TW200934809A - Liquid aligning agent liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent which providing a liquid crystal aligning film with good liquid crystal alignment, high voltage hold ratio and excellent residue image property. The above liquid crystal aligning agent comprises at least one component selected from a group consists of a polyamic acid and an imide polymer thereof, wherein the polyamic acid is obtained by a reaction of a tetracarboxylic dianhydride and a diamine comprising a specific bisaminophenyl compound represented by the following formula (1-1). The liquid crystal aligning film formed by the above liquid crystal aligning agent preferably with a surface free energy of 38 mN/m or less.

Description

200934809 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having good liquid crystal alignment, exhibiting high voltage holding ratio, afterimage performance, and burn-in performance, and display performance of the liquid crystal alignment film. Excellent liquid crystal display element.先前 [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is widely known, and a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive film is provided. As a substrate for a liquid crystal display element, two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a unit cell of a sandwich structure, and the long axis of the liquid crystal molecules is One substrate is continuously twisted 90 degrees toward the other substrate. In addition, s TN (Super Twisted Nematic) liquid crystal display elements and IPS (in-plane switching) type liquid crystal display elements having a higher contrast ratio than TN liquid crystal display elements have been developed. An OCB (Optically Compensatory Bend) type liquid crystal display element having a high viewing angle dependency and a high-speed response of a video screen, and a VA (Vertical Alignment) type liquid crystal display element using a nematic liquid crystal having negative dielectric anisotropy. Among these liquid crystal display elements, a liquid crystal alignment film made of an organic film such as poly-4-200934809 yttrium imine, polyamide or polyester which aligns liquid crystal molecules is used. In particular, polyimine is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like. A liquid crystal alignment film made of a poly-imine, which can be applied to a substrate by a solution of a polyimine precursor precursor polyamine or a soluble polyimine dissolved in an organic solvent. A coating film is formed and formed by grinding as needed. φ Heretofore, as one of the problems of the liquid crystal display element, it is exemplified that after the cumulative driving time is long, an afterimage (so-called burn-in) can be observed. In order to improve this afterimage phenomenon, some experiments have been carried out before. Almost all of them focus on the relationship between the uneven distribution of the DC voltage component applied during the "burning of the screen" and the driving of the liquid crystal display element, and the accumulation (residual DC voltage), thereby improving the "burning screen" by reducing the residual DC voltage. For example, in Patent Document 1, it is considered that a liquid crystal alignment film made of a specific polyamine synthesized using a specific diamine having a chroman structure can effectively reduce the residual DC voltage, and attempts to improve burn-in thereby. However, in the liquid crystal alignment film of Patent Document 1, in the examples, the effect of improving the afterimage is not sufficiently verified, and there is no significant defect other than the occurrence of afterimage in the liquid crystal display element, for example, heterogeneity based on liquid crystal alignment. The resulting display unevenness is considered. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the invention is to provide a liquid crystal alignment film capable of forming a liquid crystal alignment film having excellent liquid crystal alignment properties and exhibiting high voltage holding ratio and excellent afterimage performance. An aligning agent. Another object of the present invention is to provide a liquid crystal display element excellent in afterimage performance and burn-in performance. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are achieved by a first liquid crystal alignment agent comprising at least one selected from the group consisting of polylysine and its ruthenium iodide polymer. Proline is produced by reacting tetradecanoic dianhydride with a monoamine containing a compound represented by the following formula (1).

- 〇 test (1_, X is a divalent organic group containing an aromatic ring or -NH-*' -COO-*' -OCO-*' -NHCO-* ' -S- S 〇2&quot; 200934809 -CONH-* , -CO-*, -CH2〇-* (where 'the above has a "*," the linkage is located on the side of the color-filled structure), a methylene group or an alkylene group Y of 2 to 8 carbon atoms Is -〇-*, -S-*, -S〇2-*, -NH-*, -COO-*, -OCO-* '-NHCO_*, -CONH-*, -CO-*, (where The above-mentioned linkage is bonded to an amine phenyl group, a methylene group or an alkylene group having 2 to 8 carbon atoms, and the two Ys may be the same or different, and each of R1, Ru and Rin is a hydrogen atom. Or a monovalent organic group. Q The above objects and advantages of the present invention are achieved by a liquid crystal alignment film comprising the liquid crystal alignment agent, and third, by a liquid crystal display element having the liquid crystal alignment film. MODES: The liquid crystal alignment agent of the present invention comprises at least one selected from the group consisting of polylysine and a quinone imidized polymer thereof, which comprises a tetracarboxylic dianhydride and a formula (1) It is obtained by reacting a diamine of the compound shown.醯 <Polyuric acid> The above polylysine can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (1). [Tetracarboxylic dianhydride] As the above polyamine Examples of the tetracarboxylic dianhydride used in the synthesis of the acid include butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2-dimethyl-1. , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl 200934809 -1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 , 4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3&amp;,4,5,913-hexahydro-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphthalene [1,2-indolyl]-furan-1,3-dione, 1,3,3&amp;,4,5,91)-hexahydro-5-A 5-(- ❹ Hydrogen-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5 , 9b-hexahydro: 5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl )-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5- -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-l,3-dione, l,3,3a,4,5,9b-six Hydrogen-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&amp ;,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxoindole-3-furanyl)-naphthalene [l,2-c]-furan-1 ,3-dione, l,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro - 3'-(tetrahydrofuran-2',5'-dione), 3,5,6-tricarboxy-2-carboxymethylnorbornane - 2:3,5:6-dianhydride, 4,9- Dioxatricyclo[5.3.1.0''6] 十一 200934809 alkane-3,5,8,10-tetraketone, a compound represented by the following formula (Τ_I) and (Τ_II), etc. Dianhydride and alicyclic tetracarboxylic dianhydride;

R4 R4 9

(In the formulas (Τ-Ι) and (Τ-ΙΙ), R1 and R3 are each a divalent organic group having an aromatic ring, and each of R2 and R4 is a hydrogen atom or an alkyl group, and each of a plurality of R2 and R4 may be present. Same or different) pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltricarboxylic acid Dihydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Dihydride, 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, φ 3,3',4,4'-tetraphenylnonane tetracarboxylic dianhydride, 1,2 , 3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis (3,4-·2 Carboxyphenoxy)diphenylphosphoric dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluorohetero Propyl diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(o-benzene) Dicarboxylic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, Phenyl-bis(triphenyl 200934809 phthalic acid) dianhydride 'bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)- 4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-double (dehydration partial Triglyceride), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-.bis (4) -Hydroxyphenyl)propane-bis(hydrogen trimellitate), an aromatic tetracarboxylic acid dianhydride or the like such as a compound represented by the following formula (T-1) to (T-4).

