TW201003253A - Liquid crystal aligning agent, liquid crystal display element, polyamic acid, polyimide and compound - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent capable of forming a liquid crystal alignment layer with good heat-resistance, and having good printability but without occurrence of bubbles during coating, and the formed coating has sufficient thickness uniformity. The above liquid crystal aligning agent comprising at least one polymer selected from the group consist of a polyamic acid and a polyimide formed by dehydration and ring closure the polyamic acid, wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine which comprising a specific compound represented by the following formula (A). (in formula (A), RI and RII each independently are C1 to 30 alkyl group.)

Description

• 201003253 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent, a liquid crystal display element, a polylysine, a polyimine, and a compound. More specifically, the present invention relates to a liquid crystal alignment agent which is excellent in printability and which can form a liquid crystal alignment film having excellent heat resistance, and a liquid crystal display element which can perform high-quality display, can suppress display deterioration due to thermal stress, and can be driven for a long period of time. . [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 device is provided with two substrates facing each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a cell having a sandwich structure, and a long axis of the liquid crystal molecules is directed from one substrate to the substrate. The other substrate is continuously twisted by 90 degrees. In addition, an STN (Super Twisted Nematic) type liquid crystal display element capable of achieving higher contrast than a TN type liquid crystal display element, an IPS (in-plane switching) type liquid crystal display element having a small viewing angle dependency, and an IPS type change have been developed. An FFS (Fringe Field Stomach-Change) type liquid crystal display element, a VA (Vertical Alignment) type liquid crystal display element, and an OCB excellent in high-speed response of a video picture with improved aperture ratio of the display element portion to improve brightness Optical compensation type liquid crystal display element, etc. As a liquid crystal alignment film in these liquid crystal display elements, a material of gs % polyphthalic acid, polyimine, polyamine, polyester, etc., 201003253 liquid crystal made of polyamic acid or polyimine The alignment film is excellent in heat resistance, mechanical strength, affinity with liquid crystal, etc., and is used in many liquid crystal display elements (see, for example, Patent Documents 1 to 3). In the liquid crystal alignment agent, in order to improve the film thickness uniformity of the formed coating film, particularly the uniformity between the film thickness at the center portion of the substrate and the film thickness at the edge, an attempt has been made to add a decane coupling agent (Reference) Patent Document 4). However, the liquid crystal alignment agent to which the decane coupling agent is added improves the film thickness uniformity of the formed coating film, but bubbles are likely to be generated during the application of the liquid crystal alignment agent, and such bubbles become pinholes of the liquid crystal alignment film. There is a problem that the liquid crystal alignment property and the like are damaged. A liquid crystal alignment film which is excellent in heat resistance and which does not generate bubbles at the time of coating, is excellent in printability, and a uniform film thickness uniformity of the formed coating film is not known. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2003- 1978-A (Patent Document 3) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In view of the above, it is an object of the present invention to provide a liquid crystal alignment film which is excellent in heat resistance and which is capable of forming a film of a coating film which is excellent in printability without causing a bubble of 201003253 during coating. A liquid crystal alignment agent having a sufficiently good thickness uniformity. Another object of the present invention is to provide a liquid crystal display element which can perform high-quality display and which does not deteriorate in display performance even when driven for a long period of time. A further object of the present invention is to provide a polymer for preparing a liquid crystal alignment agent having the above advantages and a compound as a raw material thereof. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above object of the present invention, first, is achieved by a liquid crystal alignment agent comprising a group consisting of polylysine and polyamidene obtained by dehydrating and ring-closing the polyamic acid. At least one polymer obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A),

(In the formula (A), R1 and each independently are an alkyl group having 1 to 30 carbon atoms). The above object of the present invention is, in the second, achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. The above object of the present invention, and a third, a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A) or a dehydration ring closure of the 201003253 polyglycine Polyimine is achieved. The above object of the present invention, fourth, is achieved by the compound represented by the above formula (A). The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film which does not deteriorate even when a long-term thermal stress is applied. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be applied to various liquid crystal display elements such as TN type, STN type, IPS type, FFS type, VA type, OCB type, ferroelectricity, and antiferroelectricity. The liquid crystal display element of the present invention having such a liquid crystal alignment film can perform high-quality display, and the display performance is not deteriorated even when driven for a long period of time. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, for example, for watches, portable game machines, word processors, notebook computers, car navigation systems, video cameras, portable information terminals, digital cameras, Display devices such as mobile phones, various monitors, and LCD TVs. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention comprises at least one polymer selected from the group consisting of polylysine and polyamidene obtained by dehydrating and ring-closing the polyamic acid, the polyamic acid being composed of tetracarboxylic acid The anhydride is obtained by reacting a diamine containing the compound represented by the above formula (A). [Tetracarboxylic dianhydride] As the 201003253 tetracarboxylic dianhydride for synthesizing the polyglycine contained in the liquid crystal alignment agent of the present invention, for example, butane tetracarboxylic dianhydride, 1, 2, 3, 4 may be mentioned. - cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4 - cyclobutane tetracarboxylic 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, 3,3 ',4,4'-Dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2 ,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3·furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91?-hexahydro-5-methyl-5-(tetrahydro-2,5-di Oxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-six Hydrogen-7- Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5 , 9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l ,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-indole]-furan- 1,3-diketone, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, 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 acid 201003253 Anhydride I3,5,6. Tricarboxy-2-residue norbornene-2:3,5:6-dianhydride, 4,9·dioxa Tricyclic [5.3.1 · 〇μ] deca-alkane _3 5 8 ^ ^ ^ U ketone, compound of the following formula (Τ-Ι) and (T-π) Aliphatic or alicyclic tetracarboxylic dianhydride;

