TW200846790A - Liquid crystal aligning agent and liquid crystal display - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent containing a polyamic acid obtained by using an aliphatic tetracarboxylic acid dianhydride represented by the formula (1) below and p-phenylenediamine, and an imidized polymer of such a polyamic acid. (In the formula, R<1>-R<6> independently represent a hydrogen atom or an alkyl group having 1-20 carbon atoms; and m and n independently represent an integer of 0-3.) The liquid crystal aligning agent has good coating property and high initial voltage holding ratio, and enables to obtain a liquid crystal alignment film which is small in decrease of voltage holding ratio even when light or thermal stress is applied to a liquid crystal display or the liquid crystal display is operated for a long time.

Description

200846790 IX. Description of the Invention [Technical Field] The present invention relates to novel liquid crystal alignment agents and liquid crystal display elements. In more detail, the structure having a structure derived from a specific aliphatic tetracarboxylic dianhydride is excellent in coating property at the time of formation of a liquid crystal alignment film, exhibits high voltage holding ratio, and applies light or heat stress to the liquid crystal panel for a long period of time. When the liquid crystal panel is driven for a long period of time, a novel liquid crystal alignment agent capable of suppressing a decrease in voltage holding ratio, and a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film. [Prior Art] From the viewpoint of space saving, low power consumption, etc., the liquid crystal display element represented by the liquid crystal display has been used for the timepiece 'portable type game machine and word processor since the liquid crystal desktop type computer was first mass-produced. Notebook PCs, car navigation devices, camcorders, PDAs, digital cameras, portable phones, various monitors, LCD TVs, and other applications are progressing, and the active development department continues. As a liquid crystal display element, a nematic liquid crystal having positive dielectric anisotropy is used, and a TN (twisted nematic) liquid crystal display element in which a long axis of liquid crystal molecules is continuously twisted from one substrate to the other substrate by 90° is used. 'Or a STN (Super Twisted Nematic) type liquid crystal display element which is more contrasted than a TN type liquid crystal display element, and is widely used. In addition, in recent years, in order to further improve the display quality of liquid crystal displays, VA (vertical alignment) type liquid crystal display elements with low viewing angle dependence, and [ps (in-plane switching) type liquid crystal display elements, and small viewing angle dependence and image screens -6 - 200846790 An optical compensation bending (OCB) type liquid crystal display element excellent in high-speed responsiveness was developed. In the liquid crystal display device, the member for controlling the alignment of the liquid crystal is a liquid crystal alignment film. The liquid crystal alignment film is obtained by a roll coating method, a spin coating method, or an offset printing method by using a liquid crystal alignment agent containing a ruthenium imidized polymer obtained by imidating polyacrylic acid or the polyamic acid. An inkjet method or the like is applied to a substrate, followed by a method of heating and drying the coated surface. Here, the coating unevenness of the liquid crystal alignment film is directly related to the alignment failure of the liquid crystal, and is a major factor for significantly lowering the display quality of the liquid crystal panel. In the liquid crystal alignment agent used in the past, in order to improve the electrical properties such as the voltage holding ratio, it is considered to improve the sulfhydrylation rate of the polyimine, but the ruthenium imidization ratio and the liquid crystal alignment agent are used. The coating property has a trade-off relationship, and it is highly desirable to start a liquid crystal alignment agent having excellent electrical properties and coating properties. Heretofore, as a method for improving the voltage holding ratio, there has been reported an example of adding a polyfunctional epoxy compound to polylysine (Special Kaiping 1 0 - 1 6 8 4 5 5 ) by polyproline and quinone An example of attempting to improve the skeleton of a tetracarboxylic dianhydride or a diamine, which is a raw material of a polymer, (Japanese Patent No. 3 5 72690 and JP-A No. 200 1-22 848 1 ), and an acrylic polymer is added to the polyamic acid. Example (Charter No. 3206 1 69) and so on. However, the initial voltage holding ratio and reliability of these reports (even if light or thermal stress is applied to the liquid crystal panel, or the liquid crystal panel is driven for a long time, the voltage holding ratio does not change), the improvement effect cannot be said to be sufficient, and there is no At the same time, it is reviewed from the viewpoint of improving the coating property at the time of formation of the liquid crystal alignment film. In recent years, as liquid crystal panels are suitable for liquid crystal TVs or high-quality monitors, in order to achieve high-quality performance in liquid crystal alignment films, in addition to the local voltage retention rate, it is also eager to change the reliability of good voltage retention. Coating and twinning at the time of formation of a liquid crystal alignment film. SUMMARY OF THE INVENTION The present invention has been completed on the basis of the above circumstances, and therefore the object of the present invention is to give a good coating property, a high initial voltage holding ratio, and even to apply light or heat to a liquid crystal display element. Stress, or a liquid crystal display element that drives a liquid crystal display element for a long period of time, a liquid crystal alignment agent of a liquid crystal alignment film having a small voltage retention ratio, and a liquid crystal alignment film formed by the liquid crystal alignment agent, can display a liquid crystal display of a long-term image for a long time. element. Other objects and advantages of the invention will be apparent from the description. According to the present invention, the above objects and advantages of the present invention can be attained by a liquid crystal alignment agent containing one or more aliphatic tetracarboxylic dianhydrides represented by the following formula (1) and optionally other tetracarboxylic acids. a polyglycolic acid obtained by polyaddition reaction of an acid dianhydride with a phenylenediamine and, if necessary, other diamines, and a ruthenium imidized polymer obtained by subjecting the polyamic acid to ruthenium iodide At least one polymer selected.

(wherein R1 to R6 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms;

200846790 base, m and η each independently represent an integer of 〇~3). Further, according to the present invention, the above-described object of the present invention can be achieved by a display element comprising the above-mentioned liquid crystal alignment agent alignment film. Advantageous Effects of Invention According to the liquid crystal alignment agent of the present invention, it is possible to obtain a liquid crystal alignment which can impart applicability, high initial voltage holding ratio, and even if the liquid is applied with light or thermal stress or the liquid crystal panel is driven for a long period of time. A liquid crystal alignment agent for the film. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Polyuric acid and ruthenium iodide polymer] The poly-proline acid used in the present invention is obtained by reacting an aliphatic tetracarboxylic dianhydride represented by the formula (1) with an optionally dianhydride and a parabens. The diamine is taken up with other diamines as needed. The ruthenium iodide polymer used in the present invention is obtained by dehydration ring closure of an acid.

The tetracarboxylic dianhydride and the tetracarboxylic dianhydride represented by the above formula (1) are used for synthesizing a liquid crystal display element which is formed by a Fe crystal contained therein and which exhibits good pressure on a crystal display element. Reducing the retention rate of the above-mentioned other tetracarboxylic acid polyaddition reaction to the above-mentioned polyamine carboxylic acid dianhydride 1 as needed, other synthetic polyglycine-9 - 200846790 and / or ruthenium polymerization The material exhibits excellent coating properties, high initial voltage holding ratio, and high reliability of the liquid crystal display element. In the present invention, the polyamic acid synthesized by the tetracarboxylic dianhydride represented by the above formula (o) is used in the calcination procedure after the application of the liquid crystal alignment agent, and the tetracarboxylic dianhydride used in the past is used. Compared with the synthesized polyaminic acid, the thermal imidization is easy to carry out, and a liquid crystal alignment film having a high sulfonium imidization ratio can be obtained, so that a high initial voltage holding ratio can be given, and even for a liquid crystal display element a liquid crystal alignment film which is applied with light or thermal stress or which drives the liquid crystal panel for a long period of time and has a small decrease in voltage holding ratio. In the present invention, the ratio of use of the tetracarboxylic dianhydride represented by the above formula (1) is Based on the carboxylic acid dianhydride, it is preferably 5 to 100% by mole, more preferably 25 to 100% by mole, and particularly preferably 50 to 100% by mole. In the above formula (1), each of R1 to R6 The hydrogen atom or the alkyl group having 1 to 20 carbon atoms is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a methyl group. m and η are each independently 〇3. An integer, preferably 〇 or 1, particularly preferably m = n = 0, a structure represented by the following formula (2) or a formula of m = 1 and n = 0 3) the configuration shown.

