TW200930747A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent, which can show good liquid crystal alignment and excellent voltage hold ratio and residue image characteristic in not only TN type and STN type, but also vertical alignment type liquid crystal display element. The aligning agent comprising at least one polymer selected from the group consist of a polyamic acid and an imide polymer thereof, the polyamic acid is prepared by the reaction of tetracarboxylic dianhydride and diamine, the tetracarboxylic dianhydride comprising 1, 2, 3, 4-cyclobutyltetracarboxylic dianhydride, the diamine comprising a compound represent by the following formula (1) and a specific compound represent by n-hexadecyl 3, 5-bis (4-aminobenzamido) benzoate.

Description

200930747 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film excellent in voltage holding ratio and afterimage performance, and a liquid crystal display element excellent in afterimage performance. [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 substrate surface of a transparent conductive film such as an ITO ® (indium oxide-tin oxide) film is provided. A liquid crystal alignment film is formed on the substrate, and two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a unit cell of a sandwich structure, and liquid crystal molecules are formed. The long axis is continuously twisted 90 degrees from one substrate to the other. Further, an STN (Super Twisted Nematic) type liquid crystal display element capable of achieving higher contrast than a TN type liquid crystal display element has been developed. The alignment of the liquid crystal molecules in the above TN type and STN type liquid crystal display elements is usually controlled by a liquid crystal alignment film which has been subjected to a rubbing treatment. (In contrast, an MVA (Multi-Domain Vertical Alignment) type liquid crystal display element in which protrusions are provided on a transparent conductive film and the liquid crystal molecules are aligned to improve viewing angle performance has been developed (see Patent Document 1 and Patent Document 1), an EVA (Reinforced Vertical Alignment) type liquid crystal display element in which liquid crystal molecules are aligned by a special electrode structure (see Non-Patent Document 2), and a vertical alignment type liquid crystal display element using a photo-alignment method (see Non-Patent Document 3) A vertical alignment type liquid crystal display element. These vertical alignment type liquid crystal display elements are excellent in viewing angle performance, contrast, and the like, and can be polished in the process of forming a liquid crystal alignment film, and are also excellent in a manufacturing process. However, compared with the TN type and STN type liquid crystal display elements described above, the performance is not very good, and in particular, it is required to improve the vertical alignment and the residual image performance of the liquid crystal display element. In order to solve the above problems, an attempt has been made. A combination of voltage retention and afterimage performance, which is synthesized from a diamine compound having an allyl group. The imine or its quinone imidized polymer is used for a liquid crystal alignment film to improve the voltage holding ratio and thereby improve the residual property (see Patent Document 2), but even with this technique, the afterimage performance improvement is still insufficient. In addition, it has also been attempted to use a polyphthalic acid synthesized from a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride as a liquid crystal alignment agent. In order to improve the voltage holding ratio, the residual charge, and the afterimage performance (see Patent Documents 3 to 6), there is a problem that a sufficient voltage holding ratio cannot be obtained by using these techniques. [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-258605 Patent Document 2] International Publication No. WO2005/052028 (Patent Document 3) Japanese Patent Application No. 2001-206 No. 68 (Patent Document 4) Japanese Patent Application Laid-Open No. Hei No. 2001-5119 (Patent Document 5) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Special Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〕 "Liquid Crystal", Vol. 3, No. 4, p272 (1999). [Non-Patent Document 3] "Jpn Appl. phys.", Vol. 36, p428 (1997) [Invention] The present invention is in view of the above The purpose of the present invention is to provide a TN type and an STN type which can be formed to exhibit good liquid crystal alignment, voltage retention and afterimage performance when applied to a vertical alignment type liquid crystal display element. A liquid crystal alignment agent excellent in liquid crystal alignment film, and a liquid crystal display element excellent in residual properties. 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 at least one polymer selected from the group consisting of polylysine and a ruthenium iodide polymer thereof. The amine acid is obtained by reacting a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride contains 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and the diamine contains the following formula (1). a compound represented by the following formula (2),

(In the formula (2), η is an integer of 16 to 18). The above object "second" of the present invention is achieved by a liquid crystal display element of the present invention, which has a liquid crystal alignment film formed of the above liquid crystal alignment agent. [Embodiment] <Polyproline> The polyphthalic acid contained in the liquid crystal alignment agent of the present invention can be obtained by subjecting a tetracarboxylic acid containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride The anhydride is synthesized by reacting a diamine containing the compound represented by the above formula (1) and the compound represented by the above formula (2). [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of the above polyamic acid contains at least 1,2,3,4-cyclobutanetetracarboxylic dianhydride. In the synthesis of the above polyamic acid, other tetracarboxylic dianhydrides other than 1,2,3,4-cyclobutanetetracarboxylic dianhydride may be used in combination. Examples of these other tetracarboxylic dianhydrides include butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, and 1,3-two. Methyl-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-cyclohexyl Alkane tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxyl Norbornane-2-acetic acid dianhydride '2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di Oxo-3-furanyl)-naphthalene [l,2-c]-furan-l,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-( Tetranitro-2,5-monooxy-3-indolyl)-cai[l,2-c]-indolyl-1,3-dione, 1,3,3&,4,5,91) - hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-cai [l,2-c]-furan-1,3-dioxene, l, 3,3a,4,5,9b-hexachloro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1 , 3-dione

