TW200932789A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent forming a liquid crystal aligning film which has good printability, show high voltage hold ratio, together with a stable pretilt angle independent from the process conditions used. The above liquid crystal aligning agent comprises (A) a polyamic acid obtained from a reaction of a 1, 2, 3, 4-cyclobutantetracarboxylic dianhydride containing tetracarboxylic dianhydride and a diamine, and (B) a polyimide formed by dehydration and ring closure a polyamic acid obtained from a reaction of a tetracarboxylic acid and a diamine containing a specific mono-substitute phenylenediamine represented by the following formula (d-1): wherein comparing to the total amount of (A) number of polyacic acid structures contained in the polyamic acid and (B) number of imide ring structures contained in the polyimide, the amount ratio of (B) number of imide ring structures contained in the polyimide is 10 to 50%.

Description

200932789 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent which exhibits a high voltage retention ratio and a high pretilt angle, which is excellent in printability and which does not depend on the processing conditions employed, and which exhibits a high voltage holding ratio and a pretilt angle stable liquid crystal alignment film; A liquid crystal alignment film; and a liquid crystal display element capable of obtaining a 髙 quality display. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is widely known, and a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive film is provided. As a substrate for a liquid crystal display element, two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap, and the long axis of the unit cell liquid crystal molecule constituting the sandwich structure is formed. The substrate is continuously twisted 90 degrees from one substrate to another. In addition, an STN (Super Twisted Nematic) liquid crystal display element capable of achieving higher contrast than a TN liquid crystal display element, an IPS (in-plane switching) type liquid crystal display element having a small viewing angle dependency, and an IPS change have been developed. The electrode structure, the FFS (Fringe Field Conversion) type liquid crystal display element and the VA (Vertical Alignment) type liquid crystal display element which improve the aperture ratio of the opening of the display element to improve the brightness, and the viewing angle dependence is small, and the video picture has excellent high-speed response. 0 CB (optical compensation bending) type liquid crystal display element. As a material of the liquid crystal alignment film in these liquid crystal display elements, a resin material such as polylysine, polyimine, polyamine, or polyester is known, and in particular, it is made of polyamic acid or polyimine. The liquid crystal alignment film is excellent in heat resistance, mechanical strength, affinity with liquid crystal, and the like, and is used in a large display element (see, for example, Patent Documents 1 to 3). In recent years, in addition to the transmissive liquid crystals which have been known for a long time, reflective and semi-transmissive liquid crystal display elements are also popularized in the application range of liquid crystal display elements and the progress of liquid crystal display is rapidly progressing, and liquid crystal display elements are rapidly progressing. The hugeness of the manufacturing equipment has also been developed. However, with the large-area liquid crystal alignment film formed on a large production plate, the processing conditions are difficult to achieve the same. When a conventional liquid crystal alignment liquid crystal alignment film is used, in particular, the liquid crystal alignment film may have different tilting sounds, which hinders the realization of the uniform display. In this case, Patent Document 4 proposes a liquid crystal alignment agent excellent in processing. According to Patent Document 4, the liquid crystal alignment agent of the polyamine or polyimine obtained by the diamine has a voltage holding ratio, and when the liquid crystal alignment film is formed, the enthalpy deviation, the pretilt angle can also exhibit stable enthalpy. However, the liquid crystal alignment agent described in ® does exhibit excellent high dependence of the pretilt angle on the processing conditions, but it is particularly problematic in terms of printability and thus needs to be improved. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇〇6_ 321783 [Patent Document 5] Japanese Patent Laid-Open No. 6-222366, Part 4 liquid crystal display element, with the accompanying component itself and the production line at a large base to form a large area in all areas. Pre-conditional dependence is specific, and high processing conditions are not available. Patent Document 4: Pressure retention ratio: current coating property, r report, bulletin, bulletin t, 200932789 [Patent Document 6] 曰本特开平6— 281937 [Patent Document 7] Japanese Laid-Open Patent Publication No. Hei 5-107544 (Non-Patent Document 1) TJ Scheffer et al., J. Appl. Phys., Vol. 19, 2013 (1980) = [Summary of the Invention] Providing a liquid crystal alignment agent which is excellent in printability and exhibits high voltage holding ratio and which can produce a liquid crystal alignment film having a stable pretilt angle without depending on processing conditions; liquid crystal alignment showing high voltage holding ratio and high pretilt angle ; And a liquid crystal display capable of obtaining a high-quality display device. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention, first, are achieved by a liquid crystal alignment agent comprising: (A) a tetracarboxylic acid containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride a polylysine obtained by reacting a dianhydride with a diamine, and (B) a poly (decanoic acid) dehydration ring closure obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (d) Polyimine,