-10 - 200846790

The tetracarboxylic dianhydride represented by the above formula (1) may be used alone or in combination of two or more. As the tetracarboxylic dianhydride different from the tetracarboxylic dianhydride represented by the above formula (1), if necessary, other tetracarboxylic acid monoanhydride used together with the tetracarboxylic dianhydride represented by the above formula (丨), for example, Examples thereof include butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid monoanhydride, and 1,2-dimethyl- 1,2,3,4-cyclobutane tetracarboxylic acid. Anhydride, 1,3 - monomethyl fluorene, 2,3,4 -cyclobutane tetracarboxylic dianhydride, 1,3 - monochloro-1,2,3,4-cyclobutane tetracarboxylic dianhydride, Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentane tetracarboxylic acid monohydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ,, 4,4, dicyclohexyltetracarboxylic acid monoanhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-carboxy-norbornane- 2 -acetic acid dianhydride, 2 ,3,4,5-tetrahydrofuran tetracarboxylic acid monoanhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo- 3 furanyl)-naphthyl Π,2-c]-furan-i,3-dione, 1,3,3&amp;,4,5,91)-hexahydro-5-methyl-5-(tetrahydro-255-dioxo-one 3 —furanyl)-naphthoquinone [l52_c] —ι,3 —dione, l,3,3a,4,5,9b—hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-1,3-furanyl)-naphtho Π,2-χ]-furan-1,3-dione, -11 - 200846790

1,3,3&amp;54,5,915-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan 1,3 -dione, l53,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1, 2-c]-furan-1,3-dione, 1,3,3&amp;,4,5,913-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo- 3-furan Base)-naphtho[1,2_c]-furan-1,3-dione, 1,3,3&amp;,4,5, external hexahydro-8-ethyl-5-(tetrahydro-2,5 -dioxo- 3 -mercapto)-naphtho[l,2-c]-furan-1,3-dione, l53,3a,4,5,9b-hexahydro-5,8-dimethyl Base one 5 (tetrahydro-2,5-dioxo-1,3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, 5- (2,5-dioxo) Tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2·2.2]-octyl-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione- 6-spiro- 3'-(tetrahydrofuran-2' 5'-dione), 3,5,6-tricarboxy- 2-carboxyl-bornane- 2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8 - an aliphatic or alicyclic tetracarboxylic dianhydride of a tetracarboxylic dianhydride or a compound represented by the following formulas (4) and (5);

-12- 200846790

(5) (wherein R15 and R17 each represent a divalent organic group having an aromatic ring, and R16 and R18 each represent a hydrogen atom or an alkyl group, and plural R16 and R18 may be the same or different). Pyromellitic dianhydride, 3,3',4,4' benzophenone tetracarboxylic dianhydride, 2,3,3',4' benzophenone tetracarboxylic dianhydride, 2,2 ',3,3'-dibenzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyl Diphenyldecane tetracarboxylic dianhydride '3,3',4,4' tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4' Bis(3,4 column dicarboxyphenoxy)diphenyl thio dianhydride, 4,4 5 -bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'-double (3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4' Monobiphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenylene-bis(triphenyl) Phthalic anhydride) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl Dihydride, bis(triphenylphthalic acid)-4,4' diphenylmethane dianhydride, ethylene glycol-bis(dehydrotrimellitic acid ester), propylene glycol-bis(dehydro trimellitic acid) Ester), 1,4-butanediol-double (dehydrotrimellitic acid ester), 1,6-hexanedi-13- 200846790 alcohol-double (dehydrotrimellitic acid ester), 1,8-octyl a diol-double (dehydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane-double (dehydrotrimellitic acid ester), and the following formulas (6) to (8) An aromatic tetracarboxylic dianhydride such as a compound represented by each.

〇(8) -14- 200846790 Among these, from the viewpoint of exhibiting good liquid crystal alignment, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid is preferred. Acid dianhydride, 1,3-dimethyl- 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5 —cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene a 1,2-dicarboxylic anhydride, i,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-1,3-furanyl)-naphtho[1,24 Furan-1,3-dione, 1,353 &amp;,4,5,913-hexahydro-8-methyl-5-(tetrachloro-2,5-dioxo-3-furanyl)-Caihe [1,2-〇] furan-1,3-dione, 1,3,3&amp;,4,5,9-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5 -dioxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione, bicyclo[2·2·2]-oct-7-ene-253,5,6 — Tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3 One (tetrahydrofuran-2,5,monodiketone), 3,5,6-tricarboxy-2-carboxyl-bornane- 2:3,5:6-dianhydride, bicyclo[3.3.0]octane- 2,4,6,8-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-dibenzophenone tetracarboxylic dianhydride, 2,3,3,,4, - benzophenone tetracarboxylic dianhydride, 2,2',3,3, benzophenone tetradecanoic acid dianhydride, 3,3',4,4'-biphenyl fluorene tetraphthalic acid dianhydride And 1,4,5,8-naphthalenetetracarboxylic dianhydride, and a compound represented by the following formula (9) to (11) among the compounds represented by the above formula (4), and the compound represented by the above formula (5) Among the compounds, a compound represented by the following formula (1 2 ) is used. Particularly preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, I,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, I, 2, 4, 5 monocyclohexane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, l,3,3a,4,5,9b-hexahydro-5_ (four-15-200846790 hydrogen-2 ,5-dioxo-3-(furyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl 5- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2_c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane 2,4-dione- 6-spiro- 3'-(tetrahydrofuran-2',5'-dione), 3,5,6-tricarboxy- 2-carboxy-norbornane-2:3,5·· 6 - dianhydride, bicyclo [3.3.0] octane - 2,4,6,8-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4' benzophenone IV A carboxylic acid dianhydride and a compound represented by the following formula (9). The other tetracarboxylic acid different from the tetracarboxylic dianhydride represented by the above formula (1) which is used as needed may be used alone or in combination of two or more kinds.

0 0

(11) -16- (12) (12)200846790

The liquid crystal alignment agent of the present invention exhibits a high initial voltage holding ratio by using a diamine-containing p-phenylenediamine as an essential component and, if necessary, other diamines. In the present invention, the proportion of the use of the phenylenediamine is preferably from 5 to 100 mol%, more preferably from 10 to 1 mol%, and particularly preferably from 2 5 to 1%. 〇〇 耳 %. The other diamines ' differ depending on the mode of the liquid crystal alignment agent of the present invention, and preferred compounds are different. When the liquid crystal alignment agent of the present invention is used in the TN mode, the STN mode, the OCB mode or the VA mode, as the diamine for the synthesis of the main component polymer, it is preferably used in addition to the p-phenylenediamine. 13) or a diamine having a pretilt expression portion represented by the following formula (14).

-17- •••(13) 200846790 is independently a hydrogen atom or a methyl group, R9 is a linear 2〇 alkyl group, and R1() and R11 are each independently (wherein R7 and R8 are each or branched). Carbon number 1 ~ two-valent organic base)

•••(14) (wherein a is 0 or 1, Rl2 is derived from the bond (·〇-), ore (&lt;〇-), carbonyloxy (-C00O, oxygen ore (_0C0·) a divalent bond group or an organic group selected from a guanamine bond (-NHCO-, -CONH-), a thioether bond (-S-), and a methylene group, and a R12-based divalent organic group different from Rl2, R14 a group selected from a group having a steroid skeleton, a fluorine atom-based group, and a linear or branched alkyl group having a carbon number of 1 to 30. These diamine systems having a pretilt expression portion The compound of the following formula (1 5 ) and (1 6 ) -18- 200846790

Specific examples of the diamine represented by the above formula (14) include compounds represented by the following formulas (17) to (21). -19- 200846790

H2n

Cf3 • · · (19) -20 - 200846790

•••(20)

