JP5454754B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal aligning agent that has a high voltage holding ratio and good image sticking characteristics regardless of the use temperature, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display device including the film.

Conventionally, a cell of a sandwich structure is formed by forming a nematic liquid crystal layer having positive dielectric anisotropy between two substrates having a liquid crystal alignment film formed on the surface via a transparent conductive film, There is known a TN liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell in which the major axis of liquid crystal molecules is continuously twisted by 90 degrees from one substrate toward the other substrate.
Further, the addition of a chiral agent achieves a state in which the major axis of the liquid crystal molecules is continuously twisted between the substrates by 180 degrees or more, and an STN (Super Twisted Nematic) type liquid crystal display element utilizing the birefringence effect generated thereby. Is also present. More recently, a homeotropically aligned nematic liquid crystal layer having negative dielectric anisotropy between opposing substrates and a cholesteric liquid crystal layer in which the helical axis is parallel to the substrate normal are formed. A guest-host type reflective liquid crystal display element in which a dye is added to the above has also been developed. The alignment of the liquid crystal in these liquid crystal display elements is usually expressed by a liquid crystal alignment film subjected to a rubbing treatment. Here, as a material for the liquid crystal alignment film constituting the liquid crystal display element, polyimide, polyamide, polyester, and the like are conventionally known. In particular, polyimide is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like.

  Up to now, studies have been made on improving display quality, including higher definition of liquid crystal display elements, and lowering power consumption, and it has made remarkable progress as a high-performance display element. High voltage holding ratio, high reliability, and low image sticking characteristics A liquid crystal display element having the above has been developed. However, in recent years, in addition to the conventional transmission type, the range of use of liquid crystal display elements such as a reflection type and a semi-transmission type has been expanded. As a result, the required performance for liquid crystal alignment films has become increasingly severe. In particular, liquid crystal display elements intended for low image sticking have stricter demands for image sticking characteristics, and the performance of conventional liquid crystal display elements cannot be said to be sufficient. Among liquid crystal alignment films composed of polyamic acid, which is a precursor of conventional polyimide, and imide-based polymers having a structure obtained by dehydrating and cyclizing it, a liquid crystal display element is formed using the liquid crystal alignment film. When prepared, there are many aligning agents whose seizure characteristics are lowered depending on the use temperature even if the liquid crystal alignment ability is excellent and sufficient voltage holding ratio and reliability are obtained.

  An object of the present invention is made of polyamic acid and / or polyimide, which is a precursor of polyimide that is useful as a liquid crystal alignment film, and can exhibit a high voltage holding ratio, and exhibits low image sticking characteristics regardless of operating temperature. It is in providing the liquid crystal aligning agent shown.

  Another object of the present invention is to provide a liquid crystal alignment film obtained from the liquid crystal aligning agent and having excellent performance as described above.

  Still another object of the present invention is to provide a liquid crystal display device comprising the liquid crystal alignment film of the present invention.

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

  The above objects and advantages of the present invention are, according to the present invention, firstly, the following formula (I-1)

(Wherein P ¹ is a tetravalent organic group and includes a tetravalent organic group represented by the following formula (A):

Q ¹ is a divalent organic group and has the following formula (B), (C), (D) or (E):

Each of R1 to R11 is independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms. )
A polyamic acid having a polyamic acid bonding units consisting of repeating units represented in <br/> formula (I-2)

(Where P ² is a tetravalent organic group and Q ² is a divalent organic group.)
A polyimide having an imide bond unit represented by
The proportion of the imide bond number of units to the total number of bonds unit of which is a mixture made from the polymer and amic acid bond unit and imide bond units is achieved by a liquid crystal aligning agent characterized by occupying 5% to 80%.

  According to the present invention, the above objects and advantages of the present invention are secondly achieved by a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention.

  According to the present invention, thirdly, the above objects and advantages of the present invention are achieved by a liquid crystal display device including the liquid crystal alignment film of the present invention.

The liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention exhibits a low voltage seizure property regardless of the high voltage holding ratio and operating temperature, as compared with the conventional liquid crystal alignment film, and is a TN liquid crystal display element and STN liquid crystal display element. The liquid crystal display element can be suitably used to form various liquid crystal display elements such as a reflective liquid crystal display element and a transflective liquid crystal display element.
The liquid crystal display element of the present invention can be effectively used in various devices, and is suitable for display devices such as desk calculators, watches, table clocks, mobile phones, counting display boards, word processors, personal computers, and liquid crystal televisions. Can be used.

  Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent in this invention contains the polymer which has a repeating unit represented by the said Formula (I-1), and a repeating unit represented by the said Formula (I-2).
The polymer, Ru mixture der of a polyimide having a repeating unit represented by the above formula polyamic acid with the formula having a repeating unit represented by (I-1) (I- 2). Furthermore, in addition to these polyamic acid / polyimide mixtures , a polyamic acid having no tetravalent organic group represented by the above formulas (B) to (E) may be added.
The polyamic acid is obtained by ring-opening polyaddition of a tetracarboxylic dianhydride and a diamine compound. Polyimide is usually obtained by dehydrating and ring-closing polyamic acid. The partially imidized polymer can be usually obtained by a method of synthesizing a block copolymer by bonding an amic acid prepolymer and an imide prepolymer.
Ratio of the number of imide bonds units to the total number of bonds unit of amic acid bond unit and imide bond units is required to be 5 to 80 mol%. Preferably, it is 50-80 mol%. If it is less than 5%, there is a possibility that the image sticking characteristics are lowered, and if it exceeds 80 mol%, there is a possibility that the voltage holding ratio is lowered.

<Polyamic acid and polyimide>
[Tetracarboxylic dianhydride]
The tetravalent organic group represented by P ¹ in the repeating unit (amic acid unit) represented by the above formula (I-1) and the repeating unit (imide unit) P represented by the above formula (I-2) ^{All of the} tetravalent organic groups represented by ² are groups derived from tetracarboxylic dianhydride.
P ¹ in the above formula (I-1) has a tetravalent organic group represented by the following formula (A).

The tetravalent organic group represented by the above formula (A) is derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride constituting P ¹ or P ² include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentylacetic 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- At least one of diones can be mentioned as a preferable one.

  Examples of other tetracarboxylic dianhydrides used in the synthesis of polyamic acid or polyimide include, for example, butanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetra Carboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2, , 4,5-tetrahydrofurantetracarboxylic 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 a, 4,5,9b-Hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 , 3a, 4,5,9b-Hexahydro-8-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, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), a compound represented by each of the following formulas (II) and (III) Aliphatic and alicyclic tetracarboxylic dianhydrides such as;

(Wherein R ¹ and R ³ represent a divalent organic group having an aromatic ring, R ² and R ⁴ represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ⁴ are the same. But it may be different.)
3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenyl Silane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic 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) ) Gife Nylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenyl Phosphine 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 (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1, -Octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate), represented by each of the following formulas (1) to (4) Aromatic tetracarboxylic dianhydrides such as compounds can be mentioned. These other tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  Among these other tetracarboxylic dianhydrides, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 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, 3 -Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), among the compounds represented by the above formula (II) Of the compounds represented by formulas (5) to (7) and the compound represented by formula (III) above, the compound represented by formula (8) below can exhibit good liquid crystal alignment. From the viewpoint of being able to.

[Diamine compound]
The divalent organic group represented by Q ¹ in the repeating unit (amic acid binding unit) represented by the above formula (I-1) and the repeating unit (imide bonding unit) represented by the above formula (I-2) ) Is a group derived from a diamine compound.
Q ¹ in the above formula (I-1) has at least one of divalent organic groups represented by the following formulas (B) to (E).

(Here, R1 to R11 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.)
Specific examples of the diamine compound that gives the divalent organic groups (B) to (E) include 1,4-diaminocyclohexane, bicyclo [2.2.1] heptane-2,6-bis (methylamine), Preferable examples include 1,3-bis (aminomethyl) cyclohexane, a compound represented by the following formula (9), and the like.