-10- 200934809

F3 /CH3

F3 /CH3

-11- 200934809 The benzene ring of the above aromatic tetracarboxylic dianhydride may be substituted by one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. They may be used alone or in combination of two or more. In the synthesis of polylysine contained in the liquid crystal alignment agent of the present invention, the above-mentioned medium is preferably selected from the group consisting of butane tetracarboxylic dianhydride and 1, from the viewpoint of enabling liquid crystal alignment which is excellent in performance. 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 〇1,2,3,4-ring Pentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&amp;,4,5,913-hexahydro-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene [l,2-c]-furan-1,3·dione, 1,3,3&amp;,4,5,91)-hexahydro-8-methyl-5-( Tetraammine-2,5-?-oxo-3-indolyl)-cai[l,2-c]-indolyl-1,3--one, l,3,3a,4,5,9b- Hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-£:]-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- beryllyl)-3-methyl-3-cyclohexene-1, 2-Dicarboxylic anhydride, 3,5,6-tricarboxy-2-resin methylnorbornazole - 2:3,5:6-dianhydride, 4,9-dioxane [5.3.1.02'6] i--Alkane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3 ,3,,4,4,-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, anthracene, 4,5,8-naphthalenetetracarboxylic acid The compound represented by the following formula (τ-5) to (T-7) in the compound represented by the above formula (TI) and the compound represented by the above formula (τ-Π) in the following formula-12-200934809 A tetracarboxylic dianhydride of at least one of the groups consisting of the compounds represented by the formula (Τ - 8) (hereinafter referred to as "specific tetracarboxylic dianhydride").

More preferably, the specific tetracarboxylic dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a. ,4,5,ΜΑ Hydrogen-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3, 3&amp;,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1 , 3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2 ,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorborn Alkane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraketone, pyromellitic dianhydride And at least-13-200934809 of the compound represented by the above formula (T-7) is a particularly preferable 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. 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 20 mol% or more based on the total amount of the tetracarboxylic dianhydride used. The specific tetracarboxylic dianhydride preferably contains 40 mol% or more, and more preferably contains 50 mol% or more. It is possible to synthesize a polylysine having excellent electrical properties or a quinone imidized polymer thereof by using tetracarboxylic acid = anhydride' containing the above respective compounds in the range described above. Thus, it is possible to obtain an excellent liquid crystal alignment agent containing them. The advantages of display performance are therefore preferred. [Diamine] The diamine used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention contains the compound represented by the above formula (1). X in the above formula (1) is preferably -〇-*, -COO-* or -OCO-* (wherein the connection key with 'above" is on the side of the color-filled structure), and γ is preferably - 〇-*, -COO-*, -OCO-*, -NH-* or -NHCO-* (where 'the above linkage with a bond to the aminophenyl group'), R1, R11 and RIU are preferably each It is a hydrogen atom or a methyl group. More specifically, the compound represented by the above formula (1) may, for example, be a compound represented by the following formulas (1 to 1) to (1 to 14). -14- 200934809

-15- 200934809

-16 - 200934809

In the above formula u), the position of the two groups γ is preferably 3,5-position relative to the group -17-200934809 group X. Further, the position of the amine group, preferably relative to the group Y, is each a para position. The diamine used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention may be a compound represented by the above formula (1), or a compound represented by the above formula (1) or the other two. A combination of amines. Examples of such other diamines include p-phenylenediamine, m-nonylphenylamine, 4,4'-monoaminodiphenylmethane, and 4,4,-diaminodiphenylethane. 4,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenyl maple, 4,4'-diaminobenzamide, 4,4,-diaminodiphenyl Ether, i,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4,-diaminobiphenyl , 2,2'-bis(trifluoromethyl).4,4,-diaminobiphenyl, 3,3,-bis(trifluoromethyl)-4,4,-diaminobiphenyl, 5 -amino-1-(4,-aminophenyl)-1,3,3-trimethylindan, 6-aminoaminophenyl)_ι,3,3-trimethylindan, 3 , 4'-diaminodiphenyl ether, 3,3,-diaminodibenzophenone, 3,4'-diaminobenzophenone, 4,4,-diaminobenzophenone, 2 , 2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-double (4-Aminophenyl)hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]millate, 1,4-bis(4-aminophenoxy)benzene, anthracene, 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-Diaminoguanidine, 9,9-bis(4-aminophenyl)anthracene, 4,4,-methylene-bis(2-chlorophenyl-18-200934809 amine), 2,2',5 , 5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene Diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2, double An aromatic diamine such as (trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; φ 1,1-between Xylylenediamine' 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 1,4-diaminocyclohexane, isophor Ketone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene dimethylene diamine, tricyclo[6.2.1.0'7] undecene dimethyl diamine, 4,4'-methylenebis(cyclohexylamine), 1,3- An aliphatic diamine such as X-aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane; and an alicyclic diamine; 2,3-diaminopyridine, 2,6-di Aminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium, 5,6-nonanediamine-2 ,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-tri-trap, 1,4-bis(3-aminopropyl) piperene, 2,4 -diamino-6-isopropoxy-1,3,5-three tillage, 2,4-diamino-6-methoxy-1,3,5-tri-trap, 2,4-diamine -6-phenyl-1,3,5-tri-trap, 2,4-diamino-6-methyl-s-trin, 2.4-diamino-1,3,5-triazine, 4 ,6-Diamino-2-vinyl-s-trin, 2.4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-di.amino-1,3 -dimethyl uracil, 3,5-diamino-1,2,4-triazole, 6,9-diamine-19- 200934809 -2-ethoxy acridine lactate, 3,8 -diamino-6-phenylphenanthridine, i,4.diaminopiperidinium, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-di Amino carbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminosostazole, N-phenyl-3,6-diaminocarbazole Ν, Ν, - bis (4-amino phenyl) benzidine, represented by the following formula (D-I) compound

(In the formula (D-I), R5 is a monovalent organic group having a cyclic structure containing a nitrogen atom, X1 is a divalent organic compound selected from the group consisting of pyridine, pyrimidine, triparty, piperidine, and piperene. a group), a compound represented by the following formula (D-Π)

(wherein H6 is a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triterpene, piperidine, and piperazine, and X2 is a divalent organic group, respectively, and exists Each of the plurality of X2 may be the same 'may be different', such as a diamine having two primary amine groups and a nitrogen atom other than the primary amino group in the molecule, and a compound represented by the following formula (D-) Diamine