C18h37 (2) When the liquid crystal alignment agent of the present invention is used in the TN method, the STN method, the NS method or the VA method, the TN method, the STN method or the OCB method, the above formula (1 3) is used. And at least one diamine having a pretilt expression portion selected by the diamine represented by each of (1), and stably exhibiting a pretilt angle of a liquid crystal of 1 to 30°. In this case, the amount of the diamine having the pretilt expression portion is preferably 0.5 to 30 mol%, more preferably 0.7 to 20 mol%, and particularly preferably 1 to 15 based on the entire diamine. Moer%. Further, as the diamine having a pretilt angle expression site, at least one of the diamines represented by the above formulas (15) to (21) is particularly preferable. When the VA method of the TN method, the STN method, the OCB method, or the VA method is used for the liquid crystal alignment agent of the present invention, it is preferable to use the above-described pretilt angle expression portion from the viewpoint of exhibiting excellent vertical alignment of the liquid crystal. The diamine represented by the above formula (14) in the amount of the diamine in the range of from 21 to 2008 is preferably used in an amount of from 8 to 60 mol%, more preferably from 9 to 50 mol%, based on the entire diamine. , especially good for 1〇~25mol%. Further, as the diamine having a pretilt expression portion, it is preferred to use a diamine each represented by the above formulas (17) to (21), and particularly preferably a one represented by the above formula (17) or (18). Diamine. On the other hand, when the liquid crystal alignment agent of the present invention is used in the IPS method or the FFS method, the diamine having the pretilt expression portion can be used, but it is preferable to use a diamine other than the diamine having the pretilt expression portion described later. The diamine is used as the other diamine to synthesize the main component polymer. The diamine which is used for the synthesis of the main component polymer of the liquid crystal alignment agent of the present invention, which is used for the phenyldiamine and the diamine having the pretilt expression portion, may, for example, be the following diamine. Examples of the exophenylene diamine, 4,4, diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide , 4,4'-diaminodiphenyl hydrazine, 2,2, dimethyl- 4,4'-diaminobiphenyl, 4,4'-diamino-N-benzimidanilide , 4,4, monodiaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3, monodimethyl-4,4, monodiaminobiphenyl, 5-amino-1 One (4, monoaminophenyl)-^,3-trimethylindan, 6-S virgin-1—(4-amine oxime), ι, 3,3 — 2 3,4'-diaminodiphenyl ether, 3,3,~diaminobenzophenone, 3,4, monodiaminobenzophenone, 4,4,monodiaminobenzophenone Ketone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4 Mono(4-monoaminophenoxy)phenyl]leafene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-, 4-bis(4~•22 - 200846790 amine Phenoxy group) Benzene 1,1 -bis(4-monoaminophenoxy)benzene bis ( 3-aminophenoxy)benzene, 9,9-bis(4-aminophenylmonohydroindole, 2,7-diaminopurine, 9,9-bis(4-aminophenyl 4,4) 'Methylene-mono-(2-chloroaniline), 2,2',5,5'-tetrachloro-diaminobiphenyl, 2,2'-dichloro- 4,4'-diamino a 5, methoxybiphenyl, 3,3'-dimethoxy- 4,4'-diamine-linked 1,4,4'-(p-phenylene isopropylidene) bisaniline, 4 , 4'-(i-isopropylidene)diphenylamine, 2,2'-double [4-(4-amino-2-methylphenoxy)phenyl]hexafluoropropane, 4,4'-diamine Base 2,2' trifluoromethyl)biphenyl, 4,4'-diamino- 2,2'-dimethyl, 4,4'-double [(4-amino- 2-trifluoro) Methyl)phenoxy]-phenyl, 1,3-bis(4-monoaminophenoxy)- 2,2-dimethyl-4,4'-bis(4-aminophenoxy)biphenyl Aromatic diamine 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-dipyridine, 2,4-diaminopyridine, 5,6-diamino-2 ,3-dicyano 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamine —6 —amino group — 1,3,5 —three tillage, 1,4 bis(3-aminopropyl) 2,4-amino- 6-isopropoxy-, 1,3,5 — two B, 2, 4 - 6 - methoxy-1,3,5-diindole, 2,4-diamino-6- 1,3,5-three tillage, 2,4-diamino a 6-methyl-s--three-U and: amino- 1,3,5-diindole, 4,6-monoamino-2-vinyl-s, 2,4-diamino--5 - phenylthiazole, 2,6-diaminostilbene diamine-1,3-dimethyl uracil, 3,5-diamino-1,2,4,6,9-diamino- 2 - ethoxylated acridine lactate, 3,8-di-segment, 1,3-)-10) fluorene, fluorene- 4,4,5, di-diphenyl, meta-extension benzene-difluoro-double (linked Phenyl octafluoropropane, aminopyrrolidone, monodimethylpiperazine, diaminobenzene, 1-4, bis-trinyl, 5 5 6 - three-seat g-based 6 -23- 200846790 Phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, and the following formulas (22) and (23) Each of the compounds represented has two grades 1 in the molecule a diamine of an amine group and a nitrogen atom other than the amine group of the first stage;

R19

(wherein R19 represents a monovalent organic group having a ring structure of a nitrogen atom selected from pyridine, pyrimidine, trityl, piperidine and piperazine, and X represents a divalent organic group).

(wherein R2^ represents a divalent organic group having a ring structure of a nitrogen atom selected from pyridine, pyrimidine, di D, piperidine and piperazine η) 1,3 —bis(aminomethyl) Cyclohexene, iota, 3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene one makeup, octamethylenediamine, nine yam Diamine, 4,4 diaminoheptamethyldiamine, 1,4 diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienyl diamine, hexahydro A 4,7~methylene-extension-based benzylidene-bi-24. 200846790 Amine, tricyclo[6.2.1.02,7]-e-denyl dimethyldiamine, 4,4, a An aliphatic or alicyclic diamine such as bis(cyclohexylamine); a diamine organooxane represented by the following formula (24);

(wherein R21 each represents a hydrocarbon group having 1 to 12 carbon atoms, and R21 each may be the same or different, and ρ is an integer of 1 to 3, and q is an integer of 1 to 20). These diamines and the other diamines other than the diamine having the pretilt angle expression site may be used alone or in combination of two or more kinds thereof, preferably 4,4'-diaminobiphenyl. Methane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 9, 9 bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-double (4 Monoaminophenoxy)biphenyl, 4,4'-diamino- 2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diamino- 2,2' Dimethylbiphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, the above formula (22) Among the compounds shown by the following formula (26), the compound represented by the following formula (25) and the compound represented by the above formula (23) are represented by the following formula (26). , 1,3-bis(aminomethyl)cyclohexane, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), a compound represented by the above formula (24) 3,3'-(tetramethyldioxan-1,3-diyl)bis(propylamine) represented by the following formula (27).

(2 5) η2ν^\^^νη Η2Ν

2

2 • · · (2 6)