Examples of other diamine compounds used for the synthesis of polyamic acid or polyimide include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diamino. Diphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene 2,2′-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-amino) Phenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-dia Nobenzophenone, 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), 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) Aromatic diamines such as phenoxy] -octafluorobiphenyl, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate;
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, tetrahydrodicyclopentadienylenediamine, hexahydro Fats such as -4,7-methanoindanylene methylene diamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl diamine, 1,4-cyclohexane diamine, 4,4'-methylene bis (cyclohexyl amine) Aliphatic and cycloaliphatic diamines;
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- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 Intramolecular such as phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas (IV) to (V) A diamine having two primary amino groups and a nitrogen atom other than the primary amino group;

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

(Wherein X represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, R ⁶ represents a divalent organic group, and a plurality of X May be the same or different.)
Monosubstituted phenylenediamine represented by the following formula (VI); diaminoorganosiloxane represented by the following formula (VII);

(Wherein R ⁷ represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ⁸ represents a steroid skeleton, A monovalent organic group having a group selected from a fluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms is shown.)

(In the formula, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁹ may be the same or different, p is an integer of 1 to 3, and q is 1 to 20) Is an integer.)
Examples include compounds represented by the following formulas (10) to (14). These other diamine compounds can be used alone or in combination of two or more.

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)
Among these other diamine compounds, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 1,3-bis (aminomethyl) cyclohexane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2 , 7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) 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, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl -3,5-diaminobenzoate, compounds represented by the above formulas (10) to (14), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6- Diaminoacridine, compound represented by the following formula (15) among compounds represented by the above formula (IV), compound represented by the following formula (16) among compounds represented by the above formula (V), and the above Of the compounds represented by the formula (VI), the following formulas (17) to (23), 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-dia Nobenzoeto, compounds represented by the bis-aminopropyl disiloxane, each of the compounds represented by (VII) preferred.

[Synthetic reaction of polyamic acid]
The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The synthetic reaction of polyamic acid is preferably carried out in an organic solvent under a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide And aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of the organic solvent used (a) is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable that

[Poor solvent]
The organic solvent can be used in combination with an alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, or the like, which is a poor solvent for polyamic acid, as long as the polyamic acid to be produced does not precipitate. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 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 methoxypropionate, ethyl ethoxypropionate, 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- Chill 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-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. The polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent and then precipitated with a poor solvent, or a method in which the step of distilling off with an evaporator under reduced pressure is performed once or several times.

[Imidized polymer]
The imidized polymer constituting the liquid crystal aligning agent of the present invention can be prepared by dehydrating and ring-closing the polyamic acid as described above. The polyimide used in the present invention may be partially dehydrated and ring-closed with an imidization rate of less than 100%. The “imidation ratio” here is a value representing the ratio of the repeating unit having an imide ring or an isoimide ring as a percentage in all repeating units of the polymer. The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C., the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease.

  On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC.

  The imidized polymer obtained in the above method (i) may be used for the preparation of a liquid crystal aligning agent as it is, or may be used for the preparation of a liquid crystal aligning agent after purifying the obtained imidized polymer. . On the other hand, in the method (ii), a reaction solution containing an imidized polymer is obtained. This reaction solution, after removing the dehydrating agent and the dehydrating ring-closing catalyst, may be used as it is for preparing the liquid crystal aligning agent, may be used after preparing the liquid crystal aligning agent after isolating the imidized polymer, or You may use for preparation of a liquid crystal aligning agent, after refine | purifying an imidation polymer. In order to remove the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. Isolation and purification of the imidized polymer can be performed by performing the same operation as described above as the method for isolating and purifying polyamic acid.