(Τ-Ι) (ΜΙ) 200930747, 1,3,3&,4,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-di-generation)-naphthalene [l ,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexanitrotetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1 , 2-£:]-furan on 5 l,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo 3 naphthalene [l,2- c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexanitro-5-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-(:]-furan, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexancan anhydride, bicyclo[2.2_2]-oct-7- Alkene-2,3,5,6-tetracarboxylic dianhydride, 3 [3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,,5, 5-( 2,5-Dioxotetrahydro-3-furanyl-3-methyl-3-cyclohexanic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5: 6. An aliphatic or a fatty acid such as a compound represented by bis-oxotricyclo[5 .3 .1 ·02'6; decane-3,5,8,1 fluorene-tetraketone, lowering or (Τ-II) In the case of cyclic tetradecanoic acid (formulae (I) and (Τ-II), 1^ and R3 represent an aromatic ring group, R2 and R4 represent a hydrogen atom or an alkyl group, and each of R4 may be the same. and also Different) pyromellitic dianhydride, 3,3',4,4, benzophenone tetracarboxylic dianhydride, -3 -furanyl ί-methyl-5-( 3-diketone, -furanyl )-, 8-dimethyl-1,3-1,3-one, 2-dicarboxylic acid-oxabicyclo-dione), -1,2-dicarboxyl dry, 4,9-di L (T-I The dianhydride has a plurality of R2 and '3,3,,4,4'- 200930747 diphenyl-tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-di

Methyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4 '-Bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4' - bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4 , 4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether Anhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-di(anhydroelellitic acid ester) , 1,4-butanediol-bis(anhydrotrimellitic acid ester), 1,6-hexanediol-di(hydrogen trimellitate), 1,8-octanediol-bis (dehydrated benzene) Triester), 2,2-bis(4-hydroxyphenyl)propane-two (Dehydrated trimellitate), an aromatic tetracarboxylic dianhydride such as a compound represented by the following formula (T-1) to (T-4). They may be used alone or in combination of two or more. 200930747

Among them, butane tetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride are preferred from the viewpoint of enabling liquid crystal alignment which is excellent in performance. 1,2,3,4-cyclopentanetetracarboxylic 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, l,3,3a,4,5,9b - Hexahydro-8-methyl-5-(-10-200930747 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-furanyl)-naphthalene [l,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-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxa Tricyclic [5.3.1.02'6]-!-alkane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid Anhydride, 3, 3' 4,4'-diphenyltricarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the above formula Among the compounds represented by the formula (TI), the compound represented by the following formula (T-5) to (T-7) and the compound represented by the following formula (T-8) in the compound represented by the above formula (T-II) . Particularly preferred other tetracarboxylic dianhydrides are pyromellitic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

200930747 c

(T-8) The tetraphthalic acid dianhydride used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention preferably contains 40 mol% or more, 1, 2, 3 with respect to all the tetracarboxylic dianhydride. 4-cyclobutanetetracarboxylic dianhydride, more preferably 6 〇 mol% or more. Further, in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention, it is preferable to use a tetraphthalic acid dianhydride other than the 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Contains pyromellitic dianhydride or 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. In this case, the ratio of use of pyromellitic dianhydride is preferably 10% or less, more preferably 1 to 10% by mole, and still more preferably 3 to 8%, based on the total of the tetracarboxylic dianhydride. ear. /. . The ratio of use of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride is preferably 50 mol% or less, more preferably 15 to 45 mol% relative to all tetradecanoic acid dianhydrides. Further preferably 20 ~40 mol%. Further, pyromellitic dianhydride and ruthenium 2,3,5-di residue cyclopentyl acetic acid dianhydride may be used in combination in a preferred range. By using a tetracarboxylic dianhydride containing each tetracarboxylic dianhydride in the above ratio, a polymer having good solubility to the following solvent can be obtained, and 'the liquid crystal alignment film formed of the liquid crystal alignment agent containing the same is excellent in the alignment property. From this point of view, it is better. [Diamine] The diamine used in the synthesis of the polyamic acid contains the compound represented by the above formula (1) and the compound represented by the above formula (2). -12- 200930747 In the synthesis of the above polylysine, it is also possible to use other diamines other than them. Examples of these other diamines include an amine having a steroid skeleton and other diamines. The diamine having a steroid skeleton may, for example, be a compound represented by the following formula (D _ I).