CH3

CH 3 H2N-^CH2^~Si—0—SI-~ CH3 ch3 nh2 • (2 7) As a more excellent one, 4,4′-diaminodiphenylmethane, 2,2′ Dimethyl- 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,7-diaminopurine, 3,3'-(tetramethyldioxanium Alkyl-1,3-diyl)bis(propylamine), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(aminomethyl) ring Hexane, 2,2-bis(4-monophenyl)hexafluoropropane and 4,4'-diamino- 2,2'-di(trifluoromethyl-26-200846790)biphenyl. &lt;Synthesis of Polylysine&gt; The ratio of the use of the tetracarboxylic dianhydride to the diamine for the synthesis reaction of the polyaminic acid of the present invention, and the tetracarboxylic acid for the 1 equivalent of the amine group contained in the diamine The acid anhydride group of the acid dianhydride is preferably in a ratio of 0.2 to 2 equivalents, more preferably in a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is carried out in an organic solvent, preferably at -20 to 150 ° C, more preferably at a temperature of 0 to 1 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamide. An aprotic polar solvent such as N,N-dimethylformamide, dimethylhydrazine, tau-butyrolactone, tetramethylurea or hexamethylphosphonium; m-cresol, xylenol, phenol A phenol solvent such as a halogenated phenol. In addition, when the total amount (a) of the tetracarboxylic dianhydride and the diamine is (b), the total amount (a + b ) of the reaction solution is preferably 0.1 to 30. The amount by weight. In the above organic solvent, a weak solvent of polylysine, that is, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like can be used in a range in which the produced polyamine does not precipitate. Specific examples of the weak solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butylene glycol, triethylene glycol, diacetone alcohol, and ethylene glycol. Monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propyl Acid ester, ethyl-27- 200846790 ethoxy propionate, propyl carbonate, diethyl oxalate, diethyl propionate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether , ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro-butane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane 'Benzene, toluene, Xylene and the like. These weak solvents may be used singly or in combination of two or more. As described above, a reaction solution obtained by dissolving polyamic acid was obtained. Then, by injecting the reaction solution into a large amount of a weak solvent to obtain a precipitate, the precipitate was dried under reduced pressure to obtain a polyamic acid. Further, the polyaminic acid can be purified by re-dissolving the polyaminic acid in an organic solvent, followed by one or several times of precipitation in a weak solvent. &lt;醯i-Iminylated Polymer&gt; The quinone imidized polymer used in the liquid crystal alignment agent of the present invention can be synthesized by subjecting the above polyamic acid to dehydration ring closure. The ruthenium iodide polymer described herein includes a partial quinone imine polymer which is partially ruthenized by the above polyamic acid, and a 1% hydrazine imidized polymer, which will be collectively described below. It is "醯iminated polymer". The ruthenium iodide polymer used in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of 10 to 100%, more preferably 2 to 99%, and particularly preferably -28- 200846790 40~98%. Here, the "yttrium imidization ratio" means the ratio of the number of quinone imine rings in the polymer to the total number of valinate structures and the number of quinone rings in the polymer. At this time, a part of the quinone ring may also be an isoindole ring. As a method of synthesizing a ruthenium iodide polymer, (I) a method of synthesizing the polypyridic acid by heating to close the dehydration ring, (II) dissolving the above polylysine in an organic solvent, A dehydrating agent and a dehydration ring-closing catalyst are added to the solution, and if necessary, heating is carried out to synthesize the dehydration ring, and the above reaction conditions are appropriately controlled to obtain a polymer having a desired ruthenium iodide ratio. In the above method (I) for heating poly-proline, the reaction temperature is preferably from 50 to 300 ° C, more preferably from 100 to 250 ° C. When the reaction temperature is lower than 50 °C, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 300 ° C, the molecular weight of the obtained ruthenium-imided polymer decreases. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of the polyamic acid in the above (II), as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trichloroacetic anhydride can be used. . The amount of the dehydrating agent used is preferably from 0.01 to 20 moles per 1 unit of repeating unit of poly-proline. Further, as the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, the 'dehydrating agent and dehydration ring-closing catalyst system are not limited by these examples. Dehydration The amount of the closed-loop catalyst used is preferably 0 _ 0 1 to 1 0 mol for the dehydrating agent used in 1 mol. Further, as the organic solvent used for the reaction of the dehydration ring closure, the same organic solvent as those exemplified for the synthesis of the polyglycine is -29-200846790. Further, the reaction temperature of the dehydration ring-closure reaction is preferably 〇 18 (TC, more preferably 60 to 150 ° C. Further, by subjecting the reaction solution thus obtained to the same method as the purification of poly-proline Operation, the ruthenium-imiding polymer can be refined &lt;end-modified polymer&gt; The poly-proline or quinone imidized polymer constituting the liquid crystal alignment agent of the present invention can also be modified with molecular weight. By using this terminal-modified polymer, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention, etc. Such a terminal modification type can be used by synthesizing polyglycine. The acid anhydride, the monoamine compound, the monoisocyanate compound, and the like are added to the reaction system to synthesize the compound. Here, examples of the acid monoanhydride include a dicarboxylic acid monoanhydride, and for example, maleic anhydride and phthalic anhydride are mentioned. Ikonic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecane anhydride, etc. Further, as the monoamine compound, for example, aniline and cyclohexane may be mentioned. Amine, p-ethylaniline, positive Amine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine Further, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-dodecylamine, etc. Further, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. Logarithmic viscosity&gt; The logarithmic viscosity of the polyamic acid and the ruthenium iodide polymer obtained above is preferably from 0.05 to 10 dl/g, more preferably from 0.05 to 5 dl/g, more preferably from 0.05 to 10 dl/g. g 〇 The logarithmic viscosity (η1η ) in the present invention is determined by using N-methyl-2-pyrrolidone as a solvent, and for a solution having a concentration of 0.5 g/100 ml, a viscosity of 30 ° C is measured. It is obtained by the following formula (a).

In (solution flow time / solvent flow time) 77" = ---- · · · (a) (weight concentration of polymer)

&lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention is composed of a polyphthalic acid and a ruthenium iodide polymer dissolved in an organic solvent. The liquid crystal alignment agent of the present invention may contain a structure containing the aliphatic tetracarboxylic dianhydride represented by the above formula (1) of the present invention in order to improve the baking resistance and the coating film property at the time of formation of the liquid crystal alignment film. Polyuric acid or quinone imidized polymer other than polyamine or quinone imidized polymer. The other polyamine or ruthenium iodide polymer may be one or more kinds depending on the purpose, and it is particularly preferable to add one or more kinds of 1,2,3,4-cyclobutanetetracarboxylic acid. Anhydride, I,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5 - 3 Carboxycyclopentyl acetic acid dianhydride, 1,3,3&amp;,4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c Furan-1,3-dione, 1,3,3&amp;,4,5,9匕hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo- 3-furanyl ) a naphtho[l,2-c]furan-1,3-dione, 3-oxabicyclo[3·2·1]octane-2,4-dione- 6-spiro- 3'-( Tetrahydrofur-31 - 200846790 —- 2 ',5 '-dione), 3,5,6-dimercapto- 2 -carboxy-original borneol- 2:3,5:6-dianhydride, bicyclo[3.3 .0] one or more acid dianhydrides selected from octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride, and phenylenediamine, 4,4' Diaminodiphenylmethane, 4,4'-diaminodiphenylthio , 1,5-diaminonaphthalene, 2,7-diaminoguanidine, 4,4'-diaminodiphenyl ether, 9,9-bis(4-aminophenyl)anthracene, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-mono(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis( 4-monoaminophenyl)hexafluoropropane, 4,4'-diamino- 2,2'-bis(trifluoromethyl)biphenyl, 4,4,monodiamine- 2,2' Polydecylamine obtained by reacting one or more diamines selected from dimethylbiphenyl and 3,3-(tetramethyldioxane-1,3-diyl)bis(propylamine) acid. The amount of the polyglycolic acid or the ruthenium iodide polymer which does not contain the unit derived from the aliphatic tetracarboxylic dianhydride represented by the above formula (1), and the content of The total amount of the polymer of the unit of the aliphatic tetracarboxylic dianhydride represented by the formula (1) is preferably 10 to 900 parts by weight, more preferably 25 to 500 parts by weight, particularly preferably 100 to 100%. 400 parts by weight. In the liquid crystal alignment agent of the present invention, in order to increase the initial voltage holding ratio, and to apply light or thermal stress to the liquid crystal display element, or to drive the liquid crystal display element for a long period of time, in order to reduce the amount of change in the voltage holding ratio (giving high reliability) ) 'A compound having an epoxy group may also be added. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether-32- 200846790, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3 ,5,6-tetraglycidyl- 2,4-hexanediol, N,N,N,,N,-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-bi-shrink Glycerylaminomethyl)cyclohexane, N,N,N,,N,-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-four Glycidyl-4,4'-diaminobenzene, N,N,N',N'-tetraglycidyl- 4,4,monodiaminodiphenyl ether, N,N,N',N A tetraglycidyl-2,2,monodimethyl- 4,4'-diaminobiphenyl group or the like is preferred. Among these epoxy group-containing compounds, in view of excellent reactivity with the polyglycolic acid and the quinone imidized polymer of the present invention, it is particularly preferable to use a diamine skeleton as a mother nucleus in the molecule. A compound having an epoxy group containing a nitrogen atom. Further, the amount of the compound having an epoxy group is preferably from 〇 to 60 parts by weight, more preferably 1 part by weight, based on the total amount of the polyamic acid and the ruthenium iodide polymer of the present invention. It is 5 to 50 parts by weight. Further, in the liquid crystal alignment agent of the present invention, a functional decane compound may be contained from the viewpoint of improving adhesion to the surface of the substrate. Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropylamine. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilene, N-B Oxyl-yl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriamine, N-33-200846790 Trimethoxydecylpropyltriazine Amine, ίο-trimethoxydecyl-1,4,7-triazadecane, 1〇3-triethoxydecyl-1,4-4,7-triazadecane, 9-trimethoxy矽alkyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, N-benzyl-3-aminopropyldimethoxy Base sand N, N-nodal group 3- 3-aminopropyl diethoxy decane, N-phenyl 3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, N-bis(ethylene oxide 3-amine Propyltrimethoxydecane, N-bis(ethylene oxide)-3-aminopropyltriethoxydecane, etc. The amount of such functional decane compounds added, for a total of 1 〇〇 by weight of the invention The polyamic acid and the ruthenium iodide polymer are preferably from 0 to 60 parts by weight, more preferably from 50 to 50 parts by weight.