In the formula (d), W is an alkyl group having 1 to 12 carbon atoms, and Rii is a halogen atom or a group having 1 to 12 carbon atoms, and X is a formula (X-1) to (X). —4) A divalent group represented by either, η is an integer of 0 to 4, 200932789 〇II C 〇(X-1) 〇II 〇II C (X-2) 0 II C -NH——(X -3) 〇NH II C (X-4) wherein the amount of the proline structure possessed by (A) polyphthalic acid and (B) the number of quinone ring structures possessed by polyimine The sum of the amounts of the structure of the chiral acid and (B) the amount of the quinone ring structure of the polyimine is 10 to 50%. The above objects and advantages of the present invention 'second' are aligned by the above liquid crystal. The liquid crystal alignment film formed by the agent is achieved. The above objects and advantages of the present invention, and thirdly, are achieved by a liquid crystal display element having the above liquid crystal alignment film. According to the present invention, it is possible to provide a liquid crystal alignment agent which is excellent in printability, exhibits a high voltage holding ratio, and can produce a liquid crystal alignment film having a stable pretilt angle without depending on the processing conditions employed. The liquid crystal alignment film of the present invention formed of the above liquid crystal alignment agent exhibits high voltage holding ratio and high pretilt angle, and the liquid crystal display element of the present invention having such a liquid crystal alignment film can obtain a high quality display, for example, applicable Display devices for calculators, watches, desk clocks, counting panels, typewriters, personal computers, LCD TVs, etc. 200932789 [Embodiment] The liquid crystal alignment agent of the present invention comprises at least: (A) a reaction of a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with a diamine. Polyimine, and (B) a polyimine obtained by dehydrating a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (d), preferably further Containing (C) a compound having at least one epoxy group in the molecule. <(A) Polyproline> φ (A) Polyproline contained in the liquid crystal alignment agent of the present invention can be obtained by containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride The tetracarboxylic dianhydride is synthesized by reacting with a diamine. [Tetracarboxylic dianhydride] As the tetracarboxylic dianhydride used for the synthesis of (A) polyglycine, only 1,2,3,4-cyclobutanetetracarboxylic dianhydride may be used, or 1 may be used. 2,3,4-cyclobutanetetracarboxylic dianhydride is used in combination with other tetracarboxylic dianhydrides. Examples of the other tetracarboxylic dianhydride which can be used herein include anthracene tetracarboxylic dianhydride and 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-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,3,4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,4 ,5-tetrahydrofuran tetracarboxylic dianhydride, i,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2 -c]-furan-l,3-diindole, l,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furan 200932789 Cyclo)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,915 -hexahydro-7-ethyl-5-(tetrahydro-2,5- Oxo-3-furanyl)-naphthalene [1,2-(;]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-indolyl]-furan-1,3-dioxanone, 1,3,3a ,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1 , 3 -dione, 5-(2,5-dioxotetrahydrofuranyl)_3-methyl-3-cyclohexene·1,2-dicarboxylic acid di-P,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), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6 -Tricarboxy-2-carboxymethylnorbornane - 2:3, 5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0'6]undecane-3,5,8, An aliphatic or alicyclic tetracarboxylic dianhydride such as a 10-tetraone or a compound represented by the following formula (7'-1) or (1'-11)

200932789 (In the formulas (Τ-I) and (Τ-II), 'R1 and R3 each represent a divalent organic group having an aromatic ring, and R2 and R4 each represent a hydrogen atom or a plurality of R2 and R4 present in the hospital' May be the same or different); pyromellitic dianhydride, 3,3,,4,4,-benzophenone tetrahydro acid dianhydride, 3,3,4,4,diphenylphosphonium tetracarboxylate Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3,,4,4,-diphenyl ether tetracarboxylate Acid dianhydride, 3,3,,4,4,-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic dianhydride, 1,2 , 3,4-furan tetracarboxylic dianhydride, 4,4'·bis(3,4-O dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4′-bis (3,4-di Carboxyphenoxy) Diphenyl succinic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3,,4,4'-perfluorohetero Propyldiphthalic dianhydride, 3,3',4,4'- |> Biphenyltetracarboxylic dianhydride, 2,2',3,3,-biphenyltetracarboxylic dianhydride, double (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(triphenyl phthalate) Dicarboxylic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(dehydrated trimellitate), propylene glycol-bis(de-water trimellitate), 1,4-butane Alcohol-bis(hydrogen trimellitate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2, An aromatic tetracarboxylic dianhydride such as a compound represented by the following formula (T-1) to (T-4); 2-bis(4-phenyl)propane-bis(hydrogen trimellitate). They may be used alone or in combination of two or more. -10- 200932789

〒H3 /Ch3

Among them, from the viewpoint of enabling liquid crystal alignment which is excellent in performance, butane tetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid are preferred. Anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-11 - 200932789 dianhydride, l,3,3a,4,5,9b - Hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&, 4, 5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione 1,3,3&,4,5,91?-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1, 2-c]-furan-1,3-dione, 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), 5-(2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4 ,9-dioxatricyclo[5·3·l·02,6]^^-alkane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4 '-benzophenonetetracarboxylic dianhydride, 3,3 , 4,4'-diphenyl maple tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the above a compound represented by the following formula (T-5) to (T-7) in the compound represented by the formula (TI) or a compound represented by the following formula (T-8) in the compound represented by the above formula (T-II); . Particularly preferred are 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo. -3-furanyl)-naphthalene [l,2-C]-furan-l,3-® diketone, 1,3,3&,4,5,913-hexahydro-8-methyl-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene [1,2-indolyl]-furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4- Diketo-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclo Hexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[ 5.3.1.02 '6] undecane-3,5,8,10-tetraketone, pyromellitic dianhydride and a compound represented by the above formula (T-5). -12- 200932789

(Τ-5)

Ο The tetracarboxylic dianhydride used for the synthesis of (poly)polyamine is preferably contained in an amount of 1% by mole or more, more preferably 30% by mole or more, based on the total amount of the tetracarboxylic dianhydride. Containing 50 mol% or more of 1,2,3,4-cyclobutane tetracarboxylic dianhydride. Examples of the diamine used for the synthesis of the (A) polyphthalic acid include p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, and 4,4,-diaminodi Phenylethane, 4,4,-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4,-diamine linkage Benzene, 4,4,-diaminobenzimidamide, 4,4,-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2,-dimethyl-4,4'- Diaminobiphenyl, 3,3,-bis(trifluoromethyl)-4,4,-diaminobiphenyl, 5-amino J-13- 200932789-1-(4'-aminophenyl -1,3,3-trimethylindan, 6-amino-1_(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diamino Diphenyl 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]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,3-bis(3-aminophenoxyl) Benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl-2,7-diaminopurine, 〇9 , 9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-di Aminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-di Amine bud, 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4- (4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4 An aromatic diamine such as '-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; 1,1-m-xylylenediamine, 1,3-propanediamine, Butanediamine, pentanediamine, hexamethyleneamine, heptanediamine, octanediamine, decanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene Diamine, hexahydro-4,7-methylene dimethylene diamine, tricyclo[6.2.1.02,7]undecene dimethyldiamine, 4,4'-methylene bis (cyclohexane) Amine), 1,3-bis(aminomethyl)cyclohexane, 1 An aliphatic or alicyclic diamine such as 4-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamine -6-dimethylamino-1,3,5-three tillage, 1,4- -14- 200932789 bis(3-aminopropyl) pipe trap, 2,4-diamino-6-isopropoxy Base-1,3,5-tripper, 2,4-diamino-6-methoxy-1,3,5-trin, 2,4-diamino-6-phenyl-1,3 , 5-triad, 2,4-diamino-6-methyl-s-tripper, 2,4-diamino-1,3,5-tri-n' 4,6-diamino-2 -vinyl-s-tripper, 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, 3,6-diaminocarbazole, N-methyl-3 ,6-diamine mercaptocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-amine Phenyl Benzidine, a compound represented by the following formula (D-Ι): hexa(4) h2n nh2 (in the formula (D-I), R5 represents a ring containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triterpene, piperidine and pipe trap a monovalent organic group of a structure, X1 represents a divalent organic group, and a compound represented by the following formula (D-II)

