to the total amount of all the tetracarboxylic dianhydride and all the diamine compounds used in the liquid crystal aligning agent of the present invention. % Or more is preferable. Less than,
A method for producing a polyamic acid or polyimide that can be used in the present invention will be described.

[Tetracarboxylic acid dianhydride] Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid include butanetetracarboxylic acid dianhydride, 1,
2,3,4-cyclobutanetetracarboxylic dianhydride,
1,2-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro- 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic dianhydride, 1,2,4,5
-Cyclohexanetetracarboxylic dianhydride, 3,3 ',
4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4, 5-Tetrahydrofuran tetracarboxylic 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-5-methyl-5 (tetrahydro-2,5-dioxo-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, Three
a, 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-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,
2,2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, aliphatic and alicyclic tetracarboxylic acids such as compounds represented by the following formulas (I) and (II) Acid dianhydride;

[0016]

[Chemical 3]

(Where R is¹ And R³ Has an aromatic ring
Represents a divalent organic group, R² And R ^Four Is a hydrogen atom
Or an alkyl group, and a plurality of R² And R^Four 
May be the same or different. )

Pyromellitic dianhydride, 3-trifluoromethyl pyromellitic dianhydride, difluoro-2,3,
5,6-benzenetetracarboxylic dianhydride, ditrifluoromethyl-2,3,5,6-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride 3,3 ', 4,4'-
Biphenyl ether tetracarboxylic dianhydride 3,
3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic acid 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 acid dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4 -Bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride,
2,3,3 ′, 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 (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate) ) 1,4-butanediol-bis (anhydrotrimeritate), 1,6-hexanediol-bis (anhydrotrimeritate), 1,8-octanediol-bis (anhydrotrimeritate), 2,2-
Examples thereof include aromatic tetracarboxylic dianhydrides such as bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate) and compounds represented by the following formulas (1) to (4). These may be used alone or in combination of two or more.

Of the above tetracarboxylic dianhydrides,
Examples of the tetracarboxylic dianhydride having the group (1-1) include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride. Anhydrous etc. are mentioned. Further, as the tetracarboxylic acid dianhydride containing a fluorine atom, 3-trifluoromethyl pyromellitic dianhydride, difluoro-2,
3,5,6-benzenetetracarboxylic dianhydride, ditrifluoromethyl-2,3,5,6-benzenetetracarboxylic dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalate Acid dianhydride, 2,2-bis [4- (3,
4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride and the like. Of these, 3, 3 ', 4,
4'-biphenyltetracarboxylic dianhydride, 3,3 ',
Particularly preferred is 4,4'-perfluoroisopropylidene diphthalic acid dianhydride and the like.

Among the other tetracarboxylic acid dianhydrides, preferred are 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,
3,4-cyclobutanetetracarboxylic dianhydride, 1,
2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b
-Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,
3-dione, 1,3,3a, 4,5,9b-hexahydro-
5-methyl-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-5, Examples thereof include 8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione and pyromellitic dianhydride.

[Diamine Compound] The diamine compound used in the synthesis of the above polyamic acid is, for example, p-
Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,
4'-diaminobiphenyl, 2,2'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino -1
-(4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl)-
1,3,3-Trimethylindane, 3,4'-diaminodiphenyl ether, 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-aminophenoxy) 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), 4,4'-bis (4- Amino-3-trifluoromethylphenoxy) biphenyl, 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-phenyleneisopropylidene) 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, 4,4'-
Bis [3- (4-aminophenoxy) propoxy] biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4 ′
An aromatic diamine such as-(4-aminophenoxy) biphenyl;

1,1-meta-xylylenediamine, 1,3-
Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine,
1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine,
Aliphatic and cycloaliphatic diamines such as hexahydro-4,7-methanoindanylene dimethylene diamine, tricyclo [6.2.1.02,7] -undecylenedimethyl diamine, 4,4'-methylene bis (cyclohexyl amine);

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-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-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas (III) to (IV), A diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino groups;

[0024]

[Chemical 4]

(In the formula, R ⁵ is pyridine, pyrimidine,
Represents a monovalent organic group having a ring structure containing a nitrogen atom selected from triazine, piperidine and piperazine, and X
Represents a divalent organic group. )

[0026]

[Chemical 5]

(In the formula, R ⁶ is pyridine, pyrimidine,
Represents a divalent organic group having a ring structure containing a nitrogen atom selected from triazine, piperidine and piperazine;
Represents a divalent organic group, and a plurality of X's may be the same or different. )