(Τ-Ι) (Τ-ΙΙ) (wherein R1 and R3 each represent a divalent organic group having an aromatic ring, R and R represent a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may be the same, Also different); tetrabasic dianhydride, 3,3',4,4,-benzophenonetetracarboxylic dianhydride, 3,3',4,4,-diphenylphosphonium tetracarboxylic dianhydride '丨,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene tetradecanoic acid anhydride, 3,3,4,4'-diphenyl ether tetradecanoic acid diterpene , 3,3,,4,4,-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3, 4-furantetramethylene dianhydride, 4,4'-bis(3,4-dimercaptophenoxy)diphenyl sulfide dianhydride 4,4'-bis(3,4-dicarboxyphenoxy Diphenyltriamine, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'·perfluoroisopropylidene Phthalic acid dianhydride, 3,3,,4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) Phenylphosphine oxide. 201003253 dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, between Phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4 diphenyl ether dianhydride, bis(triphenylphthalic acid)-4, 4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-bis (dehydrated trimellitate) Acid ester), 1,6-hexanediol-bis(hydrogen trimellitate), 1,8-octanediol-bis(hydroper trimellitate), 2,2-bis(4-hydroxybenzene) An aromatic tetracarboxylic dianhydride such as a compound represented by each of the following formulas (T-1) to (T-4); a propane-bis(hydrogen trimellitate). They may be used singly or in combination of two or more. -10- 201003253

?Ha /CH3

The tetracarboxylic acid-11-201003253 acid dianhydride for synthesizing the poly-proline contained in the liquid crystal alignment agent of the present invention preferably contains a butane four selected from the above, from the viewpoint of exhibiting good liquid crystal alignment. Carboxylic dianhydride, 12,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 , 4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,33,4,5,91?-hexahydro-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-8- 5-(4-hydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,33,4,5 , 91?-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3 - Diketone, 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-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02 '6] undecane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4 , 4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid bis[anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the above formula The compound represented by the following formula (T-5) to (T-7) and the compound represented by the above formula (T-II) in the compound represented by the formula (T-II) are represented by the following formula (T-8). At least one of the group consisting of compounds (hereinafter referred to as "specific tetracarboxylic dianhydride") of tetracarboxylic dianhydride. -12- 201003253

As the specific tetracarboxylic dianhydride, it is particularly preferably selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3& ,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1 ,3,3&,4,5,913-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1 , 3-dione, 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-carboxynorbornane- 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the above At least one of the groups consisting of the compounds represented by the formula (T-5). The tetracarboxylic-13-201003253 acid dianhydride used for synthesizing the polyamic acid contained in the liquid crystal alignment agent of the present invention preferably contains 50 mol% or more, and particularly preferably 80%, based on the total tetracarboxylic dianhydride. Mole% or more of the specific tetracarboxylic dianhydride as described above. [Diamine] The diamine used for the synthesis of the poly-proline contained in the liquid crystal alignment agent of the present invention contains the compound represented by the above formula (A). The alkyl group having 1 to 30 carbon atoms as R1 in the above formula (A) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 11 to 30 carbon atoms. The group is more preferably a linear alkyl group having 1 to 10 carbon atoms or a branched chain having 11 to 30 carbon atoms. Specific examples of the linear alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group and a fluorenyl group. The branched alkyl group having 11 to 30 carbon atoms may, for example, be 1-methyldodecyl, 1-methyltetradecyl or 1-methylhexadecyl. Specific examples of the compound represented by the above formula (A) include, for example, N,N-dihexyl-1,2,4-benzenetriamine, N,N-dioctyl-1,2,4-benzenetriamine , ί N,N-bis(1-methyldodecyl)-1,2,4-benzenetriamine, 1 bis(1-methyltetradecyl)-1,2,4-benzenetriene Amines, etc. As the diamine for synthesizing the polyamic acid contained in the liquid crystal alignment agent of the present invention, the compound represented by the above formula (A) may be used alone, or the compound represented by the above formula (A) may be used in combination with other diamines. . As other diamines which can be used in the present invention, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane can be mentioned. 4,4'-Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl-14- 201003253 飒, 3,3'-dimethyl-4,4'-diamine linkage Benzene, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)- 1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4 , 4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2.2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]milled, 1,4-double ( 4-aminophenoxy)benzene, 1,3-bis(4-amino group Oxy)benzene, 1.3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9 -Dimethyl-2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 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, 4,4'-(p-phenylene diisopropylidene)diphenylamine '4,4'-(m-phenylene di Isopropyl)diphenylamine, 2,2'-bis[4-(4-amino k -2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino- An aromatic diamine such as 2,2'-bis(trifluoromethyl)biphenyl or 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoglycol Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro•4,7-methylene dimethylene diamine, tricyclic [6.2.1.02'7] eleven alkylene dimethyl-15- 201003253 Aliphatic groups such as amide-amine, 4,4-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane Or alicyclic ring @1丨安; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diamine oxime ratio, 2.4-diaminopyran, 5,6-di Amino-2,3-dicyanopyrrole, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino 丨, 3,5_ Three tillage, U4-bis(3.amino)propyl) piperazine, 2,4.diamino-6-isopropoxy-1,3,5-triazine, 2.4-diamino-6- Methoxy-1,3,5-tripper, 2,4.diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s- Triterpenoid, 2,4-diamino-1,3,5-tri-trap, 4,6-diamino-2-vinyl-s-triad, 2,4-diaminophenylthiazole, 2 ,6-Diamino 嘌呤' 5,6-diamino-1,3-dimethyl urethane, 3,5-diamino-1,2,4·triazole, 6,9-di Amino-2-ethoxy acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperidine, 3,6-diaminoacridine, double (4_Aminophenyl)phenylamine, 3,6-diamine-based miso, Ν-methyl-3,6-diamine, Ν-ethyl-3,6-diamine Carbazole, Ν- phenyl-3,6-diamino-carbazole, Ν, Ν, the compounds bis (4-amino phenyl) benzidine, represented by the following formula (D-Ι),