(In the formula (D-II), 'R6 represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, tri-till, piperidine, and a pipe trap. 'X2 represents a divalent organic group, and exists. Each of the plurality of X2 may be the same or different) a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amine group; (DH) -15- 200932789 The following formula (D - III) represents Monosubstituted phenylenediamine, /—VR7-R8 L (D-iH) ΝΗ, (in the formula (D-III), R7 is selected from -〇., (3)_, _ΝΗ(:()_, -CONH- and a divalent organic group of CO-, R8 represents a monovalent organic group or a carbon atom having a group selected from the group consisting of a residue skeleton, a difluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group. a number of 6 to 30 alkyl groups) (but the above formula (d)

Except for the compound represented); a diamine organooxane represented by the following formula (D - iv)

Nh2 R9 (D-IV) (In the formula (D-IV), R9 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R9 groups may be the same or different, and p is an integer of 1 to 3, q An integer of 1 to 20); a compound represented by the following formula (D-i) or (D-5)

-16 - 200932789

〒H3 /Ch3

(D-5) (Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5). These diamines may be used alone or in combination of two or more. As the diamine used for synthesizing (A) polyglycine, it preferably contains at least one diamine selected from the group consisting of p-phenylenediamine, 4,4'-diaminodi Benzene, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4,-diaminobiphenyl, 2,2,- Bis(trifluoromethyl)-4,4,-diaminobiphenyl, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2--17- 200932789 [4-(4-Aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)benzene Hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4,-(p-phenylene diisopropylidene)diphenylamine, 4,4'- Phenyldiisopropylidene)diphenylamine, ίο bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 14-cyclohexanediamine, 4,4,_methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, a compound represented by the above formula (D-1)~(D-5), 2,6 -diaminopyridine, 3,4-diaminopyridinium, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3 , 6-diaminocarbazole, © N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-di a compound represented by the following formula (D-6) in the compound represented by the above formula (D-I), a compound represented by the following formula (D), an aminocarbazole, an N,N'-bis(4-aminophenyl)benzidine a compound represented by the following formula (D-7) in the compound represented by -II),

Dodecyloxy-2,4·diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2 in the compound represented by the above formula (D-III), 4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, heptadecyloxy-2,5-diamino Benzene, cetyloxy-2,5-diamino-18- 200932789 Benzene, 18-epoxy-2,5-aminophenyl, the following formula (D-8)~(D-16) Compound represented

19- 200932789

And a compound of the above formula (D~IV), wherein the 1,3-record, - try (3 - limb 碁 Q propyl)-tetramethyldioxane, more preferably contains 1 relative to all diamines The diamine of at least one of them is more preferably contained in an amount of more than 3 mol%, more preferably more than 50 mol%. The diamine used for synthesizing (A) polyglycine is preferably a diamine which does not contain the diamine represented by the above formula (d). [(A) Synthesis of Polyproline] (A) Poly(A) can be synthesized by reacting tetradecanoic dianhydride as described above with = amine. The ratio of the tetracarboxylic dianhydride to the (A) polyamic acid synthesis reaction and the diamine is -20-200932789. The ratio is preferably relative to the equivalent of one amine group contained in the diamine to make the tetraresic acid dianhydride. The acid anhydride group has a ratio of 0.5 to 2 equivalents, more preferably 0.7 to 12 equivalents. The synthesis reaction of poly-proline is preferably carried out in an organic solvent at a temperature of from _2 〇 to 15 Q ° C, more preferably from 〇 to 10,000 Å, preferably from 0 5 to 48 hours, more preferably 1 ~24 hours. Here, 'the organic solvent is not particularly limited as long as it can dissolve the produced (A) polyphthalic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethyl group. An aprotic polar solvent such as acetamide, N,N-dimethylformamide, dimethyl hydrazine, T-butyrolactone 'tetramethylurea, hexamethylphosphonium triamine; m-methylphenol, a phenolic solvent such as xylenol, phenol or halogenated phenol. The amount of the organic solvent (including the amount of the poor solvent when used in combination with the poor solvent described below) (a), preferably the total amount of the tetracarboxylic dianhydride and the diamine (b) relative to the total amount of the reaction solution (a + b) is an amount of 0.1 to 3 0% by weight. In the above organic solvent, (A) poor solvent alcohols of polyacrylic acid, ketones, esters, oxime ethers, halogenated hydrocarbons may be used in combination in the range in which the produced polyaminic acid is not precipitated. , hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and lactic acid. Ethyl ester, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxy propyl Ethyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene Alcohol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol-21 - 200932789 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, isoamyl propionate, isoamyl isobutyrate, isoamyl ether and the like. In the case of the synthesis of (A) polylysine, when the organic solvent is used in combination with a poor solvent, the use ratio of the poor solvent is preferably 10% by weight or less based on the total amount of the organic solvent and the poor solvent. Preferably it is 5% by weight or less. 〇 As described above, a reaction solution in which (A) poly-proline is dissolved is obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or the (A) polylysine contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent, or the separated (A) may be polymerized. After the purification of proline, the liquid crystal alignment agent is supplied. (A) Separation of polylysine by a method in which the above reaction solution is introduced into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or a method of decompressing the reaction solution by an evaporator under reduced pressure get on. In addition, the process of re-dissolving the (A) polyproline acid® in an organic solvent and then precipitating it with a poor solvent once or several times can be performed by (A) refining by a vacuum distillation process using an evaporator. Polylysine. <(B) Polyimine] (B) Polyimine contained in the liquid crystal alignment agent of the present invention can be reacted with a diamine containing a compound represented by the above formula (d) by reacting a tetradecanoic dianhydride And synthesis. [Tetracarboxylic dianhydride] As the tetraruthenic dianhydride used for the synthesis of (B) polyacid imide, -22-200932789 1,2,3,4-cyclobutanetetracarboxylic dianhydride and The same compound of the other tetracarboxylic dianhydride which can be used in the synthesis of (A) polyphthalic acid. Synthesis of (B) a tetracarboxylic dianhydride used in polyimine, preferably containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,3,3&,4,5,913-hexahydrogen At least one tetrakisonic acid dianhydride selected from the group consisting of -8-methyl-5-(tetrahydro-, dioxo-furanyl-naphthalene----furan-^-dione, More preferably, the tetracarboxylic dianhydride containing at least one of 10 mol% or more of all tetracarboxylic dianhydrides further preferably contains 30 mol% or more, and particularly preferably contains 6 〇Q mol% or more. The diamine used in the synthesis of (B) polyimine contains the compound represented by the above formula (d). As Ri in the above formula (d), a methyl group, an ethyl group or a propyl group is preferred. 'preferably trifluoromethyl, perfluoroethyl or perfluoropropyl. As η, preferably 0 or 1» is bonded to the position of the two amine groups on the benzene ring on the left side of the above formula (d)' Preferably, it is located at 3 and 5 positions relative to χ.