Monosubstituted phenylenediamines represented by the following formula (V); Diaminoorganosiloxanes represented by the following formula (VI);

[0029]

[Chemical 6]

(In the formula, R ⁷ is —O—, —COO—, —
OCO-, -NHCO-, -CONH- and -CO-
Represents a divalent organic group selected from, R ⁸ represents a steroid skeleton, a monovalent organic group or an alkyl group having 6 to 30 carbon atoms having a group selected from a trifluoromethyl group and a fluoro group. )

[0031]

[Chemical 7]

(In the formula, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, a plurality of R ⁹ may be the same or different, p is an integer of 1 to 3, and q is 1-2
It is an integer of 0. )

Examples thereof include compounds represented by the following formulas (9) to (13). These diamine compounds may be used alone or in combination of two or more.

[0034]

[Chemical 8]

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)

Among the above diamine compounds, the diamine compound having the group (1-2) is 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3 '. -Dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-
Diaminobiphenyl, 4,4'-bis (4-amino-3-
Trifluoromethylphenoxy) biphenyl, 2,2 ',
5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5 '
-Dimethoxybiphenyl, 3,3'-dimethoxy-4,
4'-diaminobiphenyl, 4,4'-diamino-2,
2'-bis (trifluoromethyl) biphenyl, 4,
4'-bis [(4-amino-2-trifluoromethyl)
Phenoxy] -octafluorobiphenyl, 4,4'-
Bis [3- (4-aminophenoxy) propoxy] biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4 ′
Examples include-(4-aminophenoxy) biphenyl and the like. Of these, those having a fluorine atom include
2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-diamino-2,2'-bis (Trifluoromethyl) biphenyl,
4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl. Further, as the diamine compound containing no fluorine group (1-2) and containing a fluorine atom, 2,2-bis [4- (4
-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis [4- (4-amino-2-
Examples include trifluoromethylphenoxy) phenyl] hexafluoropropane and compounds represented by the following formulas (20) and (21) among the compounds represented by the above formula (V).

Among the other diamine compounds, preferred are p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene and 2,7-diamino. Fluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 4,4 '-(p-phenyl Diened isopropylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) Benzene, 4,4′-bis (4-aminophenoxy) biphenyl, represented by the above formulas (9) to (13) A compound, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, represented by the following formula (14) among the compounds represented by the above formula (III) A compound represented by the following formula (15) among the compounds represented by the above formula (IV) and a compound represented by the following formula (16) among the compounds represented by the above formula (V):
The compound represented by (19) may be mentioned.

[0038]

[Chemical 9]

[Synthesis of Polyamic Acid] The use ratio of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamic acid is such that 1 equivalent of amino group of diamine is used.
The ratio of the acid anhydride group of the tetracarboxylic dianhydride is preferably 0.2 to 2 equivalents, and more preferably 0.3 to 1.
It is a ratio of 2 equivalents. The synthesis reaction of the polyamic acid is carried out in an organic solvent under the temperature condition of usually -20 ° C to 150 ° C, preferably 0 to 100 ° C.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide. Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. Further, the amount (α) of the organic solvent used is usually the total amount (β) of the tetracarboxylic dianhydride and the diamine compound, and the total amount (α + β) of the reaction solution.
It is preferable that the amount is 0.1 to 30% by weight with respect to.

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 so long as the polyamic acid to be produced does not precipitate. Specific examples of such a poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, 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 malonate, diethyl ether,
Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran,
Dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-
Examples thereof include dichlorobenzene, hexane, heptane, octane, benzene, toluene and xylene.

As described above, a reaction solution obtained by dissolving polyamic acid 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. Further, the polyamic acid can be purified by performing the step of dissolving the polyamic acid again in the organic solvent and then precipitating it in the poor solvent once or several times.