The organic solvent constituting the liquid crystal alignment agent of the present invention is the same as the solvent exemplified for the synthesis reaction of polyglycine. In particular, from the viewpoint of printability, a solvent having a boiling point of 1 60 ° C or higher is preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethyl. Aa, γ-butyrolactone, tetramethylurea, hexamethylphosphonium, m-formic acid, xylene, benzoic acid, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, three Ethylene glycol, diacetone alcohol, butyl lactate, butyl acetate, ethyl ethoxy propionate, propyl carbonate, diethyl oxalate, diethyl propionate, ethylene glycol monobutyl ether (butyl solution) Fiber), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate , diethylene glycol monoethyl ether acetate, I, 4 dichlorobutane, o-dichlorobenzene and the like. Among these, N-34-200846790 monomethyl-2-pyrrolidone, r-butyrolactone, diacetone alcohol, ethylene glycol monobutyl ether (butyl cellosolve), and carbonic acid extension are preferred. Propyl ester, diethylene glycol diethyl ether. A particularly preferable solvent composition is a combination of the above solvents, and it is preferred that the polymer does not precipitate in the alignment agent, and the surface tension of the alignment agent becomes a composition in the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the organic solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, etc., but is preferably 1 to 1 〇% by weight range. In other words, the liquid crystal alignment agent of the present invention is applied onto the surface of the substrate to form a coating film formed of a liquid crystal alignment film. When the solid concentration is less than 1% by weight, the film thickness of the coating film is too small to be obtained. When the solid content of the liquid crystal alignment film exceeds 1% by weight, the film thickness of the coating film becomes too large, and a satisfactory liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent increases, and the coating property is deteriorated. The viscosity of the liquid crystal alignment agent of the present invention (measuring the viscosity of the liquid crystal alignment agent at 25 ° C using a rotary viscometer) must be appropriately adjusted according to the coating method of the liquid crystal alignment agent, preferably 3 to 100 mPa · s, More preferably, it is 3 to 50 m P a · s, and particularly preferably in the range of 3 to 3 5 m P a · s. Further, the range of the particularly preferable solid content concentration differs depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the spin coating method, it is particularly preferably in the range of 1.5 to 4.5% by weight. In the printing method, the solid content concentration is in the range of 3 to 9 % by weight, and therefore the solution viscosity is particularly preferably in the range of 12 to 50 mPa·s. In the ink jet method, the solid content concentration is in the range of 1 to 5% by weight, and therefore, the solution viscosity is particularly preferably in the range of 3 to 15 mPa to 35 to 200846790 • S. When the liquid crystal alignment agent of the present invention is prepared, the temperature is preferably from 0 ° C to 200 ° C, more preferably from 10 ° C to 10 ° C, particularly preferably from 2 ° C to 60 ° C. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) coating the liquid crystal alignment agent of the present invention on one surface of the substrate on which the patterned transparent conductive film is provided, for example, by a f-coating method, a spin coating method, a printing method, an inkjet method, or the like, The coated film is then formed by heating the coated surface. Here, as a method of applying a liquid crystal alignment agent to a substrate, a spin coating method is preferred for a small substrate, a printing method is preferred for a medium substrate, and a large printing method is preferred for a large substrate. Ink method. Further, as the substrate, for example, glass made of float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, cyclic polyolefin can be used. A transparent substrate made of plastic. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ) and indium oxide-tin oxide (In 2 〇 3 -SnO 2 ) can be used. ΪΤΟ film and so on. In the patterning of the transparent conductive film, a photolithography method or a method in which a photomask is used in advance can be used. As the reflective electrode, a metal such as A1 or Ag, an alloy containing such a metal, or the like can be used. However, as long as there is sufficient reflectance, it is not limited by these. In the coating of the liquid crystal alignment agent, in order to make the adhesion between the surface of the substrate and the transparent conductive film or the reflective electrode and the coating film better, the functional decane compound may be preliminarily coated on the surface of the substrate, 36-200846790, A functional titanium compound or the like. After application with a liquid crystal alignment agent, it is intended to prevent dripping of the liquid of the applied alignment agent, and preliminary heating (prebaking) is usually carried out. The prebaking temperature is preferably from 30 to 300 ° C, more preferably from 40 to 200 ° C, and particularly preferably from 50 to 150 ° C. Then, a calcination (post-baking) step is carried out for the purpose of completely removing the solvent or the like. The calcination temperature is preferably from 80 to 300 ° C, more preferably from 120 to 25 ° C. As described above, the liquid crystal alignment agent of the present invention forms a coating film as an alignment film by removing an organic solvent after coating, but the liquid crystal alignment agent of the present invention contains a polyaminic acid or a ruthenium imidization ratio. In the case of a low ruthenium imidized polymer, dehydration ring closure may be carried out by further heating to form a more imidized coating film. The film thickness of the formed coating film is preferably 0.001 to 1/zm, more preferably 0.005 to 0.5/zm. (2) The surface of the coating film to be formed may be subjected to a rubbing treatment in a predetermined direction by, for example, winding a cloth made of fibers such as nylon, crepe or cotton to control the alignment angle of the liquid crystal molecules. Further, in addition to the rubbing treatment method, a method of irradiating the surface of the coating film with polarized ultraviolet light to control the alignment property may be employed. Further, in order to remove fine powder (foreign matter) generated during the rubbing treatment or the like, the surface of the coating film is cleaned, and it is preferred to wash the formed liquid crystal alignment film by isopropyl alcohol and/or pure water. . Further, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be changed, for example, by partially irradiating ultraviolet rays as shown in JP-A-6-2 22 3 66 or JP-A-6-28 1 973. Pre-tilt treatment, or 'partially forming a photoresist film on the rubbed liquid crystal alignment film' as shown in JP-A-5-107544, after performing rubbing treatment in a different direction from the previous rubbing treatment, before removing -37 - 200846790 The photoresist film is used to improve the alignment characteristics of the liquid crystal display element by changing the alignment property of the liquid crystal alignment film. (3) Two substrates in which the liquid crystal alignment film is formed as described above are produced, and the two substrates are arranged to face each other with a gap (cell gap) therebetween, and the peripheral portions of the two substrates are bonded together using a sealant on the surface of the substrate. The liquid crystal is injected and filled in the cell gap divided by the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, a polarizing plate is disposed on the outer surface of the liquid crystal cell, that is, on the outer surface side of each of the substrates constituting the liquid crystal cell, thereby obtaining a liquid crystal display element. Here, as the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, or a terphenyl liquid crystal can be used. Biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cetane liquid crystal, or the like. Further, in such liquid crystals, for example, a cholesteric liquid crystal such as chol chloride, cholesterol phthalate or steroid carbonate may be added; and the trade names "C-1 5" and "CB-15" (MERCK) A palm powder which is sold, and a ferroelectric liquid crystal such as an oxyoxybenzylidene group or an amino-2-methylbutylcinnamate. The polarizing plate which is bonded to the outer surface of the liquid crystal cell is a polarizing film called a "ruthenium film" which is formed by absorbing iodine while stretching the polyvinyl alcohol, and a cellulose acetate protective film is used. A polarizing plate formed by sandwiching the polarizing plate or the film itself. The present invention will be more specifically described by the following examples, but the invention is not limited by the examples. The measurement of the imidization ratio, the measurement of the voltage holding ratio, the reliability evaluation of the voltage holding ratio, and the printability test in the examples and the comparative examples were evaluated by the following methods. [Measurement of hydrazine imidation rate] The polymer was dried under reduced pressure at room temperature, and then subjected to a superconducting nuclear magnetic resonance absorption apparatus (NMR, manufactured by Nippon Denshi Co., Ltd., trade name: EX-90A). In the hydrazine (DMSO_d6), tetramethyl decane was used as a reference material, and iH-NMR was measured. From the obtained data, the ratio of the peak area (near lOppm) derived from the proton of the NH group in the polymer to the peak area of other protons was calculated, and the ruthenium amination ratio was calculated. [Measurement of Voltage Retention Rate] For a liquid crystal display device, a voltage of 5 volts was applied with a pulse of 60 μs and a pulse of 167 ms, and then 1 was released from the release in an atmosphere of 60 ° C. Voltage retention after 67 ms. The measuring device is a VHR-1 manufactured by Dongyang Technology Co., Ltd. When the voltage holding ratio was 99.0% or more, it was judged as "good", and the other cases were judged as "poor". [Response evaluation of voltage holding ratio] -39- 200846790 After measuring the voltage holding ratio by the above measuring method 'The liquid crystal display element was stored at a temperature of 1 ° C in a constant temperature oven for 10 曰 stress, and then allowed to cool to room temperature. The amount of change in the pre-thermal stress retention ratio was calculated by determining the voltage holding ratio of the liquid crystal display element as described above. The amount of change in the voltage holding ratio was determined to be "good" within the initial period, and the other cases were judged to be good." [Printability test] Using a liquid crystal alignment film printer (Japanese photo printing (each of the liquid crystal alignment agents prepared in the following examples and comparative examples (component concentration is adjusted to 4.5 to 6.5% by weight)) is applied to the electrode. The transparent electrode surface of the glass substrate The IΤ film of the transparent electrode having a film thickness of 20 μm was formed at a spacing of 1 〇〇//m to form a preliminary drying at 80 ° C for 1 minute on the stripe hot plate. Adding φ at 200 ° C for 1 minute, forming a liquid crystal having a film thickness of about 60 nm, observing the peripheral portion of the liquid crystal alignment film with a magnification of 20 times, and determining that there is no coating unevenness as "good" * * The case of the case was judged as "poor". The results of the evaluation of the printability were summarized in Table 2. Synthesis Example 1 (Synthesis of Polylysine P-1) 35.913 g of tetracarboxylic dianhydride was used. (0·1709, tetracarboxylic dianhydride represented by formula (2), 12.433 g (manufactured by 0.0570, 5% of the voltage 値 after thermal measurement is again broken), the total solid is attached Transparent electric 200nm, shape, on the heating plate, alignment film. Crystalline agent to the ear) above the molars -40 - 200846790 pyromellitic dianhydride, as a diamine 18.860 grams (0.1 744 moles) of phenylenediamine, 30.3 76 grams (0.05 8 1 mole) The diamine represented by the formula (17) was dissolved in 400 g of fluorenyl-methyl-2-pyrrolidone, and the reaction was allowed to proceed for 4 hours at 60 ° C. Then, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol, and dried under reduced pressure at 4 ° C for 24 hours to obtain 88 g of polylysine having a logarithmic viscosity of 70.70 dl/g (this was regarded as "polymer P- 1"). Synthesis Example 3 (Synthesis of ruthenium iodide polymer P-3) 25.690 g (0.093 0 mol) of tetracarboxylic dianhydride represented by the above formula (3) was regarded as two as a tetracarboxylic dianhydride. 9.2135 g (0.0852 mol) of amine to phenylenediamine, 4.9668 g (0.0095 mol) of the diamine represented by the above formula (17) dissolved in 140 g Ν-methyl-2-pyrene ratio The reaction was carried out at 60 ° C for 5 hours in a little ketone. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol, and dried at 40 ° C for 24 hours under reduced pressure to obtain 31 g of polyamic acid having a logarithmic viscosity of 0 · 72 dl / g. 3 g of the polylysine was dissolved in 400 g of N-methyl-2-pyrrolidone, 6.3 g of pyridine and 8.1 g of acetic anhydride were added, and the dehydration ring was closed at 1 1 ° C for 4 hours. The mixture was precipitated, washed, and decompressed in the same manner as above to obtain a 26 g yttrium imidized polymer having a logarithmic viscosity of 0.6 8 dl/g and a ruthenium iodide ratio of 48% (this was regarded as "polymer P-3". "). Synthesis Example 6. Synthesis of ruthenium iodide polymer P-6 -41 - 200846790 16.7061 g (0.0795 mol) of tetracarboxylic dianhydride represented by the above formula (2) as tetracarboxylic dianhydride 2.9198 g (0.0270 mol) of diphenylamine as a diamine, 6.2216 g (0.0119 mol) of the diamine represented by the above formula (17), 7.8713 g (0.0397 mol) 4,4' 0.10 g (〇·〇〇1 6 mol) aniline as a monoamine diphenylmethane and a monoamine as a terminal modification was dissolved in 140 g of N-methyl-2-pyrrolidone at 6 The reaction was allowed to proceed for 4 hours at 0 °C. Next, the reaction solution was poured into a large amount of excess methanol to precipitate a reaction product. Then, it was washed with methanol, and dried at 40 ° C for 24 hours under reduced pressure to obtain 32 g of polyamic acid having a logarithmic viscosity of 0.60 dl/g. 30 g of the obtained polyamic acid was dissolved in 400 g of N-methyl-2-pyrrolidone, 10.8 g of pyridine and 13.9 g of acetic anhydride were added, and the dehydration ring was closed at 1 l ° C for 4 hours, as described above. The precipitate was precipitated, washed, and decompressed to obtain 27 g of a ruthenium iodide polymer having a logarithmic viscosity of 5555 g/g and a ruthenium iodide ratio of 75% (this was referred to as "polymer P-6"). Synthesis Example 2, Synthesis Examples 4 and 5, and Synthesis Examples 7 to 1 4, Comparative Synthesis Examples i to 5 Except that the tetracarboxylic dianhydride and the diamine were changed to those described in Table 1, respectively, Synthesis Example 1 was synthesized. In the same manner as in Synthesis Example 6, the poly-proline and the ruthenium-based polymer shown in Table 1 were obtained (these were regarded as the polymers "P-2", "P-4", and "P", respectively. -5", "P-7" ~ "p-i9"). When the respective polymers are synthesized into a specific polyamic acid, a polymer having a viscosity as described in -42 to 200846790 of Table 1 can be obtained by appropriately adjusting the weight ratio of the tetracarboxylic dianhydride to the diamine used. . Further, the ruthenium imidization ratio is obtained by appropriately adjusting the amounts of pyridine and acetic anhydride added, and each of the polymers having the ruthenium iodide ratio shown in Table 1 can be obtained. Further, each of the tetracarboxylic dianhydrides A to F and the diamine G to fluorene represents the following compounds. Acid dianhydride: tetracarboxylic dianhydride dianhydride represented by the above formula (2) · · tetrahydro acid dianhydride dianhydride C represented by the above formula (3): 2,3,5-tricarboxyl Cyclopentyl acetic acid dianhydride dianhydride D: pyromellitic dianhydride dianhydride dianhydride: 1,2,3,4-cyclobutane tetracarboxylic dianhydride dianhydride F: l, 3, 3a, 4 ,5,9b-hexahydro-8.methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione Diamine G: diamine diamine oxime represented by the above formula (17): p-phenylenediamine diamine I: 4,4,-diaminodiphenylmethanediamine J: the above formula (15) Diamine diamine oxime: diamine diamine L represented by the above formula (27): diamine diamine oxime represented by the following formula (2 8 ): 2,2 '-dimethyl-4,4 '-Diaminobiphenyl-43- 200846790 Ό,