The position of the substituted phenoxy group on the right side of the ring of the hexene is preferably the alignment of X. The position of the group - 〇-rh is preferably located at the para position of the oxygen atom. When n is 1, the position at which the group Ri is attached is preferably the ortho position of the group _〇_rh. Preferable specific examples of the compound represented by the above formula (d) include a compound represented by the following formula (d ~ (d-6)).

-23- 200932789 h2n

〇 ^_NHKI}~0_~O~'0^CF3 (ci-2)

❹ H2N h2n

<y

(d-5) 0 〜CF, — (d-6) H2N Ο-Qp ❹ h2n h2n

C—NH As the amine used for the synthesis of the (B) polyimine, only the compound represented by the above '(d)' may be used or the compound represented by the above formula (d) may be used in combination with other diamines. As the other diamine which can be used herein, the same diamine as the above compound which is a diamine used for the synthesis of (A) polyphthalic acid can be mentioned. The diamine used in the synthesis of the (B) polyimine is preferably contained in an amount of 0.5 mol% or more, more preferably 1 mol% or more, and particularly preferably 2 mol% or more of the above formula (d). ) the compound indicated. The diamine used in the synthesis of (B) polyimine, in addition to the compound of the above formula (d), in addition to the compound of the above formula (d), preferably contains p-phenylenediamine and bisaminopropyltetramethyldioxy At least one selected from the group consisting of alkane. More preferably, it contains at least 20 mol% or more, more preferably 50 to 99 mol%, and particularly preferably ～98 mol% of at least one of them. [(B) Method for synthesizing polyimine] (B) Polyfluorene can be obtained by reacting a diamine of the compound represented by the above formula (d) with a tetracarboxylic dianhydride as described above. The amine is dehydrated and closed to synthesize. The synthesis of the polyamic acid can be carried out in accordance with the synthesis of the above (A) polyproline, in addition to the use of the tetracarboxylic acid described above and the diamine containing the compound represented by the above formula (d). The dehydration ring closure of polylysine can be (i) by heating the poly-proline acid method or (Π) by dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and as needed The method of heating is OK. The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50. (: The dehydration ring-closure reaction cannot be sufficiently carried out, and if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained quinned imidized polymer may decrease. The reverse time is preferably 0.5 to 24 hours, more preferably 1 to 12 On the other hand, in the above-mentioned method of adding a dehydration and dehydration ring-closure catalyst to a polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the agent, for the repeating unit of 1 mole of poly-proline, preferably 0.01 to 20 moles of the amine 70 and the anhydride solution into the reagent as the phase -25-200932789 In addition, as a dehydration ring-closing catalyst, A tertiary amine such as pyridine, trimethylpyridine, dimethylpyridinium or triethylamine is used. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 with respect to 1 mol of the dehydrating agent. In addition, as the organic solvent used in the dehydration ring-closure reaction, an organic solvent exemplified as the solvent used in the synthesis of (A) polylysine may be mentioned. The temperature is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C, and the reaction time is preferably from 5 to 24 hours, more preferably from 1 to 12 hours. e The above method (i) is obtained. The (B) polyimine may be directly supplied to the liquid crystal alignment agent, or the obtained (B) polyimine may be purified and then supplied to the liquid crystal alignment agent. Further, in the above method (Π) In the process, a reaction solution containing (B) polyimine is obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, and the liquid crystal alignment agent can be supplied after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and The (B) polyimine is separated and supplied to the liquid crystal alignment agent, or the separated (B) polyimine may be purified and then supplied to the liquid crystal alignment agent. The dehydrating agent is removed from the reaction solution. The dehydration ring-closure catalyst may be, for example, a method such as solvent replacement. (B) The separation and purification of the polyimine may be carried out in the same manner as described above for the separation and purification method of (A) polyglycine. In the present invention The (B) polyimine may be a fully dehydrated ring-closed product of a proline acid unit contained in a precursor poly-proline, a complete dehydration ring-closing product having only a quinone ring or a poly-proline The valeric acid unit having only a part of the dehydration ring closure, the guanamine unit and the quinone ring coexisting 醯-26- 200932789 product having a small imidization rate. (B) Polyimine used in the present invention The imidization ratio of hydrazine is preferably 40% or more, more preferably 80% or more. Here, the "r-imidization ratio" means the number of methionine units in the polyimine and the quinone ring. In the total amount, the ratio of the amount of the quinone ring is expressed as a percentage. At this time, a part of the quinone ring may be an isoindole ring. The imidization ratio can be determined by dissolving (B) polyimine in a suitable deuterated solvent, such as deuterated dimethyl sub-milling, using tetramethyl decane as the reference material, © iH- at room temperature NMR was determined from the measurement results by the formula shown by the following formula (1).醯imination rate (%)=(1 - Α^Α'αίχΙΟΟ (i) (In equation (i), A1 is the peak area originating from the NH matrix near the chemical shift of 10 ppm, and A2 is derived from other The peak area of the proton, α is the ratio of the number of other protons relative to one NH matrix in the polymer precursor (polyglycolic acid). [End-modified polymer] 〇 (A) The proline and (B) polyimine may also be a terminally modified polymer having a molecular weight adjustment. The terminal modified polymer may be added to the reaction system during the synthesis of the polyamic acid. A molecular weight modifier such as a monobasic acid anhydride, a monoamine compound or a monoisocyanate compound is synthesized. Here, examples of the monobasic acid anhydride include maleic anhydride 'phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, and n-dodecane. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, and the like n-Hexylamine, n-heptylamine, n-octylamine, positive Amine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, positive ten Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The use ratio of the molecular weight modifier as described above is relative to 100%. The total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. [Solution viscosity] The above (A) The viscosity of the solution is preferably from 20 to 800 mPa_s, more preferably from 30 to 500 mPa.s, and the viscosity of the solution is (A) when the solution is at a concentration of 10% by weight. a good solvent (for example, N-methyl-2-pyrrolidone, r-butyrolactone, etc.) of each of polyacrylic acid or (B) polyimine, which is determined by an E-type rotational viscometer at 25 t O [(A) Polyampinic acid and (B) Polyimine use ratio] The liquid crystal alignment agent of the present invention contains (A) polylysine and (B) polyimine as described above, The use ratio is: the sum of the number of the proline structure possessed by (A) polyphthalic acid and (B) the sum of the number of the quinone ring structure and the number of the proline structure of the polyimine, ( B) The ratio ratio of the quinone ring structure (hereinafter, also referred to as "average ruthenium imidation ratio") of the polyimine is 10 to 50%. The average ruthenium ratio is preferably 1 〇~40%. By using the ratio of (A) polyglycine and (B) polyimine to fall within the range of -28-200932789, it is possible to obtain a liquid crystal alignment film having the liquid crystal alignment agent of the present invention. The liquid