[Synthesis of Polyimide] The polyimide constituting the liquid crystal aligning agent of the present invention can be synthesized by dehydrating and ring-closing the above polyamic acid. The polyimide used in the present invention may be partially dehydrated and ring-closed with an imidization ratio of less than 100%. The “imidization ratio” as used herein is a value of the ratio of repeating units having an imide ring or an isoimide ring in all repeating units of the polymer, which is expressed as a percentage. The dehydration ring closure of polyamic acid
It is carried out by a method of heating (i) a polyamic acid, or (ii) a method of dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating the solution if necessary. The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 50.
It is 200 ° C., and more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C, the dehydration ring closure reaction may not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the polyimide obtained may decrease. On the other hand, above (ii)
In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of polyamic acid, the dehydrating agent may be an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. The amount of the dehydrating agent used depends on the desired imidization ratio, but it is preferably 0.01 to 20 mol per 1 mol of the repeating unit of the polyamic acid. Further, as the dehydration ring-closing catalyst, for example, pyridine,
Tertiary amines such as collidine, lutidine and triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. The imidization ratio can be increased as the amount of the dehydrating agent and dehydrating ring-closing agent used increases. The imidization ratio is preferably 40% or more from the viewpoint of the afterimage erasing speed of the liquid crystal display device.
Examples of the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The polyimide can be purified by performing the same operation as in the method for purifying polyamic acid on the reaction solution thus obtained.

[Terminal-Modified Polymer] The polyamic acid and the polyimide used in the present invention may be terminal-modified polymers having a controlled molecular weight. By using this terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, and n-tetradecylsuccinic anhydride. , N-hexadecyl succinic acid anhydride and the like. 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 and the like can be mentioned. . Examples of monoisocyanate compounds include phenyl isocyanate and naphthyl isocyanate.

[Logarithmic Viscosity of Polymer] The polyamic acid and / or polyimide obtained as described above has a logarithmic viscosity (η _ln ) of preferably 0.05 to 10 d.
1 / g, more preferably 0.05 to 5 dl / g.
The value of the logarithmic viscosity (η _ln ) in the present invention is 0.5 g / _n using N-methyl-2-pyrrolidone as a solvent.
The viscosity of a 100 ml solution is measured at 30 ° C., and the viscosity is determined by the following formula (i).

Ln (flow time of solution / flow time of solvent) η _ln = ───────────────────── (i) (weight concentration of polymer)

[Liquid Crystal Alignment Agent for In-Plane Liquid Crystal Display Device] The liquid crystal alignment agent of the present invention is usually constituted by dissolving and containing the above polyamic acid and / or polyimide in an organic solvent. The temperature when preparing the liquid crystal aligning agent of the present invention,
It is preferably 0 ° C to 200 ° C, more preferably 20 ° C.
C to 60C. Examples of the organic solvent that constitutes the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,
γ-butyrolactone, γ-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, etc. Can be mentioned.

The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of a substrate to form a resin film serving as a liquid crystal aligning film. It is too small to obtain a good liquid crystal alignment film, and the solid content concentration is 10% by weight.
If it exceeds, the thickness of the resin 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 properties.

The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound and an epoxy compound from the viewpoint of improving the adhesiveness to the substrate surface within a range that does not impair the desired physical properties. Examples of such a functional silane-containing compound include 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 Silane, N-
Ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-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-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxy Silane etc. can be mentioned. Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6
-Tetraglycidyl-2,4-hexanediol, N,
N, N ', N',-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4, 4'-diaminodiphenylmethane, 3- (N
Examples include -allyl-N-glycidyl) aminopropyltrimethoxysilane and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