〇CF3r&quot;S,0 (2 8) 44- 200846790 Table 1

The polymer dianhydride·[) indicates the molar ratio of the molar ratio to the amount of all diamines and amines in the amount of all acid dianhydrides.醯 imidization ratio (%) Synthesis Example 1 P-1 A (75), D (25) G (25), H (75) 0.70 0 Synthesis Example 2 P-2 B(100) G(50) &gt H(50) 0.73 0 Synthesis Example 3 P-3 B(100) G(10), H(90) 0.68 48 Synthesis Example 4 P-4 A(100) G(20), H(80) 0.60 50 Synthesis Example 5 P-5 A(100) G(10), H(70)' 1(20) 0.64 79 Synthesis Example 6 P-6 A(100) G(15), H(34), 1(50) Aniline (2) 0.55 75 Synthesis Example 7 P-7 D(50), E(50) 1(100) 0.72 0 Synthesis Example 8 P-8 B(100) H(100) 0.81 91 Synthesis Example 9 P-9 A ( 50), F(50) J(1.5), K(10), H(87) Stearylamine (3) 0.50 95 Synthesis Example 10 P-10 A(50), F(50) K(10), H (88.5) Stearylamine (3) 0.48 94 Synthesis Example 11 P-11 A(50), F(50) L (3), K(10), Η(86·25), aniline (1.5) 0.52 89 Synthesis Example 12 P-12 B(50), F(50) L(5)5K(10), Η(84·25), aniline (1·5) 0.50 90 Synthesis Example 13 P-13 E(100) Μ(100) 0.85 0 Synthesis Example 14 P-14 D(50), E(50) Μ(100) 0.90 0 Comparative Synthesis Example 1 P-I5 C(IOO) G(20), H(80) 0.62 50 Comparative Synthesis Example 2 P-16 C(100) G(10), H(70), 1(20) 0.64 78 Comparative Synthesis Example 3 P -17 C(100) H(100) 0.79 90 Comparative Synthesis Example 4 P-18 C(50), F(50) J(1.5), K(10)5H(87) Stearylamine (3) 0.52 92 Comparison Synthesis Example 5 P-19 C(50), F(50) K(10), Η(88·5) Stearylamine (3) 0.51 93 -45- 200846790 Example 1 The polymer obtained in Synthesis Example 1 ( In p-1), N-methyl-2-pyrrolidone and ethylene glycol are added in a manner of mixing N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether in a weight ratio of 30/70. Monobutyl ether, and for the polymer (P-1), 20 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane is added. The liquid crystal alignment agent was set to have a solid concentration of 3 · 5 % by weight. However, when the printability test was carried out, it became a liquid crystal alignment agent having a solid concentration of 6.5% by weight. After sufficiently stirring the mixture, it was filtered using a filter having a pore size of 〇. 2 # m, and a transparent conductive film made of an ITO film was provided on one surface of the glass substrate, and coated on a hot plate by a spin coater. The preliminary drying was carried out at 80 ° C for 1 minute, followed by baking in a clean oven (under nitrogen) at 200 ° C for 1 hour to prepare a transparent electrode substrate having a liquid crystal alignment film having a film thickness of 60 nm. Next, after coating the outer edges of the liquid crystal alignment film on the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, an epoxy resin adhesive containing alumina balls having a diameter of 5.5 // m is applied. In the opposite way, the liquid crystal alignment film faces are overlapped and pressed to harden the adhesive. Next, a negative liquid crystal (1^1^(:-2 〇3 8 ) manufactured by MERCK Co., Ltd.) was filled from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to form a VA type. Liquid crystal display element. The results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element are shown in Table 2. Example 2 Polymer of Synthesis Example 2 was used instead of Polymer (P-1)'-46-200846790 The liquid crystal alignment agent and the VA liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except for the material (P-2). Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Example 3 In place of the polymer (P-1), the polymer (P-3) obtained in Synthesis Example 3 was used, and the solvent composition was N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether mixed weight. The liquid crystal of the present invention was obtained in the same manner as in Example 1 except that the ratio of N, N, N', N' tetraglycidyl- 4,4'-diaminodiphenyl-phenylene was not added. An alignment agent and a VA type liquid crystal display element. The obtained liquid crystal display element is shown in Table 2. The result of the valence voltage retention rate and its reliability. Example 4 In place of the polymer (P-1), the polymer (P_4) obtained in Synthesis Example 4 was used. The solvent composition was N-methyl-2-pyrrolidone/ The liquid crystal alignment agent and the VA liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except that the weight ratio of ethylene glycol monobutyl ether was changed to 5 0/5 0. Table 2 shows the evaluation of the obtained liquid crystal display device. The result of the voltage holding ratio and its reliability. Example 5 In place of the polymer (P - 1 ), the polymer (P-5) obtained in Synthesis Example 5 was used, and the solvent composition was 7-butyrolactone/N-methyl group. A liquid crystal alignment agent and a VA liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except that the ketone/ethylene glycol monobutyl ether was used in a weight ratio of 40/30/30. The results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element are shown in 2. Example 6 Using (p_6) instead of the polymer (Ρ·1): (p-7)=5〇·· 50 (weight ratio) of the polymer (P-6) obtained in Synthesis Example 6 and the polymer obtained in Synthesis Example 7 (P_) 7), and the solvent composition is r-butyrolactone/N-methyl-2-pyridinone/ethylene glycol monobutyl ether mixed weight ratio = 40/3 5/25, as in the case of Example 1. The liquid crystal alignment agent and the VA liquid crystal display element of the present invention were obtained. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Example 7 The polymer obtained in Synthesis Example 8 (P- 8), adding 7-butyrolactone / ethylene glycol monobutyl ether in a weight ratio of 90/10, adding r-butyrolactone and ethylene glycol monobutyl ether, and then for the polymer (P- 8), adding 10 parts by weight of N, N, N', N' tetraglycidyl-4,4'-diaminodiphenylmethane to a liquid crystal alignment having a solid concentration of 5.3 wt% The agent (however, when the printability test was carried out, it became a liquid crystal alignment agent having a solid concentration of 4.5% by weight). After sufficiently stirring this, it was filtered using a filter having a pore size of 0.2 // m to prepare a liquid crystal alignment agent of the present invention. The liquid crystal alignment agent of the present invention prepared as described above was coated on the transparent -48-200846790 conductive film formed by comb-shaped IOK film on one surface of a glass substrate having a thickness of 1 mm, at 18 〇 using a spin coater. After drying at ° C for 1 hour, a film having a dry film thickness of 80 nm was formed. The formed coating film surface was subjected to a rubbing treatment using a friction machine to form a liquid crystal alignment film having a roll wound with an anti-loning cloth. Here, the rubbing treatment condition was that the number of revolutions of the roller was 400 rPm, and the moving speed of the platform was 3 c m / sec. (This substrate is used as the substrate A). The liquid crystal alignment agent of the present invention prepared as described above was applied to one surface of a glass substrate having a thickness of 1 mm by a spin coater, and dried at 180 ° C for 1 hour to form a film having a dry film thickness of 80 nm. The formed coating film surface was subjected to a rubbing treatment using a friction machine to form a liquid crystal alignment film having a roll wound with an anti-loning cloth. Here, the rubbing treatment conditions were that the number of revolutions of the rolls was 400 rpm, the moving speed of the stage was 3 cm/sec, and the length of the press-in of the hairs was 0.4 mm. (This substrate is used as the substrate B). Applying an epoxy resin adhesive containing alumina balls having a diameter of 17 μm to the outer edge portion of the coating film faces of the substrates A and B, the rubbing direction of each liquid crystal alignment film becomes reversed. In a parallel manner, two substrates are opposed to each other with a gap interposed therebetween, and the outer edge portions are joined to each other and pressed to cure the adhesive. Then, the liquid crystal injection port is filled with a nematic liquid crystal (MLC-2019 manufactured by MERCK Co., Ltd.) between the pair of substrates, and then the liquid crystal injection port is sealed with an epoxy-based adhesive to polarize the polarizing plate and the respective polarizing plates. The IPS type liquid crystal display element was produced by bonding the polarizing plate to both sides of the outer side of the substrate so that the rubbing direction of the liquid crystal alignment film of the substrate was uniform. Table 2 shows the results of evaluating the voltage holding ratio and reliability of the liquid crystal display element obtained in the same manner as in -49-200846790. Example 8 (P-9) : (P-13) = 2 0: 80 (weight ratio) In a manner, the polymer (P-9) obtained in Synthesis Example 9 and the polymer (P-13) obtained in Synthesis Example 13 were dissolved in r-butyrolactone/N-methyl- 2-pyrrolidone/ethylene In an alcohol monobutyl ether mixed solvent (solvent weight ratio 68/17/15), and further added to the total amount of the polymer, 2 parts by weight of N, N, N', N' tetraglycidyl group 4 is added. 