(D-III) -20- 200934809 (in the formula (D-III), R7 is -0-*, -COO-*, -NHC〇-*, -CONH-* or -CO-* (of which The bond is bonded to R8), and R8 is a monovalent organic group having a group selected from the group consisting of a steroid skeleton, a triyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or the number of carbon atoms is a diamine oxane such as a compound represented by the following formula (D-IV), 6 ff 30 alkyl group, ff H2N~(CH2-)-1 丨-(〇-Si-^j-(-CH2- ^NH2 R9 R9 (D-IV) (In the formula (D-IV), each of R9 has a carbon number of 1 group, and a plurality of V groups may be the same or may not be an integer of 1 to 3, q An integer of 1 to 20); a compound represented by the following formula (D-5): 0C0-*, "a skeleton of a fluoromethylbenzene" or a hydrocarbon of a gas-based organic oxime 12, P (D) - 1)~

-21- 200934809

H2N

H2n, &gt;nh2 &gt;〇- f〇2H4-

(D-4)

(y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5). The above aromatic diamine, monosubstituted phenylenediamine, a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group, and a compound represented by each of the above formulas (D-1) to (D to 5)- The benzene rings of 22-200934809 may be substituted by one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms, respectively. These diamines may be used singly or in combination of two or more. R7 in the above formula (D-III) is preferably -〇-*, -COO-* or -OCO-* (wherein the above-mentioned linkage is bonded to R8), and R8 is preferably selected from the group consisting of steroids a monovalent organic group of a skeleton, a linear or branched alkyl group having 8 to 30 carbon atoms or a direct bond or branched fluorine having 8 to 30 carbon atoms substituted by a fluorine atom Alkyne. Specific examples of the compound represented by the above formula (D - III) include compounds represented by the following formulas (D-6) to (D-14), and the like.

-23- 200934809

-24- 200934809 Other diamines used in the synthesis of the polylysine of the present invention preferably contain p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4-diamine selected from the above. Diphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-Diaminobiphenyl, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl Propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4- Aminophenyl)hexafluoropropane, φ 4,4′-(p-phenylene diisopropylidene)diphenylamine, 4,4,-(m-phenylene diisopropylidene)diphenylamine, 1, 4-bis(4-aminophenoxy)benzene, 4,4,-bis(4-aminophenoxy)biphenyl, 1,4-cyclohexanediamine, 4,4,-methylene Bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, the compound represented by the above formula (!)_;!)~(〇_ 5), 2,6-diaminopyridine , 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diamine Oxazol, N-ethyl-3,6-diaminoisoxil, N-phenyl-3,6-diaminocarbazole, anthracene, Ν'-bis(4-aminophenyl)benzidine, upper In the compound represented by the following formula (d-15), the compound represented by the following formula (d-15) and the compound represented by the following formula (D_i6) in the compound represented by the above formula (D-II),