crystal display element has superior printing performance and its reliability is better. &lt;(c) Compound having at least one epoxy group in the molecule&gt; The liquid crystal alignment agent of the present invention preferably contains (C) intramolecular purpose for the purpose of improving the adhesion of the formed liquid crystal alignment film to the substrate. At least one epoxy group compound (hereinafter referred to as "(C) epoxy compound"). Preferred examples of such (C) epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 16-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5 ,6-tetraglycidyl- 2,4-hexanediol, 1^,:^,:^',&gt;1'-tetraglycidyl-111-xylylenediamine, 1,3-double (N , N-diglycidylaminomethyl)cyclohexane, &gt;^, &gt;^', :^-tetraglycidyl-4,4'-diaminodiphenylmethane, :^,: ^-Diglycidyl-benzylamine, N,N-diglycidyl-amine methylcyclohexane, and the like. The content ratio of these epoxy compounds in the liquid crystal alignment agent of the present invention is preferably 40 parts by weight or less based on 100 parts by weight of the total of (A) polyphthalic acid and (B) polyimine. Preferably, it is 0.1 to 30 parts by weight. &lt;Other components&gt; The liquid crystal alignment agent of the present invention contains (A) polycapric acid and (B) polyimine as described above as an essential component, and preferably further contains the above (C) epoxy group compound. The liquid crystal alignment agent of the present invention, in addition to the above (A) polyphthalic acid and (B) poly-29-200932789 quinone imine and optionally (c) epoxy compound, does not impair the effects of the invention. It may further contain other ingredients. Examples of other components include a functional decane compound and the like. The functional decane compound may, for example, be 3-aminotrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltriethyl Oxydecane, N-(2-amino)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3 -ureidopropyltrimethoxydecane, 3-ureidodecyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane N-ethoxycarbonyl-3-aminopropyl Triethoxydecane, N-triethoxydecane, propyltriethylenetriamine, N-trimethoxydecylpropyltriethyleneamine, 10-trimethoxydecane-1,4,7-three Azadecane, 10-triethoxyalkyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaacetate, 9-triethyl Oxidylalkyl-3,6-diazaindolyl acetate, benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethyldecane, N- Phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-amine propyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyl Trimethoxy decane, N-bis(oxyethylene)_3_aminopropyltriethoxydecane, and the like. The content ratio of these functional decane compounds in the liquid crystal alignment agent of the present invention is preferably 10 parts by weight or less based on 100 parts by weight of (A) polyphthalic acid and (B) polyimine. &lt;Liquid Crystal Aligning Agent&gt; The liquid crystal aligning agent of the present invention is (A) polylysine, styrene, and preferably further (c) epoxy compound as described above, and optionally the present The ethyl ethyl propyl group and the hydrazino group N-oxy group are composed of (B) containing -30-200932789, and other components are preferably dissolved in an organic solvent. The organic solvent to be used in the liquid crystal alignment agent of the present invention may be exemplified as the solvent used in the (A) polyphthalamide synthesis reaction, and the mixture may be appropriately selected as (A) polydecylamine. A poor solvent exemplified in combination with an acid synthesis reaction. Preferred examples of the organic solvent to be used in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactone, and N,N-dimethylformamide. , N,N-dimethylacetamide, 4-hydroxy-4-methylindol-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether 'ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether , ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. These solvents may be used singly or in combination of two or more. G The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the liquid crystal alignment agent other than the solvent to the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, etc., preferably 1 to 10 weight. The range of %. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, and it is difficult to obtain a liquid crystal having good performance. When the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick and it is also difficult to obtain a liquid crystal alignment film having good performance 'and '-31 - 200932789, and the viscosity of the liquid crystal alignment agent increases, resulting in coating. The performance of the dressing deteriorates. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when the spin coating method is employed, it is preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is particularly preferable that the solid content concentration is in the range of 3 to 9 % by weight, so that the solution viscosity can be made to fall within the range of 12 to 50 mPa a·s. When the ink jet method is employed, it is particularly preferable to make the solid content concentration in the range of 1 to 5 % by weight, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa 's. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a patterned transparent conductive film by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. Next, the solvent is preferably removed by heating (prebaking). Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly (aliphatic ring) can be used. Plastic transparent substrate such as olefin). As the transparent conductive film provided on one side of the substrate, a NESA film made of tin oxide (Sn02) (registered trademark of PPG, USA), an ITO film of -32-200932789 indium-tin oxide (In203-Sn02), or the like can be used. These transparent conductive film patterns may be formed by, for example, forming a pattern by photolithography after forming a transparent conductive film without a pattern, or directly forming a pattern by using a mask having a desired pattern when the transparent conductive film is formed. A method of forming a transparent conductive film or the like. Before the application of the liquid crystal alignment agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional decane compound, a functional titanium compound or the like may be previously coated on the surface of the substrate. 〇 The prebaking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The prebaking time should be appropriately set depending on the kind of the heater to be used. For example, when heating is performed using a hot plate, &lt;) is preferably 45 seconds to 30 minutes, more preferably 45 seconds to 20 minutes. Then, in order to completely remove the solvent and the like, a post-heating (post-baking) process is performed. The post-baking temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the post-baking time should be appropriately set depending on the type of the heater to be used, for example, when a hot plate is used. When heated, it is preferably from 3 to 60 minutes, and more preferably from 7 to 30 minutes. The liquid crystal alignment agent of the present invention forms a coating film as an alignment film by removing an organic solvent after coating, and when the polymer contained in the liquid crystal alignment agent of the present invention is a polyamic acid or a quinone ring structure and In the case of a polyimide having a proline structure, after the coating film is formed, it may be subjected to dehydration ring closure by further heating to form a coating film which is further imidized. The thickness of the coating film formed by the chase is preferably 0.001 to Ιμπι, more preferably 0.005 to 0.5 μπ χ 33-33- 200932789 (2) a roller pair wrapped with a cloth such as nylon, rayon, cotton or the like The formed coating film surface is subjected to a rubbing treatment in which rubbing is performed in a certain direction. Thus, the alignment energy of the liquid crystal molecules can be generated on the coating film to form a liquid crystal alignment film. In addition, the coating film for the liquid crystal alignment film shown in the patent document 5 (Japanese Patent Laid-Open No. Hei 6-222366) or the patent document 6 