(In the formula (D-Ι), R5 is a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triple well, yttrium, and pipe trap, and X1 is divalent. The organic group, R6 is a compound having a carbon number of 1 to 4, -16-201003253 al is an integer of 0 to 3, and a compound represented by the following formula (D-Π) has two amine groups in a molecule. And a diamine of a nitrogen atom other than the amine group of the grade

(In the formula (D-II), R7 is a divalent organic group 'X2 each is a nitrogen atom-containing ring having a group selected from the group consisting of rhodium steepness, methylene steepness, triterpene, piperazine, and hydrazine. The structure of the divalent organic group, the plurality of X2 may be the same, or different 'R8 each is a carbon number of 1 to 4 of the hospital base 'a2 each is an integer of 〇~3); the following formula (D- a monosubstituted phenylenediamine such as a compound represented by III),

(In the formula (D-III), R9 is a divalent organic group 'R1 selected from the group consisting of -〇-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-. a monovalent organic group having a skeleton or a group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or a carbon number of 6 ～30 alkyl, R11 is an alkyl group having 1 to 4 carbon atoms, 33 is an integer of -17 to 201003253 0 to 3; and a diamine-based organic oxygen such as a compound represented by the following formula (D-IV) hospital'

H2N s

2,| y12 R1——si-R1 i o \ 121-12 RIs——R

C 2 H2

IV) (DI (in the formula (D-IV), R12 each represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R12 groups may be the same or different, and each s is an integer of 1 to 3, and t is An integer of 1 to 20; a compound represented by the following formula (D-1) to (D-5), -18-201003253

CH h2n

H2n 13⁄4 h2i

(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. The benzene ring of the above aromatic diamine may be optionally substituted by one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms in the range of -19 to 201003253. R6, R8 and R11 in the above formulae (D-I), (D-Η) and (D-ΙΠ) are each preferably a methyl group, and each of al, a2 and a3 is preferably 0 or 1, more preferably ruthenium. Other diamines which can be used in the present invention are preferably selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenylmethane, 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-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-double (4-Aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane , 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-bis(4-aminobenzene) Oxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 1, 3-bis(aminomethyl)cyclohexane, a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2 , 4 · diaminopyrimidine, 3,6-diamino acridine, 3,6-diaminocarbazole, methyl-3,6-diaminocarbazole, N-ethyl-3,6- Diamine Carbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)benzidine, the following formula (D) in the compound represented by the above formula (DI) -6) a compound represented by the following formula (D-7) in the compound represented by the above formula (D-II),

-20- 201003253 (D.7) Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene in the compound represented by the above formula (D-III) , cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy Base-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (D-8)~ (D-16) in the group consisting of the compound and the compound represented by the above formula (D-IV) in the group consisting of 1,3-bis(3-aminopropyl)-tetramethyldioxane At least one (hereinafter referred to as "other specific diamine").

H2n

-21 - 201003253

f K

Oco—cf3

(D-14)