[Terminal modification]
The polyamic acid and the imidized polymer may be of a terminal modified type with a controlled molecular weight. By using this terminal-modified polymer, 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 monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic anhydride and the like. Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecylamine. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. Can do. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

[Solution viscosity]
The polymer used in the aligning agent of the present invention preferably has a viscosity of 20 to 800 mPa · s, and has a viscosity of 30 to 500 mPa · s, when a 10% by weight solution is obtained. It is more preferable.
The solution viscosity (mPa · s) of the polymer was measured at 25 ° C. using an E-type rotational viscometer for a solution diluted to a predetermined solid content concentration using a predetermined solvent.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is constituted by dissolving and containing the polyamic acid and the imidized polymer in an organic solvent. In the polymer constituting the liquid crystal aligning agent of the present invention, the number of amic acid bond units accounts for 20 to 95% based on the total number of bond units of polyamic acid bond units and imide bond units, and the number of imide bond units is Used to occupy 5-80%.
As an organic solvent which comprises the liquid crystal aligning agent of this invention, the same thing as the solvent illustrated as what is used for the synthesis reaction of a polyamic acid can be mentioned. These can be used alone or in admixture of two or more. In addition, the same poor solvents exemplified as those that can be used together in the synthesis reaction of the polyamic acid can be appropriately selected and used together. A particularly preferable solvent composition is a composition obtained by combining the above-mentioned solvents, wherein no polymer is precipitated in the aligning agent, and the surface tension of the aligning agent is in the range of 25 to 40 mN / m. It is.

The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility and the like, and 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 substrate surface to form a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of this coating film is too small. It is difficult to obtain a good liquid crystal alignment film. When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent is increased, so that the coating properties tend to be inferior. The particularly preferable solid content concentration range varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
Moreover, the temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 20-60 degreeC.

The liquid crystal aligning agent for forming the liquid crystal alignment film of the present invention contains a compound having at least one epoxy group in the molecule (hereinafter also referred to as “epoxy group-containing compound”) from the viewpoint of improving the adhesion to the substrate surface. It is preferable that Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo-neopentyl glycol diglycidyl ether, N, N, N ', N' - tetraglycidyl -m- xylene diamine, 1,3-bis (N, N - diglycidyl aminomethyl) cyclohexane, N, N, N ', N' - it can be mentioned as being preferred and tetraglycidyl-4,4'-diaminodiphenylmethane The The blending ratio of these epoxy group-containing compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.

Moreover, the liquid crystal aligning agent of this invention may contain the functional silane containing compound. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 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-aminopropyltriethoxysilane, etc. can be mentioned.
The blending ratio of these functional silane-containing compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the polymer.

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

(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spinner method, a printing method, an ink jet method, etc. Is heated to form a coating film. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ² O ₃ —SnO ₂ ), etc. Can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask in advance is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is, for example, 80 to 300 ° C, and preferably 120 to 250 ° C. The liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film that becomes an alignment film by removing the organic solvent after coating. It can also be a membrane. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) A rubbing process is performed in which the formed coating film surface is rubbed in a certain direction with a roll wound with a cloth made of a fiber such as nylon, rayon, or cotton. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film.
Further, by partially irradiating the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. A resist film is partially formed on the surface of the liquid crystal alignment film that has been subjected to a treatment for changing the pretilt angle or a rubbing treatment as disclosed in JP-A-5-107544, which is different from the previous rubbing treatment. The visibility characteristics of the liquid crystal display element can be improved by removing the resist film after performing the rubbing treatment in the direction and changing the liquid crystal alignment ability of the liquid crystal alignment film.

(3) Two substrates on which the liquid crystal alignment film is formed as described above are manufactured, and the two substrates are separated by a gap (cell gap) so that the rubbing directions in the respective liquid crystal alignment films are orthogonal or antiparallel. ), And the periphery of the two substrates are bonded together using a sealant, and liquid crystal is injected and filled in the cell gap defined by the substrate surface and the sealant, and the injection hole is sealed. A liquid crystal cell is constructed. And a liquid crystal display element is obtained by arrange | positioning a polarizing plate to the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell.
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.

Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal. Liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-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 film or an H film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films. The polarizing plate which consists of itself can be mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The imidation ratio, voltage holding ratio, and coating property of the imidized polymer in Examples and Comparative Examples were evaluated by the following methods.