H2n 〇X1-R5 NH2 (DI) (In the formula (D-I), X1 represents a divalent organic group selected from the group consisting of -〇-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO- a group, R5 represents a monovalent organic group having a steroid skeleton, a compound represented by the following formula (D-II), (D-Π)

(In the formula (D -11), the X 2 table is not selected from the group consisting of -〇_, · c 〇〇, _ 〇c 〇, _ n η 匚〇_ , -CONH-, and -CO-divalent organic groups, R6 represents a divalent organic group having a steroid skeleton). As a specific example thereof, the compound represented by the above formula (D-.) may, for example, be a compound represented by the following formula (D-1} to (D-6); 200930747 Ο

Ο

-14-200930747 (D - 7) - The compound represented by the formula (D-II), for example, may be, for example, a compound represented by the following formula (D-9).

Examples of the other diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl 4,4'-diaminodiphenyl sulfide. 4,4'-diaminodiphenyl milling, yl-4,4'-diaminobiphenyl, 4,4'-diaminobenzamide, phenyldiphenyl ether, 1,5-diaminonaphthalene, 2 , 2'-Dimethyl-4,4'-diamino 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethylaminobiphenyl, 3 , 3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1 -(yl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3, benzophenone, 3,4'-diaminobenzophenone, 4,4' -diaminodiphenylamine, m-phenylethane, 3,3,-dimethyl 4,4,-diamino, phenyl, -4,4,-di, 5-amino 4'-aminobenzene 3'-diaminoglycol, 2,2-double 200930747 [4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 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-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 Base-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, Ο 1,4,4'-(p-phenylene isopropylidene) Aniline, 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'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluoro An aromatic diamine such as biphenyl; 1,1-m-xylylenediamine, 1,3-dipropylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-Diaminoheptanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylene quinone dimethylene Diamine, three [6.2.1.02,7]undecene dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 1,4- An aliphatic or alicyclic diamine such as bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5 ,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5- Triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2.4-diamino-6-methoxy Base-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2 ,4-diamino-1,3,5- -16- 200930747 Triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2 ,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethyl Oxyloacyl lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenyl Amine, 3,6-diaminocarbazole , N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-di ( 4-aminophenyl)benzidine's compound represented by the following formula (D-III),

〇X3~R7 , -πη Η2Ν νη2 (In the formula (D-III), R7 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and pyridazine, X3 a compound represented by a divalent organic group), a compound represented by the following formula (D-IV),

(In the formula (D-IV), 'R8 represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and fox azine, and χ4 represents a divalent organic group, and exists. Each of the plurality of X4 may be the same or different) a diamine having two primary amino groups and a nitrogen atom other than the primary amino group; a compound represented by the following formula (D-V), -17-200930747 h2n

X5-r9 nh2 (DV) (In the formula (D_V), X5 represents a divalent organic group selected from 〇_, _C00_' _〇c〇, _nhc〇, -CONH-, and -CO-' R9 means that there is gas a monovalent organic group of an atom or an alkyl group having 6 to 30 carbon atoms; a compound represented by the following formula (D-VI),

H2N-( CH

(In the formula (D_VI), R1 represents a hydrocarbon group having 1 to 12 carbon atoms, and each of the plurality of R1Gs may be the same or different, p is an integer of 丨3, and q is an integer of 1 to 20); a compound represented by the following formula (D_1〇) or (D-u),

(an integer of 〜5 in the formula (D - 1 〇)). y is an integer of 2 to 12, and Z in the formula (D-11) may be used alone or in combination of two or more. -18-200930747 wherein a diamine or p-phenylenediamine having a steroid skeleton is preferred. , 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-dual [ 4-(4-Aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diiso) Propyl)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-cyclohexanediamine, 4 , 4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-di Aminoguanidine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)benzidine, the above The compound represented by the following formula (D-12) in the compound represented by the formula (D-III), and the compound represented by the following formula (D-13) in the compound represented by the above formula (D-IV), 〇

H2n -〇-nO c3h6 (D-13) Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene in the compound represented by the above formula (D-V) ,hexadecaneoxy-2,4-diaminobenzene, -19- 200930747 18-yard oxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane Oxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (D-14)~(D - a compound represented by the compound or 1,3 -bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D - VI).