The diamine for synthesizing the poly-proline contained in the liquid crystal alignment agent of the present invention preferably contains 0.1 mol% or more, more preferably -22-201003253 0_1 30 30 mol%, based on the entire diamine. Preferably, it contains 〇20% by mole of the compound represented by the above formula (A). Further, the diamine used in the present invention preferably contains other specific diamines as described above in addition to the compound represented by the above formula (A). The use ratio of the other specific diamine at this time is preferably 30 mol% or more, more preferably 50 mol% or more, and particularly preferably 80 mol% or more based on the entire diamine. [Synthesis of Poly-Proline) The poly-proline contained in the liquid crystal alignment agent of the present invention can be produced by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A). The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably from 1 to 2 equivalents of the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. Preferably, it is a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from -20 to 150 ° C, more preferably from 0 to 100 ° C, preferably from 0.1 to 24 hours, more preferably 0.1. ~12 hours. Here, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the produced polyamic acid, and examples thereof include N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, and the like. An aprotic polar solvent such as hydrazine, hydrazine-dimethylformamide, dimethyl sulfoxide, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-methylphenol, xylenol A phenolic solvent such as phenol or halogenated phenol. The amount of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. Further, when the organic -23-201003253 solvent is used in combination with the poor solvent described below, the amount (a) of the above organic solvent is understood to mean the total amount of the organic solvent and the poor solvent. In the organic solvent, a solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like may be used in combination with a polyglycine in a range in which the produced polyamine is not precipitated. . 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, diglyme, 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, g Alkane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. When an organic solvent is used in combination with a poor solvent, the use ratio of the poor solvent can be appropriately set within a range in which the produced polyamine does not precipitate. It is preferably 50% by weight or less based on the total amount of the solvent, more preferably 40% by weight or less, still more preferably 30% by weight or less. As described above, a reaction solution in which polylysine was dissolved was obtained. It is possible to carry out the preparation of the reaction solution directly to the liquid crystal alignment agent, and it is also possible to carry out the preparation of the supply liquid after separating the polyamic acid contained in the reaction solution from -24 to 201003253 or to perform the separation of the polymerization solution. Amino acid is formulated for liquid crystal alignment agent. The separation of the polyamic acid can be carried out by introducing a reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate by a pressure of the precipitate, or by subjecting the reaction solution to a distillation. Further, the poly[polyimine] liquid crystal alignment agent of the present invention can be purified by performing one or several times of re-dissolving the amine acid in an organic solvent, followed by a method using a poor solvent or a step of distilling off under reduced pressure with an evaporator. The polyimine which may be contained, the polyamino acid dehydration ring closure oxime described above is imidized to obtain the tetracarboxylic acid used in the synthesis of the above polyimine, and the synthesis of the polyglycolic acid described above. A tetracarboxylic acid dianhydride compound used in the process. The preferred type of tetracarboxylic dianhydride is the same as the preferred use of polylysine. As the polydiamine to be used in the synthesis of the liquid crystal alignment agent of the present invention, the same diamine as that used in the synthesis of the above polyamic acid can be mentioned. In other words, the diamine used in the synthesis of the liquid crystal alignment agent of the present invention contains the compound represented by the above formula (A), and the compound of the above formula (II) may be used as the compound of the above formula (A). A combination of amines. Preferably, the preferred ratio of use of other diamines and diamines is also in the case of poly-proline. The polyimine contained in the liquid crystal alignment agent of the present invention can be prepared by a crystal alignment agent and then supplied. The polycondensate is decompressed in a reducer: proline. It can be obtained by the phthalic anhydride, and it can be combined with the diamine of the quinone imine in the same ratio, and the type represented by the formula (A) can be the same. It is a raw material poly-25- 201003253. The proline acid structure of the proline acid has a complete dehydration ring closure of the complete yttrium imide. It can also be a partial valerate structure dehydration ring closure, a proline structure and a quinone ring structure coexist. Part of the quinone imide. The polyimine contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of 30% or more, more preferably 80% or more, and particularly preferably 85% or more. The above-mentioned ruthenium amination ratio means the total amount of the structure of the guanidine structure and the number of the quinone ring structure of the polyimine, and the ratio of the number of the quinone ring structure is expressed by a percentage. At this time, a part of the quinone imine ring may also be an isoindole ring. The hydrazine imidization rate can be determined by dissolving the polyimine in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine) and using tetramethyl decane as a reference material to determine 1H-NMR at room temperature. The measurement results were obtained by the following formula (I). Ruthenium amination rate (%) = (l-A'/A^ a )xl〇〇(I) (In formula (I), 'A1 is the peak area derived from the NH matrix near the chemical shift i〇ppin 'A2 is the peak area derived from other protons, and α is the relative (the number of protons of one sulfhydryl group in the polyimine precursor (polyproline), the number of other protons). The dehydration ring closure is preferably carried out by (1) heating the polyaminic acid or (ii) by dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 200 ° C', more preferably 60 to 170 ° C. When the reaction temperature is less than 50. (:, -26 - 201003253 The dehydration ring-closure reaction is not sufficient. If the reaction temperature exceeds 20 (TC, the molecular weight of the obtained polyimine will decrease. The reaction time is preferably from 1 to 0 to 2 hours, more preferably 1. 〇~1 2 hours. In addition, in the above method (ii), a method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamic acid solution As the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is determined according to the desired ruthenium imidation ratio, preferably 1 mol relative to the polyglycolic acid. The structure of the proline is 0.01 to 20 mol. Further, as the dehydration ring-closing catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited thereto. The amount of use is preferably 0.01 to 10 moles relative to the dehydrating agent used in 1 mole. The more the amount of the above dehydrating agent and the dehydration ring-closing catalyst, the higher the yield of hydrazine imidation. The organic solvent may, for example, be an organic solvent exemplified as a solvent used in the synthesis of polyglycolic acid. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. Preferably, it is 1.0 to 24 hours, more preferably 1.0 to 12 hours. The polyimine prepared in the above method (i) can be directly supplied to a liquid crystal alignment agent, or the obtained polyfluorene can be obtained. After the imine is refined The preparation of the liquid crystal alignment agent is supplied. Further, in the above method (ii), a reaction solution containing a polyimine is obtained, and the reaction solution may be directly supplied to a liquid crystal alignment agent, or may be dehydrated from the reaction solution. After the agent and the dehydration ring-closing catalyst are supplied to the liquid crystal alignment agent, the poly-imine can be separated and supplied to the liquid crystal alignment agent, or the poly-imine of the separation -27-201003253 can be purified and then supplied to the liquid crystal alignment. Preparation of the agent: The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and a method such as solvent replacement can be used. The separation and purification of the polyimine can be carried out as described above as a separation and purification method of polyglycine. The same operation is carried out. - Terminal-modified polymer - The poly-proline or polyimine which may be contained in the liquid crystal alignment agent of the present invention may also be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating performance and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be produced by adding a molecular weight modifier to a polymerization reaction system during the synthesis of poly-proline. The molecular weight modifier may, for example, be a monoanhydride, a monoamine compound or a monoisocyanate compound. As the above-mentioned monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber may be mentioned. Anhydride, etc. Examples of the above I monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine 'n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound ', for example, phenyl isocyanate or naphthyl isocyanate. The ratio of use of the molecular weight modifier to the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid is preferably 30 -28 to 201003253 parts by weight, more preferably 20 parts by weight. The following. -Solid viscosity - Polylysine or polyimine prepared as above, preferably having a solution concentration of 10% by weight, having a solution viscosity of 20 to 800 mPa.s, more preferably 30 to 500 mPa .s solution viscosity. The solution viscosity (mPa's) of the above polymer is a polymer solution having a concentration of 10% by weight in a good solvent (for example, T-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer.値 measured by an E-type rotary viscometer at 25 °C. <Other Additives> The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of polylysine as described above and polyimine which is imidized by hydrazine as an essential component, and if necessary, May contain other ingredients. Examples of such other components include other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compounds"), functional decane compounds, and the like. The above other polymers may be used for the purpose of improving solution properties and electrical properties. The other polymer is a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A), and a polyazide obtained by dehydrating the polyamic acid. The polymer other than the amine' is, for example, a polylysine obtained by reacting a tetracarboxylic dianhydride with a diamine which does not contain the compound represented by the above formula (A) (hereinafter referred to as "other polylysine"). Polyimine (hereinafter referred to as "other poly-29-201003253 quinone imine"), which is obtained by dehydration of the polylysine, a polyphthalamide, a polyester, a polyamide, a polyxanthine A cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like. Of these, it is preferred that it be poly-proline or other polyimine, more preferably other poly-proline. The ratio of the use ratio of the other polymer to the total amount of the polymer (refers to the polyamic acid obtained by reacting the above tetracarboxylic dianhydride with the diamine containing the compound represented by the above formula (A) and the polyproline The total amount of polyimine and other polymers obtained by dehydration ring closure. The same as below, 'preferably 50% by weight or less'; more preferably 11 to 40% by weight, further preferably 〇·1~ 30% by weight. Preferred examples of the epoxy group-based compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl acid. Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 - Tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) Methyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, anthracene, hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine - diglycidyl-aminomethylcyclohexanthes and the like. The mixing ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0 to 30 parts by weight, per 100 parts by weight of the total amount of the polymer. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, Ν-(2-aminoethyl-30- 201003253)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-methyldimethoxy Decane, 3-ureidopropyltrimethoxydecane, 1,3-trimethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxy N-ethoxycarbonyl-3-aminopropyltriethoxy Decane, N-triethoxypropyltriethylenetriamine, N-trimethoxydecylpropyltrile: amine, 10-trimethoxydecane-1,4,7-triazadecane, 10-three Ethyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diacetate, 9-triethoxydecyl-3,6-diazaindole Acetyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-yl group Ethoxy decane, N-bis(oxyvinyl)-3-aminopropyltrioxane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, etc. The mixing ratio of the compound capable of Silane with respect to the total amount of polymer parts, preferably 40 parts by weight or less. The liquid crystal alignment agent of the present invention is preferably at least one polymer selected from the group consisting of polyacrylamides as described above, and other additives which are optionally blended and contained in an organic solvent as the liquid crystal alignment of the present invention. Examples of organic solvents which can be used in the agent are, for example, N-methyl-2-pyrrolidone, butyrolactone, r-butyl N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxyl -pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methyl ester, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl Ether, ethylene glycol n-butyl ether (butyl propyl propyl 3- ureidopropyl decane, fluorenyl alkyl trioxy decyl azadecyl ester, N-benzyl triethoxy-3-amine Propyl methoxy hydrazine 100 weight valine acid and if necessary, agent, can be decylamine, 4-methyl-2-oxypropionic acid ether, ethylene two fiber agent), -31- 201003253 Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ether acetate Diethylene glycol monoethyl ether acetate, diisobutyl ketone, propionate, isoamyl isobutyrate, diisoamyl ether, and the like. They may be used singly or in combination of two or more. The solid content concentration in the liquid crystal alignment agent of the present invention (the total weight of the components other than the liquid crystal alignment solvent other than the solvent is appropriately selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10 parts by weight. That is, the liquid crystal alignment agent of the present invention is formed on the surface of the substrate as follows, preferably by heating to form 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 to obtain good results. Liquid crystal alignment film; on the other hand, when the solid content is more than 10% by weight, the thickness of the coating film is too thick to obtain a good liquid film, and the viscosity of the liquid crystal alignment agent is increased, resulting in coating properties. The preferred 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, the k-good solid content concentration is in the range of 1.5 to 4.5% by weight. The concentration of the solid content is in the range of 3 to 9 wt%, so that the viscosity of the solution falls within the range of 12 to 50 mPai. When the spray is used, the solid content is preferably 1~ The range of 5 wt% is such that the viscosity of the solution falls 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 0 ° C - (:, more preferably 20 ° C to 60 °) C. Monomethyl isoprene, or ratio in the agent) Amount % coated film, without super-crystal matching. Applied, special brush method, ink method, can, 2〇〇-32- 201003253 <LCD Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the alignment agent as described above. The liquid crystal display element of the present invention can be produced, for example, by a ruthenium step. For the step (1), the substrate used and the liquid crystal are preferably used. The coating method and the heating temperature after coating the liquid crystal alignment agent are different in the mode. Steps (2) and (3) are in various operation modes (1) First, by applying the liquid crystal of the present invention on the substrate. Coating a surface to form a coating film on the substrate. (1-1) When manufacturing a TN type, STN type or VA type liquid crystal, two substrates