[Liquid Crystal Display Device] The horizontal electric field type liquid crystal display device of the present invention can be manufactured, for example, by the following method. (1) The liquid crystal aligning agent of the present invention is applied to, for example, a conductive film formation surface of a substrate provided with a comb-teeth-patterned transparent conductive film and a surface of a counter substrate on which a conductive film is not provided, respectively. Application is performed by a method such as a roll coater method, a spinner method, or a printing method, and then the application surface is heated to form a resin film. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone or polycarbonate can be used. As the transparent conductive film provided on one surface of the substrate, a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Co., USA), indium oxide-tin oxide (In ₂ O ₃ —Sn) is used.
An ITO film made of O ₂ ) or the like can be used, and a photo-etching method or a method using a mask in advance is used for patterning these transparent conductive films. When applying the liquid crystal aligning agent, in order to further improve the adhesiveness between the substrate surface and the transparent conductive film and the resin film, a functional silane-containing compound, a functional titanium-containing compound, etc. are previously applied to the surface of the substrate. You can also do it. The heating temperature after applying the liquid crystal aligning agent is 80 to 300 ° C., preferably 120 to 300 ° C.
It is set to 250 ° C. Incidentally, the liquid crystal aligning agent of the present invention containing a polyamic acid forms a resin film to be an alignment film by removing the organic solvent after coating, but further heating promotes dehydration ring closure and is more imidized. It may be a resin film. The film thickness of the formed resin film is usually 0.001 to 1 μm, preferably 0.1.
005 to 0.5 μm. (2) A rubbing treatment is performed in which the formed resin film surface is rubbed in a certain direction with a roll around which a cloth made of fibers such as nylon, rayon, and cotton is wound. As a result, the ability of aligning the liquid crystal molecules is imparted to the resin film to form a liquid crystal alignment film. Further, by partially irradiating the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. Different from the previous rubbing treatment, a resist film is partially formed on the surface of the liquid crystal alignment film subjected to a treatment for changing the pretilt angle or a rubbing treatment as disclosed in Japanese Patent Laid-Open No. 5-107544. It is possible to improve the visibility characteristics of the liquid crystal display element by removing the resist film after performing the rubbing treatment in the direction and performing a treatment for changing the liquid crystal aligning ability of the liquid crystal aligning film. (3) A substrate on which the transparent conductive film is formed as described above and a substrate on which the transparent conductive film is not patterned are prepared one by one so that the rubbing directions of the respective liquid crystal alignment films are parallel to each other. The two substrates are arranged so as to face each other with a gap (cell gap) therebetween, and the peripheral portions of the two substrates are bonded together by using a sealant, and liquid crystal is placed in the cell gap defined by the substrate surface and the sealant. A liquid crystal cell is constructed by filling and filling the filling hole. And
A polarizing plate is attached to the outer surface of the liquid crystal cell, that is, the other surface of each of the substrates constituting the liquid crystal cell, so that the polarization direction thereof matches the rubbing direction of the liquid crystal alignment film formed on the one surface of the substrate. A liquid crystal display device is obtained by combining them.

Here, as the sealant, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as spacers can be used. Examples of the liquid crystal include nematic type liquid crystal and smectic type liquid crystal, and among them, nematic type liquid crystal is preferable, for example, Schiff base type liquid crystal, azoxy type liquid crystal,
Biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, to these liquid crystals, for example, 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). It is also possible to use by adding such as. Furthermore, p-decyloxybenzylidene-p
Ferroelectric liquid crystals such as -amino-2-methylbutyl cinnamate can also be used. Further, as a polarizing plate to be attached to the outer surface of a liquid crystal cell, a polarizing film or an H film in which a polarizing film called an H film that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films A polarizing plate composed of itself can be mentioned.

[0052]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The evaluation method for each liquid crystal display element produced by the following examples and comparative examples is shown below.

[Water Contact Angle of Resin Film] A liquid crystal aligning agent was applied onto a glass substrate using a spinner, and the temperature was maintained at 80 ° C. for 1 minute.
After that, by drying at 180 ° C for 1 hour, the dry film thickness 6
By forming a resin film of 00 angstrom and dropping 1.0 μl of water drop by contacting it on the film surface, and measuring the angle between the contact point of the liquid drop and the film surface and the tangent line of the liquid drop from the film surface. I asked.

[Pencil Hardness of Resin Film] A liquid crystal aligning agent was applied using a spinner on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm, and then at 80 ° C. for 1 minute, and thereafter. A resin film having a dry film thickness of 600 Å was formed by drying at 180 ° C. for 1 hour, and this resin film was subjected to a pencil hardness test according to JIS K5400.

[Evaluation of Liquid Crystal Display Element] The oriented liquid crystal display element was driven by a rectangular wave of 5 V and 60 Hz, and the presence or absence of display defects was visually observed. Reliability In a high-temperature and high-humidity environment (temperature 70 ° C, relative humidity 80%), a liquid crystal display element is driven by a rectangular wave of 5 V and 60 Hz, and after a lapse of 1500 hours, the presence or absence of white spot-like display defects is detected by a polarizing microscope. Observed at.

(Synthesis Example 1) 294.2 g (1.0 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-bis (4-aminophenoxy) biphenyl 368. 4 g (1.0 mol) and N-methyl-2-
It was dissolved in 6000 g of pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a logarithmic viscosity (ηln) of 0.86.
dl / g of polyamic acid [this is referred to as "polymer (A-
1) ”. ] 591.5 g was obtained.

(Synthesis Example 2) 294.2 g (1.0 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 2,2'-dimethyl-4,4'-diaminobiphenyl 212 0.3 g (1.0 mol) was dissolved in 6000 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a logarithmic viscosity (ηln) of 0.76d.
1 / g of polyamic acid [this is "polymer (A-2)"
And ] 475.3g was obtained.