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. A part of the process of irradiating the ultraviolet ray to change the pretilt angle of a part of the liquid crystal alignment film, or forming a protective film on the surface of the liquid crystal alignment film portion as shown in Patent Document 7 (Japanese Laid-Open Patent Publication No. Hei 5-107544) After the polishing process is performed in a different direction from the previous polishing process, the treatment of the protective film is removed, so that each region of the liquid crystal alignment film has a different liquid crystal alignment energy, which can improve the field of view performance of the obtained liquid crystal display element. (3) As described above, two substrates in which a liquid crystal alignment film is formed on the surface are formed, and two substrates are placed opposite each other through a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or anti-parallel, and two substrates are used. The peripheral portion 贴 is bonded with a sealant, and liquid crystal is injected into the cell gap which is separated from the surface of the substrate and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, a polarizing plate is separately provided on each outer surface of the liquid crystal cell to obtain a liquid crystal display element. Here, as the sealant, for example, an epoxy resin containing alumina balls as a curing agent and a separator, or the like can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an azo azo liquid crystal, a biphenyl liquid crystal, or a phenylcyclohexane can be used. Liquid crystal, ester liquid crystal, -34- 200932789 terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal liquid crystal, etc. Further, in these liquid crystals, a cholesteric liquid crystal such as cholesteryl choline, cholesteryl phthalate or cholesteryl carbonate may be further added; and the products are sold under the trade names "C · 15" and "CB-15" (manufactured by MERCK). A chiral agent; used for ferroelectric liquid crystals, such as a methoxy benzylidene-p-amino-2-methyl butyl cinnamate. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate formed by sandwiching a polarizing film called "H film" obtained by stretching a polyethylenol and simultaneously absorbing iodine, in a protective film of acetate. A polarizing plate made of the enamel film itself. . [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to these Examples. The following ruthenium imidization ratio of polyimine is obtained by dissolving polyimine at room temperature under reduced pressure in a deuterated dimethyl sub-mill with tetramethyl decane as a reference substance. 1H-NMR was measured at room temperature, and the measurement result was calculated by the above formula (i). Further, the solution viscosity of the polymer was measured by using an E-type rotational viscometer at 25 ° C for the polymer solution. &lt;(A) Synthesis Example of Polylysine&gt; Synthesis Example 1 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and Diamine compound 2,2'-dimethyl-4,4'--35- 200932789 One limb basal 212g (l. 〇mol) dissolved in 37〇gN•methyl_2_lalocane A mixture of a ketone and 3 3 00 g of γ-butyrolactone was allowed to react under a pressure of 4 Torr for 3 hours to obtain about 3 700 g of a solution containing 10% by weight of polyglycolic acid (A-hydrazine). The solution had a solution viscosity of 16 〇 raPa.s. Synthesis Example 2 ❹ 98 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride 98 g (0-50 mol) and pyromellitic dianhydride 1 〇 9 g (〇5〇莫Ear), as well as 4,4'-monoaminodiphenylcarbendrie i98g (l. 〇mole) as a limb compound dissolved in 230g N-methyl-2-indole and 2060g γ- In a mixed solvent composed of vinegar vinegar, 'after reacting at 40 ° C for 3 hours, 1 340 g of γ-butyrolactone was added to obtain about 3 600 g of polyglycine (Α 2 2) containing 1 〇 wt%. Solution. The solution had a solution viscosity of 125 mPa.s. &lt;(B) Synthesis Example of Polyimine] Synthesis Example 3 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, u2g (0.50 mol) and 1,3, 3a,4,5,9b-hexahydro-8-methyl_5_(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-l,3- Diketone 157g (0.50 mole)' p-phenylenediamine as a monoamine compound 88g (0.8l mole), bisaminopropyltetramethyldioxane 25g (0.10 mole) and 3,5.diamine 4-(4trifluoromethoxyphenoxy)cyclohexyl benzoate (a compound represented by the above formula (d-1)) 33 g (〇.〇80 mol), and aniline as a monoamine) The solution containing poly-proline was obtained by reacting in 1 250 g of N-methyl-2-pyrrolidone at 6 Torr for 6 hours. A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution of -36-200932789 having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 50 m P a.s. To the obtained polyacrylic acid solution, 25 ug of N-methyl-2-indole ketone was added, and 397 g of pyridine and 410 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system) to obtain 17〇. 〇g contains a solution of 17% by weight of polyamidiamine (B-1) having a ruthenium iodide ratio of 94%. A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a concentration of polyφ quinone imine of 6.0% by weight, and the viscosity of the solution was determined to be 1 2.0 m P a. s 〇 &lt; Comparative Synthesis Example of Imine> Comparative Synthesis Example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 112 g (0.50 mol) and 1,3,3a,4,5 , 9b-hexahydro·8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-C]-furan-l,3-dione 157g ( 0.50 mol), p-phenylenediamine as a diamine compound 88 g (〇_81 mol), diaminopropyl-based tetramethyl oxalate 25 g (0.10 mol) and 3,5-diaminobenzene Formic acid 4_(4'-trifluoromethoxybenzylideneoxy)cyclohexyl ester 35g (〇〇8〇莫耳), and aniline as a monoamine 1.4g (0.015 mole) dissolved in 125〇gN In the -2-pyrrolidone, it was allowed to react at 60 ° C for 6 hours to obtain a solution containing a poly-enzyme. Take a small amount of this solution 'added: NU methyl-2_pyrrolidone, formulated into a solution of 10% by weight of female acid; the solution viscosity is Η mPa s 〇 to the obtained poly-proline solution An additional 25 〇〇g N_methyl_2_卩比略院-37-200932789 ketone' was further added with 397.2 g of pyridine and 410.1 g of acetic anhydride, and a dehydration ring-closure reaction was carried out for 4 hours at 〇 ° °c. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system) to obtain 1 80. 0 g of a solution containing 17% by weight of polyimine (B-2) having a ruthenium iodide ratio of 95%. A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 8.0% by weight, and the solution viscosity was determined to be 1 3.0 mPa·s ° 〇Comparative Synthesis Example 2 2,3,5-tricarboxycyclopentyl acetic acid dianhydride of carboxylic acid dianhydride 110 g (0.50 mol) and 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(four Hydrogen-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-l,3-dione 160g (0.50 mole)' p-phenylenediamine as diamine compound 96g (0.87 mol), 1,3-bis(3-aminopropyl)tetramethyldioxane 25g (〇.1〇莫耳) and 3,6-bis(4-aminobenzonitrile) Cetyl 13 g (0.020 mol), and 8.1 g (0.030 mol) of N-octadecylamine as a monoamine dissolved in 960 g of N-methyl-2-pyrrolidone © to make it at 60 ° C The reaction was carried out for 6 hours to obtain a solution containing polylysine. A small amount of this solution was added, and γ-butyrolactone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was measured to be 60 mPa·s. Then, '2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution', 400 g of pyridine and 41 g of acetic anhydride were further added, and dehydration ring-closure reaction was carried out for 4 hours at 11 (TC). The solvent in the system was replaced with a new γ-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction were removed to the outside of the system) to obtain •38-200932789 200 (^ containing 15% by weight) a solution of polyamidiamine (8-3) having a sulfhydrylation rate of 95%. A small amount of the solution is added, and N-methyl-2-pyrrolidone is added to prepare a solution having a polyamidene concentration of 6.0% by weight. The measured solution viscosity was 16.0 mP a·s ° Comparative Synthesis Example 3 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 224 8 (1.0 mol) as tetracarboxylic dianhydride, and as a diamine compound P-phenylenediamine 