provided with a patterned transparent conductive film are used as an offset printing method or a spin coating method. Method or inkjet printing method, on the surface of its bright conductive film The liquid crystal alignment agent of the present invention is applied by heating each of the coated surfaces to form a coating film. Here, as a substrate, for example, glass such as float glass or soda lime glass; polybutylene terephthalate/polybutylene terephthalate, A transparent substrate made of plastic such as polyether oxime, polycarbonate or 3 hydrocarbons. As a film provided on one surface of the substrate, tin oxide (NESA film (Nippon Memorabilia) manufactured by SnO Co., Ltd.), and indium oxide-tin oxide (a transparent conductive film of an ITO pattern made of In2〇3-SnO〇) can be used. A method of forming a pattern by photolithography after forming a bright conductive film, or a method of using a photomask having a desired pattern when forming a film, etc. In order to further improve the surface of the substrate and to transparent the liquid crystal of the present invention when the agent is applied: (1) ) (3) The alignment agent is more commonly used than the required $. The alignment agent, when: the component is shown, 'a pair, preferably each formed through, then, pass, you can use ^ ethylene glycol ester, poly ( The alicyclic olefin transparent conductive PPG company film, etc., forms a pattern-free transparent conductive film in the liquid crystal alignment conductive film and the coating -33- 201003253 film can also form a coating film surface in the substrate surface The pretreatment of the functional decane compound, the functional ruthenium compound, and the like is performed in advance. The heating temperature after the application of the liquid crystal alignment agent is preferably 3 〇 to 3 Torr (rc, more preferably 40 to 250 ° C, heating). Time is preferably 1 60 minutes, more preferably 10 to 30 minutes. The thickness of the formed coating film is preferably 〇.〇〇, more preferably 0.005 to 0.5# m. (1-2) On the other hand, when manufacturing an IPS type liquid crystal display element In the case of a roll coating method, a spin coating method or an ink jet printing method, a conductive film forming surface of a substrate provided with a transparent conductive film forming a comb-tooth pattern, and a side of the opposite substrate not provided with a conductive film are preferably used. The liquid crystal alignment agent of the present invention is applied separately, and then the coated surfaces are heated to form a coating film. The substrate and the material of the transparent conductive film, the method of forming the transparent conductive film pattern, and the pretreatment of the substrate are used. The above (1-1) is the same. The heating temperature after the application of the liquid crystal alignment agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the heating time is preferably 1 to 60 minutes, more preferably 1〇. ~ 30 minutes. The preferred thickness of the formed coating film is the same as that of the above U-1). For any of the above (1-1) and (1-2), the liquid crystal alignment agent of the present invention is coated. The organic solvent is removed to form a coating film as an alignment film, and the liquid crystal alignment agent of the present invention contains a poly When the amine acid or the quinone imidized polymer having both the quinone ring structure and the proline structure is formed, it may be subjected to a dehydration ring-closure reaction by further heating after forming a coating film to form -34- 201003253. (2) When the liquid crystal display element produced by the method of the present invention is a VA type liquid crystal display element, the coating film formed as described above may be used as a liquid crystal alignment film as it is, or may be subjected to the following as needed. On the other hand, when a liquid crystal display element other than the VA type is manufactured, the coating film formed as described above is subjected to a rubbing treatment to form a liquid crystal alignment film. The sanding treatment can be carried out by rubbing the surface of the coating film formed as described above in a certain direction by a roll wrapped with a cloth made of a fiber such as nylon, rayon, cotton or flower. Thus, the coating film is imparted with alignment energy of liquid crystal molecules to form a liquid crystal alignment film. In the liquid crystal alignment film formed as described above, the liquid crystal is shown in, for example, the patent document 5 (Japanese Laid-Open Patent Publication No. Hei 6-222366) or the patent document 6 (JP-A No. 6-28 1 93 7). The portion of the alignment film is irradiated with ultraviolet rays to change the pretilt angle of the partial region of the liquid crystal alignment film, or the liquid crystal alignment film is shown in Patent Document 7 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei. After the photoresist film is partially formed on the surface, the photoresist film is removed in a direction different from the previous sanding process, and the liquid crystal alignment film has different liquid crystal alignment energy in each region, so that the obtained liquid crystal display device can be improved. Field of view performance. (3) Two substrates on which the liquid crystal alignment film was formed as described above were prefabricated, and liquid crystal cells were produced by arranging liquid crystal between the two substrates disposed opposite each other. Here, when the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other with the rubbing direction of each of the coating films being opposite to each other at a predetermined angle of -35 - 201003253, for example, vertically or anti-parallel. For the production of the liquid crystal cell, for example, the following two methods can be mentioned. The first method is a previously known method. First, by placing two substrates relatively through a gap (cell gap), the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together with a sealant to the cells surrounded by the substrate surface and the sealant. After filling the liquid crystal in the gap, the injection hole is closed, and the liquid crystal cell can be obtained. The second method is called the 'DF (One Drop Fill) method. Applying, for example, an ultraviolet curable sealant material to a predetermined portion of one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, and 'bonding another substrate to make the liquid crystal alignment film relatively The liquid crystal cell can be obtained by irradiating ultraviolet light to the entire surface of the substrate to cure the sealant. In the case of any of the methods, it is necessary to further reduce the flow alignment during liquid crystal injection by further heating the liquid crystal cell produced as above to a temperature at which the liquid crystal used is in an isotropic phase and then slowly cooling to room temperature. V" Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and an intermediate spacer can be used. The liquid crystal may, for example, be a nematic liquid crystal or a dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferred. When it is a v A type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable, and for example, a diamine-36-201003253-based benzene liquid crystal, a sorghum liquid crystal, a Schiff base liquid crystal, or the like can be used. An azo-based liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like. When it is a TN type liquid crystal cell or a S TN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, or a triplet can be used. a benzene liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be further added; chiral agents sold under the trade names of C-15 and CB-15 (manufactured by MERCK Co., Ltd.); It is used for a ferroelectric liquid crystal or the like such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate obtained by sandwiching a polarizing film called a "ruthenium film" obtained by stretching and dispersing polyvinyl alcohol and absorbing iodine, in a cellulose acetate protective film, or A polarizing plate made of the enamel film itself. [Examples] Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited to the examples. The solution viscosity of the following polymers was measured by a Ε-type viscometer at 25 °C. <Synthesis Example of Compound represented by Formula (A)> Synthesis Example 1 N,N-dioctylbenzenetriamine was synthesized according to the following Synthesis Scheme 1'. -37- 201003253