Particularly preferred other diamines are diamines having a steroid skeleton in which a compound represented by the above formula (D-I) or (D-π) is preferred. Φ The diamine used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent is preferably contained in an amount of 40 mol% or more based on the total diamine. The compound represented by the above formula (1) preferably contains 50 to 80 mol%. Further preferably, it contains 55 to 75 mol%. The diamine used for the synthesis of the above polyamic acid preferably contains 20 mol% or more of the compound represented by the above formula (2) with respect to all the diamines, and more preferably 30 to 60 mol%, more preferably -20-200930747, further Good contains 35~55 m. /. . In the diamine used in the synthesis of the polyamic acid, the diamine having a steroid skeleton is preferably contained as the other diamine. In this case, the ratio of the diamine having a steroid skeleton is preferably relative to all. The diamine is 50% by mole or less, more preferably 10% to 30% by mole. By using a diamine containing various diamines in the above ratio, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having excellent voltage holding ratio and afterimage performance can be obtained, which is preferable. 〇 [Synthesis of poly-proline] The poly-proline which may be contained in the liquid crystal alignment agent of the present invention can be obtained by including tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride The compound represented by the above formula (1) is obtained by reacting a diamine of the compound represented by the above formula (2). The ratio of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.5 to 2 equivalents, more preferably the ratio of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine. The synthesis reaction of the poly-proline in a ratio of 0.7 to 1.2 equivalents is preferably carried out in an organic solvent, preferably at a temperature of -20 to 150 ° C, more preferably 0 to 100 ° C. Good for 1 to 48 hours, better for 2 to 1 2 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid, and examples thereof include 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N. - dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropionamine and other indoleamine-21 - 200930747 compounds, dimethyl sub-milling, r-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine and other aprotic compounds; Phenolic compounds such as phenol, xylenol, phenol, and halogenated phenol. The amount of the organic solvent (a) is usually preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0 to 1 to 30% by weight based on the total amount (a + b) of the reaction solution. . 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, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butylene. Glycol, triethylene glycol, ethylene glycol monomethyl ether 'ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, acetic acid Butyl ester, methyl methoxypropionate, ethyl ethoxypropionate, 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 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, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, Trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isova Ether, etc. When the organic solvent is used in combination with the poor solvent, the amount of the poor solvent to be used can be appropriately set within a range in which the produced polyaminic acid is not precipitated, and is preferably 30% by weight or less, and more preferably 20% based on the total amount of the solvent. Below weight%. -22- 200930747 The reaction solution in which polylysine was dissolved was obtained as described above. The reaction solution may be directly supplied to the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent, or the separated polyamic acid may be refined. The preparation of the liquid crystal alignment agent is supplied. The separation of the polyamic acid can be carried out by adding the above-mentioned reaction solution to a large amount of poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure or by subjecting the reaction solution to distillation under reduced pressure using an evaporator. Further, poly-proline can be purified by repeating the process of re-dissolving the polyamine in a solvent of a solvent and then precipitating it with a poor solvent or by vacuum distillation using an evaporator. <醯i-Iminylated Polymer> The ruthenium iodide polymer which may be contained in the liquid crystal alignment agent of the present invention can be obtained by hydrazine imidization by dehydration ring closure as described above. The tetracarboxylic dianhydride used in the synthesis of the above ruthenium iodide can be exemplified by the same compound as the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid. And as a ruthenium imidization contained in the liquid crystal alignment agent of the present invention

The diamine used in the synthesis of the Q polymer may, for example, be the same diamine as the diamine compound used in the synthesis of the above polyamic acid. The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention may be a complete ruthenium imide of a glycine structure containing all of the proline structure contained in the polyproline acid material, or may be a part of the proline structure dehydration. Closed-loop, a partial ruthenium imide of a proline structure with a quinone ring structure. The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium amination ratio of 60% or more, more preferably 70% or more, further preferably -23 - 200930747 80% or more. A liquid crystal alignment agent capable of forming a liquid crystal alignment film excellent in afterimage performance can be obtained by using a ruthenium iodide polymer having a ruthenium iodide ratio of 6 〇 or more. The above ruthenium iodide ratio means the total amount of the alanine structure and the quinone ring structure in the brewed imidized polymer, and the ratio of the number of the quinone ring structure is expressed as a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The ruthenium imidization rate can be determined by dissolving the ruthenium iodide polymer in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine) and tetramethyl decyl decane as a reference material at room temperature. - NMR, which was determined from the measurement results according to the following formula (i). Ruthenium amination rate (%) = (1 - aVa2x α )xl00 (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 protons. The peak area, α is the ratio of the number of other protons relative to the one ruthenium matrix in the ruthenium polymer precursor (polyglycolic acid). ^ Dehydration ring closure of poly-proline is preferably (1) by heating poly-proline, or (ii) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and as needed The reaction temperature in the method of heating the polyamic acid of the above (i) is carried out by heating, preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. The reaction time is preferably from 1 to 120 hours, more preferably from 2 to 4 hours. When the reaction temperature is less than 50 °C, the dehydration and ring closure reaction cannot be carried out sufficiently. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained ruthenium iodide polymer may be lowered. -24- 200930747 On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), as the dehydrating agent, for example, acetic anhydride, propionic anhydride, trifluoroacetic anhydride or the like can be used. Anhydride. The amount of the dehydrating agent is determined depending on the desired hydrazine imidation ratio, preferably 0.01 to 20 moles per mole of the methionine structure of the 1 mole of polyglycine. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably from 0.01 to 10 moles per mole of the dehydrating agent used. The more the amount of the above-mentioned dehydrating agent and dehydration ring-closing catalyst, the higher the yield of ruthenium. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used in the synthesis of polylysine. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably from 1 to 24 hours, more preferably from 2 to 8 hours. In the above method (ii), a reaction solution containing the ruthenium iodide polymer as described above is obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be supplied to the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and may also be separated from the sulfiminated polymer and then supplied to the liquid crystal alignment agent. Formulation 'or it is also possible to refine the separated quinone imidized polymer and then supply it to the liquid crystal alignment 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 employed. The separation and purification of the ruthenium iodide polymer can be carried out in the same manner as the above-described separation and purification method as polylysine, and the polymer contained in the liquid crystal alignment agent of the present invention Amino acid or hydrazine imidization polymerization-25 - 200930747 The material may also be a terminal modified polymer having a molecular weight adjustment. By using such a terminal-modified polymer, the coating characteristics and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be produced by adding a molecular weight modifier or the like to a polymerization reaction system during the synthesis of poly-proline. The molecular weight modifier may, for example, be a monobasic acid anhydride, a monoamine compound or a monoisocyanate compound. As the above monobasic acid anhydride, 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 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 may, for example, be 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 20 parts by weight or less, more preferably 10 parts by weight or less. . A solution viscosity - the polyaminic acid or quinone imidized polymer obtained as above, preferably having a solution viscosity of 20 to 800 mPa*s when formulated into a solution having a concentration of 10% by weight, more preferably 30 to 500 The solution viscosity of mPa.s. The solution viscosity (mPa·s) of the above polymer is a good solution of the polymer (for example, r-butyrolactone) to prepare a polymer solution having a concentration of 10% by weight -26 - 200930747, with type E Rotational viscometer measured at 25 ° C. <Other Additives> The liquid crystal alignment film of the present invention contains at least one polymer selected from the group consisting of polylysine as described above and a ruthenium iodide polymer thereof. The polymer contained in the liquid crystal alignment agent of the present invention is preferably a ruthenium iodide polymer. The liquid crystal alignment film of the present invention contains the polymer as described above as an essential component, and may further contain other components as needed. Examples of such other components include compound 0 (hereinafter referred to as "epoxy compound") having two or more epoxy groups in the molecule, and a functional decane compound. Examples of the epoxy group compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl Base-2,4-hexanediol, N,N,N',N'_tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) ring Hexane, N, N, N', N'-M tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethyl Oxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. The ratio of use of the above epoxy group compound is relative to 1 part by weight of the total amount of the polymer (refers to the total amount of the above polylysine and its ruthenium iodide polymer contained in the liquid crystal alignment agent). It is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight. As the above functional decane compound, for example, 3-aminopropane-27 - 200930747 〇