[Method for measuring imidization rate of imidized polymer]
The solution of the imidized polymer was poured into pure water, and the obtained precipitate was dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. It was determined by the formula shown by the following formula (ii).
Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 ------ (ii)
A ¹ : NH group proton-derived peak area (10 ppm)
A ² : Peak area derived from other protons α: Number ratio of other protons to one proton of NH group in polymer precursor (polyamic acid)

[Voltage holding ratio]
A voltage of 5 V was applied to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from release of application was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation. The case where the voltage holding ratio was 95% or more was judged as good, and the other cases were judged as bad.

[Burn-in test]
A cell having an ITO electrode as shown in FIG. 1 is produced. A DC voltage of 8.0 V was applied to electrode A, and a DC voltage of 0.5 V was applied to electrode B at temperatures of 40 ° C. and 80 ° C. for 20 hours. After releasing the stress, DC voltage 0.1-3.0V is applied to electrodes A and B in increments of 0.1V. The image sticking characteristics were determined based on the luminance difference between the electrodes A and B at each voltage. When the brightness difference was large, it was judged that the burn-in characteristic was bad.

Synthesis example 1
2,3,5-tricarboxycyclopentylacetic acid dianhydride 179.34 g (0.8 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 62.86 g (0.2 mol), p-phenylenediamine 82.46 g (0 as diamine compound) 7625 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, 19.83 g (0.1 mol) of 4,4′-diaminodiphenylmethane and 4- (4′-trifluoromethoxybenzoy) Roxy) cyclohexyl-3,5-diaminobenzoate 13.15 g (0.03 mol), 1.40 g of aniline as monoamine (0.0 5 mol) was dissolved in N- methyl-2-pyrrolidone 1,550G, by reacting for 6 hours at 60 ° C., to obtain a polyamic acid solution having a viscosity of 60 mPa · s. In the resulting polyamic acid, 1,920 g of N-methyl-2-pyrrolidone was dissolved, 237.4 g of pyridine and 306.4 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidation reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the imidation reaction were removed from the system in this operation), and the solid content was 15 Solution viscosity at a solid content concentration of 10% by weight (N-methyl-2-pyrrolidone solution) 45 mPa · s, solid content concentration at 6.0% by weight (N-methyl-2-pyrrolidone solution) 1,500 g of an imidized polymer (A-1) solution having a viscosity of 12 mPa · s and an imidization ratio of 88% was obtained.

Synthesis example 2
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.09 g (0.50 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.50 mol), p-phenylenediamine as a diamine compound 90.03 g (0 8325 mol), 24.85 g (0.10 mol) of bisaminopropyltetramethyldisiloxane, and 29.69 g (0.06 mol) of the diamine compound represented by the above formula (23), 1.40 g of aniline as a monoamine (0.015 mol) was dissolved in 970 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a solution viscosity of 5 To obtain a polyamic acid of mPa · s. The obtained polyamic acid was dissolved in 2,800 g of N-methyl-2-pyrrolidone, 158.2 g of pyridine and 204.2 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (pyridine and acetic anhydride used for the imidation reaction were removed from the system by this operation), and the solid content concentration was 17 Solution with a viscosity of 50 mPa · s at a solid content concentration of 10% by weight (N-methyl-2-pyrrolidone solution) and a solid content concentration of 6.0% by weight (N-methyl-2-pyrrolidone solution) 1,600 g of an imidized polymer (A-2) solution having a viscosity of 13 mPa · s and an imidization ratio of 93% was obtained.

Synthesis example 3
110 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic 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 160 g (0.5 mol), p-phenylenediamine 96 g (0.865 mol) as the diamine compound, 1 , 3-bis (3-aminopropyl) tetramethyldisiloxane 25 g (0.1 mol) and 3,6-bis (4-aminobenzoyloxy) cholestane 13 g (0.02 mol), N-octadecylamine as monoamine A solution viscosity of 60 m is obtained by dissolving 8.1 g (0.03 mol) in 960 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 6 hours. To obtain a polyamic acid solution of a · s. Next, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 400 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with unused γ-butyrolactone (the pyridine and acetic anhydride used in the imidization reaction were removed from the system in this operation), and the solid content concentration was 15.0 wt. %, Solution viscosity at a solid content concentration of 10% by weight (γ-butyrolactone solution), 70 mPa · s, solution viscosity at a solid content concentration of 6.0% by weight (γ-butyrolactone solution), imidation rate of 95 % Imidized polymer (A-3) solution 1,500 g was obtained.