-25- 200934809

HzN~czy~N\ )~°3η6~~/~\-nh2 '( D - 1 6 ) The compound represented by the above formula (D - III) and the 1,3- in the compound represented by the above formula (D_ IV) At least one selected from the group consisting of bis(3-aminopropyl)-tetramethyldioxime, more preferably a group selected from the group consisting of p-phenylenediamine and a compound represented by the above formula (D-III) At least one of them. The diamine used in the synthesis of the polylysine of the present invention preferably contains 5 mol% or more of the diamine represented by the above formula (1), more preferably 5 to 50 mol%, further based on the total amount of the diamine. It preferably contains 8 to 40 mol%. The diamine used in the synthesis of the polyamic acid of the present invention preferably further contains at least one selected from the group consisting of the present-amine and the compound represented by the above formula (D-III). When the diamine contains p-phenylenediamine, the total amount of the p-phenylenediamine relative to the diamine is preferably 95 mol% or less, more preferably 50 to 80 mol%. Further, when the diamine contains the compound represented by the above formula (D_ ΠΙ), the compound represented by the above formula (D - Ιπ) is preferably 40 mol% or less, more preferably 1 to 3, based on the total amount of the diamine. 〇% by mole, more preferably 1 to 20% by mole. Here, when the diamine contains the compound represented by the above formula (D_, the total use ratio of the compound represented by the above formula (1) and the compound represented by the above formula (D - III) is preferably 'relative to the total amount of the diamine'. More than 5 mol% and 50 mol% or less, more preferably 8 to 40 mol%. -26- 200934809 A liquid crystal capable of exhibiting stability can be synthesized by using a diamine containing each compound in the above range. Since the alignment polyphosphoric acid or the quinone imidized polymer thereof has an advantage that the liquid crystal alignment agent containing them does not cause display defects such as misalignment, it is preferable. [Synthesis of polylysine The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.2 to 2 based on the equivalent of the amine group contained in the diamine, and the anhydride group of the tetracarboxylic φ acid dianhydride is 0.2 to 2 The ratio of the equivalent is more preferably from 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably in an organic solvent, preferably from -20 to 150 ° C, more preferably from 〇 to 100 ° C. Under temperature conditions, the preferred reaction time is 0.1 to 99 hours, preferably carried out. 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-dimethyl B. An aprotic polar solvent such as guanamine, N,N-dimethylformamide, dimethyl hydrazine, ru-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-methylphenol, a phenolic solvent such as xylenol, benzoquinone or halogenated phenol, etc. The amount of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is relative to the total amount of the reaction solution ( a + b) is an amount of 0.1 to 30% by weight. Further, when the above organic solvent is used in combination with the poor solvent described below, the amount of the above organic solvent U) means the total amount of the organic solvent and the poor solvent. -27- 200934809 In the above organic solvent, alcohols, ketones, vinegars, and ethers which are generally considered to be poor solvents of polyamido acid may be used in combination in the range in which the produced polyaminic acid is not precipitated. Classes, halogenated hydrocarbons, hydrocarbons, and the like. Specific examples of such a poor solvent include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, Ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxylate Ethyl propionate, 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, B 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, isoamyl ether, and the like. When the organic solvent is used in combination with the above-mentioned poor solvent, the use ratio of the poor solvent is preferably 80% by weight or less, more preferably 60% by weight or less, and still more preferably 50% based on the total amount of the organic solvent and the poor solvent. Below weight%. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline acid contained in the solution may be separated and supplied to the liquid crystal alignment agent, or the separated polycondensation may be used. After the acid is refined, the liquid crystal alignment agent is supplied. The separation of the polyamic acid can be carried out by adding the above reaction solution to a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate by depressurization or by subjecting the reaction solution to a reduced pressure by an evaporator. Further, the poly-proline can be purified by a method in which the poly-proline is redissolved in an organic solvent once or several times, and then precipitated by a poor solvent or distilled under reduced pressure using an evaporator. &lt;醯i-Iminylated Polymer&gt; The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention can be obtained by dehydrating and ring-closing the polylysine obtained as described above. The tetracarboxylic dianhydride used in the synthesis of the ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention is the same as the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid. In the case where the tetracarboxylic dianhydride preferably contains the above-mentioned tetracarboxylic dianhydride, the preferred use ratio of the specific tetracarboxylic dianhydride to the polytetradecanoic acid is also higher than that of the polycarboxylic acid. the same. Wherein the specific tetracarboxylic dianhydride used in the synthesis of the ruthenium iodide polymer is preferably selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4, 5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,33 ,4,5,91&gt;-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthoquinone, 2-c]-furan-1,3- Diketone, 3- -29- 200934809 oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetra-1-2,5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl)--3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylalkane-2: At least one of the group consisting of 3,5:6-dianhydride and 4,9-dioxatricyclo[5,3 ·1.〇2'6]·-3,5,8,10-tetraketone Particularly preferred is tricarboxycyclopentyl acetic acid dianhydride. [Diamine] φ is used in the synthesis of the above quinone imidized polymer to exemplify the same as the diamine used in the synthesis of the above polylysine. Synthesis of ruthenium iodide polymer] The ruthenium iodide polymerization contained in the liquid crystal alignment agent of the present invention is a complete ruthenium of all the guanidine structural units of the precursor polyglycine. Amine compounds, acid amide or cell may be a closed loop portion of the coexistence of the ring acyl imine (PEI) thereof. The ruthenium imidization ratio of the quinone imine is preferably 30% or more, more preferably 40% yttrium. The "yttrium imidation ratio" refers to the number of decylamine and the number of quinone rings in the polymer. The total amount of 醯, expressed as the ratio of the ratio of the number of quinone imine rings. At this time, a part of the quinone ring may also be an amine ring. The hydrazine imidization rate can be determined by measuring the 1H-NMR at room temperature by using a tetramethyl-based reference substance in a deuterated solvent in which the ruthenium-imiding polymer is dissolved (for example, deuterated dimethyl sub-milling). The formula (1) is determined, and the furan 3-methylnorbornane undecane 2,3,5-:amine can be a diamine. J, can be dehydrated and dehydrated. This acid structure is divided into appropriate sands according to the following. • 30- 200934809 醯 imidization rate (%) = (1 - AVA^dOxlOO (i) (in formula (1), A1 is near chemical shift 10 ppm The peak area originating from the NH proton, A2 is the peak area derived from other protons, and α is one proton in the ruthenium polymer precursor (polyglycolic acid), other protons The number of ratios of the ruthenium imidization polymer constituting the liquid crystal alignment agent of the present invention can be obtained by dehydration ring closure of the above polyglycine. The dehydration ring closure of polyglycine can be (1) by heating the polyamine The method of acid, or (ii) by dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. The above-mentioned (i) heating poly-proline The reaction temperature in the method is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring closure reaction cannot be sufficiently performed, and if the reaction temperature exceeds 200 ° C, There is a case where the molecular weight of the obtained quinone imidized polymer is lowered. The time should preferably be from 0.1 to 99 hours, more preferably from 0.5 to 72 φ hours. On the other hand, as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyphthalic acid solution of the above (ii) An acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride may be used, and the use ratio of the dehydrating agent is preferably 0.01 to 20 mol per mol of the repeating unit of the polyglycolic acid. A tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, the -31-200934809 phase-concentrated water 24 is directly entangled in the ruthenium, and is not limited to these. The use ratio of the dehydration ring-closure catalyst is preferably 0.01 to 1 Torr for the dehydrating agent used for 1 mol, and the organic solvent used in the