/(CH2)7CH3 HN( \(CH2)7CH3

/(CH2)7CH3 n( \(CH2)7CH3

/ (CH2)7CH3 N\ '(CH2)7CH3 Synthetic Route 1 Under a nitrogen atmosphere, in a 300 ml three-necked flask, 11.2 g (0.06 mol) 2,4-dinitrofluorobenzene, l. 〇g (〇.〇66 mol) fluorinated planer, 14.5 g (0.6 mol) of di-n-octylamine was mixed, 60 ml of dimethyl sulfoxide was added thereto, and the solution was stirred. The solution was heated and stirred at 110 ° C for 6 hours under nitrogen to carry out a reaction. After completion of the reaction, 200 ml of chloroform was added to the reaction mixture, and the monkeys were extracted 4 times with 100 ml of ion-exchanged water. The organic layer was dehydrated with magnesium sulfate and then removed by filtration. The filtrate was concentrated and the solvent was further removed to give 23.7 g of dinitro intermediate. Then, to a 300 ml three-necked flask under nitrogen atmosphere, -38-201003253 12.2 g (0.03 mol) was added, and 180 ml of ethanol was further added according to the dinitro intermediate synthesized above, 10.9 g of palladium carbon (Pd/C). Stir at 70 ° C for 1 hour. Then, 18.4 ml of hydrazine monohydrate was added dropwise, and the mixture was stirred at 80 ° C for 3 hours under nitrogen to cause a reaction. After the completion of the reaction, the catalyst was removed by passing the reaction, and the filtrate was concentrated to remove the solvent. The obtained viscous liquid was purified by column chromatography (chloroform/acetone = 10/1 (volume ratio)) to re-concentrate and remove the solvent to obtain 7.1 g of hydrazine, Ν·dioctyl-1,2,4- Triphenylamine. The 1H-NMR spectrum of this compound is shown in Fig. 1. <Synthesis Example of Other Polylysine> Synthesis Example 2 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic acid Dianhydride l〇9g (〇.50mol), 4,4'-diaminodiphenylmethane I98g (1.0 mol) as diamine dissolved in 230g N-methyl-2-pyrrolidone and 2060g r-butyl In a mixed solvent of a lactone composition, after reacting at 40 ° C for 3 hours, 'add 1 3 5 0 gr - butyrolactone to obtain a content!约 A solution of weight % polyaminic acid (A-1) of about 4000 g. The solution has a solution viscosity of 1 25 mPa·s. Synthesis Example 3 1,2,3,4-cyclobutanine tetraresic acid dianhydride as tetrabasic acid dianhydride 196 g (1.0 mol) as a diamine 2,2,·Dimethyl_4,4′·diaminobiphenyl 212g (l_0 mole) is dissolved in 370g Ν·methyl_2_lapropanolide and 33〇〇g γ·butyrolactone After reacting for 3 hours at 4 ° C in a mixed solvent, about 4000 g of a solution containing poly-proline (A-2) was obtained. The solution viscosity of this solution is -60-201003253 is 1 60 mPa·s. <Synthesis and Synthesis Example 4 of Polyiminide 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride 11.2 m.) and 1,3,3&, 4, 5,913_hexahydro_8-methyl-5(tetrachloro-2,5-dioxo-3-furanyl)-naphthalene n,2_c]-furan-u.dione i5.7g (〇.〇5〇莫Ear), pentylene diamine as a diamine, 9.0 g (0.084 mol), U bis(3aminopropyl)-tetramethyldioxane 2_5 g (0.010 mol) and the above synthetic method i N,N--octyl-i,2,4-phenylenediamine 1.7g (〇.〇〇5〇莫耳), and aniline oxime as a monoamine. 28g (0.0030 mol) dissolved in 96g N In the methyl-2-bromolactone, the reaction was carried out at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-indole ketone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 60 mPa·s. Then, 270 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 40 g of pyridine and 41 g of acetic anhydride were further added to carry out a dehydration ring-closure reaction at ii ° C for 4 hours. After the dehydration ring closure reaction, 'the solvent in the system was replaced with a new T-butyrolactone (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 15% by weight of hydrazine. A solution of polyamidolimine (B-1) having an imidization ratio of about 95% is about 250 g. Take a small amount of the obtained polyenzyme sublimb solution 'Add 7-butyrolactone' to form a solution with a concentration of 6.0% by weight of the brewing imine, and determine the viscosity of the solution to be 16 mPa·-40-201003253 <Preparation and evaluation of liquid crystal alignment agent > Example 1 (I) Preparation of Liquid Crystal Aligning Agent The polyglycolic acid (A-1)-containing solution prepared in the above Synthesis Example 2 and the polyethylenimine (B) obtained in the above Synthesis Example 4 were prepared. a solution of -1), which is mixed with poly-proline (A-1): polyimine (Bl) = 80:20 (weight ratio), to which r-butyrolactone (BL), N-A is added Base-2-pyrrolidone (NMP) and butyl cellosolve (BC), 10 parts by weight of N, N, N', N'-four as an epoxy compound in a total amount relative to 100 parts by weight of the polymer Glycidyl-4,4'-diaminodiphenylmethane was thoroughly stirred to prepare a solution of BL:NMP: BC = 71 : 17 : 1 2 (by weight) and a solid content concentration of 6.0% by weight. This solution was filtered through a filter having a pore size of l/m to prepare a