Synthesis example 4
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 106.52 g (0.985 mol) of p-phenylenediamine as a diamine compound, and A polyamic acid solution having a solution viscosity of 210 mPa · s was prepared by dissolving 7.842 g (0.015 mol) of ru-3,5-diaminobenzoate in 3,100 g of N-methyl-2-pyrrolidone and reacting at room temperature for 3 hours. Obtained. Next, 3,400 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 400 g of pyridine and 300 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with unused γ-butyrolactone (the pyridine and acetic anhydride used for the imidization reaction were removed from the system in this operation), and the solid content concentration was 9.0 wt. %, A solution viscosity of 15.0 mPa · s at a solid content concentration of 3.1% by weight, and 2,300 g of an imidized polymer (A-4) solution having an imidization ratio of 90% were obtained.

Synthesis example 5
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.09 g (0.5 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine 87.86 g (0 as diamine compound) 8125 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, and 35.07 g of 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate (0. 08 mol), 1.40 g (0.015 mol) of aniline as a monoamine was dissolved in 1,250 g of N-methyl-2-pyrrolidone. And a polyamic acid having a solution viscosity of 55 mPa · s was obtained by reacting at 60 ° C. for 6 hours. The resulting polyamic acid was dissolved in 2,500 g of N-methyl-2-pyrrolidone, 397.2 g of pyridine and 410.1 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with unused N-methyl-2-pyrrolidone (in this operation, pyridine and acetic anhydride used for the imidization reaction were removed from the system), and the solid content concentration 17.0 wt%, when the solid content concentration is 10 wt% (N-methyl-2-pyrrolidone solution), the solution viscosity is 50 mPa · s, and when the solid content concentration is 6.0 wt% (N-methyl-2-pyrrolidone solution) 1,800 g of an imidized polymer (A-5) solution having a solution viscosity of 13.0 mPa · s and an imidization ratio of 95% was obtained.

Synthesis Example 6
196.11 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 142.25 g (1 of 1,3-bis (aminomethyl) cyclohexane as diamine compound 0.0 mol) was dissolved in 2,200 g of N-methyl-2-pyrrolidone, reacted at 40 ° C. for 3 hours, and then diluted with 2,250 g of γ-butyrolactone. A polyamic acid (polyamic acid (B-1)) solution having a solution viscosity of 180 mPa · s was obtained.

Synthesis example 7
196,11 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 170.30 g of diamine compound represented by the above formula (9) as diamine compound ( 1.0 mol) was dissolved in 3230 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. A polyamic acid (polyamic acid (B-2)) solution having a solution viscosity of 150 mPa · s was obtained.

Synthesis example 8
200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 210 g of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine compound (1 0.0 mol) is dissolved in 370 g of N-methyl-2-pyrrolidone and 3300 g of γ-butyrolactone and reacted at 40 ° C. for 3 hours to obtain a polyamic acid (polyamic acid (B-3)) solution having a solution viscosity of 160 mPa · s. Obtained.

Synthesis Example 9
1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.05 g (0.50 mol), pyromellitic dianhydride 109.06 g (0.50 mol), diamine compound as tetracarboxylic dianhydride As a solution, 200.24 g (1.0 mol) of 4,4′-diaminodiphenyl ether was dissolved in 230 g of N-methyl-2-pyrrolidone and 2,100 g of γ-butyrolactone and reacted at 25 ° C. for 3 hours. Thereafter, 1,400 g of γ-butyrolactone was added to obtain a polyamic acid (polyamic acid (B-4)) solution having a solution viscosity of 200 mPa · s.