1〇68 (〇.99 mol) and 3,5-diaminobenzoic acid cholesteryl ester 7.8 g (0.015 mol) dissolved in 3100 g N-methyl-2-D ratio In the pyrrolidone, it was allowed to react at room temperature for 3 hours to obtain a polyaminic acid solution having a solution viscosity of 210 mPa's. Then, the obtained polyaminic acid solution was obtained. Add 3400g of N-methyl-2-pyrrolidone, add 400g of pyridine and 300g of acetic anhydride, and carry out dehydration ring-closure reaction at 110 ° C for 4 hours. After dehydration ring closure reaction, by using the solvent in the system with new γ-butane The ester was subjected to solvent replacement (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction were removed to the outside of the system) to obtain 2700 § 9% by weight of polyamidiamine (8-4) having a ruthenium iodide ratio of 90%. © solution. A small amount of this solution was added, and γ-butyrolactone was added to prepare a solution having a concentration of polyethylenimine of 3.1% by weight, and the viscosity of the solution was determined to be 15.0 mPai. Example 1 &lt;Preparation of Liquid Crystal Aligning Agent &gt; The solution containing poly-proline (A-1) prepared in the above Synthesis Example 1 and the solution containing polyethylenimine (B-1) obtained in the above Synthesis Example 3 were each polymerized The amount of conversion (A - 1): (B - 1) = 80:20 (weight ratio) was mixed, and r-butyrolactone (BL), N-methyl-2-pyrrolidone-39-200932789 was added thereto. (NMP) and butyl cellosolve (BC), further adding 2 parts by weight of N, N, N, N'-tetraglycidyl as an epoxy compound -4,4'-diaminodiphenylmethane, having a solvent composition of BL: NMP: BC = 71: 17: 12 (weight ratio), a solution having a solid content concentration of 6% by weight. The liquid crystal alignment agent (S-1) was prepared by filtration for the filter. Further, the average oxime imidization ratio of the polymer in the liquid crystal alignment agent (S-1) was 19%. The liquid crystal alignment agent (S-1) was evaluated as follows. φ <Evaluation of the coating property> The liquid crystal alignment agent (S-1) prepared above was applied to a glass substrate with a transparent electrode made of an ITO film by a liquid crystal alignment film printing machine (manufactured by Nippon Photo Printing Co., Ltd.). On the transparent electrode surface, heat on a hot plate at 80 ° C for 1 minute (pre-baking) to remove the solvent, and then heat on a hot plate at 200 ° C for 1 minute (post-baking), on the transparent electrode of the substrate. A coating film having an average film thickness of 600 A was formed on the surface. The coating film formed here was observed with a microscope having a magnification of 20 times, and unevenness in printing and pores were observed without Φ, and the coating property was good. &lt;Production of Liquid Crystal Cell&gt; A coating film of a liquid crystal alignment agent (S-1) was formed on the transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film in the same manner as described above. The coating film was subjected to a sanding treatment at a roller rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a pile extrusion length of 0.4 mm by a sander equipped with a roller for winding a rayon cloth. The substrate was then ultrasonically washed in ultrapure water for 1 minute, and dried in a clean oven at 100 ° C for 10 minutes. A liquid crystal alignment film was formed on the transparent electrode surface of the -40-200932789 glass substrate. This operation was repeated to produce a pair (two pieces) of a glass substrate having a liquid crystal alignment film on the surface of the transparent electrode. On the outer edge of the surface of each of the pair of substrates having the liquid crystal alignment film, an epoxy resin binder to which an alumina ball having a diameter of 5.5 μm is applied is applied, and the liquid crystal alignment film faces are opposed to each other and the two substrates are opposed to each other. The polishing direction of the liquid crystal alignment film is parallel, and the pressure is combined and pressed to cure the adhesive. Then, the liquid crystal injection port was filled with a nematic liquid crystal (MLC-6221, manufactured by MERCK Corporation) through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to form a liquid crystal cell. &lt;Evaluation of voltage holding ratio&gt; A voltage of 5 V was applied to the liquid crystal cell produced above at 60 ° C for a time span of 167 msec, the voltage application time was 60 μsec, and then the voltage was released to 167 msec. After the voltage holding ratio, the measured enthalpy exceeded 99%, and the voltage holding ratio was good. In addition, the measuring device was model VHR-1 manufactured by TOYO Corporation. © &lt;Evaluation of display quality&gt; When the voltage of 5 V was ON'OFF (applied or released), the alignment of the liquid crystal cell was observed by a polarizing microscope, and the alignment defect was not observed. The defect is displayed and the display quality is good. In addition, here, "display defect" means reverse tilt and reverse twist. &lt;Evaluation of pre-tilt angle dependence on processing conditions&gt; (1) Production of liquid crystal cell The above-prepared liquid crystal alignment agent (S-1) was applied by spin coating to -41 - 200932789 with transparent ITO film The transparent electrode surface of the glass substrate (thickness: 1 mm) of the electrode was heated on a hot plate adjusted to the temperature shown in Table 1 for 1 minute (prebaking) to remove the solvent, and then heated on a hot plate at 210 ° C. After 10 minutes (post-baking), two substrates each having a coating film having an average film thickness shown in Table 1 on the transparent electrode surface were separately produced under each condition. Table 1 Prebaking temperature (°C) Average film thickness (A) Coating film formation conditions 1 50 600 Coating film formation conditions 2 80 600 Coating film formation conditions 3 100 600 Coating film formation conditions 4 80 400 Coating film formation conditions 5 80 900 The substrate on the transparent conductive film was subjected to polishing treatment, ultrasonic cleaning, and drying in the same manner as in the above <Production of Liquid Crystal Cell>. The two substrates having the same prebaking temperature and the same average film thickness were used as a pair, and the adhesion of the epoxy resin to which the alumina balls having a diameter of 18 μm were applied was coated on the outer edges of the faces having the liquid crystal alignment films. After the agent, the liquid crystal alignment film faces are opposed to each other, and the polishing directions of the liquid crystal alignment films of the two substrates are reversed in parallel, and the pressure is combined and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC - 5 0 8 1 manufactured by MERCK Co., Ltd.) was charged between a pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to form a coating film. Five groups of liquid crystal cells having different conditions were formed. (2) Measurement of the pretilt angle According to Non-Patent Document 1 (TJ Scheffer et al., J. Appl. Phys., -42 - 200932789, Vol. 19 '2013 (1980)) 'by the crystal rotation method using He-Ne clock, The pretilt angle was measured for the liquid crystal cell produced above. The results of the measurements are shown in Table 3. At this time, among the pretilt angles respectively obtained under the respective conditions shown in Table 1, the difference (maximum difference) between the highest pretilt angle and the lowest pretilt angle was 0.6. In the following, it can be considered that the pretilt angle is favorable in terms of processing conditions. Example 2 and Comparative Examples 1 to 6 As a solution containing a polymer, a solution containing the polymer shown in Table 2 was used in an amount of 换算 as shown by Ο in Table 2 in terms of the weight of the polymer contained therein. In the same manner as in Example 1, except that the solvent composition and the solvent composition were as shown in Table 2, liquid crystal alignment agents (S-2) and (R-1) to (R-6) were separately prepared and carried out. Evaluation. The evaluation results are shown in Table 3.