(Synthesis Example 3) 294.2 g (1.0 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-bis (4-aminophenoxy) biphenyl 184. 2 g (0.5 mol) and 2,2'-dimethyl-4,4'-diaminobiphenyl 106.2 g (0.5
Was dissolved in 6000 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate is separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours,
Polyamic acid having a logarithmic viscosity (ηln) of 0.84 dl / g [this is referred to as "polymer (A-3)". ] 544.6 g
Got

(Synthesis Example 4) 294.2 g (1.0 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-bis (4-aminophenoxy) biphenyl 294. 7 g (0.8 mol) and 2,2'-dimethyl-4,4'-diaminobiphenyl 21.2 g (0.2 mol) were dissolved in N-methyl-2-pyrrolidone 6000 g and reacted at room temperature for 6 hours. Let Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid having an inherent viscosity (ηln) of 0.90 dl / g [this was referred to as "polymer (A-4)". ". ] 571.6 g
Got

(Synthesis Example 5) 294.2 g (1.0 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-bis (4-aminophenoxy) biphenyl 73. 7 g (0.5 mol) and 2,2'-dimethyl-
169.8 g (0.5 mol) of 4,4′-diaminobiphenyl was dissolved in 6000 g of N-methyl-2-pyrrolidone, and the mixture was reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid having an inherent viscosity (ηln) of 0.72 dl / g [this was referred to as “polymer (A-5)”]. ". ] 462.6 g
Got

(Synthesis Example 6) Pyromellitic dianhydride 10
9.1 g (0.5 mol) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.1 g (0.5 mol) and 4,4'-diaminodiphenyl ether 100.1 g
(1.0 mol) and N-methyl-2-pyrrolidone 600
It was dissolved in 0 g and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid having an inherent viscosity (ηln) of 0.98 dl / g [this was referred to as “polymer (A-6)”]. ". ] 25
8.3 g was obtained.

Synthesis Example 7 224.2 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride
And p-phenylenediamine 108.1 g (1.0 mol)
And were dissolved in 6000 g of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity (ηln) of 0.69 dl / g [this was referred to as “polymer (A-7)”]. ". ] 293.7 g
Got

(Synthesis Example 8) 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-
Dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione 294.2 g (1.0 mol) and p-phenylenediamine 75.7 g (0.7 mol) and 2,2 ′
-Ditrifluoromethyl-4,4'-diaminobiphenyl 137.2 g (0.3 mol) was dissolved in N-methyl-2-pyrrolidone 6000 g, and the mixture was reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate is separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a logarithmic viscosity (ηln) of 0.78d.
1 / g of polyamic acid [this is "polymer (A-8)"
And ] 455.6g was obtained.

Synthesis Example 9 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-
Dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione 314.3 g (1.0 mol) and p-phenylenediamine 108.1 g (1.0 mol) were added to N-.
It was dissolved in 6000 g of methyl-2-pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. afterwards,
The precipitate is separated and washed with methyl alcohol, then under reduced pressure 4
By drying at 0 ° C. for 15 hours, the logarithmic viscosity (ηl
n) 0.82 dl / g of polyamic acid [This is referred to as "polymer (A-9)". ] 352.5g was obtained.

(Synthesis Example 10) 1,3,3a, 4,5,9b-
Hexahydro-8-methyl-5 (tetrahydro-2,5
-Dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione 314.3 g (1.0 mol) and 2,
32 'g (1.0 mol) of 2'-ditrifluoromethyl-4,4'-diaminobiphenyl and N-methyl-2-
It was dissolved in 6000 g of pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a logarithmic viscosity (ηln) of 0.65.
dl / g of polyamic acid [this is referred to as "polymer (A-1
0) ”. ] 589.9 g was obtained.

(Synthesis Example 11) 224.2 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 54.1 g (0.5 mol) of p-phenylenediamine and 2,2'- 160.1 g (0.5 mol) of ditrifluoromethyl-4,4'-diaminobiphenyl was dissolved in 6000 g of N-methyl-2-pyrrolidone, and 6
Reacted for hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. After that, the precipitate is separated and washed with methyl alcohol, and the pressure is reduced to 40
By drying at ℃ for 15 hours, logarithmic viscosity (ηl
n) 0.62 dl / g of polyamic acid [This is referred to as "polymer (A-11)". ] 391.5 g was obtained.