dehydration ring-closure reaction is exemplified as the solvent used in the synthesis of proline. Further, the reaction temperature of the deblocking reaction is preferably 〇180 ° C, more preferably 10 150 ° C. The reaction time is preferably 〇·1 to 48 hours, more preferably 〇.5 〜 hours. . The quinone imidized polymer obtained in the above method (1) may be supplied to a liquid crystal alignment agent, or the obtained sulfonated polymer may be purified and then supplied to a liquid crystal alignment agent. In the method (ii), the reaction solution containing the ruthenium iodide polymer is obtained, and the reaction solution can be directly supplied to the liquid crystal alignment agent, and the liquid crystal alignment can be removed from the reaction solution by removing the dehydrating agent and the dehydration ring-closing catalyst. The preparation of the agent may also be carried out by dispensing the ruthenium iodide polymer and then supplying it to the liquid crystal alignment agent, or may further purifying the separated ruthenium iodide polymer and then supplying the liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reverse solution, and a method such as a reagent replacement can be employed. Separation and purification of the ruthenium iodide polymer can be carried out in the same manner as the separation and purification methods of polyglycine. - Terminal-modified polymer - The above-mentioned poly-proline and its quinone-imidized polymer may also be a terminal-modified polymer having a molecular weight adjustment. This terminal modified type -32-200934809 can be synthesized by adding a molecular weight modifier to the reaction system during the synthesis of polyamic acid. The molecular weight modifier may, for example, be a monoanhydride, a monoamine compound or a monoisocyanate compound. Here, examples of the monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, and n-hexadecane. Succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, D-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 molecular weight modifier is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on the total amount of the tetracarboxylic acid dianhydride and the diamine used in the synthesis of the polyglycolic acid. 〇-solution viscosity - the polylysine and the quinone imidized polymer obtained as above, preferably have a solution viscosity of 20 to 800 mPa-s when formulated into a solution having a concentration of 10% by weight, respectively, more preferably 30 ~500 mPa's solution viscosity. The solution viscosity (mPa's) of the above polymer is a polymer solution prepared by using a good solvent (for example, N-methyl-2-pyrrolidone, etc.) of the polymer to a concentration of 1% by weight, using an E-type rotational viscometer. The enthalpy of -33-200934809 was measured at 25 °C. &lt;Other components&gt; The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of polyglycines and quinone imidized polymers thereof as described above. The liquid crystal alignment agent of the present invention may further contain other components in addition to at least one selected from the group consisting of the above polylysine and its ruthenium iodide polymer, without impairing the effects of the present invention. Examples of such other components include a polymer other than the above-mentioned polyaminic acid and its quinone imidized polymer (hereinafter referred to as "other polymer"), and a compound having at least two epoxy groups in the molecule. (hereinafter referred to as "epoxy compound"), a functional decane compound, and the like. &lt;Other Polymers&gt; Examples of the other polymer include polyacrylic acid (hereinafter referred to as "other polyamic acid") and yttrium imidized polymer (hereinafter referred to as "other oxime"). Imineated polymer"), polyphthalate, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) Derivatives, poly(meth)acrylates, and the like. Among them, as the other polymer, at least one selected from the group consisting of other polyamines and other quinone-imided polymers is preferably used. These other polylysines and their ruthenium iodide polymers, in addition to the tetracarboxylic dianhydride and the diamine not containing the compound represented by the above formula (1), The synthesis of ruthenium imidized polymers is -34-200934809. The tetracarboxylic dianhydride used as the raw material at this time preferably contains at least one selected from the group consisting of alicyclic tetracarboxylic dianhydride and pyromellitic dianhydride, and particularly preferably contains 1, 2, At least one of the group consisting of 3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride. As the diamine, a diamine containing an aromatic diamine, particularly preferably a 4,4'-diaminodiphenylmethane and a 2,2'-dimethyl-4,4'-diamine group are preferably used. A diamine of at least one of the group consisting of benzene. As other polymers, it is more preferable to use other poly φ valine. When the liquid crystal alignment agent of the present invention contains other polymers, the content ratio of the other polymers is preferably 75% by weight or less based on the total amount of the polyamic acid and its ruthenium iodide polymer and other polymers. More preferably, it is 65% by weight or less, further preferably 60% by weight or less. The liquid crystal alignment agent of the present invention may contain an epoxy compound from the viewpoint of improving the adhesion to the surface of the substrate. Preferred examples of such an epoxy compound include ethylene glycol diglycidyl ether, hydrazine polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol condensed water. Glycerol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol Diglycidyl ether, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(heart diglycidylaminomethyl)cyclohexane, 叱心^1 '川'-tetraglycidyl- 4,4'-diaminodiphenylmethane, anthracene, fluorene-di-glycol-35- 200934809 oil-benzylamine, n,n-diglycidyl-amine Methylcyclohexane, n, n-diglycidyl-cyclohexylamine, and the like. The mixing ratio of these epoxy compounds is preferably a total amount of 100 parts by weight of the polymer (refers to the total amount of the above polylysine and its ruthenium iodide polymer and other polymers. The same applies hereinafter). 40 parts by weight or less is more preferably 1 to 30 parts by weight. The functional decane compound may, for example, be 3-amino φ propyl trimethoxy decane, 3-aminopropyl triethoxy decane, 2-aminopropyl trimethoxy decane or 2-amino group. Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl 3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane Base 〇-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazanonane, 9-trimethoxydecyl-3,6-diaza Heteroalkyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, methyl 9-trimethoxydecyl-3,6-diazadecanoate, 9 · Methyl triethoxy decyl-3,6-diazepine, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethyl Baseline, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidoxy-36-200934809 methyltrimethoxy Decane, propylene oxide methyl triethoxy decane, 2-glycidoxyethyl trimethoxy decane, 2-glycidoxyethyl triethoxy decane, 3-glycidoxy Propyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like. The mixing ratio of the functional decane compound is preferably 40 parts by weight or less based on 100 parts by weight of the total amount of the polymer. &lt;Liquid Crystal Alignment Agent&gt; φ The liquid crystal alignment agent of the present invention is at least one selected from the group consisting of polylysine as described above and its ruthenium iodide polymer, and optionally other components if necessary The component is preferably dissolved in an organic solvent. The organic solvent which can be used for the liquid crystal alignment agent of the present invention may, for example, be N-methyl-2-pyrrolidone, r-butyrolactone, r-butylide or N,N-dimethylformamide. N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, B Ethyl oxypropionate 'ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, Ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether An acid ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate, and the like. They can be used alone, or -37- 200934809 can be used in combination of two or more. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the liquid crystal alignment agent other than the solvent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 10 parts by weight. The range of %. 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, and when the solid content concentration is less than 1% by weight, the thickness of the coating film 0 is caused. Too small to obtain a good liquid crystal alignment film; on the other hand, when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased. The coating performance is deteriorated. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when the spin coating method is employed, the particularly preferable solid content concentration is in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is particularly preferable to make the solid content concentration to be in the range of 3 to 9 % by weight, so that the solution viscosity can be made to fall within the range of 12 to 50 mPa's. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa 's. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. -38- 200934809 The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (4). (1) Applying the liquid crystal alignment agent of the present invention to the substrate provided with the patterned transparent conductive film by an appropriate coating method such as an offset printing method, a spin coating method, or an inkjet printing method, and then passing The coated surface is heated to form a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and alicyclic ring can be used. A transparent substrate made of plastic such as polyolefin. As the transparent conductive film provided on one side of the substrate, for example, a NESA film made of tin oxide (Sn〇2) (registered trademark of PPG, USA) or an indium oxide-tin oxide (In2〇3- Sn〇2) ITO film can be used. Wait. The pattern of these transparent conductive films can be formed by photolithography or a method of using a mask in advance when forming a transparent conductive film. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a ruthenium functional decane compound, a functional titanium compound or the like may be applied to the surface of the substrate in advance. After the application of the liquid crystal alignment agent, it is preferred to perform preheating (prebaking) for the purpose of preventing the coating agent liquid from sagging. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 100 ° C. The prebaking time is preferably from 0.1 to 60 minutes, more preferably from 0.5 to 30 minutes. Then, after the solvent is completely removed, it is preferred to further carry out a heating (post-baking) process. The post-baking temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. » -39- 200934809 The post-baking time is preferably from 0.5 to 180 minutes, more preferably from 1 to 120 minutes. The liquid crystal alignment agent of the present invention forms a coating film as an alignment film by coating the organic solvent as described above, and when the phthalic acid structure remains in the polymer contained in the liquid crystal alignment agent of the present invention, it is also possible to form a coating film. The film is subjected to a dehydration ring-closure reaction by further heating to form a further ruthenium-coated film. The thickness of the formed coating film is preferably 0.001 to 1 μm, more preferably © 0.005 to 〇.5 μm. (2) The coating film formed as above may be used as a vertical alignment type liquid crystal alignment film as it is, or may be optionally subjected to the following polishing treatment. Further, when the liquid crystal alignment agent of the present invention is applied to a level-aligned liquid crystal alignment film such as a TN type or an STN type, it is necessary to polish the coating film formed as above. In the above-mentioned polishing treatment, the coating film surface may be rubbed with a certain amount of rubbing by a roll wrapped with a cloth made of a suitable fiber such as nylon, rayon or cotton, and used as a liquid crystal alignment film. In addition, a part of the liquid crystal alignment film shown in the patent document 2 (Japanese Laid-Open Patent Publication No. Hei 6-222366) or the patent document 3 (Japanese Laid-Open Patent Publication No. Hei 6-281937) a process of changing the pretilt angle of a portion of the liquid crystal alignment film by irradiation with ultraviolet rays, or after forming a protective film on a part of the surface of the liquid crystal alignment film, as shown in Patent Document 4 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. The treatment for removing the protective film after the sanding treatment is performed in a direction different from that of the first -40-200934809 pre-grinding treatment, so that each region of the liquid crystal alignment film has a different liquid crystal alignment energy, which can improve the field of view performance of the obtained liquid crystal display element. (3) The liquid crystal alignment film obtained as described in the above (1) to (2) can then be cleaned as needed. As the washing solvent, for example, water, acetone, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, vinegar acid can be used. Butyl ester, tetrahydrofuran, hexane, heptane 'octane, and the like. In order to improve the cleaning efficiency, at least one selected from the group consisting of a method of adding a surfactant to a cleaning solvent, a method of washing with a heating solvent, a method of combining with a brushing, and a method of using ultrasonic waves may be used. Use together. After the cleaning, it may be used as a liquid crystal alignment film as it is, or it may be further washed with a suitable solvent, and then the solvent may be removed by heating as needed. (4) Two substrates on which the liquid crystal alignment film is formed are formed, and the two ruthenium substrates are placed opposite each other through a gap (cell gap), and in the case of polishing, the polishing directions of the respective liquid crystal alignment films are perpendicular or opposite to each other. In parallel, the peripheral portions of the two substrates are bonded together with a sealant, and liquid crystal is injected into the gap between the substrate and the sealant, and the injection holes are closed to form a liquid crystal cell. Then, the liquid crystal display element of the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell. Here, as the sealing agent, for example, for example, An epoxy resin or the like containing alumina balls as a curing agent and a separator. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferred, and for example, a Schiff base liquid crystal, an azo-based liquid crystal, a biphenyl liquid crystal, or a phenyl ring may be used. An alkane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. In addition, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added under the trade names "C-15" and "CB-15" (Merck) A commercially available chiral agent or a ferroelectric liquid crystal such as methoxybenzylidene-p-amino-2-methylbutylcinnamate. The polarizing plate to which the outer surface of the liquid crystal cell is bonded is a polarizing plate or a crucible formed by sandwiching a polarizing film called "H film" obtained by stretching the polyvinyl alcohol and simultaneously absorbing iodine, in a protective film of acetate. A polarizing plate made of the film itself. © &lt; Surface Free Energy of Liquid Crystal Alignment Film&gt; The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention has a characteristic that the surface free energy is smaller than that of the conventional liquid crystal alignment film. It is presumed that due to this characteristic, the liquid crystal display element having the same can exhibit uniform liquid crystal alignment, and the afterimage performance is also excellent. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can have a surface free energy of 38 mN/m or less, and can also reach 37 mN/m or less, and -42 to 200934809 can even reach 36 mN/m or less. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is particularly suitable for use as a liquid crystal alignment film for a vertical alignment type liquid crystal display device. [Examples] Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited to the examples. In the following examples, the ruthenium imidization ratio of the ruthenium iodide polymer is obtained by dissolving the ruthenium iodide polymer under sufficient reduced pressure at room temperature and then dissolving it in deuterated dimethyl hydrazine. 1H-NMR was measured at room temperature using tetramethylnonane as a reference material, and the measured 1H-NMR spectrum was calculated according to the above formula (i). The solution viscosity of the polymer solution was measured at 25 °C using an E-type rotational viscometer. Synthesis Example 1 (Synthesis Example of Compound represented by the above formula (1)) To a 500 ml three-necked flask, O 21.5 g (0.05 mol) of DL-α-tocopherol and 5.3 g (0.0525 Mo) were placed under a nitrogen atmosphere. The ear) triethylamine and 150 ml of tetrahydrofuran were stirred underneath. A solution consisting of 10.9 g (0.0525 mol) of 3,5-dichlorobenzamide chloride and 50 ml of tetrahydrofuran was added dropwise thereto over 30 minutes. The solution was then stirred at room temperature for 3 hours to carry out a reaction. Then, the salt precipitated from the reaction system was filtered off, and tetrahydrofuran was distilled off from the solution. To the solid obtained as a result, 200 ml of chloroform was added to dissolve them all, and the organic layer was washed with distilled water. -43- 200934809 After the machine layer is dehydrated with magnesium sulfate, it is concentrated by a rotary evaporator, and the obtained crude product is purified by silica gel column chromatography (developing solvent: chloroform), and then recrystallized from ethanol to obtain a dichloro intermediate. 29.5g. Ο Then 'under nitrogen atmosphere' in a 1000 ml three-necked flask, the above synthesized intermediate 15.lg (〇.〇25 mol), 4-nitrophenol 7.3 g (0.0525 mol) and cesium carbonate 20.7 g (〇.15 mol) was mixed, and 300 ml of dimethylformamide was added thereto, followed by further stirring. The solution was stirred under nitrogen at room temperature for 6 hours to carry out a reaction. After the completion of the reaction, 300 ml of distilled water was added to the reaction solution, and the mixture was thoroughly stirred, and then extracted with 300 ml of chloroform, and the obtained organic layer was washed with distilled water. Then, the organic layer was dehydrated with magnesium sulfate, and concentrated using a rotary evaporator. The obtained crude product was recrystallized from ethanol to give 17.2 g of the compound of the following formula (1 - 5 a: u) (compound (1 - 5) — la)).