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Claims (1)

200932789 VII. Patent application scope: 1. A liquid crystal alignment agent comprising: (A) reacting a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutane tetracarboxylic dianhydride with a diamine The polylysine obtained, and (B) a polyazide obtained by dehydration of a polyglycine prepared by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (d) amine, A Rii ❹ (6) (In the formula (d), R1 is an alkyl group having a carbon number of 丨~丨2, a silane atom or a halogenated alkyl group having a carbon number of 1 to 12, and X is a formula (χ) — υ ~ (X — 4) Any of the divalent groups represented by 〇(Χ-1) 〇· II C- ο o=c NI I ο OHMO \1/ 2 3 (Χ-(Χ- ο — ΝΗ—C—(Χ_4) η is an integer of Ο~4,) relative to the amount of the proline structure of the (Α) polypergic acid and the indole pentaamine ring structure of the (β) polyanilin The amount of the proline structure is -47-200932789, and the ratio of the amount of the quinone imine ring structure of the (b) polyimine is 10 to 50%. 2. The liquid crystal of the first item of the patent application An alignment agent, wherein the tetracarboxylic dianhydride used to prepare the (B) polyimine is composed of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,3,3a, 4,5,9b a group consisting of hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione At least one anhydride selected from the group. 3. The liquid crystal alignment agent of claim 1 or 2, which further contains 0 relative to 1 〇〇 The total amount of (A) poly-proline and (B) polyimine, 0.1 to 30 parts by weight (C) of a compound having at least one epoxy group in the molecule. 4. A liquid crystal alignment film, such as application A liquid crystal alignment agent according to any one of the first to third aspects of the invention, wherein the liquid crystal display element is characterized by having a liquid crystal alignment film according to item 4 of the patent application. 〇-48- 200932789 IV. Designated representative Figure: (1) The representative representative of the case is: No. (2) A brief description of the symbol of the representative figure: 〇/ i ® 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Μ 〇❹