(Synthesis Example 12) 1,3,3a, 4,5,9b-
Hexahydro-8-methyl-5 (tetrahydro-2,5
-Dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione 294.2 g (1.0 mol) and p-
54.1 g (0.5 mol) of phenylenediamine and 2,
2'-Ditrifluoromethyl-4,4'-diaminobiphenyl 160.1 g (0.5 mol) and N-methyl-2-
It was dissolved in 6000 g of pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a logarithmic viscosity (ηln) of 0.70.
dl / g of polyamic acid [this is referred to as "polymer (A-1
2) ”. ] 437.6g was obtained.

Synthesis Example 13 112.1 g (0.5 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 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
57.2 g (0.5 mol) and 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl 320.2 g
(1.0 mol) and N-methyl-2-pyrrolidone 600
It was dissolved in 0 g and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity (ηln) of 0.82 dl / g [this was referred to as “polymer (A-13)”. ". ] 5
29.7 g was obtained.

Synthesis Example 14 112.1 g (0.5 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 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
57.2 g (0.5 mol) and p-phenylenediamine 5
4.1 g (0.5 mol) and 160.1 g of 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl
(0.5 mol) and N-methyl-2-pyrrolidone 600
It was dissolved in 0 g and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity (ηln) of 0.94 dl / g [this was referred to as "polymer (A-14)". ". ] 4
18.2 g was obtained.

(Synthesis Example 15) 444.2 g of 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride
(1.0 mol) and p-phenylenediamine 108.1 g
(1.0 mol) and N-methyl-2-pyrrolidone 600
It was dissolved in 0 g and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity (ηln) of 0.68 dl / g [this was referred to as "polymer (A-15)". ". ] 5
22.6 g were obtained.

(Synthesis Example 16) 444.2 g of 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride
(1.0 mol) and 4,4'-diaminodiphenylmethane 1
98.3 g (1.0 mol) was dissolved in 6000 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours.
Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a logarithmic viscosity (ηln) of 0.70 dl /
g of polyamic acid [This is referred to as "polymer (A-16)". ] 599.7g was obtained.

Synthesis Example 17 224.2 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 334.3 g (1.0
Was dissolved in 6000 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate is separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours,
Polyamic acid having a logarithmic viscosity (ηln) of 0.71 dl / g [this is referred to as "polymer (A-17)". ] 503.6
g was obtained.

(Synthesis Example 18) 1,3,3a, 4,5,9b-
Hexahydro-8-methyl-5 (tetrahydro-2,5
-Dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione 314.3 g (1.0 mol) and 2,
2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 334.3 g (1.0 mol) was dissolved in N-methyl-2-pyrrolidone 6000 g, and the mixture was reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity (ηln) of 0.63 dl / g [this was referred to as “polymer (A-18) ". ] 581.4 g was obtained.

(Synthesis Example 19) 224.2 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 2,2-bis [4- (4-amino-2-trifluorophenoxy) Phenyl] hexafluoropropane 4
70.3 g (1.0 mol) was dissolved in 6000 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours.
Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain a logarithmic viscosity (ηln) of 0.66 dl /
g of polyamic acid [This is referred to as "polymer (A-19)". ] 590.4 g was obtained.

Synthesis Example 20 224.2 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 108.1 g (0.5 mol) of p-phenylenediamine and the above formula (9). Specific diamine compound represented by
1.4 g (0.5 mol) was dissolved in 6000 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity (ηln) of 0.62 dl / g [this was referred to as "polymer (A-20)". ". ] 512.6g was obtained.

(Synthesis Example 21) 30.0 g of the polymer (A-7) obtained in Synthesis Example 7 was dissolved in 570 g of γ-butyrolactone, and 33.3 g of pyridine and 25.8 of acetic anhydride.
g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours. By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.64 dl / g [this will be referred to as "polymer (B-7)". 28.1 g of white powder of

(Synthesis Example 22) 30.0 g of the polymer (A-8) obtained in Synthesis Example 8 was dissolved in 570 g of γ-butyrolactone to give 33.3 g of pyridine and 25.8 of acetic anhydride.
g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours. By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having an inherent viscosity (ηln) of 0.79 dl / g [this will be referred to as “polymer (B-8)”]. ] 27.4g of white powder was obtained.

(Synthesis Example 23) 30.0 g of the polymer (A-9) obtained in Synthesis Example 9 was dissolved in 570 g of γ-butyrolactone, 33.3 g of pyridine and 25.8 acetic anhydride.
g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours. This polymer solution is reprecipitated with diethyl ether to obtain a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.81 dl / g [this will be referred to as "polymer (B-9)". ] White powder of 27.3g was obtained.