Trimethoxy decane, 3-aminopropyltriethoxy decane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, fluorenyl-(2-aminoethyl)-3- Aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethyl Oxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylene Triamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane-1,4,7-triazadecane, 10-triethoxydecyl-1,4, 7-Triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate , N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-benzene 3-aminopropyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3- Propyl triethoxy silane-yl and the like. The proportion of the functional decane compound to be used is preferably 2 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the total amount of the polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is preferably at least one selected from the group consisting of the above polylysine and its ruthenium iodide polymer, and other additives optionally mixed as needed. It is composed of an organic solvent. The above-mentioned organic solvent may, for example, be a solvent exemplified as a solvent used in the polyamido acid synthesis reaction. Further, it is also possible to appropriately select a poorly dissolved stomach which is exemplified in combination with the synthesis reaction of polylysine. -28 - 200930747 As a particularly preferable organic solvent used in the liquid crystal alignment agent of the present invention, for example, N-methyl-2·pyrrolidone, r-butyrolactone, r-butylide, N,N-dimethyl Carbamide, N, N_: methyl acetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionate Ester, 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 Ethyl 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 kinds. The solid content concentration of the liquid crystal alignment agent of the present invention (the total weight of components other than the solvent in the liquid crystal alignment agent is a ratio of the total weight of the liquid crystal alignment agent) It is suitably selected in terms of volatility, etc., and is preferably in the range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described below, preferably by heating 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. Therefore, a good liquid crystal alignment film cannot be obtained; on the other hand, when the solid content concentration exceeds 10% by weight, 'the coating film thickness is too thick to obtain a good liquid crystal alignment film' and the viscosity of the liquid crystal alignment agent increases. This leads to poor coating properties. The particularly preferable solid content concentration range ' differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, 'when the spin coating method is employed' is preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, the content of the solid -29-200930747 is in the range of 3 to 9 wt%, so that the solution can be in the range of 12 to 50 mP a.s. When the ink jet method is employed, the concentration is particularly preferably in the range of 1 to 5 % by weight, so that the solution can be in 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 - and more preferably 20 ° C to 60 ° C. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the above-described hair styling agent as described above. The liquid crystal display device of the present invention can be produced, for example, by the following steps (1 V). (1) First, a pair of transparent conductive films having a pattern is provided in a pair, and a surface on which each of the transparent conductive films is formed is passed through A liquid crystal alignment agent of the present invention is applied by a suitable coating such as a method, a spin coating method, an offset printing method, or an inkjet printing method, and then a coating film is formed by heating each. Here, as the substrate, an example can be used. Glass such as glass or soda lime glass; polyethylene terephthalate, butylene glycol dicarboxylate, polyether maple, polycarbonate, poly (aliphatic plastic transparent substrate). The transparent conductive material is obtained by using a NESA film made of tin oxide (Sn02) (an injection of PPG, USA), an ITO film made of indium tin oxide (ln203 - SnO 2 ), or the like, and a transparent conductive film can be obtained, for example, in formation. a method of forming a pattern by photolithography after patterning an electric film, or a method of using a mask having a desired pattern when transparently forming, etc.