4'-Diaminodiphenylmethane was used as a liquid crystal alignment agent having a solid concentration of 3.5% by weight (however, when a printability test was carried out, a liquid crystal alignment agent having a solid content concentration of 6.0% by weight) was prepared. After sufficiently stirring the mixture, it was filtered using a filter having a pore size of 0.2 / m to prepare a liquid crystal alignment agent of the present invention. A transparent conductive film made of an ITO film was provided on one surface of the glass substrate, and the liquid crystal alignment agent was applied by a spin coater, and preliminarily dried at 80 ° C for 1 minute on a hot plate, followed by a hot plate. The film was fired at 2 10 ° C for 10 minutes to form a transparent electrode substrate having a liquid crystal alignment film having a film thickness of 60 nm. The film was rubbed by a friction machine at a roll rotation number of 400 rpm, a table moving speed of 30 mm/sec, and a hand and foot press-in length of 4.4 mm, and the rubbing machine had a roll wound with a crepe cloth. . The liquid crystal alignment film-coated substrate was ultrasonically washed in pure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes. Next, on the outer edge of each of the liquid crystal alignment films of the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, an alumina ball having a diameter of -50 to 200846790 5 .5 // m is applied. After the epoxy resin adhesive is applied, the liquid crystal alignment film faces are opposed to each other, and are laminated and pressed to harden the adhesive. Then, the liquid crystal injection port is filled with a nematic liquid crystal (MLC-622 1 manufactured by MERCK Co., Ltd.), and the liquid crystal injection port is sealed with an acrylic photocurable adhesive to bond the polarizing plate to the outside of the substrate. On both sides, a TN type liquid crystal display element is fabricated. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Example 9 In place of the polymers (P-9) and (P-13), the polymer obtained in Synthesis Example 10 was used as (P-10): (P-7) = 50:50 (weight ratio). -1 〇) and the polymer (P-7) obtained in Synthesis Example 7, for the total amount of the polymer, N,N,N',N'-tetraglycidyl-4,4'-diamino group The amount of diphenylmethane added was changed to 20 parts by weight, and the solvent composition was 7-butyrolactone/N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether mixed weight ratio = 71/17/12 The liquid crystal alignment agent and the TN liquid crystal display element of the present invention were obtained in the same manner as in Example 8. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Example 1 In place of the polymer (P-9), the polymer (P -1 1 ) obtained in Synthesis Example 11 was used, and for the total amount of the polymer, N, N, N, N, and IV were shrunk. The amount of glyceryl-4,4'-diaminodiphenylmethane added was changed to 10 parts by weight 'and the solvent composition was T-butane vinegar/N-methyl- 2 - lysine-51 - 200846790 ketone / The liquid crystal alignment agent of the present invention and the TN type liquid crystal display element were obtained in the same manner as in Example 8 except that the ethylene glycol monobutyl ether mixture weight ratio was 72/15/13. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Example 1 1 In place of the polymer (P-9), the polymer (P-12) obtained in Synthesis Example 12 was used, and for the total amount of the polymer, N, N, N', N'-tetraglycidyl was used. The amount of bis- 4,4'-diaminodiphenylmethane added was changed to 10 parts by weight, and the solvent composition was γ-butyrolactone/N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether The liquid crystal alignment agent and the TN liquid crystal display element of the present invention were obtained in the same manner as in Example 8 except that the mixing weight ratio was 72/15/13. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Example 12 In place of the polymer (P-13), the polymer (P-14)' obtained in Synthesis Example 14 was used, and the solvent composition was 7-butyrolactone/N-methyl-2-pyrrolidone/ethylene The liquid crystal alignment agent and the tn liquid crystal display element of the present invention were obtained in the same manner as in Example 8 except that the weight ratio of the alcohol monobutyl ether was 72/16/12. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Comparative Example 1 -52- 200846790 In place of the polymer (p-1), the polymer (P-15) obtained in Comparative Synthesis Example 1 was used, and the solvent composition was N-methyl-2-pyrrolidone/ethylene glycol. A liquid crystal alignment agent and a VA liquid crystal display element were obtained in the same manner as in Example 1 except that the butyl ether mixed weight ratio was 50/50. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Comparative Example 2 In place of the polymer (P -1 ), the polymer (P-16) obtained in Comparative Synthesis Example 2 was used. A liquid crystal alignment agent was obtained in the same manner as in Example 1 except that the composition was r-butyrolactone/N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether in a weight ratio of 40/3 0/30. VA type liquid crystal display element. Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Comparative Example 3 A liquid crystal alignment agent and an IPS liquid crystal display element were obtained in the same manner as in Example 7 except that the polymer (P-7) obtained in Comparative Synthesis Example 3 was used instead of the polymer (P-8). Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Comparative Example 4 A liquid crystal alignment agent -53-200846790 and a TN liquid crystal display element were obtained in the same manner as in Example 8 except that the polymer (P-18) obtained in Comparative Synthesis Example 4 was used instead of the polymer (P-9). Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Comparative Example 5 A liquid crystal alignment agent and a quinoid liquid crystal display element were obtained in the same manner as in Example 9 except that the polymer (Ρ-1 9 ) obtained in Comparative Synthesis Example 5 was used instead of the polymer (Ρ-10). Table 2 shows the results of evaluating the voltage holding ratio and the reliability of the obtained liquid crystal display element. Table 2 Polymer Voltage Retention Rate (VHR) Printed Polyuryl Amidine Aminated Polymer VHR (%) Initial 値 Determination VHR Reliability Example 1 Ρ-1 - 99· 1 Good Good Good Example 2 Ρ- 2 - 99.2 Good Good Good Example 3 - Ρ-3 99.3 Good Good Good Example 4 嘱Ρ-4 99.6 Good Good Good Example 5 - Ρ-5 99.8 Good Good Good Example 6 Ρ-7 Ρ-6 99.7 Good Good Good Example 7 • Ρ-8 99.7 Good Good Good Example 8 Ρ-13 Ρ-9 993 Good Good Good Example 9 Ρ-7 Ρ-10 99.2 Good Good Good Example 10 Ρ-13 Ρ-11 99.5 Good Good Practice Π Ρ-13 Ρ-12 99.4 Good Good Good Example 12 Ρ-14 Ρ-9 99.3 Good Good Good Comparative Example 1 • Ρ-15 98.3 Poor Defects Comparative Example 2 - Ρ-16 98.7 Adverse Defects Comparative Example 3 - Ρ-17 98.9 Adverse failure Good Comparative Example 4 Ρ-13 Ρ-18 98.9 Adverse failure Good Comparative Example 5 Ρ-7 Ρ-19 98.7 Good defect good ・54- 200846790 It is known from the results of Table 2 above, By embodiment 1 The 12 resulting liquid crystal alignment agent obtained in Example liquid crystal alignment film were lower compared with Comparative Example, lines showed high voltage holding ratio and good reliability, and exhibits excellent coatability of the liquid crystal alignment agent. It is apparent that the above characteristics of the liquid crystal alignment agent of the present invention can be adjusted by the selection of the structure of the tetracarboxylic dianhydride represented by the above formula (1) and the content thereof. As described above, according to the present invention, it is possible to provide a liquid crystal alignment agent which exhibits a high voltage retention ratio and is excellent in coating properties of a liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film and having a beautiful image.