(Synthesis Example 24) 30.0 g of the polymer (A-10) obtained in Synthesis Example 10 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.67 dl / g [this will be referred to as "polymer (B-10)". ] White powder 29.0g was obtained.

(Synthesis Example 25) 30.0 g of the polymer (A-11) obtained in Synthesis Example 11 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.60 dl / g [this will be referred to as "polymer (B-11)". 28.2 g of a white powder of

(Synthesis Example 26) 30.0 g of the polymer (A-12) obtained in Synthesis Example 12 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.68 dl / g [this will be referred to as "polymer (B-12)". ] White powder of 27.7g was obtained.

(Synthesis Example 27) 30.0 g of the polymer (A-13) obtained in Synthesis Example 13 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.82 dl / g [this will be referred to as "polymer (B-13)". ] White powder 26.4g was obtained.

(Synthesis Example 28) 30.0 g of the polymer (A-14) obtained in Synthesis Example 14 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.91 dl / g [this will be referred to as "polymer (B-14)". ] White powder 28.9g was obtained.

(Synthesis Example 29) 30.0 g of the polymer (A-15) obtained in Synthesis Example 15 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
This polymer solution is reprecipitated with diethyl ether to obtain a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.66 dl / g [this will be referred to as "polymer (B-15)". ] White powder 25.3g was obtained.

(Synthesis Example 30) 30.0 g of the polymer (A-16) obtained in Synthesis Example 16 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
This polymer solution is reprecipitated with diethyl ether to obtain a polymer (polyimide) having an inherent viscosity (ηln) of 0.71 dl / g [this will be referred to as "polymer (B-16)". 27.1 g of white powder of

(Synthesis Example 31) 30.0 g of the polymer (A-17) obtained in Synthesis Example 17 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
This polymer solution is reprecipitated with diethyl ether to obtain a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.70 dl / g [this will be referred to as "polymer (B-17)". 28.5 g of white powder of

(Synthesis Example 32) 30.0 g of the polymer (A-18) obtained in Synthesis Example 18 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.60 dl / g [this will be referred to as "polymer (B-18)". ] White powder of 27.7g was obtained.

(Synthesis Example 33) 30.0 g of the polymer (A-19) obtained in Synthesis Example 19 was mixed with γ-butyrolactone 570.
3 g of pyridine and acetic anhydride 2
5.8 g was added, and dehydration ring closure was performed at 110 ° C. for 4 hours.
By reprecipitating this polymer solution with diethyl ether, a polymer (polyimide) having a logarithmic viscosity (ηln) of 0.68 dl / g [this will be referred to as "polymer (B-19)". ] White powder 26.7g was obtained.

Comparative Synthesis Example 1 109.1 g (0.5 mol) of pyromellitic dianhydride and 98.1 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride 4,4'-diaminodiphenylmethane 198.3
g (1.0 mol) and N-methyl-2-pyrrolidone 60
It was dissolved in 00 g and reacted at room temperature for 6 hours. Then
The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the precipitate was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to give a polyamic acid having an inherent viscosity (ηln) of 0.95 dl / g [this was referred to as “polymer (a-1) ". ] 3
62.3 g was obtained.

Comparative Synthesis Example 2 109.1 g (0.5 mol) of pyromellitic dianhydride and 1,2-dimethyl-1,
2,3,4-cyclobutanetetracarboxylic dianhydride 11
2.1 g (0.5 mol) of 4,4'-diaminodiphenylmethane and 198.3 g (1.0 mol) of N-methyl-
2-Pyrrolidone was dissolved in 6000 g and reacted at room temperature for 6 hours. Then, the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. After that, the precipitate is separated and washed with methyl alcohol, and the pressure is reduced to 40 ° C. at 1 ° C.
By drying for 5 hours, logarithmic viscosity (ηln) of 0.
89 dl / g of polyamic acid [this is referred to as "polymer (a-
2) ”. ] 358.6 g was obtained.

Example 1 2 g of the polymer (A-1) obtained in Synthesis Example 1 was dissolved in γ-butyrolactone to obtain a solution having a solid content concentration of 4% by weight, and this solution was filtered with a filter having a pore size of 1 μm. The mixture was filtered to prepare a liquid crystal aligning agent. When the water contact angle of the resin film was measured using the obtained liquid crystal aligning agent, it was 68 °. The pencil hardness of the resin film was measured and found to be 4H.