The viscosity falls so that the viscosity of the solid falls to 20,000 ° C. The liquid crystal-(3) substrate is used as a coating method such as a roll coating method such as a float poly(p-phenylene to hydrocarbon) film, and can be labeled as a pattern transparent conductive film shape. -30- 200930747 When coating, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, it is also possible to apply a functional decane compound to the surface of the substrate surface on which the coating film is to be formed. The pretreatment of the functional titanium compound or the like, the heating temperature after application of the liquid crystal alignment agent is preferably from 30 to 300 t: more preferably from 40 to 250 ° C, and the heating time is preferably from 1 to 30 minutes, more preferably 5 to 20 minutes. The thickness of the formed coating film is preferably 〇·〇〇!~1μπι, more preferably 0.005 to 0.5μπχ 〇η (2) Then, a roller pair wound with a cloth made of fibers such as nylon, rayon, cotton or the like is used. 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 is generated on the coating film to form a liquid crystal alignment film. Further, the vertical alignment type liquid crystal display element is also not subjected to the rubbing treatment. In this case, the above coating film can be directly used as a liquid crystal alignment film. Further, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is disclosed in, for example, Patent Document 7 (JP-A-H06-222366) or Patent Document.

A process of irradiating a part of a liquid crystal alignment film with ultraviolet rays to change a pretilt angle of a partial region of a liquid crystal alignment film, or performing a patent document 9 (Japanese Patent Laid-Open No. Hei No. Hei No. Hei 6-281939) In the case where a protective film is formed on the surface of the liquid crystal alignment film portion, the process of removing the protective film after polishing in a direction different from the previous polishing process is shown in the '107544, 'the liquid crystal alignment film has different liquid crystals in each region. The alignment energy can improve the viewing angle characteristics of the resulting liquid crystal display element. (3) A pair of substrates forming the liquid crystal alignment film as described above are placed oppositely through the gap (cell -31 - 200930747 gap), so that the polishing direction of the liquid crystal alignment film of the two substrates is perpendicular or anti-parallel, and the peripheral portions of the two substrates are used. The sealant is bonded, and liquid crystal is injected into the cell gap which is divided by 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 attached to the outer surface of the liquid crystal cell so that the polarization direction thereof is uniform or perpendicular to the rubbing direction of the liquid crystal alignment film formed on each of the substrates, whereby a liquid crystal display element can be obtained. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a separator, or the like can be used. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal ©, and among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. An alkane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine, a liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, in these liquid crystals, cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate may be further added; and the trade names are "C-15" and "CB-15" (manufactured by MERCK Co., Ltd.). A chiral agent for sale; a ferroelectric liquid crystal such as decyloxybenzylidene-p-amino-2-methylbutyl cinnamate or the like. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate or a ruthenium film formed by sandwiching a polarizing film called a "ruthenium film" obtained by stretching a polyvinyl alcohol and absorbing iodine. A polarizing plate made by itself. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the examples. -32- 200930747 In addition, in the following synthesis examples, the ruthenium imidization rate in the ruthenium iodide polymer is dissolved in deuterated dimethyl by drying the ruthenium iodide polymer under reduced pressure at room temperature. In the hydrazide, 1H-NMR ' was measured at room temperature using tetramethyl decane as a reference material, and the measurement result was obtained according to the above formula (1). Synthesis Example 1 98 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride, and 2,4-diamino·anthracene as a diamine compound _ Diallyl aniline 61 g (0.3 mol) and 3,5-bis(4-aminobenzhydrylamino)benzoic acid n-hexadecyl ester 123 g (0.2 mol) dissolved in 1127 g N-methyl-2 In the pyrrolidone, the reaction was carried out at 60 ° C for 6 hours to obtain a polymer solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was measured to be 50 mPa·s. Then, 1 409 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at 11 °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (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 about 1 300 g of hydrazine. A polymer solution of an imidization polymer (A-1) having an imidization ratio of about 94%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 60 mPa·s. Synthesis Example 2 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g -33 - 200930747 (0.5 mol) as a tetracarboxylic dianhydride, and 2,4-diamino as a diamine compound -N,N-diallylaniline 61 g (0.3 mol) and 3,5-bis(4-aminobenzimidino)benzoic acid n-octadecyl ester 128 g (0.2 mol) dissolved in 1149 g N- The methyl-2-pyrrolidone was reacted at 60 ° C for 6 hours to obtain a polymer solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken, and N·methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 52 mPa·se.