Then, 16.2 g (0.02 mol) of the above synthesized compound (1 - 5 - la) and 45.1 g (0.2 mol) of tin chloride dihydrate were mixed in a 300 ml three-necked flask under a nitrogen atmosphere. Ethyl acetate of 15 〇ml -44 - 200934809 was added thereto, and the resulting solution was heated and stirred under reflux for 3 hours under nitrogen to carry out a reaction. After completion of the reaction, the reaction solution was mixed with 400 ml of a saturated aqueous potassium fluoride solution and thoroughly stirred, and the mixture was separated, and the obtained organic layer was washed with distilled water. The organic layer was dehydrated with magnesium sulfate, and concentrated by a rotary evaporator. The obtained crude product was recrystallized from ethanol to give 14.2 g of the compound of the formula (1 - 5 - 1) (Compound (1 - 5 - 1) )).

Comparative Synthesis Example 1 (Synthesis of Comparative Diamine) The compound (Compound (R-1)) represented by the following formula (R-1) as a comparative diamine is disclosed in Patent Document 1 (JP-A-2001-97969) The method described in the synthesis.

Synthesis Examples 2 to 9 and Comparative Synthesis Example 2 (Combination of ruthenium iodide-45-200934809) To N-methyl-2-pyrrolidone, the kinds and amounts of diamines shown in Table 1 were sequentially added and Tetracarboxylic dianhydride, a total amount of tetracarboxylic dianhydride and diamine (b) is 20% by weight relative to the total amount of the reaction solution (a+b), and is reacted at 6 (TC 4) In an hour, a solution containing poly-proline (A-1)~(A-8) and (a-1), respectively, is obtained. These solutions are each taken in small amounts and separately added with N-methyl-2-pyrrolidone to form a poly A solution in which the valine acid concentration is 10% by weight, and the measured solution viscosity is shown in Table 1. To the polyglycine-containing solution prepared above, the proline acid per lysine is present. The number of units was added to the amounts of pyridine and acetic anhydride shown in Table 1, respectively, and heated at 110 ° C for 4 hours to carry out a dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was treated with a new N-methyl-2. - Pyrrolidone is subjected to solvent replacement (in this operation, pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system) to obtain 15 weights each. a solution of % amidized polymer (B-1)~(B-8) and (b~〇1). The oxime imidization ratio of each ruthenium iodide polymer and a small amount of each solution and added to N- The solution viscosity measured by a solution of methyl-2-pyrrolidone in a concentration of 10% by weight of a ruthenium-imiding polymer is shown in Table 1. Synthesis Examples 10 and 1 1 (synthesis of poly-proline) To N - In the methyl-2-pyrrolidone, the kinds and amounts of the diamine and the tetracarboxylic dianhydride shown in Table 1 are sequentially added to form a total amount of the tetracarboxylic dianhydride and the diamine (b) with respect to the total of the reaction solution. The amount (a+b) is 20% by weight of the -46-200934809 solution, which is allowed to react at 60 ° C for 4 hours to obtain polyamine acids (A - 9), (A - 10), (a - 2 ), respectively. And (a-3) solution. Each solution was taken in small amounts, and N-methyl-2-pyrrolidone was added separately to prepare a solution having a valine acid concentration of 10% by weight. The measured solution viscosity is listed in Table 1. Comparative Synthesis Examples 3 and 4 (Comparison of polyamines for comparison) To N-methyl-2-pyrrolidone, the types and amounts of diamines and dicarboxylic acids shown in Table 2 were added sequentially, respectively, to 1 mol. Dicarboxylic acid To the mixture, diphenyl phosphate and pyridine are added as a condensing agent, respectively, to form a diamine, a dicarboxylic acid, a triphenyl phosphite and a pyridine (b) relative to the reaction solution. A total amount (a+b) of a 20% by volume solution was allowed to react at 120 ° C for 3 hours to obtain a solution containing polydecylamine (a-2) and (a-3), respectively. N-methyl-2-pyrrolidone was separately added to prepare a solution having a concentration of polyamidamine in a weight %, and the measured solution viscosity is listed in Table 2. Some of these are concentrated in the weight of 10 -47 - 200934809

醯imination polymerization solution viscosity (mPa.s) CO s vn 1—( 1 1 On 醯 imidization rate (%) CO oo g oo L〇1 1 cn v〇 name B-1 Β-2 B- 4 B-5 1_ B-6 B-7 OO 1 PQ 1 1 i—H i X) dehydration ring closure reaction acetic anhydride (mole multiple) 〇〇1 1 p shame steepness (mole multiple) P p S 1 1 p Polyuric acid solution viscosity (mPa-s) 〇1 &lt; s OO 1 ^ s CO »—H Customer name A-1 1 &lt; CO 1 &lt; inch 1 &lt; 1 &lt; 1 &lt; A-7 oo 1 &lt; ON 1 &lt; o T &lt; 1 4 1 cd Tetracarboxylic dianhydride (Morby) Tl(lOO) Tl(lOO) Tl(lOO) Tl(lOO) Tl(lOO) Tl(lOO) Tl (lOO) 1 Tl(lOO) T-2(100) T-2(50)+T-3(50) Tl(lOO) Diamine (Morby) Dl(25)+D-5(75) Dl (25)+D-5(75) Dl(10)+D-2(10&gt;fD-5(80) Dl(10)+D-2(10)+D-5(80) Dl(10)+ D-3(10)+D-5(80) Dl(20)fD-3(5)+D-5(80) Dl(10&gt;fD-3(15&gt;fD-5(80) Dl(25) +D-5(50)+-D-6(25) 1 D-7(100) D-6(100) D-4(25)+D-5(75) Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Synthesis Example 11 Comparative Synthesis Example 2 200934809 Table 2 Diamine II Acid Polyamide (Morby) (Morby) Name Solution Viscosity (mPa.s) Comparative Synthesis Example 3 Dl(25)+D-5(75) Cl(lOO) a-2 121 Comparative Synthesis Example 4 Dl (25)+D-6(75) ci(ioo) a-3 143 In Tables 1 and 2, the abbreviations of diamine and tetracarboxylic dianhydride have the following meanings respectively. _ [Diamine] D-1: Compound (1-5-1) D-2: Compound D-3 represented by the above formula (D-8): Compound D-4 represented by the above formula (D-10): Compound (R-1) D-5: Pair Phenylenediamine D-6: 4,4'-diaminodiphenylmethane D-7: 2,2'-dimethyl-4,4'-diaminobiphenyl [tetracarboxylic dianhydride] T — 1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride T—2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride T-3: pyromellitic dianhydride [dicarboxyl Acid] C-1: terephthalic acid Example 1 The amount of the quinone-containing imine prepared in the above Synthesis Example 2 was measured in an amount equivalent to 100 parts by weight in terms of conversion to the ruthenium iodide polymer (B-1) a solution of a polymer (B_-49-200934809 1) to which r·butyrolactone (BL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added, and 5 parts by weight were further added. Epoxy compound N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, formulated in a solvent composition BL: NMP: BC = 40:30: A solution of 30 (weight ratio) and a solid content concentration of 4% by weight was filtered through a filter having a pore size of 0.2 / zm to prepare a liquid crystal alignment agent. The liquid crystal alignment agent was evaluated as follows. The results are shown in Table 3. (1) Evaluation of surface free energy of liquid crystal alignment film 0 The liquid crystal alignment agent prepared above was applied by spin coating on a transparent conductive film made of ITO film provided on one surface of a glass substrate having a thickness of 1 mm at 80°. The film was heated at C for 1 minute (prebaking), and further heated at 200 ° C for 60 minutes (post-baking) to form a coating film (liquid crystal alignment film) having a film thickness of 0.08 μm. The contact angle between water and diiodomethane was measured for the liquid crystal alignment film, and the surface free energy of the liquid crystal alignment film was determined by the extended Fowkes equation using these measurements. (2) Production of liquid crystal display element The above-prepared liquid crystal alignment agent was applied by spin coating on a transparent conductive film made of ITO film provided on one surface of a glass substrate having a thickness of 1 mm, and heated at 80 ° C. After a minute (prebaking), it was further heated at 200 ° C for 60 minutes (post-baking) to form a coating film (liquid crystal alignment film) having a film thickness of 0.08 vm. This operation was repeated to manufacture two (a pair of) substrates having a liquid crystal alignment film. On each outer edge of the pair of substrates having a liquid crystal alignment film, an epoxy resin adhesive having a diameter of 3.5 μm is applied, and the liquid crystal alignment film surface is relatively recombined and pressed, and then The adhesive cures. Next, a negative liquid crystal (manufactured by Merck & Co., Ltd., -50-β 200934809 MLC-6608) was attached to the substrate through a liquid crystal injection port, and then closed with an acrylic photocurable adhesive, and polarized light was applied to both outer sides of the substrate. Board, made of liquid crystal display elements. (3) Evaluation of the vertical alignment property. When the 8 V AC voltage (peak-peak) was not applied to the liquid crystal display element manufactured above, the display element was not observed from the vertical direction, and no uniform display was observed. A uniform whiteness was evaluated as "good" when a voltage was applied. (4) Evaluation of voltage holding ratio At a temperature of 60 ° C, a liquid crystal display element manufactured over 167 msec was applied with a voltage of 5 V for 60 μsec, and then the voltage was released from the voltage to 167 mm. The measurement apparatus was manufactured by Toyo Technology Co., Ltd. (5) Evaluation of afterimage performance Two liquid crystal displays manufactured in the same manner as above were prepared. 直流 A DC voltage of IV was applied to one of the electrodes, and another voltage was applied for two hours. Then, when the two liquid crystals were displayed at 2.5 V, the difference (gray difference) at 256 gray scales was examined. "Good" when the 値 is below 15 gray levels. In the same manner as in Example 1, except that the solution of the material of Table 3 was used as the polymer-containing solution, and the kind of the compound shown in Table 3 and the compound were used, the same procedure as in Example 1 was carried out. When the liquid crystal injection port is sealed to form a vertical alignment type applied voltage and when the liquid crystal display has an applied voltage as shown, the holding voltage 5 seconds after the voltage application time is "VHR-1" under the vertical alignment time span. . The component, the brightness residual image performance of the applied electrical component of the DC display element applied with a 5 V at room temperature can be evaluated as the epoxy-based liquid crystal alignment agent containing the polymerization ratio shown in the above, -51-200934809 t Evaluation. The results are shown in Table 3. Further, in Examples 13 to 16 and Comparative Example 5, two kinds of solutions containing a polymer were used.