Next, a liquid crystal display element was produced by the following procedure. The liquid crystal aligning agent of the present invention prepared as described above was applied using a spinner on a transparent conductive film made of an ITO film provided in a comb shape on one surface of a glass substrate having a thickness of 1 mm, and the temperature was 180 ° C. Dry film thickness 6 by drying for 1 hour
A resin film of 00 angstrom was formed. The formed resin film surface was subjected to a rubbing treatment using a rubbing machine having a roll around which a cloth made of nylon was wound to obtain a liquid crystal alignment film. Here, the rubbing treatment conditions are: the rotation number of the roll is 400 rpm, the moving speed of the stage is 3 cm / sec,
The length of pushing in the hair was 0.4 mm. (This substrate is referred to as “substrate A”) Similarly, the liquid crystal aligning agent of the present invention prepared as described above is applied to one surface of a glass substrate having a thickness of 1 mm by using a spinner, and the liquid crystal aligning agent is applied at 180 ° C. for 1 hour. A resin film having a dry film thickness of 600 angstrom was formed by drying for a time. The formed resin film surface was subjected to a rubbing treatment using a rubbing machine having a roll around which a cloth made of nylon was wound to obtain a liquid crystal alignment film. The rubbing treatment conditions were as follows: the rotation speed of the roll was 400 rpm, the moving speed of the stage was 3 cm / sec, and the pushing length of the fluff was 0.4 mm. (This substrate is referred to as “substrate B”).
After applying an epoxy resin adhesive containing aluminum oxide spheres of μm by a screen printing method, two substrates are arranged facing each other with a gap so that the rubbing directions of the respective liquid crystal alignment films are antiparallel. The outer edge portions were brought into contact with each other and pressure-bonded to cure the adhesive. Next, after filling a nematic liquid crystal (MLC-2019, manufactured by Merck & Co., Inc.) between the pair of substrates through the liquid crystal inlet, the liquid crystal inlet is sealed with an epoxy adhesive, and a polarizing plate is provided on both sides of the substrate. Were laminated so that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film of each substrate, to fabricate a horizontal electric field type liquid crystal display device of the present invention. When the obtained liquid crystal display element was evaluated, the orientation was good, no white spots were observed in the reliability test, and the reliability was good. The evaluation results are shown in Table 1.

[Examples 2-34, Comparative Examples 1-2] A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the polymers shown in Tables 1 and 2 were used. And the pencil hardness was evaluated. The examples using two kinds of polymers were used in a weight ratio of 4/1. The evaluation results are also shown in Tables 1 and 2. Further, a lateral electric field type liquid crystal display device was produced and evaluated in the same manner as in Example 1 except that the obtained liquid crystal aligning agent was used. The evaluation results are also shown in Tables 1 and 2.

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

According to the liquid crystal aligning agent of the present invention, when a liquid crystal aligning film is formed, the liquid crystal is highly reliable regardless of process conditions such as film thickness and rubbing conditions, and is suitable for a horizontal electric field type liquid crystal display device. An alignment film is obtained. Furthermore, a liquid crystal display device having an alignment film formed by using the liquid crystal aligning agent of the present invention is excellent in liquid crystal alignment and reliability and can be effectively used in various devices. For example, desktop calculators, wrist watches, clocks, and coefficients. It is used for display devices such as display boards, word processors, personal computers, and liquid crystal televisions.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H090 HB08Y HC05 HC08 LA01                       MB01                 4F071 AA60 AF04 AF25 AF29 AG21                       AH19 BA02 BB02 BC02                 4J043 RA34 SA06 TA22 TA41 UA13                       VA04 ZA01 ZA31 ZA51 ZB11                       ZB23

Claims (3)

[Claims] 1. A lateral electric field method comprising forming a resin film containing at least one selected from polyamic acid and polyimide, having a water contact angle of 65 ° or more and a pencil hardness of HB or more. Liquid crystal aligning agent for liquid crystal display devices. 2. A liquid crystal aligning agent for a horizontal electric field type liquid crystal display device, which contains a polyamic acid and / or a polyimide satisfying at least one of the following (1) and (2). (1) It has at least one group represented by the following formula (1-1) and the following formula (1-2). [Chemical 1] (In the formula, R ^a , R ^b , R ^c and R ^d each independently represent a halogen atom or a monovalent organic group, m and n each independently represent an integer of 0 to 3, and p and q are respectively Each independently represents an integer of 0 to 4.) (2) Contains a fluorine atom. 3. A horizontal electric field type liquid crystal display device comprising a liquid crystal alignment film obtained from the liquid crystal aligning agent according to claim 1.