Then, 1437 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added thereto, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring-closure reaction, the solvent in the system was replaced with a new γ-butane·' ester (in this operation, the guanidine and acetic anhydride used in the dehydration ring-closure reaction were removed to the outside of the system) to obtain about 131. 〇g contains a polymer solution of a ruthenium iodide polymer (Α-2) having a ruthenium iodide ratio of about 95%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 1% by weight, and the viscosity of the solution was determined to be 63 mPa·s. Synthesis Example 3 93 g (0.48 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 5 g of pyromellitic dianhydride (〇.〇3 mol), And 2,4-diamino->^,:^-diallylaniline 618 (0.3 mol) and 3,5-bis(4-aminobenzhydrylamino)benzoic acid as a diamine compound The hexaalkyl ester i23g (02 mole) was dissolved in 1129 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours to obtain a polymer solution containing poly-proline. A small amount of the obtained polyaminic acid solution was added to N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of -34 to 200930747 10% by weight. The solution viscosity was 55 inpa · S. Then, 1411 g of N-methyl-2-laredanone was added to the obtained polyamic acid solution, and 198 g of nJt steep and 204 g of acetic anhydride were further added thereto at 11 Torr. (: 4 hours of dehydration ring closure reaction. After the dehydration ring closure reaction, 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 Outside the system, about 1 320 g of a polymer solution containing a ruthenium iodide polymer (Α-3) having a ruthenium iodide ratio of about 94% is obtained. A small amount of the ruthenium iodide polymer solution is added to the γ_ The ester solution was formulated into a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 65 mPa·s. Synthesis Example 4' 1,2,3,4-cyclobutanine tetracarboxylic acid as tetracarboxylic dianhydride Acid dianhydride 93g (0,48 moles) and pyromellitic dianhydride 5g (0.03 moles), and 2,4-diamino-N,N-diallylaniline as a diamine compound 61g (0_3) Mole) and n-octadecyl 3,5-bis(4-aminobenzimidino)benzoate 128 g (〇.2 mol) dissolved in 1152 g of N-methyl-2-pyrrolidone at 60 The reaction was carried out for 6 hours at ° C to obtain a polymer solution containing poly-proline. A small amount of the obtained poly-branched acid solution was added, and N-methyl-2-pyrrolidinium was added to prepare a poly-proline concentration. 1 〇% by weight of the solution, the measured solution viscosity is 5 6 m P a · s. Then, M40g N-methyl-2-pyrrolidone is added to the obtained polyamic acid solution, and then 198g of pyridine and 204g of acetic anhydride are added. The dehydration ring-closure reaction was carried out for 4 hours at ll 〇 ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent (in this operation, the pyridinium used in the dehydration ring-closure reaction was The acetic anhydride was removed to the outside of the system to obtain a polymer solution of about 35-35 - 200930747 1310 g of a ruthenium iodide polymer (A-4) having a ruthenium iodide ratio of about 93%. The solution was added to a γ-butyrolactone solution to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 65 mPa·s. Synthesis Example 5 1,2,3 as tetracarboxylic dianhydride , 4-cyclobutane tetracarboxylic dianhydride 93 g (0.48 mol) and pyromellitic dianhydride 5 g (0.03 mol), and 2,4-diamino-N,N-diene as diamine compound Propylaniline 71g (0.35 mol), U 3,5-bis(4-aminobenzhydrylamino)benzoic acid n-hexadecyl ester 61g (0.1 mol) and above 26 g (0.05 mol) of the compound represented by the formula (D-3) was dissolved in 1029 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain a polymer solution containing polyglycine. The obtained polyaminic acid solution was added with N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 50 mPa·s. Then, the obtained polyamine was obtained. 1 2 86 g of N-methyl-2-pyrrolidone was added to the acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (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 about 1 300 g of hydrazine. A polymer solution of an imidization polymer (Α-5) having an imidization ratio of about 93%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the viscosity of the solution was measured to be 60 mPa·s. Synthesis Example 6 -36 - 200930747 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride 64 g (0.33 mol), 2,3,5-tricarboxycyclopentyl acetic acid Dihydride 34 § (0.15 mol) and pyromellitic dianhydride 5 g (0,03 mol), and 2,4-diamino-N,N-diallylaniline as a diamine compound 61 g (0.3 Mohr) and 3,5-bis(4-aminobenzimidino)benzoic acid n-hexadecyl ester 123g (0.2 mol) dissolved in 1146g N-methyl-2-pyrrolidone, reacted at 60 ° C After 6 hours, a polymer solution containing polylysine was obtained. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 1% by weight, and the solution viscosity was determined to be 5 5 m P a · s. Then, 1433 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added thereto, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent (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 about 1 300 g of the solvent. A polymer solution of a ruthenium iodide polymer (Α-6) having a ruthenium iodide ratio of about 93%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 65 mPa·s. Comparative Synthesis Example 1 98 g (0-5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride, and 2,4-diamino-N as a diamine compound, N-diallylaniline 61g (0.3 mol) and 4-[4-(4·trans n-heptylcyclohexyl)phenoxy]-1,3-diaminobenzene 76 g (0.2 mol) are soluble In 941 g of N-methyl-2-pyrrolidone, the reaction was carried out at 60 ° C for 6 hours to obtain a poly-proline-containing polymer-37-200930747 solution. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was measured to be 48 mPa-s. Then, 1 177 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 198 g of pyridine and 204 g of acetic anhydride were further added thereto, and the 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 γ-butyrolactone solvent (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 about 1300 g of the solvent. A polymer solution of a ruthenium iodide polymer (8-1) having a ruthenium iodide ratio of about 95%. A small amount of the ruthenium iodide polymer solution was added, and a γ-butyrolactone solution was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 55 mPa·s. Example 1 <Preparation of Liquid Crystal Aligning Agent> To a solution containing the ruthenium iodide polymer (A-1) prepared in the above Synthesis Example 1, 7-butyrolactone (BL), N-A was added. Base-2-pyrrolidone (NMP) and butyl cellosolve (BC) in a solvent composition of BL: Ν Μ P : BC = 7 1 : 1 7 : 1 2 (by weight), solid content concentration of 4% by weight The solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. <Evaluation of voltage retention rate>