Example 1
The polyimide (A-1) obtained in Synthesis Example 1, the polyamic acid (B-1) obtained in Synthesis Example 6 and the polyamic acid (B-3) obtained in Synthesis Example 8 were converted into polyimide (A-1). ): Polyamic acid (B-1): polyamic acid (B-3) = 10: 50: 40 (weight ratio) γ-butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio) 71/17/12) and dissolving 10 parts by weight of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane as an epoxy group-containing compound with respect to 100 parts by weight of the polymer. A solution with a solid content concentration of 3.5% by weight was prepared, and after sufficient stirring, the solution was filtered using a filter having a pore size of 1 μm to prepare the liquid crystal aligning agent of the present invention. Imidation rate The above liquid crystal aligning agent is applied onto a transparent conductive film made of an ITO film provided on one surface of a 1 mm thick glass substrate using a spinner (rotation speed: 2500 rpm, application time: 1 minute) And it dried at 200 degreeC for 1 hour, and formed the film with a dry film thickness of 0.08 micrometer. A rubbing machine having a roll in which a rayon cloth was wound around this film was subjected to a rubbing treatment at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / second, and a hair foot pushing length of 0.4 mm. The liquid crystal alignment film coated substrate was ultrasonically cleaned in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of transparent electrodes / transparent electrode substrates having the liquid crystal alignment film of the liquid crystal alignment film coated substrate, the liquid crystal alignment film The adhesive was cured by overlapping and pressing so that the surfaces were opposed. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarizing plates are formed on both sides of the substrate. Were laminated to prepare a liquid crystal display element. The voltage holding ratio of the obtained liquid crystal display element was evaluated. The liquid crystal aligning agent obtained in the present invention showed a high voltage holding ratio of 99% or more. Moreover, when the image sticking test was conducted, good results were shown regardless of the stress temperature.

Examples 2, 3 and Comparative Examples 1-5
Polyimides (A-1) to (A-5) obtained in Synthesis Examples 1 to 5, polyamic acids (B-1) to (B-4) obtained in Synthesis Examples 6 to 9, and an epoxy group-containing compound N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane is dissolved in a mixed solvent containing γ-butyrolactone as a main component to obtain a solution having a solid content concentration of 3.5% by weight. The liquid crystal aligning agent of the present invention was prepared by filtering the solution through a filter having a pore size of 1 μm. Using each of the thus prepared liquid crystal aligning agents, a film was formed on the substrate surface in the same manner as in Example 1, and a liquid crystal display element was manufactured using the substrate on which the liquid crystal aligning film was formed. . And the voltage holding rate was evaluated. A seizure test was also conducted. The results are shown in Table 1.

Explanatory drawing of the cell with an ITO electrode created for the burn-in test.

Claims (5)

The following formula (I-1)

(Wherein P ¹ is a tetravalent organic group and includes a tetravalent organic group represented by the following formula (A):

Q ¹ is a divalent organic group and has the following formula (B), (C), (D) or (E):

Each of R1 to R11 is independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms. )
A polyamic acid having an amic acid bond unit comprising a bond unit represented by formula (I-2)

(Where P ² is a tetravalent organic group and Q ² is a divalent organic group.)
A polyimide having an imide bond unit represented by
Which is a mixture made from a polymer of and the liquid crystal aligning agent ratio of the number of imide bonds unit is characterized in that account for 5% to 80% of the total number of bonds unit of amic acid bond unit and imide bond units.
P ¹ or P ² is 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3 2. A tetravalent organic group derived from at least one tetracarboxylic dianhydride selected from -furanyl) -naphtho [1,2-c] -furan-1,3-dione. Liquid crystal aligning agent. The liquid crystal aligning agent of Claim 1 or 2 which further contains 0.1-30 weight part of compounds which have at least 1 epoxy group in a molecule | numerator with respect to 100 weight part of said polymers. The liquid crystal aligning film formed from the liquid crystal aligning agent in any one of Claims 1-3. A liquid crystal display element comprising the liquid crystal alignment film according to claim 4.

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