-52- 200934809 Table 3 Touring ages (mN/m) pieces (Lin) mm (heterogeneous) Vertical orientation (%) Enzyme 雠mm. GW) Example 1 Β-1 ( 100) El(5) 36 Good&gt;99.5 12 Example 2 Β-2(100) E-l(3) 36 Good&gt;99.5 9 Example 3 Β-3(100) E-l(3) 35 Good&gt;99.5 10 Example 4 Β-3(100) - 36 Good &gt;99.5 12 Example 5 Β-3(100) E-2(10) 34 Good &gt;99.5 13 Example 6 Β-3(100) E-3(10) 36 Good &gt; 99.5 8 Example 7 Β-4(100) E-l(3) 35 Good &gt;99.5 10 Example 8 Β-4(100) E-3(10) 37 Good &gt;99.5 10 Example 9 Β- 5(100) El(5) 36 Good&gt;99.5 12 Example 10 Β-6(100) El(5) 35 Good&gt;99.5 8 Example 11 Β-7(100) El(5) 35 Good&gt; 99.5 7 Example 12 Β-8(100) El(5) 36 Good&gt;99.5 9 Example 13 Β-3(50)+Α-9(50) — 38 Good&gt;99.5 11 Example 14 B-3 (50) fA-10(50) E-2(10) 37 Good &gt;99.5 14 Example 15 Β-4(50&gt;+Α-9(50) El(5) 36 Good&gt;99.5 13 Example 16 Β-4(50&gt;+-Α-9(50) E-2(10) 38 Good&gt;99.5 12 than shed 1 al(lOO) — 39 Good 99.0 43 比难J2 al(100) El(5) 40 Good 99.0 22 Comparative Example 3 a-2(100) — 41 Good 97.5 38 Comparative Example 4 a-3(100) El(5) 39 Good 98.0 25 Comparative Example 5 a-3(50)+A-10(50) E-2(10) 41 Poor 96.5 28 In Table 3, the number of 値 in the parentheses after the polymer name is contained in the polymer solution used. The amount (parts by weight) of the polymer. The epoxy group-53-200934809, the number of ruthenium in the back bracket is the use ratio (parts by weight) of each epoxy compound. The abbreviations of the epoxy compounds are respectively the following meanings. E - 1: N, N, N', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl E-2: ^", "-tetraglycidyl Base-4,4'-diaminodiphenyl ketone E-3: Ν, Ν, Ν', Ν'-tetraglycidyl metaxylylenediamine. ❿ [Simple description of the diagram] Μ . [Main component symbol description] None. ❹ -54-

Claims (1)

200934809 VII. Patent application scope: 1. A liquid crystal alignment agent characterized in that it comprises at least one selected from the group consisting of polylysine and its ruthenium iodide polymer. The acid dianhydride is obtained by reacting a diamine containing a compound represented by the following formula (1), In the formula (1), X is a divalent organic group containing an aromatic ring or -〇-*, -S-* ' -S〇2-* ' -NH-* ' -COO-* ' -OCO-* ' -NHCO-* '-CONH-*, -CO-*, -CH2〇·*, methylene or carbon number 2~8 The alkylene group (wherein the above-mentioned "*" linkage is located on the side of the color-filled structure), and γ is each 〇_*, -S-*, -S〇2-*, -NH·*, -COO -*, -OCO-*, -NHCO-*, -C〇NH-氺, -CO-*, methylene or an alkylene group having 2 to 8 carbon atoms (wherein, with "*" above The linking bond is bonded to the amine phenyl group), and the two Ys may be the same or different from each other, and each of R1, R11 and R111 is a hydrogen atom or a monovalent organic group. 2. The liquid crystal alignment agent of claim 1, wherein the diamine further contains at least one selected from the group consisting of p-phenylenediamine and a compound represented by the following formula (D-III), h2n (D-III) -55· 200934809 In the formula (D-ΙΙΙ), R7 is _〇_*, _c〇〇·*, -OCO-*-CONH-* or -CO-*, (of which, R8 linkage), R8 is a skeleton valent organic group having a group selected from the group consisting of a steroid skeleton, a trifluoromethylmethoxyphenyl group, and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms Or 3. The liquid crystal alignment agent of claim 1 or 2, wherein the dianhydride contains 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal alignment film formed of a liquid crystal alignment agent as disclosed in claims 1 to Q. 5. For the liquid crystal alignment film of claim 4, the surface of the liquid crystal alignment film is 38 mN/m or less. A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 4 or 5. , -NHCO-*, a linkage to a phenyl, trifluoro or a group of 1 fluoroalkyl. Among them, the free energy of any of the three carboxylic acids is the patent scope. -56- 200934809 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 4E 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None.