-55-

Claims (1)

200846790 X. Patent Application No. 1 · A liquid crystal alignment agent characterized by containing an aliphatic tetracarboxylic dianhydride represented by the following formula (1) and optionally a carboxylic dianhydride and p-phenylenediamine And at least one polymer selected from the polyamine obtained by polyaminating the other diamine as needed and the imidization of the polyamic acid to imidize the polymer, (wherein R1 to R6 are each independently a hydrogen atom or a carbon number of 1 to 20, and 111 and 11 each independently represent an integer of 0 to 3). 2. The liquid crystal alignment agent of claim 1, wherein the aliphatic tetracarboxylic dianhydride represented by the following formula (2) is obtained by the other four additions ( 1) The combination of the formula in the alkyl group Combination of the formula -56- 200846790 4. The liquid crystal alignment agent of any one of claims 1 to 3, wherein the other diamine contains a diamine having a pretilt expression portion as shown by the structure of the following formula (13), (wherein R7 and R8 each independently represent a hydrogen atom or a methyl group, r9 is a linear or branched alkyl group having 1 to 20 carbon atoms, and RU and RM are each independently a divalent organic group). 5. The liquid crystal alignment agent according to any one of the above claims, wherein the diamine 'R12^R13 having a pretilt expression portion as shown in the structure of the following formula (14) as the other diamine ^_R14 h2n Nh2 参· • (14) -57- 200846790 (wherein a is 0 or 1, R12 is derived from an ether bond (-Ο-), carbonyl), a carbonyloxy group (-COO-), an oxycarbonyl group (-0 ( :0-), indoleamine (-NHCO-, -CONH-), thioether bond (-S-) and methylene 2-valent bond group or organic group, R13 is different from R12, and the divalent R14 system is a group of a steroid skeleton, a group having a fluorine atom, and a group selected from a group having a linear or branched alkyl group of 30). The agent according to any one of claims 1 to 3, which further contains a compound containing two or more epoxy groups containing an epoxy group in the molecule. A liquid crystal alignment agent which is formed by the liquid crystal alignment agent according to any one of the claims. A liquid crystal display element comprising the liquid crystal alignment film of the seventh aspect. Base (the organic group selected by -CO- bond, carbon number 1~ at least 1 of liquid crystal alignment) 1st to 3rd Patent No. -58- 200846790 七明说单单符符表 is the map of the generation of the map Table: Case map This table', generation /-N ZS fixed one or two fingers c C No eight, if the case has a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: no -5-