The liquid crystal alignment agent prepared above was applied to a transparent electrode surface of a glass substrate having a transparent electrode made of a ruthenium film by a liquid crystal alignment film printing machine (manufactured by Nippon Photographic Printing Co., Ltd.), and heated at 80 ° C. The plate was heated for 1 minute and then heated on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 A -38 - 200930747. This operation was repeated to manufacture two (one pair) substrates having a coating film. When the coating film on these substrates was observed with a microscope having a magnification of 20 times, it was found that printing unevenness and pores were excellent in coating properties. On the outer edges of the pair of substrates having the coating film having the liquid crystal alignment film, an epoxy resin binder to which alumina balls having a diameter of 5.5 μm is applied is applied, and the liquid crystal alignment film faces are relatively overlapped. And press to cure the adhesive. Next, a negative liquid crystal (manufactured by MERK Corporation, MLC-2 0 3 8) is interposed between the pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photocurable adhesive mixture to prepare a voltage for evaluation. The retention rate of the liquid crystal cell 〇 at 6 TC ambient temperature, within 167 milliseconds, within the time span, a voltage of 5V was applied to the liquid crystal cell, the voltage application time was 60 microseconds, and then the voltage was released from the voltage to 1 67 milliseconds. The voltage holding ratio was measured. The measuring device was VHR-1 manufactured by TOTO Corporation, and the voltage holding ratio was 95°/. In the above case, the voltage holding ratio was rated as “acceptable.” ^ &lt;Evaluation of afterimage performance&gt; In addition to the substrate having the IT0 electrode shown in Fig. 1, the liquid crystal cell for evaluation of after-image performance was produced by the method described in the above <Evaluation of voltage holding ratio>. A DC voltage of 6.0 V was applied to the electrode A, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After the voltage was released, it was evaluated that the electrode A and the electrode A and B were applied with a gradient of 0.1 V at a voltage of 0.1 V. B brightness of the corresponding area If the difference in luminance is small, the afterimage performance is evaluated as "good", and when the luminance difference is large, the afterimage performance is evaluated as "poor". -39- 200930747 Examples 2 to 6 and Comparative Example 1 A solution of the polymer listed in 1 was prepared and evaluated in the same manner as in Example 1 except that the solution containing the ruthenium iodide polymer (A-1) was used. The evaluation results are shown in Table 1. Table 1 Liquid crystal alignment agent liquid crystal polymer type coating voltage retention rate afterimage performance Example 1 A-1 Good good example 2 A-2 Good good example 3 A-3 Good good example 4 A-4 Good and good example 5 A-5 Good good example 6 A- 6 Good good comparative example 1 B-1 Good and bad [Simplified description of the drawing] Fig. 1 shows the liquid crystal cell manufactured by the evaluation of afterimage performance Mode diagram. €) [Main component symbol description] -far No 0 -40-

Claims (1)

200930747 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 its ruthenium iodide polymer. The carboxylic acid dianhydride is obtained by reacting a dicarboxylic acid dianhydride containing 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and the diamine contains a compound represented by the following formula (1) and a compound represented by the following formula (2), Η2ν· ΟΗ2 CH—CH2 (1) ch2—ch=ch2 NH, In the formula (2), n is an integer of 16 to 18. 2. The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic acid dianhydride further contains pyromellitic dianhydride in an amount of from 1 to 10 mol% based on the total of the tetracarboxylic dianhydride. The liquid crystal alignment agent according to claim 1 or 2, wherein the diamine further contains a diamine having a steroid skeleton. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride further contains 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising a compound having two or more epoxy groups in the molecule. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 5, wherein the liquid crystal display element is formed. 〇 -42 -