liquid crystal alignment agent. (II) Evaluation of liquid crystal alignment agent (1) Evaluation of printability The liquid crystal alignment agent prepared above was applied to a transparent electrode made of an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Paper Co., Ltd.). Glass L. The transparent electrode surface of the substrate is heated on a hot plate of 8 (TC for 1 minute (prebaking) to remove the solvent, and then heated on a hot plate at 200 ° C for a minute (post-baking) to form an average film thickness. The coating film was 600 A. The coating film was observed under a microscope at a magnification of 20 times to investigate whether or not printing unevenness and pinholes were observed. At this time, uneven printing and pinholes were not observed, and the printability was good. (2) Coating film Evaluation of Film Thickness Uniformity The film thickness of the center portion of the substrate and the position near the center of the substrate from the outer edge of the substrate of 15 mm were measured by a probe type film thickness meter (manufactured by KLA Tencor - 41-201003253, Inc.). Film thickness: The film thickness uniformity of 20A or less was evaluated as "good", and the film thickness difference exceeded 20A, and the film thickness uniformity was evaluated as "poor", and the film uniformity was good at this time. (3) Fabrication of liquid crystal cells The liquid crystal alignment agent prepared above was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Japan Photo Printing Co., Ltd.) on a hot plate at 80 ° C. After heating for 1 minute (prebaking), the solvent was removed, and then heated on a 200 hot plate for 10 minutes (post-baking) to form a coating film having an average film thickness of 600 A. Using a sander equipped with a roller wound with a rayon cloth, The coating film was polished to produce liquid crystal alignment energy at a roller rotation speed of 500 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 〇.4 mm. Then, super-pure water was used. The ultrasonic wave was washed for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to prepare a pair of (two pieces) substrates having a liquid crystal alignment film. K. Then, On the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5/zm is applied, and the liquid crystal alignment film faces are relatively pressed and pressed together. Binder Then, a nematic liquid crystal (MLC-622 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 produce a liquid crystal cell. 4) Evaluation of heat resistance stability -42- 201003253 At the ambient temperature of 70 °C, the liquid crystal cell manufactured above: & hour superimposed 6.0 V alternating current (peak-peak) 30 Hz, 3.0 V moment 500 00 hours After that, the liquid crystal cell was visually observed, and it was found that the evaluation of the shoulder stability was "good", and it was found that the heat resistance was "bad" when the display was poor, and the heat resistance stability of the liquid crystal cell was good at this time. Example 2 In Example 1, except that the solution containing the proline (A-1) prepared in the above Synthesis Example 3 was used instead of the solution 1 containing the poly-proline (A-1); Example 1 was similarly prepared. The liquid crystal alignment agent was evaluated, and no uneven printing and pores were observed, the printability was good, and the film thickness uniformity and the heat resistance stability of the obtained liquid crystal cell were good [Simplified illustration] Fig. 1 The 1H-NMR spectrum of N,N-dioctyl-1,2,4 prepared in Synthesis Example 1. [Explanation of main component symbols] S plus 500 i-wave, : heat resistance: evaluation of properties: containing polyfluorene, and film coating, and coating film 〇-benzenetriamine -43-

Claims (1)

201003253 VII. Patent Application Range: 1. A liquid crystal alignment agent characterized by comprising at least one polymer selected from the group consisting of polylysine and polyamidene which is obtained by dehydrating and ring-closing the polyamic acid. The polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A). R11 In the formula (A), R1 and R11 are each independently an alkyl group having 1 to 30 carbon atoms. 2. The liquid crystal alignment agent of claim 1, wherein the polymer is polyimine, and the sulfhydrylation ratio is 30% or more. 3. A liquid crystal display element is characterized by having an application A liquid crystal alignment film formed by the liquid crystal alignment agent of the first or second aspect of the patent. A poly-proline which is obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A). 5. A polyimine is formed by dehydration of a polycarboxylic acid obtained by reacting a tetracarboxylic dianhydride with a diamine having a compound represented by the above formula (a compound represented by the above-mentioned formula). Expressed by the above formula (A) - 44 -